WO1991008235A1 - Production de dispersions polymeres stables avec des polymeres amphoteres comme stabilisant - Google Patents

Production de dispersions polymeres stables avec des polymeres amphoteres comme stabilisant Download PDF

Info

Publication number
WO1991008235A1
WO1991008235A1 PCT/EP1990/001970 EP9001970W WO9108235A1 WO 1991008235 A1 WO1991008235 A1 WO 1991008235A1 EP 9001970 W EP9001970 W EP 9001970W WO 9108235 A1 WO9108235 A1 WO 9108235A1
Authority
WO
WIPO (PCT)
Prior art keywords
stabilizers
polymer dispersions
volatile
emulsion polymerization
unsaturated monomers
Prior art date
Application number
PCT/EP1990/001970
Other languages
German (de)
English (en)
Inventor
Dieter Feustel
Herbert Fischer
Ludwig Schieferstein
Karl-Heinz Stritzke
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1991008235A1 publication Critical patent/WO1991008235A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene

Definitions

  • the invention relates to a process for the preparation of stable polymer dispersions by radical emulsion polymerization of vinyl-unsaturated monomers in an aqueous medium in the presence of a catalyst and amphoteric polymers as stabilizers.
  • the invention further relates to polymer dispersions prepared in this way and their use.
  • Emulsion polymerization is particularly suitable for simple process control.
  • the choice of the emulsifier is a very important factor for the process control and the properties of the latex.
  • the emulsifier should, on the one hand, and a stable emulsion between the monomer and water phases later form a stable latex on the other hand. Since the emulsifier remains in the finished product, it should not impart any negative properties to it. For example, it is often undesirable if the emulsifiers used float when the latex dries and lead to graying and / or inadequate water resistance of the film formed.
  • emulsifiers or surfactants in emulsion polymerization generally produces fine-particle dispersions with particle sizes of 0.1 ⁇ m to 0.3 ⁇ m and, when protective colloids are used, coarse-particle dispersions with particle sizes greater than 1 ⁇ m can be. It is generally assumed that the fine or coarse particle size is the result of different reaction mechanisms.
  • the polymerization in the presence of emulsifiers and / or surfactants takes place in micelles and leads to particles which are smaller than the originally dispersed mono-droplets, while in the presence of protective colloids the reaction drips in the mono and therefore their size for the size of the polymer particles is responsible.
  • Water-soluble starters can often achieve the simultaneous operation of both reaction mechanisms.
  • dispersions with bimodal particles or at least those with a very broad particle size distribution are generally formed.
  • the mean particle diameter is approximately in the range from 0.2 to 2 ⁇ m.
  • A stands for a straight-chain or branched C - to C5-alkylene group, a phenylene group or a substituted phenylene group.
  • These polyesters have been claimed as suitable emulsifiers for emulsion polymerization, ⁇ -unsaturated monomers. In order to increase the solubility in water, those polyesters whose acidic groups are completely neutralized are particularly preferred. Utilization of the different solution behavior at different pH values or a practical water insolubility at the isoelectric point is not previously described.
  • DE 36 24813 discloses further amphoteric polymers and their use as dispersion aids.
  • water-soluble polymers formed from monomers of acrylic acid and / or methacrylic acid with an ethylenically unsaturated amidamine.
  • the use of these polymers in emulsion polymerization has not been previously described, nor has the use of a different solution behavior at different pH values.
  • the object of the present invention is to develop a method for producing stable polymer dispersions by radical emulsion polymerization of vinylically unsaturated monomers.
  • the use of emulsifiers and / or surfactants should be avoided.
  • the process is said to lead to polymer dispersions with improved water resistance and increased gloss effect in the films which can be produced therefrom.
  • the polymer dispersions should have improved shear strength.
  • This object was achieved according to the invention by a process for the preparation of stable polymer dispersions by free-radical emulsion polymerization of vinylically unsaturated monomers in an aqueous medium in the presence of a catalyst and amphoteric polymers as stabilizers, characterized in that amphoteric polymers which are only soluble in predominantly dissociated form are used and these stabilizers - in order to increase the water resistance of the films which can be prepared from the polymer dispersions - are precipitated from aqueous solution in a first process step by adjusting the isoelectric point by means of non-volatile acid or base, in a second process step after setting of the pH value desired for the emulsion polymerization are brought back into solution by means of volatile acid or base and then with the addition of neutral, if appropriate with non-volatile neutralizing agents alized vinylically unsaturated monomers, the catalyst and, if desired, other auxiliaries the emulsion polymerization is carried out in a manner known per se.
  • vinylically unsaturated, ethylenically unsaturated and ⁇ , ⁇ -unsaturated are used synonymously in the literature.
  • polymer emulsion and polymer dispersion are also used synonymously. This applies in particular to the Anglo-Saxon literature.
