WO1998024821A2 - Procede pour la preparation de polymeres par polymerisation en emulsion - Google Patents

Procede pour la preparation de polymeres par polymerisation en emulsion Download PDF

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WO1998024821A2
WO1998024821A2 PCT/EP1997/006812 EP9706812W WO9824821A2 WO 1998024821 A2 WO1998024821 A2 WO 1998024821A2 EP 9706812 W EP9706812 W EP 9706812W WO 9824821 A2 WO9824821 A2 WO 9824821A2
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monomers
acid
water
polymerization
weight
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PCT/EP1997/006812
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German (de)
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WO1998024821A3 (fr
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Reinhold J. Leyrer
Gerald Wildburg
Alexander Haunschild
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Basf Aktiengesellschaft
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Priority to AU55604/98A priority Critical patent/AU5560498A/en
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Publication of WO1998024821A3 publication Critical patent/WO1998024821A3/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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a process for the preparation of polymers by aqueous emulsion polymerization of ethylenically unsaturated monomers which contain at least one hydrophobic monomer a) with a solubility in water L ⁇ 0.01 g / 1 (25 ° C., 1 bar) and optionally further the monomers a) comprise copolymerizable monomers b).
  • the polymerization of ethylenically unsaturated monomers with a water emulsion is an important process for the preparation of commercially important polymers, for example those based on acrylate, vinyl ester or styrene / butadiene. It is preferably carried out as a radical polymerization, but it can also be carried out with the aid of suitable water-resistant transition metal catalysts.
  • conventional hydrophobic monomers such as styrene, butyl acrylate, ethylhexyl acrylate, butadiene or other monomers, can be polymerized by this method, this method fails if the monomers do not have a minimum degree of water solubility.
  • Usual monomer concentrations in the aqueous phase are in the range of about 0.1 g / 1 (cf. A. Echte, p.323). If the solubility in water is too low, for example L ⁇ 0.01 g / 1, a polymerization reaction can still take place, but it then no longer takes place as an emulsion polymerization but as a suspension polymerization. In this way, j e-docn does not obtain finely divided, stable polymer dispersions, but rather coarse-particle polymer dispersions, in which the polymer precipitates as a coagulate.
  • the aqueous emulsion polymerization method fails, since the hydrophobic monomers m the monomer droplets and the somewhat more hydrophilic monomers polymerize the micelles so that no copolyme ⁇ sation takes place.
  • the preparation of copolymers from hydrophobic monomers and water-soluble monomers is also problematic since the latter generally polymerize in the water phase.
  • aqueous polymer dispersions in the presence of starch or starch derivatives as protective colloids is known in principle.
  • EP-A 0 134 449, EP-A 0 134 451, DE-A 39 22 784, EP-A 0 276 770, EP-A 0 334 515 and EP-A 0 536 597 describe this the production of aqueous polymer dispersions by radical, aqueous emulsion polymerization of ethylenically unsaturated monomers in the presence of starches, modified starches or starch degradation products.
  • EP-A 0 710 675 describes the emulsion polymerization of hydrophobic monomers in the presence of molecules which have a hydrophobic cavity. Cyclodextres are mentioned as preferred molecules with hydrophobic cavity.
  • the emulsion polymerization of lauryl acrylate or lauryl methacrylate is brushed together with other monomers in the presence of cyclodextrms.
  • the comparatively high price of cyclodextrms is a disadvantage.
  • the present invention is therefore based on the object of providing a process for the preparation of polymers by aqueous emulsion polymerization of hydrophobic monomers, the solubility of which in water is not sufficient for an emulsion polymerization, in which the use is more difficult to produce and therefore expensive molecules with hydrophobic cavities are not required.
  • hydrophobic monomers can be polymerized by aqueous emulsion polymerization if the polymerization is carried out in the presence of noncyclic polysaccharides which are capable of forming inclusion compounds, for example by forming a helical structure.
  • the present invention thus relates to a process for the preparation of polymers by aqueous emulsion polymerization of ethylenically unsaturated monomers, comprising at least one hydrophobic monomer a) with a solubility in water L ⁇ 0.01 g / 1 (at 25 ° C. and 1 bar) and optionally further, with the monomers a) copolymerizable monomers b), which is characterized in that the polymerization is carried out in the presence of at least one non-cyclic polysaccharide, which is capable of forming final compounds.
