Classifications

• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
  • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
  • A61L15/42—Use of materials characterised by their function or physical properties
  • A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
  • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
  • C08F220/288—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polypropylene-co-ethylene oxide in the alcohol moiety
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
  • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen

Definitions

• the present invention relates to water-soluble heat-sensitive copolymers based on (meth) acrylate.
• the present invention relates to water-soluble thermosensitive copolymers, which can be used for the manufacture of disposable hygiene articles in toilets because of their capacity to form films capable of breaking down or rapidly disintegrating in an aqueous medium.
• the copolymers of the invention which can also be used, as components of disposable or water-disintegrable hygiene articles: (1) as a binder connecting the fibers of the fibrous (nonwoven) sheets which form the upper envelope of the article; or
• thermosensitive or thermosensitive copolymers is understood to mean copolymers which are soluble in water below a certain critical temperature commonly called LCST, but which become insoluble in water at temperatures higher than LCST. . So, for example, the movies prepared from these copolymers are said to be “water-disintegrable” or “water-dispersible”.
• copolymers must be easily dispersible in water (5-20 ° C.) with stirring in order to be able to be eliminated by a flushing effect without clogging the pipes, but that at human body temperature (37 ° C), they must be insoluble in water and body fluids to guarantee the integrity of these items during their use.
• the composition of the polymers must be able to be adjusted so that they have an LCST which is both lower than the temperature of the human body (37 ° C) and higher than the temperature of the toilet water. (5-20 ° C), so as to guarantee, on the one hand, the non-solubility in water at 37 ° C and good dispersibility or solubility in water at 5-20 ° C.
• one of the approaches consists in formulating the binder which must connect the fibers of the nonwoven, so that it causes the disintegration of the fibrous web in an aqueous medium.
• water-dispersible adhesives connecting the various components of the hygiene article are proposed in American patents US-A-4,522,967 and US-A-5,527,845.
• thermosensitive products having a significant difference in solubility at the critical LCST temperature and in particular a significant difference in solubility between the temperature of the human body 37 ° C and that of toilet water 5- 20 ° C;
• hydroxypropylcellulose (LCST ⁇ 44 ° C) and methylated hydroxypropylcellulose whose hydrophobic modification by methylation of hydroxypropylcellulose makes it possible to reduce the LCST in the range of 19-35 ° C
• PVME polyvinyl methyl ether
• poly-NIPAM poly N-isopropyl acrylamide having an LCST of 35 ° C
• new compositions of heat-sensitive copolymers which meet these criteria by providing access to a wide range of LCSTs which can vary between 6 and 95 ° C, including the range 20 to 35 ° C for the particular application envisaged.
• the adjustment of the LCST in this temperature range is possible by varying parameters such as the transfer agent, the nature and the rate of the monomers used for the copolymerization, the synthesis temperature, the mode of introduction of the monomers. (batch or semi-continuous), the molar masses of the copolymers.
• the low LCST values (approximately 20 to 24 ° C.) can be obtained by varying the number of alkylene oxide units present, as well as the composition and the transfer agent, and the adjustment of the LCST at low temperatures (20-24 ° C) allows rapid soluble / insoluble transition kinetics at skin temperature (37 ° C) unlike higher LCST systems (PVME and poly-NIPAM).
• the hydrophobic units are directly incorporated into the structure of the new water-soluble heat-sensitive copolymers of the present invention.
• These new heat-sensitive polymers make it possible to prepare water-dispersible films. They can also be used with hydrophobic polymers in proportions which preserve the water disintegrability of the films of the formulated product. They can also be used for the formulation of binders for fibrous webs as well as for water-dispersible adhesives for the manufacture of water-disintegrable hygiene articles.
