EP0114834A1 - Method for the preparation of polymer dispersions and utilization thereof - Google Patents

Method for the preparation of polymer dispersions and utilization thereof

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Publication number
EP0114834A1
EP0114834A1 EP83901919A EP83901919A EP0114834A1 EP 0114834 A1 EP0114834 A1 EP 0114834A1 EP 83901919 A EP83901919 A EP 83901919A EP 83901919 A EP83901919 A EP 83901919A EP 0114834 A1 EP0114834 A1 EP 0114834A1
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EP
European Patent Office
Prior art keywords
weight
monomers
reaction conditions
liquid under
vinyl
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.)
Pending
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EP83901919A
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German (de)
French (fr)
Inventor
Herbert Eck
Manfred Hannebaum
Christof Kemenater
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Wacker Chemie AG
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Wacker Chemie AG
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Publication of EP0114834A1 publication Critical patent/EP0114834A1/en
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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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • 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
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • 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
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents

Definitions

  • the present invention relates to an improved process for the preparation of aqueous polymer dispersions stabilized by protective colloid, in particular by polyvinyl alcohol (PVAL), by single-stage radical polymerization of vinyl halides and / or vinyl alkanoates, optionally together with up to 50% by weight of other ethylenically unsaturated compounds copolymerizable therewith.
  • protective colloid in particular by polyvinyl alcohol (PVAL)
  • PVAL polyvinyl alcohol
  • this new process can also be used to prepare dispersions of ethylene-containing polymers which also contain contents of more than 10% by weight, even more than 15% by weight. % and also more than 20% by weight of ethylene units in the polymer still have a high rate of attraction and are therefore also very suitable as adhesives.
  • the invention relates to a process for the preparation of aqueous polymer dispersions which are stabilized by protective colloid, preferably only by protective colloid in the production, with contents of 20 to 75, preferably 20 to 70, in particular 30 to 50% by weight on total weight, by single-stage polymerization of vinyl halides, preferably vinyl chloride, and / or vinyl alkanoates, preferably vinyl acetate, optionally together with at most 50 percent by weight, based on the total weight of the monomers liquid under the reaction conditions, of other ethylenically unsaturated compounds copolymerizable therewith at temperatures from 0 to 120 ° C, preferably 20 to 100 ° C, and pressures up to 200 bar by means of at least partially water-soluble radical initiator systems and, if appropriate, in the presence of customary additives.
  • the process is characterized in that with the dosing of protective colloid, preferably at least one PVAL with a degree of hydrolysis of 70 to 99.8 mol% and an average degree of polymerization of 200 to 3000, as the first dispersing agent only after a conversion of 1 to 60% by weight .-%, preferably 2 to 25 wt .-%, based on the total weight of the monomers liquid under the reaction conditions, is started.
  • protective colloid preferably at least one PVAL with a degree of hydrolysis of 70 to 99.8 mol% and an average degree of polymerization of 200 to 3000
  • the remaining amount of these monomers ie 60 to 99% by weight, or in particular 70 to 95% by weight, are. metered in the course of the polymerization, preferably in proportion to their consumption. It has proven to be advantageous in many cases to keep the concentration of these monomers in the reaction mixture approximately at the level which has been submitted until the metering has ended, for. B. 0.2 and 30, preferably 1 to 21, in particular 1.5 to 18 wt .-% (based on total weight of the reaction mixture). But it is of course possible to deviate from it, e.g. B. if special effects are to be achieved.
  • “monomers which are liquid under the reaction conditions” are understood to mean those ethylenically unsaturated polymerizable compounds which can be liquefied in the range from 0 to 120 ° C. and up to 200 bar or are ready-to-use liquids.
  • examples include primarily the vinyl halides, such as vinyl fluoride, vinyl bromide, preferably vinyl chloride, and the vinyl alkanoates (vinyl esters of saturated straight-chain or branched-chain carboxylic acids, preferably having up to 20 carbon atoms), such as vinyl formate, propionate, butyrate,
  • the sum of these monomers is at least 50% by weight, preferably at least 80% by weight. -% of the total amount of the monomers liquid under the given reaction conditions.