  • the polysaccharides according to the invention include both unmodified polysaccharides and modified, i.e. partially or completely de-derivatized polysaccharides on the OH groups.
  • Polysaccharides according to the invention are soluble in water or at least swellable in water. It is preferably a starch soluble in water or swellable in water or a chemically modified starch.
  • the starches which are soluble or swellable in water are, for example, native starches which have been water-soluble or swellable in water by boiling, or starch degradation products which are enzymatically hydrolysed, in particular by acid-catalyzed hydrolysis catalyzed hydrolysis or oxidation can be obtained from the native starches.
  • Such degradation products are also referred to as dextrins, rust dextrins or saccharified starches.
  • Their production from native starches is known to the person skilled in the art and is described, for example, by G. Tegge, Starke und Starkederivate, EAS Verlag, Hamburg 1984, pp. 173ff and S 220ff and in EP-A 0441 197.
  • Virtually all starches of vegetable origin can be used as native starches, for example starches from corn, wheat, potatoes, tapioca, rice, sago and sorghum.
  • Chemically modified starches are also preferred according to the invention.
  • Chemically modified starches are to be understood as those starches or starch degradation products in which the OH groups are at least partially present in derivatized, for example etherified or esterified, form.
  • the chemical modification can probably be made on the native strong as well as on the degradation products. It is also possible to transfer the chemically modified starches afterwards to their chemically modified breakdown products. 5
  • Starch can be esterified using both inorganic and organic acids, their anhydrides or their chlorides. Usual esterified starches are phosphated and / or acetylated starches or starch degradation products. An etherification of the
  • OH groups can be carried out, for example, with organic halogen compounds, epoxides or sulfates in aqueous alkaline solution.
  • suitable ethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers, allyl ethers and cationically modified ethers, e.g. (trisalkylammonium) alkyl ethers and (t ⁇ salkyl-
  • starches or starch degradation products can be neutral, cationic, amonic or amphiphilic.
  • the manufacture of modified starches and starch degradation products is known to the person skilled in the art (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5 ed, Vol.
  • waterless starch degradation products and their chemically modified derivatives which are obtained by hydrolysis, oxidation or enzymatic
  • starch degradation products are also referred to as “saccharified starches” (see G. Tegge, 5 220ff). Saccharified starches and their derivatives are. as such ⁇ m ⁇ commercially available e.g. C'pur products C1909,
  • 01908, 01910, 01912, 01915, 01921, 01924, 01932 or 01934 from Cerestar Deutscnlan ⁇ GmbH, Krefeld) o ⁇ er can be obtained by breaking down commercially available starches according to known methods, for example by oxidative hydrolysis with peroxides or enzymatic hydrolysis from the starches or chemically modified starches -
  • starch degradation products or chemically modified ones are particularly preferred.
  • starch degradation products with a weight-average molecular weight M ⁇ ; J in the range from 500 to 500,000 daltons, in particular in the range from 1000 to 30,000 daltons and very particularly preferably in the range from 3000 to 10,000 daltons.
  • Such starches are at 25 ° C. and 1 bar water completely soluble, the soluble
  • the weight of the saccharified starches to be used according to the invention are based on determinations by means of gel permeation chromatography under the following conditions:
  • differential refractometer e.g. ERC 7511
  • flow 0.8 ml / mm.
  • Pump (e.g. ERC 64.00)
  • Calibration The calibration was carried out in the low molecular weight range with glucose, venom, maltose and maltopentose. Pullulan standards with a polydispersity ⁇ 1.2 were used for the high molecular weight range.
  • the weight ratio of polysaccharide: monomer a) is in the range from 100: 1 to 1,5000, preferably in the range from 10: 1 to 1: 100 and very particularly preferably in the range from 1: 1 to 1:50.
  • hydrophobic monomers are understood to mean those monomers whose water solubility is L ⁇ 0.0 1 g / 1 at 25 ° C. and 1 bar.
