US3809535A - Dry cleaning of textiles - Google Patents

Abstract

A METHOD OF WASHING SOLID, MORE PARTICULARLY TEXTILE ARTICLES WITH AN ORGANIC SOLVENT, IMPROVED BY ADDING AN INTENSIFIER. THE INTENSIFIER IS A PRIMARY OR SECONDARY AMIDE OF A DICARBOXYLIC ALIPHATIC ACID OR ANHYDRIDE WHEREIN ONE CARBON ATOM IN THE CHAIN CONNECTING THE TWO ACID GROUPS BEARS AN ALKYL OR ALKENYL RADICAL CONTAINING AT LEAST SIX CARBON ATOMS. THE METHOD GIVES BETTER WHITENESS AND MORE PARTICULARLY PREVENTS THE RE-DEPOSITION OF DIRT.

Description

United States Patent 01 lice 3,809,535 Patented May 7, 1974 3,809,535 DRY CLEANING F TEXTILES Jean Neel, Lyon, and Bernard Papillon, Lyon-la-Mulatli ere, France, assignors to Societe Rhoue-Progil, Paris,

rance No Drawing. Filed Dec. 15, 1971, Ser. No. 208,436

Int. Cl. D061 1/00 US. Cl. 8-142 Claims ABSTRACT OF THE DISCLOSURE A method of washing solid, more particularly textile articles, with an organic solvent, improved by adding an intensifier.

The intensifier is a primary or secondary amide of a dicarboxylic aliphatic acid or anhydride wherein one carbon atom in the chain connecting the two acid groups bears an alkyl or alkenyl radical containing at least six carbon atoms.

The method gives better whiteness and more particularly prevents the re-deposition of dirt.

The invention relates to an improvement to dry cleaning of textiles, i.e., the washing of textile fibres or articles with non-aqueous solvents. The invention relates more particularly to the use of a novel kind of adjuvants which improve cleaning and give more thorough bleaching or cleaning. The invention relates to the novel kind of drycleaning intensifiers and to baths containing the aforementioned adjuvants.

Dry cleaning is an activity which has recently become widely extended and which uses large tonnages of solvents. The solvents are mainly chlorinated hydrocarbons, more particularly perchloroethylene and trichloroethylene which, owing to their nonflammability and other advantageous properties, have become the main solvents used in this branch of industry. Whatever solvent is used, however, i.e. petrol, hexane or other aliphatic or benzene hydrocarbons, or chlorinated, chlorofluorinated or other solvents, the solvent does not usually produce adequate cleaning by itself; it is well known to add surface-active agents soluble in the given solvent to the cleaning bath, For example it has become conventional to add agents such as the following to the solvents: amine alkyl-aryl sulphonates, ethoxylated derivatives of aliphatic amines or alcohols, or alkyl-polyethoxy-phenols. In spite of the aforementioned additives, which are often accompanied by optical blueing agents and bleaching agents, progress still needs to be made in the art of cleaning with solvents, since the results are not yet perfect; the degree of cleaning, or the whiteness of textile fibres or articles cleaned by the aforementioned method usually leaves something to be desired. It is therefore necessary to find agents which, when added to dry-cleaning baths, improve the aforementioned results; this is the problem which the invention proposes to solve.

The invention provides a novel kind of adjuvants for dry-cleaning baths which substantially improve the degree of cleaning compared with that obtained with conventional surface-active agents. In addition, the novel adjuvants are particularly effective when used together with conventional surfactants in the presence of a small proportion of water in the solvent; the resulting cleaning is much more thorough than could be obtained with either of the additivesi.e., the adjuvant according to the invention and the conventional agent-if used alone.

The intensifier according to the invention comprises one or more primary or secondary amides derived from an aliphatic diacid or anhydride, bearing an alkyl or alkenyl substituent, and an aliphatic polyamine, the number of carbon atoms in the substituent being greater than in the polyamine.

The length of the chain of the hydrocarbon substituent is such that the intensifier is soluble in the given solvent; this means that the chain must usually contain at least 6 carbon atoms, preferably more than 12 C. In the case of chlorinated solvents, the best intensifiers are those in which the hydrocarbon substituent forms a chain of 18 to 200 carbon atoms, preferably 24 to C.

