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WO1998004593A1 - Resine acrylique solide utilisant un reacteur tubulaire continu - Google Patents

Resine acrylique solide utilisant un reacteur tubulaire continu Download PDF

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Publication number
WO1998004593A1
WO1998004593A1 PCT/US1997/011727 US9711727W WO9804593A1 WO 1998004593 A1 WO1998004593 A1 WO 1998004593A1 US 9711727 W US9711727 W US 9711727W WO 9804593 A1 WO9804593 A1 WO 9804593A1
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WO
WIPO (PCT)
Prior art keywords
styrene
feedstock
acrylic resin
reactor
polymerization initiator
Prior art date
Application number
PCT/US1997/011727
Other languages
English (en)
Inventor
George Roth
George A. Smith
Reuben Grinstein
Paul D. Whyzmuzis
Shruti Singhal
Steve Boucher
Brenda Taipale
Roger Lovald
David Devore
Jim Yosh
Original Assignee
Henkel Corporation
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 Corporation filed Critical Henkel Corporation
Priority to AU36518/97A priority Critical patent/AU3651897A/en
Publication of WO1998004593A1 publication Critical patent/WO1998004593A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • 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
    • C08F2/02—Polymerisation in bulk

Definitions

  • the field of this invention is a process for making acrylic resins suitable as polymeric surfactants used in emulsion polymerization, as pigment grinding resins and for preparing dispersions used as overprint varnishes.
  • Poly ( ⁇ -methyl styrene-co-acrylic acid-co-styrene), an acrylic resin is used as a polymeric surfactant in emulsion polymerizations, as a pigment grinding resin and for preparing dispersions used to make overprint varnishes.
  • the resin is suspended in water and made into a dispersion, also known as a latex, by neutralizing it with a base such as 28% ammonium hydroxide.
  • the base allows the acrylic resin to form polymeric surfactant micelles which have two chief advantages over solvent based systems. Firstly, they have lower viscosity, which is especially evident in high-solids systems More importantly, however, is that being substantially solvent free, they are more environmentally friendly than solvent-based systems.
  • the acrylic resin has been made by bulk polymerization in a continuous-stirred tank reactor (CSTR).
  • CSTR continuous-stirred tank reactor
  • the CSTR is charged with styrene, ⁇ - methyl styrene, acrylic acid, a polymerization initiator and a solvent or just with styrene, ⁇ -methyl styrene and acrylic acid Reaction temperatures range from 180°C to 300°C and residence times are from 1 to 60 minutes. Of course, level control is very important. However, pressure is not controlled The once- through percent conversion is on the order of 75%.
  • the acrylic resin/unreacted monomer reaction product is sent to a devolatilizer for stripping of unreacted monomers for reuse. What emerges from the devolatilizer is the desired acrylic resin, suitable for flaking, pelletizing, pulverization, etc.
  • the continuous tube reactor also known as the linear flow reactor, has seen wide use in polymerizations because of its simplicity No level controls are required, and because there is no stirring, there is no need for expensive, rotating seals capable of withstanding the pressure, temperature and solvent effects of the reaction.
  • CTR continuous tube reactor
  • acrylics it has been used in suspension polymerizations; the monomers employed are usually water soluble.
  • the invention is a bulk polymerization process for preparing a solid acrylic resin, which comprises the steps of: charging into a continuous tube reactor, a feedstock of at least one vinylic monomer and a polymerization initiator; maintaining a flow rate through the reactor sufficient to provide a residence time of the feedstock in the reactor of from about one minute to about one hour; maintaining a pressure of about 80 psig to about 500 psig; maintaining the resulting molten resin mixture with a heat transfer medium within the range from about 180°C to a maximum of about 260°C; and devolatilizing the molten resin mixture exiting the reactor to remove unreacted monomers to provide a solid acrylic resin upon cooling.
  • a preferred embodiment comprises the additional step of recycling the unreacted monomers recovered during the devolatilization step and charging them into the continuous tube reactor as a fraction of the feedstock.
