WO2020003331A1 - Polyvinylamine-based material with stability characteristics in the presence of water and process for its production - Google Patents
Polyvinylamine-based material with stability characteristics in the presence of water and process for its production Download PDFInfo
- Publication number
- WO2020003331A1 WO2020003331A1 PCT/IT2019/050136 IT2019050136W WO2020003331A1 WO 2020003331 A1 WO2020003331 A1 WO 2020003331A1 IT 2019050136 W IT2019050136 W IT 2019050136W WO 2020003331 A1 WO2020003331 A1 WO 2020003331A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyvinylamine
- groups
- group
- production
- previous
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 15
- 239000000203 mixture Substances 0.000 claims abstract description 17
- -1 amide isocyanates Chemical class 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 125000001033 ether group Chemical group 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 150000001298 alcohols Chemical class 0.000 claims abstract description 4
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 4
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 150000002170 ethers Chemical class 0.000 claims abstract description 4
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 150000004820 halides Chemical class 0.000 claims abstract description 4
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 4
- 150000003949 imides Chemical class 0.000 claims abstract description 4
- 239000012948 isocyanate Substances 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000013464 silicone adhesive Substances 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 150000001454 anthracenes Chemical class 0.000 claims 1
- 229940088710 antibiotic agent Drugs 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 125000002348 vinylic group Chemical group 0.000 claims 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 6
- 150000007942 carboxylates Chemical class 0.000 abstract description 3
- 235000013824 polyphenols Nutrition 0.000 abstract description 3
- OIMWEHOYHJJPJD-UHFFFAOYSA-N pyridine;pyrimidine Chemical class C1=CC=NC=C1.C1=CN=CN=C1 OIMWEHOYHJJPJD-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003440 styrenes Chemical class 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
- B01D67/00113—Pretreatment of the casting solutions, e.g. thermal treatment or ageing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
- B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
- B01D71/0211—Graphene or derivates thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/02—Homopolymers or copolymers of vinylamine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/02—Homopolymers or copolymers of vinylamine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
Definitions
- This invention relates to a polyvinylamine-based material with stability characteristics in the presence of water and process for its production.
- polyvinylamine is a cationic polyelectrolyte, which posses the highest concentration of amminic groups amongst the various polymers which make up this category, such as polyallylamine, polyethylenimine and chitosan. Due to this intrinsic characteristic, polyvinylamine can be advantageously used in different sectors, including that of modifying surfaces and/or e/o interfaces.
- polyvinylamine Due to its considerable reactivity, it is possible to create links of the polyvinylamine with various kinds of supports or polymers.
- the presence of PVAm on the cellulose fibres allows a better adhesion between the latter to be obtained, thereby improving the resistance of paper film to abrasion. This behaviour is particularly useful in the case of packaging.
- polyvinylamine is suitable for modifying polymers in order to render the surfaces antibacterial, thereby improving the conservation di food.
- polyvinylamine is often able to combine the adhesion of two surfaces with characteristics which are not immediately compatible (for example, silicone and rubber), but which are polar.
- PVAm has interesting properties its that of membranes.
- this polymer is a possible compound for improving the transport of CO2 from one side of the membrane to the other.
- this compound could be incorporated in membranes for separation of the CO2, thereby facilitating its absorption.
- PVAm its high solubility in water.
- the high solubility in water of PVAm becomes, however, a disadvantage, since the membranes must often work in damp conditions, and maybe actually in water.
- PVAm gels, or even dissolves, thereby destroying the membrane in the presence of high contents of water, PVAm gels, or even dissolves, thereby destroying the membrane.
- PVAm-based material with the addition of one or more compounds which contain laminar particles and preferably graphene and its derivatives, obtained by means of a thermal treatment of a mixture of PVAm and of said one or more compounds, which remain stable both in the presence of high moisture content and in direct contact with water.