The carboxylic acid entering into the composition of the primary amides or secondary amides (imides) according to the invention may have their two carboxylic groups in all positions from 11-13 to ot-w. Since, for economic reasons, the products used are mainly derived from C to C diacids (or anhydrides), i.e. from malonic to adipic acid, the carboxylic groups are at the two ends of a chain formed by l to 4 CH and the alkyl or alkenyl substituents is attached to one of the carbon atoms in the chain. In addition, however, to the aforementioned acidsi.e. malonic, succinic, glutaric and adipic acid-a number of others can be used as the base of the primary amides or imides according to the invention.

For example, the base can also comprise derivatives corresponding e.g. to pimelic, suberic, azelaic, sebacic acid, etc., i.e. heptane-, octane-, nonaneor decane-dioic acid respectively, bearing a long alkyl or alkenyl group on one of the carbon atoms connecting the two COOH or --CO--OCO groups.

In addition to the aforementioned ot-w diacids, the amide derivatives according to the invention can come from acids whose carboxyl groups are in positions other than the oc-w positions in their aliphatic chains. Suitable acids correspond e.g. to: 2,5-dicarboxylhexane; 1,4-dicarboxyhexane; 1,6 dicarboxyoctane; 5,7 dicarboxyundecane; 1,4-dicarboxydodecane; 1,8-dicarboxyoctadecane (a derivative of oleic acid), etc.

The polyamines from which the amide group of the intensifiers according to the invention is derived are preferably alkylene-polyamines but can if required comprise alcohol-amines, phenol-amines or aromatic amines, provided that they contain at least two atoms of aminated nitrogen per molecule. The following substances are preferred examples of the first group: ethylene-diamine; diethylene-triamine, triethylene-tetramine, tetraethylenepentamine, pentaethylene-hexamine, pentamethylene-diamine, hexamethylene-diamine, tripropylene-tetramine, tetrapropylene-pentamine, etc., or polyalkylene-polyamines or mixtures of heavy polyalkylene polyamines obtained as residues in the manufacture of the aforementioned substances. Cyclic polyamines are also suitable, more particularly piperazine and derivative thereof substituted on the nitrogen atom by one or more alkyl groups, e.g. N- ethyl, N-methyl, N-isopropyl, N-methyl-(fi-amino-ethyD- piperazine etc. The alkyl groups of the aforementioned polyamines may also be branched.

The amides according to the invention may also be derived from other amines such as: alkylor dialkylamino-alkyl amines such as methyl-amino-, propylamine, dimethylamino-ethylamine, diethylamino-butylamine; aryl polyamines such as phenylene dior tri-amine, triamino toluene, triamino-triphenyl-methane, diamino-diphenolamine, triamine-phenol, etc.; or alcohol-amines such as di-l,3-amino-2-propanol, 1,2-diamino-3-propanol, triaminohexanol etc.

In some cases, more particularly when the number of nitrogen atoms in the amine is relatively large, it may be advantageous to block all or some of the amine groups which have not been converted into amide, by substitution or an addition reaction. For example, depending on the particular embodiment of the invention, the primary or secondary amide in the intensifier contains nitrogen atoms bearing hydrocarbyl radicals, inter alia aryl, more particularly alkyl radicals, acyl groups, aryl-soulphonic radicals, or alkoxy or polyoxyalkylene groups. Similarly, one or more of the amine groups can be blocked by adding a molecule of an organic, mineral or mixed acid.

The amine groups can be blocked before or during the preparation of the amide. Appropriate reagents, inter alia alkyl halides such as methyl, ethyl, propyl, butyl or amyl chloride or bromide, are described in American Pat. No. 2,638,450, which also cites some examples of polyalkylene-polyamines, e.g. N-alkylated polyamines. Of course, the aforementioned examples in no way limit the present invention.

The reagents can also be acids or acid anhydrides and halides such as acetic, propionic and butyric acid and anhydrides and chlorides thereof; other reagents are nonlimitatively cited in American Pat. No. 2,568,876. Advantageously, aryl-sulphonic groups are fixed with sulphonic acids whose alkali metal salts are known surfactants and whose amine salts are used in conventional dry cleaning. For example, the following substances are suitable: arylsulphonic acids in which the aryl group is benzene, toluene, octyl-benzene, dodecyl-benzene, naphthalene, butyl naphthalene, n-naphthol, etc. Preferably the sulphonic group is in the para position of the alkyl group in benzene deivatives and in the a or 5 position in the naphthalenes. Alkylsulphonic acids such as octyl-, laurylor oleyl-sulphonic acid can also be used.

