EP0441675B1 - Polymeric material grafted with phosphate-containing grafts and use - Google Patents
Polymeric material grafted with phosphate-containing grafts and use Download PDFInfo
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- EP0441675B1 EP0441675B1 EP19910400192 EP91400192A EP0441675B1 EP 0441675 B1 EP0441675 B1 EP 0441675B1 EP 19910400192 EP19910400192 EP 19910400192 EP 91400192 A EP91400192 A EP 91400192A EP 0441675 B1 EP0441675 B1 EP 0441675B1
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- polymeric material
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/20—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
- D06M14/22—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
Definitions
- the present invention relates to a polymeric material, in particular textile, on the polymer structure of which have been implanted by the technique of grafting chains with repeating patterns, called grafts. It relates more particularly to a grafted polymeric material of which at least certain grafts are made up of the succession of phosphate patterns, as well as various uses of this material.
- the grafting technique is well known. It consists, for example, of activating a polymeric material and then bringing the activated material into contact with a solution of a polymerizable monomer under very precise temperature and duration conditions. The activation has the effect of creating radical sites on the material, from which the polymerization reaction of the monomer develops.
- grafting allows the characteristics specific to the starting material to be preserved while giving it new characteristics due to the presence of grafts.
- this technique has been used to modify the dye affinity of a textile or to give a material ion-exchange properties. In each case, it is necessary to determine the polymerizable monomer suitable for giving the grafted material the desired properties.
- the aim which the applicant has set for himself is to propose a grafted polymer material which can meet a large number of different uses.
- grafted polymeric material in which at least certain grafts are made up of a succession of phosphate units of formula: in which R1 is chosen from the group consisting of H and alkyls, R2 is chosen from the group of alkylene and alkylene oxides and / or polyoxides, and R3+ and R4+ are either distinct from each other , each being chosen from the group consisting of H+, the monovalent metal ions, the cations comprising N+, either together and in this case R3R42+ is a divalent metal ion.
- R1 is chosen from the group consisting of H and alkyls
- R2 is chosen from the group of alkylene and alkylene oxides and / or polyoxides
- R3+ and R4+ are either distinct from each other , each being chosen from the group consisting of H+, the monovalent metal ions, the cations comprising N+, either together and in this case R3R42+ is a divalent metal ion.
- R3+ and R4+ are H+ and the polymeric material can be used as an ion exchanger in a medium which can have an extreme pH, either very acid (pH 0) or very alkaline (pH 12).
- the phosphated termination (-PO3 H2) of the graft motif has the particularity of having cation exchange properties, with a strong function and a weaker function, and also complexing properties with respect to metal ions. divalent.
- R3+ and R4+ or R3R42+ are chosen from metal ions having recognized antiseptic properties, such as Ag+, Zn2+, Cu2+, Sn2+, Hg2+ or from antiseptic molecules in the form of cations , in particular from the family of quaternary ammoniums and chlorhexidine, and the polymeric material can be used as an antiseptic material in a medium whose pH can be between 0 and 12. If the grafted polymeric materials with antiseptic activity were known, they exhibited l 'major drawback of not being able to be washed under normal conditions at alkaline pH; the aforementioned material of the invention removes this dissatisfaction.
- R3R42+ is Ca2+
- the material is based on a chemically and biologically inert polymer, and it can be used as a bone substitute.
- the material is polypropylene in fibrous form, and the rate grafting is greater than 20%.
- the material is based on cellulose, the grafting rate being greater than 20% and it can be used as a composite material without binder.
- the grafting rate being greater than 20%, the grafted polymeric material has flame retardant properties.
- the grafted polymeric material has an appearance which is similar to that of ivory.
- the material is in fibrous form, the grafting rate is greater than 20%, R3R42+ is a cation preferably chosen from the family of alkaline earths.
- R3R42+ is a cation preferably chosen from the family of alkaline earths.
- it comprises in the fibrous mass a compatible mineral filler, for example kaolin powder.
- R1 is CH3 and R2 is the group (CH2 - CH2).
- This process comprises a step of grafting the polymeric material with at least one ethylenic ester of phosphoric acid of formula: in which R1 is chosen from the group consisting of H and alkyls and R2 is chosen from the group of alkylene and alkylene oxides and / or polyoxides.
- the polymeric material is a polypropylene fabric. It is subjected to an electronic irradiation of 10kGy, then immersed in a solution of ethylene glycol phosphate methacrylate (MAEGP) containing from 0.5 to 1g / l of copper sulphate to delay the homopolymerization.
- MAEGP solution is deoxygenated by bubbling nitrogen through it. The assembly is then heated at 100 ° C for 3 hours.
- Table 1 below gives the values of the grafting rate (A) and the graft fixing capacity (B) as a function of the concentrations of the impregnation solution in MAEGP (C1) and in copper sulfate (C2) .
- the grafting rate Tg (A) is measured after extraction, it is equal to: in which P1 is the weight of the grafted material and P o its weight before grafting.
- the values given for the grafting rate (A) are average values over ten tests, with very good reproducibility (difference at most of 2%).
- This first example illustrates the possibility of obtaining with the MAEGP very high grafting rates, leading to high fixing capacities (B), both in exchange for ions and in complexation.
- the MAEGP solution is obtained by simple dilution of a 76% concentrated primary solution which is kept during storage without special precautions other than the addition of 200 ppM of stabilizers. 2nd example.
