EP2147021A1 - Utilisation de tensioactifs non ioniques en tant qu'émulsifiants pour la polymérisation en émulsion - Google Patents

Utilisation de tensioactifs non ioniques en tant qu'émulsifiants pour la polymérisation en émulsion

Info

Publication number
EP2147021A1
EP2147021A1 EP08735103A EP08735103A EP2147021A1 EP 2147021 A1 EP2147021 A1 EP 2147021A1 EP 08735103 A EP08735103 A EP 08735103A EP 08735103 A EP08735103 A EP 08735103A EP 2147021 A1 EP2147021 A1 EP 2147021A1
Authority
EP
European Patent Office
Prior art keywords
alcohol
emulsifiers
emulsion polymerization
alcohols
mol
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Withdrawn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
EP08735103A
Other languages
German (de)
English (en)
Inventor
Thorsten Roloff
Thomas Schliwka
Katharina Hömberg
Thomas Mausberg
Douglas Rhubright
Mike Wiggins
Wolfgang Breuer
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.)
Cognis IP Management GmbH
Original Assignee
Cognis IP Management 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 Cognis IP Management GmbH filed Critical Cognis IP Management GmbH
Publication of EP2147021A1 publication Critical patent/EP2147021A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

Definitions

  • the invention relates to the use of special nonionic surfactants as emulsifiers for emulsion polymerization.
  • These surfactants are adducts of ethylene oxide and / or propylene oxide with diterpene alcohols selected from the group consisting of abietyl alcohol, dihydroabietyl alcohol, tetrahydroabietyl alcohol and dehydroabietyl alcohol.
  • Emulsion polymerization is a special method of polymerization in which low-water-soluble monomers are emulsified in water with the aid of emulsifiers and polymerized using water-soluble initiators such as potassium peroxodisulfate or redox initiators.
  • water-soluble initiators such as potassium peroxodisulfate or redox initiators.
  • Anionic and / or nonionic surfactants are the essential ingredients here.
  • Alkyphenol-based products such as the corresponding ethoxylates and ether sulfates are still considered to be standards in the emulsion polymerization process under discussion, although the question of more environmentally friendly products is increasingly being asked.
  • emulsifiers for emulsion polymerization.
  • DE-A-15.95.393 describes stable aqueous emulsions of aqueous special ternary acrolein-acrylonitrile-ethyl acrylate copolymers, which are especially suitable for leather finishing. These are obtained by washing in aqueous medium using classical emulsifiers such as sodium lauryl sulfate and, after a special len mixed redox process, namely in the presence of hydrogen peroxide and ascorbic acid, optionally in addition in the presence of iron (II) salts.
  • Example 1 after completion of the emulsion polymerization, ie to the already finished emulsion, an ethoxylated with 30 mol of ethylene oxide Hydroabietinalkohol and expressly for the subsequent stabilization of the latex.
  • US-A-2,606,178 is concerned with styrene polymerization by emulsion polymerization. It is expressly stated that nonionic emulsifiers are poorly suited for this purpose (compare page 2, lines 48-50).
  • the invention proposes special anionic emulsifiers which are obtained as follows: Adducts of ethylene or propylene oxide are prepared on hydrocarbon acids or alcohols, e.g. of tall oil, lorol or hydroabietyl alcohol and then sulfated or sulfonated. The corresponding sulfates or sulfonates are used as anionic emulsifiers.
  • WO-A-2004/065518 describes specific nitrogen-containing substances which are characterized by formula (I). They contain as radical R a cycloaliphatic Hydrocar- byl distr, in particular abietyl, hydroabietyl, dihydroabietyl and tetrahydroabietyl.
  • R a cycloaliphatic Hydrocar- bylised, in particular abietyl, hydroabietyl, dihydroabietyl and tetrahydroabietyl.
  • the compounds (I) are accessible by alkoxylating amines with the stated cycloaliphatic hydrocarbyl groups.
  • the compounds (I) are used in the field of extraction of oil or gas from subterranean formations.
  • emulsifiers for the emulsion polymerization you should in particular cause that only a very small coagulum occurs.
  • a further object was to provide compounds which, when used as emulsifiers in emulsion polymerization, lead to polymer dispersions (aqueous latices) having a good freeze-thaw stability.
  • a further object was to provide compositions which, when used as emulsifiers in the emulsion polymerization, lead to polymer dispersions (aqueous latices) having good electrolyte stability.
  • adducts 3-20 mol of ethylene and / or propylene oxide with 1 mol of diterpene alcohols selected from the group of abietyl alcohol, dihydroabietylalcohol, tetrahydroabietylalcohol and dehydroab- tylalkohol are suitable as (nonionic) emulsifiers for emulsion polymerization.
  • the present invention accordingly provides for the use of adducts of 3-20 mol of ethylene and / or propylene oxide with 1 mol of diterpene alcohols selected from the group of abietyl alcohol, dihydroabietyl alcohol, tetrahydroabietyl alcohol and dehydroabietyl alcohol as emulsifier (nonionic) for the emulsion polymerization.
