FR2657896A1 - POLYMERIC MATERIAL HAVING PHOSPHATE GRAFTS AND USES. - Google Patents

Abstract

At least some grafts of the grafted polymeric material according to the invention consist of phosphate units of general formula: (CF DRAWING IN BOPI) in which R1 is H or an alkyl, R2 an alkylene, an alkylene oxide and / or polyoxide and R3 + and R4 + are either distinct and chosen from H +, monovalent metal ions, cations comprising N +, or combined, R3 R4 2 + being a divalent metal ion. There are many uses for this material: as an ion exchanger at wide pH, R3 + and R4 + being H +; as antiseptics, R3 + and R4 + being metal ions with antiseptic activities such as Ag +, Zn2 +, Cu2 +, or quaternary ammoniums or chlorhexidine; as a bone substitute, R3 R4 2 + being Ca2 +; as a composite without binder, the degree of grafting being at least 20%. The starting polymeric material is for example based on polypropylene, cellulose or silk. Preferably the process consists in grafting the material using an ethylenic ester of phosphoric acid of general formula: (CF DRAWING IN BOPI)

Description

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  POLYMERIC MATERIAL HAVING PHOSPHATE GRAFTS AND USES

  The present invention relates to a polymeric material, in particular a textile material, on the polymeric structure of which have been implanted by the technique of grafting repetitive patterned chains, called grafting grafts. It concerns more particularly a grafted polymeric material of which at least some grafts consist of the succession. phosphates, as well as

  various uses of this material.

  The grafting technique is well known. It consists, for example, in activating a polymeric material and then putting the activated material in contact with a solution of a polymerizable monomer under conditions of a precise temperature and duration. Activation has the effect of creating free radical sites on the material, from which develops the

  polymerization reaction of the monomer.

  The grafting makes it possible most often to preserve the characteristics specific to the starting material while conferring on it new characteristics due to the presence of the grafts. In particular, this technique has been implemented to modify the dye affinity of a textile or to give to a material of ion exchange properties In each case, it is necessary to determine the polymerizable monomer suitable for

  give the grafted material the desired properties.

  The goal set by the applicant is to propose a grafted polymeric material that can respond to a large number of

different uses.

  This object is achieved by the grafted polymeric material according to the invention, in which at least some grafts consist of a succession of phosphate units of formula R 1

(-CH -C-)

2 C C = O on R 2

P = O

O O

R 3 + R 4 +

  wherein R 1 is selected from the group consisting of H and the alkyls, R 2 is selected from the group of alkylenes and alkylene oxides and / or polyoxides, and R 3 + and R + are either distinct from one of the other, each being selected from the group consisting of H +, the monovalent metal ions, the cations comprising N +, or confused and in this case RR 2 + is an ion

divalent metal.

  To the applicant's knowledge, if the phosphate monomers are known per se, they have never been used in a grafting reaction to give a polymeric material

  graft according to the invention, which has multiple uses.

  According to a first use, R + and R + are H + and the

3 4

  Polymeric material can be used as an ion exchanger in a medium that can have an extreme pH, either very acidic (p H 0) or very alkaline (p H 12). The phosphatic termination (-PO 3 H 2) of the graft pattern has the particularity of having cation exchange properties, with a strong function and a weaker function, and also complexing properties

  vis-à-vis divalent metal ions.

  According to a second use, R + and R + or R R 2 + are chosen from metal ions having properties

+ 2 + 2 + 2 + 2 +

  recognized antiseptics, such as Ag, Zn, Cu, Sn, Hg or among antiseptic molecules in the form of cations, in particular of the family of quaternary ammoniums and chlorhexidine, and the polymeric material can be used as an antiseptic material in a medium whose The antiseptically grafted polymeric materials have been known to have the major disadvantage that they can not be washed under normal alkaline conditions; the aforementioned material of the invention removes this dissatisfaction.

2 + 2 +

  According to a third use, R 3 R 4 is Ca, the material is based on a chemically and biologically inert polymer, and it can be used as a bone substitute. For example, the material is polypropylene in fibrous form, and the rate tl 1 & l

3 2657896

grafting is greater than 20%.

  According to a fourth use, the material is based on cellulose, the grafting rate being greater than 20% and it is

  usable as a composite material without binder.

  According to a fifth use, the grafting rate being greater than 20%, the grafted polymeric material has

flame retardant properties.

