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  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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  • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
  • C09D101/08—Cellulose derivatives
  • C09D101/26—Cellulose ethers
  • C09D101/28—Alkyl ethers
  • C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
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  • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
  • D06M15/03—Polysaccharides or derivatives thereof
  • D06M15/05—Cellulose or derivatives thereof
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  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
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  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
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  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
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  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
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  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
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  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
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  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3564—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing phosphorus
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  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
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  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material

Definitions

• the present invention relates to the hydrophilic modification of the substrates, requiring treatment in an aqueous medium with polymers soluble in water, and the obtaining of hydrophilic modified dry substrates. It enhances the adsorption of these polymers on substrates, based on a treatment in water at a suitable temperature, in the presence of water-soluble polymers of heat-sensitive nature and of suitable compositions.
• the invention also covers the case where the hydrophilic modification of the substrates is only temporary.
• a first objective is to promote the adsorption of water-soluble or hydrophilic polymers on substrates imperatively requiring treatment in an aqueous medium in the presence of these polymers.
• the polymers being water-soluble or hydrophilic are, by their very high affinity with water, tend to remain in the aqueous medium instead of being adsorbed on the substrates that is desired to treat and thus modify the surface .
• a second objective is to produce temporary hydrophilic and "washable” coatings on the substrates which need to be treated in an aqueous medium. It involves providing two solutions to two different problems, the first relating to the adsorption of polymer for - '"" the formation of a hydrophilic coating on substrates intended for various applications, and the second dealing with desorption. or the elimination of the so-called “washable” hydrophilic coating on the substrates after applications. In this case, it is necessary, as previously, to promote the adsorption of water-soluble or hydrophilic polymers on substrates which imperatively require treatment.
• the second part of the problem consists in proposing, after using the modified substrates for a given application, a method allowing the desorption of these polymers on the hydrophilic modified substrate also in an aqueous medium in order to avoid the accumulation of the polymer after a series of adsorption steps.
• Polymers have been used for many decades for the modification of the properties of various substrates such as paper, textile, metal, and wood, concrete. It is often sought through these modifications, the provision or improvement of various properties, in particular the mechanical, antistatic properties, the feel, the resistance to aqueous liquids, to greases by hydrophobic and oleophobic modification of the substrates, the wettability and the aptitude. easily remove dirt during washing thanks to the hydrophilic modification of the substrates.
• the polymer can be functionalized so as to promote various interactions with the substrate, in particular:
• Precipitation of the polymer during the treatment of substrates in an aqueous medium is an approach often used to cause precipitation of the polymer on the support.
• a second additive is an approach often used to cause precipitation of the polymer on the support.
• the cellulosic fibers are treated with anionic latexes of styrene / butadiene copolymer.
• a cationic water-soluble polymer additive is incorporated to destabilize the latex which consequently precipitates on the paper fibers (for example American patents US-A-4 121 966, US -A-2 745 744).
• This precipitation approach thus makes it possible to successfully adsorb a polymer which having no functional pattern of attachment to the support.
• it has the disadvantage of incorporating a third body into the formulation.
• the present invention provides a new method based on the radical change in the solubility in water of certain water-soluble polymers as a function of temperature. More specifically, it takes advantage of the particular properties of heat-sensitive polymers, that is to say polymers soluble in water below a certain temperature commonly called LCST, but which become insoluble above this temperature LCST.
• a water-soluble polymer having an LCST for substrates to be treated in an aqueous medium by a water-soluble polymer, it proposes on the one hand, to choose a water-soluble polymer having an LCST, and on the other hand, to carry out the aqueous treatment of said substrate preferably at a temperature greater than or equal to the LCST in order to precipitate the polymer which has become insoluble in water, and thus promoting the fixation or adsorption of said water-soluble polymer on the surface of the substrate.
• the latter In the case of treatments which cannot be carried out at a temperature higher than the LCST of the thermosensitive polymer, the latter must have functional or compatibilizing patterns allowing it to be fixed on the substrate.