  • the vinyl chloride and vinyl acetate mentioned, and also one or more of the other vinyl halides and / or alkanoates up to 20% by weight, particularly preferably, such monomers can also be used:
  • Mono- and dialkyl, glycidyl and hydroxyalkyl esters of ethylenically unsaturated mono- and dicarboxylic acids e.g. B. esters of (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid with (un) branched C 1 - to C 20 -alkanols, such as methanol, ethanol, n- and iso-propanol, n-, sec.- and tert.-butanol,
  • Polyalcohols such as ethylene, propylene and butylene glycol and pentaerythritol;
  • Vinylidene halides such as vinylidene chloride
  • ethylenically unsaturated mono- and dicarboxylic acids their anhydrides, their amides and their N-methylolamides etherified with (poly) alkoxyl groups (ethoxyl or propoxyl groups), e.g. B. (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, maleic anhydride, crotonic acid, crotonic acid amides;
  • Vinyl derivatives of heterocyclic compounds e.g. B. N-vinyl pyridine and N-vinyl pyrrolidone;
  • ⁇ -olefins e.g. B. propylene, butylene, octene, dodecene.
  • Monomers with strongly polar groups e.g. B. vinyl sulfonate, the carboxylic acids, amides and anhydrides should preferably be used in total only 5% by weight, in particular 2% by weight, based on the monomers under the reaction conditions.
  • Di- and polyvinyl and allyl compounds of di- and polycarboxylic acids and phenols as well as vinyl and allyl (meth) acrylate and / or crotonate can be used in amounts of 0 to 2, preferably up to 0.5% by weight, based on the liquid monomers are copolymerized.
  • the monomers from the groups mentioned can be added or metered into the reaction vessel individually or as premixes, and after the start of metering * as a pre-emulsion. It is possible to introduce some or all of these monomers in whole or in part and to meter in the rest. For the sake of simplicity, it is often preferred to premix the desired monomers from the group mentioned and to use them as a mixture and thus to keep the composition of this monomer phase largely constant over the course of the reaction for a relatively long time.
  • ethylene is also used as a comonomer in a further preferred embodiment of the process according to the invention.
  • the reaction vessel is charged with ethylene up to a partial pressure of 200 bar, preferably up to 80 bar, before or during the reaction.
  • This loading is preferably carried out before the reaction, so that the liquid reaction mixture can dissolve part of the ethylene up to the equilibrium of the gas space with the liquid phase.
  • the ethylene can be added once, or its partial pressure can last for a long time, in particular until the end of the metering of the monomers which are liquid under the reaction conditions are kept largely constant by subsequent metering.
  • the particle size distribution of the resulting dispersions can be controlled in a simple manner by the time and the amount of the protective colloid being added for the first time.
  • the polymerization rate can be increased, since the lower viscosity allows the heat of reaction to be dissipated more quickly.
  • This lower viscosity of dispersions produced according to the invention, even with high levels, is particularly surprising since it is known that the viscosity can be increased by adding protective colloid to aqueous dispersions.
  • Another advantage of the method according to the invention is that in the preferred use of dispersions prepared according to the invention for the production of redispersible powders, e.g. B. for use in Construction sector as an adhesive or additive to hydraulically setting compositions, because of the lower grafting of the protective colloid, in particular the polyvinyl alcohol (PVAL), there is more free protective colloid at the end of the polymerization. This at least partially eliminates the need to add the protective colloid, in particular PVAL, during or after drying.
  • PVAL polyvinyl alcohol
  • the protective colloids used are those which are generally customary for the polymerization, for.
  • At least one polyvinyl alcohol with a degree of hydrolysis of from 70 to 99.8 mol% (corresponding to the saponification number from approx. 10 to approx. 257) is preferred, preferably 74 to 99.5 mol% (corresponding to the saponification number from approx. 20 to approx. 240) ) and with an average degree of polymerization of 200 to 3000 (corresponding to an approximate Höppler viscosity of a 4% by weight aqueous solution at 20 ° C. of approx. 3 to approx.
  • the protective colloid in particular the PVAL, is used in a total amount of 0.5 to 15% by weight, preferably 3 to 10% by weight, based on the monomers which are liquid under the reaction conditions. If comonomers are additionally used which are known to stabilize dispersion (e.g. vinyl sulfonate), z. B. even the addition of about 1 to 3 wt .-% protective colloid provide very good results.
  • the polymerization is preferably carried out by means of so-called redox initiator systems, which generally consist of a combination of at least one peroxidic compound and * reducing agent.
  • redox initiator systems which generally consist of a combination of at least one peroxidic compound and * reducing agent.
  • One or all of these components can be initially introduced, the other component and optionally the rest of the partially introduced component or optionally both components are then metered in during the polymerization.
  • the oxidation component can be introduced and the polymerization is controlled by metering in the reduction component. This is generally the preferred embodiment.
  • peroxidic compounds are preferred examples of the oxidation component: Ammonium and potassium persulfate, -peroxodisulfate, hydrogen peroxide, alkyl hydroperoxides, such as tert. -Butyl hydroperoxide, peroxodiphosphates, such as potassium, sodium and ammonium peroxodiphosphate, and mixtures thereof.