- the mechanical stability of the PVAm it is mixed with compounds which contain laminar particles and preferably graphene and its derivatives (few layer graphene, graphene nanoplates, graphene CVD, nano graphite, graphene oxide, graphite oxide, graphene nanoribbons, graphene quantum dots, etc) which have been prepared or are in solutions with dispersants which contain at least:
- an ether group preferably with a number of repetitive units from 5 to 400 units, and more preferably an ethoxyl group, and
- the substituent of the aromatic group can be a functional group such as: amines, amides, imides, amide isocyanates, sulphuric groups, phosphoric groups, carboxylates, phenolics, alcohols, ethers, aldehydes, anhydride esters, styrenes, nitroaromatics, pyrimidine pyridines, imidazoles, azobenzenes, anthracene naphthenes, diphenols, halides, alkanes and alkenes with or without further aromatics present in chain.
- amines, amides, imides, amide isocyanates, sulphuric groups, phosphoric groups carboxylates, phenolics, alcohols, ethers, aldehydes, anhydride esters, styrenes, nitroaromatics, pyrimidine pyridines, imidazoles, azobenzenes, anthracene naphthenes, diphenol
- the material according to the invention has been shown to be particularly efficient when obtained using graphene according to the teachings of patent EP2890633.
- the preparation of the material according to the invention can alternatively be obtained with the normal mixing techniques used industrially or directly during the production of the laminar material.
- the material obtained in this way is then treated at a temperature of between 20 and 500 °C, preferably between 80 and 250 °C, in order to obtain an optimum interaction between PVAm and the compound which contains the laminar material and its dispersant.
- the product obtained in this way is mechanically stable even if it is immersed in water for months and it can perform its functions in sectors such as, by way of a non-limiting example: the production of membranes (supported or not), coatings to improve the mechanical properties, coatings to functionalize surfaces, materials for biological applications, adhesives, inks for offset, rotogravure, inkjet, spray printing.
- the aim of the invention is to provide a polyvinylamine-based material with stability characteristics in the presence of water and process for its production which allows the limitations of the prior art polyvinylamine- based materials to be overcome and to obtain the technical results described above.
- a further aim of the invention is that said polyvinylamine-based material and said process for its production can be implemented with substantially low costs, with regard both to the production costs and the management costs.
- Another aim of the invention is to provide a polyvinylamine-based material with stability characteristics in the presence of water and process for its production which are simple, safe and reliable.
- a first specific object of this invention therefore relates to a process for the production of a polyvinylamine-based material, comprising the following steps:
- the substituent of the aromatic group can be a functional group such as: amines, amides, imides, amide isocyanates, sulphuric groups, phosphoric groups, carboxylates, phenolics, alcohols, ethers, aldehydes, anhydride esters, styrenes, nitroaromatics, pyrimidine pyridines, imidazoles, azobenzenes, anthracene naphthenes, diphenols, halides, alkanes and alkenes with or without further aromatics present in chain,
- a functional group such as: amines, amides, imides, amide isocyanates, sulphuric groups, phosphoric groups, carboxylates, phenolics, alcohols, ethers, aldehydes, anhydride esters, styrenes, nitroaromatics, pyrimidine pyridines, imidazoles, azobenzenes, anthracen
- said one or more compounds which contain laminar particles are selected amongst graphene and its derivatives, said ether group is a group comprising from 5 to 400 base units and said ether group is an ethoxyl group.
- said temperature treatment is preferably performed between 80-250 °C, for a time of at least 5 seconds.
- said mixing step and before said treatment in temperature step there is preferably a step wherein said polyvinylamine-based mixture is deposited in the form of a membrane or coating; and, after said mixing step and before said treatment in temperature step, there is a step wherein said polyvinylamine-based mixture is mixed with adhesive mixtures, and more preferably said adhesive mixtures are mixtures based on vinyl, acrylic, polyurethane, epoxy and silicone adhesives.
- a second specific object of this invention relates to a polyvinylamine- based material which can be obtained by means of the above-mentioned process.