  According to a sixth use, the grafted polymeric material has an appearance similar to that of ivory For this the material is in fibrous form, the grafting rate is greater than 20%, RR 2 + is a cation chosen preferably in the family of alkaline earths It preferably comprises in the fibrous mass a mineral filler compatible for example with the

kaolin powder.

  In the preferred version of the polymeric graft material of

  the invention, R 1 is CH 3 and R 2 is the group (CH 2 -CH 2).

  It is another object of the invention to claim a process for producing the abovementioned grafted polymeric material. This method comprises a first step of grafting the polymeric material with at least one ethylenic ester of phosphoric acid of formula:

CH = C C O R 2 P

R 1 O O OH

  wherein R is selected from the group consisting of H and the alkyls and R 2 is selected from the group of alkylenes and

  alkylene oxides and / or polyoxides.

  Other features and benefits will appear at the

  reading the description that will be made of several examples

  embodiment and use of polymer materials with phosphatic grafts, illustrated by the single figure which is a schematic perspective representation of a shaped object for purification made from the graft polymer material

phosphate.

4 2657896

  1 example The polymeric material is a polypropylene fabric.

  It is subjected to an electron irradiation of Ok Gy, then immersed in a solution of ethylene glycol phosphate methacrylate (MAEGP) containing from 0.5 to 1 g / l of copper sulphate to delay the homopolymerization. The MAEGP solution is deoxygenated by bubbling nitrogen The assembly is then heated to 100 C during

3 hours.

  Table 1 below gives the grafting rate (A) and graft fixation capacity (B) values as a function of the concentrations of the MAEGP (C 1) and copper sulphate (C) impregnation solution. 2) The degree of grafting Tg (A) is measured after extraction, it is equal to: Pl Po Tg = Pl in which Pl is the weight of the grafted material and Po its weight

before grafting.

  : C 1 (%): C 2 (%): A (%): B (meq / g):

: :::

: 5: 0.5: 28: 1.3

: 10: 0.5: 42: 2:

: 15: 1: 52: 2.5:

  The values given for the grafting rate (A) are average values over ten tests, with a very good

  reproducibility (difference of not more than 2%).

  This first example illustrates the possibility of obtaining with the MAEGP very high grafting rates, leading to high binding capacities (B), both in ion exchange and

in complexation.

  It should also be noted that the MAEGP solution is obtained by simply diluting a concentrated primary solution at 76% which is stored during storage without any particular precautions.

  than the addition of 200 μM stabilizers.

  EXAMPLE The textile material is a cotton fabric The grafting operation is carried out by impregnating a 30% MAEGP solution, by dewatering the impregnated fabric such that the transport rate is 100%, and then irradiating the material. impregnated in medium

inert under vacuum.

  Various tests have been carried out, using irradiation doses ranging between 10 and 30 k Gy The grafting rates obtained are almost constant, being between

  , 1 and 17% regardless of the dose.

  The textile material is a nonwoven containing 80% viscose and 20% polyester. The grafting conditions are the same as for example 2. The grafting rate is 17.4%.

doses of 10 and 20 k Gy.

  Moreover, tests were carried out with irradiation in the presence of air, and no longer in an inert medium. The grafting rate obtained was 12.8% for irradiation at

  l O k Gy and 12.9% for irradiation at 20 k Gy.

  EXAMPLE The grafted materials according to Examples 1, 2 and 3 above have grafts having repeating units of the general formula CH 3

(CH C -

Co O CH CH 2

PO 3 H 2

  These materials are capable of exchanging and complexing metal ions known for their antiseptic action, such as silver, copper, zinc, tin, mercury, within concentration limits which depend on the fixing capacity

graft material.

  The complexation is almost immediate, by a simple impregnation, padding of material grafted in a bath

  containing the different metal salts.

  By acting on the concentrations of metal ions, and on the mode of application in a single bath or in successive baths, it is possible to obtain a material having a spectrum of antiseptic activity which can be modulated according to the fixed metal ion (s). (3 + + o 2 +

  fixed (R 3, R 4 or R 3 R 4) and their concentration.

  The abovementioned materials (Examples 1 to 4) are perfectly stable from very acidic pH (PH 0) to basic pH

  (p H 12) corresponding to the usual washing media.