  • An environmental benefit of the invention ts that, for many embodiments, no solvent is required to make the resin and coating systems made from it are predominantly water based, rather than solvent based.
  • the monomers are polymerized using a single-pass flow-through tubular reactor.
  • a monomer blend and a polymerization initiator blend are separately introduced and then combined via stainless steel tubing
  • the monomer blend may be preheated by pumping through a preheating section of tubing which is dipped into an oil bath set for a preselected temperature.
  • the preheating ensures that the temperature of the monomer blend will be increased to a desired initiation temperature level prior to entering the tubular reactor
  • the preheating step is not essential to the process
  • the combined flows then enter a static mixer where the two streams are homogeneously mixed.
  • the reactor consists of a single tube or a series of tubes of increasing diameter bound in a coil with a single pass.
  • the tubes are plain with no static mixer or other mixing elements therein or in combination therewith after the combined flows enter the tubular reactor
  • the coil is immersed into a circulating oil bath preset at the desired temperature Initiation and polymerization occur as the combined flows enter the tubular reactor, conversion is high and the reaction is
  • the single-pass flow-through tubular reactor will efficiently accomplish the desired result under the stated conditions
  • the particular reactor used for the following examples is constructed of five 20 foot lengths of Va inch outside diameter (O.D.) tube, three lengths of 20 foot 3/4 inch O.D. tube and two lengths of 1 inch O.D, tube, all 18 gauge 316 stainless steel. They are joined in series and contained in a shell that is 21 feet long and 8 inches in diameter which contains recirculating hot oil as the heat
  • the design details are not particularly critical, and the reactor size can be scaled up or down within limits.
  • the back pressure of the reactor is sensitive to the tube diameter, length and roughness, the number and radii of the connections as well as the changing Theological properties of the reaction mixture as it is converted to polymer as it travels the length of the tubing
  • the optimal pressure control for each reactor design must be developed experimentally as the conversion rate, as will be seen, is a strong function of the pressure in a CTR
  • the minimum pressure which is about 80 psig, should be higher than the vapor pressures of the monomers at the heating oil temperature The upper bound will depend on the
  • the optimal pressure range is from about 100 to about
  • the conversion can vary from 60% to 99%
  • the pressure is not a variable independent of the temperature
  • the pressure in a CTR may be a variable that is at least partially independent of the temperature
  • the formation of at least some vapor phase has been observed through a transparent tube reactor as transient foaming at the initiation of polymerization, it has been suggested that perhaps the continuous dynamic phase change in the CTR inhibits the establishing of thermodynamic equilibrium within the reactor Beyond this, it can only qualitatively be stated that lower pressures increase vapor fraction and therefore reduce the residence time, hence the conversion
  • the pressure should be simultaneously optimized with both temperature and residence time If the heat transfer fluid temperature is controlled to a maximum of 260 ⁇ C
  • the lower bound for the temperature is about 180°C. At this temperature, conversion is so slow that residence times become uneconomically long and the viscosities are too high to handle
  • the preferred temperature range for this reactor and monomer/initiator mixture is from about 204°C (400 ⁇ F) to about 260°C (500°F), more preferred is 210°C (410°F) to about 246°C (475°F) It may reasonably be expected that a longer tube will require lower temperature for equal conversion, while larger O.D or thicker walls might necessitate higher temperatures Note that while the heat transfer fluid is limited to 260°C, the stream at the reactor exit can be as high as
  • the residence time lower limit is bounded by about 1 minute, conversion
  • the preferred dwell time for this reactor is optimized simultaneously with the pressure and temperature, as described above, and is about 150 to about 250 seconds. While no solvent is required, solvent can, of course, be added Glycol ethers are the class of solvents most commonly encountered, dtethylene glycol monoethylether and diethylene glycol dimethyl ether are examples and they are typically used at levels of up to 25%
  • the feedstock should comprise at least one unreacted vinyiic monomer. It is further preferred that the feedstock comprises a blend of vinyiic monomers containing at least one acrylic monomer and at least one monoalkenyl aromatic monomer Monoalkenyl aromatic monomers that can be used include vinyl toluene, para-methyl-styrene, tert-butyl-styrene and chlorostyrene, but preferred are styrene and ⁇ -methyl-styrene Acrylic monomers that may be used include acrylic and methacrylic acid and their esters and derivatives.