- a third and last specific object of this invention is the use of the above-mentioned polyvinylamine-based material for the production of membranes, additives for the paper sector, additives for paints, substrates for biological applications, hair gel, antibacterial products, additives for adhesives.
- the solution obtained in this way was stirred for 30 min.
- the solution was spread by means of a knife on a silicone paper support and dried at 80 °C for one night. It was all subsequently treated at 220 °C in air for 4 hours.
- the solution was stirred with a magnetic stirrer for 1 hour and then sonicated in a water bath (LAVO ST3, 0.5 kW) for 30 mins. The solution was sprayed on cellulose acetate filter paper and dried at 60 °C for one night. The film was subsequently treated at a temperate of 1 10 °C in a vacuum for 1 hour.
- the solution was stirred with magnetic stirring for 1 hour. Keeping the solution in a glass bottle, it was all subjected to sonication in a water bath (LAVO ST3, 0.5 kW) for 15 mins. The system was then spread on a silicone polymer support by means of a casting knife and dried at 60 °C for one night. The film was subsequently treated at a temperate of 150 °C in air for 2 hours.
- the films obtained according to examples 1 -5 were immersed in de-ionised water and left for several weeks, observing the presence of undissolved parts.
- the material obtained from examples 1 -5 was formed in a continuous film and placed to dry at 35 °C for a few days.
- a continuous film was obtained in this way with a thickness of approximately 60 micrometres.
- the above- mentioned film was treated at 150 °C for 1 .5 hours.
- a permeameter was used to measure the permeability of gas at a moisture content equal to 85% at 35 °C with a pressure in the order of 60 Barrer for carbon dioxide and 2 Barrer for nitrogen.
- the membrane was found to be stable for the entire duration of the test, which was 30 days.
- Example 8 The material obtained from examples 1 -5 was formed in a continuous film and then treated at 200 °C for 5 minutes.
- a quartz spring balance was used to measure the absorption in mass of water vapour of the sample at 35 °C at 100% of relative humidity in the order to 0.5 g of water per dry gram of film.
- the sample whilst increasing in size, remained hanging on the hook of the balance, thereby demonstrating the retention of the good mechanical properties.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
This invention relates to a process for the production of a polyvinylamine-based material, comprising the following steps: a) mixing of polyvinylamine together with one or more compounds which contain laminar particles dispersed in a dispersant containing: - an ether group, and - at least one substituted aromatic group, where the substituent of the aromatic group can be a functional group such as: amines, amides, imides, amide isocyanates, sulphuric groups, phosphoric groups, carboxylates, phenolics, alcohols, ethers, aldehydes, anhydride esters, styrenes, nitroaromatics, pyrimidine pyridines, imidazoles, azobenzenes, anthracene naphthenes, diphenols, halides, alkanes and alkenes with or without further aromatics present in chain, to obtain a polyvinylamine-based mixture: b) treatment of said polyvinylamine-based mixture at a temperature of between 20 and 500 °C. The invention also relates to a polyvinylamine-based material which can be obtained by means of said process and its uses.
Description
POLYVINYLAMINE-BASED MATERIAL WITH STABILITY CHARACTERISTICS IN THE PRESENCE OF WATER AND PROCESS FOR ITS PRODUCTION
This invention relates to a polyvinylamine-based material with stability characteristics in the presence of water and process for its production.
It is known that polyvinylamine (PVAm) is a cationic polyelectrolyte, which posses the highest concentration of amminic groups amongst the various polymers which make up this category, such as polyallylamine, polyethylenimine and chitosan. Due to this intrinsic characteristic, polyvinylamine can be advantageously used in different sectors, including that of modifying surfaces and/or e/o interfaces.
Due to its considerable reactivity, it is possible to create links of the polyvinylamine with various kinds of supports or polymers. In the case of processing paper, the presence of PVAm on the cellulose fibres allows a better adhesion between the latter to be obtained, thereby improving the resistance of paper film to abrasion. This behaviour is particularly useful in the case of packaging. Again in this sector, polyvinylamine is suitable for modifying polymers in order to render the surfaces antibacterial, thereby improving the conservation di food.
