EP0441675A1 - Phosphatgruppen enthaltende Pfropfpolymere und Verwendung - Google Patents

Phosphatgruppen enthaltende Pfropfpolymere und Verwendung Download PDF

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Publication number
EP0441675A1
EP0441675A1 EP91400192A EP91400192A EP0441675A1 EP 0441675 A1 EP0441675 A1 EP 0441675A1 EP 91400192 A EP91400192 A EP 91400192A EP 91400192 A EP91400192 A EP 91400192A EP 0441675 A1 EP0441675 A1 EP 0441675A1
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EP
European Patent Office
Prior art keywords
polymeric material
grafting
chosen
grafted
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91400192A
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English (en)
French (fr)
Other versions
EP0441675B1 (de
Inventor
Roger Chatelin
Louis Gavet
Daniel Wattiez
Jean-François Combes
Robert Massolo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institut Francais Textile et Habillement
Original Assignee
Institut Francais Textile et Habillement
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Publication date
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Publication of EP0441675A1 publication Critical patent/EP0441675A1/de
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Publication of EP0441675B1 publication Critical patent/EP0441675B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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 polymeric 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, in 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 makes it possible to preserve the characteristics specific to the starting material 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+, ie combined 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+, ie combined 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 acidic (pH O) 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 may 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). It is another object of the invention to claim a process for producing the abovementioned graft polymeric material.
  • This process comprises a first 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 sulfate to delay homopolymerization.
  • MAEGP ethylene glycol phosphate methacrylate
  • the MAEGP solution is deoxygenated by bubbling nitrogen through it. The whole is then heated at 100 ° C for 3 hours.
  • Table 1 below gives the values of the grafting rate (A) and of 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.
  • 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 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.
  • 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, the general formula:
  • Ten sheets of 250 g / m2 paper are impregnated with a 50% MAEG solution, padded so that the take-up rate is around 100%, then placed in a sealed package.
  • 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.
  • 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, diffuser or filter sleeve, in particular conical.
  • an object 1 of this type After 100% MAEG impregnation, 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 methods of separation techniques of the purification, purification, separation of species soluble.
  • Polypropylene fibers are homogeneously distributed in a temporary compressible 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 ambient 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 mass of 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.
  • 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.
  • 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 ungrafted tissue was subjected to the same test.
  • the burnt area was around 150cm3, which corresponds to classification D.
  • 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 aspect and a consistency which is 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)
  • Graft Or Block Polymers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
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

Publications (2)

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

Family

ID=9393609

Family Applications (1)

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EP19910400192 Expired - Lifetime EP0441675B1 (de) 1990-02-05 1991-01-29 Phosphatgruppen enthaltende Pfropfpolymere und Verwendung

Country Status (6)

Country Link
EP (1) EP0441675B1 (de)
JP (1) JPH06316610A (de)
DE (1) DE69109885T2 (de)
DK (1) DK0441675T3 (de)
ES (1) ES2075377T3 (de)
FR (1) FR2657896B1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0580871A4 (de) * 1992-02-13 1994-11-30 Nof Corp Wasserlösliches cellulosederivat und bioverträgliches material.
WO2002070574A3 (en) * 2001-03-02 2002-11-21 Unilever Plc Soil release polymers and laundry detergent compositions containing them
EP2194185A4 (de) * 2008-01-30 2014-04-16 Kurashiki Boseki Kk Flammenhemmendes verarbeitungsverfahren und mit flammenresistenz ausgestattetes zellulosefasermaterial

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2139926A1 (de) * 1971-05-31 1973-01-12 Kansai Paint Co Ltd
FR2214698A1 (de) * 1973-01-19 1974-08-19 Scott Paper Co
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

Patent Citations (3)

* 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
FR2139926A1 (de) * 1971-05-31 1973-01-12 Kansai Paint Co Ltd
FR2214698A1 (de) * 1973-01-19 1974-08-19 Scott Paper Co

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0580871A4 (de) * 1992-02-13 1994-11-30 Nof Corp Wasserlösliches cellulosederivat und bioverträgliches material.
WO2002070574A3 (en) * 2001-03-02 2002-11-21 Unilever Plc Soil release polymers and laundry detergent compositions containing them
EP2194185A4 (de) * 2008-01-30 2014-04-16 Kurashiki Boseki Kk Flammenhemmendes verarbeitungsverfahren und mit flammenresistenz ausgestattetes zellulosefasermaterial

Also Published As

Publication number Publication date
ES2075377T3 (es) 1995-10-01
FR2657896A1 (fr) 1991-08-09
EP0441675B1 (de) 1995-05-24
DE69109885D1 (de) 1995-06-29
JPH06316610A (ja) 1994-11-15
DK0441675T3 (da) 1995-08-07
DE69109885T2 (de) 1995-11-02
FR2657896B1 (fr) 1992-05-29

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