  What has just been said for the metal ions known for their antiseptic action is also true for certain antiseptic molecules in cationic form, in particular the molecules of the quaternary ammonium family, for example the benzalkonium cation of general formula

CH CH

_ 3 \, 3 -

n-CH 2.1 N (D (CH 2) n

CH 3

  with N between 7 and 18, for example the cation corresponding to the malachite green dye of general formula

CH CH

NOT

C N

  CH 3 for example a cation derived from quinoline, of general formula: CH 3

H 2 N N -R

/ \

  1- For example, a chlorhexidine cation, of the general formula C1-c, NH-C NH NH (CH 2) 6 NH C NH NH NHCl

NH NO NE NH

H H H H

  For example, ten sheets of paper of 250 g / m 2 are impregnated with a 50% solution of MAEG, padded so that the transport rate is about 100%, then placed in a sealed package. packaging a primary vacuum until the water vapor tension at room temperature is reached, ie about 20 mm of mercury before sealing the package The whole is irradiated under ionizing radiation until reaching a dose

from Ok Gy (l M Rad).

  The grafted cellulosic material that is obtained has a compact and homogeneous structure, to the point that the various constituent layers of the initial ten leaves can no longer

to be separated.

  Thus, a complex material based on cellulose and with a high content of phosphatic units was produced without

binder.

  EXAMPLE On reading Example 5 above, it is understood that it is very easy to shape the starting polymeric materials and to make objects from grafted polymeric materials, compact, keeping the imposed shape. A particularly advantageous application of this possibility lies in the realization of ion exchanger / complexing objects, directly usable, without the usual equipment such as filtration equipment or ion exchange column These objects will have for example the form of strainer , from

  diffuser or filter sleeve, in particular conical.

  FIG. 1 shows an object of this type. After impregnation with 100% MAEG, a sheet 2 of paper was wound on itself and for a portion around the end 3 of a cylindrical tube 4. end portion of said end 3, covered by the sheet 2, is pierced with

several orifices 5.

  The assembly thus formed is placed in a sealed package and undergoes the same treatment as that described in Example 5 above. After grafting, a compact object 1 is obtained which is directly usable as an ion exchanger / complexing agent. to be purified is introduced through the free end 6 of the tube 4, according to the arrow F It diffuses through the terminal orifices 5 in the body 7 of the exchanger; the dissolved bodies in the ionic state are retained by ion exchange or complexation and the water coming out of the object 1

  according to the arrows G is a purified water.

  In the embodiment above, the thickness of the winding was 1 cm and the flow rate observed under 0.5 bar of pressure was perfectly compatible with the usual processes of separation techniques of the purification, purification,

separation of soluble species.

  It should be noted that, since all the phosphate monomer (MAEG) is polymerized, its overall weight reaches 50% by weight of the cellulose. The object 1 obtained is perfectly stable, forming a

homogeneous set.

  polypropylene fibers are homogeneously distributed in a compressible temporary mold and impregnated with a solution of MAEGP in such quantity and concentration that there is no excess The whole is exposed to gamma radiation (source cobalt for example) so as to deliver a dose of Ok Gy to the entire product The operation is carried out at room temperature or, better, at 800 C so as to increase the diffusion of

  monomer throughout the mass of the fibers during their grafting.

  The object obtained, after demolding, is homogeneous, of great strength. This object is immersed in a solution of calcium chloride at 20% until complete diffusion of the solution in the mass of the object. was complete by calculation of the stoichiometry Under the above conditions, the grafting rate was of the order of 25% in MAEGP, which allowed 4 X

  binding by complexation of calcium of the order of 5%.

  The object obtained can be used as bone substitute Calcium is, as in bone, linked to a phosphate function, which obeys the same laws as those prevailing in the body,

  reserve or restore calcium as needed.

  It is understood that the shape and structure of the object will be determined according to the destination of the bone substitute. It may in particular be provided with vascularization cavities and / or a central channel, so that said substitute is closer to the bone.

  still, as to its use, natural bone.

  Other basic materials than polypropylene fibers can be envisaged It is however necessary that they are chemically and biologically inert, and that the object has a high mechanical strength This resistance is obtained by an adequate orientation of the fibers preferably in the longitudinal direction, in the case of a long bone, or according to a distribution in the volume of the object which is a function of the constraints. For example, a silk fabric of 30 g / m 2 is impregnated with a 30% solution of MAEGP and then activated under accelerated electrons at a rate of

  dose of 2 Ok Gy (2 M Rad) under partial vacuum of 20 mm Hg.

  After drying, the fabric is weighed; the degree of grafting is 36% The harder feel imparted by the grafting is corrected by impregnation of a softener known as SAPAMINE OC, which is an amide derivative of a carboxylic acid of the cationic type, used as a finishing primer for wool and

the silk.