  • Acrylic acid is preferred
  • the preferred blend comprises styrene, ⁇ -methyl styrene and acrylic acid
  • Styrene and ⁇ -methyl styrene are hydrophobic, while acrylic acid is hydrophilic, especially when neutralized to a salt
  • the hydrophobic portion must have a certain
  • hydrophilicity can be increased via neutralization
  • the composition range of styrene plus ⁇ -methyl styrene versus acrylic acid that has produced successful dispersions is about 50 to about 80 wt.% styrene plus ⁇ -methyl styrene and about 18 to about 40 wt.% acrylic acid, balance being initiator and any solvent
  • the ratio of styrene to ⁇ -methyl styrene is broader, as both are of the same character, hydrophobic, and may vary from about 2.5.1 to about 20:1.
  • the preferred ranges are about 25 to 60 % styrene, about 2 to 35 % alpha-methyl styrene and about 25 to 50 % acrylic acid. Recycling of the monomers recovered from the reaction mass exiting the reactor as distillate from the devolatilization step is a preferred embodiment. As will be seen in the examples, the properties of the acrylic resins so produced, especially glossiness of the coatings made therefrom, are significantly improved. Typically, about 10wt % of the feed consists of recycled monomer, however, at least about 80 wt.% of the recovered monomers can be recycled. The recycled monomers may require pre-processing such as purification
  • the polymerization initiator is of the free radical type with a half-life ranging from about 1 to about 10 hours at about 90 to about 100°C.
  • initiators with half-lives of about 10 hours at about 100°C may be azo-type, such as azo-bis isobutyronitrile (AIBN), 1-tert-amylazo-1- cyanocyclohexane and 1 -tert-butylazo-1 -cyanocyclohexane. They may also be peroxides and hydroperoxides such as tert-butylperoctoate, tert- butylperbenzoate, dicumyl peroxide and tert-butyl hydroperoxide. Preferred are di-tert-butyl peroxide and cumene hydroperoxide.
  • the quantity of initiator typically used ranges from 0.0005:1 to 0.06:1 moles initiator per mole monomer.
  • di-tert-butyl peroxide When di-tert-butyl peroxide is used it is preferred that it is at about 0.002 to 0.05 mole ratio, preferably from 0.003 to 0.04 mole ratio.
  • reaction product exits the CTR, it is devolatilized to separate the molten acrylic resin, which can be flaked or pelletized after cooling. This then can be used to prepare dispersions.
  • a typical formula would be prepared as follows:
  • Charge #1 is 201.52 g acrylic resin, 102.16 g de-ionized (Dl) water, 4.99 g
  • Charge #2 is 146.58 g styrene and 27.60 g 2-ethylhexylacrylate.
  • Charge #3 is 1.99 g ammonium persulfate and 5.30 g Dl water.
  • Charge #4 is 1.24 g t-butyl hydroperoxide (70%).
  • the reactor is blanketed with nitrogen to quench any free radicals present; nitrogen is not involved in the actual resin chemistry in any way.
  • Examples 1 through 10 explore variations of the reaction parameters, particularly pressure, on the percent conversion (one-pass yield) and the properties of coatings made from dispersions prepared from the acrylic resins produced by the CTR Example 11 describes a preferred embodiment wherein the monomers are recycled and surprisingly form a product not only better than that had from virgin monomers, with respect to gloss on white, but also superior to the nearest commercial equivalent, Joncryl 678 Joncryl's properties as a control are shown in example 1
  • Example 12 shows the effect of varying monomer ratios on the yield obtained, as well as the highest yield obtained All percents are weight percents and all molecular weights are weight average
  • the composition of Joncryl 678 is believed to be about 30% styrene, 40% ⁇ -methyl styrene and 30% acrylic acid.