- the textile material is cotton fabric.
- the grafting operation is done by impregnating a 30% solution of MAEGP, by wringing out the impregnated tissue such that the take-up rate is 100%, then irradiation of the impregnated material in an inert medium under vacuum.
- the materials grafted according to Examples 1,2 and 3 above have grafts having repeating units of the general formula: 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 of the material. graft.
- the aforementioned materials are perfectly stable from very acidic pHs (pH 0) to basic pHs (pH 12) corresponding to the usual washing media.
- antiseptic molecules in cationic form in particular the molecules of the family of quaternary ammoniums, for example the benzalkonium cation of general formula: with n between 7 and 18, for example the cation corresponding to the malachite green dye of general formula: for example a cation derived from quinoline, of general formula: for example a chlorhexidine cation, of general formula: 5th example.
- Ten sheets of paper of 250 g / m2 are impregnated with a 50% MAEGP solution, padded so that the take-up rate is around 100%, then placed in a sealed packaging.
- a primary vacuum is created in the packaging until the vapor pressure of water at room temperature is reached, that is to say about 20mm of mercury before sealing the packaging.
- the whole is irradiated under ionizing radiation ⁇ , until reaching a dose of 10kGy (1MRad).
- the grafted cellulosic material which is obtained has a compact and homogeneous structure, to the point that the various constituent layers of the ten initial sheets can no longer be separated.
- a complex material was produced, based on cellulose and with a high content of phosphate patterns, without using a binder. 6th example. Reading example 5 above, it is understood that it is very easy to shape the starting polymeric materials and to produce objects from grafted, compact polymeric materials, keeping the imposed shape.
- a particularly advantageous application of this possibility lies in the production of ion exchange / complexing objects, which can be used directly, without the usual equipment such as filtration equipment or ion exchange column.
- These objects will for example have the shape of a strainer, a diffuser or a filter sleeve, in particular conical.
- an object 1 of this type After 100% impregnation of MAEGP, a sheet 2 of paper was rolled up on itself and partly around the end 3 of a cylindrical tube 4. The extreme part 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.
- a compact object 1 is obtained which is directly usable as an ion / complexing exchanger.
- the water to be purified is introduced through the free end 6 of the tube 4, according to arrow F. It diffuses through the terminal orifices 5 into the body 7 of the exchanger; the bodies dissolved in the ionic state are retained by ion exchange or complexation and the water which leaves the object 1 according to the arrows G is purified water.
- 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 species soluble.
- phosphate monomer MAEGP
- its overall mass reaches 50% by weight of the cellulose.
- the object 1 obtained is perfectly stable, forming a homogeneous whole. 7th example.
- Polypropylene fibers are homogeneously distributed in a compressible temporary mold and impregnated with a solution of MAEGP in an amount and in a concentration such that there is no excess.
- the whole is exposed to gamma radiation (cobalt source for example) so as to deliver a dose of 10kGy to the entire product.
- the operation takes place at room temperature or, better, at 80 ° C. so as to increase the diffusion of the monomer throughout the mass of the fibers during their grafting.
- the object obtained, after demolding, is homogeneous, of great solidity.
- This object is immersed in a 20% calcium chloride solution until the solution is completely diffused throughout the object. It is checked that the diffusion was complete by calculation of the stoichiometry. Under the aforementioned conditions, the grafting rate was around 25% in MAEGP, which allowed fixation by calcium complexation of the order of 5%.
- the object obtained can be used as a bone substitute.
- Calcium is, as in bone, linked to a phosphate function, which obeys the same laws as those prevailing in the body, to reserve or restore calcium as needed.
- 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 more similar, in terms of its use, to natural bone.
- the fabric After drying, the fabric is weighed; the grafting rate is 36%.
- the harder feel imparted by grafting is corrected by impregnating a softener known under the name SAPAMINE OC, which is an amide derivative of a carboxylic acid of the cationic type, used as a finishing finish for wool and silk.
- the fabric which has regained its flexibility is subjected to a fireproofing test according to standard ASTM D 1230.83.
- the burnt area is around 40cm3, which corresponds to classification B.
- the non-grafted tissue was subjected to the same test.
- the burnt area was around 150cm3, which corresponds to classification D. 9 ° example.
- Polypropylene fibers and kaolin powder are evenly distributed in a temporary mold compressible, then it is carried out as in Example 7 above, as regards grafting and immersion in a solution of calcium chloride.
- the object obtained, after polishing, has an appearance and consistency similar to that of ivory. It can also be sculpted and engraved in the mass.
- the presence of the mineral filler 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 accordingly.
- the invention is not limited to the embodiments and uses which have been described by way of nonlimiting examples, but covers all variants thereof.
- other monomers can be used with the phosphate monomer, carrying out a co-grafting.
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Description
La présente invention concerne un matériau polymérique, notamment textile, sur la structure polymérique duquel ont été implantées par la technique de greffage des chaînes à motifs répétitifs, dénommées greffons. Elle concerne plus particulièrement un matériau polymérique greffé dont au moins certains greffons sont constitués de la succession de motifs phosphatés , ainsi que diverses utilisations de ce matériau.The present invention relates to a polymeric material, in particular textile, on the polymer structure of which have been implanted by the technique of grafting chains with repeating patterns, called grafts. It relates more particularly to a grafted polymeric material of which at least certain grafts are made up of the succession of phosphate patterns, as well as various uses of this material.