  • Hydrophobic monomers a) include C 1 oC 4 o-alkyl esters, preferably Ci 4 -C 3 o-alkyl esters of monoethylenically unsaturated carboxylic acids, preferably methacrylic acid and acrylic acid - hereinafter referred to as (meth) acrylates - for example 2-propylhept-l-yl -, Lauryl, Myristyl, Palmi yl, Stearyl, Arachmyi, Behenyl, Lignoceryl and Cerotmyl (meth) acrylates as well as Polyisobuten (meth) acrylates, in which the polyisoputenyl residue has a number-average degree of oligomerization in the range of 3 bs 10 has
  • the monomers a) further comprise the D 1 -C 4 -o 4 -alkyl esters, preferably the D 1 -C 3 _ 4 -C 30 -alkyl esters of monoethylenically unsaturated dicarboxylic acids, for example the esters of maleic acid, fumaric acid or itaconic acid with 2- Propylhept-l-yl, lauryl, myristyl, palmityl, stearyl, arachmy, behenyl, lignoceryl or cerotmyl alcohol.
  • D 1 -C 4 -o 4 -alkyl esters preferably the D 1 -C 3 _ 4 -C 30 -alkyl esters of monoethylenically unsaturated dicarboxylic acids, for example the esters of maleic acid, fumaric acid or itaconic acid with 2- Propylhept-l-yl, lauryl, myristyl, palmityl, stearyl,
  • Another class of monomers of group a) are the methyl and allyl esters of aliphatic C 10 -C 40 -, preferably C 4 -C 3 oC rbon acid, for example Vmyl or allyl laurate, Vmyl or allyl mypstat, Vmyl or allyl palmitate, Vmyl or allyl stearate, Vmyl or allyl lachmate, Vmyl or allyl behenate, Vmyl or allyl lignocerate and Vmyl or allyl cerotate.
  • Further monomers of group a) are C: oC 4 C) -alkyl vinyl ether and ( a Cio-C 40 alkyl allyl ether, preferably C 4 -C 3 o-alkyl methyl and allyl ether, for example 2-propyl-heptyl-1-yl methyl ether, 2-propylhept-1-yl allyl ether, lauryl methyl ether, lauryl allyl ether, myristyl methyl ether, mypyl allyl ether, palmityl vinyl ether, stearyl allyl ether, palmityl allyl ether, 5 rylallyl ether, arachmylv ylether, arach ylallylether, benehylvmylether, behenylallylether, lignocerylvmylether or lignocerylallylether, cerotmylvmylether or cerotmylallylether.
  • the monomers a) also comprise ⁇ -olefins having 6 to 10 40 C atoms, preferably having 10 to 30 C atoms, such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Octadecene and C 2 o C 2 -olefs and monoethylenically unsaturated oligomers of propene with 3 to 50 propylene units and isobutene with 2 to 35 isobutene units, preferably 3 to 10-isobutene units-15 th.
  • ⁇ -olefins having 6 to 10 40 C atoms, preferably having 10 to 30 C atoms, such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Octadecene and C 2 o C 2 -olefs and monoethylen
  • Another class of monomers a) are N-alkyl-substituted amino ethyl unsaturated carboxylic acids in which the alkyl radical has 10 to 40 carbon atoms, preferably 10 to 30 carbon atoms.
  • the N-alkylamides of acrylic acid and methacrylic acid are preferred - hereinafter referred to as (meth) acrylamides - e.g. N-decyl (meth) acrylamide, N-dodecyl (meth) acrylic amide, N-tetradecyl (meth) acrylamide, N-hexadecyl (meth) acrylamide, N-octadecyl (meth) acrylamide.
  • the monomers a) mentioned which are derived from fatty alcohols having 10 to 40 carbon atoms, such as the alkyl esters of monoethyl unsaturated carboxylic acids and the alkyl vinyl or alkyl alkyl ethers, instead of the alkyl radicals, ethoxylated aluminum
  • the monomers mentioned a) can be copolymerized alone or together with suitable comonomers b)
  • Suitable monomers b) include in principle all monomers which can be polymerized by free radical, aqueous emulsion polymerization. These include C 2 -C 5 -eflems such as ethylene, propylene, n-butene, isobutene, vinyl aromatic monomers with 8 to 14 carbon atoms, such as styrene, ⁇ -methylstyrene, 2-, 3- or 4-methylstyrene ,
  • Vmyl-butyrate Vmylvalerat, Vmylhexanoat, Vmyl-2-ethylhexanoate as well as Vmyl- and Allylester aromatic C ⁇ -C 2 o ⁇ monocarboxylic acids, such as Vmyl- or Allylbenzoat or Vmyl- or Allylnaph- thoat.
