FR2807759A1 - Hydrosoluble thermosensitive copolymer for use as in disposable hygiene products as a component of hydrosoluble films for or as a binder for fibrous components of such products - Google Patents

Abstract

A copolymer of thermosensitive solubility obtained from a specified monomer composition The monomer composition comprises (all hydrosoluble): (A) 1-98 mol.% of a compound of formulae (I) or (II) (below); (B) 2-95 mol.% ethylenically unsaturated carboxylic acid or anhydride; (C) 0-70 mol.% of a compound of formulae (III) or (IV) (below); (D) 0-30 mol.% of a compound of formulae (V) or (VI); (E) compounds of formula (VII) or (VIII) or ethylenically unsaturated monomers which are sulfonated or silanated or phosphonated or have phosphate groups or monomers having N-vinyl groups, or compounds of formula (IX), acrylonitrile, allyl alcohol, vinylpyridine, N-(meth)acryloyltris(hydroxymethyl) methylamine, 2-sulfoethyl (meth)acrylate, 2-(acetoacetoxy)ethyl (meth)acrylate. CH2=C(R<1>)-C(O)-O-(R<2>-O)n-R<3> (I); H-C(R<4>)=C(R<5>)-Y<1>-O-(R<6>-O)o-R<7> (II); CH2-C(R<8>)-C(O)-O-(R<9>-O)p-(R<10>-O)q-R<11> (III); H-C(R<12>)=C(R<13>-Y<2>-O-(R<14>-O)r-(R<15>-O)S-R<16> (IV) CH2=C(R<17>)-C(O)-O-(R<18>-O)t-R<19> (V); H-C(R<20>)=C(R<21>)-Y<3>-O-(R<22>-O)u-R<23> (VI); CH2=C(R<24>)-C(O)-A<1>-B<1>-N<+>(R<27>,R<25>,R<26>) X<-> (VII); CH2=C(R<28>)-C(O)-A<2>-B<2>-N(R<29>,R<30>) (VIII); CH2=C(R<31>)-C(O)-N(R<32>,R<33>) (IX); R<1>, R<3>, R<7>, R<8>, R<11>, R<16>, R<17>, R<24>, R<28>, R<31> = H, CH3; R<2>, R<6>, R<9>, R<10>, R<14>, R<15>, R<18>, R<22> = 2-4C alkylene optionally bearing one or more OH groups; n, o, p, r, t, u = 1-70; R<4>, R<5>, R<12>, R<13>, R<20>, R<21> = H, 2-4C alkyl; Y<1>, Y<2>, Y<3> = null, 1-4C alkyl; q, s = 1-40; R<19>, R<23> = 2-40C alkyl chain, 6-60C aryl or aralkyl; A<1>, A<2> = -O-, -NH-; B<1>, B<2> = -CH2CH2-, - CH2CH2CH2-, CH2CHOHCH2-; R<27> = H, CH3, 2-16C alkyl chain; X<+> = monovalent anion; R<29>, R<30> = CH3, 2-16C alkyl chain; R<32>, R<33> = H, 1-5C alkyl optionally bearing one or more OH groups, alkoxy(1-5C)alkyl(1-5C). Independent claims are included for the procedure of preparation by radical polymerization in an aqueous medium, for a mixture in aqueous medium of on or more of the claimed polymers with a hydrophobic (co)polymer, for the use of the claimed polymers for the fabrication of hydrodispersible or hydrodisintegrable films, especially those forming part of hydrodisintegrable hygiene articles, for such films, for use of the polymers as binders for fiber tissues or as components of adhesives, especially those forming part of hydrodisintegrable hygiene articles and hygiene articles, especially disposable comprising in any form the claimed copolymer or a mixture with at least 50 wt.% of hydrophobic polymer.

Description

THERMOSENSITIVE HYDROSOLUBLE COPOLYMERS, THEIR MANUFACTURE AND THEIR USE FOR THE PREPARATION OF FILMS, ADHESIVES AND BINDERS FOR FIBROUS TABLES, IN PARTICULAR FOR THE MANUFACTURE OF HYDRODEDINTEGRABLE HYGIENE ARTICLES, and their use in the manufacture of thermosensitive copolymers and their use in hydrosoluble copolymers for their production of thermosensitive copolymers. the preparation of films, adhesives and binders for fibrous webs, in particular for the manufacture of water-disintegrated hygiene articles.

In particular, the present invention relates to water-soluble heat-sensitive copolymers which can be used for the manufacture of disposable hygiene articles in toilets due to their ability to form films capable of quickly breaking apart or disintegrating in an aqueous medium under agitation, the copolymers of the invention can also be used, as components of disposable hygiene articles, (1) as a binder for the preparation of fibrous (non-woven) webs which form the upper shell of the article ; or (2) for the formulation of adhesives to bond the different constituents of the article; or (3) as a component of the lower shell polymer compound generally based on polyolefin.

It is specified that by thermosensitive water-soluble copolymers or of a thermosensitive nature is meant copolymers which are soluble in water below a certain critical temperature commonly called LCST, but which become insoluble in water at temperatures above the LCST .

In the particular application to hygiene articles, it is indicated that said copolymers must be easily dispersible in water (5-20 C) with stirring in order to be able to be removed by a flushing effect without blocking the pipes, but that body temperature (37 C), they must be insoluble in water and body fluids to ensure the integrity of these items during use. In other words, for this application, the composition of the polymers must be able to be adjusted so that they exhibit an LCST both below the temperature of the human body (37 C) and above the temperature of the water in the toilet (5 -20 C), so as to guarantee, on the one hand, non-solubility in water at 37 C and good dispersibility or solubility in water at 5-20 C.

For many years, manufacturers of disposable items such as diapers, incontinence garments, and feminine hygiene products have been under great pressure over the problem posed by rejection of these products. Although notable progress has been made in addressing these problems, one of the weak links is the inability to manufacture articles which would easily disintegrate in water while still having good mechanical strength in contact with bodily fluids. Reference is made to British patent application GB-A-2 241 372 and to American patent US-A-4 186 233. A -default, the possibility for the user to throw the products into the toilet is greatly reduced, otherwise eliminated. In addition, the ability of the product to disintegrate in a landfill is quite limited, as many of the components of the product, which may be biodegradable or photodegradable, are encapsulated in plastic which takes a long time to degrade by. following the rupture of the encapsulation in the plastic material.

International applications PCT WO / 96 20831 and WO / 97 18082 describe plastic film compositions capable of disintegrating in the presence of water. As opposed to films, those skilled in the art also seek to develop fibrous or non-woven webs (international applications WO / 98 36117 and WO / 98 29590, French patent application FR-A-2 709 055) which have the ability to disintegrate in water. Under these conditions, one of the approaches consists in formulating the binder which is to join the fibers of the nonwoven so that it causes the disintegration of the fibrous web in an aqueous medium. Furthermore, water-dispersible adhesives connecting the various components of the hygiene article are proposed in US patents US-A-4,522,967 and US-A-527,845.

The different types of water-dispersible polymers proposed for the manufacture of fiber films, binders for fibrous webs and adhesives are described in British patent application GB-A 284 820. This document highlights five types of products (1) products sensitive to pH with the inconvenience of adding an ingredient (acid or base) or pre-wetting the article before disposal; (2) products sensitive to enzymes which have drawbacks comparable to the previous products (3) products sensitive to ionic strength, that is to say insoluble in saline aqueous medium and soluble in non-saline or weakly saline aqueous medium; (4) temperature-sensitive products (thermosensitive) having a significant difference in solubility at the critical LSCT temperature and in particular a notable difference in solubility between the temperature of the human body 37 C and that of the toilet water 5- 20 C ; and (5) the foregoing hydrophilic products formulated with hydrophobic substances which provide a gain in mechanical strength to the article when wet (in contact with body fluids).

