WO1998022524A1 - Procede de reticulation continue de produits de condensation et d'addition - Google Patents

Procede de reticulation continue de produits de condensation et d'addition Download PDF

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Publication number
WO1998022524A1
WO1998022524A1 PCT/EP1997/006433 EP9706433W WO9822524A1 WO 1998022524 A1 WO1998022524 A1 WO 1998022524A1 EP 9706433 W EP9706433 W EP 9706433W WO 9822524 A1 WO9822524 A1 WO 9822524A1
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Prior art keywords
cylinder
reaction
water
carboxylic acids
soluble
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PCT/EP1997/006433
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German (de)
English (en)
Inventor
Jürgen DECKER
Hubert Meixner
Wolfgang Reuther
Günter Scherr
Ulrich Steuerle
Volkmar WEBERNDÖRFER
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Basf Aktiengesellschaft
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Publication of WO1998022524A1 publication Critical patent/WO1998022524A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/28—Moving reactors, e.g. rotary drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1806—Stationary reactors having moving elements inside resulting in a turbulent flow of the reactants, such as in centrifugal-type reactors, or having a high Reynolds-number
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1887—Stationary reactors having moving elements inside forming a thin film
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C08G73/022—Preparatory process from polyamines and epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C08G73/0286—Preparatory process from polyamidoamines and epihalohydrins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00168—Controlling or regulating processes controlling the viscosity

