EP0441675B1 - Phosphatgruppen enthaltende Pfropfpolymere und Verwendung - Google Patents

Phosphatgruppen enthaltende Pfropfpolymere und Verwendung Download PDF

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Publication number
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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Prior art keywords
polymeric material
grafting
grafted
grafted polymeric
material according
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EP19910400192
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English (en)
French (fr)
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EP0441675A1 (de
Inventor
Roger Chatelin
Louis Gavet
Daniel Wattiez
Jean-François Combes
Robert Massolo
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Institut Francais Textile et Habillement
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Institut Francais Textile et Habillement
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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
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Biochemistry (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Graft Or Block Polymers (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (17)

  1. Gepfropftes Polymermaterial, dadurch gekennzeichnet, daß mindestens bestimmte Pfropfzweige aus einer Abfolge von Einheiten bestehen, unter denen sich phosphatgruppenhaltige Einheiten der allgemeinen Formel
    Figure imgb0014
     befinden, worin R₁ unter Wasserstoff und Alkylgruppen und R₂ unter Alkylenen, Alkylenoxiden und/oder Polyalkylenoxiden ausgewählt sind und R₃⁺ und R₄⁺ entweder voneinanander unabhängige Reste sind, von denen jeder unter H⁺, einwertigen Metallionen und Kationen, die N⁺ enthalten, ausgewählt ist, oder gemeinsam einen Rest R₃R₄²⁺ bilden, der ein zweiwertiges Metallion darstellt.
  2. Polymermaterial nach Anspruch 1, dadurch gekennzeichnet, daß R₁ Wasserstoff und R₂ (CH₂-CH₂) ist.
  3. Verwendung des gepfropften Polymermaterials nach Anspruch 1 oder 2, in dessen Formel R₃⁺ und R₄⁺ H⁺-Ionen sind, als Ionenaustauscher in Medien, deren pH-Wert im Bereich von 0 bis 12 liegen kann.
  4. Verwendung des gepfropften Polymermaterials nach Anspruch 1 oder 2, in dessen Formel R₃⁺ und R₄⁺ oder R₃R₄²⁺ unter Metallionen mit anerkannten antiseptischen Eigenschaften, wie z.B. Ag⁺, Zn²⁺, Cu²⁺, Sn²⁺ und Hg²⁺, ausgewählt sind, als Material mit antiseptischen Eigenschaften in Medien, deren pH-Wert im Bereich von 0 bis 12 liegen kann.
  5. Verwendung des gepfropften Polymermaterials nach Anspruch 1 oder 2, in dessen Formel R₃⁺ und R₄⁺ unter Kationen ausgewählt sind, die N⁺ enthalten und anerkannte antiseptische Eigenschaften aufweisen, wie z.B. Benzalkonium, Malachitgrün, Chinolinderivate und Chlorhexidin, als Material mit antiseptischen Eigenschaften in Medien, deren pH-Wert im Bereich von 0 bis 12 liegen kann.
  6. Verwendung des gepfropften Polymermaterials nach Anspruch 1 oder 2, in dessen Formel R₃R₄²⁺ Ca²⁺ ist, als Knochenersatz.
  7. Verwendung des gepfropften Polymermaterials nach Anspruch 6, wobei das Polymermaterial ein Material auf der Basis orientierter, chemisch und biologisch inerter Fasern ist und der Pfropfungsgrad mindestens 20 % beträgt.
  8. Verwendung des gepfropften Polymermaterials nach Anspruch 7, wobei das Polymermaterial Polypropylen ist.
  9. Verwendung des gepfropften Polymermaterials nach Anspruch 1 oder 2, wobei das Polymermaterial ein Material auf Cellulosebasis ist und der Pfropfungsgrad mindestens 20 % beträgt, als Verbundmaterial ohne Bindemittel.
  10. Verwendung des gepfropften Polymermaterials nach Anspruch 1 oder 2, das einen Pfropfungsgrad von mehr als 20 % aufweist, als flammfestes Polymermaterial.
  11. Verfahren zur Herstellung des gepfropften Polymermaterials nach Anspruch 1, dadurch gekennzeichnet, daß es einen Pfropfungsschritt umfaßt, bei dem ein ethylenisch ungesättigter Phosphorsäureester der allgemeinen Formel
    Figure imgb0015
     in der R₁ unter Wasserstoff und Alkylgruppen und R₂ unter Alkylenen, Alkylenoxiden und/oder Polyalkylenoxiden ausgewählt sind, auf das Polymermaterial aufgepfropft wird.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß das Polymermaterial auf Cellulosebasis mit einer Lösung des ethylenisch ungesättigten Phosphorsäureesters imprägniert, in Form gebracht und anschließend bestrahlt wird.
  13. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß das Polymermaterial, wenn es chemisch und biologisch inert ist, nach der Pfropfung in eine Calciumchloridlösung eingetaucht wird.
  14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, daß das Polymermaterial aus Polypropylenfasern besteht und die Fasern so orientiert sind, daß sie nach der Fixierung des Calciums einen festen Gegenstand ergeben, der als Knochenersatz geeignet ist.
  15. Verfahren zur Herstellung eines gepfropften Polymermaterials nach Anspruch 10, das als flammfestes Polymermaterial verwendbar ist, dadurch gekennzeichnet, daß das Polymermaterial, wenn es sich um Seide handelt, nach der Pfropfung mit einem Amidderivat einer Carbonsäure imprägniert wird, das als Weichmacher wirkt.
  16. Verfahren nach Anspruch 11 zur Herstellung eines Gegenstands, der das Aussehen von Elfenbein hat, dadurch gekennzeichnet, daß das Polymermaterial faserig ist, nach der Pfropfung in eine Lösung eines Erdalkalisalzes getaucht und einer Endbearbeitung unterzogen wird, z.B. durch Polieren, Schnitzen oder Gravieren.
  17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß man vor der Pfropfung einen anorganischen Füllstoff, beispielsweise Kaolinpulver, homogen in der Masse des faserigen Polymermaterials verteilt.
EP19910400192 1990-02-05 1991-01-29 Phosphatgruppen enthaltende Pfropfpolymere und Verwendung Expired - Lifetime EP0441675B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9001622A FR2657896B1 (fr) 1990-02-05 1990-02-05 Materiau polymerique a greffons phosphates et utilisations.
FR9001622 1990-02-05

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EP0441675A1 EP0441675A1 (de) 1991-08-14
EP0441675B1 true EP0441675B1 (de) 1995-05-24

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JP (1) JPH06316610A (de)
DE (1) DE69109885T2 (de)
DK (1) DK0441675T3 (de)
ES (1) ES2075377T3 (de)
FR (1) FR2657896B1 (de)

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Publication number Priority date Publication date Assignee Title
JP3138316B2 (ja) * 1992-02-13 2001-02-26 科学技術振興事業団 水溶性グラフト重合体
WO2002070574A2 (en) * 2001-03-02 2002-09-12 Unilever Plc Soil release polymers and laundry detergent compositions containing them
JP5396283B2 (ja) * 2008-01-30 2014-01-22 倉敷紡績株式会社 難燃加工方法および難燃化セルロース系繊維素材

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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JPH06316610A (ja) 1994-11-15
EP0441675A1 (de) 1991-08-14
FR2657896B1 (fr) 1992-05-29
DE69109885T2 (de) 1995-11-02
FR2657896A1 (fr) 1991-08-09
ES2075377T3 (es) 1995-10-01
DE69109885D1 (de) 1995-06-29
DK0441675T3 (da) 1995-08-07

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