EP1891119A1 - Procede de production de polymeres solubles dans l'eau a haut poids moleculaire et pulverulents destines a etre utilises dans des processus de separation solide/liquide - Google Patents

Procede de production de polymeres solubles dans l'eau a haut poids moleculaire et pulverulents destines a etre utilises dans des processus de separation solide/liquide

Info

Publication number
EP1891119A1
EP1891119A1 EP06761992A EP06761992A EP1891119A1 EP 1891119 A1 EP1891119 A1 EP 1891119A1 EP 06761992 A EP06761992 A EP 06761992A EP 06761992 A EP06761992 A EP 06761992A EP 1891119 A1 EP1891119 A1 EP 1891119A1
Authority
EP
European Patent Office
Prior art keywords
water
kneading unit
soluble
drying
phase
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Withdrawn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
EP06761992A
Other languages
German (de)
English (en)
Inventor
Matthias Hahn
Antje Lieske
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP1891119A1 publication Critical patent/EP1891119A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • 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
    • C08F2/32—Polymerisation in water-in-oil emulsions
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/24—Treatment of polymer suspensions

Definitions

  • the present invention relates to a process for the preparation of powdered high molecular weight water-soluble polymers for use in solid / liquid separation processes.
  • the invention relates to a process for the modification and drying of inverse polymer dispersions by means of the kneading technology with recovery of the solvents used.
  • High molecular weight water-soluble cationic polymers play a crucial role in many areas. They are used in the paper industry, water treatment and wastewater treatment, in the splitting of emulsions, etc. Such polymers can be prepared either in solution or by heterophasic techniques. Since high molar masses For optimum efficacy in the abovementioned ranges and these are barely attained with conventional solution polymerization, inverse emulsion polymerization represents the current state of the art.
  • the reaction mixture consists of two phases, an organic continuous and an aqueous dispersed phase, in which the monomers and additives are dissolved. At least one emulsifier serves to stabilize the inverse emulsion.
  • the resulting polymer dispersions have particle sizes between 200 nm and 10 .mu.va, the active ingredient content is between 30 and 50%.
  • WO 2004/018087 describes the modification and drying of water-soluble polymers. According to the aforementioned WO document, it is proposed to carry out the polymerization in a kneading reactor and subsequent drying in a special apparatus. The disadvantage here is that this is very complex and in relation to the solid powdery products unsatisfactory results in terms of molecular weight and water solubility can be achieved.
  • the invention combines the generally accepted benefits of polymerizing water-soluble monomers in inverse emulsion (achieving maximum molecular weights for a given monomer system) with the advantages associated with solid modification.
  • the proportion of the water phase in the total emulsion is between 30 and 90% by mass, preferably between 50 and 75% by mass. It has also proved to be advantageous if the monomer content of the aqueous phase is between 10 and 90% by mass, preferably between 50 and 70% by mass.
  • the aqueous phase preferably contains monomers which are selected from water-soluble cationic and nonionic monomers. Examples of these are (meth) acrylic esters, cationic N-substituted (meth) acrylamides, DADMAC, (meth) acrylamide and corresponding N-substituted derivatives.
  • the water phase may contain water-soluble multifunctional monomers (crosslinkers) in proportions of 0 to 5 mol% with respect to the monomers.
  • crosslinkers are, for example, bisacryloylamides, diacrylates, bisdiallyl compounds and other crosslinkers known from the prior art.
  • the proportion of the oil phase in the water-in-oil emulsion according to the present invention is preferably 10 to 70% by mass, particularly preferably 25 to 50% by mass. From a material point of view, it is favorable if the oil phase is selected from hydrocarbons or mixtures thereof, in particular from mineral oils, isoparaffin and synthetic oils.
  • the water-in-oil emulsion according to feature a) still contains 0.5 to 10% by mass of an emulsifier or mixture thereof. Suitable examples here are emulsifiers of the Span or Tween type, polymeric emulsifiers and also fatty acid amides and other emulsifiers corresponding to the prior art.
  • the polymerization is then started by addition of a radical source (water or oil-soluble persulfates, azo compounds and redox systems).
  • the polymer dispersion which has been prepared as described above under a) is converted into a kneading unit for drying and dried in the kneading unit using elevated temperature and reduced pressure. It has been found that in particular the use of the kneading technique for the drying step is very favorable.
  • the kneader is then preferably equipped with a vacuum system and a possibility for gassing with protective gas and a condensation system for distilled off solvents.
  • the construction of the kneading units leads to good mixing and constant renewal of the surface.
  • the increasingly viscous polymer mass is broken down into small particles, which makes the weaving process very effective.