  • amphoteric polymers which can be used according to the invention are assigned to the group of polymeric surfactants and have particularly good emulsifying properties.
  • such polymers are referred to as stabilizers. These show such a good emulsifying effect that there is no need for surfactants and / or emulsifiers in the process according to the invention.
  • the suitable stabilizers are only soluble in predominantly dissociated form in strongly polar solvents such as water. At their isoelectric point, the ionic groups of the molecule are predominantly in the form of associated counterion pairs. Are in this form the stabilizers suitable according to the invention are practically water-insoluble.
  • the most extensive water insolubility of the amphoteric polymers used is used at the isoelectric point.
  • the pH of a solution containing stabilizers is therefore set to about the isoelectric point before the polymerization begins with non-volatile acid or base. Most of the stabilizer precipitates.
  • the pH is then adjusted to the value desired for the emulsion polymerization using volatile acid or base. This value must differ from the isoelectric point.
  • the stabilizer is brought back into solution in this way, if appropriate with further addition of water.
  • the other components necessary for carrying out the polymerization such as monomers, catalyst and, if desired, further auxiliaries are, if appropriate, neutralized with a non-volatile neutralizing agent before they are added.
  • the emulsion polymerization is carried out in the manner known to the person skilled in the art.
  • the process mentioned offers the advantage that the polymer dispersions prepared in this way can be drawn into films which, after drying, have improved water resistance and a high gloss effect.
  • the dispersions also have very good shear strength.
  • the desired effect of increased water resistance has not been finally clarified, but it can be assumed that during the drying process the volatile acid or base also passes from the film into the gas phase and the non-volatile acid or base remains, so that the isoelectric point is re-established in the drying film. This leads to the stabilizers contained being converted into an almost insoluble form.
  • the stabilizers can possibly be better integrated into the polymer structure of the filming emulsion polymers.
  • amphoteric copolymers which are formed from monomers of types A, B and optionally C, as stabilizers.
  • Type A is vinylically unsaturated monomers with cationic or cation-forming groups.
  • N can have the values 1 to 20.
  • X is hydrogen or a methyl group.
  • Rj, R 2 and Y represent hydrogen, alkyl and / or aralkyl groups.
  • H 2 C C
  • Type B is vinylically unsaturated monomers with anionic and / or anion-forming groups.
  • X can be hydrogen or a methyl group.
  • Y is a carboxyl group or a (CH 2 ) n -S0 H group, where n can have the values 0 to 10.
  • the proton of the carboxyl group or the sulfonate group can also be replaced by other cations.
  • the cations of non-volatile bases, for example those of the alkali metals, are suitable.
  • Acrylic acid and / or methacrylic acid or salts thereof are preferred as compounds of the type mentioned.
  • Type C is a nonionic vinyl unsaturated monomer.
  • Styrenes such as halostyrenes, alkylstyrenes, cyanostyrenes, hydroxystyrenes, nitrostyrenes and / or vinyl styrenes are preferred here.
  • esters and / or amines of (meth) acrylic acid are preferred.
  • the expression (meth) acrylic acid here means methacrylic acid or acrylic acid.
  • the molar ratio A: B is in the range from 5: 100 to 40: 100, since this range has proven to be particularly favorable for the application properties of the polymer surfactant.
  • type C can also be present, but not more than 95 mol%, based on the total amount of monomers (A + B + C). A content of C to 50 mol% is preferred.
  • Amphoteric polyesters and / or polyurethanes are also preferably used as stabilizers in processes according to the invention. However, these are only suitable if the polyol units in the polymer chains of the polyesters or polyurethanes are 5 to 100 equivalent% from compounds of the type
  • polyesters are the reaction product of polyols and honorary carboxylic acids
  • polyurethanes are the product of polyols and polyfunctional isocyanates.
  • a proportion of 100 equivalent% of polyol units of the compounds of the type mentioned would accordingly be present if there were no further polyols as reaction components (apart from those of the type mentioned).
  • each n can in each case be independent assume the numerical values from 1 to 20.
  • methylene groups can also be replaced by phenylene and / or substituted phenyl groups.
  • the proton of the sulfonate group can also be replaced by other cations. Suitable cations are those of the non-volatile bases e.g. that of the alkali metals.
  • Stabilizers which have an average molecular weight of 2,000 to 100,000 are particularly suitable. However, stabilizers with an average molecular weight of 4,000 to 20,000 are preferably used, since they stabilize the emulsion or dispersion in an outstanding manner and do not “float” when the dispersion dries on.
  • the stabilizers should be present in an amount which is sufficient to bring about the desired emulsifying effects. On the other hand, the proportion of stabilizers should not be too high, both for economic reasons and for influencing the application properties of the emulsion polymers to be prepared.
  • a stabilizer content of 0.1 to 10% by weight, based on the initial amount of monomers, is therefore preferably used. Very good results are achieved if 3 to 8% by weight of stabilizers are preferably used.