  The fabric that has regained its flexibility is subjected to a fireproofing test according to ASTM D 1230 83. The burned surface is about 40 cm, which corresponds to the classification B. For comparison the non-grafted tissue was subjected to the same test The burned surface was about 150 cm 3, which corresponds to the classification D. 9 example Polypropylene fibers and kaolin powder are distributed homogeneously in a temporary mold r comprimable, then it is process as in Example 7 above, with regard to grafting and immersion in a solution of calcium chloride The object obtained, after polishing, has an appearance and a consistency which is similar to that of

  ivory It can also be carved and engraved in the mass.

  The presence of the minimum load improves the quality of the polishing and modifies the hardness of the material Other fibers can be used, and the grafting technique will be adapted

Consequently.

  The invention is not limited to the embodiments and use which have been described by way of non-limiting examples, but covers all variants thereof. Particularly during the grafting of other monomers can be implemented.

  with the phosphate monomer, performing a co-grafting.

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Claims (15)

  1 grafted polymeric material characterized in that at least some grafts consist of a succession of units among which phosphate units of general formula R (-CH 2 C-) C O on t R 2 P = O O O R + R +   Wherein R 1 is selected from the group consisting of H and the alkyls, R 2 is selected from the group of alkylene and alkylene oxides and / or polyoxides and R + and R + are either distinct from each other; the other, each being selected from the group consisting of H +, the monovalent metal ions, the cations comprising N +, or confused and in this case RR 2 is an ion divalent metal.   Material according to Claim 1, characterized in that R 1 is H and R 2 is (CH 2 CH 2).   3 Use of the grafted polymeric material according to one of   1 or 2 as an ion exchanger in a medium of which   the p H may range from 0 to 12, in which R 3 + and R 4 + are H 4 Use of the grafted polymeric material according to one of the   claims 1 or 2 as a material having properties   antiseptics in a medium whose p H can range from 0 to 12 in which R and R + or R R 2 are chosen from ions 3 4 34   metallic substances with recognized antiseptic properties, such 2 + 2 + 2 + 2 +   that Ag +, Zn, Cu, Sn, Hg Use according to claim 4 characterized in that R 3 and R + are chosen from the cations comprising N and having recognized antiseptic properties such as benzalkonium,   malachite green, quinoline derivatives and chlorhexidine. 12 2657896   6 Use of the grafted polymeric material according to one of   Claims 1 or 2 as a bone substitute in which R 3 R 42 + is Ca 2 +.   The use according to claim 6 of the graft polymeric material in which the polymeric material is based on chemically and biologically inert oriented fibers and wherein the   grafting rate is at least 20%.   8 Use according to claim 7 of the polymeric material   graft in which the polymeric material is polypropylene.   9 Use of the grafted polymeric material according to one of   Claims 1 or 2 as a binderless composite material in   which the polymeric material is cellulose-based and the grafting is at least 20%.   Process for producing a grafted polymeric material according to Claim 1, characterized in that it comprises a first step of grafting said material with an ethylenic ester of phosphoric acid of general formula: OH - CH 2 = C O RC O R 2 P 2, 2 I He R 1 O OOH   wherein R 1 is selected from the group consisting of H and the alkyls, and R 2 is selected from the group of alkylene and   alkylene oxides and / or polyoxides.   11 Process according to claim 10 characterized in that the polymeric material being based on cellulose is impregnated with a solution of the ethylenic ester of phosphoric acid, shaped and then irradiated and in that the grafting rate is greater than 20%.   12. Process according to claim 10, characterized in that the polymeric material which is chemically and biologically inert is, after grafting, immersed in a solution of calcium chloride. 13. Process according to claim 12, characterized in that the material consists of polypropylene fibers and in that the fibers are oriented to give, after fixing the calcium,   a rigid object, able to be a bone substitute.   The method of claim 10 for rendering a polymeric flame retardant material characterized in that the degree of grafting is greater than 20%.   Process according to Claim 14, characterized in that, since the polymeric material is silk, the latter is, after grafting, impregnated with an amide derivative of a carboxylic acid which acts as softener.   Method according to Claim 10 for producing an object having the appearance of ivory, characterized in that the polymeric material is fibrous, in that the degree of grafting is greater than 20%, in that after grafting the material is immersed in a solution of an alkaline earth salt and is subjected to a finishing treatment such as polishing, carving or etching. Process according to Claim 14, characterized in that, before grafting, a mineral filler, for example powder, is homogeneously distributed in the mass of the fibrous polymeric material. of kaolin.