  • water-soluble sulfites and sulfoxylates such as alkali (Na, K) or ammonium sulfite or hydrogen sulfite or alkali (Na, K) or zinc formaldehyde sulfoxylate.
  • Hydrogen / noble metal catalyst components are also suitable as activators with the simultaneous use of small amounts of heavy metal salts.
  • Suitable initiator systems are u. a. "Fundamental Principles of Polymerization" G.F. Alelio, John Wiley and Sons Inc.,
  • radical initiators e.g. B. the persulfates or peroxodiphosphates in the absence of a reducing agent possible. Both in this system and in the aforementioned, traces of salts of suitable heavy metals, e.g. B.- of iron or copper added.
  • anionic and / or nonionic emulsifiers in amounts of 0 to 4% by weight, preferably up to 2% by weight, based on the solids content of the dispersion , are added.
  • anionic and / or nonionic emulsifiers in amounts of 0 to 4% by weight, preferably up to 2% by weight, based on the solids content of the dispersion , are added.
  • alkali or alkaline earth metal salts of alkylated benzene and naphthalenesulfonic acids such as sodium benzyl sulfonate, alkali alkyl sulfonates, such as, for.
  • alkylsulfuric acids such as sodium lauryl sulfate, sodium alkyl
  • the process according to the invention is preferably carried out at pH values from 2.5 to 7. However, this range can also be exceeded or undershot if necessary.
  • customary buffer substances can also be added, e.g. B. bicarbonates, borates, acetates, citrates, mixtures of primary and secondary phosphates of the alkali metals.
  • the process according to the invention is preferably produced by the metering process, but the entire amount of monomers can be introduced.
  • at least one monomer can be introduced in whole or in part, while the others are metered in whole, and optionally the rest of the partially introduced monomers.
  • the addition of protective colloid is preferred at the earliest when the (easy to determine) solid content of the dispersion of 2 units -%, preferably 5% by weight, and at the latest at a solids content of 40% by weight, more preferably 30% by weight, in particular 20% by weight.
  • the dispersions produced by the process according to the invention are suitable as adhesives, for coating paper, fabrics and nonwovens, from natural or synthetic fibers, glass fibers, wood fibers, etc., as additives or as binders in concrete and mortar mixtures.
  • the viscosities of the PVALs in mPas were determined by Höppler, those of the dispersions using the Epprecht rheometer, the measuring unit being given in ().
  • the pH was kept at 2.5 to 5 by metering in ammonia or formic acid. The remaining amounts of monomer were metered in continuously as in the previous procedure.

Abstract

Procédé pour la préparation de dispersions aqueuses ainsi que de copolymérisation d'émulsions d'halogénures vinyliques et/ou d'esters de vinyle et le cas échéant d'autres monomères, sous la présence d'émulgateurs. Pour stabiliser les dispersions obtenues, on ajoute au début de la polymérisation des colloïdes de protection. Les dispersions, à teneur en solides élevées ont des petites viscosités et une viscosité structurelle basse. Elles sont appropriées pour la préparation de poudres pouvant être de nouveau dispersées.Process for the preparation of aqueous dispersions as well as of copolymerization of emulsions of vinyl halides and / or of vinyl esters and, where appropriate, of other monomers, in the presence of emulsifiers. To stabilize the dispersions obtained, protective colloids are added at the start of the polymerization. The high solids dispersions have low viscosities and low structural viscosity. They are suitable for the preparation of powders which can be dispersed again.

Description

Verfahren zur Herstellung von Polymerdispersionen und ihre Verwendung.Process for the preparation of polymer dispersions and their use.
Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Herstellung von durch Schutzkolloid, insbesondere durch Polyvinylalkohol (PVAL) stabilisierten wäßrigen Polymerdispersionen durch einstufige radikalische Polymerisation von Vinylhalogeniden und/oder Vinylalkanoaten gegebenenfalls zusammen mit bis zu 50 Gew.-% anderen damit copolymerisierbaren ethylenisch ungesättigten Verbindungen.The present invention relates to an improved process for the preparation of aqueous polymer dispersions stabilized by protective colloid, in particular by polyvinyl alcohol (PVAL), by single-stage radical polymerization of vinyl halides and / or vinyl alkanoates, optionally together with up to 50% by weight of other ethylenically unsaturated compounds copolymerizable therewith.