La technique de greffage est bien connue. Elle consiste par exemple à activer un matériau polymérique puis à mettre le matériau activé en contact avec une solution d'un monomère polymérisable dans des conditions de température et de durée bien précises. L'activation a pour effet de créer des sites radicalaires sur le matériau , à partir desquels se développe la réaction de polymérisation du monomère.The grafting technique is well known. It consists, for example, of activating a polymeric material and then bringing the activated material into contact with a solution of a polymerizable monomer under very precise temperature and duration conditions. The activation has the effect of creating radical sites on the material, from which the polymerization reaction of the monomer develops.
Le greffage permet le plus souvent de conserver les caractéristiques propres au matériau de départ tout en lui conférant des caractéristiques nouvelles dues à la présence des greffons. En particulier cette technique a été mise en oeuvre pour modifier l'affinité tinctoriale d'un textile ou pour donner à un matériau des propriétés d'échanges d'ions.Dans chaque cas , il est nécessaire de déterminer le monomère polymérisable adapté pour donner au matériau greffé les propriétés recherchées.In most cases, grafting allows the characteristics specific to the starting material to be preserved while giving it new characteristics due to the presence of grafts. In particular, this technique has been used to modify the dye affinity of a textile or to give a material ion-exchange properties. In each case, it is necessary to determine the polymerizable monomer suitable for giving the grafted material the desired properties.
Le but que s'est fixé le demandeur est de proposer un matériau polymérique greffé pouvant répondre à un grand nombre d'utilisations différentes.The aim which the applicant has set for himself is to propose a grafted polymer material which can meet a large number of different uses.
Ce but est atteint par le matériau polymérique greffé selon l'invention, dans lequel au moins certains greffons sont constitués d'une succession de motifs phosphatés de formule :
dans laquelle R₁ est choisi parmi le groupe constitué par H et les alkyles, R₂ est choisi parmi le groupe des alkylènes et des oxydes et/ou polyoxydes d'alkylènes, et R₃⁺ et R₄⁺ sont soit distincts l'un de l'autre, chacun étant choisi parmi le groupe constitué par H⁺ , les ions métalliques monovalents, les cations comportant N⁺, soit confondus et dans ce cas R₃R₄²⁺ est un ion métallique divalent.This object is achieved by the grafted polymeric material according to the invention, in which at least certain grafts are made up of a succession of phosphate units of formula:
in which R₁ is chosen from the group consisting of H and alkyls, R₂ is chosen from the group of alkylene and alkylene oxides and / or polyoxides, and R₃⁺ and R₄⁺ are either distinct from each other , each being chosen from the group consisting of H⁺, the monovalent metal ions, the cations comprising N⁺, either together and in this case R₃R₄²⁺ is a divalent metal ion.
A la connaissance du demandeur, si les monomères phosphatés sont connus en eux-mêmes , ils n'ont jamais été mis en oeuvre dans une réaction de greffage pour donner un matériau polymérique greffé selon l'invention, qui présente de multiples utilisations.To the knowledge of the applicant, if the phosphate monomers are known in themselves, they have never been used in a grafting reaction to give a grafted polymeric material according to the invention, which has multiple uses.
Selon une première utilisation, R₃⁺ et R₄⁺ sont H⁺ et le matériau polymérique est utilisable comme échangeur d'ions dans un milieu qui peut avoir un pH extrême, soit très acide (pH 0) soit très alcalin (pH 12). La terminaison phosphatée (-PO₃ H₂) du motif du greffon présente la particularité d'avoir des propriétés d'échange de cations , avec une fonction forte et une fonction plus faible, et aussi des propriétés complexantes vis-à-vis d'ions métalliques divalents.According to a first use, R₃⁺ and R₄⁺ are H⁺ and the polymeric material can be used as an ion exchanger in a medium which can have an extreme pH, either very acid (pH 0) or very alkaline (pH 12). The phosphated termination (-PO₃ H₂) of the graft motif has the particularity of having cation exchange properties, with a strong function and a weaker function, and also complexing properties with respect to metal ions. divalent.
Selon une deuxième utilisation , R₃⁺ et R₄⁺ ou R₃R₄²⁺ sont choisis parmi des ions métalliques ayant des propriétés antiseptiques reconnues, tels que Ag⁺, Zn²⁺, Cu²⁺, Sn²⁺,Hg²⁺ ou parmi des molécules antiseptiques sous forme de cations, en particulier de la famille des ammoniums quaternaires et la chlorhexidine, et le matériau polymérique est utilisable comme matériau antiseptique dans un milieu dont le pH peut être compris entre 0 et 12. Si les matériaux polymériques greffés à activité antiseptique étaient connus, ils présentaient l'inconvénient majeur de ne pas pouvoir être lavés dans des conditions normales à pH alcalin ; le matériau précité de l'invention lève cette insatisfaction.According to a second use, R₃⁺ and R₄⁺ or R₃R₄²⁺ are chosen from metal ions having recognized antiseptic properties, such as Ag⁺, Zn²⁺, Cu²⁺, Sn²⁺, Hg²⁺ or from antiseptic molecules in the form of cations , in particular from the family of quaternary ammoniums and chlorhexidine, and the polymeric material can be used as an antiseptic material in a medium whose pH can be between 0 and 12. If the grafted polymeric materials with antiseptic activity were known, they exhibited l 'major drawback of not being able to be washed under normal conditions at alkaline pH; the aforementioned material of the invention removes this dissatisfaction.