  • Suitable monomers are all those which contain at least one ethylenically unsaturated or vinyl group. It has long been known to the person skilled in the art that such monomers can be added to polymers in an aqueous medium under the conditions of emulsion polymerization. These include, for example, vinyl compounds, styling and acrylates and their derivatives. Suitable vinyl compounds include, for example, vinyl chloride and vinyl esters such as vinyl acetate, vinyl propionate but also vinyl fatty acid esters such as vinyl laurate.
  • Suitable styrene compounds are styrene, halostyrenes such as chlorostyrene, fluorostyrene and iodostyrene, alkylstyrenes such as methylstyrene and 2,4-diethylstyrene, cyanostyrenes, hydroxystyrenes, nitrostyrenes, aminostyrenes and / or phenylstyrenes.
  • suitable (meth) acrylates are acrylic acid and methacrylic acid and their salts and esters. The alcohol component of these esters preferably contains 1 to 6 carbon atoms.
  • mixtures of such ethylenically unsaturated monomers can of course also be polymerized, provided that these can be polymerized.
  • Suitable catalysts are typically free radical initiators or redox catalysts.
  • Useful free radical catalysts are e.g. Common peroxides such as hydrogen peroxide, peracetic acid, butyl peroxide, dibenzoyl peroxide, perbenzoic acid and persulfates, perphosphates and peroxycarbonates.
  • Suitable redox catalyst systems are, for example, sodium persulfate / sodium formaldehyde sulfoxylate, cumene hydroperoxide / sodium metabisulfite, hydrogen peroxide / ascorbic acid and sulfur dioxide / ammonium persulfate.
  • Azo compounds such as 4,4'-azo-bis (cyanopentanoic acid) are also suitable.
  • the catalysts are used in conventional catalytically active concentrations.
  • further components customary for emulsion polymerization are used. These are e.g. Buffers and / or any other constituents which can be used in addition to the stabilizers and catalysts according to the invention in the emulsion polymerization reaction mixture and which are known from the prior art for emulsion polymerization processes.
  • the stabilizers which can be used according to the invention can be prepared immediately before the process according to the invention is carried out by suitable polymerization processes known to the person skilled in the art. This is preferably carried out in the same reaction container as the subsequent method according to the invention.
  • the invention further relates to polymer dispersions produced by the process described above.
  • These stable polymer dispersions are notable for high shear stability and improved water resistance of the films which can be produced therefrom. They contain 20 to 65% by weight of dispersed or emulsified homo- or copolymer based on ethylenically unsaturated monomers. In addition, 0.02 to 6.5% by weight of amphoteric polymers are contained as stabilizers, which is practical at their isoelectric point are insoluble in water. Neutralizing agents, catalysts and / or secondary products are contained in minor amounts, as are the additives, if desired, which are known and which are known to the person skilled in the art for emulsion polymerization, in conventional amounts. The rest, 100% by weight, is water.
  • the neutralizing agents contained are volatile and non-volatile acids or bases, the amount of the non-volatile neutralizing agent being chosen such that the polymer dispersion, after the volatile neutralizing agent has escaped, has approximately the pH of the isoelectric point of the stabilizer .
  • Polymer dispersions whose polymer particles have an average particle diameter of 0.05 ⁇ m to 3 ⁇ m, in particular of 0.1 ⁇ m to 1 ⁇ m, have particularly favorable properties.
  • the polymer dispersions or emulsion polymers prepared according to the invention have a wide range of uses. They are preferably used in adhesives, in particular for gluing paper and / or wood. Due to their high shear strength, the gloss effect and the increased water resistance of their films, the polymer dispersions are preferably used in finishing agents for textiles. For the same reasons, another preferred use is in the field of paper making and finishing.
  • the water resistance of the polymer films was checked by storing the 100 ⁇ m thick films on a glass plate in a closed, half-filled glass container.
  • the height of the water level was chosen so that one half of the film was immersed in water, while the other half only came into contact with the gas phase (with 100% humidity).
  • the duration of the experiment was 5 hours.
  • the water resistance of the films was assessed visually based on the degree of cloudiness of the film.
  • the films produced from the polymer dispersions according to Examples 1 and 2 were found to be completely waterproof in this test, i.e. they showed no cloudiness nor did they detach from the subsurface. This water resistance was also achieved if drying was carried out at 100 ° C. for 4 hours instead of 2 weeks at room temperature.
  • the test was carried out using a Klaxon stirrer, i.e. a circular disc with a diameter of approx. 2 cm, which is attached centrally and at right angles to the stirring axis. After stirring for 15 minutes at 10,000 revolutions / min, no coagulum formation was observed in either case.
  • Klaxon stirrer i.e. a circular disc with a diameter of approx. 2 cm, which is attached centrally and at right angles to the stirring axis. After stirring for 15 minutes at 10,000 revolutions / min, no coagulum formation was observed in either case.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

