WO2000034362A2 - Procede permettant de preparer une dispersion polymere - Google Patents

Procede permettant de preparer une dispersion polymere Download PDF

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Publication number
WO2000034362A2
WO2000034362A2 PCT/NL1999/000736 NL9900736W WO0034362A2 WO 2000034362 A2 WO2000034362 A2 WO 2000034362A2 NL 9900736 W NL9900736 W NL 9900736W WO 0034362 A2 WO0034362 A2 WO 0034362A2
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WO
WIPO (PCT)
Prior art keywords
polymer
monomer units
process according
dispersion
dicarboxylic acid
Prior art date
Application number
PCT/NL1999/000736
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English (en)
Other versions
WO2000034362A3 (fr
Inventor
Hendrik Jan Van Den Berg
Mathijs Hubert Gertrudes Maassen
Original Assignee
Dsm N.V.
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Filing date
Publication date
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU16963/00A priority Critical patent/AU1696300A/en
Publication of WO2000034362A2 publication Critical patent/WO2000034362A2/fr
Publication of WO2000034362A3 publication Critical patent/WO2000034362A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • 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
    • 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
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates

Definitions

  • the invention relates to a process for the preparation of a polymer dispersion by converting a polymer containing ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units and vinyl monomer units in an aqueous medium at a temperature of at least 100 °C.
  • Disperse polymer phase is here understood to be a continuous liquid phase containing a disperse polymer phase.
  • a drawback of the known process is that it always leads to dispersions which remain stable only in a basic medium (pH > 7) . Strong dilution with water, like when the dispersion is added to a paper sizing composition, or a drop in the pH resulting from the addition of an acid component often leads to precipitation of polymer particles from the disperse phase.
  • Another drawback of the known process is that it leads to dispersions m which the polymer is entirely or almost entirely lmidised, because the dicarboxylic acid monomer units m the polymer are converted into dicarboxylic lmide units with the ammonia present.
  • compositions for paper sizing leads to a composition that insufficiently reduces paper's property of absorbing water and neither does the use of this composition for paper sizing result m paper with good mkjet -printing properties for example with respect to wickmg, bleeding and blackness.
  • the invention aims to provide a dispersion which does not or virtually not possess the aforementioned drawbacks.
  • this aim is achieved because the preparation is carried out in the presence of a caustic solution.
  • the process according to the invention can be excellently used to obtain a dispersion that can be substantially diluted with water, or to which acid components can be added without the disperse polymer phase precipitating.
  • Another advantage is that the process according to the invention can be excellently used to obtain a dispersion in which not all or virtually all the ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units are lmidised.
  • a lower degree of lmidation leads to a dispersion which, when used in a paper sizing, results in a paper sizing composition that sufficiently reduces paper's property of absorbing water and the use of this composition moreover results in paper with good ink ⁇ et- printing properties.
  • Another advantage of the process according to the invention is that it can be carried out without a strong ammonia odour being released.
  • dispersions can be obtained which do not, or virtually not, smell of ammonia.
  • Another advantage of the process according to the invention is that use can be made of polymers which could hitherto not or poorly be dissolved or dispersed in an aqueous medium.
  • a known drawback of a solution of a polymer containing ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units and vinyl monomer units is its strong tendency to stabilise any foam formed in a paper sizing composition.
  • a paper sizing composition containing the dispersion obtainable with the process according to the invention does however not stabilise any foam formed, which substantially improves the preparation and application of such a composition.
  • a 'caustic solution' is understood to be a solution of LiOH, NaOH or KOH or mixtures thereof in an aqueous medium.
  • aqueous medium Preferably use is made of KOH or NaOH.
  • Other solvents besides water may optionally be present during the preparation of the dispersion. Preferably, however, water is used.
  • the amount of caustic solution that must be used in the process according to the invention is a function of the amount of polymer and the amount of ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units and can be easily determined by a person skilled in the art.
  • the amount of caustic solution is chosen so that between 0.01 and 2.0 mol OH ⁇ ions per mol of ⁇ - ⁇ unsaturated dicarboxylic acid monomer units is present at the beginning of the preparation. Less than 0.01 mol OH- ions per mol of ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units present in the polymer results in impractically low reaction rates.
  • the amount of caustic solution is chosen so that between 0.1 and 1.0 mol OH " ions per mol of ⁇ - ⁇ - unsaturated dicarboxylic acid monomer units present in the polymer is present at the beginning of the preparation. Between those limits for the OH " concentration the reaction proceeds well and dispersions with a pH ⁇ 7 can be obtained.
