EP1401878A1 - Utilisation d'esters de polyglycerine et de leurs derives alkoxyles et anioniques comme emulsifiants dans la polymerisation en emulsion - Google Patents

Utilisation d'esters de polyglycerine et de leurs derives alkoxyles et anioniques comme emulsifiants dans la polymerisation en emulsion

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Publication number
EP1401878A1
EP1401878A1 EP02753044A EP02753044A EP1401878A1 EP 1401878 A1 EP1401878 A1 EP 1401878A1 EP 02753044 A EP02753044 A EP 02753044A EP 02753044 A EP02753044 A EP 02753044A EP 1401878 A1 EP1401878 A1 EP 1401878A1
Authority
EP
European Patent Office
Prior art keywords
sodium
esters
acid
potassium
polyglycerol
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP02753044A
Other languages
German (de)
English (en)
Inventor
Hendrik Ahrens
Uwe Falk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
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 Clariant GmbH filed Critical Clariant GmbH
Publication of EP1401878A1 publication Critical patent/EP1401878A1/fr
Withdrawn legal-status Critical Current

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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
    • 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

Definitions

  • esters of polyglycerol and their alkoxylated and anionic derivatives as emulsifiers in emulsion polymerization
  • the present invention relates to the use of fatty acid polyglycerol esters and their alkoxylated and anionic derivatives as emulsifiers in emulsion polymerizations.
  • the emulsifiers used for the emulsion polymerization according to the prior art are mostly anionic and nonionic emulsifiers.
  • Common anionic emulsifiers are sodium, potassium and ammonium salts of fatty acids, sodium alkylbenzenesulfonates, sodium alkylsulfonates, sodium olefin sulfonates, sodium polynaphthalene sulfonates, sodium dialkyldiphenylether disulfonates, sodium, potassium and ammonium alkyl sulfates, sodium, potassium and ammonium alkyl sulfates, glycol ether sulfates, sodium, potassium and ammonium mono- and dialkyl sulfosuccinates and monoalkylpolyoxethyl sulfosuccinates, as well as alkyl polyethylene glycol ether phosphoric acid mono-, di- and triesters and their mixtures and alkylphenol polyethylene glycol ether phosphoric acid mono-, di- and triester and their mixtures, as well as their sodium, potassium and ammonium salts.
  • Alkylphenol polyethylene glycol ether, alkyl polyethylene glycol ether, fatty acid polyethylene glycol ether, ethylene / propylene glycol block polymers and sorbitan ester polyethylene glycol ether are usually used as nonionic emulsifiers.
  • Emulsion polymerizations using anionic and nonionic emulsifiers are usually carried out in the total batch or in Feed process carried out, in which only a small part of the monomers to be polymerized is placed in the polymerization vessel and the larger part (50 to 100% by weight) is added as the polymerization progresses.
  • the anionic or nonionic emulsifiers are optionally used in the feed or in the reactor receiver during the emulsion polymerization, or are added subsequently to the polymer dispersion prepared for stabilization.
  • the invention thus relates to the use of esters between polyglycerol with 2 to 100 glycerol units and at least one carboxylic acid with 6 to 42 carbon atoms as an emulsifier in the emulsion polymerization.
  • Polyglycerols are compounds of the formula (1)
  • n is the degree of condensation. n is between 2 and 100, preferably between 3 and 20.
  • the polyglycerol esters are preferably prepared with carboxylic acids of 6 to 26, in particular 8 to 18, carbon atoms.
  • the carboxylic acids can be aliphatic, aliphatic-unsaturated, cycloaliphatic, cycloaliphatic-unsaturated or aromatic. It is preferably monocarboxylic acids.
  • the carboxylic acids are native saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, hexosanoic acid and montanic acid, native unsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid, rapeseed oil fatty acid and erucic acid, synthetic saturated carboxylic acid such as margaric acid, cyclic carboxylic acids such as naphthenic acid, benzoic acid, phenylacetic acid and resin acids such as abietic acid, levopimaric acid and neoabietic acid.
  • native saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, hexosanoic acid and montanic acid
  • native unsaturated carboxylic acids such as oleic acid, lin
  • the esters preferably contain polyglycerol and the carboxylic acid in a molar ratio of at least 1: 1, in particular in a ratio of 1: 1 to 1:10, especially 1: 1 to 1: 5.
  • esters are used in alkoxylated form.
  • the alkoxylated esters of polyglycerols contain alkoxy groups on one or more of the free OH groups of the polyglycerol, which can optionally be derivatized.
