EP1252207A2 - Wässrige salzdispersionen von wasserlöslichen (co)polymeren auf basis van kationischen monomeren, ihr herstellungsverfahren und ihre verwendung - Google Patents

Wässrige salzdispersionen von wasserlöslichen (co)polymeren auf basis van kationischen monomeren, ihr herstellungsverfahren und ihre verwendung

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Publication number
EP1252207A2
EP1252207A2 EP01907647A EP01907647A EP1252207A2 EP 1252207 A2 EP1252207 A2 EP 1252207A2 EP 01907647 A EP01907647 A EP 01907647A EP 01907647 A EP01907647 A EP 01907647A EP 1252207 A2 EP1252207 A2 EP 1252207A2
Authority
EP
European Patent Office
Prior art keywords
parts
monomers
water
weight
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01907647A
Other languages
English (en)
French (fr)
Inventor
Alain Riondel
Denis Tembou N'zudie
Didier Vanhoye
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema SA
Original Assignee
Atofina SA
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Filing date
Publication date
Application filed by Atofina SA filed Critical Atofina SA
Publication of EP1252207A2 publication Critical patent/EP1252207A2/de
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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
    • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F220/70—Nitriles; Amides; Imides
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
    • 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

Definitions

  • the present invention relates to salt-free aqueous dispersions of water-soluble copolymers based on cationic monomers, to the preparation of these dispersions and to their applications.
  • the water-soluble polymers are used for different applications and, in particular, as flocculants for the treatment of urban, waste and industrial water, the dehydration of the sludge generated, as thickeners and soil treatment agents.
  • aqueous systems of such water-soluble polymers with a high dry extract are gelatinous and have very high viscosities, which make their handling and storage difficult.
  • the problem posed to a person skilled in the art is the production of such aqueous systems but having both a high dry extract and a low viscosity.
  • Conventional processes for the synthesis of these polymers include solution, reverse suspension and reverse emulsion polymerization.
  • Solution polymerization and reverse suspension polymerization lead to powdered products which have the disadvantage of generating dust at the time of use, being difficult to dissolve in water and being unable to train aqueous solutions of high concentration polymers which can be easily handled.
  • these two methods have a disadvantage in terms of productivity, on the one hand because of the low concentration of monomer used during the polymerization, and, d 'on the other hand, because of a drying and / or grinding step inducing an increase in the cycle time and an additional cost of energy consumption.
  • the reverse emulsion process which has been known for about two decades leads to a product having a polluting organic solvent.
  • European patent EP-B-170 394 describes a dispersion of polymer gel particles larger than 20 ⁇ m in a solution of dispersant of poly (sodium acrylic) or of poly (diallyldimethylammonium chloride).
  • this product has the disadvantage of having a high viscosity after a long storage period, the viscosity can only be reduced after shearing or stirring.
  • European patent applications EP-A-183,466 and EP-A-525,751 American patents US-A-4,929,655 and US-A-5,006,590, and European patent application EP-A-657,478 propose the case of precipitating polymerization in a saline medium of water-soluble monomers, including the polymer precipitates in the form of particles, then is dispersed by means of agitation and stabilized by low-mass polymer dispersants, which are soluble in saline medium. Furthermore, these particles are difficult to stabilize because of their large size (2-50 ⁇ m).
  • dispersant two approaches can be envisaged to achieve this stabilization objective: on the one hand by viscosifying the continuous phase through the associative effects provided by the dispersant to avoid sedimentation of the particles, and, on the other hand, promoting effective adsorption of the dispersant on the surface of the particles for better efficiency as a protective colloid, to avoid coalescence of the particles.
  • the hydrophobic units present in the structure of the dispersant can greatly contribute to this.
  • These dispersants must have low masses, to ensure their solubility in a saline aqueous medium and have cationic functions necessary for flocculation.
  • the typical dispersants for these polymerizations are poly (diallyldimethylammonium chloride) or the copolymer of diallyldimethylammonium chloride / (meth) acryloxyethyl-dimethylhexadecylammonium chloride (cf. European patent application EP-A-657,478). In the latter case, it is described that the associative nature can be ensured by the alkyl chains of (meth) acryloxyethyldimethylhexadecyl chloride. ammonium.