Among the heat-sensitive products claimed in the literature for this application, there may be mentioned in particular (1) hydroxypropylcellulose (LSCT 44 C) and methylated hydroxypropylcellulose, the hydrophobic modification of which by methylation of the hydroxypropylcellulose makes it possible to reduce the LCST in the range 19-35 C (U.S. Patent US-A-5,770,528); (2) polyvinyl methyl ether (PVME) having an LCST = 35 C (PCT international application WO / 98 29157; (3) poly N-isopropyl acrylamide (poly NIPAM) having an LCST of 35 C (PCT international application W0 / 97 24150). A person skilled in the art seeks for the application to hygiene products compositions of thermosensitive polymers having LCSTs of between 20 and 60 C, preferably between 20 and 35 C, preferably between 23 and 2 C, and preferably of the order of 24 C.

In accordance with the present invention, new compositions of thermosensitive copolymers are proposed which meet these criteria by allowing access to a wide range of LCSTs which may vary between 14 and 75, in particular the range of 20 to 35 for the particular application envisaged. The adjustment of the LCST in this temperature range is possible by adjusting the parameters such as the transfer agent, the nature and the rate of the monomers used for the copolymerization. In addition, the low values of LCST (approximately 20 to 24 C) can be obtained by adjusting the number of alkylene oxide units present, as well as on the composition and the transfer agent, and the adjustment of the LCST. at low temperatures (20-24 C) makes it possible to have rapid soluble / insoluble transition kinetics at skin temperature (37 C) unlike systems with a higher LCST (PVME and poly-NIPAM).

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 hydrodeintegrability 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.

dans laquelle - R1 représente H ou -CH3 ; - R2 représente un reste alkylène en C2-C4 qui comporte éventuellement un ou plusieurs groupes OH ; _ - R3 représente H ou -CH3 ; et - n est un nombre entier compris entre 1 et 70 ;

dans laquelle R4 et R5 représentent chacun indépendamment hydrogène ou alkyle en C2-C4 ; Y1 est une liaison simple ou un reste alkylène en C1-C4 ; R6 représente un reste alkylène en C2-C4 qui comporte éventuellement un ou plusieurs groupes OH ; - R7 représente H ou -CH3 ; et - o est un nombre entier compris entre 1 et 70 ; (B) de 2 ' 95 parties en moles d'au moins un monomère hydrosoluble choisi parmi les acides carboxyliques à insaturation éthylénique et les anhydrides d'acides carboxyliques à insaturation éthylénique ; (C) de 0 a 70 parties en moles d'au moins un composé hydrosoluble choisi parmi ceux des formules (III) et (IV)

dans laquelle :. The present subject therefore firstly relates to water-soluble heat-sensitive copolymer, characterized in that it is obtained from a composition of monomers comprising, per 100 parts in moles (A) from 1 to 98 parts in moles of least one water-soluble compound chosen from those of the following formulas (I) and (II)

in which - R1 represents H or -CH3; - R2 represents a C2-C4 alkylene residue which optionally comprises one or more OH groups; _ - R3 represents H or -CH3; and - n is an integer between 1 and 70;

wherein R4 and R5 each independently represent hydrogen or C2-C4 alkyl; Y1 is a single bond or a C1-C4 alkylene residue; R6 represents a C2-C4 alkylene residue which optionally contains one or more OH groups; - R7 represents H or -CH3; and - o is an integer between 1 and 70; (B) from 2 to 95 mole parts of at least one water-soluble monomer selected from ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides; (C) from 0 to 70 parts by moles of at least one water-soluble compound chosen from those of formulas (III) and (IV)

in which :.

dans laquelle - et R13 représentent chacun indépendamment hydrogène ou alkyle en C2-C4 ; - est une liaison simple ou un reste alkylène en C1-C4 ; - R14 et R15 représentent chacun indépendamment un radical alkylène en C2-C4 comportant éventuellement un ou plusieurs groupes OH, R14 et R15 étant différents l'un de l'autre - R16 représente H ou -CH3 ; - r est un nombre entier compris entre 1 et 70 ; et - s est un nombre entier compris entre 1 et 40 ; (D) de 0 30 parties en moles d'au moins un composé hydrosoluble choisi parmi ceux des formules (V) et (VI)

dans laquelle - R17 représente H ou -CH3 ; - R18 représente un reste alkylène en C2-C4 qui comporte éventuellement un ou plusieurs groupes OH ; - R19 représente une chaîne alkyle en C2-C40, aryle ou aralkyle en C6-C60 ; et - t est un nombre entier compris entre 1 et 70 ;

dans laquelle - R20 et R21 représentent chacun indépendamment hydrogène ou alkyle en C2-C4 ; - y3 est une liaison simple ou un radical alkylène en Cl-C4 ; - R22 représente un reste alkylène en C2-C4 qui comporte éventuellement un ou plusieurs groupes OH ; - R23 est un reste alkyle en C2-C40, aryle ou aralkyle en C6-C60 ; et - u est un nombre entier compris entre 1 et 70 ; (E) de 0 à 30 parties en moles d'au moins un monomère hydrosoluble choisi parmi (E1) les composés hydrosolubles de formule (VII

dans laquelle - R24 représente H ou -CH3 ; - A1 représente -0- ou -NH- ; - B1 représente -CH2CH2-, -CH2CH2CH2- -CH2CHOHCH2- ; - R25 et R26 représentent chacun indépendamment -CH3 ou une chaîne alkyle en C2-C16 - R27 représente H, -CH3 ou une chaîne alkyle en C2-C16 ; - Xe représente un anion monovalent, tel que C1-, SCNe, CH3S03e et Bre ; (E2) les composés hydrosolubles de formule (VIII) .

dans laquelle - A2 représente -0- ou -NH- ; - B2 représente -CH2CH2-, -CH2CH2CH2- ou -CH2CHOH CH2- ; - R28 représente H ou -CH3 ; et - R2g et R30 représentent chacun indépendamment -CH3 ou une chaîne alkyle en C2-C16 (E3) les monomères hydrosolubles sulfonés à insaturation éthylénique et leurs sels ; (E4) les monomères hydrosolubles silanés à insaturation éthylénique ; (E5) les monomères hydrosolubles à fonction phosphate insaturation éthylénique ; (E6) les monomères hydrosolubles phosphonés à insaturation éthylénique et leurs sels ; (E7) monomères hydrosolubles ayant des groupes N- vinyle ; (E8) les composés hydrosolubles de formule (IX)

dans laquelle - R31 représente H ou -CH3 ; - R32 et R33, identiques ou différents, représentent chacun indépendamment H, alkyle en Cl-5 qui comporte éventuellement un ou plusieurs groupes OH ou (alcoxy en Cl-5)- alkyle en Cl-5 (E9) l'acrylonitrile ; (E10) l'allyl alcool ; (E11) la vinylpyridine ; (E12) la N-(méth)acryloyltris(hydroxyméthyl)méthylamine ; (E13) le 2-sulfoéthyl(méth)acrylate ; et (E14) le 2-(acétoacétoxy)éthyl(méth)acrylate. Le ou les monomères (A) de formule (I) préférés Sont notamment choisis parmi les composés de formule (Ia)

dans laquelle R l, R3 et n sont tels que définis ci-dessus. ou les monomères (A) de formule (II) préférés sont notamment choisis parmi les composés de formule IIa) ou (IIb)

dans lesquelles R4 à R7 et o sont tels que définis ci- dessus. ' Le ou les monomères (B) sont notamment choisis parmi l'acide méthacrylique et l'acide acrylique, l'acide méthacrylique étant préféré. - R8 represents H or -CH3; - And R10 each independently represent a C2-C4 alkylene residue which optionally comprises one or more groups R9 and _ R10 being different from each other; - R11 represents H or -CH3; - p is an integer between 1 and 70; and - q is an integer between 1 and 40;