  • the hydrophobicity index is here defined as: (A/B) . C, where A is the amount of OH " ions in mol present at the beginning of the preparation and B the amount of ⁇ - ⁇ - unsaturated dicarboxylic acid monomer units in mol present in the polymer at the beginning of the preparation, and C is the molar percentage of ⁇ - ⁇ - unsaturated dicarboxylic acid monomer units in the polymer that is converted.
  • the ratio of the caustic solution and the amount of ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units present in the polymer is in all cases such that sufficient hydrophobic groups are formed in the polymer, so that a dispersion is obtained.
  • the process according to the invention is characterised in that the preparation is carried out in the presence of at most 1 mol NH3 per mol of ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units present in the polymer.
  • the use of at most 1 mol NH3 per mol of ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units present in the polymer results in a viscous mass in the reactor, which is difficult to stir, before a dispersion is formed. This phase which is difficult to stir hinders a simple, reliable process control.
  • a caustic solution and at most 1 mol NH3 per mol of ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units present in the polymer such a phase that is difficult to stir no longer occurs.
  • the process is characterised in that the preparation is carried out in the presence of between 0.2 and 0.75 mol NH3 per mol of ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units present in the polymer.
  • the process according to the invention is carried out so that at most 75% of the ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units initially present in the polymer is imidised.
  • Dispersions prepared according to this last preferred embodiment are excellently suitable for being added to a paper sizing composition because the resulting compositions then possess even better inkje -printing properties and are moreover much less sensitive to changes in pH in the composition than compositions that contain dispersions prepared in the absence of a caustic solution. Changes in the pH of such compositions may occur when components are added to the composition, such as starch solutions or anti- foaming agents.
  • the polymer contains ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units and vinyl monomer units, ' ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units' are here understood to be dicarboxylic anhydride groups and/or dicarboxylic acid groups containing monomer units.
  • anhydride groups containing monomer units are used.
  • Suitable ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units are for example maleic anhydride (MA) , maleic acid, itaconic acid, itaconic anhydride, fumaric acid and fumaric anhydride.
  • the polymer contains maleic anhydride monomer units as the ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units.
  • Suitable vinyl monomer units are for example vinyl -aromatic monomer units or vinyl monomer units containing at least 4 carbon atoms.
  • the polymer contains as the vinyl monomer units vinyl - aromatic monomer units such as for example units of styrene and/or ⁇ -methyl styrene.
  • the polymer contains styrene units as the vinyl monomer units.
  • a copolymer that contains vinyl monomer units and ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units can be prepared with the aid of the known processes, for example with the aid of the process described for the preparation of a copolymer of MA monomer units and styrene by Hanson and Zimmerman, Ind. Eng. Chem., vol. 49, No. 11 (1957), pp .1803 -1807.
  • the molar percentage of ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units in the polymer can vary within a wide range, for example between 5 and 50 mol . % . In a preferred embodiment the polymer contains 10-40 mol . % ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units .
  • the molar weight of the polymer may vary within a wide range.
  • a polymer preferably has a weight average molecular weight of higher than 80,000 kg/kmol . The weight average molecular weight is preferably lower than 180,000 kg/kmol.
  • solutions of polymers containing ⁇ - ⁇ -unsaturated dicarboxylic acid monomer units and vinyl monomer units are very viscous when the polymers have a relatively high molecular weight and the solutions have a relatively high solid substance content (SSC) .
  • a dispersion obtainable with the process according to the invention may however have a high solid substance content while the viscosity remains low, even when the dispersion has been prepared from a polymer with a relatively high molecular weight.
  • the amount of time required to prepare a dispersion from the polymer will depend on the chosen temperature, the reactor, the amounts of reagents and the like. In the case of a relatively low concentration of caustic solution it will take longer for a dispersion to be formed and the conversion of the polymer may be incomplete.
  • the process according to the invention can be carried out in pressure vessels of many different types.
  • the pressure vessel is fitted with means for stirring.
  • the process according to the invention is characterised in that the preparation is carried out at a temperature of between 120 and 180°C.
  • a lower reaction temperature generally results in longer reaction times. Higher temperatures can lead to decomposition of the polymer.
  • An emulsifier can be added to the reaction mixture. Suitable emulsifiers are for example the sodium salt of (C1 Q -C13) alkylbenzene sulphonic acid, stearyldimethylbenzylammonium chloride and ethylene oxide-propylene oxide copolymers .