• the present invention therefore firstly relates to a water-soluble thermosensitive copolymer, characterized in that it is obtained from a composition of monomers comprising, per 100 parts by moles:
• R 2 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 3 represents H or -CH3
• - n is an integer between 1 and 70;
• R 4 and R- 3 each independently represent hydrogen or C2-C4 alkyl
• Y 1 is a single bond or an alkylene residue in
• R ' represents H or -CH3
• - o is an integer between 1 and 70;
• - R 8 represents H or -CH3
• R 9 and R 10 each independently represent a c 2 ⁇ c 4 alkylene residue ⁇ 1 --'- optionally contains 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 70;
• R 1 and R1 -1 "" 3 each independently represent hydrogen or C2-C4 alkyl
• - Y 2 is a single bond or an alkylene residue in c l ⁇ c 4 '"
• R 14 and R 15 each independently represents an alkylene radical in C 2 -C 4 optionally comprising one or more OH groups, R 14 and R 1 being different from each other;
• - R 16 represents H or -CH3;
• - r is an integer between 1 and 70;
• - s is an integer between 1 and 40;
• R 1 1 -R 0 represents a C 2 -C 4 alkylene residue which optionally comprises one or more OH groups (in particular the C 3 -C 4 compounds comprise at least one OH group in order to ensure their solubility in water );
• - represents a C 2 -C 4Q alkyl, aryl or aralkyl chain in g-Cgg; and - t is an integer between 1 and 70;
• R 2 ⁇ and R 21 each independently represent hydrogen or C 1 -C 4 alkyl;
• - Y 3 is a single bond or an alkylene radical
• C 2 -C alkylene residue which optionally comprises one or more OH groups (in particular the C3-C4 compounds comprise at least one OH group in order to ensure their solubility in water);
• R 23 is a C 2 -C 4Q alkyl, aryl or Cg-Cgg aralkyl radical; and u is an integer between 1 and 70;
• CH X ⁇ (VII) in which: - R 2 represents H 0U -CH3;
• - A 1 represents -O- or -NH-
• Bl represents -CH 2 CH ⁇ , -CH 2 CH 2 CH 2 - or -CH 2 CHOHCH 2 -;
• R 2iD and R 26 each independently represent -CH3 or a C 2 ⁇ C l ⁇ alkyl chain ;
• R 2 represents H, -CH3 or a C 2 -C 16 alkyl chain
• - X ⁇ represents a monovalent anion, such as Cl ⁇ , SCN ⁇ , CH 3 S0 3 e and Br ⁇ ;
• a 2 represents -O- or -NH-
• B represents —CH CH -, ⁇ CH CH CH or
• R 28 represents H or -CH 3 ;
• R 29 and R 30 independently represent -CH3 or a C 2 "c l ⁇ 'alkyl chain
• (E3) the water-soluble monomers chosen from ethylenically unsaturated carboxylic acids and their salts, and ethylenically unsaturated carboxylic acid anhydrides; (E4) water-soluble ethylenically unsaturated monomers;
• - R 31 represents H or -CH3
• R 32 and R 33 identical or different, each independently represent H, C- j __5 alkyl which optionally contains one or more OH groups, or (C- j __5 "alkoxy") - alkyl ;
• thermosensitive water-soluble copolymer having an LCST of ⁇ ° C to 95 ° C.
• the preferred monomer (s) of formula (I) are chosen in particular from the compounds of formula (la):
• the preferred monomer (s) (A) of formula (II) • are especially chosen from the compounds of formula (IIa) or (Ilb):
• R 4 R 5 C CI-0- [Rfi b -0] o -R (Ha) /
• the monomer (B) is in particular 2-acrylamido-2-methylpropane sulfonic acid (AMPS).
• AMPS 2-acrylamido-2-methylpropane sulfonic acid
• the preferred monomer (s) of formula (III) are chosen in particular from the compounds of formula (IIIa) or (IIIb):
• CH 2 [CH 2 -CH 2 -0] -R1 1 1 1 (Illb) in which R 8 , R 11 , p and q are as defined above.
• the monomer (s) (D) of formula (V) and (VI) are for example those in which R 18 and R represent -CH 2 -CH 2 -.
