WO2003054026A1 - Utilisation de sulfates d'ether comme emulsifiants pour polymerisation en emulsion - Google Patents

Utilisation de sulfates d'ether comme emulsifiants pour polymerisation en emulsion Download PDF

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Publication number
WO2003054026A1
WO2003054026A1 PCT/EP2002/013693 EP0213693W WO03054026A1 WO 2003054026 A1 WO2003054026 A1 WO 2003054026A1 EP 0213693 W EP0213693 W EP 0213693W WO 03054026 A1 WO03054026 A1 WO 03054026A1
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WO
WIPO (PCT)
Prior art keywords
ether sulfates
aqueous
radical
total
emulsion polymerization
Prior art date
Application number
PCT/EP2002/013693
Other languages
German (de)
English (en)
Inventor
Carsten Baumann
Uwe Held
Nataly Lausberg
Sandra Heldt
Thomas Mausberg
Original Assignee
Cognis Deutschland Gmbh & Co. Kg
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 Cognis Deutschland Gmbh & Co. Kg filed Critical Cognis Deutschland Gmbh & Co. Kg
Publication of WO2003054026A1 publication Critical patent/WO2003054026A1/fr

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    • 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
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic

Definitions

  • the invention relates to the use of ether sulfates as emulsifiers for emulsion polymerization.
  • the ether sulfates are distinguished by the fact that they have a reduced content of inorganic salts compared to conventional commercially available products.
  • ether sulfates for example fatty alcohol ether sulfates
  • emulsifiers for emulsion polymerization
  • Products are used that always have a certain content of inorganic salts due to the manufacturing process.
  • this salt content in the case of commercially available ether sulfates is as a standard in the range from about 0.5 to 1.5% by weight, based on the total amount of a 30% by weight aqueous form of the ether sulfate.
  • a 30% by weight aqueous form of an ether sulfate is to be understood to mean that 100 g of the product contain 70 g of water and 30 g of dissolved and / or dispersed solid, the solid being predominantly the ether sulfate. Accordingly, whenever there is talk of ether sulfates in specialist publications or in patent applications, it is in fact always implied that these are products which contain the stated amount of salt. 100 g of a 30% by weight aqueous form of a conventional ether sulfate accordingly contain 30 g of solids and 70 g of water, the solids content predominantly containing the ether sulfate, but also about 0.5 to 1.5 g of salt. Salt is understood to mean sodium chloride and / or sodium sulfate. Description of the invention
  • the object of the present invention was to provide ether sulfates which, when used as emulsifiers in emulsion polymerization, lead to polymer dispersions (aqueous latices) with improved freeze-thaw stability. Furthermore, when used as emulsifiers for emulsion polymerization, these ether sulfates should have the effect that only an extremely small amount of coagulum formation and / or fine coagulum formation occurs.
  • the present invention relates to the use of ether sulfates selected from the group of the compounds of the general formulas (Ia) and (Ib)
  • the radical R is an alkyl, aryl or alkaryl radical with a total of 8 to 22 carbon atoms, it being possible for the alkyl radical to be saturated or unsaturated, straight-chain or branched,
  • N is a number in the range from 2 to 50
  • M e is a monovalent inorganic cation
  • M z is a divalent inorganic cation, as emulsifiers for the emulsion polymerization, characterized in that a 30% by weight aqueous form of the ether sulfates has a total of less than 2000 ppm - based on the total composition - of inorganic salts of the formulas M e 2 S0 4 , M e Cl, M z S0 4 and ⁇ vf Cl 2 .
  • M e 2 S0 4 is the sulfuric acid salt of such Cations M e .
  • M e Cl is the chloride of such a cation M e . If, for example, M e is a sodium cation, M e 2 S0 4 is sodium sulfate and M e Cl is sodium chloride.
  • Suitable cations M e are lithium, sodium, potassium and ammonium. Sodium is very particularly preferred as the cation M e . In a preferred embodiment, only ether sulfates are used in which the cation is sodium - these compounds are therefore those compounds of the formula (Ia) in which M e is sodium.
  • M z S0 4 is the sulfuric acid salt of such a cation M z .
  • M Z C1 2 is the chloride of such a cation M Z. If, for example, M z is a magnesium cation, M z S0 4 is magnesium sulfate and M Z C1 2 is magnesium chloride.
  • Examples of suitable cations M z are magnesium and calcium.
  • Aqueous latices which are obtained by using these ether sulfates, which have a reduced salt content compared to conventional ether sulfates, by "Emulsron polymerizing "" " are distinguished by improved freeze-thaw stability.
  • the aqueous polymer dispersions which are accessible using the ether sulfates according to the invention have less coagulum formation and / or fine coagulum formation than the corresponding polymer dispersions which are accessible using the commercially available ether sulfates (with a higher salt content).
  • the latex particles in aqueous polymer dispersions which are accessible using the ether sulfates according to the invention are smaller, ie finer, than the latex particles in corresponding polymer dispersions which are accessible using the commercially available ether sulfates (with a higher salt content).
  • a 30% by weight aqueous form of the ether sulfates has a total of less than 1000 ppm - based on the total composition - of the above-mentioned inorganic salts of the formulas M e 2 S0 4 , M e Cl, M z S0 and M Z C1 2 open.
  • the index n can assume values in the range from 2 to 50. Values in the range from 2 to 30 are preferred.
  • Particularly preferred ether sulfates (la) and (Ib) are fatty alcohol ether sulfates, especially those in which the radical R is lauryl, myristyl, cetyl, stearyl or oleyl. Due to their origin from natural raw materials, mixtures of different individuals (la) or (Ib) which differ in the nature of the rest R are preferably used in the fatty alcohol ether sulfates. In other words, the compounds (Ia) or (Ib) can be used individually or in a mixture with one another.