The alkoxy or poly-oxyalkylene groups can be fixed on all or some of the nitrogen atoms in the starting amine or the final amide by a conventional condensation reaction with an oxide of an olefin or a poly-oxyalkylene. Ethylene oxide and propylene oxide are the most common reagents but others can of course be used, e.g. the oxides of butenes, amylenes or hexenes.

The primary or secondary amides according to the invention can be on one or more of the amine groups of the starting polyamine. In other words, the number of mols of polyamine may vary with respect to the number of mols of diacid or anhydride; the ratio may vary for instance from 0.5 to 2 but is preferably between 0.5 and 1.

The following formula non-limitatively illustrates the composition of a series of homologous imides according to the invention:

The aforementioned imides come from the condensation of an anhydride wilth a polyethylene-polyamine in which R is an alkyl or alkenyl group preferably having between 18 and 120 carbon atoms in the chain, n is usually between 0 and 6; Z is a hydrogen atom or one of the aforementioned groups blocking the amine group, e.g. an alkyl, an acyl, a moiety of an alkylor arylsulphonic acid, or a polyoxyalkylene group; Q is a hydrogen atom or a blocking group similar to but not necessarily identical with Z, and the sum (m+p) is usually between 2 and 7, since the amino chain need not be very long.

In the particular case where, for example, R is a straight polypropylene chain containing 13 propylene links, n=2; Q=H; (m' +P) =4 and Z is paradodecyl-benzene-sulphonic acid radical; the product is a polypropenyl-glutaric 4 monoimide of tetraethylene pentamine in which the terminal, non-amido nitrogen atom is blocked in the form of dodecylbenzene sulphonates:

The aforementioned illustration relates to a monoimide, i.e. a secondary mono-amide, but a di-imide could of course also be used according to the invention; in the latter case the Z group is a second glutaric acid or anhydride radical (2 mole of diacid per mol of polyamine). In the special case of polypropenyl-glutarimide, therefore, the last-mentioned formula has the same configuration at the right and at the left end.

Since the condensation of diacids or anhydrides with polyamines is well known, there is no need to describe it here; we shall merely mention that it is usually performed between and 250 C. with elimination of the water formed, e.g. in the form of an azeotropic mixture with benzene or toluene. Condensations of the aforementioned kind are described inter alia in the U.S. patents cited hereinbefore. Similarly, an aliphatic chain can be fixed on to dicarboxylic acids by conventional methods; for example the fixing of polyolefin chains onto diacids such as maleic, fumaric, itaconic or citraconic acid is described in U.S. Pat. No. 2,283,214. Since maleic anhydride is particularly plentiful in industry, succinimides, which are derived from this raw material, are among the cheapest intensifiers according to the invention.

The novel adjuvants to dry-cleaning baths are compatible with all solvents commonly used in the art-i.e. chloro, fluoroor chlorofluoro-hydrocarbons, more particularly aliphatic hydrocarbons, and specially trichloroethylene and perchloroet'hylene; benzene type hydrocarbons, inter alia benzene, toluene, xylenes and naphtha solvent, aliphatic hydrocarbons such as hexane, heptane, octane, mineral oil, gas oil and petroleum ether. Of course, one skilled in the art can choose the intensifier which is most suitable for a particular bath.

The bath, besides containing one or more intensfiers according to the invention, can contain normal adjuvants such as optical blueing agents, chemical bleaching agents l(peroxides), finishing agents, antistatic agents and the The baths may also advantageously contain a small proportion of water, which facilitates the elimination of hydrophilic dirt; the products according to the invention are most efiicient in such cases. When water is present in the dry-cleaning organic solvent, it is advisable to add a small proportion of surfactant to the intensifiers according to the invention, in order to emulsify the water in the solvent. Various ionic or non-ionic surfactants can be used; amine alkyl-aryl-sulphonates are particularly suitable and are widely used in the dry or wet washing of textiles. In such cases it is found that the intensifiers according to the invention cooperate with the surfactants, resulting in considerably improved cleaning.

Although there is no critical maximum proportion of amide to be incorporated according to the invention in the organic solvent used for dry cleaning, a content of 50 g. per litre is usually plenty, and the preferred quantity is usually between approx. 0.1 and 15 g. of intensifier dissolved in each litre of solvent used. More particularly, the proportions of intensifier are lowest in baths containing water. The proportions of surfacants, when used, may be of the same order. The proportion of water the advantage of using which has already been mentioned, preferably does not exceed 100 g./l., the best proportions being between 0 and 20 g./l.