Definitions

  • WO-A-94/12560 discloses water-soluble condensates containing amino groups, which can be obtained by first partially amidating polyalkylene polyamines, preferably polyethyleneimine, by reaction with, for example, monocarboxylic acids and then crosslinking the reaction products formed with at least bifunctional crosslinking agents. water-soluble polyalkylene polyamines can react.
  • WO-A-94/14873 also discloses water-soluble, crosslinked amino-containing condensation products which, by Michael addition of, for example, polyalkylene polyamines, polyamidoamines or polyamidoamines grafted with ethyleneimine onto monoethylenically unsaturated carboxylic acids, salts, esters, amides or nitriles of monoethylenically unsaturated acids and subsequent reaction with at least bifunctional crosslinkers are available.
  • the polymers described above are used as dewatering, flocculating and retention agents in the manufacture of paper.
  • EP-B-0 498 583 discloses a process for the continuous implementation of an emulsion polymerization or a suspension polymerization in a cylinder stirrer (annular gap reactor).
  • the mixture to be polymerized is placed in a space between an inner cylinder and
  • the object of the present invention is to improve the space-time yield in the crosslinking of water-soluble, amino groups.
  • the object is achieved according to the invention with a process for the continuous crosslinking of water-soluble condensation and addition products containing amino groups with at least bifunctional crosslinking agents in aqueous solution or in water-soluble are organic solvents at temperatures of 20 to 180 ° C to form crosslinked, water-soluble reaction products, which in 20 wt. % aqueous solution at 20 ° C. has a viscosity of 50 to 2000 mPas if a mixture of water-soluble condensation or addition products containing amino groups and crosslinking agent or both reactants are separated from one another
  • the viscosity of the reaction product is measured at the reactor outlet using an on-line viscometer.
  • the amount of crosslinking agent is metered on the basis of this measured variable.
  • the continuous crosslinking is preferably carried out in a cylinder stirrer at Taylor numbers from 30 to 1000.
  • Water-soluble condensation and addition products containing amino groups are known. They have essentially already been described above as prior art. Both homopolymers of ethyleneimine and polymers which contain, for example, ethyleneimine grafted on are suitable for this purpose.
  • the homopolymers are prepared, for example, by polymerizing ethyleneimine in aqueous solution in the presence of catalysts such as acids, Lewis acids or alkylating agents such as methyl chloride, ethyl chloride, propyl chloride, ethylene chloride, chloroform or tetrachlorethylene.
  • the polyethyleneimines thus obtainable have a broad molecular weight distribution and molecular weights of, for example, 129 to 2-10 6 , preferably 430 to 1-10 6 .
  • polyamidoamines grafted with ethyleneimine, which are described in US Pat. No. 4,144,123 which is cited in the prior art.
  • the polyamidoamines are produced, for example, by reacting dicarboxylic acids with 4 to 10 carbon atoms with polyalkylene polyamines, which preferably contain 3 to 10 basic nitrogen atoms in the molecule.
  • Suitable dicarboxylic acids are, for example, succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. Mixtures of adipic acid and glutaric acid or maleic acid and adipic acid can also be used.
  • Adipic acid is preferably used to prepare the polyamidoamines.
  • the condensation of the dicarboxylic acids with the polyalkylene polyamines is usually carried out in the temperature range from, for example, 100 to 220 ° C., the water formed in the reaction being distilled off from the reaction mixture.
  • the condensation can optionally also be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms, e.g. in the presence of caprolactam.
  • lactones or lactams of carboxylic acids having 4 to 8 carbon atoms e.g. in the presence of caprolactam.
  • Michael addition products also come from as water-soluble addition products containing amino groups
  • polymers containing ethyleneimine units is known from WO-A-94/12560.
  • These compounds are water-soluble, partially amidated polyethyleneimines which can be obtained by reacting polyethyleneimines with monobasic carboxylic acids or their esters, anhydrides, acid chlorides or acid amides.
  • the molar masses of the polyethyleneimines in question can be up to 2 million and are preferably in the range from 1000 to 50,000.
  • the polyethyleneimines are partially amidated with monobasic carboxylic acids, so that, for example, 0.1 to 90, preferably 1 to 50% of the amidable nitrogen atoms in the polyethyleneimines are present as amide groups.
  • Other suitable water-soluble amino-containing macromolecular compounds are partially quaternized polyethyleneimines and phosphonomethylated polyethyleneimines.
  • Crosslinkers which contain blocked isocyanate groups are also suitable, for example trimethylhexamethylene diisocyanate blocked with 2, 2, 3, 6-tetra-methylpiperidinone-4.
  • Such crosslinkers are also known, cf. for example DE-A-4 028 285 and crosslinkers containing aziridine units based on polyethers or substituted hydrocarbons, for example 1,6-bis-N-aziridinohexane, cf.
  • Halogen-free crosslinking agents are therefore preferably used for the production of condensates containing amino groups or addition products containing amino groups, which are each soluble in water.
  • the halogen-free crosslinkers are at least bifunctional and are preferably selected from the group consisting of:
  • Suitable crosslinkers of group (1) are ethylene carbonate, propylene carbonate and urea. From this group of monomers, propylene carbonate is preferably used. The crosslinkers in this group react to form urea compounds containing amino groups.
  • Suitable halogen-free crosslinkers of group (2) are, for example, monoethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid and the amides, esters and anhydrides derived therefrom.
  • the esters can be derived from alcohols having 1 to 22, preferably 1 to 18, carbon atoms.
  • the amides are preferably unsubstituted, but can carry a C ⁇ ⁇ to C 22 alkyl radical as a substituent.
  • R C x to C 22 alkyl
  • Suitable dicarboxylic acid esters are, for example, dimethyl oxalate, diethyl oxalate, diisopropyl oxalate, dimethyl succinate, diethyl succinate, diisopropyl succinate, di-n-propyl succinate, di-adipyl adipate, diisobutylate of adipate and adipate of adipate.
  • Suitable esters of ethylenically unsaturated dicarboxylic acids are, for example, maleic acid di- thylester, diethyl maleate, diisopropyl maleate, dimethyl itaconate and diisopropyl itaconate.
  • Substituted dicarboxylic acids and their esters such as tartaric acid (D-, L-form and as a racemate) and tartaric acid esters such as tartaric acid dimethyl ester and tartaric acid diethyl ester are also suitable.
  • At least dibasic saturated carboxylic acids include, for example, tri- and tetracarboxylic acids such as citric acid, propane tricarboxylic acid, ethylenediaminetetraacetic acid and butane tetracarboxylic acid.