Selon un procédé de production de dispersions polymères stables, on provoque la polymérisation radicalaire par émulsion de monomères vinyliquement insaturés dans un milieu aqueux en présence d'un catalyseur et de polymères amphotères qui servent de stabilisants. Afin d'obtenir avec la dispersion polymère des films présentant une meilleure imperméabilité à l'eau et une forte brillance, on utilise comme stabilisant des polymères amphotères pratiquement insolubles dans l'eau à leur point isoélectrique. La polymérisation par émulsion est effectuée avec une valeur de pH qui diverge du point isoélectrique et qui est obtenue par adjonction de neutralisants volatils et non volatils.
PCT/EP1990/001970 1989-11-25 1990-11-17 Production de dispersions polymeres stables avec des polymeres amphoteres comme stabilisant WO1991008235A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3939034.9 1989-11-25
DE3939034A DE3939034A1 (de) 1989-11-25 1989-11-25 Herstellung stabiler polymerdispersionen mittels amphoterer polymerer als stabilisatoren

Publications (1)

Publication Number Publication Date
WO1991008235A1 true WO1991008235A1 (fr) 1991-06-13

Family

ID=6394178

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1990/001970 WO1991008235A1 (fr) 1989-11-25 1990-11-17 Production de dispersions polymeres stables avec des polymeres amphoteres comme stabilisant