  • this dispersant takes place in an aqueous medium, thus only allowing the use of the second comonomer which, admittedly, is less hydrophilic than diallyldimethylammonium chloride, but must be water-soluble. This point considerably limits the hydrophobic nature of these dispersing copolymers. It is important to specify that an increase in the hydrophobic character should make it possible to obtain an improved fluidity dispersion.
  • cationic or amphoteric copolymers are obtained by polymerizing in the presence of dispersant, water and salts, a mixture of water-soluble monomers.
  • the typical monomer mixture for this type of polymerization consists of
  • EP-A-0 717 056 claims dispersions of amphoteric water-soluble polymers based on cationic monomers, including (meth) acryloxyethyldimethyldimethyl benzyl ammonium chloride, and anionics (acrylic acid), synthesized in the presence of dispersant.
  • cationic monomers including (meth) acryloxyethyldimethyldimethyl benzyl ammonium chloride, and anionics (acrylic acid), synthesized in the presence of dispersant.
  • salt can limit the use of these dispersions for certain applications (thickeners or agents facilitating the cleaning of the textile for example).
  • German patent application DE-A-4 216 167 and American patent US-A-5 403 883 describe a technique for obtaining low-viscosity salt-free dispersions by polymerization in the presence of the dispersant poly (diallyldimethylammonium chloride), of a mixture of hydrophilic, hydrophobic and optionally amphiphilic monomers.
  • European patent application EP-A-0 670 333 describes dispersions of crosslinked polymers obtained by adding a crosslinking agent such as N-methylol acrylamide or N, -methylene bisacrylamide to the mixture of monomers to be polymerized. .
  • Post-addition of the same dispersant allows a reduction in the viscosity of the systems described above (Canadian Patent No. 3,123,460). However, it has the effect of increasing the level of dispersant and leading to a dispersion having a low level of dispersed polymer.
  • the present invention therefore firstly relates to an aqueous dispersion without salt of a water-soluble copolymer obtained from a composition of monomers, comprising per 100 parts by moles: (a) from 0.5 to 99.5 parts by moles of at least one monomer of formula (I):
  • R, 1 represents H or -CH- R ⁇ represents -CH3 -C 2 H 5 -C 3H n 7 or "C ⁇ Hg and the compound (I) is optionally quaternized on one of the nitrogen, which is symbolized by the fact that the R J , X fc and associated with this nitrogen are in square brackets; when the compound (I) is quaternized on a single nitrogen, R 3 and X ⁇ have the following meanings:
  • R represents -CH ⁇ -CgHc ⁇ ; and X e represents Cl ® or CH 3 OS0 3 ⁇ ; or
  • R J represents - (CP ⁇ pCH with p integer from 3 to 11; and X ⁇ represents Br ⁇ or I ⁇ ; when the compound (I) is quaternized on the two nitrogen atoms, the two X e can be identical or different and the two R J can be the same or different, in which case:
  • R 3 represents -CH 2 -CgH 5 ; and X ⁇ represents Cl ⁇ ; or
  • R 3 represents - (CH 2 ) p CH3 with integer p from 3 to 11; and X ⁇ represents Br ⁇ or I ⁇ ;
  • X ⁇ represents Cl ® or CH 3 OS0 3 ⁇ ⁇
  • the other represents -Ct ⁇ C r ⁇
  • the associated X ® representing Cl ®
  • - R ° represents H or -CH3; - R 9 and R 10 , identical or different, each independently represent H or C- ] __5 alkyl;
  • - R 11 represents H or -CH3
  • - A 1 represents -0- or -NH-
  • B 1 represents -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CHOHCH 2 -;
  • - R, R and R each independently represent hydrogen, alkyl, C- j _-Cg hydroxyalkyl, C] _-Cg cycloalkyl, C5- C-J_2 Cg-C- ] aryl or C ⁇ - alkylaryl
  • X 1 represents a monovalent anion, such that
  • ethylenically unsaturated carboxylic acids ethylenically unsaturated sulfuric acids, ethylenically unsaturated sulfonic acids, and their derivatives, such as, for example, salts;
  • - R represents -CH3 -C 2 H 5 -C 3 H 7 and
  • R J represents -CH3, -C ⁇ H ⁇ or -C3H7; and X ® represents Cl ® or CH3OSO3 ® ; and
  • the two X® can be identical or different and the two R- can be identical or different;
  • composition of monomers which may contain, per 100 parts by mole of (a) + (b): (c) up to 30 mole parts of at least one hydrophobic monomer; and or
  • the preferred monomer of formula (I) is the compound of formula (la):
  • ethylenically unsaturated carboxylic acids mention may be made of (meth) acrylic acid and itaconic acid.
  • the monomers (c) can be chosen from
  • R, 17 represents H or CH3
  • Z represents -O- or -NH- or -NR 19 with Rli is alkyl in C j __ ⁇ ; - R 18 is alkyl in C j __3 2, cycloalkyl C 5-12 ar yl th or C 6-12 ar ylalkyl in Cg_3 2;
  • the monomers (d) can be chosen from: the monomers with a methylol function; and • monomers having at least two polymerizable unsaturations.
  • methylol-functional monomers mention may be made of N-methylol acrylamide and, as examples of monomers having at least two polymerizable unsaturations, mention may be made of N, N-methylene bisacrylamide and dimethacrylate. ethylene glycol.
  • the monomers (e) can be chosen from those of formula (VII):
  • Z 1 is -0- or -NH- or -NR 22 -, with R 22 representing alkyl in C j __g or hydroxyalkyl C-
  • - m is an integer between 1 and 60;
  • R, 21x represents C- ] __3g alkyl, C _ 50 aryl or C _ ⁇ aralkyl Mention may be made, as examples of monomers of formula (VII), of polyethoxylated (iich) acrylates with 10, 20 or 40 ethylene oxide units.
