EP1214358A1 - Procede de diminution de la quantite de monomere residuelle dans des dispersions polymeres aqueuses - Google Patents

Procede de diminution de la quantite de monomere residuelle dans des dispersions polymeres aqueuses

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Publication number
EP1214358A1
EP1214358A1 EP00960569A EP00960569A EP1214358A1 EP 1214358 A1 EP1214358 A1 EP 1214358A1 EP 00960569 A EP00960569 A EP 00960569A EP 00960569 A EP00960569 A EP 00960569A EP 1214358 A1 EP1214358 A1 EP 1214358A1
Authority
EP
European Patent Office
Prior art keywords
aftertreatment
alkyl
polymer dispersion
monomers
aqueous
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Withdrawn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
EP00960569A
Other languages
German (de)
English (en)
Inventor
Claudia Wood
Reinhard Schneider
Eberhard Beckmann
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1214358A1 publication Critical patent/EP1214358A1/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Withdrawn legal-status Critical Current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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/006—Removal of residual monomers by chemical reaction, e.g. scavenging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/919—Catalyst injection technique in addition polymerization processes

Definitions

  • the invention relates to a method for reducing the amount of residual monomers in aqueous polymer dispersions by chemical aftertreatment with an initiator system.
  • Aqueous polymer dispersions after their preparation by a radically initiated aqueous emulsion polymerization, contain, in addition to a polymer solids content of generally 30 to 75% by weight, an undesirable proportion of non-
  • Residual monomers This is due to an incomplete polymerization of the ethylenically unsaturated monomers used in the main radical polymerization, which usually up to a monomer conversion of 95% by weight and preferably from 98 to
  • redox systems can be used for the chemical aftertreatment of aqueous polymer dispersions, the reducing agents of which comprise an adduct of hydrogen sulfite anion and a ketone with 3 to 8 C atoms and / or the conjugate acid of this adduct.
  • the aftertreatment is carried out in the presence of
  • EP-A 767 180 recommends a redox initiator system made from organic hydroperoxides for the reduction of residual monomer contents, which are not or only very poorly soluble in water and among other things. Adducts of aldehydes, the carbon chain of which has 4 to 6 carbon atoms and bisulfites.
  • DE-A 19743759 discloses reducing agents of sulfinic acid derivatives accessible on the basis of substituted carbonyl compounds, which include can also be used as a component of redox initiator systems in free-radically initiated aqueous emulsion polymerization.
  • the object of the present invention was to provide a new, effective process for reducing the amount of residual monomers in aqueous polymer dispersions.
  • the amount of residual monomers should be reduced without the formation of micro-coagulum and should be easy to use technically.
  • R 1 is hydrogen, an alkyl or an aryl group, and / or
  • R 2 represents a hydrogen atom, an alkyl, alkenyl, cycloalkyl or aryl group, which group may have 1, 2 or 3 substituents which are independent of one another are selected from hydroxy, alkyl, O-alkyl, halogen and trihalomethyl, and
  • R 2 is an alkyl, alkenyl, cycloalkyl or aryl group
  • R 3 can also be a methyl group
  • the at least one oxidizing agent of the redox initiator system should be able to form free radicals.
  • hydrogen peroxide is preferably used as the oxidizing agent.
  • potassium peroxide, sodium peroxide, sodium perborate and other precursors which form hydrogen peroxide in aqueous medium are also frequently used.
  • ammonium, potassium or sodium persulfate, peroxodisulfuric acid and their mono- and di-ammonium, potassium or sodium salts, as well as ammonium, potassium or sodium perphosphate or diperphosphate, potassium permanganate and other salts of peracids can also be used, for example become.
  • organic hydroperoxides such as tert are also suitable. -Butyl hydroperoxide and cumene hydroperoxide. It is also possible to use mixtures of different oxidizing agents.
  • the amount of the at least one oxidizing agent added according to the invention in the aftertreatment is usually in the range from 0.001 to 5% by weight, preferably 0.002 to 3% by weight, particularly preferably 0.003 to 2% by weight, very particularly preferably 0 , 01 to 1 wt .-% and preferably 0.02 to 0.5 wt .-%, based on the total amount of monomers used to prepare the polymer dispersion.
  • reaction products from carbonyl compounds of the general formula I with inorganic dithionites such as sodium dithionite, potassium dithionite, magnesium dithionite, calcium dithionite, strontium dithionite, barium dithionite, are used as at least one reducing agent and zinc dithionite or mixtures thereof.
  • inorganic dithionites such as sodium dithionite, potassium dithionite, magnesium dithionite, calcium dithionite, strontium dithionite, barium dithionite.
  • sodium dithionite is preferably used.
