WO2006013286A1 - Polymeres amphiphiles sequences contenant des fonctions reactives, structures auto-assemblees gelees de ces polymeres, leurs preparations et leurs utilisations - Google Patents
Polymeres amphiphiles sequences contenant des fonctions reactives, structures auto-assemblees gelees de ces polymeres, leurs preparations et leurs utilisations Download PDFInfo
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- WO2006013286A1 WO2006013286A1 PCT/FR2005/001739 FR2005001739W WO2006013286A1 WO 2006013286 A1 WO2006013286 A1 WO 2006013286A1 FR 2005001739 W FR2005001739 W FR 2005001739W WO 2006013286 A1 WO2006013286 A1 WO 2006013286A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- Uncrosslinked polymers are thermoplastic products whose solvent resistance is low and the hardness of the films often insufficient for the formulation of coating compositions whose purpose is to protect a surface. It is desired to graft on these polymers reactive functions capable of reacting with another reactive antagonist function in order to form a covalent bond allowing the crosslinking of the polymer. This has the effect of helping to improve the solvent resistance and the hardness of the film.
- this requires the use of special conditions to perform the chemical deblocking and thus trigger the desired reaction after storage such as a high temperature stay.
- the unlocking can generate volatile by-products that can be toxic. This is particularly the case for oximes used for blocking the isocyanate functions or ammonia used during the blocking of acetoacetoxy functions.
- amphiphilic amphiphilic di or triblock polymer that is to say comprising at least one hydrophobic block and a hydrophilic block, the hydrophobic block comprising at least one reactive function.
- the subject of the invention is also a frozen self-assembly structure of these amphiphilic amphiphilic di or triblock polymers, that is to say comprising at least one hydrophobic block and a hydrophilic block, the hydrophobic block comprising at least one reactive function.
- the subject of the invention is also an aqueous dispersion of these amphiphilic amphiphilic di or triblock amphiphilic polymers, that is to say comprising at least one hydrophobic block and a hydrophilic block, the hydrophobic block comprising at least one reactive function in the form of a frozen self-assembly structure.
- the subject of the invention is also a one-component system stable in an aqueous medium comprising an aqueous dispersion of these amphiphilic amphiphilic di or triblock amphiphilic polymers, that is to say comprising at least one hydrophobic block and one hydrophilic block, the hydrophobic block comprising at least one less a reactive function in the form of a frozen self-assembly structure in an aqueous solution comprising at least one water-soluble or water-dispersed polymer carrying an antagonistic reactive function.
- the present invention therefore firstly relates to an amphiphilic amphiphilic di or triblock polymer, that is to say comprising at least one hydrophobic block and a hydrophilic block, the hydrophobic block comprising a sufficient quantity of at least one function reactive.
- reactive function any function capable of reacting with another reactive function called said antagonist to form a covalent bond.
- the reactive functions that are useful for the present invention, mention may be made especially of the epoxy function, the primary, secondary or tertiary amine function, the aldehyde function, the acetal function, the acetoacetoxy function, the ureido function, the isocyanate function, the function alcohol, the carbodiimide function, or the carboxylic acid function.
- the reactive functions are chosen from the epoxy function, the acetoacetoxy function, the alcohol function or the carboxylic acid function.
- the reactive functions of the hydrophobic block are provided by one or more monomers used in the synthesis of the amphiphilic diblock or triblock sequence polymer.
- the monomer carrying the reactive function is not available.
- a monomer carrying a precursor of the reactive functional group it is possible to use a monomer carrying a precursor of the reactive functional group, then to carry out the polymerization of the monomer and to carry out a chemical modification of the polymer thus obtained, such as, for example, hydrolysis to obtain the polymer bearing the reactive function.
- block polymers can be obtained by addition polymerization methods such as cationic polymerization processes, anionic polymerization processes, or controlled radical polymerization processes.
- the block polymers by condensation polymerization processes.
- addition polymerization methods and in particular controlled radical polymerization processes are used.
- an epoxy function can be provided by a monomer chosen from glycidyl esters such as acrylate or glycidyl methacrylate.
- an epoxy function is provided by glycidyl acrylate.
- a primary amine function can be provided by a monomer chosen from vinylformamide. The polymer is then hydrolyzed.
- a tertiary amine function can be provided by a monomer chosen from dimethylaminoethyl methacrylate or dimethylaminoethyl acrylate.