wherein - and R13 each independently represent hydrogen or C2-C4 alkyl; - is a single bond or a C1-C4 alkylene residue; - R14 and R15 each independently represent a C2-C4 alkylene radical optionally comprising one or more OH groups, R14 and R15 being different from each other - R16 represents H or -CH3; - r is an integer between 1 and 70; and - s is an integer between 1 and 40; (D) from 0 to 30 parts by moles of at least one water-soluble compound chosen from those of formulas (V) and (VI)

in which - R17 represents H or -CH3; - R18 represents a C2-C4 alkylene residue which optionally comprises one or more OH groups; - R19 represents a C2-C40 alkyl, aryl or C6-C60 aralkyl chain; and - t is an integer between 1 and 70;

wherein - R20 and R21 each independently represent hydrogen or C2-C4 alkyl; - y3 is a single bond or a C1-C4 alkylene radical; - R22 represents a C2-C4 alkylene residue which optionally comprises one or more OH groups; - R23 is a C2-C40 alkyl, aryl or C6-C60 aralkyl residue; and - u is an integer between 1 and 70; (E) from 0 to 30 parts by moles of at least one water-soluble monomer chosen from (E1) the water-soluble compounds of formula (VII

in which - R24 represents H or -CH3; - A1 represents -0- or -NH-; - B1 represents -CH2CH2-, -CH2CH2CH2- -CH2CHOHCH2-; - R25 and R26 each independently represent -CH3 or a C2-C16 alkyl chain - R27 represents H, -CH3 or a C2-C16 alkyl chain; - Xe represents a monovalent anion, such as C1-, SCNe, CH3S03e and Bre; (E2) the water-soluble compounds of formula (VIII).

in which - A2 represents -O- or -NH-; - B2 represents -CH2CH2-, -CH2CH2CH2- or -CH2CHOH CH2-; - R28 represents H or -CH3; and - R2g and R30 each independently represent -CH3 or a C2-C16 alkyl chain (E3), water-soluble sulfonated ethylenically unsaturated monomers and their salts; (E4) water-soluble silane ethylenically unsaturated monomers; (E5) water-soluble monomers containing an ethylenically unsaturated phosphate function; (E6) water-soluble ethylenically unsaturated phosphonated monomers and their salts; (E7) water soluble monomers having N-vinyl groups; (E8) the water-soluble compounds of formula (IX)

in which - R31 represents H or -CH3; - R32 and R33, identical or different, each independently represent H, C1-5 alkyl which optionally comprises one or more OH or (C1-5 alkoxy) - C1-5 alkyl (E9) acrylonitrile; (E10) allyl alcohol; (E11) vinylpyridine; (E12) N- (meth) acryloyltris (hydroxymethyl) methylamine; (E13) 2-sulfoethyl (meth) acrylate; and (E14) 2- (acetoacetoxy) ethyl (meth) acrylate. The preferred monomer (s) (A) of formula (I) are chosen in particular from the compounds of formula (Ia)

in which R 1, R 3 and n are as defined above. or the preferred monomers (A) of formula (II) are chosen in particular from the compounds of formula IIa) or (IIb)

in which R4 to R7 and o are as defined above. The monomer (s) (B) are in particular chosen from methacrylic acid and acrylic acid, methacrylic acid being preferred.

dans lesquelles R8, R11, p et q sont tels que définis ci- dessus. The preferred monomer (s) (C) of formula (III) are chosen in particular from the compounds of formula (Ia) or (IIIb)

in which R8, R11, p and q are as defined above.

The monomer (s) (D) of formula (V) and (VI) are, for example, those in which R18 and R22 represent -CH2-CH2-.

The compound (s) (E1) of formula (VII) are chosen in particular from halides (such as chlorides) of (meth) acryloxyethyltrimethylammonium. In particular, mention may be made of acryloxyethyltrimethylammonium chloride.

The compound (s) (E2) of formula (VIII) are chosen in particular from dimethylaminoethyl acrylate and methacrylate.

The compound (s) (E3) are, for example, 2-acrylamido-2-methyl-propanesulfonic 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.

Furthermore, the water-soluble thermosensitive copolymer 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 mercaptoethanol, isopropanol, alkylmercaptans, such as methyl mercaptan, ethyl mercaptan, etc., carbon tetrachloride and triphenylmethane, the transfer agent (s) having been used in an amount in particular of <B> 0.05 </ B> 8% by weight relative to the total weight of the monomers.

The LCST of the water-soluble thermosensitive copolymer according to the invention can be between 14 C and 75 C, in particular between 20 and 35 C, preferably between 23 and 28 C and preferably be of the order of 24 C. As already indicated. , and as illustrated by the examples, a person skilled in the art will be able without difficulty to adjust the LCST of the copolymers of the invention. In particular, it emerges from the examples below that - 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 transfer agent is eliminated; - The LCSTs of the copolymers 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 units; - It is possible to incorporate functional units in the copolymers of the invention while preserving their heat-sensitive nature; the functionalization of the copolymers according to the invention with cationic units, hydrophobic units based on a fatty alkyl chain, sulfonic acid units, phosphate acid units, leads to an increase in the LCST; and - in addition to providing specific properties for the final application, the functionalization can thus also contribute to the adjustment of the LCST of the copolymers.

A subject of the present invention is also 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 medium (alcohols or ketones for example), preferably in aqueous medium, 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 which generates free radicals, chosen in particular from persulphates, such as ammonium and potassium persulphates, peroxides and diazo compounds, such as 2.2 'hydrochloride. -azobis aminopropane), the initiator (s) 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, 2-methyl-anthraquinone or chlorothioxanthone.

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, preferably operating between 50 and 95 C.

As indicated above, the LSCT of the targeted copolymer can be adjusted as a function of the composition of the monomers and / or the amount of the chain transfer agent used and / or the temperature and / or the process carried out. batchwise or semi-continuously. The present description indicates to the person skilled in the art elements from which he will be able without any difficulty whatsoever to make such an adjustment.

The present invention also relates to mixing at least one water-soluble thermosensitive copolymer as defined above or prepared by the process as defined above, with at least one hydrophobic (co) polymer such as poly (methyl methacrylate) or polyolefins.

The invention also relates to the use of a copolymer as defined above or prepared by a process as defined above, or of a mixture as defined above comprising at most 50% by weight of ( co) hydrophobic polymer (s) relative to the total polymers, for the manufacture of water-dispersible or hydrodesintegrable films, in particular entering into the constitution of water-disintegrable hygiene articles. The films prepared from each heat-sensitive polymer are soluble in water at a temperature below LCST and in particular at the temperature of tap water. The formulation of these heat-sensitive polymers with hydrophobic polymers also leads to films dispersible in aqueous medium if the level of hydrophobic polymers is not too high.

The present invention also relates to these water-dispersible or water-disintegrable films obtained by drying a copolymer as defined above or prepared by a process as defined above or of a mixture as defined above comprising at most 50% by weight of hydrophobic (co) polymers relative to the total copolymers.

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 a component of adhesives as a component of a polymer compound, in particular entering into the constitution of water-disintegrated hygiene articles.

The invention also relates to hygiene articles, in particular disposable items, 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 in as a water-soluble or water-disintegratable film, either as a binder used in the preparation of fibrous webs incorporated in these articles, or for the formulation of adhesives connecting the different constituents of the hygiene article, or as a compound component of the polymer forming the lower envelope of the article.

The following Examples illustrate the present invention without, however, limiting its scope. In these Examples, parts and percentages are expressed by weight unless otherwise indicated, and the following abbreviations have been used.