  • R 2 represents a hydrogen atom, an alkyl, alkenyl, cycloalkyl or aryl group, which group can have 1, 2 or 3 substituents which are independently selected from hydroxy, alkyl, O-alkyl, halogen and trihalomethyl, and
  • R 3 can also be a methyl group.
  • Alkyl stands for straight-chain or branched alkyl groups which generally have 1 to 6 and often 1 to 4 carbon atoms. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl etc. The same applies to the alkyl group within O-alkyl.
  • Alkenyl stands for straight-chain or branched alkenyl groups, which generally have 3 to 8 carbon atoms and often 3 to 6 carbon atoms. A preferred alkenyl group is the allyl group.
  • Cyclo- alkyl is in particular C 3 - to C ⁇ -cycloalkyl, where cyclo- pentyl and cyclohexyl are particularly preferred.
  • Aryl is preferably phenyl or naphthyl. If the aryl radical is a phenyl group and is substituted, it preferably has two substituents. These are particularly available in the 2- and / or 4-position.
  • Halogen represents fluorine, chlorine, bromine and iodine, preferably chlorine and bromine and in the case of tri-halogenomethyl preferably fluorine.
  • M preferably represents an ammonium, alkali metal or equivalent of an alkaline earth or zinc ion.
  • Suitable alkali metal ions are in particular sodium and potassium ions, suitable alkaline earth metal ions are especially magnesium and calcium ions.
  • a carbonyl compound of the general formula I is preferably used, in which R 2 represents a hydrogen atom and R 3 represents -C0 2 M or -C0 2 R 4 and M and R 4 have the meanings given above. Particularly preferred is glyoxylic acid (R 2 stands for hydrogen atom and R 3 stands for -C0 2 M, where M also stands for hydrogen atom) or its monohydrate. Also of particular importance are carbonyl compounds in which R 2 is methyl, ethyl, propyl and R 3 is methyl. Acetone (R 2 and R 3 stands for methyl) is often used.
  • Carbonyl compounds of the general formula I and inorganic dithionites can be in at least one reducing agent in a molar ratio of 0.1 to 1 to 1 to 0.1, preferably 0.3 to 1 to 1 to 0.3, particularly preferably 0.5 to 1 up to 1 to 0.5 and very particularly preferably 1 to 0.5.
  • the amount of at least one reducing agent used according to the invention is usually in the range from 0.005 to 5% by weight, preferably from 0.01 to 3% by weight, particularly preferably from 0.03 to 2% by weight and very particularly preferably 0.05 to 1% by weight, based on the total amount of monomers used to prepare the polymer dispersion. Higher amounts of reducing agent are also possible, but are generally not economically viable.
  • metal compounds which are completely soluble in the aqueous medium of the polymer dispersion and whose metallic component is also capable of being present in several valence stages is advantageous for the aftertreatment.
  • the dissolved metal ions have a catalytic effect and support the electron transfer reactions between the actually effective oxidizing and reducing agents.
  • iron, copper, manganese, vanadium, nickel, cobalt, titanium, cerium or chromium ions are considered as dissolved metal ions.
  • mixtures of different, non-interfering metal ions such as the Fe 2 / 3+ / VS04- system. Iron ions are often used.
  • the dissolved metal ions are used in catalytic amounts, usually in the range from 1 to 1000 ppm, frequently from 5 to 500 ppm and often from 10 to 100 ppm, based on the total amount of monomers used to prepare the polymer dispersion.
  • the components of the redox initiator system used according to the invention are expediently used for aftertreatment of the polymer dispersion heated to about 50 to 150 ° C., preferably 60 to 120 ° C. and particularly preferably to 80 to 100 ° C., preferably under normal pressure, but if appropriate also under a pressure Pressure greater than or less than 1 bar (absolute), gradually added simultaneously or in succession with stirring, in the latter case preferably the at least one oxidizing agent being added first.
  • the simultaneous metering in of the at least one oxidizing agent and the at least one reducing agent via two separate inlets is particularly favorable.
  • the initiator components can be added, for example, from above, below or through the side of the reactor. However, the initiator system is preferably metered in from below. Since the optimal duration of the initiator metering depends on the monomer composition, the size of the
  • the duration of the initiator addition can be a few seconds or several hours. If catalytic amounts of metal compound are used in the aftertreatment, it is particularly advantageous to add them to the polymer dispersion before adding the at least one oxidizing agent and the at least one reducing agent.
  • the aftertreatment is usually carried out at a pH ⁇ 8.
  • Bases such as, for example, sodium hydroxide solution, ammonia water or triethanolamine can in principle be used to adjust the pH of the aqueous polymer dispersion.
  • a pH range of> 2 and ⁇ 8 is favorable for the aftertreatment of the aqueous polymer dispersion, a pH range between> 3 and ⁇ 7 is preferred.