  • esters of ethylenically unsaturated C 3 -C 6 mono- or C 4 -C 3 -dicarboxylic acids with C 1 -C 9 - and in particular C ⁇ -C 4 alkanols, with Cs-C o-cycloalkanols or with C 6 -C 1- aryl alcohols are particularly suitable.
  • acrylic acid methyl ester (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid isobutyl ester, (meth) acrylic acid-2-ethylhexyl ester, malemate di-ethyl ester, malemate di-n-butyl ester, fumaric acid dimethyl ester and fumararsau redi-n-butyl ester.
  • C 4 -C-conjugated dienes such as 1, 3-butadiene, isoprene, phenylbutadiene or chloroprene can also be used.
  • the monomers mentioned are referred to below as monomers b1). They generally make up 0.5 to 99.5% by weight, preferably 40 to 98% by weight and in particular 50 to 95% by weight, of the monomers to be polymerized.
  • the monomers b) also comprise hydrophilic monomers b2) whose water solubility is at least 20 g / 1, preferably at least 50 g / 1 and in particular at least 100 g / 1, in each case at 25 ° C. and 1 bar , amounts.
  • hydrophilic monomers b2) whose water solubility is at least 20 g / 1, preferably at least 50 g / 1 and in particular at least 100 g / 1, in each case at 25 ° C. and 1 bar , amounts.
  • hydrophilic monomers b2) whose water solubility is at least 20 g / 1, preferably at least 50 g / 1 and in particular at least 100 g / 1, in each case at 25 ° C. and 1 bar , amounts.
  • These are, for example, monoethylene-unsaturated C 3 -Cs carboxylic acids, their amides and their esters with amino alcohols of the formula
  • the oasis esters or basic amides derived from the compounds of the formula I or II are used in the form of the salts with strong mineral acids, sulfonic acids or carboxylic acids or in the quaternized form.
  • the anion X ⁇ for the compounds of formula I or II is the corresponding anion the mineral acids or the carboxylic acids or methosulphate, ethosulphate or halo from a quaternizing agent
  • water-soluble monomers b2) are N-Vmylpyrrolidon, N-V - nylformamide, Acrylam ⁇ do-2-methylpropanesulfonsaure, V ylphosphon acid and / or alkali or ammonium salts of Vmylsulfonsaure. These acids can also be used either in non-neutralized form or partially or up to 100% neutralized form in the polymerization.
  • Preferred water-soluble monomers b2) are selected from monoethylenically unsaturated C 3 -C 5 carboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid, monoethylenically unsaturated C 4 -C 3 dicarboxylic acids, for example maleic acid, fumaric acid or itaconic acid, and acrylonitrile, methacrylonitrile, acrylamide, Methacrylic amide, crotonic acid amide, methyl sulfonic acid, acrylamidopropane sulfonic acid, styrene sulfonic acid, vinyl phosphonic acid, the alkali metal and ammonium salts of the sulfonic and phosphonic acids mentioned, N-methyl formamide, N-methylpyrrolidone (meth) methacrylate, methylkylammonethyl (meth) methacrylate, methylkylammonethyl (meth) ammonium (meth) me
  • the monomers b) further comprise crosslinking or crosslinkable monomers b3)
  • Such monomers can serve on the one hand to increase the strength of the polymer streams obtainable from the polymer dispersions. They are then subordinated in amount, usually up to 10% by weight, preferably up to 5% by weight and in particular up to 1% by weight, based on the total amount of the amount to be polymerized.
  • the crosslinkable monomers are are polyfunctional monomers which, in addition to the ethylenically unsaturated bond, contain an epoxy, hydroxyl, N-alkylol or a carbonyl group. Examples are the N-hydroxyalkyl and N-alkylolamides of the ethylenically unsaturated carboxylic acids mentioned, for example 2-hydroxy.
  • Crosslinking compounds are understood to mean those compounds which have two or more non-conjugated, ethylenically unsaturated bonds, such as the vinyl or allyl esters of ethylenically unsaturated carboxylic acids, for example vinyl and allyl (meth) acrylate, the vinyl aromatics, for example divmylbenzene and divmylnaphthalm, polyvinyl ester or polyallyl ester of polycarboxylic acids, eg diallyl malet, diallyl fumarate and dialyl phthalate as well as tricyclodecenyl (meth) acrylate and cyclopentenyl (meth) acrylate.