  • Fatty alcohol ether sulfates are usually obtained as follows: fatty alcohols are ethoxylated by customary methods and the product thus obtained is subjected to sulfation, in particular with chlorosulfonic acid or gaseous sulfur trioxide, followed by neutralization with aqueous bases, in particular sodium hydroxide solution.
  • the fatty alcohols are usually ethoxylated at elevated temperature and pressure in the presence of suitable alkoxylation catalysts.
  • suitable alkoxylation catalysts As is known to the person skilled in the art, adducts with a broad homolog distribution are obtained in the presence of the catalytically active alkali metal alcoholates such as sodium methylate, while, for example, in the presence of hydrotalcite as catalyst, a very narrow homolog distribution (so-called "narrow range” products) takes place.
  • ether sulfates have a relatively high salt content, namely - as is notoriously known to the person skilled in the art with the commercially available ether sulfates, which are predominantly offered in the form of their sodium salts - a sodium sulfate and / or sodium chloride content in Range from about 0.5 to 1.5% by weight (based on the overall composition of a 30% by weight aqueous form of the ether sulfates); 0.5 to 1.5 wt .-% correspond to 5000 to 15000 ppm.
  • the reduction of the inorganic salt content to values below 2000 ppm and in particular below 1000 ppm required according to the present invention can be carried out per se by all methods known to the person skilled in the art.
  • the aqueous ether sulfates can be subjected to membrane extraction.
  • aqueous latices based on the ether sulfates according to the invention have better freeze-thaw stabilities than corresponding ether sulfates with a customary salt content, that is to say a sodium sulfate and / or sodium chloride content in the range from about 0.5 to 1.5% by weight (based on the total composition of a 30% by weight aqueous form of the ether sulfates).
  • the principle of determining the freeze-thaw stability can be found in the ISO 1147 standard.
  • the freeze-thaw stability of aqueous latices is determined according to ISO 1147 by cooling aqueous latices to -10 ° C. and holding them at this temperature for 16 hours. Then it is warmed to room temperature (about +20 ° C) and held at this temperature for 8 hours. Then you check whether coagulum formation has occurred or not. If this is not the case, ie if the latex dispersion was stable against coagulum formation, the cycle described (cooling and thawing) is repeated and checked again for coagulum formation. This freeze-thaw cycle is repeated until either coagulation is observed or a maximum of 5 cycles without coagulation is reached.
  • the ether sulfates according to the invention with reduced salt content can be used as sole emulsifiers (primary emulsifiers) in the emulsion polymerization.
  • emulsifiers primary emulsifiers
  • the ether sulfates according to the invention are preferably used in the form of surfactant concentrates as emulsifiers in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight and in particular 1 to 3% by weight. - calculated as surfactant concentrate and based on the polymerization mixture - used.
  • compositions according to the invention are generally suitable for use as emulsifiers in the production of aqueous latices, which are understood to mean aqueous emulsions or dispersions of polymers and / or copolymers which are usually obtainable by emulsion polymerization.
  • aqueous latices which are understood to mean aqueous emulsions or dispersions of polymers and / or copolymers which are usually obtainable by emulsion polymerization.
  • the nature of the polymers and copolymers in these aqueous latices is not subject to any particular restrictions. However, polymers or copolymers based on the following monomer units are particularly preferred: acrylic acid, acrylic acid ester, butadiene, methacrylic acid, methacrylic acid ester, styrene, vinyl acetate, vinyl versatic acid and vinyl chloride ,
  • Plastic films are made from aqueous latices in a conventional manner.
  • aqueous latices are spread out in a thin layer and this layer is then subjected to drying.
  • the layer is usually spread onto a solid surface, for example by knife coating.
  • layer thicknesses in the range from 100 to 2000 ⁇ m are set.
  • the layer can also be applied using other conventional methods, for example, spraying, brushing and dipping.
  • the aqueous latices are added with additives prior to spreading, as are usually used for coating purposes, for example anorg. and organic pigments, fillers such as carbonates, silicon dioxide, silicas, silicates and sulfates.
  • Disponil FES 77 IS fatty alcohol ether sulfate, Na salt based on a C 12 / ⁇ 4 -
  • the salt content refers to the total amount of 33% by weight product used
  • Methylolamide was prepared under a pre-emulsion. 2.5 g of potassium oxodisulfate was dissolved in 97.5 g of demineralized water and placed in a reactor. Then 150 ml of the pre-emulsion were metered into the reactor and the system was then flushed with nitrogen for 15 minutes.
  • the reactor contents were brought to a temperature of 63 ° C. Then simultaneous dosing of the pre-emulsion and a solution of 2.5 g of sodium metabisulfite in 97.5 g of demineralized water was started. The dosing time was 150 minutes. After the metering had ended, the batch was polymerized for a further 60 minutes at a bath temperature increased by 3 ° C.
  • the aqueous polymer thus prepared was characterized as follows:
  • Example 1 was repeated, using the commercially available product "Disponil FES 77 IS" instead of FAEOS / low salt.
  • 80 g of this pre-emulsion were mixed together with 161.5 g demineralized water, 11.9 g FAEOS / low salt, 0.5 g Disponil NP ' 307 and 1.5 g potassium oxodisulfate in a reactor and heated to 87.degree.
  • the rest of the pre-emulsion and a solution of 2.2 g potassium carboxydisulfate in 72.8 g demineralized water were added over a period of 3 hours.
  • a subsequent reaction was then carried out at 90 ° C. for 30 minutes.
  • the mixture was neutralized with aqueous ammonia solution at a temperature below 40 ° C.
  • Example 3 was repeated, using the commercially available product "Disponil FES 77 IS" instead of FAEOS / low salt.