AMA <SEP> methacrylic acid <SEP>
<tb> MAPEG <SEP> 6 <SEP>: <SEP> monomer <SEP> of <SEP> formula
<tb> CH3
<tb> CH2 <SEP> = <SEP> -C-0- [CH2-CH2-0] 6-H
<tb> 0
<tb> MAPEG6 <SEP> PPG3 <SEP>: <SEP> monomer <SEP> of <SEP> formula
<tb> ÎH3
<tb> CH2 <SEP> = <SEP> CCO- [CH2-CH2-0] 6- [CH2-CH-0] 3-H
<tb> 0
<tb> MAPEG <SEP> 8 <SEP>: <SEP> monomer <SEP> of <SEP> formula
<tb> CH3
<tb> CH2 <SEP> = <SEP> C <SEP> II <SEP> 0 <SEP> [CH2 <SEP> CH2 <SEP> 0] 8 <SEP> CH3
<tb> 0
<tb> MAPEG <SEP> 12 <SEP>: <SEP> monomer <SEP> of <SEP> formula
<tb> CH3
<tb> CH2 <SEP> = <SEP> -C-0 <SEP> - [CH2-CH2-0112 <SEP> 5-CH3
<tb> 0
<tb> MAPEG <SEP> 22 <SEP>: <SEP> monomer <SEP> of <SEP> formula
<tb> CH2 <SEP> = <SEP> CCO <SEP> - [CH2-CH2-0] 22 @ <B> 7 </B> -CH3
<tb> 0
<tb> MAPEG <SEP> 45 <SEP>: <SEP> monomer <SEP> of <SEP> formula
<tb> CH3
<tb> CH2 <SEP> = <SEP> CCO <SEP> - [CH2-CH2-0] 45-CH3
<tb> O
<tb> n <SEP> OE <SEP>: <SEP> average number <SEP><SEP> of <SEP> units of ethylene oxide <SEP>

ADAMQUAT <SEP> MC <SEP>: <SEP> acryloxyethyltrimethylammonium chloride <SEP>
<tb> SIPOMER <SEP> BEM
<tb> CH3
<tb> l
<tb> CH2 <SEP> = <SEP> C-II-0 <SEP> - [CH2- <SEP> -0] 25-C24H25
<tb> 0
<tb> AMPS
<tb> 0
<tb> CH2 <SEP> = <SEP> CH-C \ <SEP> ÎH3
<tb> NH-CH- <SEP> S03eNa
<tb> EMPICRYL <SEP> monomer <SEP> acid <SEP> phosphated <SEP> from <SEP> the <SEP> formula
<tb> next <SEP>.
<tb> CH3 <SEP> 0
<tb> CH2 <SEP> = <SEP> C <SEP> - <SEP> C <SEP> II
<tb> 0 <SEP> CH2-CH2-0 <SEP> - <SEP> P <SEP> - <SEP> [OH] t
<tb> s
<tb> consisting of <SEP> of
<tb> - <SEP> 60% <SEP> of <SEP> 2-propenoic acid <SEP>, <SEP> 2-methyl-, <SEP> 2-hydroxy ethyl <SEP> ester <SEP> phosphate <SEP> (s <SEP> = <SEP> 1 <SEP>;<SEP> t <SEP> = <SEP> 2) <SEP>;<SEP> and
<tb> - <SEP> 40% <SEP> of <SEP> bis <SEP> (2-methacryloyloxyethyl) phosphate
<tb> (s <SEP> = <SEP> 2, <SEP> t <SEP> = <SEP> 1)
<tb> PMMA <SEP> poly (<SEP> methyl methacrylate <SEP>) <U> Determination of the </U> LCST The LCST is the temperature at which the product changes from an opaque dispersion (insoluble polymer) to a clear solution (soluble polymer).

If it is indicated that the polymer has an LCST of <B> TOC </B>, this means that the product obtained is an aqueous solution of water-soluble polymer if the temperature is below <B> TOC </B> and that On the other hand, above <B> TOC, </B> the polymer is insoluble in water and the product is in the form of dispersions of particles of insoluble polymer in In all the Examples, the LCST is determined visually using during the cooling of the product at the end of the synthesis. <U> EXAMPLE 1 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 12 / </U> AMA Into a 1 liter reactor, is introduced with stirring (150 revolutions / minute stirring per anchor) parts of water, and the reactor is brought to a temperature of 80 ° C. under nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a monomer / agent mixture. transfer comprising - 66.9 parts of AMA; - 174.9 parts of MAPEG 12; and - 3.264 parts of mercaptoethanol (transfer agent); (2) pouring over three hours of an initiator solution containing - 48 parts of water; and - 5.9 parts of ammonium persulfate. After the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 12
<tb> mass <SEP> 72.1
<tb> molar <SEP> 25.5 This polymer has an LCST of 35 C. <U> EXAMPLE </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 12 / </U> (modification of the AMA / MAPEG 12 ratio compared to Example 1). 374 parts of water are introduced with stirring (150 revolutions / minute; anchor stirring) into a 1 liter reactor, and the reactor is brought to the temperature of 80 ° C. with nitrogen purging. When the temperature of the reaction medium is stabilized at 80 C, is introduced by continuous casting over three hours, separately and in parallel the monomers and initiator solution as follows (1) poured over three hours of a monomer / agent mixture transfer comprising - 67.9 'parts of AMA; - 153.6 parts of MAPEG 12; and - 2.992 parts of mercaptoethanol (transfer agent); (2) pouring over three hours of an initiator solution containing - 44 parts of water; and - 5.41 parts of ammonium persulfate. After the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 12
<tb> mass <SEP> 69.1
<tb> molar <SEP> 22.8 This polymer has an LCST of 40 C. It can thus be noted that an increase in the mass content of AMA from 27.9 to 30.9 has the effect of increasing the LCST of copolymer from 35 C to 40 C. <U> EXAMPLE 3 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 12 / </U> AMA Example 1 is reproduced, except that no transfer agent is incorporated.

An aqueous solution of water-soluble polymer of composition

COMPOSITION <SEP> MAPEG <SEP> 12
<tb> mass <SEP> 72.1 <SEP>,
<tb> molar <SEP> 25.5 This polymer has an LCST of 40 C. Removing the transfer agent increases the LCST from 35 to 40 C. <U> EXAMPLE 4 </U>: <U> SUMMARY OF A </U> MAPEG <U> 8 / </U> MAPEG <U> 12 / </U> AMA COPOLYMER A mixture of MAPEG 8 and MAPEG 12 was used in order to prepare a copolymer having a n0E of 8 , 5 (intermediate between 8 and 12.5).

1485 parts of water are introduced with stirring (150 revolutions / minute with anchor stirring) into a 3-liter reactor, and the reactor is brought to a temperature of 80 ° C. with nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, in the following manner, poured over three hours from a monomer / transfer agent mixture comprising - 380.4 parts of AMA; - 610 parts of MAPEG 8; - 116 parts of MAPEG 12; and - 14.96 parts of mercaptoethanol (transfer agent); pouring in three hours of an initiator solution containing - 187 parts of water; and - 27 parts of ammonium persulfate. At the end of the three hours of casting, 6.77 parts of ammonium persulfate dissolved in 44 parts of water are added and the reaction is allowed to continue for a further two hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> MAPEG <SEP> 12
<tb> mass <SEP><B> 55.0 </B><SEP> - <SEP> 10.4
<tb> molar <SEP> 22.5 <SEP> 3.0 This polymer has an LCST of 24 C. <U> EXAMPLE 5 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U > 8 / </U> MAPEG <U> 12 / </U> AMA Example 4 is reproduced, except that no transfer agent is incorporated.

25 An aqueous solution of water-soluble polymer of composition

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> MAPEG <SEP> 12
<tb> mass <SEP> 55.0 <SEP> 10.4
<tb> molar <SEP> 22.5 <SEP> 3.0 This polymer has an LCST of 24 C.

<U> SYNTHESIS EXAMPLE OF A COPOLYMER </U> MAPEG <U> 8 / </U> MAPEG <U> 12 / </U> AMA A mixture of MAPEG 8 and MAPEG 12 was used in order to prepare a copolymer having a 9 (intermediate between 8 and 12).