- a tertiary amine function is provided by dimethylaminoethyl acrylate.
- an acetoacetoxy function may be provided by a monomer chosen from acetoacetoxyethylacrylate or acetoacetoxyethylmethacrylate. Of preferably an acetoacetoxy function is provided by acetoacetoxyethylacrylate.
- a ureido function can be provided by a monomer such as 1-methacrylamido, 2-imidazolidinone ethane sold under the trade name Sipomer WAM II by Rhodia.
- an alcohol function can be provided by a monomer chosen from hydroxyethylacrylate, hydroxyethylmethacrylate, hydroxypropylacrylate or hydroxypropylmethacrylate.
- an alcohol function is provided by hydroxyethylacrylate, or hydroxypropylacrylate.
- a carboxylic acid function may be provided by a monomer selected from monocarboxylic acids such as acrylic acid or methacrylic acid, dicarboxylic acids such as fumaric acid, maleic acid, or itaconic acid.
- the reactive function is provided by a monomer chosen from glycidyl esters such as acrylate or glycidyl methacrylate, acetoacetoxyethylacrylate or acetoacetoxyethyl methacrylate, 1-methacrylamido, 2-imidazolidinone ethane, hydroxyethylacrylate, hydroxyethylmethacrylate, hydroxypropylacrylate, hydroxypropylmethacrylate, monocarboxylic acids such as acrylic acid or methacrylic acid, or dicarboxylic acids such as fumaric acid, maleic acid, or itaconic acid.
- the amount of monomers listed above is between 10% to 60% by mole fraction of monomers relative to the total number of monomers of the hydrophobic block.
- the amphiphilic block polymer of the invention may be a diblock or a triblock of formula (I) or (II) below [A] to [B] b (I), or.
- Block A is a homopolymer or a copolymer of monomers chosen from hydrophilic monomers or macromonomers or their mixture.
- Block A may also comprise from 0 to 70% by weight of hydrophobic monomers or macromonomers.
- the level of hydrophobic monomer or macromonomer used is chosen by those skilled in the art in such a way that block A remains soluble in water.
- Block B in addition to the monomers bearing the reactive functional groups comprises at least one hydrophobic monomer or macromonomer.
- Block B may further comprise from 0 to 50% by weight of hydrophilic monomers or macromonomers.
- the level of hydrophilic monomer or macromonomer used is chosen by those skilled in the art in such a way that block B remains hydrophobic.
- monomer or hydrophobic macromonomer monomers or macromonomers whose solubility in water is less than the solubility of vinyl acetate at 20 ° C. and at a pressure of 1 bar.
- polymers are synthesized by radical means
- hydrophobic monomers styrene, methylstyrene, chlorostyrene, vinyl esters of carboxylic acids having from 1 to 8 carbon atoms, such as in particular ethyl acrylate, or butyl acrylate, esters of an ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid having from 3 to 6 carbon atoms and a C 1 to C 8 alkanol, butadiene or ethylene.
- B comprises at least one hydrophobic monomer selected from styrene, methylstyrene, chlorostyrene, vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, n-acrylate and the like. butyl, 2-ethylhexyl acrylate or methyl methacrylate.
- B comprises at least one hydrophobic monomer selected from styrene, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
- B comprises at least one hydrophobic monomer selected from styrene and / or methyl methacrylate.
- Monomer or hydrophilic macromonomer means monomers or macromonomers miscible with water in all proportions.
- hydrophilic monomers examples include ⁇ , ⁇ -monoethylenically unsaturated mono- or dicarboxylic acids having from 3 to 6 carbon atoms, 2-acrylamido-2-methylpropanesulphonic acid, styrene- sulfonic acid, vinylsulfonic acid and also alkali metal salts (in particular sodium and potassium), ammonium salts and salts obtained by reaction of these acids with organic bases such as triethylamine or tetramethylammoniumhydroxide, hydroxyethyl acrylates, hydroxyethyl methacrylates, acrylamide or N-vinylpyrrolidone.
- organic bases such as triethylamine or tetramethylammoniumhydroxide, hydroxyethyl acrylates, hydroxyethyl methacrylates, acrylamide or N-vinylpyrrolidone.
- hydrophilic macromonomers examples include acrylates or methacrylates of polyethylene oxide and / or propylene, or polyvinyl alcohol.