  • the angle and shape of the kneading elements may be any particular system, i. development, the viscosity of the drying process. Another advantage is that the process described above can be operated both batchwise and continuously.
  • the temperature and the pressure can be applied to the solvent to be evaporated and the desired degree of drying. be fit.
  • the pressure is between normal pressure and 5 mbar, preferably between 200 and 300 mbar.
  • the temperature is between 20 and 200 0 C, preferably between 50 and 150 0 C.
  • Another advantage of the method according to the invention is the fact that the carrier phase is recovered again (feature c)).
  • the evaporated solvents are collected separately and can then, after any necessary purification, be recycled.
  • a further embodiment of the process according to the invention consists in the fact that it is still possible to subject the polymer dispersion obtained according to process step a), after conversion into the kneading unit, but before drying, to reactive processing. For this purpose, after reaching a desired conversion, which may be between 40 and 100%, as described above under feature b), the polymer dispersion is transferred into the kneader. During Reaktiwerarbeitung, ie before drying, modifying and / or initiator reagents are added in the kneading unit.
  • reaction tiwerarbeitung can at any pressure, optionally under protective gas and at temperatures between 20 and 150 0 C., preferably between 40 and 90 0 C.
  • the advantage of Reaktiwerarbeitung before the drying step in the same kneading unit is to be seen in the fact that a good mixing of very viscous systems combined with a good self-cleaning is achieved.
  • the individual phases are homogenized by stirring, and a water-in-oil emulsion is produced by adding the water-to-oil phase under high shear (high-speed stirrer 3000 rpm). This is transferred into a thermostatable double-walled stirred reactor with gas inlet and attached reflux condenser and the mixture is purged with N 2 for 30 minutes with stirring. Then 100 mg of tetramethylethylenediamine (TEMED), dissolved in 2 g of isoparaffin, are metered in and the batch is heated to 35 ° C. After 16 h at 35 ° C., a further 30 mg of TEMED are metered in and heated to 50 ° C. for 4 h and to 80 ° C. for a further 4 h.
  • TEMED tetramethylethylenediamine
  • the intrinsic viscosity [ ⁇ ] of the polymer in IN NaCl aqueous solution at 30 0 C was 173 cm 3 / g, the average molecular weight determined by GPC-MALLS M w 860,000 g / mol. These values were determined without a separate drying step.
  • Example 1 the drying of the polymer dispersion of Example 1 is described in a kneader.
  • the polymer dispersion is transferred to a thermostattable kneader equipped with a vacuum system
  • the intrinsic viscosity [ ⁇ ] of the polymer powder in IN aqueous NaCl solution at 30 0 C was 168 cm 3 / gm, as determined by the GPC-MALLS average molar mass M w 830,000 g / mol.
  • the average molecular weight M w is of the same order of magnitude as the molecular weight M w of Example 1. This was unpredictable, since the drying step normally causes a significant influence on the molecular weight towards low values.
  • Example 1 The procedure is initially as described in Example 1. However, the polymerization is stopped after the 35 ° C. phase at a conversion of about 60% and the emulsion is converted into the kneader described in example 2. While kneading, 50 g of water are added to the system. It creates a highly viscous dispersion. Under inert gas is heated to 50 0 C and 30 mg of TEMED in 1 g of Isopar and 100 mg of PEG diacrylate in 2 g of toluene added. After 4 h at 50 0 C is heated to 80 0 C for 4 h.
  • Example 2 the dispersion is dried on the basis of Example 2.
  • the temperature is left at 80 0 C and controls the evaporation of the solvent via a stepwise reduction of the pressure of 800 mbar within 90 minutes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production de polymères solubles dans l'eau à haut poids moléculaire et pulvérulents destinés à être utilisés dans des processus de séparation solide/liquide. L'invention concerne notamment un procédé de modification et de séchage de dispersions polymériques inverses par la technologie de malaxage avec récupération du solvant utilisé.
EP06761992A 2005-06-13 2006-06-08 Procede de production de polymeres solubles dans l'eau a haut poids moleculaire et pulverulents destines a etre utilises dans des processus de separation solide/liquide Withdrawn EP1891119A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005027221A DE102005027221A1 (de) 2005-06-13 2005-06-13 Verfahren zur Herstellung von pulverförmigen hochmolekularen wasserlöslichen Polymeren für die Anwendung in fest/flüssig-Trennprozessen
PCT/EP2006/005502 WO2006133850A1 (fr) 2005-06-13 2006-06-08 Procede de production de polymeres solubles dans l'eau a haut poids moleculaire et pulverulents destines a etre utilises dans des processus de separation solide/liquide

Publications (1)

Publication Number Publication Date
EP1891119A1 true EP1891119A1 (fr) 2008-02-27

Family

ID=37026951

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06761992A Withdrawn EP1891119A1 (fr) 2005-06-13 2006-06-08 Procede de production de polymeres solubles dans l'eau a haut poids moleculaire et pulverulents destines a etre utilises dans des processus de separation solide/liquide

Country Status (4)