  • the vinyl or allyl esters of ethylenically unsaturated carboxylic acids for example vinyl and allyl (meth) acrylate
  • the vinyl aromatics for example divmylbenzene and divmylnaphthalm
  • Water-soluble crosslinking monomers can also be used if necessary.
  • Such monomers are, for example, N, N '-methylene bisacrylamide, polyethylene glycol di (meth) acrylates, which are each derived from polyethylene glycols with a molecular weight of 126 to 3500, methyl methylpropane (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di ( meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and the di (meth) acrylates of block copolymers made from ethylene oxide and propylene oxide, 2 or 3 times polyvalent alkanols esterified with acrylic acid or methacrylic acid, such as Glycerm or Pentaeryth ⁇ t, T ⁇ allylamm, Tetraallylethylen- diamm, T ⁇ methylolpropandiallylether, Pentaerythritt
  • hydrophobic monomers a) are optionally polymerized together with monomers b1) and at least one monomer from group b2) and at least one monomer from group b3), preferably a water-soluble monomer b3).
  • the polymerization of the water-insoluble monomers and, if appropriate, the water-less monomers takes place in the manner of an emulsion polymerization in an aqueous medium, preferably in water.
  • An aqueous medium is also to be understood here as meaning mixtures of water and organic liquids which are miscible therewith.
  • Water-miscible organic liquids are, for example polyols, particularly glycols such as ethylene glycol, propylene glycol, 1, 3-butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and Glycerm, block copolymers of ethylene oxide and propylene oxide, alkoxylated C- to C 2 o _ Alkonole, Essigsaureester of Glycols and polyglycols, alcohols such as methanol, ethanol, isopropanol and butanol, acetone, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone or also mixtures of the solvents mentioned.
  • glycols such as ethylene glycol, propylene glycol, 1, 3-butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and Glycerm
  • block copolymers of ethylene oxide and propylene oxide alkoxylated C- to C 2 o
  • the proportion of water-miscible solvents in the mixture is up to 75% by weight.
  • the emulsion polymerization of the monomers is usually carried out with the exclusion of oxygen at temperatures of, for example, 20 to 200 ° C., preferably 35 to 140 ° C. and in particular at 50 to 100 ° C.
  • the polymerization can be carried out batchwise or continuously, preferably at least some of the monomers, initiators and optionally regulators are metered uniformly during the polymerization into a “solution” of the polysaccharides in an aqueous solvent. In the case of smaller batches, however, the monomers and the polymerization initiator can also be introduced and polymerized in the reactor, where appropriate cooling has to be used to ensure that the heat of polymerization is sufficiently rapidly removed.
  • starch degradation products or chemically modified starch degradation products are used as polysaccharides, these can also be generated by known processes before polymerization starts of the polymerization template, or alternatively by enzymatic or oxidative degradation from native starches or chemically modified starches.
  • the polymerization of the monomers mentioned is carried out by the aqueous emulsion polymerization process.
  • the monomers are radically polymerized, i.e. the polymerization is initiated by means of suitable radical polymerization initiators.
  • suitable radical polymerization initiators i.e. to catalyze water-resistant transition metal catalysts.
  • radicals which are capable of triggering a radical aqueous emulsion polymerization can be considered as free radical polymerization initiators.
  • peroxides for example alkali metal peroxodisulfates, and azo compounds can be used.
  • Combined systems which consist of at least one of the following are also used an organic reducing agent and at least one peroxide and / or hydroperoxide are composed, for example tert-butyl hydroperoxide with the sodium salt of hydroxymethanesulfonic acid or hydrogen peroxide with ascorbic acid.
  • Combined systems which contain a small amount of a metal compound which is soluble in the polymerization medium and whose metallic component can occur in several valence levels, for example ascorbic acid / iron (II) sulfate / hydrogen peroxide, the sodium salt of which often being used instead of ascorbic acid Hydroxymethanesulfonic acid, sodium sulfite, sodium hydrogen lfit or sodium disulfide and instead of hydrogen peroxide tert-butyl hydroperoxide or alkali peroxodisulfates and / or ammonium peroxodisulfate, preferred initiators are the ammonium or alkali metal salts of peroxosulfates Peroxodisulfates, in particular sodium or potassium peroxodisulfate.