Die Herstellung wäßriger Dispersionen von Polymeren der o.g. Art durch Emulsionspolymerisation ist prinzipiell bekannt. Das zur Stabilisierung der Dispersionen notwendige Dispergierhilfsmittel, nämlich Emulgator gegebenenfalls in Kombination mit Schutzkolloid, wird dabei im allgemeinen vorgelegt (vgl. EP-B-590, DE-B-11 80 133 und DE-A-17 70 395).The preparation of aqueous dispersions of polymers of the above. The type by emulsion polymerization is known in principle. The dispersing aid necessary for stabilizing the dispersions, namely emulsifier, if appropriate in combination with protective colloid, is generally presented (cf. EP-B-590, DE-B-11 80 133 and DE-A-17 70 395).
Zur Erzielung spezieller Effekte (z. B. Vergröberung oder bimodale Teilchengrößenverteilung) wurde auch bereits vorgeschlagen, zunächst in Abwesenheit von Emulgator die Polymerisation zu beginnen und diesen oder die Ausgangsstoffe zu seiner Bildung erst im Verlauf der Polymerisation zuzusetzen (vgl. DE-B- 15 20 849 und DE-A- 28 37 992).In order to achieve special effects (e.g. coarsening or bimodal particle size distribution), it has also already been proposed to begin the polymerization in the absence of an emulsifier and to add it or the starting materials for its formation only in the course of the polymerization (cf. DE-B-15 20 849 and DE-A-28 37 992).
Es bestand nun die Notwendigkeit, ein Verfahren zu entwickeln, mit dem Dispersionen hergestellt werden können, die sich u.a. für den Einsatz bei der Herstellung von Klebstoffen, bei der Beschichtung von Papier, Textilien, Faservliesen u. ä., sowie als Zusatz zu Mörtel und Betonmischungen und als filmbildende Bestandteile in Anstrichfarben eignen und sich auch bei hohen Festgehalten durch niedrige Strukturviskosität und niedrige Viskosität auszeichnen.There was now a need to develop a process with which dispersions can be produced which, inter alia for use in the production of adhesives, in the coating of paper, textiles, nonwovens and the like. Ä., as well as an additive to mortar and concrete mixes and as film-forming constituents in paints and are characterized by low structural viscosity and low viscosity even at high levels.
Letztere Eigenschaft ist besonders vorteilhaft, sofern beabsichtigt ist, redispergierbare Pulver herzustellen, da dann auch Dispersionen mit hohem Festgehalt problemlos verdüst werden können. So besitzen herkömmlich hergestellte Dispersionen, denen für die Herstellung von redispergierbaren Pulvern extra noch Schutzkolloide zugesetzt werden, dadurch bedingt, im allgemeinen höhere Viskosität, höhere Strukturviskosität.The latter property is particularly advantageous if the intention is to produce redispersible powders, since then dispersions with a high solids content can also be atomized without problems. For example, conventionally produced dispersions, to which protective colloids are added for the production of redispersible powders, generally higher viscosity and higher intrinsic viscosity.
Die vorstehend genannten Aufgaben können in überraschender Weise durch die vorliegende Erfindung gelöst werden. Überdies können nach diesem neuen Verfahren auch Dispersionen ethylenhaltiger Polymerisate hergestellt werden, die auch bei Gehalten von über 10 Gew.-%, ja sogar über 15. Gew . -% und auch noch über 20 Gew.-% Ethyleneinheiten im Polymeren noch eine hohe Anzugsgeschwindigkeit besitzen und daher auch als Klebstoffe sehr gut geeignet sind.The above objects can surprisingly be achieved by the present invention. In addition, this new process can also be used to prepare dispersions of ethylene-containing polymers which also contain contents of more than 10% by weight, even more than 15% by weight. % and also more than 20% by weight of ethylene units in the polymer still have a high rate of attraction and are therefore also very suitable as adhesives.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von wäßrigen Polymerdispersionen, die durch Schutzkolloid, vorzugsweise bei der Herstellung nur durch Schutzkolloid stabilisiert sind, mit Festgehalten von 20 bis 75, vorzugsweise 20 bis 70, insbesondere 30 bis 50 Gew.-%, bezogen auf Gesamtgewicht, durch einstufige Polymersation von Vinyl- halogeniden vorzugsweise Vinylchlorid, und/oder Vinylalkanoaten, vorzugsweise Vinylacetat,gegebenenfalls zusammen mit höchstens 50 Gewichtsprozent, bezogen auf Gesamtgewicht der bei den Reaktionsbedingungen flüssigen Monomeren, anderen damit copolymerisierbaren ethylenisch ungesättigten Verbindungen bei Temperaturen von 0 bis 120 º C , vorzugsweise 20 bis 100 °C , und Drücken bis 200 bar mittels zumindest teilweise wasserlöslicher Radikalinitiatorsysteme und gegebenenfalls in Gegenwart üblicher Zusatzstoffe. Das Verfahren ist dadurch gekennzeichnet, daß mit der Dosierung von Schutzkolloid, vorzugsweise mindestens einem PVAL mit einem Hydrolysegrad von 70 bis 99,8 mol-% und einem mittleren Polymerisationsgrad von 200 bis 3000, als ersten Dispergierhilfsstoff erst nach einem Umsatz von 1 bis 60 Gew.