- the blocks A may also comprise hydrophilic units resulting from a chemical transformation after polymerization of hydrophobic monomers.
- hydrophilic units resulting from a chemical transformation after polymerization of hydrophobic monomers such as polyvinyl acetate may be mentioned which, after hydrolysis, forms polyvinyl alcohol.
- Block A or (A ') preferably comprises at least one hydrophilic monomer selected from the group consisting of acrylic acid, methacrylic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and alkali metal salts (especially sodium and potassium salts), ammonium salts and salts obtained by reaction of these aforementioned acids with organic bases such as triethylamine or tetramethylammoniumhydroxide.
- hydrophilic monomer selected from the group consisting of acrylic acid, methacrylic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and alkali metal salts (especially sodium and potassium salts), ammonium salts and salts obtained by reaction of these aforementioned acids with organic bases such as triethylamine or tetramethylammoniumhydroxide.
- the block A or (A ') comprises at least one hydrophilic monomer chosen from acrylic acid, methacrylic acid and / or their alkali metal salts (in particular sodium and potassium), the salts ammonium salts and salts obtained by reaction of these aforementioned acids with organic bases such as triethylamine or tetramethylamoniumhydroxide.
- hydrophilic monomer chosen from acrylic acid, methacrylic acid and / or their alkali metal salts (in particular sodium and potassium), the salts ammonium salts and salts obtained by reaction of these aforementioned acids with organic bases such as triethylamine or tetramethylamoniumhydroxide.
- the relative proportions of the blocks A and B in the amphiphilic block polymer must be such that the length of the block A is sufficient to obtain the solubilization of the block B in an aqueous solution on the one hand, and also to obtain with the length of the Block B chosen a self-assembled aqueous solution "frozen", whether by the direct route (synthesis directly in water) or only by the indirect route (synthesis in a solvent other than water and solvent displacement).
- displacement of solvent is meant in particular solvent exchange or addition of a certain proportion of water before or after removal of the initial solvent.
- amphiphilic block polymer of the invention is thus prepared in such a way that the hydrophobic part comprising the reactive functions of each polymer formed will group together when they are in an aqueous medium and form a self-assembled structure such that this structure is in coexistence with a very low concentration of unimer.
- Very low is defined as a content of less than 10 -4 g / g, which can be determined by the existence of self-assembled structures detectable by radiation scattering techniques after ensuring that The unimer is a diblock or triblock sequence amphiphilic polymer, alone in the aqueous phase and not associated with other amphiphilic block polymers.
- amphiphilic block polymer of the invention is prepared in such a way that a "frozen" self-assembly structure is obtained, thus called to indicate that almost all the polymers are in the form of a self-assembled structure and that they are not do not move from a self-assembly structure to another self-assembly structure over times ranging from one minute to several days or months.
- the hydrophilic part is outside this self-assembled structure and forms a protective barrier between the reactive functions copolymerized with the hydrophobic parts and the antagonistic reactive functions possibly present in the aqueous phase.
- This self-assembled structure "frozen” can be in various known forms. Micelles, lamellar phases, cylindrical phases or vesicles may be mentioned in particular.
- the relative proportions of the blocks A and B in the amphiphilic block polymer must be such that the mass fraction of hydrophobe on the total mass sum b / (sum a + sum b) is between 0.1 and 0.95.
- the relative proportions of the blocks A and B in the amphiphilic block polymer must be such that the mass fraction of hydrophobe over the total mass sum b / (sum a + sum b) is between 0.3 and 0.9 .
- the total mass (sum a + sum b) is between 500 and 500,000 g / mol.
- the total mass (sum a + sum b) is between 500 and 500,000 g / mol.
- the total mass (sum a + sum b) is between 500 and 500,000 g / mol.
- the sequence B is chosen as regards its monomer composition and its length so that it presents as polymer independent, a glass transition temperature TG less than or equal to 50 0 C, and preferably a glass transition temperature TG less than or equal to 30 0 C.
- amphiphilic amphiphilic diblock or triblock sequence may be obtained by any known method of polymerization to obtain diblock or triblock sequence amphiphilic polymers.
- the diblock or triblock copolymers can be obtained by so-called living or controlled polymerization processes.
- Examples of such processes are living ionic polymerization (living anionic or living cationic), or controlled radical polymerization processes.