  • Other suitable crosslinkers of group (2) are the salts, esters, amides and anhydrides derived from the above-mentioned carboxylic acids.
  • Polyether diamines are also derived from polytetrahydrofuran which have 2 to 75 tetrahydrofuran units.
  • the polytetrahydrofurans are also converted into the corresponding ⁇ , ⁇ -polyether diamines by reaction with ammonia.
  • Polyethylene glycols or block copolymers of ethylene glycol and propylene glycol are preferably used to prepare the polyether diamines.
  • the compounds of formula (II) are obtainable, for example, by reacting alkylene glycols, polyethylene glycols, polyethyleneimines, polypropyleneimines, polytetrahydrofurans, ⁇ -diols or ⁇ , ⁇ -diamines with maleic anhydride or the other monoethylenically unsaturated carboxylic acids or carboxylic acid derivatives given above.
  • the polyethylene glycols which are suitable for the preparation of the crosslinker II preferably have molar masses of 62 to 10,000, the molar masses of the poly- ethyleneimines are preferably 129 to 50,000, those of polypropylene in 171 to 50,000.
  • suitable alkylene glycols are ethylene glycol, 1,2-propylene glycol, 1,4-butanediol and 1,6-hexanediol.
  • the ⁇ , ⁇ -diamines which are preferably used are ethylene diamine and ⁇ , ⁇ -diamines derived from approx. 400 to 5,000 each of molecular weights M w of molecular weights M w of polyethylene glycols or of polytetrahydrofurans.
  • crosslinking agents of the formula II are reaction products of maleic anhydride with ⁇ , ⁇ -polyether diamines with a molecular weight of 400 to 5000, the reaction products of polyethyleneimines with a molecular weight of 129 to 50,000 with maleic anhydride and the reaction products with ethylenediamine or triethylenetetramine Maleic anhydride in a molar ratio of 1: at least 2.
  • crosslinkers are formed to give the double bond of the monoethylenically unsaturated carboxylic acids or their derivatives, in which the monoethylenically unsaturated Carboxylic acids or their derivatives are linked via an amide group with the polyether diamines, alkylenediamines or polyalkylene polyamines and via an ester group with the alkylene glycols or polyalkylene glycols.
  • These reaction products contain at least two ethylenically unsaturated double bonds.
  • This type of crosslinker reacts with the amino groups of the compounds to be crosslinked in the manner of a Michael addition to the terminal double bonds of these crosslinkers and, if appropriate, additionally with the formation of amide groups.
  • Polyether diamines, alkylenediamines and polyalkylene polyamines can also react with maleic anhydride or the ethylenically unsaturated carboxylic acids or their derivatives with addition to the double bond in the manner of a Michael addition. This gives crosslinking agents of the formula III
  • crosslinkers of the formula (III) bring about crosslinking with the compounds containing amino groups via their terminal carboxyl or ester groups with the formation of an amide function.
  • This class of crosslinker systems also includes the reaction products of monoethylenically unsaturated carboxylic acid esters with alkylenediamines and polyalkylenepolyamines, for example the addition products of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and of polyethyleneimines with molar masses of, for example, 129 to 50,000 acrylic acid, acrylic acid, acrylic acid, for example at least 2 moles of the acrylic or methacrylic acid esters are used per mole of the amine component.
  • moles of ethylenically unsaturated carboxylic acids or their derivatives can be added to one mole of a polyalkylene polyamine containing 10 nitrogen atoms in the manner of a Michael addition. At least 2 to at most 4 mol of the ethylenically unsaturated carboxylic acids or their derivatives can be added to each 1 mol of polyalkylenediamines and alkylenediamines in the manner of a Michael addition.
  • a crosslinker of the structure is formed, for example, in the manner of a Michael addition
  • X NH 2 , OH or OR 1 and R 1 is Ci to C 22 alkyl.
  • Halogen-free crosslinkers of group (4) are reaction products which are prepared by reacting dicarboxylic acid esters which are completely esterified with monohydric alcohols having 1 to 5 carbon atoms with ethyleneimine.
  • Suitable dicarboxylic acid esters are, for example, oxalic acid dimethyl ester, oxalic acid diethyl ester, succinic acid dimethyl ester, succinic acid diethyl ester, adipic acid dimethyl ester, adipic acid diethyl ester and glutaric acid dimethyl ester.
  • the reaction of diethyl oxalate with ethyleneimine gives bis- [ß- (1-aziridino) ethyl] oxalic acid amide.
  • the dicarboxylic acid esters are reacted with ethyleneimine, for example in a molar ratio of 1 to at least 4.
  • the reactive group of these crosslinkers are the terminal aziridine groups.
  • n 0 to 22.
  • the crosslinking reaction is carried out continuously in a tubular reactor in which a mixture of water-soluble condensation or addition products containing amino groups and crosslinking agent or both reactants are continuously fed separately from one another to a tubular reactor and therein in laminar flow at Reynolds numbers of 0.005 up to 500, preferably 0.1 to 200 polycondensed.
  • the tubular reactor has, for example, a length: diameter ratio of 20 to 10,000.
  • the residence time of the reaction mixture in the reactor is, for example, in the range from 1 to 300, preferably 2 to 60, minutes
  • the temperature of the mixture is preferably adjusted to values below 10 ° C, for example in the range from 0 to + 5 ° C, so that a premature reaction follows Possibility is avoided.
  • the mixture of the two reactants is then pumped continuously into the heatable tubular reactor.
  • the reactants are preferably mixed intensively in a static mixer before they enter the reactor. However, one can also proceed in such a way that the A component and the
  • the crosslinking reaction is preferably carried out in cylindrical stirrers (annular gap reactors).
  • the reaction mixture of water-soluble amino group-containing condensation or addition products and at least one crosslinker is introduced into a space between an inner cylinder and an outer cylinder of a coaxial double cylinder from one side of the double cylinder and polycondensed therein, with at least one cylinder of the coaxial double cylinder at an angular velocity relative to other cylinder is rotated so that Taylor vortices occur in the reaction mixture and the Taylor numbers are 20 to 2000, preferably 30 to 1000.
  • Taylor vortices are pairs of counter-rotating vortices that form in a cylinder gap when one of the cylinders rotates, thereby exceeding a critical Taylor number.
  • a polyamidoamine is prepared by condensing adipic acid with diethylenetriamine and then grafted in aqueous solution with sufficient ethyleneimine that the polyamidoamine contains 6.7 ethyleneimine units grafted on per basic nitrogen group .
  • a 10% aqueous solution of the polymer has a viscosity of 22 mPas.
  • the polyamidoamine grafted with ethyleneimine is used as a 24% aqueous solution.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Paper (AREA)