-%, vorzugsweise 2 bis 25 Gew.-%, bezogen auf Gesamtgewicht der bei den Reaktionsbedingungen flüssigen Monomeren, begonnen wird.The invention relates to a process for the preparation of aqueous polymer dispersions which are stabilized by protective colloid, preferably only by protective colloid in the production, with contents of 20 to 75, preferably 20 to 70, in particular 30 to 50% by weight on total weight, by single-stage polymerization of vinyl halides, preferably vinyl chloride, and / or vinyl alkanoates, preferably vinyl acetate, optionally together with at most 50 percent by weight, based on the total weight of the monomers liquid under the reaction conditions, of other ethylenically unsaturated compounds copolymerizable therewith at temperatures from 0 to 120 ° C, preferably 20 to 100 ° C, and pressures up to 200 bar by means of at least partially water-soluble radical initiator systems and, if appropriate, in the presence of customary additives. The process is characterized in that with the dosing of protective colloid, preferably at least one PVAL with a degree of hydrolysis of 70 to 99.8 mol% and an average degree of polymerization of 200 to 3000, as the first dispersing agent only after a conversion of 1 to 60% by weight .-%, preferably 2 to 25 wt .-%, based on the total weight of the monomers liquid under the reaction conditions, is started.
In einer bevorzugten Ausführungsform werden 1 bis 40 Gew.-%, insbesondere 5 bis 30 Gew . -% der bei den Reaktionsbedingungen flüssigen Monomeren vorgelegt. Die restliche Menge dieser Monomeren, also 60 bis 99 Gew. -% , bzw. insbesondere 70 bis 95 Gew.-%, werden. im Laufe der Polymerisation, vorzugsweise im Maße ihres Verbrauches dosiert. Dabei hat es sich vielfach als vorteilhaft erwiesen, die Konzentration dieser Monomeren in der Reaktionsmischung bis zur Beendigung der Dosierung etwa auf dem Niveau zu halten, das vorgelegt worden ist, z. B. 0,2 und 30, vorzugsweise 1 bis 21, insbesondere 1,5 bis 18 Gew.-% (bezogen auf Gesamtgewicht des Reaktionsgemisches). Es ist aber selbstverständlich möglich, davon abzuweichen, z. B. wenn besondere Effekte erzielt werden sollen.In a preferred embodiment, 1 to 40 wt .-%, in particular 5 to 30 wt. -% of the monomers liquid under the reaction conditions submitted. The remaining amount of these monomers, ie 60 to 99% by weight, or in particular 70 to 95% by weight, are. metered in the course of the polymerization, preferably in proportion to their consumption. It has proven to be advantageous in many cases to keep the concentration of these monomers in the reaction mixture approximately at the level which has been submitted until the metering has ended, for. B. 0.2 and 30, preferably 1 to 21, in particular 1.5 to 18 wt .-% (based on total weight of the reaction mixture). But it is of course possible to deviate from it, e.g. B. if special effects are to be achieved.
Unter "bei den Reaktionsbedingungen flüssigen Monomeren" werden im Rahmen dieser Anmeldung solche ethylenisch ungesättigten polymersierbaren Verbindungen verstanden, die im Bereich von 0 bis 120°C und bis 200 bar verflüssigt werden können oder bereifes flüssig sind. Als Beispiele seien in erster Linie die Vinylhalogenide , wie Vinylfluorid, Vinylbromid, vorzugsweise Vinylchlorid, sowie die Vinylalkanoate (Vinylester gesättigter gerad- oder verzweigtkettiger Carbonsäuren vorzugsweise mit bis zu 20 C-Ato men) genannt, wie Vinylformiat, -propionat, -butyrat,In the context of this application, “monomers which are liquid under the reaction conditions” are understood to mean those ethylenically unsaturated polymerizable compounds which can be liquefied in the range from 0 to 120 ° C. and up to 200 bar or are ready-to-use liquids. Examples include primarily the vinyl halides, such as vinyl fluoride, vinyl bromide, preferably vinyl chloride, and the vinyl alkanoates (vinyl esters of saturated straight-chain or branched-chain carboxylic acids, preferably having up to 20 carbon atoms), such as vinyl formate, propionate, butyrate,
-ethylhexanoat, -laurat, -stearat, -isotridecanoat, Vinylester der Versatic (R) -säuren und vorzugsweise Vinylacetat.ethyl hexanoate, laurate, stearate, isotridecanoate, vinyl ester of Versatic (R) acids and preferably vinyl acetate.