1700 parts of water are introduced with stirring (150 revolutions / minute with anchor stirring) into a 3-liter reactor, and the reactor is brought to a temperature of 80 ° C. with nitrogen purging. When the temperature of the reaction medium is stabilized at 80 C, is introduced by continuous casting over three hours, separately and in parallel the monomers and initiator solution as follows (1) poured over three hours of a monomer / agent mixture transfer comprising - 336.8 parts of AMA; - 480 parts of MAPEG 8; - 188 parts of MAPEG 12; and - 13.6 parts of mercaptoethanol (transfer agent); (2) pouring over three hours of an initiator solution containing - 170 parts of water; and - 24.6 parts of ammonium persulfate.

At the end of the three hours of casting, 6.15 parts of ammonium persulfate dissolved in 40 parts of water are added and the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> MAPEG <SEP> 12
<tb> mass <SEP> 47.61 <SEP> 18.64
<tb> molar <SEP> 20.0 <SEP> 5.50 This polymer has an LCST of 24 C. <U> EXAMPLE 7 </U>: <U> SYNTHESIS OF A. COPOLYMER </U> MAPEG <U> 8 / </U> MAPEG <U> 12 / </U> AMA Example 6 is reproduced, except that no transfer agent is incorporated.

An aqueous solution of water-soluble polymer of composition

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> MAPEG <SEP> 12
<tb> mass <SEP> 47.61 <SEP> 18.64 <SEP> 33,
<tb> molar <SEP> 20.0 <SEP> 5.50 <SEP> 74, This polymer has an LCST of 26 C. <U> EXAMPLE 8 </U>: <U> SYNTHESIS OF A COPOLYMER </ U> MAPEG <U> 8 / </U> MAPEG <U> 12 / </U> AMA A mixture of MAPEG 8 and MAPEG 12 was used in order to prepare a copolymer having a n0E of 9 (intermediate between 8 and 12 ).

1800 parts of water are introduced with stirring (150 revolutions / minute with anchor stirring) into a 3-liter reactor, and the reactor is brought to a temperature of 80 ° C. with nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a monomer / agent mixture. transfer comprising - 386.8 parts of AMA; - 480 parts of MAPEG 8; - 188 parts of MAPEG 12; and 13.6 parts of mercapto ethanol (transfer agent); (2) pouring over three hours of an initiator solution containing 170 parts of water; and 24.6 parts of ammonium persulfate. At the end of the three hours of casting, 6.15 parts of ammonium persulfate dissolved in 40 parts of water are added and the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> MAPEG <SEP> 12
<tb> mass <SEP> 45.3 <SEP> 17.90 <SEP> 3
<tb> molar <SEP> 18.0 <SEP> 5.0 This polymer has an LCST of 20 C. The increase in the level of AMA therefore has the consequence of decreasing LCST which goes from 24 to 20 C. <U> EXAMPLE 9 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 8 / </U> MAPEG <U> 12 / </U> AMA A mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an n0E of 9.5 (intermediate between 8 and 12.5).

1656 parts of water are introduced with stirring (150 revolutions / minute with anchor stirring) into a 3-liter reactor, and the reactor is brought to a temperature of 80 ° C. with nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a monomer / agent mixture. transfer comprising - 309.4 parts of AMA; - 372.1 parts of MAPEG 8; - 269 parts of MAPEG 12; and - 12.24 parts of mercaptoethanol (transfer agent); (2) pouring over three hours of an initiator solution containing - 126 parts of water; and - 22.14 parts of ammonium persulfate. At the end of the three hours of casting, 5.54 parts of ammonium persulfate dissolved in 36 parts of is added and the reaction is allowed to continue for a further two hours. The reactor is cooled to and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> MAPEG <SEP> 12
<tb> mass <SEP> 39.02 <SEP> 28.21
<tb> molar <SEP> 17.30 <SEP> 8.70 This polymer has an LCST of 27 C. <U>EXAMPLE<B>10</B></U>: SYNTHESIS OF A MAPEG 8 COPOLYMER / MAPEG 12 / AMA reproduces Example 9, except that no transfer agent is incorporated.

An aqueous solution of water-soluble polymer of composition

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> MAPEG <SEP> 12
<tb> mass <SEP> 39.02 <SEP> 28.21
<tb> molar <SEP> 17.30 <SEP> 8.70 This polymer has an LCST of 29 C.

<U> EXAMPLE 11 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 8 / </U> MAPEG <U> 12 / </U> AMA A mixture of MAPEG 8 and MAPEG 12 was used to prepare a copolymer having an n0E of 10.5 (intermediate between 8 and 12.5).

1656 parts of water are introduced with stirring (150 revolutions / minute with anchor stirring) into a 3-liter reactor, and the reactor is brought to the temperature under flushing with nitrogen. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a monomer / agent mixture. transfer comprising - 292.2 parts of AMA; - 233.6 parts of MAPEG 8; - 423.4 parts of MAPEG 12; and - 12.24 parts of mercaptoethanol (transfer agent); (2) pouring over three hours of an initiator solution containing - 126 parts of water; and - 22.14 parts of ammonium persulfate. At the end of the three hours of casting, 5.54 parts of ammonium persulfate dissolved in 36 parts of water are added and the reaction is allowed to continue for a further two hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> MAPEG <SEP> 12 <SEP> AMA
<tb> mass <SEP> 24.53 <SEP> 44.47 <SEP> 31.00
<tb> molar <SEP> 11.50 <SEP> 14.50 <SEP> 74.0 This polymer has an LCST of 31.5 C. <U> EXAMPLE 12 </U>: <U> Synthesis of a </U> MAPEG <U> 22 / </U> AMA copolymer 387 parts of water are introduced with stirring (150 revolutions / minute with anchor stirring) into a 1 liter reactor, and the reactor is brought to temperature of 80 C under nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a monomer / agent mixture. transfer comprising - 49.5 parts of AMA; - 441 parts of MAPEG; and - 2.45 parts of mercaptoethanol (transfer agent); (2) pouring over three hours of initiator solution comprising - 36 parts of water; and - 4.43 parts of ammonium persulfate. After three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 22 <SEP> AIMA
<tb> mass <SEP> 81.66 <SEP> 18.34
<tb> molar <SEP> 26.0 <SEP> 74.0 This polymer has an LCST of 75 C.

<U> EXAMPLE 13 </U>: <U> Synthesis of a </U> MAPEG <U> 45 / </U> AMA copolymer In a 1 liter reactor, the mixture is introduced with stirring (150 revolutions / minute; anchor stirring) 387 parts of water, and the reactor is brought to a temperature of 80 ° C. under nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately in parallel, as follows (1) poured over three hours from a monomer / transfer agent mixture comprising - 28.4 parts of AMA; - 483 parts of MAPEG 45; and - 2.45 parts of mercaptoethanol (transfer agent); (2) pouring in three hours of an initiator solution containing - 36 parts of water; and - 4.43 parts of ammonium persulfate. After the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and a water-soluble polymeric aqueous solution of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 45
<tb> mass <SEP> 81.66
<tb> molar <SEP> 26.0 This polymer is water-soluble and does not exhibit any change in solubility in water for temperature below 90 C. This example shows that a suitable composition of monomers, in particular of nOE, is required. to obtain a thermosensitive copolymer. <U> EXAMPLE 14 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 12 / </U> AMA <U> / </U> ADAMOUAT <U> MC </U> 484 parts of water are introduced with stirring (150 revolutions / minute; anchor stirring) into a 1 liter reactor, and the reactor is brought to a temperature of 80 ° C. with nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., one introduces by continuous casting over three hours, separately monomers and initiator solution in parallel as follows (casting over three hours of a monomer / transfer agent mixture comprising - 60 , 99 parts of AMA; - 156.1 parts of MAPEG 12; - 5.64 parts of 80% solution of ADAMQUAT TM; - 2.992 parts of mercapto ethanol (transfer agent); poured in three hours of a initiator solution containing - 44 parts of water; and - 5.41 parts of ammonium persulfate. At the end of the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and recovering an aqueous solution of water-soluble polymer of composition

COMPOSITION <SEP> MAPEG <SEP> 12 <SEP> AMA <SEP> ADAMQUAT <SEP> MC
<tb> mass <SEP> 72.1 <SEP> 27.9 <SEP> 2.05
<tb> molar <SEP> 25.5 <SEP> 74.5 <SEP> 2.4 This polymer has an LSCT of 53 C.

