WO2019180126A1 - C3ms à base de pva pour inhiber la recristallisation de la glace et fabriquer des revêtements polymères qui réduisent l'adhérence de la glace - Google Patents
C3ms à base de pva pour inhiber la recristallisation de la glace et fabriquer des revêtements polymères qui réduisent l'adhérence de la glace Download PDFInfo
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- WO2019180126A1 WO2019180126A1 PCT/EP2019/057063 EP2019057063W WO2019180126A1 WO 2019180126 A1 WO2019180126 A1 WO 2019180126A1 EP 2019057063 W EP2019057063 W EP 2019057063W WO 2019180126 A1 WO2019180126 A1 WO 2019180126A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/005—Modified block copolymers
-
- 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
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
-
- 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
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D153/005—Modified block copolymers
Definitions
- This invention relates to materials and compositions to inhibit ice recrystallization and reduce ice adhesion.
- Complex coacervation is the electrostatically driven, liquid- liquid phase separation that occurs when two aqueous solutions of oppositely charged polyelectrolytes are mixed. Attaching a neutral polymer block to one or both of the polyelectrolytes leads to microphase separation and the formation of micelles, with a complex coacervate core, surrounded by a water-soluble neutral corona.
- the anionic polyelectrolyte is a poly(acrylic acid) (PAA), a poly(methylacrylic acid) (PMAA), a poly(styrene sodium sulfonate) (PSS), a poly(alpha, beta-aspartic acid) (PAsp), a poly(sodium-2-acrylamido)-2- methylpropanesulfonate) (PAMPS), or a poly(maleic acid) (PMALA).
- PAA poly(acrylic acid)
- PMAA poly(methylacrylic acid)
- PSS poly(styrene sodium sulfonate)
- PAsp poly(alpha, beta-aspartic acid)
- PAMPS poly(sodium-2-acrylamido)-2- methylpropanesulfonate)
- PMALA poly(maleic acid)
- the cationic polyelectrolyte could be a poly(4-vinyl-N- methylpyridinium iodide) (P4VMP), poly(2-vinyl-N-methylpyridinium iodide) (P2VMP), a poly(4-vinylpyridine) (P4VP), a poly(N-ethyl-4-vinyl pyridinium bromide (P4EVP), poly(2-vinylpyridine) (P2VP), a poly(2-(N,N- dimethylamino)ethyl methacrylate) (PDMAEMA), a poly(2-(N-amino)ethyl methacrylate hydrochloride) (PAEMA), a poly(4-(2-amino hydrochloride- ethylthio)-butylene) (PAETB), a poly(diallyldimethylammonium chloride) (PDADMAC), a poly(2-(N,N,N
- the material composition is a coating/film or an additive.
- the material composition being an additive it could be added to a windshield washer liquid. Upon spraying of this solution (washer liquid with the PVA-C3Ms) onto a car windshield the solvent evaporates which generates a coating.
- the oppositely charged A could be a perfluorodecanoic acid (PFD), a perfluoropentanoic acid (PFP), perfluorosebacic acid (PFSA), a metal particle, a multivalent ion or a low molecular weight anionic surfactant.
- the oppositely charged B could be or include a metal particle, a multivalent ion, or a low molecular weight cationic surfactant.
- the oppositely charged B could be a cationic surfactant such as cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), didodecyldimethylammonium bromide (DDDAB), dodecyltrimethylammonium bromide (DTAB), or dimethyldioctadecylammonium bromide (DODAB).
- CTAB cetyltrimethylammonium bromide
- CTAC cetyltrimethylammonium chloride
- DDDAB didodecyldimethylammonium bromide
- DTAB dodecyltrimethylammonium bromide
- DODAB dimethyldioctadecylammonium bromide
- a and B are close to stoichiometry.
- a and B are more or less equal amounts (ranging from A:B 40:60 to vice versa) of positively and negatively charged monomers.
- the PVA concentration in the PVA-C3M is above 0.33mM. In yet another aspect, the inhibitory concentration of the PVA-C3Ms is at about 0.33 mM. This is the concentration at which the recrystallization rate is decreased by 50%.
- FIGs. 2A-B show according to an exemplary embodiment of the invention normalized ice growth rate constant as a function of VAM concentration of C3Ms (FIG. 2A) and PVA 27 3-b-PAA353 (FIG.
- PVA-based C3Ms formed by poly(4-vinyl-/V-mcthylpyridinium iodide), P4VMP, a cationic homopolymer, with poly(vinyl alcohol )-/Vx;A.-poly(acry lie acid), PVA-b-PAA, a neutral-anionic diblock copolymer, in aqueous conditions.