• the advantage of this method lies in the fact that, under the conditions of temperature higher than the LCST, the water-soluble polymer having the thermosensitive character precipitates during the treatment in an aqueous medium of the substrate, thus improving the fixing and the adsorption on the substrate then that the other non-thermosensitive water-soluble hand polymers are soluble and tend to remain mainly in water instead of clinging to the substrate.
• thermosensitive polymer In order to further enhance the adsorption of the thermosensitive polymer on the support, it may be necessary to incorporate reactive, ionic or compatibilizing units into the structure of the polymer provided, on the one hand, that the thermosensitive nature, necessary for the precipitation of the polymer be kept, and secondly, that these patterns can generate covalent bonds (chemical reaction), ionic bonds (ionic interaction), or quite simply reinforce adsorption on the substrate. In the case of treatments that cannot be carried out at a temperature higher than the LCST of the thermosensitive polymer, these reactive, ionic or compatibilizing units are also used to fix the polymer to the substrate.
• the hydrophilic modified substrate can thus be used for applications requiring a hydrophilic surface such as increasing the wettability of the substrate with hydrophilic ingredients or the provision of barrier properties between the substrate and the hydrophobic or oleophobic substances.
• the present invention provides a method based on the radical change in the solubility in water of certain water-soluble polymers as a function of temperature and pH. It takes advantage of the particular properties of these water-soluble polymers which are both thermosensitive and sensitive to pH, that is to say polymers which are soluble in water below a certain temperature (known as LCST), but which become insoluble in water at temperatures above the LCST. These same polymers are soluble in water at basic pH whatever the temperature.
• thermosensitive and pH-sensitive polymers of the invention are chosen so that the temperature required for the step of treatment of the substrate by adsorption of polymer is preferably greater than or equal to the LCST of the polymer, the separation or the precipitation of the polymer in water promoting the attachment or adsorption of the polymer to the surface of the substrate.
• this invention provides two solutions for the desorption of the coating in an aqueous medium: (1) if the temperature of the aqueous medium is higher than the LCST of the heat-sensitive polymer, it is recommended to carry out the desorption in basic medium, insofar as certain compositions of heat-sensitive polymers proposed in the invention lose their temperature sensitivity by because of the neutralization of the carboxylic acid functions present in the structure of these polymers.
• the desorption of the coating can be done by simple soaking in water whatever the pH.
• the subject of this invention is the use of the particular properties of thermosensitive polymers to reinforce the hydrophilic modification of various substrates imperatively requiring treatment in an aqueous medium with water-soluble polymers and used for various applications such as increasing the wettability of the substrate with hydrophilic ingredients or the provision of barrier properties between the substrate and hydrophobic or oleophobic substances.
• These heat-sensitive polymers must preferably have functional, reactive, ionic or compatibilizing units to improve the fixation on the substrates, but also to be able to be applied over a wider temperature range, in particular below and above the LCST of the heat-sensitive polymers. .
• the invention in a second form, relates to temporary hydrophilic coatings on substrates which require, after use of the modified hydrophilic substrate for the aforementioned applications, the removal or leaching of the hydrophilic coating on the substrate.
• the invention provides two solutions for the desorption of the coating in an aqueous medium to avoid the accumulation of polymers on the substrates after application.
• the present invention therefore relates to a process for hydrophilic modification of a substrate, characterized by the the fact that said substrate is treated in an aqueous medium with a water-soluble polymer or copolymer modifier having thermosensitive properties.
• polymer having a thermosensitive character is understood to mean a polymer having a radical change in solubility or in hydrophilic / hydrophobic transition at a critical temperature commonly called LCST. These (co) polymers are insoluble in water above the LCST and soluble in water below the LCST. Said water-soluble thermosensitive polymer or copolymer modifier has an LCST generally between 3 and 100 ° C.
• the substrate is treated in an aqueous medium with said heat-sensitive polymer or copolymer modifier at a temperature at least equal to the LCST of said heat-sensitive polymer or copolymer in order to precipitate the latter on said substrate to time of treatment due to its hydrophobic nature in this temperature range.