  • Abietic acid (C 2O H 30 O 2) is a resin acid which is one of the diterpenes. Its structural formula is known to be represented by the following formula:
  • nonionic emulsifiers for the emulsion polymerization addition products 3-20 mol of ethylene and / or propylene oxide to 1 mol Diterpenalkohole selected from the group of abietyl alcohol, dihydroabietyl, Tetrahydroabietylalkohol and dehydroabietyl alcohol.
  • the compounds mentioned can be used individually or in a mixture.
  • An example of a particularly suitable mixture are the addition products of 3 to 20 moles of ethylene oxide to technical mixtures, the predominantly hydrogenated forms of abietyl alcohol. Very particular preference is given to addition products of from 5 to 15 mol of ethylene oxide on Abitol TM E, available from Eastman.
  • the compounds to be used according to the invention can be used as sole emulsifiers (primary emulsifiers) in the emulsion polymerization.
  • emulsifiers primary emulsifiers
  • the nonionic emulsifiers according to the invention are used in combination with anionic emulsifiers, in particular those selected from the group of fatty alcohol sulfates, fatty alcohol ether sulfates and sulfosuccinates.
  • the compounds to be used according to the invention are used in the emulsion polymerization as emulsifiers, in an amount of from 0.5 to 10% by weight, preferably from 1 to 5% by weight and in particular from 1 to 3% by weight - the% by weight Data are in each case based on the total amount of monomers used in the emulsion polymerization - used.
  • the compounds to be used according to the invention are generally suitable for use as emulsifiers in the preparation of aqueous latices, which are understood as meaning aqueous emulsions or dispersions of polymers and / or copolymers which are usually accessible by emulsion polymerization.
  • the nature of the polymers and copolymers in these aqueous latices is not particularly limited per se. However, polymers or copolymers based on the following monomer units are particularly preferred: acrylic acid, acrylic acid esters, butadiene, methacrylic acid, methacrylic acid esters, styrene, vinyl acetate and vinyl versatate.
  • the compounds to be used according to the invention give aqueous latices in particular a good freeze-thaw stability and electrolyte stability. Furthermore, they cause that produced from these latices plastic films are characterized by good resistance to alkali.
  • the "freeze-thaw stability" is a parameter known to the person skilled in the art
  • the principle of the determination of the freeze-thaw stability can be taken from the standard ISO 1147.
  • the determination of the freeze-thaw stability of aqueous latices is effected according to ISO 1147 in that aqueous latices of different minimum temperatures cools (concretely, -5, -10 and -15 0 C) and holding for 16 hours at this temperature.
  • the mixture is heated to room temperature (about +23 0 C), holding for 8 hours at this temperature If this is not the case, ie if the latex dispersion was stable against coagulation, the described cycle (cooling and thawing) is repeated and rechecked for coagulation. Tau cycle is repeated until either coagulum formation is observed or a maximum of 5 cycles without coagulum formation is reached aligem cool still stable, the process is repeated at the next lower temperature.
  • the aqueous latexes are preferably used in amounts ranging from 50 to 100 g.
  • electrostatic stability is understood to mean that a polymer dispersion with the addition of 1% strength by weight or 10% strength by weight aqueous solutions of inorganic salts with 1 to 3 valent cations (eg NaCl, CaCl 2 or A1 2 (SO 4 ) 3 ) in the volume ratio 50:50 (polymer dispersion: saline) not coagulated.
  • Coagulation in this context means the agglomeration of insufficiently stabilized latex particles into coagulum. Coagulation is assessed visually.
  • alkali resistance is understood to mean that dried plastic films or coatings have only very little or no tarnishing when stored in a 4% strength NaOH solution.
  • the production of plastic films from aqueous latices is done in a conventional manner. This spreads aqueous latices in a thin layer and then subjects this layer to drying. The spreading of the layer usually takes place on a solid surface, for example by doctoring. Typically, this provides a layer thickness in the range of 100 to 2000 microns. Except However, by doctoring the layer can also be done by other conventional methods, for example, by spraying, brushing and dipping method.
  • additives are added to the aqueous latexes before spreading, as are usually used for coating purposes, for example, anorg. and organic pigments, fillers such as carbonates, silica, silicas, silicates and sulfates.
  • Abitol-5EO, Abitol-IOEO and Abitol-15EO were prepared by addition of 5, 10 or 15 ethylene oxide (EO) to the commercially available product Abitol TM E from Eastman.