  • the amount of free-radical initiator systems used, based on the total amount of the monomers to be polymerized, is preferably from 0.01 to 2% by weight.
  • the polymerization can optionally be carried out in the presence of regulators.
  • Suitable regulators are, for example, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, hydroxylammonium sulfate and hydroxylammonium phosphate are used which contain sulfur in organically bound form, such as SH compounds containing organic compounds, such as thioapple acid, thioglycol acetic acid, mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, mercaptopropanol, mercaptoburanols, mercaptohexanol, dodecyl mercaptan and tert-dodecyl mercury can also be used of hydrazine, such as hydrazmium sulfate, n-butyral
  • transition metal catalysts use is made, for example, of water-soluble, ruthenium-based carbonyl complexes, such as those e.g. by R.H. Grubbs et al, J. Am. Chem. Soc. 1996, 118, pp. 784-790.
  • the reaction conditions given there can in principle be transferred to the method according to the invention.
  • the interfacially active substances suitable for the polymerization include polyvinyl alcohols, cellulose derivatives or copolymers containing vinylpyrrolidone.
  • a detailed description of further suitable protective colloids can be found in Mouben - 'Jeyl, Metho ⁇ en der organic Chemistry, Vol. XIV / 1, Macromoleculars Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411-420 Mixtures of emulsifiers and / or protective colloids can also be used.
  • Emulsifiers are preferably used as surface-active substances, the relative molecular weights of which, in contrast to the protective colloids, are usually below 2000 daltons. They can be of anionic, cationic and nonionic nature
  • Usable non-ionic emulsifiers include araliphatic or aliphatic non-ionic emulsifiers, for example ethoxylated mono-, di- and t ⁇ alkylphenols (EO grade: 3 to 50, alkyl radical: C 4 -C 10 ), ethoxylates of long-chain alcohols (EO grade 3 to 50, alkyl radical (C 8 -C 36 ) and polyethylene oxide / polypropylene oxide block copolymers Ethoxylates of long-chain alkali nole (alkyl radical average degree of ethoxylation 10 to 50) and among them particularly preferably those with a linear C 1 -C 3 -alkyl radical and an average degree of ethoxylation of 10 to 50 and ethoxylated monoalkylphenols.
  • araliphatic or aliphatic non-ionic emulsifiers for example ethoxylated mono-, di- and t ⁇ alkylphenols (EO grade
  • Suitable amonic emulsifiers include alkali and ammonium salts of alkyl sulfates (alkyl radical: C "-C 22 ), of sulfuric acid half-esters of ethoxylated alkanols (EO degrees. 2 to 50), alkyl radical: C 12-C_8) unc ⁇ ethoxylated alkylphenoie ( EO degree: 3 to 50, alkyl radical C 4 -C 9 ), of alkyl sulfonic acids (alkyl radical. C ⁇ 2 -C 18 ) and of alkylarylsulfonic acids (alkyl radical: C 9 -C 8 ).
  • emulsifiers can be found in Houbel-Weyl, Methods of Organic Chemistry, Vol. XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208).
  • anionic emulsifiers are bis (pnenylsulfonic acid) ethers or their alkali metal or ammonium salts which carry a C -C 22 -alkyl group on one or both aromatic rings. These compounds are generally known, for example from US Pat. No. 4,269,749, and are commercially available, for example as Dowfax® 2A1 (trademark of the Dow Chemical Company).
  • Suitable katiomscne emulsifiers are preferably quaternary ammonium halides, for example trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammomum chloride or quaternary compounds of NC 6 -C 2 o ⁇ alkylpy ⁇ dmen, -morpholmen or -lmidazium, zE Nid Lauryl.
  • polysaccharides according to the invention are used, especially if one uses catalytic, amonic or amphiphilic starches or very particularly preferably starch degradation products of this type, since they also fulfill the functions of an emulsifier or protective colloid.