  • the dispersant (co) polymer (s) (B) are chosen from (co) polymers with a molar mass of less than 600,000, in particular from 10,000 to 600,000, cationic, amphoteric or nonionic, and incompatible with the copolymer that l 'We wish to disperse (copolymer A).
  • the two polymers (A) and (B) are considered to be incompatible when their mixture in an aqueous medium leads, in a given range of composition, to phase separation between the two polymers (A) and (B).
  • dispersing (co) polymers (B) As examples of dispersing (co) polymers (B), one can indicate:
  • the preferred dispersants are:
  • - cationic polymers based on styrene, acryloxyethyltrimethyl ammonium chloride and polyethoxy methacrylate with or without hydrophobic group, the latter being either the triphenyl styryl group or an alkyl chain;
  • amphoteric polymers based on styrene, acryloxyethyltrimethyl ammonium chloride, methacrylic acid and polyethoxy methacrylate with or without hydrophobic group, the latter being either the triphenyl styryl group or an alkyl chain;
  • - cationic polymers based on styrene, diallyldimethyl ammonium chloride and polyethoxy methacrylate with or without hydrophobic group, the latter being either the triphenyl styryl group or an alkyl chain;
  • the present invention also relates to a process for manufacturing an aqueous dispersion such as defined above, characterized in that a radical polymerization in aqueous medium is carried out of the monomer (s) to (e) as defined above, in the presence of at least one polymer dispersant (B) as defined above.
  • the aqueous dispersion is prepared by using in particular:
  • the polymerization can be initiated by various means, such as free radical generators such as peroxides, diazo compounds or persulfates, or by irradiation.
  • the preferred mode according to the invention is the initiation with 2,2'-azo-bis (N, N '- dimethyleneisobutyramidine) dihydrochloride or 2,2'-azo-bis (2-aminopropane) hydrochloride.
  • These initiators can be combined with a decomposition accelerator.
  • the polymerization temperature is between -40 ° C and 160 ° C, preferably being from 30 to 95 ° C. The conversion is greater than 99%.
  • the present invention also relates to the use of dispersions of water-soluble copolymers as defined above or prepared by the process as defined above, as flocculating agents for the treatment of wastewater; fiber retention agents and fillers in papermaking processes; agents facilitating the cleaning of supports such as textiles; charge dispersing agents; inhibiting agents for the transfer of pigments and dyes to various supports such as textiles; thickeners; and dehydrating agents.
  • dispersions of water-soluble copolymers as defined above or prepared by the process as defined above, as flocculating agents for the treatment of wastewater; fiber retention agents and fillers in papermaking processes; agents facilitating the cleaning of supports such as textiles; charge dispersing agents; inhibiting agents for the transfer of pigments and dyes to various supports such as textiles; thickeners; and dehydrating agents.
  • the reactor is brought to 70 ° C. with nitrogen sweeping and stirring (150 rpm; anchor stirrer). Then introduced, when the temperature of the reaction medium is stabilized at 70 ° C., 0.2 part of ABAH. After 3 hours of reaction at 70 ° C., the temperature of the reaction medium is brought to 80 ° C. and 0.2 part of ABAH is introduced. After 2 hours of cooking at 80 ° C., cooling and recovering a 30.3% solution of water-soluble copolymer having the molar composition: styrene / ADAMQUAT MC / SIPOMER SEM / AMA 19.23 / 76.25 / 0.67 / 3.84.
  • the reactor is brought to 55 ° C., carried out for
  • Example 2 BZ obtained in Example 1; - 67.5 parts of 50% acrylamide in water;
  • ethylene glycol dimethacrylate - 0.0055 part of ethylene glycol dimethacrylate.
  • the reactor is brought to 55 ° C., a nitrogen sweep is carried out for 1 hour and 0.0075 part of VA-044 diluted in 5 parts of water is introduced. The temperature is maintained at 55 ° C. for 1 hour 30 minutes.
  • the reactor is heated to the temperature of 65 ° C.
  • 0.075 part of VA-044 diluted in 5 parts of water is added, and the reaction is allowed to proceed for an additional 2 hours at 65 ° C.
  • the reactor is heated to a temperature of 80 ° C and after 1 hour, cooled to 30 ° C, and the reactor is emptied.
  • S-ADAMQUAT 2BZ into the composition of the dispersed polymer therefore has the effect of reducing the viscosity of the dispersion.
EP01907647A 2000-01-24 2001-01-19 Wässrige salzdispersionen von wasserlöslichen (co)polymeren auf basis van kationischen monomeren, ihr herstellungsverfahren und ihre verwendung Withdrawn EP1252207A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0000833A FR2804122B1 (fr) 2000-01-24 2000-01-24 Dispersions aqueuses sans sel de (co)polymeres hydrosolubles a base de monomeres cationiques, leur procede de fabrication et leurs applications
FR0000833 2000-01-24
PCT/FR2001/000183 WO2001055225A2 (fr) 2000-01-24 2001-01-19 Dispersions aqueuses sans sel de (co)polymeres hydrosolubles a base de monomeres cationiques, leur procede de fabrication et leurs applications