  • A is C 2 - to C 4 -alkylene
  • x is a number from 1 to 500, in particular 2 to 100
  • B is hydrogen or the remainder of a di- or polyvalent inorganic or organic acid which, in addition to oxygen atoms, also has at least one phosphorus - or has a sulfur atom.
  • inorganic acids which are suitable for the formation of the alkoxylated esters are sulfuric acid and phosphoric acid.
  • the organic or inorganic acids used to esterify the alkoxy groups according to formula (2) are divalent or trivalent.
  • the organic acids are di-, tri- or polyvalent carboxylic acids, i.e. Compounds which contain 2, 3 or more carboxyl groups and which additionally have at least one functional group containing sulfur or phosphorus. Sulfur-containing functional groups, especially sulfonate groups, are particularly preferred.
  • the particularly preferred sulfonic acids / sulfonates can be aliphatic or aromatic compounds.
  • Preferred sulfonic acids / sulfonates contain 2 or 3 carboxyl groups and, including the carboxyl groups, 3 to 6 carbon atoms.
  • a particularly preferred sulfonic acid is sulfosuccinic acid.
  • the units (A-O) can be unitary or mixed alkoxy units.
  • Mixed alkoxy units can be in a random or block arrangement.
  • radicals of the formula (2) can be, for example:
  • R 3 represents a methyl group or ethyl group
  • b represents a number from 1 to 500
  • c represents a number from 1 to 100
  • the ethylene glycol, propylene glycol and butylene glycol units are random or blockwise in the
  • Polyalkylene glycol ether residue are distributed, e) a polyethylene glycol ether sulfuric acid ester of the formula (6)
  • a number from 1 to 500 and Me represent a sodium, potassium or ammonium ion, f) or a polyethylene glycol ether phosphoric acid ester of the formula (7)
  • b represents a number from 1 to 500, g) a polyethylene glycol ether sulfosuccinic acid semi-ester (Polyethylene glycol ether sulfosuccinate) of the formula (8)
  • b is a number from 1 to 500.
  • the alkoxylated esters of polyglycerol can be prepared by reacting such an ester with a C 2 -C 4 -alkylene oxide in the presence of an alkaline catalyst such as KOH, NaOH, potassium methylate or sodium methylate at temperatures between 120 and 200 ° C.
  • an alkaline catalyst such as KOH, NaOH, potassium methylate or sodium methylate at temperatures between 120 and 200 ° C.
  • the anionically derivatized esters of polyglycerol can be prepared by reacting the alkoxylated esters of polyglycerol with suitable acids.
  • the production of sulfate esters is preferably carried out with amidosulfonic acid instead of with sulfuric acid.
  • Phosphoric acid esters phosphoric acid can be used.
  • Organic acids are preferably reacted in the form of their anhydrides with the alcohols of the formula 1.
  • Functional groups are preferably inserted after the ester of the non-functionalized acid has been prepared.
  • the preparation of the sulfosuccinic acid ester can be carried out by producing the corresponding
  • the invention further relates to a process for the preparation of polymer dispersions in which olefinically unsaturated monomers are polymerized in the presence of the esters of polyglycerol.
  • the monomers used for the production of polymer dispersions by the emulsion polymerization process are, for example, vinyl monomers, such as carboxylic acid esters of vinyl alcohol, for example Vinyl acetate, vinyl propionate, vinyl ether of isononanoic acid or
  • Aryl-substituted olefins such as styrene and stilbene, olefinically unsaturated carboxylic acid esters, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, pentyl acrylate, hexyl acrylate,
  • Methacrylic acid esters olefinically unsaturated dicarboxylic acid esters, such as dimethyl maleate,
  • Methacrylic acid methacrylic acid, itaconic acid, maleic acid and fumaric acid and their
  • the above-mentioned monomers are mixed with further comonomers, preferably olefins or halogenated olefins having 2 to 8 carbon atoms, e.g. Polymerized ethylene, propene, butenes, pentenes, 1, 3-butadiene, chloroprene, vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene.
  • further comonomers preferably olefins or halogenated olefins having 2 to 8 carbon atoms, e.g. Polymerized ethylene, propene, butenes, pentenes, 1, 3-butadiene, chloroprene, vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene.
  • the water-immiscible monomers are generally used with the aid of the emulsifiers according to the invention in the finely divided aqueous phase in the form of micelles and the radical polymerization reaction started by initiators such as ammonium, sodium and potassium peroxodisulfate.