  • a dispersion was made from the experimental resin by the technique described above but neutralizing to pH 9.32. The final dispersion was 49.02% solids. Its viscosity was 530 cps, the particle size was 94.1 nm, while the gloss on black was 91.3 and the gloss on white was 82.
  • the coatings were evaluated for gloss by conventional means, i.e.
  • EXAMPLE 2 The same feedstock was used as in experiment 1. The residence time was 250 seconds, the pressure was 150 psig and the temperature was 238°C
  • the conversion was 81.8%.
  • the resulting resin had a weight average molecular weight of 7582, an acid value of 249 and a glass transition temperature (Tg) of 114°C.
  • Tg glass transition temperature
  • the dispersion was made as above, neutralized to pH 9.34. The final dispersion was 49.98% solids. Its viscosity was 510 cps, the particle size was 83.2 nm, while the gloss on black was 95,8 and the gloss on
  • the same feedstock was used as in experiment 1.
  • the residence time was 150 seconds, the pressure was 130 psig and the temperature was 238°C (460°F).
  • the conversion was 61.8%.
  • the resulting resin had a weight average molecular weight of 8098, an acid value of 255 and a glass transition temperature (Tg) of 127°C.
  • the dispersion was made as above, neutralized to pH 9.10.
  • the final dispersion was 49.48% solids. Its viscosity was 875 cps, the particle size was 74.5 nm, while the gloss on black was 93.5 and the gloss on white was 94.6.
  • EXAMPLE 4 The same feedstock was used as in experiment 1. The residence time was 250 seconds, the pressure was 130 psig and the temperature was 238°C (460° F). The conversion was 75.4%. The resulting resin had a weight average molecular weight of 8096, an acid value of 254 and a glass transition temperature (Tg) of 120.57°C. The dispersion was made as above, neutralized to pH 9.34. The final dispersion was 49.98% solids. Its viscosity was 440 cps, the particle size was 90.1 nm, while the gloss on black was 93.5 and the gloss on white was 75.0. EXAMPLE 5
  • the same feedstock was used as in experiment 1
  • the residence time was 150 seconds, the pressure was 150 psig and the temperature was 238 °C (460° F)
  • the conversion was 65.9%
  • the resulting resin had a weight average molecular weight of 7518, an acid value of 257 and a glass transition temperature (Tg) of 124°C
  • Tg glass transition temperature
  • the dispersion was made as above, neutralized to pH 948
  • the final dispersion was 51.24% solids Its viscosity was 1350 cps, the particle size was 65 nm, while the gloss on black was 95.8 and the gloss on white was 71.6
  • the same feedstock was used as in experiment 1
  • the residence time was 250 seconds, the pressure was 130 psig and the temperature was 227 °C (440°F)
  • the conversion was 82%
  • the resulting resin had a weight average molecular weight of 8339, an acid value of 250 and a glass transition temperature (Tg) of 128°C
  • Tg glass transition temperature
  • the dispersion was made as above, neutralized to pH 870
  • the final dispersion was 47.85% solids Its viscosity was 303 cps, the particle size was 71 9 nm, while the gloss on black was 95 1 and the gloss on white was 88.6
  • EXAMPLE 7 The same feedstock was used as in experiment 1 The residence time was 150 seconds, the pressure was 150 psig and the temperature was 227 °C (440°F) The conversion was 72.2% The resulting resin had a weight average molecular weight of 7093, an acid value of 256 and a glass transition temperature (Tg) of 118°C The dispersion was made as above, neutralized to pH 844 The final dispersion was 50.38% solids Its viscosity was 535 cps, the
  • EXAMPLE 8 The same feedstock was used as in experiment 1 The residence time was 250 seconds, the pressure was 150 psig and the temperature was 227°C (440°F) The conversion was 864% The resulting resin had a weight average molecular weight of 7809, an acid value of 249 and a glass transition temperature (Tg) of 111 °C The dispersion was made as above, neutralized to pH 8.35 The final dispersion was 48.61% solids Its viscosity was 323 cps, the
  • the same feedstock was used as in experiment 1
  • the residence time was 150 seconds, the pressure was 130 psig and the temperature was 227°C (440°F)
  • the conversion was 650%
  • the resulting resin had a weight average molecular weight of 7783, an acid value of 258 and a glass transition temperature (Tg) of 125°C
  • Tg glass transition temperature
  • the dispersion was made as above, neutralized to pH 849
  • the final dispersion was 4885% solids Its viscosity was 595 cps, the particle size was 65 5 nm, while the gloss on black was 92 5 and the gloss on white was 99.5.