  • pH adjustment with bases under unfavorable circumstances there may be local areas with higher levels for a short time pH values come in which the catalyzed metal ions which may have been added would be converted into poorly soluble hydroxides or hydroxo complexes.
  • EDTA ethylenediaminetetraacetic acid
  • nitrilotriacetic acid nitrilotriacetic acid
  • diethylenetriaminepentaacetic acid nitrilotriacetic acid
  • Sodium salts and / or the use of stable metal ion complexes such as, for example, iron (III) / sodium ethylenediamine tetraacetate (Fe / Na-EDTA), are particularly advantageous.
  • the process according to the invention is particularly suitable for reducing the amount of residual monomers in aqueous polymer dispersions caused by free-radically initiated aqueous dispersions Emulsion polymerization of at least one ethylenically unsaturated monomer are available.
  • the process according to the invention includes in particular in a simple manner, radically polymerizable monomers, such as, for example, the olefins ethylene, vinylaromatic monomers, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, esters of vinyl alcohol and mono- having 1 to 18 carbon atoms
  • radically polymerizable monomers such as, for example, the olefins ethylene, vinylaromatic monomers, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes
  • carboxylic acids such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid , with generally 1 to
  • alkanols such as, in particular, methyl, ethyl, n-butyl, isobutyl and 2-ethylhexyl esters of acrylic acid and methacrylic acid, Maleic acid dimethyl ester or maleic acid di-n-butyl ester, nitriles ⁇ , ⁇ -monoethylenically unsaturated carboxylic acids, such as acrylic
  • the monomers mentioned generally form the main monomers which, based on the total amount of the
  • Monomers which have an increased water solubility under the abovementioned conditions are, for example, ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids and their amides, such as e.g. Acrylic acid, methacrylic acid, maleic acid, fumarate
  • the above-mentioned monomers having increased solubility in water are normally polymerized into polymer dispersions only as modifying monomers. In this case, amounts of less than 50% by weight, generally 0.5 to 45% by weight, preferably 1 to 10% by weight, based on the total amount of the monomers to be polymerized, are used.
  • Monomers which usually increase the internal strength of the films of the aqueous polymer dispersions normally have at least one epoxy, hydroxyl, N-methylol or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds.
  • N-alkylolamides of ⁇ , ⁇ -mono-ethylenically unsaturated carboxylic acids having 3 to 10 C atoms among which the N-methylolacrylamide and the N-methylolmethacrylamide are very particularly preferred, and their esters with 1 to 4 C atoms - pointing alkanols.
  • two monomers having vinyl radicals two monomers having vinylidene radicals and two monomers having alkenyl radicals are also suitable.
  • the di-esters of dihydric alcohols with ⁇ , ⁇ -onoethylenically unsaturated monocarboxylic acids are particularly advantageous, among which acrylic and methacrylic acid are preferred.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 3-propylene glycol diacrylate, 1, 3-butylene glycol diacrylate and 1, -Blyglycolate,
  • the methacrylic acid and acrylic acid-Ci-Cs-hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate, and compounds such as diacetone acrylic amide and acetylacetoxyethyl acrylate are also of particular importance or methacrylate.
  • the above-mentioned monomers based on the total amount of the monomers to be polymerized, are usually copolymerized in amounts of 0.5 to 10% by weight.
  • the polymerization temperature is generally 20 to 150 ° C and preferably 60 to 120 ° C.
  • the polymerization may take place under pressure.
  • anionic emulsifiers are used as emulsifiers, alone or in a mixture with nonionic dispersants, in an amount of in particular 0.5 to 6% by weight of the total amount of monomers.
  • the aftertreatment of the aqueous polymer dispersion according to the invention for reducing the amount of residual monomers takes place in particular after the total amount of monomers in the free-radical emulsion polymerization has been converted to at least 95% by weight and preferably to at least 98 to 99% by weight.
  • the ratios in the main polymerization and in the aftertreatment are generally different.
  • the radical entry into the dispersion particles is easy, while this is very difficult in the aftertreatment due to the low monomer concentration and the lack of increasing oligomer radicals.
  • different initiator systems are therefore generally required for the main polymerization and the aftertreatment.
  • the process according to the invention is generally carried out under an inert gas atmosphere (for example N 2 , Ar).
  • an inert gas atmosphere for example N 2 , Ar.
  • an aftertreatment according to the invention can also be carried out if necessary in the case of aqueous polymer dispersions whose polymers have been prepared by ionic initiation or by radical solution polymerization.
  • a styrene / n-butyl acrylate dispersion was prepared as in Example 1. It had a solids content of 52% by weight and a pH of 4.3.