  • the invention also relates to a dispersion obtainable with the process according to the invention.
  • a dispersion obtainable with the process according to the invention is characterised in that the dispersion has a pH ⁇ 7.
  • the average hydrodynamic radius of the polymer particles in the dispersions obtainable with the process according to the invention may vary considerably, and lies for example between 10 and 300 nanometres (nm) .
  • a dispersion obtainable with the process according to the invention is characterised m that the dispersion contains polymer particles with an average hydrodynamic radius of between 10 and 100 nm.
  • the hydrodynamic radius can be measured with the aid of photon correlation spectroscopy (PCS) .
  • PCS photon correlation spectroscopy
  • paper sizing compositions contain one or more of the usual additives.
  • the composition according to the invention is characterised m that it contains starch as an additive.
  • the composition preferably contains an amount of dispersion such that the amount of polymer, that is, the dry weight of polymer particles in the dispersion, is between 0.2 and 10 wt.%, relative to the dry weight of the other usual additives. More preferably a paper sizing composition contains between 1 and 6 wt.% dry weight of polymer particles, relative to the dry weight of starch.
  • a composition can for example be prepared by adding a certain amount of the dispersion according to the invention to a solution of the other additives in water.
  • the invention also relates to paper provided with a paper sizing composition according to the invention.
  • the invention also relates to the use of a dispersion according to the invention m a papersizmg composition, and m particular to the use of dispersions prepared with both a caustic solution and NH 3 m a papersizmg composition.
  • the desired amounts of starting materials were combined in a 10-litre autoclave.
  • the autoclave was fitted with a stirrer and with means for taking samples from the reactor during the reaction.
  • the pressure in the autoclave was then raised with the aid of N2 to a pressure of 4.10 5 Pa (it is, however, not necessary to create excess pressure) .
  • Stirring was effected at a speed of 300 rpm.
  • the autoclave was heated until the desired reaction temperature was reached. The pressure meanwhile rose. After a certain amount of time the reaction was stopped by lowering the reaction temperature to room temperature.
  • the total mass of the starting materials in the autoclave at the beginning of the reaction was about 7.5 kg.
  • the total amount of starting materials used has no or virtually no influence on the result of a preparation.
  • the average hydrodynamic radius of the polymer particles was determined with the aid of photon correlation spectroscopy (PCS) .
  • PCS photon correlation spectroscopy
  • the measurements were conducted using a set-up from ALV-Lasermaschinesgesellschaf mbH from Langen, Germany (Coherent Innova 90 ion- argon laser; the blue line was used (488 nm) , power 50 mW) .
  • the signal was recorded with the aid of a photon multiplier from Thorn-Emi, mounted on an ALV/SP-86#053 laser goniometer (supply voltage of the photon multiplier was approximately 1700 V, measuring angle 90°) .
  • the signal was processed by an ALV 5000 Multiple Tau digital correlator fitted with the ALV5000/E for Windows software.
  • the cumulant analysis method was used to process the measured data and the Stokes-Einstein relation was used to derive a hydrodynamic radius from the measured diffusion coefficient.
  • the samples were diluted in demineralised water that had previously been filtered through a filter with openings having a diameter of 0.2 ⁇ m.
  • the samples that were obtained after a process according to the invention were diluted 500 times (to a concentration of approx. 0.04 wt.% solid substance or less) and the samples that were obtained after a comparative experiment were diluted 50 times, to approx. 0.4 wt.% solid substance.
  • the measuring cell was rinsed with dust -free water and then three times with the sample solution to be measured. Some samples, obtained in the comparative experiments, were not stable in water.
  • a buffer with a pH of 9 ⁇ 0.02 (Titrisol from Merck) or a 10 "3 M aqueous NaOH solution was used to stabilise these samples.
  • the results of the PCS measurements are given in the various tables.
  • Solid substance content The solid substance content (SSC) was determined with the aid of an infrared drying/weighing apparatus, type Mettler LP16/PM600. If polymer was still present after the reaction, it was removed through filtration through a paper filter (MN640m medium retention and filtration speed from Macherey-
  • pH measurements pH values were measured with a Knick 752 Cl pH meter, No. 051489.
  • the pH meter was calibrated at 20 °C using buffer solutions having pH values of 4.00 (citrate/HCl buffer), 7.00 and 9.00, respectively, from Merck, and was fitted with a glass electrode (3M KC1) .
  • the pH of the samples was determined at 20°C. If the solid substance content was higher, and hence also the viscosity, the samples of comparative experiments were diluted to a solid substance content of approximately 10 wt.%. Dispersions were not diluted.
  • the degree of imidation of the aqueous dispersions can for example be measured with the aid of Raman-FTIR spectroscopy by relating the intensities of absorptions to the intensities of the same absorptions measured for a completely imidised and a completely ummidised reference compound.
  • the signals were standardised m relation to the absorption signals of the aromatic rings in the polymer chains. The following absorption bands were considered in the performed measurements :