  • the same feedstock was used as in experiment 1.
  • the residence time was 200 seconds, the pressure was 140 psig and the temperature was 232 °C (450 C F).
  • the conversion was 75.4%.
  • the resulting resin had a weight average molecular weight of 7944, an acid value of 253 and a glass transition temperature (Tg) of 114°C.
  • the dispersion was made as above, neutralized to pH 8.54.
  • the final dispersion was 49.15% solids. Its viscosity was 475 cps, the particle size was 72.9 nm, while the gloss on black was 95.6 and the gloss on white was 86.0.
  • EXAMPLE 11 The feedstock used was 90% that of experiment 1 , plus 10% of the monomers recycled from the devolatilization step.
  • the residence time was 150 seconds, the pressure was 130 psig and the temperature was 216°C (420°F). The conversion was 69.7%.
  • a cut at the beginning of the run and again at the end of the run was taken.
  • the resulting resin from one cut had a weight average molecular weight of 7913, an acid value of 253 and a glass transition temperature (Tg) of 117°C.
  • Tg glass transition temperature
  • the dispersion was made as above, neutralized to pH 8.48.
  • the final dispersion was 48.00% solids.
  • the resulting resin made from the other cut had a weight average molecular weight of 7582, an acid value of 249 and a glass transition temperature (Tg) of 114 ⁇ C.
  • the dispersion was made as above, neutralized to pH 8.13
  • the final dispersion was 48.30% solids Its viscosity was 385 cps.
  • the particle size was 75.5 nm, while the gloss on black was 93.24 and the gloss on white was 106.33.
  • the resin made with recycled monomers resulted in significantly higher gloss on white than that made with neat feedstock
  • the gloss on white, as well as the gloss on black is superior to that obtained with the closest commercial equivalent.
  • Joncryl 678 Joncryl 678
  • EXAMPLE 12 The feedstock consisted of 30% ⁇ -methyl styrene, while the ratio of acrylic ac ⁇ d:styrene (AA:Styrene) was varied Reactor pressure was 220 psig, while the residence time was 240 seconds and the heat transfer fluid temperature was 246°C (475°F) The results were *

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention décrit un procédé de fabrication de résines acryliques pouvant être employées comme tensioactifs polymères, utilisés lors de la polymérisation par émulsion, comme résines de pigment abrasives ou pour préparer des dispersions utilisées en tant que vernis à surimpression. La charge d'alimentation est composée de styrène, de α-méthylstyrène, d'acide acrylique et d'un initiateur de polymérisation; elle est, de préférence, exempte de solvant. Le mélange passe dans un réacteur tubulaire continu fonctionnant dans une plage de pression régulée, avec un temps de séjour et une température relativement faibles. De manière optimale, lorsque le mélange de polymère et de monomères sort du réacteur et qu'il est libéré de matières volatiles, on utilise les monomères récupérés dans la préparation de la charge d'alimentation.