  • EO ethylene oxide
  • Disponil® FES 32 fatty alcohol ether sulfate 4EO; Sodium salt (Cognis)
  • the method is used to determine the coagulum content which forms during the polymerization.
  • the resulting dispersion is filtered through a sieve bag (Loeffler) with a mesh width of 80 ⁇ m and a known tare weight. After drying the filter bag, this is weighed back, the difference results in the mass of coagulum.
  • the coagulum content is given in percent based on the theoretical solids content of the dispersion. The theoretical solids content is calculated from the sum of all solid constituents which are not vaporizable at temperatures ⁇ 150 ° C.
  • the method is used to determine the solids content of a product or a product solution / dispersion.
  • conclusions can be drawn on the active substance and thus on the effectiveness and price-worthiness of the product in question.
  • This experimentally determined solids content may differ from the theoretical; By comparing the experimentally determined solids content to the theoretically calculated solids content, conclusions can also be drawn about the reaction.
  • the method is used to determine the flow properties of latexes that are relevant to their manufacture, handling and processing.
  • the latex to be tested is placed in a 400 ml beaker, low mold and heated to the measurement temperature.
  • the measurement is carried out with the spindle required for the measuring range, which is introduced obliquely into the sample while rotating, in order to prevent air bubbles from becoming trapped underneath the measuring body.
  • the spindle is inserted until the notch is at the same height as the latex surface.
  • the measurement takes place at 20 rpm.
  • F factor of the spindle at 20 rpm.
  • the method is used to determine the pH of a polymer dispersion.
  • a previously calibrated pH meter is used.
  • the pH is measured in undiluted dispersion.
  • the method is used to determine the mean particle size range in colloidal particle systems by automatic measurement.
  • the measurement is performed on a Beckmann Coulter N5.
  • the standard measuring angle is 90 °.
  • One to two drops of the liquid to be tested are adjusted in a beaker with demineralized water to measurement concentration.
  • the demineralized water is added from a PE disposable syringe through a filter (blue / pore size 0.2 ⁇ m).
  • the thus diluted sample is placed in a cuvette and inserted into the test slot of the device. Care must be taken that the lower part of the cuvette is not touched, as fingerprints lead to incorrect results. Before the measurement is started, the cuvette should be left in the device for three minutes at rest.
  • the duration of the measurement should take 200 seconds. It is basically a double determination to perform. As a result, the median particle size (mean diameter) is given in nm. alkali resistance
  • This method is intended to provide information about the sensitivities of polymer films to alkaline media
  • a wet film is pulled onto glass slides.
  • the wet films are then dried at room temperature for 72 hours on a horizontally leveled surface.
  • the slides with the dried films are then placed edgewise in a 4% sodium hydroxide solution and used for evaluation after 3, 6, 24, 48 or x hours.
  • the assessment is based on a 6-point scale. The result should be the corresponding number.
  • the point scale is as follows:
  • the number of cycles is given at the particular temperature at which the dispersion has become unstable, or provided with "S" if the dispersion is still stable after five cycles.
  • Table 1 illustrates u.a. the effects observed when various salt solutions were added to the dispersions. These are the results of the electrolyte stability test. For this purpose, the following investigations were carried out:
  • Example 1 Comparative Example, no nonionic emulsifier was used.
  • Example 2 Comparative Example
  • NPlO adduct of 10 mol ethylene oxide to alkylphenol
  • Examples 3 to 5 show the use of the compounds according to the invention Abitol-5EO, Abitol-IOEO and Abitol-15EO as nonionic emulsifiers.
  • DI water means demineralized water.
  • TR means dry residue.
  • the quantities in the second column of the respective examples are parts by weight; the third column names the associated components.
  • Preparation of the preemulsions The demineralized water together with the emulsifiers was weighed into a 400 ml beaker and homogenized with a magnetic stirrer. The monomers were weighed under the hood into an 800ml beaker. The aqueous phase of the preemulsion was placed in the preemulsion flask. Subsequently, the monomers were added to the flask while stirring.
  • Reactor preparation The reactor receiver was placed in a 250 ml beaker and transferred to the reactor. Subsequently, the entire apparatus was purged with nitrogen for at least 15 minutes. The nitrogen flow was maintained throughout the reaction. The thermostat was set to 85 ° C and heated without circulation.