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  • Chemical & Material Sciences (AREA)
  • General 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)

Abstract

La présente invention concerne un procédé de diminution de la quantité de monomère résiduelle dans des dispersions polymères aqueuses, par traitement ultérieur avec un système d'initiateurs redox.
EP00960569A 1999-09-08 2000-08-31 Procede de diminution de la quantite de monomere residuelle dans des dispersions polymeres aqueuses Withdrawn EP1214358A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19942776A DE19942776A1 (de) 1999-09-08 1999-09-08 Verfahren zur Verminderung der Restmonomerenmenge in wäßrigen Polymerisatdispersionen
DE19942776 1999-09-08
PCT/EP2000/008509 WO2001018070A1 (fr) 1999-09-08 2000-08-31 Procede de diminution de la quantite de monomere residuelle dans des dispersions polymeres aqueuses

Publications (1)

Publication Number Publication Date
EP1214358A1 true EP1214358A1 (fr) 2002-06-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP00960569A Withdrawn EP1214358A1 (fr) 1999-09-08 2000-08-31 Procede de diminution de la quantite de monomere residuelle dans des dispersions polymeres aqueuses

Country Status (5)

Country Link
US (1) US6639048B1 (fr)
EP (1) EP1214358A1 (fr)
AU (1) AU7282200A (fr)
DE (1) DE19942776A1 (fr)
WO (1) WO2001018070A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10206994A1 (de) * 2001-11-12 2003-05-22 Ercros Deutschland Gmbh Kunststoffdispersion und Verfahren zu ihrer Herstellung
DE10241481B4 (de) 2002-09-07 2006-07-06 Celanese Emulsions Gmbh Verfahren zum Herstellen von wässrigen Polymerdispersionen mit sehr niedrigen Restmonomergehalten und deren Verwendung

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
DE4232194A1 (de) * 1992-09-25 1994-03-31 Roehm Gmbh Verfahren zur Verringerung des Restmonomerengehaltes bei der Herstellung von Perlpolymerisaten
CN1120180C (zh) 1994-06-03 2003-09-03 巴斯福股份公司 聚合物水分散液的制备
IT1276816B1 (it) 1995-10-04 1997-11-03 Atochem Elf Italia Emulsione a basso voc
DE19741184A1 (de) 1997-09-18 1999-03-25 Basf Ag Verfahren zur Verminderung von Restmonomeren in Flüssigsystemen unter Zugabe eines Redoxinitiatorsystems
DE19839199A1 (de) 1998-08-28 2000-03-02 Basf Ag Verfahren zur Verminderung der Restmonomerenmenge in wässrigen Polymerdispersionen
DE19840586A1 (de) * 1998-09-05 2000-03-09 Basf Ag Verfahren zur Verminderung der Restmonomerenmenge in wässrigen Polymerdispersionen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0118070A1 *

Also Published As

Publication number Publication date
AU7282200A (en) 2001-04-10
DE19942776A1 (de) 2001-03-15
US6639048B1 (en) 2003-10-28
WO2001018070A1 (fr) 2001-03-15

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