Die Summe dieser Monomeren,insbesondere des Vinylchlorids und des Vinylacetats, beträgt mindestens 50 Gew.-%, vorzugsweise mindestens 80 Gew . -% der Gesamtmenge der bei den angegebenen Reaktionsbedingungen flüssigen Monomeren. Als weitere solche Monomere können, neben dem genannten Vinylchlorid und Vinylacetat, sowie einzelnen oder mehreren der anderen Vinylhalogenide und/oder -alkanoate, bis besonders vorzugsweise 20 Gew.-%, auch eingesetzt werden:The sum of these monomers, in particular the vinyl chloride and the vinyl acetate, is at least 50% by weight, preferably at least 80% by weight. -% of the total amount of the monomers liquid under the given reaction conditions. In addition to the vinyl chloride and vinyl acetate mentioned, and also one or more of the other vinyl halides and / or alkanoates, up to 20% by weight, particularly preferably, such monomers can also be used:
- Mono- und Dialkyl-, -glycidyl- und -hydroxyalkylester ethylenisch ungesättigter Mono- und Dicarbonsäuren, z. B. Ester der (Meth-) Acrylsäure, der Maleinsäure, der Fumar säure, der Crotonsäure und der Itakonsäure mit (un-) verzweigten C1- bis C20-Alkanolen, wie Methanol, Ethanol, n- und iso-Propanol, n-, sec.- und tert .-Butanol,- Mono- and dialkyl, glycidyl and hydroxyalkyl esters of ethylenically unsaturated mono- and dicarboxylic acids, e.g. B. esters of (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid with (un) branched C 1 - to C 20 -alkanols, such as methanol, ethanol, n- and iso-propanol, n-, sec.- and tert.-butanol,
2-Ethylhexanol, Octanol, Dodecanol, Alfol(R) -Alkoholen,2-ethylhexanol, octanol, dodecanol, Alfol (R) alcohols,
Polyalkoholen wie Ethylen-, Propylen- und Butylenglykol und Pentaerythrit;Polyalcohols such as ethylene, propylene and butylene glycol and pentaerythritol;
Allyl- und Vinylester der ( Meth-) Acrylsäure, der (Di-) Acetessigsäure;Allyl and vinyl esters of (meth) acrylic acid, (di) acetoacetic acid;
Vinyl- und Allylverbindungen von Silanen, Glycidylalkohol, Aminoalkoholen, α -Chloralkylcarbonsäuren, Dichlortriazinen;Vinyl and allyl compounds of silanes, glycidyl alcohol, amino alcohols, α-chloroalkyl carboxylic acids, dichlorotriazines;
Vinylidenhalogenide wie Vinylidenchlorid;Vinylidene halides such as vinylidene chloride;
Acryltrialkoxysilane;Acrylic trialkoxysilanes;
ethylenisch ungesättigte Mono- und Dicarbonsäuren, deren Anhydride, deren Amide und deren gegebenenfalls mit (Poly-) Alkoxylgruppen (Ethoxyl- oder Propoxylgruppen) veretherten N-Methylolamide, z. B. ( Meth-) Acrylsäure, (Meth-) Acrylamid, N-Methylol ( meth ) acrylamid, Maleinsäureanhydrid, Crotonsäure, Crotonsäureamide;ethylenically unsaturated mono- and dicarboxylic acids, their anhydrides, their amides and their N-methylolamides etherified with (poly) alkoxyl groups (ethoxyl or propoxyl groups), e.g. B. (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, maleic anhydride, crotonic acid, crotonic acid amides;
Vinylether;Vinyl ether;
Vinylderivate heterocyclischer Verbindungen, z. B. N-Vinylpyridin und N-Vinylpyrrolidon;Vinyl derivatives of heterocyclic compounds, e.g. B. N-vinyl pyridine and N-vinyl pyrrolidone;
Vinylsulfonsäure und deren Salze;Vinyl sulfonic acid and its salts;
α-Olefinen, z. B. Propylen, Butylen, Octen, Dodecen. Monomere mit stark polaren Gruppen, z. B. Vinylsulfonat, die Carbonsäuren, Amide und Anhydride sollten vorzugsweise insgesamt nur zu 5 Gew.-%, insbesondere 2 Gew.-%, bezogen auf die bei den Reaktionsbedingungen Monomeren , eingesetzt werden.α-olefins, e.g. B. propylene, butylene, octene, dodecene. Monomers with strongly polar groups, e.g. B. vinyl sulfonate, the carboxylic acids, amides and anhydrides should preferably be used in total only 5% by weight, in particular 2% by weight, based on the monomers under the reaction conditions.