  • seed polymers can also be used in the process according to the invention. They are preferably used as an aqueous dispersion. In principle, their composition is independent of the monomer composition to be polymerized. Preferred are seed polymers whose composition is comparable in terms of the main monomers b) to the monomer mixture to be polymerized. If the polymerization reaction is carried out in the presence of such starting polymers, these are introduced according to the invention in amounts of preferably 0.01 to 10, in particular 0.1 to 5% by weight, based on the monomers to be polymerized, in the reaction vessel. In the process according to the invention, the polymerization reaction can be followed by a conventional deodorization process (for example physical or chemical deodorization).
  • a conventional deodorization process for example physical or chemical deodorization
  • the physical processes include, for example, distillation processes, in particular steam distillation and stripping with an inert gas.
  • Chemical deodorization is generally understood to mean a radical polymerization, in particular under the action of redox imitators, as described, for example, in DE-A 44 35 423, DE-A 44 19 518 and DE-A. .A 44 35 422 are listed.
  • the dispersion obtained can be diluted with a water-miscible organic liquid.
  • the amount of organic liquid in the dispersion can be up to 75% by weight, based on the total weight of the liquid phase. Suitable organic liquids have already been mentioned above, the polyols mentioned being preferred, in particular if the dispersion is used for oil treatment
  • hydrophobically modified polymers obtainable by the process according to the invention can be used, for example, as thickeners, e.g. m cosmetic creams or lotions, as a component m lacquer formulations, as a sizing agent for paper manufacture, as a coating material, as an adhesive raw material, as a detergent additive or as a dispersant for pigments.
  • thickeners e.g. m cosmetic creams or lotions
  • m lacquer formulations e.g
  • Crosslinked polyacrylic acids which are obtainable, for example, by copolymerizing acrylic acid and hydrophobic monomers a) and optionally bl) in the presence of a saccharified starch and a water-insoluble crosslinking agent, such as divmylbenzene, are used as superabsorbents or thickeners for aqueous systems.
  • a saccharified starch and a water-insoluble crosslinking agent such as divmylbenzene
  • the dispersion according to the invention can be used for oil treatment, in particular for lowering the pour point, e.g. of crude oil, heating oil or diesel oil.
  • the stated glass transition temperatures and melting peaks were determined by means of DSC (differential calorimetry). The glass transition temperatures were evaluated using the mid-point method (according to ASTM D3418-82).
  • the weight-average molecular weights were determined by means of gel permeation chromatography (see above).
  • the K values were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 1932, pp. 58-56. The following abbreviations are used:
  • the strong numbers 1 to 5 were obtained from Cerestar Kunststoff GmbH, D-47809 Krefeld, the strong numbers 6 to 8, 10 were obtained from National Starch and Chemical GmbH, D-67435 Neustadt / W. based.
  • the Strong No. 9 was created by the A.E. Staley Manufacturmg Company, Decatur, IL 62525, 1801-USA.
  • the saccharified starch derivative was placed in a reactor together with 330 g of water. It was flushed with inert gas and heated to 80 ° C. To this mixture was added 0.5 g of sodium persulfate in the form of a 2% by weight aqueous solution. 500 g of the desired monomer mixture were mixed with 7.5 g of sodium dodecylbenzenesulfonate (in the form of a 15% strength by weight aqueous solution). 3 g of this mixture were added to the reactor. Then polymerized 15 mm at 80 ° C. The remaining amount of monomer and 2 g of sodium persulfate (as a 2% by weight aqueous solution) were then metered in over a period of 8 hours.
  • a film was produced from the polymer dispersions by casting on aluminum foil and drying at 110 ° C., and this was examined by means of DSC.
  • the measured glass temperatures are summarized in the following tables.
  • the mono used Mere and strong as well as the respective amounts are given in the following tables.
  • the amount of the individual monomers as well as the amount of starch sugared is based on the total amount of monomers.
  • Polymerization temperature The incorporation of stearyl acrylate into the polymer chain can be promoted both by increasing the dosing time, increasing the emulsifier or starch concentration and increasing the reaction temperature.
  • Feed 1 400 g of deionized water
  • Feed 2 200 g of deionized water
  • Feed 1 400 g of deionized water
  • Feed 2 200 g of deionized water, 6.6 g of sodium peroxodisulfate
  • Feed 1 400 g of deionized water
  • Feed 2 200 g of deionized water 6.6 g of sodium peroxodisulfate dispersion coagulated during production
  • This mixture was metered into the reaction mixture over the course of 4.5 hours.