The amides according to the invention can be used for dry-cleaning textiles of whatever nature and form; for example, the amides can be used to improve baths for cleaning wool, cotton, synthetic textiles, linen, jute, etc., mixed if required, in the form of yarn, fibres, cloth, knit- For comparison, the results of tests with two known adjuvants are given: isopropylamine dodecyl-benzene-sulphonate or DBSI and another commercial'amine alkylbenzene-sulphonate known as ABSA and manufactured by ERGOL-TD. In some examples, SIM imides and ting, finished clothing, etc., either white or colored. 5 DBSI surfactant were used simultaneously.

Although dry cleaning of textiles is a particularly im- The proportion of each adjuvant is given in grams per portant application of the intensifiers according to the inlitre of solvent, shown in brackets beside the correspondvention, the adjuvants can also be used to improve varing symbol. ious methods of washing or degreasing all kinds of articles with solvents, as performed every day in industry. For whiteness ofexample, improvements can be made in the action of or- EL Dirty Clean ganic baths for various metal articles before electroplating, No. fabrl fabric Total enamelling, varnishing or painting, y adding about 1 Unwashedcommuabm 25 856 1m to 5% of a primary or secondary amide according to the 2 Washing with solvent. alone--. 29.5 60.5 90.0 invention to the baths 3-- Solvent plus ABSA (1.45 g.) 36.3 57. 8 94. 0

4 Solvent plus DBSI (1.45 g.) 36 64.4 100.4

The novel intensifiers can be used in cold or hot clean- 5-- Solvent plus SIM-0.8 (1.45 g. 36.3 73.9 109.6 ing; in general they are suitable for all known methods %?26??? 133810-45 33pm 69 105-7 of cleaning with organic solvents. Solvent plus SIM- 1 (1.45 g.) as 7617 112.7

The following are non-limitative examples of the 8 i zgg y (1-45 Plus 113-3 invention.

GENERAL METHOD OF OPERATION A comparison between Examples 5-7 on the one hand and 3, 4 on the other hand shows that whereas succinimide by In all the examples, the bath contained 500 ml. of itself produces only a slight improvement over cleaning perchloroethylene in which the quantities shown in each with conventional adjuvants, it etficiently prevents the reexample of intensifier and/or other substances had been distribution of dirt (see Clean fabric column), which is dissolved. Cleaning was performed at 22 C. for minan attractive property. utes with agitation at 150 reciprocations per minute. The In Example 8, succinimide SIM-1 in association with operations were performed in a machine known as a sulphonate produces a marked improvement. Tergotometer (standardized) having four containers 30 Examples 941 for making four tests simultaneously.

In each cleaning operation, a 13 x 21 cm. strip of cot- Examples and 8 were repeated in baths containton fabric was treated after being artifically soiled in acing 6 of water p litre of perchloroethylene The cordance with the EMPA Standard of Fabric Incorpo- SultS e a follows! rated (New York) in the presence of a clean strip of the same fabric. whiteness After cleaning, the whiteness was determined with an Din Clean Elrepho apparatus (filter No. 8) in known manner on the fabric fabrlc Total previously soiled strip and On the clean strip accompany- 9 th plus 5 1,45 g 59,2 ,3 124,5 ing it. The whiteness of the first strip after washing 6 9 DB5 g.) p u I 61 70-6 13 showed the degree of cleaning, whereas the whiteness of Bath 5 111; mas (1.45 g.) plus slM- 58.8 68.4 121.2 the second indicated the amount of re-deposition of dirt. 1

In the following examples, the aforementioned two figures are used and their sum is noted since this is useful in deu l,

. 45 Accordingly, SIM ad uvants according to the invention Scnbmg the total efiiect of the adluvant tested considerably improve cleaning, when the organic solvent Examples 1 to 8 contains water.