Moreover, polyvinylamine is often able to combine the adhesion of two surfaces with characteristics which are not immediately compatible (for example, silicone and rubber), but which are polar.
Another sector where PVAm has interesting properties its that of membranes. In fact, thanks to the presence of numerous amminic groups, this polymer is a possible compound for improving the transport of CO2 from one side of the membrane to the other. Moreover, since there are many amminic groups similar CO2, this compound could be incorporated in membranes for separation of the CO2, thereby facilitating its absorption.
One of the advantages of PVAm, which is appreciated in many of its applications, is its high solubility in water. For some sectors, such as, for example, that of membranes, the high solubility in water of PVAm becomes, however, a disadvantage, since the membranes must often work in damp
conditions, and maybe actually in water. In fact, in the presence of high contents of water, PVAm gels, or even dissolves, thereby destroying the membrane.
This leads to the solution proposed according to this invention, which aims to provide a mechanically stable material based on PVAm which can be used as a membrane for the separation of CO2, as an additive for cellulose-based products, protective coating, adhesive agent, substrate for biological applications, etc.
These and other results are obtained according to the invention with a PVAm-based material with the addition of one or more compounds which contain laminar particles and preferably graphene and its derivatives, obtained by means of a thermal treatment of a mixture of PVAm and of said one or more compounds, which remain stable both in the presence of high moisture content and in direct contact with water.
In order to obtain the mechanical stability of the PVAm it is mixed with compounds which contain laminar particles and preferably graphene and its derivatives (few layer graphene, graphene nanoplates, graphene CVD, nano graphite, graphene oxide, graphite oxide, graphene nanoribbons, graphene quantum dots, etc) which have been prepared or are in solutions with dispersants which contain at least:
- an ether group, preferably with a number of repetitive units from 5 to 400 units, and more preferably an ethoxyl group, and
- at least one substituted aromatic group,
- where the substituent of the aromatic group can be a functional group such as: amines, amides, imides, amide isocyanates, sulphuric groups, phosphoric groups, carboxylates, phenolics, alcohols, ethers, aldehydes, anhydride esters, styrenes, nitroaromatics, pyrimidine pyridines, imidazoles, azobenzenes, anthracene naphthenes, diphenols, halides, alkanes and alkenes with or without further aromatics present in chain.
In particular, the material according to the invention has been shown to be particularly efficient when obtained using graphene according to the teachings of patent EP2890633.
The preparation of the material according to the invention can
alternatively be obtained with the normal mixing techniques used industrially or directly during the production of the laminar material.
The material obtained in this way is then treated at a temperature of between 20 and 500 °C, preferably between 80 and 250 °C, in order to obtain an optimum interaction between PVAm and the compound which contains the laminar material and its dispersant.
The product obtained in this way is mechanically stable even if it is immersed in water for months and it can perform its functions in sectors such as, by way of a non-limiting example: the production of membranes (supported or not), coatings to improve the mechanical properties, coatings to functionalize surfaces, materials for biological applications, adhesives, inks for offset, rotogravure, inkjet, spray printing.
The aim of the invention is to provide a polyvinylamine-based material with stability characteristics in the presence of water and process for its production which allows the limitations of the prior art polyvinylamine- based materials to be overcome and to obtain the technical results described above.
A further aim of the invention is that said polyvinylamine-based material and said process for its production can be implemented with substantially low costs, with regard both to the production costs and the management costs.
Another aim of the invention is to provide a polyvinylamine-based material with stability characteristics in the presence of water and process for its production which are simple, safe and reliable.