• the substrate to be treated does not tolerate being subjected to a temperature exceeding a value T
• the substrate is treated in an aqueous medium at a temperature below T, the water-soluble polymer or copolymer thermosensitive then being chosen from those having an LCST at most equal to the treatment temperature.
• thermosensitive water-soluble (co) polymer chooses said (co) polymer from those having functional, ionic or compatibilizing units allowing its fixation on the substrate.
• the functional units are chosen in particular from cationic, anionic, sulfonic acid, phosphatic acid, phosphate, phosphonees, hydrophobic, ethoxylated, carboxylic acid, silane, maleic, alcohol, amino, amide, sulfonate, carboxylate groups.
• Hydrophobic groups can be used to reinforce the compatibility between substrates to be treated and heat-sensitive polymers.
• the ethoxylated functions can form hydrogen bonds with the hydroxyl groups of cotton or rayon fiber textiles.
• the phosphate or phosphone functions can strengthen adhesion to metal and glass.
• the silane functions are reserved to improve adhesion on glass and concrete.
• said substrate can be treated in an aqueous medium with the water-soluble homopolymer or copolymer modifier having thermosensitive properties which has functional units (such as those indicated above) capable of bringing complementary properties other than hydrophilicity (antistatism). , adhesion, wettability, hydrophobicity, fixation of hydrophilic and hydrophobic substances, elimination of hydrophilic and hydrophobic substances), and / or which is combined with at least one other active ingredient whose retention or adsorption on the substrate results from its coating or of its encapsulation by the heat-sensitive polymer at the time of its precipitation on the substrate above the LCST.
• the water-soluble homopolymer or copolymer modifier having thermosensitive properties which has functional units (such as those indicated above) capable of bringing complementary properties other than hydrophilicity (antistatism).
• adhesion, wettability, hydrophobicity, fixation of hydrophilic and hydrophobic substances, elimination of hydrophilic and hydrophobic substances and / or which is combined with at least one other active
• the other aforementioned ingredients are chosen, for example, from hydrophobic polymers in the form of latex, aqueous polymer dispersions, fillers, enzymes, surfactants, organic materials and mineral materials; these ingredients are used to provide complementary properties to the substrates.
• the thermosensitive (co) polymer in this case acts as a transfer agent for these ingredients for more contact. intimate between them and the surface of the substrate. In addition to the coating and encapsulation following the precipitation of the thermosensitive (co) polymer, the latter can interact with these ingredients to make transport more efficient.
• the thermosensitive water-soluble homo- or copolymer can be chosen from those capable of interacting with the ingredient (s) used jointly, for example by forming hydrogen bonds with it or these.
• the substrates concerned by the treatment and modification of the properties according to the invention are chosen among others from textiles, nonwovens, metal, glass, wood, paper, leather, building substrates, carpet , fibers, polymers, concrete.
• the method according to the invention may be a hydrophilic treatment of textiles and non-woven by adsorption of the (co) polymer heat sensitive; or consist of a treatment of the paper, in particular the adsorption on the cellulose fibers for the improvement of the wet resistance of the paper and the hydrophobic and oleophobic treatment of the paper; or also consist of a treatment providing the substrates with antistatic properties, wettability, a hydrophilic or hydrophobic modification, the fixing of hydrophilic and hydrophobic substances or the elimination of hydrophilic and hydrophobic substances, barrier properties between the substrate and the hydrophobic substances or oleophobic, fixation of fatty substances.
• the present invention also relates to a method as defined above, according to which the treatment has led to a hydrophilic coating intended to be temporary having been adsorbed on said substrate.
• a hydrophilic coating intended to be temporary having been adsorbed on said substrate.
• it causes desorption of said coating: - in basic aqueous medium at a temperature above the LCST, the thermosensitive (co) polymer used carrying carboxylic acid functions and being such that it loses its sensitivity to temperature due to the neutralization of said carboxylic acid functions, or - whatever the pH at a temperature below the LCST.
