FR2642445A1 - PROCESS FOR TREATING POLYMERIC MATERIALS WITH A VIEW TO THEIR CONFERRING ANTISEPTIC PROPERTIES AND MATERIALS OBTAINED - Google Patents

Abstract

In the case of polymeric materials, having thiol functions and / or disulphide bridges, for example wool, the treatment consists in treating the material so as to make thiol functions accessible and to bring it into the presence of a solution of a mercurial derivative having an antiseptic activity, for example mercurobutol or one of its derivatives. The preliminary treatment to make thiol functions available on the wool consists of bleaching or reduction with thioglycolic acid or sodium metabisulphite. In the case of polymeric materials, having in their structure little or no thiol functions and / or disulphide bridges, for example cotton, the treatment consists in treating the material so as to fix thiol functions in its polymeric structure and in placing it in the presence of a solution of a mercurial derivative having an antiseptic activity, for example mercurobutol or one of its derivatives. The binding of thiol functions to cotton is effected by the action of ethylene sulfide.

Description

l

  PROCESS FOR PROCESSING POLYMERIC MATERIALS IN VIEW

  TO CONFERATE THEM WITH ANTISEPTIC PROPERTIES

AND MATERIALS OBTAINED

  The present invention relates to the treatment of polymeric materials, in particular textile materials such as wool, cotton,

  to give them lasting antiseptic properties.

  It also relates to the materials obtained by the process and comprises

  both antiseptic durable properties.

  French patent N 83 00 442 has already described

  of this type, in which the polymeric material is subjected to a grafting reaction in which a derivative of the

  mercurobutol, having a functional group, linked to the

  N-ol of mercurobutol, and capable of intervening in a polymerization or polyaddition reaction. During the reaction, the derivative

  Mercurobutol is placed in the graft, usually at the end of the chain.

  ne, and brings to the material thus grafted antiseptic properties.

  In this reaction it is the functional group, linked to the phe-

  nolic mercurobutol, which intervenes.

  The treatment known from the aforementioned patent has disadvantages

  vantages. On the one hand it is necessary to modify the mercurobutol and transform it into a derivative capable of intervening in a polymerization or polyaddition reaction. On the other hand, it has been found that the presence of the phenol ring has limitations in the conduct of the polymerization reaction; the phenol function has an inhibitory action which limits the development of the reaction and reduces

the yield.

  It has been found, and this is the object of the invention, a new process for the treatment of polymeric materials whose purpose is to permanently give them antiseptic properties which overcome the disadvantages of the aforementioned process. The process according to

  the invention consists of the material having in its polymeric structure

  thiol and / or disulfide bridges, to treat said material so as to make thiol functions accessible and to put said material thus treated in the presence of a solution of a

  mercurial derivative having antiseptic activity.

  Thus according to the preferred method of the invention, it is possible

  to implement any mercurial derivative having an activity

  antiseptic teat; and it is not necessary to carry out a grafting reaction, since the fixing of the mercurial derivative on the polymeric material is carried out by the well-known action of mercury on the

thiol functions.

  The preliminary treatment to make thiol functions accessible may consist of bleaching. It may preferentially

  consist of a reduction of the disulfide bridges in thiol functions.

  Especially in the case of wool, which has in its structure

  cystenic bridges, the cutting of these bridges involving the creation of thiol functions occurs under the action of a reducer

  such as thioglycolic acid or sodium metabisulfite.

  The mercurial derivative in solution is a derivative having

  antiseptic teas. This may be in particular mercurobutol or a mercurobutol derivative. It may be another mercurial derivative such as mercury phenyl borate or mercurycein, or another derivative

  mercurial recognized by the pharmacopoeia.

  It is another object of the invention to protect another

  process for treating a polymeric material in order to confer antiseptic properties, based on the same concept as the process described above, but implemented especially when the material has no or little in its polymeric structure of thiol or disulphide functions.The second method according to the invention consists of

  to treat said material so as to fix in its polymeric structure

  than thiol functions and then to put said material thus treated in the presence of a solution of a mercurial derivative, having an antiseptic activity. The attachment of the mercury derivative to the material is carried out by the action of mercury on the thiol functions which were created in the polymeric structure of the material during the first step

of the process.

  The polymeric material being a polyhydroxylated polymer, especially cotton and fibranne, the first treatment for creation

  thiol functions consist in causing the action of ethylene sulphide.

  In the same way as above, the mercurial derivative in solution

  is a derivative having antiseptic properties, for example mercurobutol or a derivative thereof, e.g.

  sodium phenyl borate or mercurycein.

  It is another object of the invention to protect a polymeric material, having durable antiseptic properties, obtained according to one of the two abovementioned processes, and which comprises in its polymeric structure mercury-related thiol functions of a derivative. mercurial

having antiseptic activity.

  Wool is the preferred material of the invention, the thiol functions resulting from the reduction of cystenic bridges being related

  mercurobutol or one of its derivatives.

  The invention and the benefits it brings will be better understood

  reading the description that will be made of several examples

  implementation of the methods of the invention and the products obtained.