A first specific object of this invention therefore relates to a process for the production of a polyvinylamine-based material, comprising the following steps:
a) mixing of polyvinylamine together with one or more compounds which contain laminar particles dispersed in a dispersant containing:
- an ether group, and
- at least one substituted aromatic group, where the substituent of the aromatic group can be a functional group such as: amines, amides, imides, amide isocyanates, sulphuric groups, phosphoric groups, carboxylates,
phenolics, alcohols, ethers, aldehydes, anhydride esters, styrenes, nitroaromatics, pyrimidine pyridines, imidazoles, azobenzenes, anthracene naphthenes, diphenols, halides, alkanes and alkenes with or without further aromatics present in chain,
to obtain a polyvinylamine-based mixture:
b) treatment of said polyvinylamine-based mixture at a temperature of between 20 and 500 °C.
Preferably, according to the invention, said one or more compounds which contain laminar particles are selected amongst graphene and its derivatives, said ether group is a group comprising from 5 to 400 base units and said ether group is an ethoxyl group.
Moreover, again according to the invention, said temperature treatment is preferably performed between 80-250 °C, for a time of at least 5 seconds.
Further, according to the invention, after said mixing step and before said treatment in temperature step, there is preferably a step wherein said polyvinylamine-based mixture is deposited in the form of a membrane or coating; and, after said mixing step and before said treatment in temperature step, there is a step wherein said polyvinylamine-based mixture is mixed with adhesive mixtures, and more preferably said adhesive mixtures are mixtures based on vinyl, acrylic, polyurethane, epoxy and silicone adhesives.
A second specific object of this invention relates to a polyvinylamine- based material which can be obtained by means of the above-mentioned process.
A third and last specific object of this invention is the use of the above-mentioned polyvinylamine-based material for the production of membranes, additives for the paper sector, additives for paints, substrates for biological applications, hair gel, antibacterial products, additives for adhesives.
The invention is now described, by way of example and without limiting the scope of the invention, with reference to the accompanying drawings.
Example 1
150 ml of a commercial solution of polyvinylamine (Lupamin® 9095, BASF Italy) at 21 % by weight was mixed with 150 ml of suspension of graphene prepared with 2-butyl pyridine phenyl tosylate (with n=70) to obtain a concentration of graphene solid, with respect to the solid of the polymeric solution, equal to 10%. The solution obtained in this way was stirred for 30 min. The solution was spread by means of a knife on a silicone paper support and dried at 80 °C for one night. It was all subsequently treated at 220 °C in air for 4 hours.
Example 2
10 ml of a commercial solution of polyvinylamine (Lupamin® 9095, BASF Italy) purified of the reaction residue until obtaining a purity of 98% with 5 ml of suspension di boron nitride prepared with 4-(phenol sulfuric)- benzene-1 -phenoletossilate (with n=20), to obtain a concentration of solid with respect to the solid of the polymeric solution, equal to 1 %. The solution obtained in this way was stirred for 30 min. The solution was deposited, by spin coating, on a PTFE support and dried at 50 °C for one night. It was all subsequently treated at 180 °C in air for 1 hour.
Example 3
15 ml of a commercial solution of polyvinylamine (Lupamin® 9095, BASF Italy) at 21 % by weight was mixed with 3 ml of suspension of Few Layer Graphene prepared with polyarylphenol ethoxylate (with n=17) to obtain a concentration of graphene solid, with respect to the solid of the polymeric solution, equal to 1 %. The solution obtained in this way was stirred with magnetic stirrer for 1 hour. Subsequently, the solution was immersed in a sonicator bath (LAVO ST3, 0.5kW) for 15 mins. The solution was spread, by means of a casting knife, on a microporous polysulfone support and dried at 50 °C for one night. It was all subsequently treated at 150 °C in air for 2 hours.
Example 4
A solution of purified polyvinylamine starting from a commercial solution (Lupamin® 9040, BASF Italy) was prepared at 2% by weight. 10 ml of the above-mentioned solution has been mixed with 1 ml of suspension di
molybdenum disulphide and glycolic acid of benzyl ethyl ethoxylate phenyl ether (with n=10), obtaining a ratio by weight between polyvinylamine and molybdenum disulphide of 0.3%. The solution was stirred with a magnetic stirrer for 1 hour and then sonicated in a water bath (LAVO ST3, 0.5 kW) for 30 mins. The solution was sprayed on cellulose acetate filter paper and dried at 60 °C for one night. The film was subsequently treated at a temperate of 1 10 °C in a vacuum for 1 hour.