• the compound or compounds (E1) of formula (VII) are chosen in particular from the halides (such as chlorides) of (meth) acryloyloxyethyltrimethylammonium.
• halides such as chlorides
• acryloyloxyethyltrimethylammonium chloride mention may be made of acryloyloxyethyltrimethylammonium chloride.
• the compound (s) (E2) of formula (VIII) are in particular chosen from acrylate and dimethylaminoethyl methacrylate.
• the compound (s) (E3) are for example methacrylic 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 especially chosen from acrylamide, methacrylamide, N-isopropyl acrylamide, N-ethoxypropylacrylamide, N-methylol-
• hydrophobic monomer (s) (F) are chosen in particular from:
• CH C- - [0-CH -], .- [0-R 35 ] T ⁇ . -0-R 3 ⁇ (X) in which :
• - R 34 represents H or -CH3
• R J is a radical 'alkylene C- j _ alkyl; is 0 or is an integer from 1 to 10;
• R 36 is an alkyl radical C] _-C3 2 or cycloalkyl
• R 3 represents an alkylene residue C- j _-Cg alkylene or a residue in C-] _-Cg halogen; - b is 0 or is an integer between 1 and 10;
• R °° represents a C-J_-C 2Q alkyl, cycloalkyl, halogenated alkyl or halogenated cycloalkyl residue, with the condition that, when b is 0, R 38 is a halogenated C- j _-C- alkyl residue ] _ or halogenated cycloalkyl;
• 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 an atom hydrogen or an alkyl radical containing 1 to 4 carbon atoms;
• - Y 4 represents a bivalent hydrocarbon chain linked to 0 by a carbon atom
• 5 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 45 and R 4 ° each independently represent hydrogen or C 2 -C 4 alkyl
• - Y 5 is a single bond or a C 1 -C 4 alkylene residue
• - R represents a C3-C4 alkylene residue
• - d is an integer between 1 and 70; and - R 48 represents H or -CH3;
• - R 49 represents H or -CH3
• R 50 and R 51 identical or different, each independently represent C 2 -C 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 (XVI) are chosen, for example, from N- (tert. -Butyl) (meth) acrylamide, N- decyl (meth) acrylamide, N-dodecyl (meth) acrylamide and N-
• the compound (F10) is in particular N-octadecyl-triethoxysilane.
• the water-soluble thermosensitive copolymer according to the invention may have been obtained from a composition of monomers as defined above. above which has been incorporated at least one chain transfer agent, chosen in particular from mercapto ethanol, isopropanol, alkyl mercaptans, such as methyl mercaptan, ethyl mercaptan, etc., carbon tetrachloride and triphenylmethane , the transfer agent (s) having been used in a proportion in particular of 0.05 to 8% by weight relative to the total weight of the monomers.
• the LCST of the water-soluble thermosensitive copolymer according to the invention may in particular be from 20 to 35 ° C, preferably from 23 to 28 ° C and preferably be of the order of
• the LCSTs of the copolymers of the invention increase with the number of ethylene oxide units of the polyethoxylated monomer used;
• the LCSTs of the copolymers of the invention increase if the level of transfer agent is increased, that is to say if the molar masses are low;
• the LCSTs of the copolymers according to the invention vary between 6 and 95 ° C. by varying the parameters of the number of ethylene oxide units, the rate of transfer agent, the ratio of the monomers (A) and (B), the presence of functional units, and the level of hydrophobic monomers;
• the present invention also relates to a process for the manufacture of a copolymer as defined above, characterized in that the radical copolymerization is carried out in an aqueous or organic solvent medium (alcohols or ketones for example) or in a, water / organic solvent, preferably in an aqueous medium (solution or dispersion), 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.