Di- und Polyvinyl- und -allylverbindungen von Di- und Polycarbonsäuren und Phenolen sowie Vinyl- und Allyl (meth)acrylat und/oder -crotonat können in Mengen von 0 bis 2, vorzugsweise bis 0,5 Gew.-%, bezogen auf die flüssigen Monomeren copolymerisiert werden. Die Monomeren aus den genannten Gruppen können einzeln oder als Vorgemische, nach Dosierbeginn* auch als Voremulsion in das Reaktionsgefäß gegeben oder dosiert werden. Es ist möglich, einzelne dieser Monomeren ganz oder teilweise vorzulegen und den Rest zu dosieren. Der Einfachheit halber wird oft vorgezogen, die gewünschten Monomeren aus der genannten Gruppe vorzumischen und als Gemisch einzusetzen und so die Zusammensetzung dieser Monomerenphase über längere Zeit während der Reaktion weitgehend konstant zu halten. *von SchutzkolloidDi- and polyvinyl and allyl compounds of di- and polycarboxylic acids and phenols as well as vinyl and allyl (meth) acrylate and / or crotonate can be used in amounts of 0 to 2, preferably up to 0.5% by weight, based on the liquid monomers are copolymerized. The monomers from the groups mentioned can be added or metered into the reaction vessel individually or as premixes, and after the start of metering * as a pre-emulsion. It is possible to introduce some or all of these monomers in whole or in part and to meter in the rest. For the sake of simplicity, it is often preferred to premix the desired monomers from the group mentioned and to use them as a mixture and thus to keep the composition of this monomer phase largely constant over the course of the reaction for a relatively long time. * from protective colloid
Neben den genannten Monomeren wird in einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens Ethylen als Comonomer mitverwendet. Dazu wird das Reaktionsgefäß bereits vor oder auch während der Reaktion mit Ethylen bis zu einem Partialdruck von 200 bar, vorzugsweise bis 80 bar beaufschlagt. Bevorzugt erfolgt diese Beaufschlagung bereits vor der Reaktion, so daß das flüssige Reaktionsgemisch einen Teil des Ethylens bis zum Gleichgewicht des Gasraums mit der flüssigen Phase lösen kann. Die Zugabe des Ethylens kann einmal erfolgen, oder sein Partialdruck kann über längere Zeit, insbesondere bis zum Ende der Dosierung der bei den Reaktionsbedingungen flüssigen Monomeren durch Nachdosieren weitgehend konstant gehalten werden.In addition to the monomers mentioned, ethylene is also used as a comonomer in a further preferred embodiment of the process according to the invention. For this purpose, the reaction vessel is charged with ethylene up to a partial pressure of 200 bar, preferably up to 80 bar, before or during the reaction. This loading is preferably carried out before the reaction, so that the liquid reaction mixture can dissolve part of the ethylene up to the equilibrium of the gas space with the liquid phase. The ethylene can be added once, or its partial pressure can last for a long time, in particular until the end of the metering of the monomers which are liquid under the reaction conditions are kept largely constant by subsequent metering.
Durch das erfindungsgemäße Verfahren können auch bei höheren Konzentrationen an bei den Reaktionsbedingungen flüssigen Monomeren, also beispielsweise über 15 oder gar über 25 Gew.-%, bezogen auf das Gesamtgewicht des Reaktionsgemisches, höhere Ethylenrnengen ins Polymerisat eingebaut werden als bei den bisherigen Verfahren. So können bevorzugte Polymerisate hergestellt werden, die höchstens 20 Gew . -% Einheiten enthalten, die sich nicht von Vinylchlorid, Vinylacetat und/oder Ethylen ableiten. Hierbei kann der Gehalt an Ethyleneinheiten bis zu 45 Gew.-%, vorzugsweise 5 bis 30 Gew.-%, bezogen auf Polymerisat, betragen. Die bei den Reaktionsbedingungen flüssigen Monomeren reagieren praktisch quantitativ ab.With the process according to the invention, even at higher concentrations of monomers which are liquid under the reaction conditions, that is to say for example more than 15 or even more than 25% by weight, based on the total weight of the reaction mixture, higher amounts of ethylene can be incorporated into the polymer than in the previous processes. In this way, preferred polymers can be produced which have a maximum of 20% by weight. -% contain units that are not derived from vinyl chloride, vinyl acetate and / or ethylene. The content of ethylene units can be up to 45% by weight, preferably 5 to 30% by weight, based on the polymer. The monomers liquid under the reaction conditions react virtually quantitatively.