Example 5
A solution of purified polyvinylamine starting from a commercial solution (Lupamin® 9040, BASF Italy) was prepared at 2% by weight. 2 ml of the above-mentioned solution has been mixed with 2 ml of suspension of Few Layer Graphene and octylphenol ethoxylate (with n=20), obtaining a ratio by weight between polyvinylamine and graphene of 1 %. The solution was stirred with magnetic stirring for 1 hour. Keeping the solution in a glass bottle, it was all subjected to sonication in a water bath (LAVO ST3, 0.5 kW) for 15 mins. The system was then spread on a silicone polymer support by means of a casting knife and dried at 60 °C for one night. The film was subsequently treated at a temperate of 150 °C in air for 2 hours.
Example 6
In order to check the interaction and stabilisation of the compound, the films obtained according to examples 1 -5 were immersed in de-ionised water and left for several weeks, observing the presence of undissolved parts.
Example 7
The material obtained from examples 1 -5 was formed in a continuous film and placed to dry at 35 °C for a few days. A continuous film was obtained in this way with a thickness of approximately 60 micrometres. The above- mentioned film was treated at 150 °C for 1 .5 hours. A permeameter was used to measure the permeability of gas at a moisture content equal to 85% at 35 °C with a pressure in the order of 60 Barrer for carbon dioxide and 2 Barrer for nitrogen. The membrane was found to be stable for the entire duration of the test, which was 30 days.
Example 8
The material obtained from examples 1 -5 was formed in a continuous film and then treated at 200 °C for 5 minutes. A quartz spring balance was used to measure the absorption in mass of water vapour of the sample at 35 °C at 100% of relative humidity in the order to 0.5 g of water per dry gram of film. The sample, whilst increasing in size, remained hanging on the hook of the balance, thereby demonstrating the retention of the good mechanical properties.
The present invention is described by way of example only, without limiting the scope of application, according to its preferred embodiments, but it shall be understood that the invention may be modified and/or adapted by experts in the field without thereby departing from the scope of the inventive concept, as defined in the claims herein.
Claims
1 ) Method for the production of a material based on polyvinylamine, comprising the following steps:
a) mixing of polyvinylamine together with one or more compounds that contain lamellar particles dispersed in a dispersant containing:
- an ethereal group, and
- at least one substituted aromatic group, where the substituent of the aromatic group may be a functional group such as: amines, amides, imides, amides, isocyanates, sulfuric groups, phosphoric groups, carboxylic groups, phenolic groups, alcohols, ethers, aldehydes, esters, anhydrides, styrenic groups, nitroaromatic groups, pyridinic groups; pyrimidinic groups, imidazoles, azobenzenes, naphthenes, anthracenes, diphenols, halides, alkanes and alkenes with or without further aromatic groups present in the chain,
to obtain a mixture based on polyvinylamine:
b) treatment of said mixture based on polyvinylamine at a temperature comprised between 20 and 500 °C.
2) Method according to claim 1 , wherein said one or more compounds containing lamellar particles are selected from graphene and its derivatives.
3) Method according to claim 1 or 2, wherein said ether group is a group comprising from 5 to 400 base units.
4 ) Method according to any one of the previous claims, wherein said ether group is an ethoxy group.
5 ) Method according to any one of the previous claims, wherein said temperature treatment is carried out between 80-250 °C.
6) Method according to any one of the previous claims, wherein said temperature treatment is carried out for a time equal to at least 5 seconds .
7) Method according to any one of the preceding claims, wherein, after said step of mixing and before said step of temperature treatment, a step is provided wherein said mixture based on polyvinylamine is deposited in the form of a membrane or coating.