Country Link
US (1) US7786190B2 (fr)
EP (1) EP1891119A1 (fr)
DE (1) DE102005027221A1 (fr)
WO (1) WO2006133850A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2648697A4 (fr) * 2010-12-10 2014-07-09 Ns Technologies Pty Ltd Procédés de formation de miniémulsions et utilisation associée pour l'administration d'agents bioactifs
DE102015222585A1 (de) 2015-11-16 2017-05-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von thermisch stabilen schmelzspinnbaren PAN-Copolymeren, PAN-Copolymere, hieraus gebildete Formkörper sowie Verfahren zur Herstellung dieser Formkörper
KR20180125482A (ko) 2016-03-22 2018-11-23 프라운호퍼 게젤샤프트 쭈르 푀르데룽 데어 안겐반텐 포르슝 에. 베. 폴리아크릴로니트릴의 용융-방사 가능한 공중합체, 용융-방사에 의해 섬유 또는 섬유 전구체를 제조하는 방법 및 이에 따라 제조된 섬유

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19955861A1 (de) * 1999-11-20 2001-05-23 Basf Ag Verfahren zur kontinuierlichen Herstellung von vernetzten feinteiligen gelförmigen Polymerisaten
FR2812295B1 (fr) * 2000-07-27 2003-01-31 Snf Sa Polymeres cationiques de haut poids moleculaire, procede pour leur preparation, et leurs applications
EP1537169A1 (fr) * 2002-08-02 2005-06-08 Ionic Solutions Limited Compositions polymeriques, leur production et leurs utilisations
AU2003249838A1 (en) * 2002-08-20 2004-03-11 Sahbi Belkhiria Reactor and process for the production and/or drying of water-soluble polymers (wsps) or their derivatives
DE10260100A1 (de) 2002-12-19 2004-07-01 Basf Ag Kationische Makromonomere enthaltende Polymere und ihre Verwendung in kosmetischen Zubereitungen
DE10331865A1 (de) * 2003-07-14 2005-03-24 Basf Ag Wässrige Polymerdispersion und deren Verwendung in der Kosmetik

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006133850A1 *

Also Published As

Publication number Publication date
WO2006133850A1 (fr) 2006-12-21
US20080234429A1 (en) 2008-09-25
DE102005027221A1 (de) 2007-01-18
US7786190B2 (en) 2010-08-31

Similar Documents

Publication Publication Date Title
DE69413883T2 (de) Dispersionspolymerisationsverfahren
DE2744727C2 (de) Verfahren zur Herstellung von selbstvernetzten Mischpolymerisaten, von Acrylsäure und acrylsaurem Alkaliacrylat
DE2800520C2 (fr)
DE2528202C2 (fr)
EP1353975B2 (fr) Procede de production de dispersions polymeres eau-dans-eau
DE69720455T2 (de) Verfahren zur herstellung von wässrigen dispersionspolymeren
EP1727853B1 (fr) Dispersions polymeres anioniques eau dans l'eau, procede de production correspondant et utilisation
DE2009218B2 (de) Verfahren zur Perlpolymerisation von äthylenisch ungesättigten Monomeren
DE3147008A1 (de) Verfahren zur herstellung von waessrigen, hochkonzentrierten bimodalen kunststoffdispersionen
DE2451599A1 (de) Verfahren zur herstellung von wasserdispergierbaren polymerzusammensetzungen
EP0674678A1 (fr) Procede de production de dispersions polymeres solubles dans l'eau a forte teneur en polymeres
DE2602917C2 (de) Verfahren zur Herstellung eines festen Polymeren aus Vinylpyrrolidon und seine Verwendung
EP0736547B1 (fr) Dispersions aqueuses de polymères
EP0264710B1 (fr) Sels de poly-ammonium quaternaires solubles dans l'eau, procédé de leur préparation et leur utilisation
EP0027850B1 (fr) Polymère en émulsion agissant comme épaississant en milieu acide et son utilisation
DE60021793T2 (de) Monodisperse Teilchen, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1891119A1 (fr) Procede de production de polymeres solubles dans l'eau a haut poids moleculaire et pulverulents destines a etre utilises dans des processus de separation solide/liquide
EP1656402A1 (fr) Composition de polymeres cationiques pulverulents solubles dans l'eau, procede de production et utilisation de ladite composition
DE1123110B (de) Verfahren zur Polymerisation von wasserloeslichen Monomeren
DE3210752C2 (fr)
DE69316863T2 (de) Verfahren zur Herstellung von nicht-wässrigen Polymerzusammensetzungen mit hohem Feststoffgehalt
DE19652040B4 (de) Verfahren zur Herstellung einer ein kationisches Polymer enthaltenden wäßrigen Lösung oder Dispersion
EP1265932A1 (fr) Procede d'agglomeration de latex de polybutadiene a fines particules
EP0557311B1 (fr) Nouvelles emulsions eau dans l'huile
EP0736546A2 (fr) Dispersions aqueuses de polymères

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20071204

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FI FR IT

DAX Request for extension of the european patent (deleted)
RBV Designated contracting states (corrected)

Designated state(s): DE ES FI FR IT

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20090603

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120103