  • % styrene with an NH3:MA molar ratio of 3:1, at 50°C (no lmide groups), and an imidised SMA powder prepared by mixing 2 g of SMA (28 wt.% MA; 72 wt.% styrene; molar weight 110,000 kg/kmol) with 0.50 g of urea in a twin-screw mim- extruder at 240°C for 5 minutes, at a speed of 100 rpm.
  • the glass transition temperature of the imidised SMA powder was 193 °C.
  • the degree of imidation calculated from the Raman absorptions corresponded well to the degree of imidation that can be calculated from the amount of ammonia that was added to the reaction mixture in the preparation of the different dispersions .
  • Table 1 presents the results of a number of preparations (carried out in the absence of NH3 ) and a number of reaction parameters.
  • the reaction time indicates the amount of time that lapsed between the moment that the reaction temperature was reached and the moment that cooling was initiated.
  • Table 2 presents the results of a number of preparations carried out in the presence of NH3.
  • Table 3 presents the results of a number of preparations prepared with different polymers .
  • Relative Scattering Intensity Scattering intensity * dilution factor/solid substance content.
  • the polydispersity index (PDI) is calculated according to the following formula: (width of the particle size distribution at half height ) 2 / (average hydrodynamic radius) 2 ) . From the PDI values obtained and values of the average hydrodynamic radii it follows that the different dispersions have different particle sizes and different particle size distributions. This is also evident from the intensities of the different signals. It is not exactly known what the polymer particles in the different dispersions look like.
  • Paper sizing compositions were prepared by successively mixing 8.5 wt.% starch (Perfectamyl A4692 supplied by AVEBE, the Netherlands) , relative to the solution's total weight, with demineralised water, adding a dispersion as described in Tables 1 and 2 to the solution thus formed so that the amount of polymer (in dry condition) was 2 wt.% relative to the amount of starch (in dry condition) .
  • An amount of paper sizing composition corresponding to 2.6 g/m 2 of polymer and starch was applied on two sides with the aid of a size press.
  • a size press comprises two rolls lying against one another. Between the rolls, above the rolls' area of contact, is a kind of slot because the rolls touch each other only at their widest points.
  • the paper sizing composition is applied in that slot, at the top between the two rolls.
  • a sheet of paper was passed between the two rolls, the sheet hence first passing through the paper sizing composition and then being passed between the two rolls.
  • the treated paper was then dried to a constant weight .
  • Paper's ability to absorb water was measured according to DIN EN 20535 and expressed as the Cobbgo value, in g/m 2 .
  • the Cobbgo value must be relatively low.
  • the printing properties such as wicking, bleeding and blackness were determined with the aid of a Hewlett- Packard (HP) 560 inkjet-printer, according to the HP testing criteria for a HP 560 printer (these criteria are obtainable from Hewlett Packard) , with the ink being water-soluble and suitable for a HP inkjet- printer of the type used.
  • HP Hewlett- Packard
  • the printing property "wicking” is a measure of the sharpness of the edges of characters printed on paper and "bleeding” is a measure of the extent to which the characters (that is, the ink used to print the characters on the paper) bleed.
  • bleeding can lead to mixing of colours at the boundaries of areas of different colours.
  • Another criterion is the blackness of characters that have been printed on a sheet of paper treated for paper sizing with a black ink containing carbon black or with a combination of inks of different colours, which combination appears black to the eye. On the whole, a deep black colour is preferred for the characters to a less black or even grey colour.
  • Table 4 shows that the untreated paper is very poorly printable (wickmg and bleeding) .
  • a surface treatment using only a starch solution improves the pnntability (wickmg en bleeding) , but because of the greatly increased ability to absorb water (which is evident from a high Cobb60 value) the ink is absorbed into the paper too much, as a result of which the blackness of characters printed onto it is insufficient.
  • Adding a dispersion obtainable with the process according to the invention to the paper sizing composition results in a low Cobb60 value. It is also clear from Table 4 that a paper sizing composition that contains a partly imidised dispersion results in better inkjet -printing properties than a composition that contains an unimidised dispersion.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé qui permet de préparer une dispersion polymère. Le procédé consiste à convertir un polymère, contenant des unités d'un monomère d'acide dicarboxylique α-β insaturé et des unités d'un monomère de vinyle, dans un milieu aqueux, à une température d'au moins 100 °C et en présence d'une solution caustique. Les dispersions obtenues par ce procédé peuvent avoir un caractère acide ou basique.
PCT/NL1999/000736 1998-12-08 1999-12-02 Procede permettant de preparer une dispersion polymere WO2000034362A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU16963/00A AU1696300A (en) 1998-12-08 1999-12-02 Process for the preparation of a polymer dispersion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1010757 1998-12-08
NL1010757A NL1010757C2 (nl) 1998-12-08 1998-12-08 Werkwijze voor de bereiding van een polymeerdispersie.