• a modifier chosen from:
• thermosensitive copolymers obtained from a composition of monomers comprising, per 100 parts by moles:
• R 1 CH 2 CC-0- [R 2 -0] n -R 3 (I)
• - R represents H or -CH3; o - R represents a C alkylene residue which optionally comprises one or more OH groups, or a C3-C4 alkylene residue which comprises one or more OH groups;
• - R represents H or -CH3; and - n is an integer between 1 and
• R and R " 3 each independently represent hydrogen or C2-C4 alkyl; -1 - Y is a single bond or a C-1-C4 alkylene residue; R ° represents a C 2 alkylene residue which optionally comprises one or more OH groups, or a C 3 -C 4 alkylene residue which comprises one or more OH groups; R 'represents H or -CH3; and o is an integer between 1 and 70;
• - R ° represents H or -CH3; - R and R each independently represent a C2-C4 alkylene residue which optionally comprises one or more OH groups, R 9 and R 10 being different from each other;
• - R 11 represents H or -CH3; - p is an integer between 1 and
• R 1 z 9- and R 1 J " -? Each independently represent hydrogen or C 2 -C 4 alkyl; o
• - Y ⁇ is a single bond or a C - ⁇ - C ⁇ alkylene residue
• R 14 and R 1 - 3 each independently represent an alkylene radical in CpC ⁇ optionally comprising one or more OH groups, R 14 and R i) being different from each other;
• - r is an integer between 1 and 70;
• - s is an integer between 1 and 40;
• - R 17 represents H or -CH3
• R 1 1 R 0 represents a C 1 -C 4 alkylene residue which optionally comprises one or more OH groups (in particular the compounds in c 3 _c 4 comprise one or more OH groups in order to ensure their solubility in water) ;
• - t is an integer between 1 and 70; in which: f ) -i
• R ⁇ u and R each independently represent hydrogen or C ⁇ C ⁇ alkyl
• - Y 3 is a single bond or a C- ] _-C 4 alkylene radical
• R 22 represents a C 1 -C 4 alkylene residue which optionally comprises one or more OH groups (in particular the C 3 -C 4 compounds comprise one or more OH groups in order to ensure their solubility in water);
• R O is alkyl C 2 -C ⁇ Q, aryl or aralkyl, Cg-Cg ⁇ ;
• - u is an integer between 1 and 70;
• - A represents -O- or -NH-
• B1 represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 9 CHOHCH 9 -;
• R and R each independently represent """CH3 or a C 2 -C ] alkyl chain;
• - R represents H, -CH3 or a C 2 -C 16 alkyl chain
• A represents -O- or -NH-;
• B 2 represents -CH 2 CH 2 -, -CH 2 CH .2 CH 2 - or -CH 2 CHOH CH 2 -;
• - R 28 represents H or -CH3;
• R 3 and R or each independently represents "" CH 3 or an alkyl chain C 2 -C j _;
• R J identical or different, each independently represent H, C 1-5 alkyl ⁇ 3 u i has - optionally one or more groups
• poly (N-substituted (meth) acrylamides) such as poly (N-isopropyl acrylamide) (NIPAM) having an LCST of 35 ° C., the preparation of which is widely described in the literature (Colloids Surf 20, 247-257, 1986 and WO 97/24150), poly (N-propylacrylamide) and poly (N-ethoxypropylacylami.de); and the copolymers of N-
• (meth) acrylamide such as NIPAM /
• - R 34 represents H or CHo
• - A ° represents -0- or -NH-
• B 3 represents -CH 2 CH -, CH 2 CH 2 CH 2 - or
• poly-MADAME ethylaminoethyl methacrylate
• (VI) the polymers obtained by hydrophilic modification of the hydrophobic polymers by polyoxyethylenated units such as polyethylene glycol (PEG) units; in particular, mention may be made of - polyamide-PEG, polyester-PEG and polyethylene-PEG.
• PEG polyethylene glycol
• the preferred monomer (s) of formula (I) are chosen in particular from the compounds of formula (la):
• CH 2 [CH 2 -CH 2 -0] n -R 3 (la) in which R 1, R " and n are as defined above.