  • 2700 g of a 10% strength by weight solution of sodium persulfate in water were added over the course of 4.5 hours.
  • the reaction temperature was always kept at about 90 ° C.
  • the monomers and the initiator were fed in such a way that a pressure of 6 bar was not exceeded.
  • the mixture was then left to react for 3 hours and the reaction mixture was chemically treated with 4 g of t-butyl hydroperoxide and 3 g of Rongalit® for 4 hours in the manner described for Examples 1 ff.
  • the solids content of the dispersion was about 18% by weight.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé pour la préparation de polymères par polymérisation en émulsion aqueuse de monomères éthyléniquement insaturés, comportant au moins un monomère hydrophobe présentant une hydrosolubilité inférieure à 0,01 g/l à 25 °C (1 atm) et éventuellement un ou plusieurs monomères copolymérisables avec celui-ci. Ce procédé est caractérisé en ce que l'on effectue la polymérisation en présence d'un polysaccharide non cyclique en mesure de former des clathrates. L'invention concerne d'autre part les polymères obtenus au moyen de ce procédé, ainsi que leur utilisation.
PCT/EP1997/006812 1996-12-06 1997-12-05 Procede pour la preparation de polymeres par polymerisation en emulsion WO1998024821A2 (fr)

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AU55604/98A AU5560498A (en) 1996-12-06 1997-12-05 Method for producing polymers by emulsion polymerization

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DE1996150790 DE19650790A1 (de) 1996-12-06 1996-12-06 Verfahren zur Herstellung von Polymerisaten durch Emulsionspolymerisation
DE19650790.1 1996-12-06

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WO1998024821A3 WO1998024821A3 (fr) 1998-07-23

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6037380A (en) * 1997-04-11 2000-03-14 Fmc Corporation Ultra-fine microcrystalline cellulose compositions and process
US6800675B1 (en) 1999-10-19 2004-10-05 Südzucker Aktiengesellschaft Mannheim/Ochsenfurt Emulsion polymerization method

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5959024A (en) * 1997-06-30 1999-09-28 National Starch And Chemical Investment Holding Corporation Acrylic latex binders prepared with saccharide stabilizers
DE19934836C1 (de) * 1999-07-24 2000-07-27 Clariant Gmbh Verwendung von Fettsäureglucamiden als Emulgatoren in der Emulsionspolymerisation
DE10125138A1 (de) 2001-05-22 2002-12-05 Basf Ag Verfahren zur Herstellung von Copolymerisaten aus Kohlenmonoxid und einer olefinisch ungesättigten Verbindung in wässrigem Medium
CA2800927C (fr) 2010-06-14 2018-09-25 Basf Se Dispersions de polymeres de composes vinyliques aromatiques et de monomeres d'acrylates preparees en presence de latex semence et de composes d'hydrate de carbone
ES2680818T3 (es) * 2014-07-10 2018-09-11 Basf Se Procedimiento para preparar dispersiones acuosas estables a la congelación-descongelación

Citations (4)

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Publication number Priority date Publication date Assignee Title
GB932389A (en) * 1959-08-24 1963-07-24 Vinyl Products Ltd Improvements in or relating to polymer emulsions or dispersions
US3138564A (en) * 1955-09-21 1964-06-23 Polymer Corp Process for grafting a monomer onto an oxidized polysaccharide
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
EP0536588A1 (fr) * 1991-10-07 1993-04-14 BASF Aktiengesellschaft Corps pour le moulage

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3138564A (en) * 1955-09-21 1964-06-23 Polymer Corp Process for grafting a monomer onto an oxidized polysaccharide
GB932389A (en) * 1959-08-24 1963-07-24 Vinyl Products Ltd Improvements in or relating to polymer emulsions or dispersions
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
EP0536588A1 (fr) * 1991-10-07 1993-04-14 BASF Aktiengesellschaft Corps pour le moulage

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6037380A (en) * 1997-04-11 2000-03-14 Fmc Corporation Ultra-fine microcrystalline cellulose compositions and process
US6800675B1 (en) 1999-10-19 2004-10-05 Südzucker Aktiengesellschaft Mannheim/Ochsenfurt Emulsion polymerization method

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AU5560498A (en) 1998-06-29
DE19650790A1 (de) 1998-06-10
WO1998024821A3 (fr) 1998-07-23

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