• hydrophobic units obtained by polymerizing hydrophobic monomers with water-soluble monomers of the present invention must however preserve both the
• the solvents such as alcohols and ketones facilitate the incorporation of the hydrophobic monomers into the structure of the water-soluble polymer, but there are known problems. linked to the use of organic solvents, in particular the safety aspect, and their elimination by drying and distillation consuming energy and cycle time.
• the preferred polymerization process of the invention is based on synthesis in an aqueous medium. Under these conditions, two problems are to be resolved:
• micellar polymerization described in the document Macromolecules 1993, 26, 4521-4532 is for example based on this principle.
• the monomers of polyethoxylated (meth) acrylate type play the role of polymerizable surfactant thus contributing to the incorporation of hydrophobic units.
• compositions of the invention comprising a mixture of water-soluble monomers and hydrophobic monomers, obtaining polymers which are both water-soluble and temperature sensitive is strongly conditioned by the nature of hydrophobic monomers to be incorporated and in particular of its degree of hydrophobia;
• the LCSTs of these copolymers depend on the composition of the water-soluble or hydrophobic monomers; (3) the LCSTs of these water-soluble copolymers with hydrophobic units can vary over a wide range from 6 to 95 ° C and more particularly in the range 18-37 ° C necessary for the application to disposable hygiene articles in toilets;
• thermosensitive units are directly incorporated into the structure of the new water-soluble heat-sensitive copolymers of the present invention.
• a person skilled in the art seeks to mix thermosensitive polymers with hydrophobic polymers to improve wet strength, but there may be problems of compatibility between the two. polymers (thermosensitive and hydrophobic).
• the copolymerization of the invention 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 the hydrochloride. of 2,2′-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 of 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 LCST of the targeted copolymer can be adjusted according to the composition of the monomers and / or the amount of chain transfer agent used and / or the temperature and / or the process. conducted batchwise or semi-continuously. The present description indicates to those skilled in the art the elements from which he can easily make any such adjustment.
• the present invention also relates to a
• the invention also relates to the use of a copolymer as defined above or prepared by a
• thermosensitive polymers 25 water-disintegrating hygiene articles.
• the films prepared from each thermosensitive polymer are soluble in water at a temperature below the LCST and in particular at the temperature of tap water.
• the formulation of these heat-sensitive polymers with
• Hydrophobic polymers also lead to films dispersible in an aqueous medium if the level of hydrophobic polymers is not too great.
• the present invention also relates to these water-dispersible or water-disintegratable films obtained by
• the invention also relates to the use of a copolymer of the invention or prepared by a process as defined above as a binder or binder component for fibrous webs or as an adhesive component or as a polymer compound component , in particular entering into the constitution of water-disintegrable hygiene articles.
• the invention also relates to articles , hygienic, in particular disposable, in the constitution of which between the copolymer of the invention or prepared by a process as defined above or the mixture as defined above, either as a water-soluble or water-disintegrable film, either as a binder used in the preparation of fibrous webs incorporated in these articles, or for the formulation of adhesives bonding the
• MAPEG 8 monomer of formula:
• MAPEG 12 monomer of formula:
• ADAMQUAT MC80 80% by weight aqueous solution of acryloyloxy ethyl triethyl ethyl ammonium chloride
• n OE average number of ethylene oxide units
• LCST is the temperature at which the product changes from an opaque dispersion (insoluble polymer) to a clear solution (soluble polymer).
• the polymer has an LCST of T ° C
• 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 is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 50 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 55-56 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 62-63 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 62-71 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 77 ° C.
• a mixture consisting of: agitation (150 revolutions / minute; agitation by anchor) 444 parts of water; 104.02 parts of AMPS; 93.52 parts of MAPEG 12 and 3.39 parts of MAM;
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 86 ° C.
• EXAMPLE 7 SYNTHESIS OF A MAPEG 12 / MAM / AMPS COPOLYMER (35 mol% in MAM)
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 40-42 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has no precipitation temperature comparable to an LCST.
• a MAPEG / AMPS copolymer is water-soluble and has no precipitation temperature.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 80 ° C.