ADAMQUAT MC therefore has the effect of increasing the LCST of the MAPEG12 / AMA copolymer from 35 C (cf. Example 1) to 53 C. <U> EXAMPLE 15 </U>: <U> SUMMARY OF A < / U> COPOLYMERE MAPEG <U> 8 / </U> AMA Into a 1 liter reactor, 528 parts of water are introduced with stirring (150 revolutions / minute; anchor stirring), and the reactor is brought to temperature of 80 C under nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a monomer / agent mixture. transfer comprising - 85.75 parts of AMA; - 155.8 parts of MAPEG 8; and - 3.264 parts of mercaptoethanol (transfer agent); (2) pouring over three hours of initiator solution containing - 48 parts of water; and - 5.9 parts of ammonium persulfate. After the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> AMA
<tb> mass <SEP> 64.27 <SEP> 35.73
<tb> molar <SEP> 25.5 <SEP> 74.5 This polymer has a 14 C LSCT. <U> EXAMPLE 16 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 8 / </U> AMA <U> / </U> ADAMOUAT <U> MC </U> 384 parts of water are introduced with stirring (150 revolutions / minute stirring by anchor) into a 1 liter reactor, and the temperature of the reactor is brought to 80 ° C. under nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a water / monomers / mixture. transfer agent comprising - 100 parts of water; - 77.60 parts of AMA; - 138.07 parts of MAPEG 8; - 7.15 parts of 80% solution of ADAMQUAT ™; - 2.992 parts of mercapto ethanol (transfer agent); (2) pouring over three hours of an initiator solution containing - 44 parts of water; and - 5.41 parts of ammonium persulfate. After the three hours of casting, the reaction is allowed to continue for two more hours.

the reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> AMA <SEP> ADAMQUAT <SEP> MC
<tb> mass <SEP> 62.13 <SEP> 35.27 <SEP> 2.60
<tb> molar <SEP> 24.5 <SEP> 73.1 <SEP> 2.40 This polymer has an LSCT established over the temperature range 27-30 C. ADAMQUAT MC therefore has the effect of increasing the LCST of the MAPEG 8 / AMA copolymer from 14 C to 27-30 C. <U> EXAMPLE 17 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 8 / </U> AMA <U> / </U> SIPOMER BEM Into a 1 liter reactor, 484 parts of water are introduced with stirring (150 revolutions / minute stirring by anchor), and the reactor is brought to the temperature of 80 ° C. under doffing. 'nitrogen. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a monomer / transfer agent mixture comprising - 77.93 parts of AMA; - 140.50 parts of MAPEG 8; - 5.735 parts of 52% solution of SIPOMER BEM; and - 2.992 parts of mercaptoethanol (transfer agent: 3fert); (3) pouring in three hours of an initiator solution containing - 44 parts of water; and - 5.41 parts of ammonium persulfate. After the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> AMA <SEP> SIPOMER <SEP> BEM
<tb> mass <SEP> 63.22 <SEP> 35.42 <SEP> 1.36
<tb> molar <SEP> 25.3 <SEP><U> 1 <SEP> 74.5 <SEP> 1 <SEP> 0.20 </U> This polymer has an LCST of 18 C between 18 and 20 C.

The SIPOMER BEM therefore has the effect of increasing the LCST of the MAPEG 8 / AMA copolymer by 14 C (see Example 15) 18-20 C. <U> EXAMPLE 18 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 8 / </U> AMA <U> / </U> SIPOMER BEM <U> / </U> ADAMOUAT <U> MC </U> In a 1 liter reactor, we introduced with stirring (150 revolutions / minute with anchor stirring) 384 parts of water, and the temperature of the reactor is brought to 80 ° C. under nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a water / monomers / mixture. transfer agent comprising - 99.99 parts of water; - 76.93 parts of AMA; - 135.8 parts of MAPEG 8; - 5.77 parts of 52% solution of SIPOMER BEM; - 7.09 parts of 80% solution of ADAMQUAT ™; and - 2.992 parts of mercaptoethanol (transfer agent); (2) pouring over three hours of an initiator solution containing - 44 parts of water; and - 5.41 parts of ammonium persulfate. After the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> AMA <SEP> SIPOMER <SEP> BEM <SEP> ADAMQUAT <SEP> MC
<tb> mass <SEP><B> 61.09 <SEP> 39.47 <SEP> 1.36 <SEP> 2.58 </B>
<tb> molar <SEP><U> 24.3 <SEP><B> 73.1 </B><SEP> 0.20 <SEP> 2.4 </U> This polymer has an LCST of <B >18'C</B> settling between 26 and 28 C.

SIPOMER BEM and ADAMQUAT MC therefore have the effect of increasing the LCST of the MAPEG 8 / AMA I copolymer from 14 C (see Example 15) to 26- C. <U> EXAMPLE 19 </U>: <U > SUMMARY </U> OF A <U> COPOLYMER </U> MAPEG <U> 8 / </U> AMA <U> / </U> AMPS In a 1 liter reactor, (150 revolutions / minute (stirring by anchor) 384 parts of water, and the reactor is brought to the temperature of 80 ° C. under nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a water / monomers / mixture. transfer agent comprising - 100 parts of water; - 77.45 parts of AMA; - 137.81 parts of MAPEG 8; - 6.12 parts of AMPS; and - 2.992 parts of mercaptoethanol (transfer agent); (2) pour in three hours an initiator solution containing - 44 parts of water; and - 5.41 parts of ammonium persulfate.

After the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and a water-soluble polymeric aqueous solution of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> AMA
<tb> mass <SEP> 62.01 <SEP> 35.20
<tb> molar <SEP> 24.5 <SEP> 73.1 This polymer has an LSCT establishing temperature range 27-29 C.

AMPS therefore has the effect of increasing the LCST of the AMA / MAPEG copolymer by 14 C (cf. Example 15) '27 9 C. <U> SYNTHESIS EXAMPLE OF A COPOLYMER </U> MAPEG <U> / / < / U> EMPICRYL 384 parts of water are introduced with stirring (150 revolutions / minute with anchor stirring) into a 1 liter reactor, and the reactor is brought to a temperature of 80 ° C. with nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a water / monomer mixture. / transfer agent comprising - 100 parts of water; - 77.00 parts of AMA; - 137.0 parts of MAPEG 8; - 7.37 parts of EMPICRYL; and - 2.992 parts of mercaptoethanol (transfer agent); (2) pouring over three hours of an initiator solution containing - 44 parts of water; and - 5.41 parts of ammonium persulfate. After the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 20 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 8 <SEP> AMA <SEP> EMPICRYL
<tb> mass <SEP> 62.01 <SEP> 35.20 <SEP> 2.78
<tb> molar <SEP> 24.5 <SEP> 73.1 <SEP> 2.40 This polymer has an LSCT of 19 C.