Selon une troisième utilisation, R₃R₄²⁺ est Ca²⁺, le matériau est à base d'un polymère chimiquement et biologiquement inerte, et il est utilisable comme substitut osseux. Par exemple le matériau est du polypropylène sous forme fibreuse, et le taux de greffage est supérieur à 20%.According to a third use, R₃R₄²⁺ is Ca²⁺, 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 grafting is greater than 20%.
Selon une quatrième utilisation, le matériau est à base de cellulose, le taux de greffage étant supérieur à 20% et il est utilisable comme matériau composite sans liant.According to a fourth use, the material is based on cellulose, the grafting rate being greater than 20% and it can be used as a composite material without binder.
Selon une cinquième utilisation, le taux de greffage étant supérieur à 20%, le matériau polymérique greffé présente des propriétés ignifugeantes.According to a fifth use, the grafting rate being greater than 20%, the grafted polymeric material has flame retardant properties.
Selon une sixième utilisation , le matériau polymérique greffé a un aspect qui s'apparente à celui de l'ivoire. Pour cela le matériau est sous forme fibreuse, le taux de greffage est supérieur à 20%, R₃R₄²⁺ est un cation choisi de préférence dans la famille des alcalino-terreux. De préférence, il comporte dans la masse fibreuse une charge minérale compatible par exemple de la poudre de kaolin.According to a sixth use, the grafted polymeric material has an appearance which is similar to that of ivory. For this, the material is in fibrous form, the grafting rate is greater than 20%, R₃R₄²⁺ is a cation preferably chosen from the family of alkaline earths. Preferably, it comprises in the fibrous mass a compatible mineral filler, for example kaolin powder.
Dans la version préférée du matériau polymérique greffé de l'invention, R₁ est CH₃ et R₂ est le groupe (CH₂ - CH₂).In the preferred version of the graft polymeric material of the invention, R₁ is CH₃ and R₂ is the group (CH₂ - CH₂).
C'est un autre objet de l'invention que de revendiquer un procédé de réalisation du matériau polymérique greffé précité. Ce procédé comprend une étape de greffage du matériau polymérique par au moins un ester éthylénique de l'acide phosphorique de formule :
dans laquelle R₁ est choisi parmi le groupe constitué par H et les alkyles et R₂ est choisi parmi le groupe des alkylènes et des oxydes et/ou polyoxydes d'alkylène.It is another object of the invention to claim a process for producing the abovementioned graft polymeric material. This process comprises a step of grafting the polymeric material with at least one ethylenic ester of phosphoric acid of formula:
in which R₁ is chosen from the group consisting of H and alkyls and R₂ is chosen from the group of alkylene and alkylene oxides and / or polyoxides.
D'autres caractéristiques et avantages apparaîtront à la lecture de la description qui va être faite de plusieurs exemples de réalisation et d'utilisation de matériaux polymériques à greffons phosphatés , illustrés par la figure unique qui est une représentation schématique en perspective d'un objet en forme pour épuration réalisé à partir du matériau polymérique à greffons phosphatés.
1° exemple. Le matériau polymérique est un tissu de polypropylène. Il est soumis à une irradiation électronique de 10kGy, puis plongé dans une solution de méthacrylate d'éthylène glycol phosphaté (MAEGP) contenant de 0,5 à 1g/l de sulfate de cuivre pour retarder l'homopolymérisation. La solution de MAEGP est désoxygénée par barbotage d'azote. L'ensemble est ensuite chauffé à 100°C pendant 3 heures.Other characteristics and advantages will appear on reading the description which will be given of several examples of embodiment and use of polymeric materials with phosphate grafts, illustrated by the single figure which is a schematic perspective representation of an object in form for purification made from polymeric material with phosphate grafts.
1st example. The polymeric material is a polypropylene fabric. It is subjected to an electronic irradiation of 10kGy, then immersed in a solution of ethylene glycol phosphate methacrylate (MAEGP) containing from 0.5 to 1g / l of copper sulphate to delay the homopolymerization. The MAEGP solution is deoxygenated by bubbling nitrogen through it. The assembly is then heated at 100 ° C for 3 hours.
Le tableau 1 ci-dessous donne les valeurs du taux de greffage (A) et de la capacité (B) de fixation des greffons en fonction des concentrations de la solution d'imprégnation en MAEGP (C₁) et en sulfate de Cuivre (C₂). Le taux de greffage Tg (A) est mesuré après extraction, il est égal à :
dans lequel P₁ est le poids du matériau greffé et Po son poids avant greffage.
in which P₁ is the weight of the grafted material and P o its weight before grafting.
Les valeurs données pour le taux de greffage (A) sont des valeurs moyennes sur dix essais, avec une très bonne reproductibilité (écart au plus de 2%).The values given for the grafting rate (A) are average values over ten tests, with very good reproducibility (difference at most of 2%).
Ce premier exemple illustre la possibilité d'obtenir avec le MAEGP des taux de greffage très importants, conduisant à des capacités de fixation (B) élevées, à la fois en échange d'ions et en complexation.This first example illustrates the possibility of obtaining with the MAEGP very high grafting rates, leading to high fixing capacities (B), both in exchange for ions and in complexation.