Abstract

La présente invention concerne un procédé de réticulation continue de produits de condensation et d'addition solubles dans l'eau et à teneur en groupes amines, faisant intervenir au moins des agents de réticulation bifonctionnels dans une solution aqueuse ou des solvants organiques solubles dans l'eau à des températures entre 20 °C et 180 °C, avec formation de produits de réaction réticulés, solubles dans l'eau et présentant, pour 20 % en poids de solution aqueuse à une température de 20 °C, un indice de viscosité de 50 à 2000 mPas. Un mélange de produits de condensation et d'addition solubles dans l'eau et à teneur en groupes amines et des agents de réticulation, ou bien les deux participants à la réaction séparément, sont acheminés en continu vers un réacteur tubulaire, à l'intérieur duquel ils s'écoulent en régime laminaire (nombres de Reynolds: 0,005 - 500), puis polycondensés en continu dans un agitateur cylindrique, cette opération consistant à faire entrer dans un compartiment intermédiaire, entre le cylindre intérieur et le cylindre extérieur d'un double cylindre coaxial, les agents participant à la réaction provenant d'un côté dudit double cylindre, aux fins de leur polycondensation. On fait entrer en rotation au moins un cylindre du double cylindre coaxial, avec une vitesse angulaire par rapport à l'autre cylindre, en sorte que des tourbillons de Taylor apparaissent dans le mélange réactionnel, avec un nombre de Taylor entre 20 et 2000. Le mélange réactionnel est ensuite isolé à la fin du cycle du réacteur.
PCT/EP1997/006433 1996-11-20 1997-11-18 Procede de reticulation continue de produits de condensation et d'addition WO1998022524A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19647926 1996-11-20
DE19647926.6 1996-11-20