- controlled radical polymerization is meant a specific radical polymerization process, also referred to as “living polymerization”, in which control agents are used such that the polymer chains in formation are functionalized by terminal groups. which can be reactivated as free radicals by reversible termination and / or transfer reactions.
- radical polymerization process controlled by dithiocarbamate type control agents of the application WO 99/31144 the radical polymerization process controlled by dithiophosphoroester type control agents of the application PCT / FR 01/02374.
- the block copolymers used according to the invention come from a controlled radical polymerization process using, as control agent, one or more compounds chosen from dithioesters, thioether thiones, dithiocarbamates, and xanthates.
- the block copolymers used according to the invention are derived from a controlled radical polymerization carried out in the presence of control agents of the xanthate type.
- the block copolymer used can be obtained according to one of the processes of applications WO 98/58974, WO 00/75207 or WO 01/42312 which implement controlled radical polymerization by control agents.
- said polymerization can be carried out especially in bulk, in solvent, or, preferably in aqueous emulsion, so as to obtain directly the copolymer in the form of an aqueous or hydro-alcoholic solution, or easily applicable to a content between 0.01 and 50% by weight.
- a solution of the copolymer with a content of between 0.01 and 50% by weight obtained directly by a polymerization process in the same organic solvent is also usable.
- the diblock or triblock copolymers can also be obtained by radical polymerization processes using a thiol end polymer in the presence of an initiator and the monomer to be polymerized. These processes are called radical telomerization processes.
- the block amphiphilic polymer is obtained by polymerization in an organic solvent. It is important that the organic solvent used to prepare the hydrophilic block A is the same as the organic solvent in which the hydrophobic block B is prepared.
- the resulting polymer can also be dried and dispersed in water to obtain, for example, a 50% dispersion.
- hydrophilic block directly in aqueous solution. Then, from this solution, a polymerization of the hydrophobic block can be carried out. Small hydrophobic block particles surrounded by a grafted hydrophilic block crown are obtained.
- the advantage of this embodiment is that it avoids the use of solvent on the one hand, and on the other hand increases the amount of reactive groups in the hydrophobic block.
- the subject of the invention is therefore also a frozen self-assembly structure of amphiphilic diblock or triblock polymers comprising the reactive functions in the hydrophobic block.
- the subject of the invention is also an aqueous dispersion of these amphiphilic amphiphilic di or triblock amphiphilic polymers, that is to say comprising at least one hydrophobic block and a hydrophilic block, the hydrophobic block comprising reactive functions in the form of a structure. self-assembly frozen.
- the subject of the invention is also a stable one-component system in an aqueous medium comprising an aqueous dispersion of these amphiphilic amphiphilic di or triblock amphiphilic polymers, that is to say comprising at least one hydrophobic block and one hydrophilic block, the hydrophobic block comprising reactive functions in the form of a frozen self-assembly structure in an aqueous solution comprising at least one polymer carrying an antagonistic reactive function.
- the amounts of reactive antagonistic functions used may vary around the stoichiometry with a molar ratio of reactive functions carried by the amphiphilic block polymer on the reactive antagonistic functions borne by the water-soluble or water-dispersed polymer of between 0.5 and 2.
- the nature of the polymer does not matter. It must comprise at least one reactive function that is antagonistic to the reactive function present in the hydrophobic part of the self-assembled frozen structure of the invention, and it must comprise a sufficient quantity of ionizable groups to ensure electrostatic repulsions with self-supporting structures. assemblies.
- sufficient quantity of ionizable groups to ensure electrostatic repulsions with self-assembled structures is meant a mole fraction of ionizable groups greater than 1% and preferably a mole fraction of ionizable groups greater than 5%.
- This two-component system has the advantage of being stable storage at room temperature in an aqueous medium.
- the user can simply dry the aqueous dispersion at room temperature.
- the protective barrier made by the hydrophilic block A no longer plays its role and the two reagents put in contact can react.
- crosslinkable two-component systems can be used in all coating compositions, varnishes, mastics, glues, adhesives. They make it possible to improve the hardness of the films, to avoid blocking phenomena, to improve the resistance to solvents or to improve the mechanical properties such as, for example, the scratch resistance.
- This resin may be added in proportions of between 10% and 200% by weight of resin relative to the weight of the amphiphilic block polymer.
- the amounts of antagonistic functions present in the water-soluble or water-dispersed polymer must be in stoichiometric ratios which take into account all the reactive functions of the block amphiphilic polymer and possibly reactive functional groups of the polyfunctional hydrophobic resin.