• The. preferred monomers (A) of formula (II) are especially chosen from the compounds of formula (Ha) or (Ilb): R 4 R 5
• the monomer (s) (B) are in particular chosen from methacrylic acid and acrylic acid, methacrylic acid being preferred.
• the preferred monomer (s) of formula (III) are chosen in particular from the compounds of formula (Illa) or (Illb):
• R 8 , R, p and q are as defined above.
• R o and R ⁇ represent -CH 2 -CH 2 -.
• the compound (s) (E1) of formula (VII) are chosen in particular from the halides (such as chlorides) of (meth) acryloxyethyltri ethylammonium. In particular, mention may be made of acryloxyethyltrimethylammonium chloride.
• the compound (s) (E2) of formula (VIII) are in particular chosen from acrylate and dimethylaminoethyl methacrylate.
• the compound (s) (E3) are for example 2-acrylamido-2-methyl-propane sulfonic acid and its salts.
• the compound (s) (E4) are chosen, for example, from (meth) acryloxyalkylsilanes.
• the monomer (s) (E6) are chosen in particular from allylphosphonic acid and its salts.
• the compound (s) (E7) are chosen in particular from N-vinylacetamide, N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam.
• the compound (s) (E8) are in particular chosen from acrylamide, methacrylamide, N-isopropyl acrylamide, N-ethoxypropylacrylamide, N, N-dimethylacrylamide, and N- (2-hydroxypropyl) (meth) acrylamide.
• the hydrophobic monomer (s) (F) are chosen in particular from:
• R 35 represents a C 1 -C 4 alkylene residue
• - w is 0 or is an integer between 1 and 10; and - R 36 represents a C- ] _-C3 2 alkyl or cycloalkyl residue, with the condition that, when w is 0, R 36 is a C ⁇ - ⁇ alkyl or cycloalkyl residue;
• R 37 represents a C 1 -C alkylene residue or a C 1 -C 4 alkylene residue halogen; - b is 0 or is an integer between 1 and 10;
• R represents a C1 ⁇ CQ alkyl residue, cycloalkyl, halogenated alkyl or halogenated cycloalkyl, with the condition that, when b is 0, R 38 is a halogenated C1 to C i alkyl residue or halogenated cycloalkyl;
• CH 2 CH-R 39 in which R 39 is an alkylcarboxylate or alkyl ether group containing 1 to 18 carbon atoms, an aryl or aralkyl group or a cycloalkyl group;
• R 40 and R 41 represents a hydrogen atom and the other represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms
• - Y represents a bivalent hydrocarbon chain linked to 0 by a carbon atom and which may include one or more heteroatoms chosen from oxygen, sulfur and nitrogen;
• R £ represents a perfluorinated radical with a straight or branched chain, containing 2 to 20 carbon atoms, preferably 4 to 16 carbon atoms;
• - R 42 represents H or -CH3
• R 43 represents a C3-C4 alkylene residue
• - c is an integer between 1 and 70
• - R 44 represents H or -CH3
• R ⁇ and R each independently represent hydrogen or C 2 -C 4 alkyl
• - Y is a single bond or a C 1 -C 4 alkylene residue
• - R 47 represents a C3-C4 alkylene residue
• - d is an integer between 1 and 70;
• - R 48 represents H or -CH3
• - R 49 represents H or -CH3
• R 50 and R 51 identical or different, each independently represent Cg-C 2 4 alkyl or cycloalkyl;
• the compounds of formula (XIV) are chosen, for example, from those comprising an R 43 which is a CH residue
• the compounds of formula (XV) are chosen by CH-, example from those having a which is a residue -CH 2 -C I'H- or c
• the compounds of formula (XVI) are chosen for example from N- (tert. -Butyl) (meth) acrylamide, N- decyl (meth) acrylamide, N-dodecyl (meth) acrylamide and N- (n- octadecyl) (meth) acrylamide.