Country Status (4)

Country Link
EP (1) EP0501980A1 (fr)
JP (1) JPH05501575A (fr)
DE (1) DE3939034A1 (fr)
WO (1) WO1991008235A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0731117A2 (fr) * 1995-03-09 1996-09-11 Vianova Resins GmbH Mélanges de polymères anioniques à formation de mousse diminuée dans l'eau
EP0810323A2 (fr) * 1996-05-31 1997-12-03 Elf Atochem S.A. Collage du papier au moyen de dispersions-latex de copolymères monomeres hydrophobes/polymères de type styrène-anhydride maléique à faible masse moléculaire
JP2008024755A (ja) * 2006-07-18 2008-02-07 Chuo Rika Kogyo Corp 熱可塑性樹脂水性分散液

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6090892A (en) * 1995-07-17 2000-07-18 Mitsui Toatsu Chemicals, Inc. Redispersible polymer and production process thereof
SG63772A1 (en) * 1996-11-05 1999-03-30 Hymo Corp Polymer dispersion method of manufacturing the same and use of the same
DE10310882A1 (de) * 2003-03-11 2004-09-23 Basf Ag Verwendung von wäßrigen Bindemitteln bei der Herstellung von Filtermaterialien
WO2017021917A1 (fr) * 2015-08-06 2017-02-09 Basf Se Dispersions polymères anioniques aqueuses, finement divisées, leurs procédés de préparation et leur utilisation à titre d'agents d'encollage dans la fabrication du papier

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1129284B (de) * 1960-05-04 1962-05-10 Basf Ag Verfahren zur Herstellung von stabilen Polymerisatdispersionen
EP0007042A1 (fr) * 1978-07-11 1980-01-23 Bayer Ag Procédé pour la préparation de latex de caoutchouc exempts d'agent émulsionnant
US4337185A (en) * 1980-06-23 1982-06-29 The Dow Chemical Company Process for making cationic structured particle latexes using reactive polymeric surfactants
DE3047688A1 (de) * 1980-12-18 1982-07-22 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung amphoterer copolymerisate und deren verwendung als emulsator
EP0150003A2 (fr) * 1984-01-18 1985-07-31 Bayer Ag Agent d'encollage cationique pour papier et procédé pour sa préparation
EP0250887A2 (fr) * 1986-05-30 1988-01-07 Nippon Paint Co., Ltd. Microparticules polymères réticulées internes avec structure de réseau tridimensionnelle

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1194638A (fr) * 1980-07-15 1985-10-01 Shinichi Ishikura Emulsification aqueuse de solides a l'aide d'un emulsifiant au polymere
DE3624813A1 (de) * 1986-07-23 1988-03-10 Stockhausen Chem Fab Gmbh Amphotere wasserloesliche polymere, verfahren zu ihrer herstellung und ihre verwendung als dispergierhilfsmittel

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1129284B (de) * 1960-05-04 1962-05-10 Basf Ag Verfahren zur Herstellung von stabilen Polymerisatdispersionen
EP0007042A1 (fr) * 1978-07-11 1980-01-23 Bayer Ag Procédé pour la préparation de latex de caoutchouc exempts d'agent émulsionnant
US4337185A (en) * 1980-06-23 1982-06-29 The Dow Chemical Company Process for making cationic structured particle latexes using reactive polymeric surfactants
DE3047688A1 (de) * 1980-12-18 1982-07-22 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung amphoterer copolymerisate und deren verwendung als emulsator
EP0150003A2 (fr) * 1984-01-18 1985-07-31 Bayer Ag Agent d'encollage cationique pour papier et procédé pour sa préparation
EP0250887A2 (fr) * 1986-05-30 1988-01-07 Nippon Paint Co., Ltd. Microparticules polymères réticulées internes avec structure de réseau tridimensionnelle