- the inventors first determined the critical micelle concentration (CMC) and preferred micelle composition (PMC) at pH 10.5 in 10 mM NaNO, solution by light scattering. Next, we checked whether the PVA-based C3Ms inhibit ice recrystallization. Therefore, we determined ice growth rate constants (k d ) over a range of polymer concentrations in the so-called sucrose sandwich assay.
- CMC critical micelle concentration
- PMC preferred micelle composition
- PVA-based C3Ms effectively inhibit ice recrystallization at vinyl alcohol (VA) monomer concentrations as low as 1 mM. Their activity was comparable to linear chains and PVA bottlebrushes. This indicated that the IRI activity of PVA is dependent on the VA monomer concentration rather than the polymer architecture. These results unveiled the potential of using PVA-based C3Ms to obtain anti-icing polymeric films.
- VA vinyl alcohol
- the invention is a material composition or a coating embodying PVA-based C3Ms (complex coacervate core micelles) as additives to inhibit ice recrystallization and polymer coatings that reduce ice adhesion.
- the invention showed in one embodiment PVA-b-PAA and P4VMP as the building blocks for the PVA-based C3Ms for these purposes.
- Other embodiments of the invention are directed to a material composition or coating that comprises PVA-C3Ms, whereby the C3Ms are A-PVA + B, or A- PVA + B-PVA block and/or graft copolymers with A and B being oppositely charged.
- the anionic polyelectrolyte can be a polymer such as PAA, poly(acrylic acid); PMAA, poly(methylacrylic acid); PSS, poly(styrene sodium sulfonate); PAsp, poly(alpha, beta-aspartic acid); PAMPS, poly(sodium-2-acrylamido)-2- methylpropanesulfonate); PMALA, poly(maleic acid) etc.
- PAA poly(acrylic acid); PMAA, poly(methylacrylic acid); PSS, poly(styrene sodium sulfonate); PAsp, poly(alpha, beta-aspartic acid); PAMPS, poly(sodium-2-acrylamido)-2- methylpropanesulfonate); PMALA, poly(maleic acid) etc.
- the cationic polyelectrolyte can be a polymer such as P4VMP, poly(4-vinyl- N-methylpyridinium iodide); P2VMP, poly(2-vinyl-N-methylpyridinium iodide); P4VP, poly(4-vinylpyridine); poly(N-ethyl-4-vinyl pyridinium bromide (P4EVP); P2VP, poly(2-vinylpyridine); PDMAEMA, poly(2-(N,N- dimethylamino)ethyl methacrylate); PAEMA, poly(2-(N-amino)ethyl methacrylate hydrochloride); PAETB, poly(4-(2-amino hydrochloride- ethylthio)-butylene);PDADMAC, poly(diallyldimethylammonium chloride); PDEAEMA, poly(2-(N,N-diethylamino)ethyl methacrylate
- C3Ms with a PVA-based block-copolymer (A-PVA or B-PVA) and an oppositely charged species.
- a and B are the same as the above-mentioned A and B electrolytes.
- An oppositely charged species can be a micelle composed of perfluorodecanoic acid (PFD), perfluoropentanoic acid (PFP), perfluorosebacic acid (PFSA), a metal particle, multivalent ions or low molecular weight ionic surfactant.
- PFD perfluorodecanoic acid
- PFP perfluoropentanoic acid
- PFSA perfluorosebacic acid
- Anionic surfactants of which the head group is sulfate, sulfonate, phosphate or carboxylates are alkyl carboxylates such as sodium stearate; alkyl sulfates such as ammonium lauryl sulfate, sodium lauryl sulfate (SLS), sodium dodecyl sulfate (SDS); alkyl-ether sulfates such as sodium laureth sulfate and sodium lauryl ether sulfate (SLES).
- Cationic surfactants are cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), didodecyldimethylammonium bromide (DDDAB), dodecyltrimethylammonium bromide (DTAB), dimethyldioctadecylammonium bromide (DODAB).
- All stock solutions were prepared in ultrapure water with 10 mM NaN0 3 .
- the pH was adjusted to 10.5 using NaOH to ensure full deprotonation of PAA.
- the polymer stock solutions were prepared at 20 mM chargeable monomer concentrations, so after mixing c tot— c + + C_— C WMP + C AA ( 1 ) and dilutions were done with the 10 mM NaNCL solution at pH 10.5.
- the polymer solutions were mixed at desired mixing ratio which was expressed as the molar ratio of cationic charges (4VMP) to the total number of chargeable monomers
- a 2 pL droplet of sample was sandwiched between two cover slides and placed in a stage attached to a Nikon ECLIPSE Ci-Pol Optical Microscope where the temperature was controlled by a Linkam LTS 420.
- a thin polycrystalline ice layer was created by rapidly freezing (20 °C/min) to -40 °C.
- the temperature was then raised (10 °C/min) to -7 °C and kept constant for one hour.