• the compound (F10) is in particular N-octadecyl-triethoxysilane.
• the water-soluble thermosensitive copolymer (I) according to the invention may have been obtained from a composition of monomers as defined above in which at least one chain transfer agent has been incorporated, chosen in particular from mercapto ethanol, isopropanol, alkylmercaptans, such as methyl mercaptan, ethyl mercaptan, etc., carbon tetrachloride and triphenylmethane, the transfer agent or agents having been used in an amount in particular from 0.05 to 8 % by weight relative to the total weight of the monomers.
• a composition of monomers as defined above in which at least one chain transfer agent has been incorporated chosen in particular from mercapto ethanol, isopropanol, alkylmercaptans, such as methyl mercaptan, ethyl mercaptan, etc., carbon tetrachloride and triphenylmethane, the transfer agent or agents having been used in an amount in particular from 0.05 to 8 % by
• the LCST of the water-soluble thermosensitive copolymer (I) according to the invention can be between 6 ° C and 100 ° C, preferably between 14 ° C and 75 ° C. As illustrated by the examples, a person skilled in the art can easily adjust the
• the LCSTs of the copolymers (I) of the invention increase with the average number of ethylene oxide units of the polyethoxylated monomer used;
• the LCSTs of the copolymers (I) of the invention increase if the transfer agent is removed; - the LCSTs of the copolymers (I) according to the invention vary between 6 and 75 ° C by varying the parameters of the number of ethylene oxide units, the presence of the transfer agent, the ratio of the monomers (A) and (B), and the presence of functional patterns; - It is possible to incorporate functional units into the copolymers of the invention while preserving their heat-sensitive character;
• a copolymer (I) as defined above the radical copolymerization is carried out in an aqueous or organic medium (alcohols or ketones for example) of the water-soluble monomers as defined above.
• the polymerization is carried out in particular with a total concentration of the monomers of between 5 and 75% by weight, in particular between 15 and 50% by weight.
• This copolymerization is carried out in the presence of at least one initiator generating free radicals, chosen in particular from persulfates, such as ammonium and potassium persulfates, peroxides and diazo compounds, such as 2, 2 'hydrochloride -azobis (2- aminopropane), the initiator or initiators generating free radicals being used in a proportion in particular of 0.1 to 5% by weight, in particular of 0.5 to 3% by weight relative to the total weight of the monomers used.
• the copolymerization can also be initiated by irradiation, for example in the presence of UV radiation and photoinitiators such as benzophenone, methyl-2-anthraquinone or chloro-2-thioxanthone.
• the length of the polymer chains can, if desired, be adjusted using chain transfer agents, such as those indicated above, used in the proportions as indicated above.
• the reaction temperature can vary within wide limits, that is to say from -40 ° C. to 200 ° C., operating preferentially between 50 and 95 ° C.
• the LSCT of the targeted copolymer can be adjusted as a function of the composition of the monomers and / or of the amount of chain transfer agent used.
• the present description indicates to those skilled in the art the elements from which he can easily make any such adjustment.
• thermosensitive polymers adsorb effectively on substrates if these substrates are treated with polymers at a temperature higher than the LCST.
• the coatings formed on the substrates can be easily removed or leached by treatment in basic medium or by treatment below the LCST whatever the pH.
• the thermosensitive polymer compositions proposed indeed allow, in addition to good adsorption on the substrates in aqueous medium, an effective desorption by playing on the sensitivity of these polymers both with the pH and with the temperature.
• MAPEG6 PPG3 monomer of formula: CHo CH,
• CH 2 CC-0- [CH 2 -CH 2 -0] g- [CH 2 -CH-0] 3 -H
• MAPEG 12 monomer of formula: CHo
• MAPEG 22 monomer of formula: CHo
• ADAMQUAT MC acryloxyethyltrimethylammonium chloride
• SIPOMER BEM acryloxyethyltrimethylammonium chloride
• MAM methyl methacrylate
• MABu butyl methacrylate
• MALAU lauryl methacrylate
• n OE average number of ethylene oxide units.