Il est aussi à noter que la solution de MAEGP est obtenue par simple dilution d'une solution primaire concentrée à 76% qui est conservée lors de stockage sans précaution particulière autre que l'addition de 200 ppM de stabilisants.
2° exemple. Le matériau textile est un tissu de coton. L'opération de greffage se fait par imprégnation d'une solution à 30% de MAEGP, par essorage du tissu imprégné tel que le taux d'emport soit de 100% , puis irradiation du matériel imprégné en milieu inerte sous vide.It should also be noted that the MAEGP solution is obtained by simple dilution of a 76% concentrated primary solution which is kept during storage without special precautions other than the addition of 200 ppM of stabilizers.
2nd example. The textile material is cotton fabric. The grafting operation is done by impregnating a 30% solution of MAEGP, by wringing out the impregnated tissue such that the take-up rate is 100%, then irradiation of the impregnated material in an inert medium under vacuum.
Différents essais ont été réalisés, mettant en oeuvre des doses d'irradiation variant entre 10 et 30 kGy. Les taux de greffage obtenus sont quasiment constants, étant compris entre 15,1 et 17% quelle que soit la dose pratiquée.
3° exemple. Le matériau textile est un non-tissé contenant 80% de viscose et 20% de polyester. Les conditions de greffage sont les mêmes que pour l'exemple 2. Le taux de greffage est de 17,4 pour des doses de 10 et de 20 kGy.Various tests have been carried out, using radiation doses varying between 10 and 30 kGy. The grafting rates obtained are almost constant, being between 15.1 and 17% whatever the dose practiced.
3rd example. 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 for doses of 10 and 20 kGy.
Par ailleurs des essais ont été réalisés avec une irradiation en présence d'air, et non plus en milieu inerte. Le taux de greffage obtenu était de 12,8% pour une irradiation à 10kGy et de 12,9% pour une irradiation à 20 kGy.
4° exemple. Les matériaux greffés selon les exemples 1,2 et 3 ci-dessus ont des greffons ayant des motifs répétitifs de formule générale :
Ces matériaux sont aptes à échanger et complexer des ions métalliques connus pour leur action antiseptique, tels que l'argent, le cuivre, le zinc, l'étain, le mercure, dans des limites de concentration qui dépendent de la capacité de fixation du matériau greffé.In addition, tests have been 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 10 kGy and 12.9% for irradiation at 20 kGy.
4th example. The materials grafted according to Examples 1,2 and 3 above have grafts having repeating units of the general formula:
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 of the material. graft.
La complexation est quasiment immédiate, par une simple imprégnation , foulardage de matériau greffé dans un bain contenant le ou les différents sels métalliques.Complexation is almost immediate, by a simple impregnation, padding of grafted material in a bath containing the different metal salt (s).
En agissant sur les concentrations en ions métalliques , et sur le mode d'application en un seul bain ou en bains successifs, il est possible d'obtenir un matériau ayant un spectre d'activité antiseptique modulable, en fonction du ou des ions métalliques fixés (R₃⁺, R₄⁺ ou R₃R₄²⁺) et de leur concentration.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 modular antiseptic activity, depending on the metal ion (s) attached. (R₃⁺, R₄⁺ or R₃R₄²⁺) and their concentration.
Les matériaux précités (exemples 1 à 4) sont parfaitement stables depuis des pH très acides(pH 0) jusqu'à des pH basiques (pH 12) correspondant aux milieux lessiviels habituels.The aforementioned materials (examples 1 to 4) are perfectly stable from very acidic pHs (pH 0) to basic pHs (pH 12) corresponding to the usual washing media.
Ce qui vient d'être dit pour les ions métalliques connus pour leur action antiseptique est également vrai pour certaines molécules antiseptiques sous forme cationique, en particulier les molécules de la famille des ammoniums quaternaires, par exemple le cation benzalkonium de formule générale :
avec n compris entre 7 et 18, par exemple le cation correspondant au colorant vert malachite de formule générale :
par exemple un cation dérivé de la quinoléine, de formule générale:
par exemple un cation de chlorhexidine, de formule générale :
5° exemple. Dix feuilles de papier de 250 g/m² sont imprégnées par une solution à 50% en MAEGP, foulardées en sorte que le taux d'emport soit d'environ 100%, puis placées dans un emballage étanche. On crée dans l'emballage un vide primaire jusqu'à atteindre la tension de vapeur d'eau à température ambiante soit environ 20mm de mercure avant de sceller l'emballage. L'ensemble est irradié sous rayonnement ionisant γ, jusqu'à atteindre une dose de 10kGy (1MRad).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 family of quaternary ammoniums, for example the benzalkonium cation of general formula:
with n between 7 and 18, for example the cation corresponding to the malachite green dye of general formula:
for example a cation derived from quinoline, of general formula:
for example a chlorhexidine cation, of general formula:
5th example. Ten sheets of paper of 250 g / m² are impregnated with a 50% MAEGP solution, padded so that the take-up rate is around 100%, then placed in a sealed packaging. A primary vacuum is created in the packaging until the vapor pressure of water at room temperature is reached, that is to say about 20mm of mercury before sealing the packaging. The whole is irradiated under ionizing radiation γ, until reaching a dose of 10kGy (1MRad).