Publications (1)

Publication Number Publication Date
EP1252207A2 true EP1252207A2 (de) 2002-10-30

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EP01907647A Withdrawn EP1252207A2 (de) 2000-01-24 2001-01-19 Wässrige salzdispersionen von wasserlöslichen (co)polymeren auf basis van kationischen monomeren, ihr herstellungsverfahren und ihre verwendung

Country Status (8)

Country Link
US (1) US20030153675A1 (de)
EP (1) EP1252207A2 (de)
JP (1) JP2003523462A (de)
KR (1) KR20020071963A (de)
CN (1) CN1419572A (de)
AU (1) AU3556201A (de)
FR (1) FR2804122B1 (de)
WO (1) WO2001055225A2 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1512676A1 (de) * 2003-09-05 2005-03-09 Taminco N.V. Verfahren zur Herstellung von (Meth)acrylatdiammoniumsalzen und ihre Verwendung als Monomere zur Herstellung von Polymeren
WO2006094556A1 (en) * 2005-03-09 2006-09-14 Taminco N.V. Polyelectrolytes based on diquaternary di-ammonium monomers
DE102007060175A1 (de) * 2007-12-13 2009-06-18 Johannes Gutenberg-Universität Mainz Quartärnisierung des Zusatzstoffs Aminoalkyl Methacrylat Copolymer E zur Verbesserung der Permeabilität und Löslichkeit von Arzneistoffen
CN101845115A (zh) * 2010-04-28 2010-09-29 北京化工大学 水基聚丙烯酰胺复合分散液的制备方法及其应用
JP5847657B2 (ja) * 2012-06-11 2016-01-27 Ｍｔアクアポリマー株式会社 製紙用歩留向上剤およびそれを用いた製紙方法
CN106749956B (zh) * 2016-11-14 2018-10-23 苏州联胜化学有限公司 一种纺织品后整理用挺弹整理剂及其制备方法、使用方法
CN109575185A (zh) * 2018-12-25 2019-04-05 上海纳米技术及应用国家工程研究中心有限公司 氟化物改性的疏水性两性型有机高分子絮凝剂的制备及产品和应用
US10961662B1 (en) 2019-12-23 2021-03-30 Polymer Ventures, Inc. Ash retention additive and methods of using the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2770527B1 (fr) * 1997-11-04 2000-01-14 Atochem Elf Sa Dispersions aqueuses salines de polymeres hydrosolubles contenant un dispersant amphiphile a base de polymere cationique ayant des motifs hydrophobes
FR2770526B1 (fr) * 1997-11-04 2000-01-14 Atochem Elf Sa Dispersions aqueuses stables a base de polymeres hydrosolubles contenant un dispersant cationique comportant des motifs hydrophobes

Non-Patent Citations (1)

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Title
See references of WO0155225A2 *

Also Published As

Publication number Publication date
WO2001055225A3 (fr) 2002-04-04
AU3556201A (en) 2001-08-07
WO2001055225A2 (fr) 2001-08-02
KR20020071963A (ko) 2002-09-13
US20030153675A1 (en) 2003-08-14
FR2804122B1 (fr) 2002-02-22
CN1419572A (zh) 2003-05-21
FR2804122A1 (fr) 2001-07-27
JP2003523462A (ja) 2003-08-05

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