- a 250 ml flask equipped with a condenser and a stirring system (magnetic stirrer, heating) is thermostatically controlled at 80 ° C.
- Rhodixan A1 xanthate, control agent, 2.19 g
- the AIBN polymerization initiator, 0.86 g
- a mixture of water (10 g) and ethanol (40 g) is introduced into the flask.
- a mixture of butyl acrylate (ABu, 42.3 g) and glycidyl methacrylate (GMA, 10.4 g) is introduced over 3 hours, while maintaining the temperature at 80 ° C. At the end of introduction of this mixture, the temperature is maintained at 80 ° C. for an additional hour in order to have a monomer conversion rate of 100%.
- Second step Synthesis of the dibloc is added, over two hours at 80 0 C, in the solution of the monoblock obtained AMPS (Acrylamido Methylpropane Sulfonic Acid, 11.5 g) previously dissolved in a mixture of water / ethanol (20/80, 30 g ). At the end of the addition, the diblock is maintained at 80 ° C. for one hour. The conversion of AMPS is greater than 99%.
- AMPS (Acrylamido Methylpropane Sulphonic Acid, 10 g), previously dissolved in a water / ethanol mixture (20/80, 30 g), is added over two hours at 80 ° C. in the solution of the monoblock obtained. At the end of the addition, the diblock is maintained at 80 ° C. for one hour. The conversion of AMPS is greater than 99%.
- This example shows the use of poly (ABu) -b-poly (AMPS) diblocs of Example A-1 containing epoxy groups in the ABu block to form in the aqueous phase storage-stable micelles / vesicles which conduct, after application and evaporation of the water, to a film which reticles on drying.
- poly (ABu) -b-poly (AMPS) diblocs of Example A-1 containing epoxy groups in the ABu block to form in the aqueous phase storage-stable micelles / vesicles which conduct, after application and evaporation of the water, to a film which reticles on drying.
- the diblock polymer of Example A-1 previously dried from the synthesis solvent, is dispersed by direct dispersion in water at a solids content of 60% by mass and left stirring until a monodisperse dispersion of average diameter is obtained. about 90 nm (characterized by light scattering with the Horiba granulometer LA-910, see Figure 1).
- This example shows the use of poly (ABu) -b-poly (APMPS) diblocks containing epoxy groups in the ABu block to form in phase aqueous storage stable micelles / vesicles which lead, after application and evaporation of water, to a film that cross-links to drying.
- AMPS poly (ABu) -b-poly
- the diblock polymer is prepared according to the protocol described in Example A-2.
- the theoretical molecular weight of each block is as follows: p (Abu-co-GMA) 7 5oo-bp (AMPS) iooo- the mole fraction of GMA in the block poly (butyl acrylate) is 10%.
- the preparation procedure consists in first making an emulsion in water containing the diblock copolymer of Example A-2 and an epoxy resin (Epikote Resin 828, designated in the following example by
- the epoxy resin is added at a low level (5% to 10%) in order to enrich the mixture in reactive groups.
- a rough initial mixture is made using a turbine (UltraTurrax) before being sheared for one minute at 11000 rpm.
- the emulsion thus obtained has a pH of between 3 and 4. It is adjusted with 10% sodium hydroxide at pH 8-8.5. Add acrylic resin (final dry extract 47%)
- Neocryl BT24 designated by PoI.Acrylic
- TBAH tetrabutylammonium hydroxide
- Example B-1 Storage stability
- the storage stability is evaluated by a viscosity monitoring of the mixtures. Indeed, the possible crosslinking of the epoxy functional groups with the carboxylic acids of the acrylic polymer must lead to gelation of the mixture. Storage of 90 days at room temperature, in solution in ethanol leads to gelation of the medium against in the case of storage in water with the diblock in the form of frozen dispersion of Example B-1, the viscosity remains stable on storage (see Figure 2).
- the diblock levels of Example A-1 are expressed as dry diblock mass relative to the dry latex.
- the properties of films derived from mixing acrylic latex with 20% by weight of the diblock dispersion of Example B-1 are evaluated by mechanical and thermal mechanical analysis (DMTA) (measured using a DMA7 from Perkin Elmer) and solvent absorption.