- Microphotographs were taken every 5 minutes and analyzed with ImageJ, followed by an in-house written Matlab script, to obtain the equivalent radius for each ice crystal (details in Supporting Information).
- the rate constants, /c d (c) were obtained from the temporal increase in the cube of the number average radius as described by LSW theory, according to
- nucleation temperature the temperature at which the greyscale intensity suddenly rises was registered as the nucleation temperature (details are discussed in Appendix B of US Provisional Application 62/646302, filed Mach 21, 2018 to which this application claims the benefit and, which is hereby incorporated for all it teaches).
- IRI assays To quantify IRI activity, we performed IRI assays over a range of vinyl alcohol VA concentrations from 0.2 to 7.5 mM. Ice growth rates were drastically decreased when VA concentrations exceed 0.3 mM. Full inhibition of ice recrystallization occurs at concentrations above 1 mM, which corresponds to 2.7 mM chargeable monomer concentration (FIG. 2A). The IRI efficacy (q) is determined from the inflection point of the curve where the ice growth rate is decreased to half of its value at zero inhibitor concentration.
- This result implies that the VA concentration is the defining factor for IRI activity instead of the architecture of the polymer chain and/or its association state.
- the block copolymer itself exhibits a somewhat lower IRI activity, which might be due to repulsive interactions between anionic polymer chains.
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Combustion & Propulsion (AREA)
- Paints Or Removers (AREA)
Abstract
L'invention concerne une composition de matériau et un procédé destinés à inhiber la recristallisation de la glace ou à réduire l'adhérence de la glace. La composition de matériau est une micelle à noyau de coacervat complexe à base de PVA (PVA-C3M). Chaque PVA-C3M comporte soit un copolymère séquencé, soit un copolymère greffé, ou une combinaison de ceux-ci. Chaque PVA-C3M est défini comme suit : (i) A-PVA+ B, (ii) B-PVA+ A, ou (iii) A-PVA + B-PVA, A et B étant chargés de manière opposée ; A représentant un polyélectrolyte anionique et B représentant un polyélectrolyte cationique. La composition de matériau peut être utilisée en tant que revêtement, film ou additif en fonction de l'application.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US201862646302P | 2018-03-21 | 2018-03-21 | |
US62/646,302 | 2018-03-21 |
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WO2019180126A1 true WO2019180126A1 (fr) | 2019-09-26 |
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PCT/EP2019/057063 WO2019180126A1 (fr) | 2018-03-21 | 2019-03-21 | C3ms à base de pva pour inhiber la recristallisation de la glace et fabriquer des revêtements polymères qui réduisent l'adhérence de la glace |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022140513A1 (fr) * | 2020-12-22 | 2022-06-30 | Fluidx Medical Technology, Llc | Compositions injectables à solidification in situ avec agents de contraste transitoires et leurs procédés de fabrication et d'utilisation |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005030282A1 (fr) * | 2003-09-25 | 2005-04-07 | Rhodia Chimie | Micelles a noyau de coacervat complexe en tant qu'agent de modification ou de traitement de surface |
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2019
- 2019-03-21 WO PCT/EP2019/057063 patent/WO2019180126A1/fr active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2005030282A1 (fr) * | 2003-09-25 | 2005-04-07 | Rhodia Chimie | Micelles a noyau de coacervat complexe en tant qu'agent de modification ou de traitement de surface |
Non-Patent Citations (4)
Title |
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CHRISTIAN C. M. SPRONCKEN ET AL: "Complex Coacervate Core Micelles Containing Poly(vinyl alcohol) Inhibit Ice Recrystallization", MACROMOLECULAR RAPID COMMUNICATIONS, vol. 39, no. 17, 1 September 2018 (2018-09-01), DE, pages 1700814, XP055595822, ISSN: 1022-1336, DOI: 10.1002/marc.201700814 * |
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; XUE, HAN ET AL: "Ice recrystallisation inhibition by hydrophilic polymers", XP002792037, retrieved from STN Database accession no. 2018:2419184 * |
DEBUIGNE ET AL., MACROMOLECULES, vol. 41, 2008, pages 2353 |
THOMAS R. CONGDON ET AL: "Influence of Block Copolymerization on the Antifreeze Protein Mimetic Ice Recrystallization Inhibition Activity of Poly(vinyl alcohol)", BIOMACROMOLECULES, vol. 17, no. 9, 12 September 2016 (2016-09-12), US, pages 3033 - 3039, XP055595991, ISSN: 1525-7797, DOI: 10.1021/acs.biomac.6b00915 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022140513A1 (fr) * | 2020-12-22 | 2022-06-30 | Fluidx Medical Technology, Llc | Compositions injectables à solidification in situ avec agents de contraste transitoires et leurs procédés de fabrication et d'utilisation |
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