In these examples, the perchloroethylene used did not Examples 12 to 15 contain water In these exam les, the intensifiers accordin to the in- T tested q l to the Invention was the vention were th: SIM-l mono-succinimides if the prelmlde of spcclmc acld i whlc}? a group replaqed vious examples in which the terminal amine had been by lmlylwiutme l havmg lwbutene blocked by dodecyl-benzene-sulphonic (-DBS) acid radi tetraethylene pentamine. The reaction product Wlll have caL The resulting general Structure would be:

a general structure of 3)iO=CH:]1l

l(CH@)*C=CH11" o=o-cn,-on-o-N- cmairman-omen,isn-ois-ctni-onnfl O=C-CHrCH-(|]"N-CHiCHjNHCHICHQNHCHZCHiNHCHQCHINH l Sample SIM-Ac was obtained by the direct action of 1 mol of DBS acid on 1 mol of SIM-1 succiniimde. The followmg abbrevlatlons are used: The second sample (SIM-Cl) was obtained by the re- SIM-1 ==the succinimide obtained from 1 mol of pentaction of DBS sulphonic acid chloride with the aforemenamine and 1 mol of succinic acid, and tioned succinimide. SIM-0.8 ==the succinimide obtained from 0.8 mol pent- The quantities of adjuvants and relative proportions of amine per l anhydride, SIM and DBSI are the same as in the preceding example.

whiteness Without water With 0.6% Water x. No, 'IS TPI Total TS 'IP Total 12 SIM-An 33.5 spa-Ac plus DBSI-.- 39.0

1 TS dirty fabric. t T? =elean-tabr1c.

. Examples 12 to 15 all show a marked improvement compared with the results of Examples 3, 4 in accordance with the prior art.

Examples 16 and 17 whiteness of- Ex. Dirty Clean No. fabric fabric Total 16.--- SIM-OET (1.45 g.) 36 68.5 104.5 17 SIMOPR (1.45 g.) 37 76. 6 113. 6

A comparison with Examples 3 and 4 shows the great improvement resulting from the use of the ethoxylated and propoxylated imides according to the invention. Furthermore, the product SIM-OPR (No. 17) gives better results than the unmodified succinimides SIM-0.8 and 1 in Examples and 7. The total whiteness obtained in the absence of water is equal to that obtained together by SIM-1 succinimide and isopropylamine dodecyl-sulphonate (Example 8).

Example 18 A mono-adipamide of triethylene-tetramine substituted by a C hydrocarbon radical in its adipic group was used as the intensifier instead of succinimide in tests similar to those in Examples 1 to 8. The results were similar to those given by SIM-0.8.

- Examples 19-24 E-n=17.5 amines 0.5 mol triethylene-tetramine per mol succinic anhydride Fn\=8 amine:tetraethylene-pentamine 0.82 mol per mol anhydride Gn=8 amine:tetraethylene-pentamine 0.82 mol per mol anhydride the amine was also dodecylated H-n=8 amine: similar to F, except that a mixture of C C carboxylic acids was first fixed on the amine Each adjuvarit was used in the proportion of 1.45 g.

per litre of trichloroethylene. The results of the washing operations are shown in the following table.

Whiteness of- Dirty Clean fabric fabric Total Solvent alone 32 64 96 Solvent plus SIM-0.8 38. 7 71. 5 110. 2 Solvent plus E 35 65 100 Solvent plus F- 37. 4 75. 2 112. 6 Solvent plus G 35.5 66 101.5 Solvent plus H 37. 6 68. 5 106. 1

The best result during these tests was given by adjuvant F, i.e. the succinimide having 8 butene links (32 carbon atoms) on the succinic group.

We claim: 1. A method for washing solid articles consisting of immersing the articles in a bath consisting of (a) an oragnic solvent belonging to the group consisting of hydrocarbon and halo-hydrocarbon dry cleaning liquids, and (b) a monoimide, added to the solvent to a concentration of 0.1 to 50 g. per litre solvent, the monoamide being defined by the formula:

where: R is a radical selected from the group consisting of alkyls and alkenyls having 18 to carbon atoms; n is an integer of 0 to 6; (m -i-p) is 2 to 7; Z and Q are hydrogen.

2. A fluid as recited in claim 1, wherein said monoimide is an imide of succinic acid one CH group of which is replaced by a polyisobuten chain having a number of carbon atoms between 18 and 120, and of an amnie selected from the group consisting of ethylene-diamine, diethylene-triamine, triethylene-tetramine, tetraethylenepentamine, pentaethylene-hexamine, pentamethylene-diamine, hexamethylene diamine, tripropylene-tetramine and tetrapropylene-pentamine.

'3. A fluid as recited in claim 2, wherein said imide has the formula:

4. A fluid as recited in claim 2, wherein the final NH group of said imide is blocked by dodecyl-benzene sulfonic acid.

5. A fluid as recited in claim 4, wherein said imide has the formula:

8-437; 252--Dig. 15, 170, 172; 260--561 R