8 ) Method according to any one of the claims 1 -7, wherein, after said
step of mixing and before said step of temperature treatment, a step is provided in which said mixture based on polyvinylamine is added to adhesive mixtures.
9. Method according to claim 8, wherein said adhesive mixtures are mixtures based on vinylic, acrylic, polyurethane, epoxy, silicone adhesives.
10) Material based on polyvinylamine obtainable by the method according to one of the previous claims.
1 1 ) Material based on polyvinylamine according to claim 10 for the use in the production of membranes, additives for the paper industry, additives for paints, substrates for biological applications, hair gels, antibacterials, additives for adhesives.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT102018000006666 | 2018-06-26 | ||
IT102018000006666A IT201800006666A1 (en) | 2018-06-26 | 2018-06-26 | Polyvinylamine-based material with characteristics of stability in the presence of water and process for its production. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020003331A1 true WO2020003331A1 (en) | 2020-01-02 |
Family
ID=63762721
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IT2019/050136 WO2020003331A1 (en) | 2018-06-26 | 2019-06-14 | Polyvinylamine-based material with stability characteristics in the presence of water and process for its production |
Country Status (2)
Country | Link |
---|---|
IT (1) | IT201800006666A1 (en) |
WO (1) | WO2020003331A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT202000023794A1 (en) * | 2020-10-09 | 2022-04-09 | Graphene Xt S R L | MATERIAL TO IMPROVE THE FILTERING CAPACITY OF FABRICS AND RELATED PROCEDURE FOR THE PRODUCTION OF FACE MASKS |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070261807A1 (en) * | 2006-05-12 | 2007-11-15 | Taggart Thomas E | Use of polyvinylamine to improve oil and water sizing in cellulosic products |
EP2597123A1 (en) * | 2011-11-23 | 2013-05-29 | Basf Se | Aqueous adhesive for fibrous and/or granular substrates |
US20140186451A1 (en) * | 2012-12-31 | 2014-07-03 | Dow Agrosciences Llc | Compositions and methods to modulate the rate of ebis production from dithiocarbamate fungicides |
EP2889335A1 (en) * | 2012-08-21 | 2015-07-01 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Aqueous liquid composition, aqueous coating liquid, funtional coating film and composite material |
CN107349804A (en) * | 2017-07-13 | 2017-11-17 | 中国科学院生态环境研究中心 | A kind of preparation method of high flux anti-acid NF membrane |
CN107376660A (en) * | 2017-09-07 | 2017-11-24 | 太原理工大学 | A kind of immobilization carrier film with lamella screening passage and its preparation method and application |
CN107469635A (en) * | 2017-09-07 | 2017-12-15 | 太原理工大学 | A kind of polyvinylamine composite function film with lamella screening passage and its preparation method and application |
-
2018
- 2018-06-26 IT IT102018000006666A patent/IT201800006666A1/en unknown
-
2019
- 2019-06-14 WO PCT/IT2019/050136 patent/WO2020003331A1/en active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070261807A1 (en) * | 2006-05-12 | 2007-11-15 | Taggart Thomas E | Use of polyvinylamine to improve oil and water sizing in cellulosic products |
EP2597123A1 (en) * | 2011-11-23 | 2013-05-29 | Basf Se | Aqueous adhesive for fibrous and/or granular substrates |
EP2889335A1 (en) * | 2012-08-21 | 2015-07-01 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Aqueous liquid composition, aqueous coating liquid, funtional coating film and composite material |
US20140186451A1 (en) * | 2012-12-31 | 2014-07-03 | Dow Agrosciences Llc | Compositions and methods to modulate the rate of ebis production from dithiocarbamate fungicides |
CN107349804A (en) * | 2017-07-13 | 2017-11-17 | 中国科学院生态环境研究中心 | A kind of preparation method of high flux anti-acid NF membrane |
CN107376660A (en) * | 2017-09-07 | 2017-11-24 | 太原理工大学 | A kind of immobilization carrier film with lamella screening passage and its preparation method and application |