  • auxiliaries and additives for use with the emulsifiers according to the invention can be protective colloids such as carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose, and partially and fully hydrolyzed polyvinyl alcohol.
  • the fatty acid polyglycerol esters according to the invention and their alkoxylated and anionic derivatives can be used during the emulsion polymerization by placing them in the reaction vessel before the start of the polymerization reaction or adding them to the reaction vessel during the polymerization reaction.
  • Another variant is the addition after completion of the polymerization reaction to improve the stability of the polymer dispersion.
  • the fatty acid polyglycerol esters according to the invention and their alkoxylated and anionic derivatives can be used both alone and in combination with other already known anionic and nonionic emulsifiers of the prior art, as described at the beginning.
  • the amount of the anionic and nonionic emulsifiers of the prior art is then preferably 0.05 to 5, in particular 0.08 to 3% and particularly preferably 0.1 to 2% by weight, based on the weight of the water-insoluble or slightly water-soluble monomers.
  • esters of polyglycerol and their alkoxylated and anionic derivatives according to the invention in amounts of 0.1 to 10, preferably 0.2 to 5, in particular 0.4 to 4 wt .-%, based on the weight of the for Preparation of the polymer dispersion used non or slightly water-soluble monomers used as emulsifiers.
  • the polymer dispersions prepared with the esters of polyglycerol and their alkoxylated and anionic derivatives according to the invention show low coagulum formation during and after the polymerization and an improvement in the shear, temperature and storage stability, the freeze / thaw stability and the electrolyte stability compared to divalent and trivalent cations such as Calcium, barium and aluminum. An improvement in the film properties of the polymer films produced from the polymer dispersions can also be observed.
  • the polymer dispersions prepared with the polyglycerol esters according to the invention form films. low water absorption, a low whitening on contact with water and good wet and dry rub fastness.
  • the reaction temperature was kept constant at 79 to 81 ° C by cooling or heating over the water bath. After 15 minutes, the remaining 1530 g of the monomer emulsion were added over a period of 3 hours. To initiate the radical polyaddition reaction, the remaining 215.7 g of the initiator solution were added over a period of 3 hours and 15 minutes via a second feed. The reaction mixture was then stirred for a further 2 hours at 80 ° C. with stirring and under a nitrogen atmosphere and then cooled to room temperature. For the preservation of the polymer dispersion produced were 3.6 g ® Nipacide CI15 (Nipa Laboratories Ltd.) was added.
  • the resulting polymer dispersion had a solids content of 50% and a coagulate of ⁇ 0.010% over a 100 ⁇ m sieve and of ⁇ 0.015% over a 40 ⁇ m sieve.
  • the resulting polymer dispersion had a solids content of 65% and a coagulum of ⁇ 0.050% over a 100 ⁇ m sieve and of ⁇ 0.080% over a 40 ⁇ m sieve.
  • the dosage of the aqueous potassium peroxodisulfate solution lasted 175 minutes.
  • the polymerization mixture was tempered at 80 ° C. by cooling or by supplying heat. After a post-polymerization time of one hour at 80 ° C., the polymer dispersion was cooled to room temperature. For the preservation of the prepared polymer dispersion, 3.3 g of ® Nipacide CI15 (Nipa Laboratories Ltd.) was added.
  • the resulting polymer dispersion had a solids content of 54% and a coagulum of ⁇ 0.10% over a 100 ⁇ m sieve.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Polymerisation Methods In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'objectif de l'invention est l'utilisation d'esters résultant de la combinaison d'une polyglycérine comportant 2 à 100 unités glycérine et d'au moins un acide carboxylique comportant 6 à 42 atomes de carbone comme émulsifiants dans la polymérisation en émulsion.
EP02753044A 2001-05-19 2002-05-07 Utilisation d'esters de polyglycerine et de leurs derives alkoxyles et anioniques comme emulsifiants dans la polymerisation en emulsion Withdrawn EP1401878A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10124547 2001-05-19
DE10124547A DE10124547A1 (de) 2001-05-19 2001-05-19 Verwendung von Estern des Polyglycerins und deren alkoxylierten und anionischen Derivaten als Emulgatoren in der Emulsionspolymerisation
PCT/EP2002/005008 WO2002094885A1 (fr) 2001-05-19 2002-05-07 Utilisation d'esters de polyglycerine et de leurs derives alkoxyles et anioniques comme emulsifiants dans la polymerisation en emulsion