• PMMA poly (methyl methacrylate)
• LCST is the temperature at which the product changes from an opaque dispersion (insoluble polymer) to a clear solution (soluble polymer).
• the product obtained is an aqueous solution of water-soluble polymer if the temperature is below T ° C and on the other hand, above T ° C, the polymer is insoluble in water and the product is in the form of dispersions of particles of polymer insoluble in water.
• the LCST is determined visually during the cooling of the product at the end of the synthesis.
• This polymer has an LCST of 35 ° C.
• This polymer has an LCST of 40 ° C. It can thus be noted that an increase in mass content of AMA from 27.9 to 30.9 has the effect of increasing the LCST of the copolymer from 35 ° C to 40 ° C.
• Example 1 is reproduced, except that no transfer agent is incorporated.
• An aqueous solution of water-soluble polymer of composition is obtained:
• This polymer has an LCST of 40 ° C. Removal of the transfer agent increases the LCST from 35 to 40 ° C.
• a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having a nOE of 8.5 (intermediate between 8 and 12.5).
• 1485 parts of water are introduced with stirring (150 revolutions / minute; stirring by anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping.
• the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
• This polymer has an LCST of 24 ° C.
• EXAMPLE 5 SYNTHESIS OF A MAPEG 8 / MAPEG 12 / AMA COPOLYMER
• Example 4 is repeated, except that no transfer agent is incorporated.
• This polymer has an LCST of 24 ° C.
• a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 9 (intermediate between 8 and 12).
• This polymer has an LCST ' of 24 ° C.
• Example 6 is repeated, except that no transfer agent is incorporated.
• An aqueous solution of water-soluble polymer of composition is obtained:
• This polymer has an LCST of 26 ° C
• a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 9 (intermediate between 8 and 12).
• 1800 parts of water are introduced with stirring (150 revolutions / minute; stirring by anchor), and the reactor is brought to temperature. 80 ° C under nitrogen sweep.
• the monomers and initiator solution are introduced by continuous casting over three hours, in the following manner:
• a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 9.5 (intermediate between 8 and 12.5).
• This polymer has an LCST of 27 ° C.
• Example 9 is repeated, except that no transfer agent is incorporated.
• An aqueous solution of water-soluble polymer of composition is obtained:
• This polymer has an LCST of 29 ° C.
• a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an nOE of 10.5 (intermediate between 8 and 12.5). 1656 parts of water are introduced into a 3 liter reactor with stirring (150 revolutions / minute; stirring with an anchor), and the reactor is brought to the temperature of 80 ° C. with nitrogen sweeping. When the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
• This polymer has an LCST of 31.5 ° C.
• This polymer has an LCST of 75 ° C, greater than 37 "C.
• This polymer is water-soluble and does not show any change in solubility in water for a temperature below 90 ° C.
• This example shows that a suitable composition of monomers, in particular nOE, is required to obtain a heat-sensitive copolymer.
• This polymer has an LSCT of 53 ° C.
• ADAMQUAT TM therefore has the effect of increasing the LCST of the MAPEG12 / AMA copolymer from 35 ° C. (cf. Example 1) to 53 ° C.
• This polymer has an LSCT of 14 ° C.
• This polymer has an LSCT over the temperature range 27-30 ° C.
• ADAMQUAT MC therefore increases the LCST of the MAPEG 8 / AMA copolymer from 14 ° C to 27-30 ° C.
• This polymer has an LCST of 18 ° C being established between 18 and 20 ° C.
• SIPOMER BEM therefore has the effect of increasing the LCST of the MAPEG 8 / AMA copolymer from 14 ° C (see Example 15) to 18-20 ° C.
• This polymer has an LCST of 18 ° C being established between 26 and 28 ° C.
• SIPOMER BEM and ADAMQUAT MC therefore have the effect of increasing the LCST of the MAPEG 8 / AMA copolymer from 14 ° C (see Example 15) to 26-28 ° C.
• This polymer has an LSCT established over the temperature range 27-29 "C.