Landscapes

  • 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

Produits d'addition de 3 à 20 moles d'oxyde d'éthylène et / ou de propylène sur 1 mole d'alcools diterpéniques, choisis dans le groupe constitué par alcool abiétylique, alcool dihydroabiétylique, alcool tétrahydroabiétylique et alcool déshydroabiétylique, qui sont parfaitement adaptés en tant qu'émulsifiants non ioniques pour la polymérisation en émulsion.
EP08735103A 2007-04-18 2008-04-09 Utilisation de tensioactifs non ioniques en tant qu'émulsifiants pour la polymérisation en émulsion Withdrawn EP2147021A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US91246707P 2007-04-18 2007-04-18
PCT/EP2008/002788 WO2008128646A1 (fr) 2007-04-18 2008-04-09 Utilisation de tensioactifs non ioniques en tant qu'émulsifiants pour la polymérisation en émulsion

Publications (1)

Publication Number Publication Date
EP2147021A1 true EP2147021A1 (fr) 2010-01-27

Family

ID=39591103

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08735103A Withdrawn EP2147021A1 (fr) 2007-04-18 2008-04-09 Utilisation de tensioactifs non ioniques en tant qu'émulsifiants pour la polymérisation en émulsion

Country Status (6)

Country Link
US (1) US20080262132A1 (fr)
EP (1) EP2147021A1 (fr)
JP (1) JP2010525086A (fr)
CN (1) CN101657472A (fr)
BR (1) BRPI0810068A2 (fr)
WO (1) WO2008128646A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080161535A1 (en) * 2006-12-21 2008-07-03 Wiggins Michael S Thickening and wetting agents
WO2018027907A1 (fr) * 2016-08-12 2018-02-15 Dow Global Technologies Llc Composition tensioactive
CN108623454B (zh) * 2017-03-23 2021-04-30 南京林业大学 一种化合物及其在表面活化中的用途与制备方法
CN108611863A (zh) * 2018-05-17 2018-10-02 苏州联胜化学有限公司 一种无磷无氮型精练剂及其制备和使用方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2606178A (en) * 1949-06-18 1952-08-05 Monsanto Chemicals Alkali sulfate salts of ethylene oxide condensation products as emulsifies for styrene polymerization
NL256899A (fr) * 1959-10-12
CH469749A (de) * 1965-03-24 1969-03-15 Ciba Geigy Verfahren zur Herstellung von stabilen wässerigen Dispersionen von ternären Mischpolymerisaten und ihre Verwendung
US3874905A (en) * 1973-06-28 1975-04-01 Union Oil Co Wax coated paper of improved water resistance