Le matériau cellulosique greffé qui est obtenu a une structure compacte et homogène, au point que les différentes couches constitutives des dix feuilles initiales ne peuvent plus être séparées.The grafted cellulosic material which is obtained has a compact and homogeneous structure, to the point that the various constituent layers of the ten initial sheets can no longer be separated.
Ainsi on a réalisé un matériau complexe , à base cellulosique et à haute teneur en motifs phosphatés, sans mise en oeuvre de liant.
6° exemple. A la lecture de l'exemple 5 ci-dessus, on comprend qu'il est très facile de mettre en forme les matériaux polymériques de départ et de réaliser des objets à partir des matériaux polymériques greffés, compacts, gardant la forme imposée.Thus, a complex material was produced, based on cellulose and with a high content of phosphate patterns, without using a binder.
6th example. Reading example 5 above, it is understood that it is very easy to shape the starting polymeric materials and to produce objects from grafted, compact polymeric materials, keeping the imposed shape.
Une application particulièrement avantageuse de cette possibilité réside dans la réalisation d'objets échangeurs d'ions/complexants,directement utilisables , sans les équipements habituels tels que matériel de filtration ou colonne d'échange d'ion. Ces objets auront par exemple la forme de crépine, de diffuseur ou de manchon filtrant, notamment conique.A particularly advantageous application of this possibility lies in the production of ion exchange / complexing objects, which can be used directly, without the usual equipment such as filtration equipment or ion exchange column. These objects will for example have the shape of a strainer, a diffuser or a filter sleeve, in particular conical.
On a représenté sur la figure unique un objet 1 de ce type. Après imprégnation à 100% de MAEGP, une feuille 2 de papier a été enroulée sur elle-même et pour une partie autour de l'extrémité 3 d'un tube cylindrique 4. La partie extrême de ladite extrémité 3, recouverte par la feuille 2, est percée de plusieurs orifices 5.There is shown in the single figure an object 1 of this type. After 100% impregnation of MAEGP, a
L'ensemble ainsi constitué est placé dans un emballage étanche et subit le même traitement que celui décrit à l'exemple 5 ci-dessus. Après greffage, on obtient un objet 1 compact qui est directement utilisable comme échangeur d'ions/complexants. L'eau à épurer est introduite par l'extrémité 6 libre du tube 4, selon la flèche F. Elle diffuse par les orifices terminaux 5 dans le corps 7 de l'échangeur ; les corps dissous à l'état ionique sont retenus par échange d'ion ou complexation et l'eau qui sort de l'objet 1 selon les flèches G est une eau épurée.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 / complexing exchanger. The water to be purified is introduced through the free end 6 of the tube 4, according to arrow F. It diffuses through the terminal orifices 5 into the body 7 of the exchanger; the bodies dissolved in the ionic state are retained by ion exchange or complexation and the water which leaves the object 1 according to the arrows G is purified water.
Dans le mode de réalisation ci-dessus, l'épaisseur de l'enroulement était de 1cm et le débit constaté sous 0,5 bar de pression était parfaitement compatible avec les procédés habituels de techniques séparatives du type épuration, purification, séparation d'espèces solubles.In the above embodiment, 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 species soluble.
Il est à noter que , tout le monomère phosphaté (MAEGP) étant polymérisé, sa masse globale atteint 50% en poids de la cellulose. L'objet 1 obtenu est parfaitement stable, formant un ensemble homogène.
7° exemple. Des fibres de polypropylène sont réparties de manière homogène dans un moule temporaire comprimable et imprégnées d'une solution de MAEGP en quantité et en concentration telles qu'il n'y ait pas d'excès. L'ensemble est exposé au rayonnement gamma (source cobalt par exemple) de façon à délivrer une dose de 10kGy à l'ensemble du produit. L'opération se passe à température ambiante ou, mieux, à 80°C de façon à augmenter la diffusion du monomère dans toute la masse des fibres lors de leur greffage. L'objet obtenu, après démoulage , est homogène, d'une grande solidité. On immerge cet objet dans une solution de chlorure de calcium à 20% jusqu'à diffusion complète de la solution dans la masse de l'objet. On vérifie que la diffusion a été complète par calcul de la stoechiométrie. Dans les conditions précitées, le taux de greffage était de l'ordre de 25% en MAEGP, qui a permis une fixation par complexation du calcium de l'ordre de 5%.It should be noted that, all the phosphate monomer (MAEGP) being polymerized, its overall mass reaches 50% by weight of the cellulose. The object 1 obtained is perfectly stable, forming a homogeneous whole.
7th example. Polypropylene fibers are homogeneously distributed in a compressible temporary mold and impregnated with a solution of MAEGP in an amount and in a concentration such that there is no excess. The whole is exposed to gamma radiation (cobalt source for example) so as to deliver a dose of 10kGy to the entire product. The operation takes place at room temperature or, better, at 80 ° C. so as to increase the diffusion of the monomer throughout the mass of the fibers during their grafting. The object obtained, after demolding, is homogeneous, of great solidity. This object is immersed in a 20% calcium chloride solution until the solution is completely diffused throughout the object. It is checked that the diffusion was complete by calculation of the stoichiometry. Under the aforementioned conditions, the grafting rate was around 25% in MAEGP, which allowed fixation by calcium complexation of the order of 5%.