- DMTA mechanical and thermal mechanical analysis
- the mixtures of the diblock dispersion of Example B-1 with the latex are applied in silicone molds (with a wet thickness of 1 mm) and dried at room temperature, the properties are monitored as a function of time. Measurements of the dynamic moduli as a function of the temperature are carried out and show a substantial increase in the glass transition temperature and the elastic modulus at 90 ° C. with time (see FIGS. 4 and 5). This evolution reflects a gradual crosslinking of the film. In addition, the crosslinking can also be evaluated by solvent swelling rate measurements.
- Film samples (of initial mass mo and approximate dimensions: 1 cm ⁇ 1 cm ⁇ 0.5 mm) are immersed in a large volume of methyl ethyl ketone for at least 24 h after which they are weighed (mi) and then dried at 50 ° C. for at least 24h and then weighed again (r ⁇ i 2 ).
- the insoluble content is given by the value m 2 / m o x1OO and the swelling ratio to the solvent is given in ml / m 2 x100.
- the level of insoluble is 100% from the first days of drying.
- the degree of swelling with the solvent decreases with the drying time, reflecting an improvement in the solvent-resistant properties of the films resulting from these compositions, thanks to the crosslinking of the epoxides with the carboxylic acids (see FIG. 6).
- Example C-2
- the preparations are applied on a glass plate (150 ⁇ m wet thickness) either directly after the preparation of the sample (fresh product) or after aging for 10 days at 38 ° C. (aged product). Three drying modes are compared: - room temperature - 1 hour at 12O 0 C
- the films then have the dry composition indicated in Table 3. It is again expected 24 hours before making Persoz hardness measurements to follow the crosslinking level of the films. Previously, some of the films are taken and dipped in Methyl Ethyl Ketone (MEC). A complete dissolution of the films indicates that there was no crosslinking.
- MEC Methyl Ethyl Ketone
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FR0407554A FR2872816B1 (fr) | 2004-07-07 | 2004-07-07 | Polymere amphiphile sequence contenant des fonctions reactives dans le bloc hydrophobe, structures auto-assemblees gelees de ces polymeres amphiphiles sequences, leurs preparations et leurs utilisations |
FR0407554 | 2004-07-07 |
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WO2006013286A1 true WO2006013286A1 (fr) | 2006-02-09 |
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CN110964214B (zh) * | 2019-12-12 | 2022-08-09 | 南京理工大学 | 一种电刺激响应型芳纶纳米纤维复合水凝胶的制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6319967B1 (en) * | 1998-08-31 | 2001-11-20 | Ppg Industries Ohio, Inc. | Thermosetting compositions containing epoxy-functional polymers prepared using atom transfer radical polymerization |
US20040033203A1 (en) * | 2002-05-31 | 2004-02-19 | L'oreal | Two-compartment device comprising at least one amphiphilic linear block polymer |
FR2845930A1 (fr) * | 2002-10-21 | 2004-04-23 | Oreal | Procede de solubilisation de composes lipophiles en solution aqueuse par des copolymeres blocs amphiphiles et composition cosmetique |
WO2004108843A1 (fr) * | 2003-06-05 | 2004-12-16 | Basf Corporation | Composition de revetement contenant un copolymere sequence exempt de polelectrolyte, hydrodispersable et un agent de reticulation, film reticule associe et systeme en couches les comprenant |
-
2004
- 2004-07-07 FR FR0407554A patent/FR2872816B1/fr not_active Expired - Fee Related
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2005
- 2005-07-06 WO PCT/FR2005/001739 patent/WO2006013286A1/fr not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6319967B1 (en) * | 1998-08-31 | 2001-11-20 | Ppg Industries Ohio, Inc. | Thermosetting compositions containing epoxy-functional polymers prepared using atom transfer radical polymerization |
US20040033203A1 (en) * | 2002-05-31 | 2004-02-19 | L'oreal | Two-compartment device comprising at least one amphiphilic linear block polymer |
FR2845930A1 (fr) * | 2002-10-21 | 2004-04-23 | Oreal | Procede de solubilisation de composes lipophiles en solution aqueuse par des copolymeres blocs amphiphiles et composition cosmetique |
WO2004108843A1 (fr) * | 2003-06-05 | 2004-12-16 | Basf Corporation | Composition de revetement contenant un copolymere sequence exempt de polelectrolyte, hydrodispersable et un agent de reticulation, film reticule associe et systeme en couches les comprenant |
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FR2872816A1 (fr) | 2006-01-13 |
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