EMPICRYL therefore has the effect of increasing the LCST of the AMA / MAPEG 8 / AMA copolymer by 14 C (see Example at 27-29 C. <U> EXAMPLE 21 </U>: <U> SUMMARY OF A COPOLYMER </U> MAPEG <U> 6 / </U> AMA Into a 1 liter reactor, 532.8 parts of water are introduced with stirring (150 revolutions / minute stirring by anchor), and the reactor is brought to the temperature of 80 ° C. under nitrogen purging. 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, in the following manner, casting over three hours d 'a monomer / transfer agent mixture comprising - 100.29 parts of AMA; - 141.12 parts of MAPEG 6; and - 3.264 parts of mercaptoethanol (transfer agent); (2) poured in three hours of a initiator solution containing - 43.2 parts of water; and - 5.9 parts of ammonium persulfate At the end of the three hours of casting, the reaction is allowed to continue for two additional hours. additional. The reactor is cooled to 8 ° C. and an aqueous solution of water-soluble polymer of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 6 <SEP> AMA
<tb> mass <SEP> 67.46 <SEP> 32.54
<tb> molar <SEP> 25.5 <SEP> 74.5 This polymer has an LCST of between 10 and 12 C. <U> EXAMPLE 22 </U>: <U> SYNTHESIS OF A COPOLYMER </U> MAPEG <U> 6 </U> PPG3 <U> / </U> AMA Into a 1 liter reactor, 436.8 parts of water are introduced with stirring (150 revolutions / minute, stirring by anchor), and the reactor at a temperature of 80 ° C. under nitrogen purging. When the temperature of the reaction medium has stabilized at 80 ° C., the monomers and initiator solution are introduced by continuous casting over three hours, separately and in parallel, as follows (1) poured over three hours from a water / monomers / mixture. transfer agent comprising - 96 parts of water; - 78.09 parts of AMA; - 163 55 parts of MAPEG 6 PPG3; and - 264 parts of mercapto ethanol (transfer agent); (2) pouring three hours of an initiator solution containing - 43, parts water; and - 5.9 parts of ammonium persulfate.

After the three hours of casting, the reaction is allowed to continue for two more hours. The reactor is cooled to 8 ° C. and a water-soluble polymeric aqueous solution of composition is recovered.

COMPOSITION <SEP> MAPEG <SEP> 6 <SEP> PPG3 <SEP> AMA
<tb> mass <SEP> 67.46 <SEP> 32.54
<tb> molar <SEP> 25.5 <SEP> 74.5 This polymer has an LCST of between 6 and 8 C. <U> EXAMPLE </U>: <U> TESTS DE </U> TRANSITION <U> SOLUBLE / INSOLUBLE </U> With the aim of determining the most suitable compositions with regard to the ability to generate a rapid insoluble / soluble transition at human body temperature (37 ° C.), the aqueous solutions of the copolymers of Examples 1 to 22 were placed in a 60 cm3 glass flask. The vial containing the copolymer in solution is then held tightly in the closed hand so that the maximum surface area of the vial is in contact with the skin. The change in appearance of the various products linked to the transition from polymer in solution in water (clear solution) to the hydrophobic polymer precipitated in water (opaque dispersion) is then observed.

The tests show a rapid transition (less than 2 minutes) from a clear solution of polymer (soluble polymer) to an opaque dispersion of polymer (insoluble) for copolymers having an average number of ethylene oxide between 8 and 9.5 and corresponding to an LCST of between 14 and 28 C. They are copolymers of Examples 15, 4, 6, 9, 7, 4, 5, 17, 18, 19, 20. These compositions are the most suitable. for application to disposable hygiene articles.

For all the copolymer compositions prepared previously, it was noted during the cooling in the reactor which follows the polymerization, that the passage from an opaque dispersion of polymer (insoluble) to the clear solution of polymer (soluble) proceeded rapidly. over a very low temperature range between 1 C and 2 C with the exception of the copolymers of Examples 16, 17, 18 and 19. This observation does not concern the copolymer of Example 13 which remains soluble in water ( up to 90 C). <U> EXAMPLE 24 </U>: PREPARATION OF FILMS AND TESTS FOR SOLUBILITY <U> OF FILM </U> The solutions of the copolymers (15 g) of Examples 1 to 22 are placed in an 8 cm Teflon cup. diameter and dried for 48 hours at 50 C in an oven. Films are obtained after cooling, which are all soluble in less than 20 minutes in tap water at 18 ° C. It is also possible to obtain films after drying the polymer solutions at room temperature (20 ° C.). <U> EXAMPLES 25 to 27 </U>: MIXTURES OF THERMOSENSITIVE POLYMERS WITH HYDROPHOBIC POLYMERS AND <U> PREPARATION OF POLYMERIC FILMS </U> <U> FORMULAS </U> The thermosensitive copolymer solution of Example 4 (LCST of 24 C) was mixed with a latex of PMMA (dispersion in water of the particles of PMMA) so as to obtain the following polymer compositions - 70% of heat-sensitive copolymer and 30% of PMMA (Example 25 of the invention); - 50% of heat-sensitive copolymer% of PMMA (comparative Example 26); - 30% of heat-sensitive copolymer% of PMMA (comparative Example 27).

A thin film (0.5 mm) was prepared from these mixtures after drying at 50 ° C. (oven), then placed in a press at 150 ° C. The water-dispersibility tests of the films with stirring (magnetic stirring 250 revolutions / minute in a beaker of 2 liters of water) in tap water at 18 C, show that the composition comprising 30% of PMMA is water-disintegratable, that is to say that the film disintegrates into small pieces in less than 20 minutes. The compositions containing higher levels of PMMA (50 and 70%) are not water-disintegratable, that is to say that the films retain their integrite.

Claims (12)

CLAIMS 1 - Water-soluble thermosensitive copolymer, characterized in that it obtained from a composition of monomers comprising, per 100 parts by moles (A) from 1 to 98 parts by moles of at least one water-soluble compound chosen from those of the following formulas (I) and (II)

in which - R1 represents H or - R2 represents a C2-C4 alkylene residue which optionally comprises or more OH groups; - R3 represents H or - and - n is an integer between 1 and 70;

wherein - R4 and R5 each independently represent hydrogen or C2-C4 alkyl; - Y1 is a single bond or a C1-C4 alkylene residue; - R represents a C2-C4 alkylene residue which optionally comprises one or more OH groups; - R7 represents H or -CH3; and - o is an integer between 1 and 70; (B) from 2 to 95 parts by moles of at least one water soluble monomer selected from ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic acid anhydrides; (C) from 0 to 70 parts by moles of at least one water-soluble compound chosen from those formulas (III) and (IV)

in which - R8 represents H or -CH3; - R9 and R10 each independently represent a C4 alkylene residue which optionally comprises one or more OH groups, R9 and R10 being different from each other; - R11 represents H or -CH3; - p is an integer between 1 and 70; and - q is an integer between 1 and 40;

wherein - R12 and R13 each independently represent hydrogen or C2-C4 alkyl; - Y2 is a single bond or a C1-C4 alkylene residue; - R14 and R15 each independently represent a C2-C4 alkylene radical optionally comprising one or more OH groups, R14 and R15 being different from each other; - R16 represents H or -CH3; - r is an integer between 1 and 70; and - s is an integer between 1 and 40; (D) from 0 to 30 parts by moles of at least one water-soluble compound chosen from those of formulas (V) and (VI)

in which - R17 represents H or -CH3; - R18 represents a C2-C4 alkylene residue which optionally comprises one or more OH groups; - R19 represents a C2-C40 alkyl, aryl or -C60 aralkyl chain; and - t is an integer between 1 and 70;

in which - R20 and R21 each independently represent hydrogen or C2-C4 alkyl; - Y3 is a single bond or a C1-C4 alkylene radical; - R22 represents a C2-C4 alkylene residue which optionally comprises one or more OH groups; - R23 is a C2-C40 alkyl, aryl or C6-C60 aralkyl residue; and - u is an integer between 1 and 70; (E) from 0 to 30 parts by moles of at least one water-soluble monomer chosen from (E1) the water-soluble compounds of formula (VII)

in which - R24 represents H or -CH3; - Ai represents -O- or -NH-; - B1 represents -CH2CH2-, -CH2CH2CH2- or -CH2CHOHCH2-; - R25 and R26 each independently represent -CH3 or a C2-C16 alkyl chain - R27 represents H, -CH3 or a C2-C16 alkyl chain - Xe represents a monovalent anion, such as <B> cilium </B> CH3S03e and Bre; (E2) the water-soluble compounds of formula (VIII)