Publications (1)

Publication Number Publication Date
EP1401878A1 true EP1401878A1 (fr) 2004-03-31

Family

ID=7685468

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02753044A Withdrawn EP1401878A1 (fr) 2001-05-19 2002-05-07 Utilisation d'esters de polyglycerine et de leurs derives alkoxyles et anioniques comme emulsifiants dans la polymerisation en emulsion

Country Status (6)

Country Link
US (1) US20040143057A1 (fr)
EP (1) EP1401878A1 (fr)
JP (1) JP2004526851A (fr)
BR (1) BR0209289A (fr)
DE (1) DE10124547A1 (fr)
WO (1) WO2002094885A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10211801B4 (de) 2002-03-16 2004-09-30 Clariant Gmbh Kosmetische und pharmazeutische Zubereitungen enthaltend einen oxalkylierten Polyglycerinester
DE10307171B4 (de) * 2003-02-20 2009-04-16 Clariant Produkte (Deutschland) Gmbh Copolymere enthaltende landwirschaftliche Mittel
DE10342870A1 (de) 2003-09-15 2005-05-12 Clariant Gmbh Flüssige Zusammensetzungen enthaltend oxalkylierte Polyglycerinester
US10370493B2 (en) 2016-01-29 2019-08-06 Evonik Degussa Gmbh Polyglycerol alkoxylate esters and preparation and use thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4158092A (en) * 1974-07-25 1979-06-12 Hoechst Aktiengesellschaft Process for the manufacture of vinyl chloride polymer dispersions with a low monomer content
DE2509937C3 (de) * 1975-03-07 1981-04-16 Hoechst Ag, 6000 Frankfurt Vorrichtung zur Nachbehandlung von Homo- und Copolymerisaten des Vinylchlorids
JPS6045647B2 (ja) * 1978-06-16 1985-10-11 信越化学工業株式会社 塩化ビニル系重合体の製造方法
US4650827A (en) * 1983-11-02 1987-03-17 Allied Corporation Stable water-in-oil emulsions
US4581413A (en) * 1984-12-24 1986-04-08 The B. F. Goodrich Company Vinyl dispersion resins
US4797458A (en) * 1986-09-02 1989-01-10 The B.F. Goodrich Company Colloidal stable vinyl halide polymerizations with mercaptan chain transfer agents
TW201758B (fr) * 1988-06-28 1993-03-11 Catalyst co ltd
EP0563794B1 (fr) * 1992-03-30 1996-12-27 Sumitomo Chemical Company Limited Méthode d'obtention de résines de chlorure de vinyle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02094885A1 *

Also Published As

Publication number Publication date
JP2004526851A (ja) 2004-09-02
BR0209289A (pt) 2004-07-13
DE10124547A1 (de) 2002-11-28
WO2002094885A1 (fr) 2002-11-28
US20040143057A1 (en) 2004-07-22

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