• This polymer is water-soluble and is in the form of a slightly cloudy dispersion. It has a precipitation temperature comparable to an LCST at around 80 ° C.
• This polymer is not water-soluble and is in the form of an opaque dispersion. It has no precipitation temperature comparable to an LCST.
• This polymer is not water-soluble and is in the form of an opaque dispersion. It has no precipitation temperature comparable to an LCST.
• EXAMPLE 14 (Comparative): SYNTHESIS OF A MAPEG 12 / MALAU / AMPS COPOLYMER
• a first initiator solution is introduced as a spot - and another initiator solution is introduced by continuous casting over an hour and a half as follows:
• This polymer is not water-soluble and is in the form of an opaque and relatively viscous dispersion. It has no precipitation temperature comparable to an LCST.
• This polymer is not water-soluble and is. present as a slightly cloudy dispersion. It has no precipitation temperature comparable to an LCST.
• MALAU does not allow the synthesis by this method, of water-soluble thermosensitive polymers.
• the final product is in the form of an opaque dispersion which does not exhibit precipitation at high temperature (above 90 ° C.).
• This series of syntheses confirms the observations made using the MABU; we can classify the three hydrophobic monomers used in order of increasing hydrophobicity: MAM ⁇ MABU ⁇ MALAU
• EXAMPLE 16 (Comparative): SYNTHESIS OF A MAPEG 12 / MAM / AMPS COPOLYMER
• a mixture consisting of: agitation (150 revolutions / minute; agitation by anchor) 444 parts of water; 122.03 parts of AMPS; 49.94 parts of MAPEG 12; and 28.53 parts of MAM;
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 30-32 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 35-38 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 50 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 61-62 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 70-72 ° C.
• This polymer is in the form of a translucent gel. It has a precipitation temperature comparable to an LCST at 80 ° C.
• an increase in the molar ratio n (A MPS ) n ( M A PE G 12 ) is results in a decrease in the precipitation temperature.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 37-38 ° C.
• a first initiator solution is introduced in spot and another initiator solution is introduced by continuous casting over an hour and a half as follows:
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 34 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 26-27 ° C.
• This polymer is not water-soluble and is in the form of an opaque dispersion at room temperature. It has a precipitation temperature comparable to an LCST at a temperature below 15 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at a temperature below 26-27 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 50 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 13-15 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at - a temperature below 55-56 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 45-47 ° C.
• a mixture consisting of: agitation (150 revolutions / minute; agitation by anchor) 445 parts of water; 55.83 parts of AMPS; 103.7 parts of MAPEG 12; 26.03 parts of MAM; and 15.47 parts of AMA;
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 25-27 ° C.
• EXAMPLE 33 SYNTHESIS OF A MAPEG 12 / MAM / AMPS COPOLYMER
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 50 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 73 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 90 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 37-38 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 54 ° C.
• EXAMPLE 38 SYNTHESIS OF A MAPEG 8 / MAM / AMPS COPOLYMER
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 77 ° C.
• a decrease in molar masses results in an increase in the precipitation temperature.
• This polymer is water soluble and is in the form of a translucent solution of pale yellow • and relatively viscous. It has a precipitation temperature comparable to an LCST at 50 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 50 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 50 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 50 ° C.
• EXAMPLE 43 SUMMARY OF A MAPEG 8 / MAM / AMPS COPOLYMER
• This polymer is water-soluble and is in the form of a translucent solution. It has a change in appearance (precipitation) comparable to an LCST at a temperature of 20 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 50 ° C.
• EXAMPLE 46 (Comparative): SYNTHESIS OF A MAPEG 12 / MAM / AMPS COPOLYMER
• This polymer is water-soluble and is in the form of a translucent solution. It has no precipitation temperature comparable to an LCST.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 64 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 37-38 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 75 ° C.
• This polymer is water-soluble and is in the form of a translucent solution. It has a precipitation temperature comparable to an LCST at 57 ° C.

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