in which - A2 represents -O- or -NH-; - B2 represents -CH2CH2-, -CH2CH2CH2- or -CH2CHOH CH2-; - R28 represents H or -CH3; and - R29 and R30 each independently represent -CH3 or a C2-C16 alkyl chain (E3), water-soluble sulfonated ethylenically unsaturated monomers and their salts; (E4) water-soluble silane ethylenically unsaturated monomers; (E5) water-soluble monomers containing an ethylenically unsaturated phosphate function; (E6) water-soluble ethylenically unsaturated phosphonated monomers and their salts; (E7) water soluble monomers having N-vinyl groups; (E8) the water-soluble compounds of formula (IX)

in which - R31 represents H or -CH3; - R32 and R33, identical or different, each independently represent H, C 1-5 alkyl which optionally comprises one or more OH or (C 1-5 alkoxy) - C 1-5 alkyl (E9) acrylonitrile; (E10) allyl alcohol; (E11) vinylpyridine; (E12) N- (meth) acryloyltris (hydroxymethyl) methylamine; (E13) 2-sulfoethyl (meth) acrylate; and (E14) 2- (acetoacetoxy) ethyl (meth) acrylate. 2 - Water-soluble thermosensitive copolymer according to claim 1, characterized in that the monomer (s) (A) of formula (I) are chosen from the compounds of formula (Ia)

wherein R1, and n are as defined in claim 1. 3 - Water-soluble thermosensitive copolymer according to one of claims 1 and 2, characterized in that the monomer (s) of formula (II) are chosen from the compounds of formula (IIa) or (IIb)

in which R4 to and o are as defined in claim 1. 4 - Water-soluble thermosensitive copolymer according to one of claims 1 to 3, characterized in that the monomer (s) (B) are chosen from methacrylic acid and acrylic acid. 5 - Water-soluble thermosensitive copolymer according to one of claims 1 to 4, characterized in that the preferred monomer (s) (C) of formula (III) are in particular chosen from the compounds of formula (IIIa) or (IIIb)

wherein R8, R11, p and q are as defined in claim 1. 6 - Water-soluble thermosensitive copolymer according to one of claims 1 to 5, characterized in that the compound (s) (E1) of formula (VII) are chosen from (meth) acryloxyethyltrimethylammonium halides. 7 - Water-soluble thermosensitive copolymer according to one of claims 1 to 6, characterized in that the compound (s) (E2) of formula (VIII) are chosen from dimethylaminoethyl acrylate and methacrylate. 8 - Water-soluble thermosensitive copolymer according to one of claims 1 to 7, characterized in that the compound (s) (E3) are chosen from 2-acrylamido-2-methyl-propane sulfonic acid and its salts. 9 - Water-soluble thermosensitive copolymer according to one of claims 1 to 8, characterized in that the compound or compounds (E4) are chosen from (meth) acryloxyalkylsilanes. 10 - Water-soluble thermosensitive copolymer according to one of claims 1 to 9, characterized in that the monomer (s) (E6) are chosen from allylphosphonic acid and its salts. 11 - Water-soluble thermosensitive copolymer according to one of claims 1 to 10, characterized in that the compound or compounds (E7) are chosen in particular from N-vinylacetamide, N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam . 12 - Water-soluble thermosensitive copolymer according to one of claims 1 to 10, characterized in that the compound (s) (E8) are chosen from acrylamide, methacrylamide, N-isopropylacrylamide, N-ethoxypropyl-acrylamide, N, N-dimethylacrylamide, and N-hydroxypropyl) (meth) acrylamide. - Water-soluble thermosensitive copolymer according to one of claims 1 to 12, characterized in that it was obtained from a composition of monomers as defined in one of claims 1 to 12 which has been incorporated at least a chain transfer agent. - Water-soluble thermosensitive copolymer according to one of claims 1 to 13, characterized in that the chain transfer agent (s) is or are chosen from mercaptoethanol, isopropanol, alkylmercaptans, carbon tetrachloride and triphenylmethane . - Water-soluble thermosensitive copolymer according to one of claims 13 and 14, characterized in that the chain transfer agent or agents were used in an amount of 0.05 to 8% by weight relative to the total weight of the monomers. 16 - Water-soluble heat-sensitive copolymer according to one of claims 1 to 15, characterized in that it has an LCST of between 14 C and 75 C, in particular between 20 and 35 C. 17 - Water-soluble heat-sensitive copolymer according to one of claims 1 to 16, characterized in that it is present in aqueous solution. 18 - A method of manufacturing a copolymer as defined in one of claims as defined in one of claims 1 to 17, characterized in that the radical polymerization is carried out in aqueous or organic medium, such monomers as defined in one of claims 1 to 12. - Process according to claim 18, characterized in that the polymerization is carried out with a total concentration of monomers of between 5 and 75% by weight, in particular from 15 to 50% by weight. 20 - Process according to one of claims 18 and 19, characterized in that the copolymerization is carried out in the presence of at least one initiator which generates free radicals, chosen in particular from persulphates, peroxides and diazo compounds, or the initiators being used in a proportion of in particular 0.1 to 5% by weight, in particular 0.5 to 3% by weight, relative to the total weight of the monomers used. 21 - Method according to one of claims 18 and 19, characterized in that the copolymerization is carried out by initiating irradiation, for example in the presence of UV radiation from photoinitiators such as benzophenone, methyl anthraquinone and chloro- 2-thioxanthone. 22 - Process according to claims 18 to 21, characterized in that the copolymerization is carried out in the presence of at least one chain transfer agent, used in particular at a rate of <B> 0.05 </B> to 8% by weight relative to the total weight of the monomers, and being chosen in particular from mercaptoethanol, isopropanol, alkyl mercaptans, carbon tetrachloride and triphenyl methane. 23 - Method according to one of claims 18 to 22, characterized in that the copolymerization is carried out at a temperature of -40 C to 200 C, in particular 50 to 95 C. 24 - Method according to one of claims 18 to 23, characterized in that the LCST of the targeted copolymer is adjusted as a function of the composition of the monomers and / or the amount of the chain transfer agent used and / or the temperature and / or the process carried out batchwise or semi-continuously. 25 - Mixture in aqueous medium of at least one water-soluble heat-sensitive copolymer as defined in one of claims 1 to 17 or prepared by a process as defined in one of claims 18 to 24, with at least one (co ) hydrophobic polymer. 26 - Use of a copolymer as defined in one of claims 1 to 17 or prepared by a process as defined in one of claims 18 to 24, or of a mixture as defined in claim 25 comprising at most 50% by weight of hydrophobic (co) polymer (s) relative to the total polymers, for the manufacture of water-dispersible or water-disintegrable films, in particular entering into the constitution of water-disintegrable hygiene articles. 27 - Water-dispersible or hydro-disintegratable films obtained by drying a copolymer as defined in one of claims to 17 or prepared by a process as defined in one of claims 18 to 24, or of a mixture such as as defined in claim 25 comprising at most 50% by weight of hydrophobic (co) polymer relative to the total copolymers 28 - Use of a copolymer as defined in one of claims 1 to 17 prepared by a process as defined to one of claims 18 to 24 as a binder or binder component for fibrous webs or as an adhesive component or as a component of a polymer compound, in particular entering into the constitution of water-disintegrated hygiene articles. 29 - Hygiene articles, particularly disposable, in the constitution of which between the copolymer as defined in one of claims 1 to 17 or prepared by a process as defined in one of claims 18 to 24, or of a mixture as defined in claim 25 comprising at most 50% by weight of hydrophobic (co) polymer relative to the total copolymers, either as a water-soluble or water-disintegratable film, or as a binder used in the preparation of incorporated fibrous webs in these articles, either for the formulation of adhesives connecting the different constituents of the hygiene article, or as a component of the compound of the polymer forming the lower envelope of the article.