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

Abstract

L'invention concerne des sulfates d'éther de formules générales (Ia) et (Ib) R-(O-CH2CH2)n-OSO3Me (Ia), [R-(O-CH2-CH2) n-OSO3]2Mz (Ib), dans lesquelles le reste R représente un reste alkyle, aryle ou alkaryle, présentant au total 8 à 22 atomes C, ce reste alkyle pouvant être saturé ou insaturé, ramifié ou linéaire ; n représente un nombre compris entre 2 et 50 ; Me un cation monovalent inorganique et Mz un cation bivalent inorganique, une forme commerciale aqueuse à 30 % en poids des sulfates d'éther contenant au total, par rapport à la composition totale, moins de 2 000 ppm de sels inorganiques de formules Me2SO4, MeC1, MzSO4 et MzCl2. Ces sulfates d'éther s'utilisent comme émulsifiants pour la polymérisation en émulsion. Des réseaux aqueux, obtenus par polymérisation en émulsion à l'aide de ces sulfates d'éther qui présentent une teneur en sel réduite par rapport aux sulfates d'éther classiques, se caractérisent par une stabilité congélation-dégel améliorée et par une proportion de coagulat et/ou coagulat fin réduite.
PCT/EP2002/013693 2001-12-13 2002-12-04 Utilisation de sulfates d'ether comme emulsifiants pour polymerisation en emulsion WO2003054026A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10161273.7 2001-12-13
DE2001161273 DE10161273A1 (de) 2001-12-13 2001-12-13 Verwendung von Ethersulfaten als Emulgatoren für die Emulsionspolymerisation

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WO2003054026A1 true WO2003054026A1 (fr) 2003-07-03

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006056332A1 (fr) * 2004-11-25 2006-06-01 Cognis Ip Management Gmbh Utilisation de sulfates d'ethers polyglycoliques d'alcools gras pour la polymerisation en emulsion
EP2267038A1 (fr) * 2009-06-27 2010-12-29 Cognis IP Management GmbH Tensioactif copolymérisable
US8193281B2 (en) 2009-06-27 2012-06-05 Cognis Ip Management Gmbh Copolymerizable surfactants (2)
CN102993617A (zh) * 2011-09-08 2013-03-27 罗门哈斯公司 可溶性壳聚合物组合物及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1033166A2 (fr) * 1999-03-04 2000-09-06 Kao Corporation Composition tensioactive pour polymerisation en émulsion

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1033166A2 (fr) * 1999-03-04 2000-09-06 Kao Corporation Composition tensioactive pour polymerisation en émulsion

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006056332A1 (fr) * 2004-11-25 2006-06-01 Cognis Ip Management Gmbh Utilisation de sulfates d'ethers polyglycoliques d'alcools gras pour la polymerisation en emulsion
EP2267038A1 (fr) * 2009-06-27 2010-12-29 Cognis IP Management GmbH Tensioactif copolymérisable
JP2011016996A (ja) * 2009-06-27 2011-01-27 Cognis Ip Management Gmbh 共重合性界面活性剤（１）
US8183320B2 (en) 2009-06-27 2012-05-22 Cognis Ip Management Gmbh Copolymerizable surfactants (1)
US8193281B2 (en) 2009-06-27 2012-06-05 Cognis Ip Management Gmbh Copolymerizable surfactants (2)
CN102993617A (zh) * 2011-09-08 2013-03-27 罗门哈斯公司 可溶性壳聚合物组合物及其制备方法
CN102993617B (zh) * 2011-09-08 2014-12-10 罗门哈斯公司 可溶性壳聚合物组合物及其制备方法

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