Example 1

  A piece of unbleached wool is prepared so as to eliminate the suintine

  and the waxes that hinder the wettability. In the laboratory, this preparation

  was extracted by soxhlet extraction with a solvent, by

  dichloromethane, then by treatment in an aqueous solution.

O

  wetting (sunaptol at 1 o in the presence of ammonia to 2 / .oo)

  gradually in twenty minutes to 55 C and maintained at this

temperature for 15 minutes.

  The piece of wool is then rinsed with fresh water slightly acidified in acetic medium and then treated again with a solution O

  aqueous composition containing a nonionic wetting agent at 1 /.

  After spinning and drying the piece of wool thus prepared, the latter, weighing 3.2 g, is immersed in 100 ml of a 0.25 g solution of 2-bromomercuri-4-tert-butylphenol allyl-ether (25% solution). % water and 75% ethanol). This solution is heated at 50 ° C. for 1 hour. The piece of wool thus treated undergoes a soxhlet extraction, then

  the mercury present in the polymeric structure of the sample is

  Dry ion. This contains 1.12 mg / g of mercury.

Example 2

  A piece of Ecrtma wool was previously whitened, in accordance with the operating mode described in Example 1. After wringing and drying, it was immersed for 1 hour in 100 ml of a 0.8% solution of thioglycolic acid, brought to room temperature. C; it is washed with fresh water and then with alcohol before being immersed for 1 h, as in example 1, in 100 ml of a 0.25 g solution of bromomercuri-2 tert-butyl-4

  phenol allyl ether raised to 50 ° C.

  After extraction with soxhlet, the piece of wool contains between and S mg / g of mercury.

Example 3

  Example 2 above is reproduced with two differences: the reduction

  This is done not with thioglycolic acid but with a 2 g / l solution of sodium metabisulphite, and treatment in the 0.25 g solution of 2-bromomercuri-4-tert-butylphenol allyl ether is made

at room temperature.

  After extraction with soxhlet, the piece of wool contains 6 to 7 mg / g of mercury.

Example 4

  A piece of wool prepared as in Example 1 is immersed for one hour at room temperature in 100 ml of an 80% solution.

  ethanol and 20% water containing 100 mg of mercurobutol.

  After soxhlet extraction and drying, the piece of wool contains

of the order of 1 mg / g of mercury.

Example 5

  A piece of wool prepared as in Example I is immersed for one hour at ambient temperature in 100 ml of a 75% solution.

  of water containing 100 mg of mercury phenyl borate.

  After extraction with soxhlet and drying, the piece of wool contains

2.10 mg / g of mercury.

Example 6

  A piece of wool prepared as in Example 1 is immersed for 1 hour at room temperature in 100 ml of an aqueous solution of mercurescein (5 ml of a 2% solution of mercurescein diluted with

ml with distilled water).

  After soxhlet extraction and drying, the piece of wool contains

0.35 mg / g of mercury.

Example 7

  A piece of cotton is first treated with sodium hydroxide for 20 minutes, before being rinsed with water and then with alcohol. It is

  then treated at 80 ° C. in ethylene sulphide for 40 hours.

  After successive rinsing with benzene, with alcohol and with water, the quantity of crude thiol functions on the cotton is measured. The rate

  The thiol function obtained is of the order of 9%.

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Claims (10)

  1. A process for treating polymeric materials with a view to imparting antiseptic properties, characterized in that it consists in treating said material so as to render thiol functional and to put said material thus treated in the presence of a solution. a mercurial derivative having antiseptic activity. 2. Method according to claim 1 characterized in that, the material having in its polymeric structure thiol functions and / or disulfide bridges, the treatment to render   accessible thiol functions consists of a whitening.   3. Method according to claim 1 characterized in that, the material having in its polymeric structure thiol functions and / or disulfide bridges, the treatment to make accessible thiol functions consists of a reduction of disulfide bridges.   4. Method according to claim 3 characterized in that, the material being wool, it is treated with the acid   thioglycolic acid or sodium rietabisulfite.   5. Method according to claim I characterized in that the treatment to make thiol functions accessible consists in   to fix in its polymeric structure thiol functions.   6. Process according to claim 5, characterized in that, the material being a polyhydroxylated polymer, the treatment for fixing the thiol functions consists in causing said ethylene sulfide material.   7. Method according to one of claims I to 6 characterized in that   that the mercurial derivative in solution is mercurobutol or one of its derivatives.   8. Process according to claim 7, characterized in that the mercurobutol derivative is 2-bromomercuri-4-tert-butylphenol-allyl ether. 9. Polymeric material having antiseptic properties obtained according to the process of claim I, characterized in that it comprises thiol functions bonded to the mercury of a derivative.   mercurial having antiseptic activity.   10. The polymeric material as claimed in claim 9, characterized in that the mercurial derivative is mercurobutol or one of its derivatives.   I1. Polymeric material according to Claim 10, characterized in that the mercurobutol derivative is bromomercuri-2 tert-butyl 4-phenol allyl ether.