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0731117A2 (fr) * 1995-03-09 1996-09-11 Vianova Resins GmbH Mélanges de polymères anioniques à formation de mousse diminuée dans l'eau
EP0731117A3 (fr) * 1995-03-09 1997-10-22 Hoechst Ag Mélanges de polymères anioniques à formation de mousse diminuée dans l'eau
EP0810323A2 (fr) * 1996-05-31 1997-12-03 Elf Atochem S.A. Collage du papier au moyen de dispersions-latex de copolymères monomeres hydrophobes/polymères de type styrène-anhydride maléique à faible masse moléculaire
FR2749328A1 (fr) * 1996-05-31 1997-12-05 Atochem Elf Sa Collage du papier au moyen de dispersions-latex de copolymeres monomeres hydrophobes/polymeres de type styrene- anhydride maleique a faible masse moleculaire
EP0810323A3 (fr) * 1996-05-31 1997-12-10 Elf Atochem S.A. Collage du papier au moyen de dispersions-latex de copolymères monomeres hydrophobes/polymères de type styrène-anhydride maléique à faible masse moléculaire
JP2008024755A (ja) * 2006-07-18 2008-02-07 Chuo Rika Kogyo Corp 熱可塑性樹脂水性分散液

Also Published As

Publication number Publication date
EP0501980A1 (fr) 1992-09-09
JPH05501575A (ja) 1993-03-25
DE3939034A1 (de) 1991-05-29
DE3939034C2 (fr) 1993-04-22

Similar Documents

Publication Publication Date Title
DE3939918A1 (de) Polymere stabilisatoren fuer die emulsionspolymerisation
DE2840010C3 (de) Pfropfmischpolymerisate
DE2452585B2 (de) Verfahren zur Herstellung scherstabiler wäßriger Copolymerisat-Dispersionen
EP0121230A1 (fr) Copolymères contenant un ester d'acide crotonique, procédé de leur préparation et leur usage comme épaississant dans des systèmes aqueux et dans l'apprêtage
EP0080635B1 (fr) Dispersion de polymère aqueuse auto-réticulante
EP0058313B1 (fr) Agent d'encollage cationique pour papier et procédé pour sa préparation
DE4201604A1 (de) Fluorhaltige copolymerisate und daraus hergestellte waessrige dispersionen
EP0048320B1 (fr) Dispersions aqueuses de matières synthétiques sans émulsifiant
EP0150003A2 (fr) Agent d'encollage cationique pour papier et procédé pour sa préparation
EP0054231B1 (fr) Agents d'encollage du papier et leur procédé de fabrication
WO1991008235A1 (fr) Production de dispersions polymeres stables avec des polymeres amphoteres comme stabilisant
EP0027850A2 (fr) Polymère en émulsion agissant comme épaississant en milieu acide et son utilisation
EP0960889B1 (fr) Liant contenant des groupes phosphates ou phosphonates pour la protection contre la corrosion
DE3800845A1 (de) Pfropfcopolymerisate, ein verfahren zu deren herstellung und deren verwendung
EP0051144B1 (fr) Dispersions de polymères à fines particules comprenant des monomères contenant de l'azote polymérisé
DE2454397C2 (de) Verfahren zur Herstellung scherstabiler kationischer wäßriger Copolymerisat- Dispersionen
EP0845014B1 (fr) Polyacrylamide a faible poids moleculaire
EP0073296A1 (fr) Procédé de préparation de dispersions de résines synthétiques acryliques
EP0059262B1 (fr) Procédé de préparation d'un polymère en émulsion totalement soluble
EP0029144B1 (fr) Revêtement aqueux pour surfaces en bois
EP0736546A2 (fr) Dispersions aqueuses de polymères
DE69119134T2 (de) Wässrige Emulsionspolymere, hergestellt mit vernetzbaren nichtionischen Emulgiermitteln
DE19612483C2 (de) Copolymere
EP0351663B1 (fr) Polymères en émulsion
DE2446217C3 (de) Verfahren zur Oberflächenleimung von Papier

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1990916294

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1990916294

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1990916294

Country of ref document: EP