PCT/US1997/011727 1996-07-26 1997-07-16 Resine acrylique solide utilisant un reacteur tubulaire continu WO1998004593A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU36518/97A AU3651897A (en) 1996-07-26 1997-07-16 Solid acrylic resin using a continuous tube reactor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68686096A 1996-07-26 1996-07-26
US08/686,860 1996-07-26

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WO1998004593A1 true WO1998004593A1 (fr) 1998-02-05

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6255403B1 (en) 1998-07-10 2001-07-03 S. C. Johnson Commercial Markets, Inc. Process for producing polymers by free radical polymerization and condensation reaction, and apparatus and products related thereto
US6355727B1 (en) 1998-07-10 2002-03-12 S. C. Johnson Commercial Markets, Inc. Continuous bulk polymerization and esterification process
US6552144B1 (en) 1999-07-14 2003-04-22 Johnson Polymer, Inc. Process for the continuous production of gel free polymers, and powder and liquid coating applications containing gel free polymers
US6605681B1 (en) 2000-07-12 2003-08-12 Johnson Polymer, Inc. Process for the continuous production of epoxylated addition polymers, and powder and liquid coating applications containing epoxylated addition polymers
DE102008000914A1 (de) 2008-04-01 2009-10-08 Evonik Röhm Gmbh Verfahren zur Synthese von verbesserten Bindemitteln und veränderter Taktizität
WO2010091919A1 (fr) 2009-02-12 2010-08-19 Evonik Röhm Gmbh Procédé de synthèse de liants améliorés présentant une distribution granulométrique définie

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713434A (en) * 1982-06-11 1987-12-15 Rohm Gmbh Chemische Fabrik Continuous emulsion polymerization process
US4948847A (en) * 1987-09-11 1990-08-14 Dainippon Ink And Chemicals, Inc. Production of styrene resins by continuous bulk polymerization
US5194525A (en) * 1988-12-12 1993-03-16 Dainippon Ink And Chemicals, Inc. Continuous mass polymerization process for making styrene copolymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713434A (en) * 1982-06-11 1987-12-15 Rohm Gmbh Chemische Fabrik Continuous emulsion polymerization process
US4948847A (en) * 1987-09-11 1990-08-14 Dainippon Ink And Chemicals, Inc. Production of styrene resins by continuous bulk polymerization
US5194525A (en) * 1988-12-12 1993-03-16 Dainippon Ink And Chemicals, Inc. Continuous mass polymerization process for making styrene copolymers

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6255403B1 (en) 1998-07-10 2001-07-03 S. C. Johnson Commercial Markets, Inc. Process for producing polymers by free radical polymerization and condensation reaction, and apparatus and products related thereto
US6346590B1 (en) 1998-07-10 2002-02-12 S. C. Johnson Commercial Markets, Inc. Process for producing polymers by free radical polymerization and condensation reaction, and apparatus and products related thereto
US6355727B1 (en) 1998-07-10 2002-03-12 S. C. Johnson Commercial Markets, Inc. Continuous bulk polymerization and esterification process
US6689853B2 (en) 1998-07-10 2004-02-10 Johnson Polymer, Llc Process for producing polymers by free radical polymerization and condensation reaction, and products related thereto
US6858678B2 (en) 1998-07-10 2005-02-22 Johnson Polymer, Llc Continuous bulk polymerization and esterification process and compositions including the polymeric product
US6552144B1 (en) 1999-07-14 2003-04-22 Johnson Polymer, Inc. Process for the continuous production of gel free polymers, and powder and liquid coating applications containing gel free polymers
US6605681B1 (en) 2000-07-12 2003-08-12 Johnson Polymer, Inc. Process for the continuous production of epoxylated addition polymers, and powder and liquid coating applications containing epoxylated addition polymers
DE102008000914A1 (de) 2008-04-01 2009-10-08 Evonik Röhm Gmbh Verfahren zur Synthese von verbesserten Bindemitteln und veränderter Taktizität
WO2010091919A1 (fr) 2009-02-12 2010-08-19 Evonik Röhm Gmbh Procédé de synthèse de liants améliorés présentant une distribution granulométrique définie
DE102009000814A1 (de) 2009-02-12 2010-08-19 Evonik Röhm Gmbh Verfahren zur Synthese von verbesserten Bindemitteln mit definierter Korngrößenverteilung

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