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008128646A1 *

Also Published As

Publication number Publication date
CN101657472A (zh) 2010-02-24
US20080262132A1 (en) 2008-10-23
WO2008128646A1 (fr) 2008-10-30
JP2010525086A (ja) 2010-07-22
BRPI0810068A2 (pt) 2014-10-21

Similar Documents

Publication Publication Date Title
DE69501872T2 (de) Wässrige fluorpolymeremulsion und verfahren zu dessen herstellung
DE3319340C2 (fr)
DE69304525T2 (de) Aufkonzentrieren von fluoropolymerdispersion unter verwendung von hochsauren acrylpolymeren
EP0182282B1 (fr) Agent émulsifiant de polymérisation
DE3017543A1 (de) Waessrige dispersionen auf basis von (meth)acrylsaeurealkylester-polymerisaten mit zwei ausgepraegten, praktisch sich nicht ueberlappenden maxima in der teilchengroessenverteilung innerhalb spezieller teilchengroessenbereiche, sowie verfahren zu ihrer herstellung und ihre verwendung
EP0081083A2 (fr) Procédé de préparation de dispersions aqueuses bimodales de polymères à haute concentration
DE19833347A1 (de) Formaldehydarme Dispersion von Mikrokapseln aus Melamin-Formaldehyd-Harzen
EP0257413A2 (fr) Utilisation de copolymères d'éthylène-acétate de vinyle particuliers pour modifier le PVC
DE2706308A1 (de) Verfahren zum herstellen von polymerisatemulsionen des vinyltyps
DE2811481C2 (fr)
EP2147021A1 (fr) Utilisation de tensioactifs non ioniques en tant qu'émulsifiants pour la polymérisation en émulsion
DE2513162C2 (de) Wäßriger Latex auf der Basis eines Acrylcopolymeren
EP0195328B1 (fr) Dérivés de l'acide amino-succinique et leur utilisation comme émulsifiant pour dispersions de polymères
EP1512703B1 (fr) Utilisation de tensio-actifs copolymerisables dans la polymerisation en emulsion
DE2145888B2 (de) Waessrige polytetrafluoraethylendispersion
EP0004062B1 (fr) Dispersions aqueuses de matières plastiques à base de polymères vinyliques, procédé pour leur préparation et leur utilisation
DE60209451T2 (de) Wässrige Beschichtungszusammensetzung, welche Ionenaustauscherharze enthält
DE2008643A1 (de) Kationische synthetische Latices und Verfahren zu deren Herstellung
EP0073296A1 (fr) Procédé de préparation de dispersions de résines synthétiques acryliques
DE1519201B2 (de) Waessriges ueberzugsmittel
DE2900752C2 (fr)
EP0196596B1 (fr) Emulsifiants à base d'acide sulfosuccinamique ramifié pour la préparation de dispersions résistant notamment au cisaillement
DE60204833T2 (de) Emulsionspolymerisationsverfahren enthaltend die Verwendung von Ligninsulfonat(en) als Stabilisator(en), erhaltene Dispersionen und deren Verwendungen
DE1669735B2 (de) Verfahren zum Agglomerieren wäßriger Dispersionen von Emulsionspolymerisaten mit Erweichungspunkten oberhalb 20 Grad C
DE2250517A1 (de) Kontinuierliche herstellung von waessrigen dispersionen von vinylacetat-aethylenmischpolymerisaten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091009

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17Q First examination report despatched

Effective date: 20100129

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20100609