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19828742A1 (de) * 1998-06-27 1999-12-30 Basf Coatings Ag Taylorreaktor für Stoffumwandlungen, bei deren Verlauf einer Änderung der Viskosität v des Reaktionsmediums eintritt
DE19960389A1 (de) * 1999-12-15 2001-07-05 Basf Coatings Ag Taylorreaktor für Stoffumwandlungen mit vorgeschaltetem Mischaggregat
US7651670B2 (en) 2001-10-04 2010-01-26 Basf Coatings Ag Method for continuously polymerizing in mass quantities and taylor reactor for carrying out this method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0498583A1 (fr) * 1991-02-05 1992-08-12 Nippon Paint Co., Ltd. Méthode de polymérisation en continue et appareil
DE4124948A1 (de) * 1991-07-27 1993-01-28 Basf Ag Verfahren zum kontinuierlichen pfropfen von nh-gruppen enthaltenden verbindungen mit ethylenimin
DE4244194A1 (de) * 1992-12-24 1994-06-30 Basf Ag Wasserlösliche Kondensationsprodukte aus Aminogruppen enthaltenden Verbindungen und Vernetzern, Verfahren zu ihrer Herstellung und ihre Verwendung
EP0732352A1 (fr) * 1995-03-13 1996-09-18 Wolff Walsrode Ag Réticulation de produits contenant des groupes amino dans milieu aqueux

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0498583A1 (fr) * 1991-02-05 1992-08-12 Nippon Paint Co., Ltd. Méthode de polymérisation en continue et appareil
DE4124948A1 (de) * 1991-07-27 1993-01-28 Basf Ag Verfahren zum kontinuierlichen pfropfen von nh-gruppen enthaltenden verbindungen mit ethylenimin
DE4244194A1 (de) * 1992-12-24 1994-06-30 Basf Ag Wasserlösliche Kondensationsprodukte aus Aminogruppen enthaltenden Verbindungen und Vernetzern, Verfahren zu ihrer Herstellung und ihre Verwendung
EP0732352A1 (fr) * 1995-03-13 1996-09-18 Wolff Walsrode Ag Réticulation de produits contenant des groupes amino dans milieu aqueux

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19828742A1 (de) * 1998-06-27 1999-12-30 Basf Coatings Ag Taylorreaktor für Stoffumwandlungen, bei deren Verlauf einer Änderung der Viskosität v des Reaktionsmediums eintritt
WO2000000280A1 (fr) * 1998-06-27 2000-01-06 Basf Coatings Ag REACTEUR DE TAYLOR POUR TRANSFORMATIONS DE MATIERES ACCOMPAGNEES D'UNE MODIFICATION DE LA VISCOSITE ξ DU MILIEU DE REACTION
US7122161B1 (en) 1998-06-27 2006-10-17 Basf Coatings Ag Taylor reactor for materials conversion in the course of which a change in viscosity of the reaction medium occurs
DE19960389A1 (de) * 1999-12-15 2001-07-05 Basf Coatings Ag Taylorreaktor für Stoffumwandlungen mit vorgeschaltetem Mischaggregat
DE19960389B4 (de) * 1999-12-15 2009-01-15 Basf Coatings Ag Verfahren zur Polymerisation olefinisch ungesättigter Monomere mittels eines Taylorreaktors
US7651670B2 (en) 2001-10-04 2010-01-26 Basf Coatings Ag Method for continuously polymerizing in mass quantities and taylor reactor for carrying out this method

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