Publications (2)

Publication Number Publication Date
WO2000034362A2 true WO2000034362A2 (fr) 2000-06-15
WO2000034362A3 WO2000034362A3 (fr) 2000-11-16

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NL (1) NL1010757C2 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1454925A1 (fr) * 2003-03-04 2004-09-08 DSM IP Assets B.V. Procédé de préparation d'une dispersion aqueuse d'un polymère, dispersions ainsi préparées et leur utilisation
WO2011098574A1 (fr) 2010-02-12 2011-08-18 Topchim N.V. Dispersion de polymère aqueux contenant des nanoparticules dispersées et procédé de préparation de celle-ci

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1720746A1 (de) * 1967-11-04 1971-07-15 Bayer Ag Verfahren zur Herstellung von cyclische Imidgruppen enthaltenden emulgatorfreien Polymerisatlatizes
US3798194A (en) * 1968-10-07 1974-03-19 Dow Chemical Co Preparation of latexes by direct dispersion of acidic organic polymers into aqueous alkaline media containing certain alkanols
EP0003240A1 (fr) * 1977-12-28 1979-08-08 Union Carbide Corporation Emulsions de résines vinyliques et leur utilisation comme compositions d'enduction
US4324872A (en) * 1980-11-24 1982-04-13 Gulf Oil Corporation Alkali soluble blends of an ionomer resin and an alkenyl succinic anhydride
GB2269822A (en) * 1992-08-17 1994-02-23 Oxy Wax Limited Method of preparing an aqueous dispersion

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3160400B2 (ja) * 1992-12-22 2001-04-25 三井化学株式会社 塗被紙用組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1720746A1 (de) * 1967-11-04 1971-07-15 Bayer Ag Verfahren zur Herstellung von cyclische Imidgruppen enthaltenden emulgatorfreien Polymerisatlatizes
US3798194A (en) * 1968-10-07 1974-03-19 Dow Chemical Co Preparation of latexes by direct dispersion of acidic organic polymers into aqueous alkaline media containing certain alkanols
EP0003240A1 (fr) * 1977-12-28 1979-08-08 Union Carbide Corporation Emulsions de résines vinyliques et leur utilisation comme compositions d'enduction
US4324872A (en) * 1980-11-24 1982-04-13 Gulf Oil Corporation Alkali soluble blends of an ionomer resin and an alkenyl succinic anhydride
GB2269822A (en) * 1992-08-17 1994-02-23 Oxy Wax Limited Method of preparing an aqueous dispersion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 9431 Derwent Publications Ltd., London, GB; Class A18, AN 94-253473 XP002113192 & JP 06 184994 A (MITSUI TOATSU CHEM INC), 5 July 1994 (1994-07-05) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1454925A1 (fr) * 2003-03-04 2004-09-08 DSM IP Assets B.V. Procédé de préparation d'une dispersion aqueuse d'un polymère, dispersions ainsi préparées et leur utilisation
WO2011098574A1 (fr) 2010-02-12 2011-08-18 Topchim N.V. Dispersion de polymère aqueux contenant des nanoparticules dispersées et procédé de préparation de celle-ci

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WO2000034362A3 (fr) 2000-11-16
NL1010757C2 (nl) 2000-06-19
AU1696300A (en) 2000-06-26

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