L'objet obtenu est utilisable comme substitut osseux. Le calcium est, comme dans l'os, lié à une fonction phosphate, qui obéit aux mêmes lois que celles régnant dans l'organisme, de réserve ou de restitution du calcium en fonction des besoins.The object obtained can be used as a bone substitute. Calcium is, as in bone, linked to a phosphate function, which obeys the same laws as those prevailing in the body, to reserve or restore calcium as needed.
On comprend que la forme et la structure de l'objet seront déterminées en fonction de la destination du substitut osseux. Il peut être notamment pourvu de cavités de vascularisation et/ou d'un canal central, de sorte que ledit substitut se rapproche plus encore, quant à son utilisation, de l'os naturel.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 more similar, in terms of its use, to natural bone.
D'autres matériaux de base que les fibres de polypropylène peuvent être envisagés. Il est toutefois nécessaire que ceux-ci soient chimiquement et biologiquement inertes, et que l'objet ait une résistance mécanique élevée. Cette résistance est obtenue par une orientation adéquate des fibres préférentiellement dans le sens longitudinal, dans le cas d'un os long, ou selon une distribution dans le volume de l'objet qui est fonction des contraintes.
8° exemple. Un tissu de soie de 30g/m² est imprégné à l'aide d'une solution à 30% de MAEGP puis activé sous électrons accélérés à une dose de 20kGy (2MRad) sous vide partiel de 20 mm de mercure.Other basic materials than polypropylene fibers can be envisaged. However, these must be chemically and biologically inert, and the object must have 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.
8 ° example. A 30g / m² silk fabric is impregnated using a 30% MAEGP solution and then activated under accelerated electrons at a dose of 20kGy (2MRad) under partial vacuum of 20 mm of mercury.
Après séchage , le tissu est pesé ; le taux de greffage est de 36%. Le toucher plus dur conféré par le greffage est corrigé par imprégnation d'un adoucissant connu sous le nom SAPAMINE OC, qui est un dérivé amide d'un acide carboxylique du type cationique, utilisé comme apprêt de finition pour la laine et la soie.After drying, the fabric is weighed; the grafting rate is 36%. The harder feel imparted by grafting is corrected by impregnating a softener known under the name SAPAMINE OC, which is an amide derivative of a carboxylic acid of the cationic type, used as a finishing finish for wool and silk.
Le tissu qui a retrouvé toute sa souplesse est soumis à un test d'ignifugation selon la norme ASTM D 1230.83. La surface brûlée est d'environ 40cm³, ce qui correspond au classement B.The fabric which has regained its flexibility is subjected to a fireproofing test according to standard ASTM D 1230.83. The burnt area is around 40cm³, which corresponds to classification B.
A titre de comparaison le tissu non greffé a été soumis au même test. La surface brûlée était d'environ 150cm³, ce qui correspond au classement D.
9° exemple. Des fibres de polypropylène et de la poudre de kaolin sont réparties , de manière homogène dans un moule temporaire comprimable , puis il est procédé comme dans l'exemple 7 ci-dessus, en ce qui concerne le greffage et l'immersion dans une solution de chlorure de calcium. L'objet obtenu, après polissage, a un aspect et une consistance qui s'apparente à celle de l'ivoire. Il peut aussi être sculpté et gravé dans la masse.For comparison, the non-grafted tissue was subjected to the same test. The burnt area was around 150cm³, which corresponds to classification D.
9 ° example. Polypropylene fibers and kaolin powder are evenly distributed in a temporary mold compressible, then it is carried out as in Example 7 above, as regards grafting and immersion in a solution of calcium chloride. The object obtained, after polishing, has an appearance and consistency similar to that of ivory. It can also be sculpted and engraved in the mass.
La présence de la charge minérale améliore la qualité du polissage et modifie la dureté du matériau. D'autres fibres peuvent être utilisées , et la technique de greffage sera adaptée en conséquence.The presence of the mineral filler 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 accordingly.
L'invention n'est pas limitée aux modes de réalisation et d'utilisation qui ont été décrits à titre d'exemples non limitatifs, mais en couvre toutes les variantes. En particulier lors du greffage d'autres monomères peuvent être mis en oeuvre avec le monomère phosphaté, réalisant un co-greffage.The invention is not limited to the embodiments and uses which have been described by way of nonlimiting examples, but covers all variants thereof. In particular during grafting, other monomers can be used with the phosphate monomer, carrying out a co-grafting.
Claims (17)
- Grafted polymeric material characterized in that at least some of the grafts consist of a series of groups including phosphate groups of general formula :
- Material according to claim 1, characterized in that R₁ is H and R₂ is (CH₂ - CH₂).
- Use of the grafted polymeric material according to one of claims 1 or 2 as ion exchanger in a medium, the pH of which may vary from 0 to 12, in which R₃⁺ and R₄⁺ are H⁺.
- Use of the grafted polymeric material according to one of claims 1 or 2 as material having antiseptic properties in a medium the pH of which may vary from 0 to 12, in which R₃⁺ and R₄⁺ or R₃R₄²⁺ are selected from the metal ions having recognized antiseptic properties, such as Ag⁺, Zn²⁺, Cu²⁺, Sn²⁺, Hg²⁺.