CN107469635A (en) * | 2017-09-07 | 2017-12-15 | 太原理工大学 | A kind of polyvinylamine composite function film with lamella screening passage and its preparation method and application |
Non-Patent Citations (3)
Title |
---|
DATABASE WPI Week 201801, Derwent World Patents Index; AN 2017-78927Q, XP002788447 * |
DATABASE WPI Week 201801, Derwent World Patents Index; AN 2017-81859S, XP002788446 * |
DATABASE WPI Week 201804, Derwent World Patents Index; AN 2017-877842, XP002788445 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT202000023794A1 (en) * | 2020-10-09 | 2022-04-09 | Graphene Xt S R L | MATERIAL TO IMPROVE THE FILTERING CAPACITY OF FABRICS AND RELATED PROCEDURE FOR THE PRODUCTION OF FACE MASKS |
Also Published As
Publication number | Publication date |
---|---|
IT201800006666A1 (en) | 2019-12-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Crosslinked organic–inorganic hybrid chitosan membranes for pervaporation dehydration of isopropanol–water mixtures with a long-term stability | |
US10689545B2 (en) | Dispersion, method for coating objects with this dispersion, and use of the dispersion | |
Ghiggi et al. | Preparation and characterization of polyethersulfone/N-phthaloyl-chitosan ultrafiltration membrane with antifouling property | |
Chen et al. | Biofouling control of halloysite nanotubes-decorated polyethersulfone ultrafiltration membrane modified with chitosan-silver nanoparticles | |
Jiang et al. | Immobilization of horseradish peroxidase in phospholipid-templated titania and its applications in phenolic compounds and dye removal | |
CN104128102A (en) | Cyclodextrin modified composite organic solvent nanofiltration membrane and preparation method thereof | |
Razali et al. | Effects of polyaniline nanoparticles in polyethersulfone ultrafiltration membranes: Fouling behaviours by different types of foulant | |
Zhang et al. | Characterization of citric acid crosslinked chitosan/gelatin composite film with enterocin CHQS and red cabbage pigment | |
CN102327746A (en) | Anti-pollution cyclodextrin-polymer composite nano-filtration membrane and preparation method thereof | |
Meera et al. | Mesoporous and biocompatible surface active silica aerogel synthesis using choline formate ionic liquid | |
El-Sakhawy et al. | Carboxymethyl cellulose acetate butyrate: A review of the preparations, properties, and applications | |
WO2020003331A1 (en) | Polyvinylamine-based material with stability characteristics in the presence of water and process for its production | |
CN107149881A (en) | A kind of dopamine modifying polymer film and preparation method thereof | |
Zhao et al. | Polyelectrolyte complex nanofiltration membranes: performance modulation via casting solution pH | |
JP2011080171A (en) | Composite porous material and method for producing the same | |
KR20220143001A (en) | Water-Redispersible Graphene Powder | |
Prasad et al. | Preparation and characterization of 4A zeolite‐filled mixed matrix membranes for pervaporation dehydration of isopropyl alcohol | |
Arumugham et al. | Development of new hybrid ultrafiltration membranes by entanglement of macromolecular PPSU‐SO3H chains: Preparation, morphologies, mechanical strength, and fouling resistant properties | |
WO2018210217A1 (en) | Method for Scavenging Airborne Formaldehyde | |
CN105031872A (en) | Composition for removing methyl aldehyde and benzene series through biomass and preparing method | |
WO2020073064A4 (en) | Membranes for membrane distillation desalination technology | |
WO2009002127A2 (en) | Natural adhesive using garlic and fabricating method of the same | |
Liu et al. | Polyaniline-poly (vinylidene fluoride) blend microfiltration membrane and its spontaneous gold recovery application | |
CN106474945A (en) | A kind of antibacterial polyamide polymeric membrane and its preparation method and application | |
EP2582622B1 (en) | Use of nanoparticles for the long-term "dry" storage of peroxide radicals |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19742964 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19742964 Country of ref document: EP Kind code of ref document: A1 |