• the AMPS therefore has the effect of increasing the LCST of the AMA / MAPEG copolymer from 14 ° C. (cf. Example 15) to 27-29 ° C.
• This polymer has an LSCT of 19 ° C.
• EMPICRYL therefore increases the LCST of the AMA / MAPEG 8 / AMA copolymer from 14 ° C (see Example 15) to 27-29 ° C.
• This polymer has an LCST of between 10 and 12 ° C.
• This polymer has an LCST of between 6 and 8 ° C.
• a liter of 10% aqueous solution of a heat-sensitive copolymer previously prepared in Examples 1 to 23 is introduced with stirring (300 rpm) using a magnetic bar. brings the assembly to a given processing temperature (Tad). After stabilization at the desired treatment temperature (Tad), the calibrated and weighed piece of tissue is introduced with stirring which is left to soak with stirring for 30 minutes. The treated tissue is then recovered using tweezers, and quickly steamed at 100 ° C for 6 hours. The difference in weight between the dry treated or modified hydrophilic fabric and the untreated starting fabric gives the weight of polymer adsorbed on the fabric during the soaking or treatment operation.
• Table 1 groups the polymer masses adsorbed as a function of the average number of ethylene oxide (nOE) and of the LCST.
• Table 1 Mass of MAPEG / AMA copolymer adsorbed on the treated fabric at 50 ° C. as a function of the average number of ethylene oxide nOE of the MAPEGs and of the LCST
• the polymer is not or only slightly adsorbed on the fabric if the LCST (75 ° C) is higher than the soaking or treatment temperature (50 ° C).
• the polymer being in a soluble form, preferentially remains in water instead of adsorbing on the fabric.
• the increase in the treatment temperature of the fabric above the LCST (78 ° C and 92 ° C) allows the adsorption of the precipitated polymer on the fabric .
• Table 6 gives the values obtained for the treatments carried out above the LCST of the polymer. We use for comparison the mass of polymer adsorbed on the hydrophilic modified dry tissue after the previous treatments in an acid medium.
• Desorption of hydrophilic coating on the fabric by treatment in basic medium Comparison between the initial mass of polymer adsorbed on the tissue after treatment in acidic aqueous medium in the presence of 10% solution of polymer and the final mass of polymer remaining on the tissue after treatment in basic aqueous medium in the presence of 10% polymer solution
• This polymer has an LCST of 0 ° C.
• This polymer has an LCST of 45 ° C.
• EXAMPLE 27 SYNTHESIS OF A MAPEG 12 / AMA / MAM COPOLYMER
• This polymer has an LCST being established in a temperature range between 40 ° C and 25 ° C.
• the mixture is stirred (150 rpm; agitation by anchor) 556.25 parts of water, and the reactor is brought to the temperature of 80 ° C under nitrogen sweep.
• the temperature of the reaction medium is stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel:
• This polymer has an LCST of 22 ° C.
• This polymer is not soluble in the temperature range above 4 ° C studied.
• This polymer has an LCST of 36 ° C.
• This polymer is not water-soluble and is in the form of an opaque dispersion despite the low rate of hydrophobic units. It has a change of appearance
• This polymer is not soluble and is in the form of an opaque dispersion. A change in appearance (precipitation) appears at 40 ° C, comparable to an LCST.
• the most suitable hydrophobic monomers are those having a hydrophobic character which is not too marked, such as methyl methacrylate. Its incorporation rate can go up to 40 mol%. As soon as the hydrophobic character becomes important as it is the case of butyl methacrylate and lauryl methacrylate, the rate necessary for the preservation of thermosensitivity and the solubility in water is low, namely of the order of 5 % and 0.1 mol%.
• a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having a nOE of 8.5.
• This polymer has an LCST of 18 ° C.
• a mixture of MAPEG 8 and MAPEG12 was used to prepare a copolymer having an nOE of 10.5.
• This polymer has an LCST of 35 ° C.
• a mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer, having an nOE of 9.5.
• This polymer has an LCST of 27 ° C.

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