- Use of the grafted polymeric material according to one of claims 1 or 2 as material having antiseptic properties in a medium the pH of which may vary from 0 to 12, in which R₃⁺ and R₄⁺ are selected from the cations comprising N⁺ and having recognized antiseptic properties such as benzalkonium, Malachite Green, derivatives of quinoline and chlorohexine.
- Use of the grafted polymeric material according to one of claims 1 or 2, as substitute for bone in which R₃R₄²⁺ is Ca²⁺.
- Use according to claim 6 of the grafted polymeric material in which the polymeric material is based on chemically and biologically oriented inert fibers and in which the extent of grafting is at least 20%.
- Use according to claim 7 of the grafted polymeric material in which the polymeric material is polypropylene.
- Use of the grafted polymeric material according to one of claims 1 or 2 as composite material without a binder in which the polymeric material is cellulose-based and the extent of grafting is at least 20%.
- Use of the grafted polymeric material according to one claims 1 or 2, of which the extent of grafting is higher than 20%, as fireproof polymeric material.
- Process for the manufacture of a grafted polymeric material according to claim 1, characterized in that it comprises a first step of grafting of the said material by an ethylenic ester of the phosphoric acid of general formula :
- Process according to claim 11, characterized in that the cellulose-based polymeric material is impregnated with a solution of the ethylenic ester of the phosphoric acid, moulded then irradiated.
- Process according to claim 11, characterized in that the polymeric material, being chemically and biologically inert, is, after grafting, immersed in a solution of calcium chloride.
- Process according to claim 13, characterized in that the polymeric material consists of polypropylene fibers and in that the fibers are oriented in order to give, after binding of the calcium, a rigid article capable of being a substitute for bone.
- Process for the manufacture of a grafted polymeric material usable as fireproof polymeric material according to claim 10, characterized in that the polymeric material being silk, it is impregnated, after grafting, with an amide derivative of a carboxylic acid acting as softener.
- Process according to claim 11, for the manufacture of an article having the appearance of ivory, characterized in that the polymeric material is fibrous, in that after grafting, the material is immersed in a solution of an alkaline earth salt and that it is subjected to a finishing treatment such as polishing, carving or engraving.
- Process according to claim 16, characterized in that, before grafting, a mineral filler, for example kaolin powder, is distributed homogeneously in the mass of the fibrous polymeric material.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9001622A FR2657896B1 (en) | 1990-02-05 | 1990-02-05 | POLYMERIC MATERIAL WITH PHOSPHATE GRAFT AND USES THEREOF. |
FR9001622 | 1990-02-05 |
Publications (2)
Publication Number | Publication Date |
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EP0441675A1 EP0441675A1 (en) | 1991-08-14 |
EP0441675B1 true EP0441675B1 (en) | 1995-05-24 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP19910400192 Expired - Lifetime EP0441675B1 (en) | 1990-02-05 | 1991-01-29 | Polymeric material grafted with phosphate-containing grafts and use |
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EP (1) | EP0441675B1 (en) |
JP (1) | JPH06316610A (en) |
DE (1) | DE69109885T2 (en) |
DK (1) | DK0441675T3 (en) |
ES (1) | ES2075377T3 (en) |
FR (1) | FR2657896B1 (en) |
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JP3138316B2 (en) * | 1992-02-13 | 2001-02-26 | 科学技術振興事業団 | Water-soluble graft polymer |
AU2002246051A1 (en) * | 2001-03-02 | 2002-09-19 | Unilever Plc | Soil release polymers and laundry detergent compositions containing them |
EP2194185B1 (en) * | 2008-01-30 | 2016-10-26 | Kurashiki Boseki Kabushiki Kaisha | Flame retardant processing method, and cellulosic fiber material imparted with flame retardancy |
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US4001150A (en) * | 1970-11-25 | 1977-01-04 | Kansai Paint Company, Ltd. | Composition for preparing electroconductive resin comprising an unsaturated polyester and phosphoric or sulfonic unsaturated ester |
US3814703A (en) * | 1971-05-31 | 1974-06-04 | Kansai Paint Co Ltd | Composition for forming an electrically conductive resin film |
GB1455783A (en) * | 1973-01-19 | 1976-11-17 | Scott Paper Co | Flame retardant phosphorus-containing acrylic and methacrylic esters and amides |
-
1990
- 1990-02-05 FR FR9001622A patent/FR2657896B1/en not_active Expired - Fee Related
-
1991
- 1991-01-29 DE DE1991609885 patent/DE69109885T2/en not_active Expired - Fee Related
- 1991-01-29 ES ES91400192T patent/ES2075377T3/en not_active Expired - Lifetime
- 1991-01-29 EP EP19910400192 patent/EP0441675B1/en not_active Expired - Lifetime
- 1991-01-29 DK DK91400192T patent/DK0441675T3/en active
- 1991-02-05 JP JP6086991A patent/JPH06316610A/en active Pending
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FR2657896A1 (en) | 1991-08-09 |
EP0441675A1 (en) | 1991-08-14 |
JPH06316610A (en) | 1994-11-15 |
ES2075377T3 (en) | 1995-10-01 |
DK0441675T3 (en) | 1995-08-07 |
DE69109885T2 (en) | 1995-11-02 |
FR2657896B1 (en) | 1992-05-29 |
DE69109885D1 (en) | 1995-06-29 |
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