Weiterhin kann durch den Zeitpunkt und die Menge der erstmaligen Schutzkolloidzugabe in einfacher Weise die Teilchengrößenverteilung der entstehenden Dispersionen gesteuert werden. Überdies kann die Polymerisationsgeschwindigkeit erhöht werden, da aufgrund der niedrigeren Viskosität eine raschere Abfuhr der Reaktionswärme möglich ist.Furthermore, the particle size distribution of the resulting dispersions can be controlled in a simple manner by the time and the amount of the protective colloid being added for the first time. In addition, the polymerization rate can be increased, since the lower viscosity allows the heat of reaction to be dissipated more quickly.
Diese niedrigere Viskosität von erfindungsgemäß hergestellten Dispersionen auch mit hohen Festgehalten ist insbesondere deshalb überraschend, da bekannt ist, daß durch Zusatz von Schutzkolloid zu wäßrigen Dispersionen deren Viskosität gesteigert werden kann. Ein weiterer Vorteil des erfindungsgemäßen Verfahrens liegt darin, daß bei der bevorzugten Verwendung erfindungsgemäß hergestellter Dispersionen zur Herstellung redispergierbarer Pulver, z. B. für den Einsatz im Bausektor als Kleber oder Zusatzmittel zu hydraulisch abbindenden Massen, aufgrund der geringeren Pfropfung des Schutzkolloids, insbesondere des Polyvinylalkohols (PVAL), am Ende der Polymerisation mehr freies Schutzkolloid vorhanden ist. Dies erübrigt zumindest teilweise weiteren Zusatz des Schutzkolloids, insbesondere von PVAL, bei oder nach der Trocknung.This lower viscosity of dispersions produced according to the invention, even with high levels, is particularly surprising since it is known that the viscosity can be increased by adding protective colloid to aqueous dispersions. Another advantage of the method according to the invention is that in the preferred use of dispersions prepared according to the invention for the production of redispersible powders, e.g. B. for use in Construction sector as an adhesive or additive to hydraulically setting compositions, because of the lower grafting of the protective colloid, in particular the polyvinyl alcohol (PVAL), there is more free protective colloid at the end of the polymerization. This at least partially eliminates the need to add the protective colloid, in particular PVAL, during or after drying.
Als Schutzkolloide werden die für die Polymerisation allgemein üblichen eingesetzt, z. B. Cellulosederivate oder wasserlösliche Polymerisate wie teilverseiftes Polyvinylacetat oder Vinylpyrrolidonpolymerisate. Bevorzugt wird mindestens ein Polyvinylalkohol mit einem Hydrolysegrad von 70 bis 99,8 mol-% (entsprechend Verseifungszahl von ca. 10 bis ca.257), vorzugsweise 74 bis 99,5 mol-% (entsprechend Verseifungszahlen von ca. 20 bis ca.240) und mit e m mittleren Polymerisationsgrad von 200 bis 3000 (entsprechend einer ungefähren Höppler-Viskosität einer 4 Gew.-%igen wäßrigen Lösung bei 20 ºC von ca. 3 bis ca. 50 mPas). Das Schutzkolloid, insbesondere der PVAL, wird in Mengen von insgesamt 0,5 bis 15 Gew.-%, vorzugsweise von 3 bis 10 Gew.-%, bezogen auf die bei den Reaktionsbedingungen flüssigen Monomeren, eingesetzt. Werden zusätzlich Comonomere verwendet, die bekanntermaßen dispersionsstabilisierend (z. B. Vinylsulfonat), so kann z. B. schon der Zusatz von ca. 1 bis 3 Gew.-% Schutzkolloid sehr gute Ergebnisse liefern.The protective colloids used are those which are generally customary for the polymerization, for. B. cellulose derivatives or water-soluble polymers such as partially saponified polyvinyl acetate or vinyl pyrrolidone polymers. At least one polyvinyl alcohol with a degree of hydrolysis of from 70 to 99.8 mol% (corresponding to the saponification number from approx. 10 to approx. 257) is preferred, preferably 74 to 99.5 mol% (corresponding to the saponification number from approx. 20 to approx. 240) ) and with an average degree of polymerization of 200 to 3000 (corresponding to an approximate Höppler viscosity of a 4% by weight aqueous solution at 20 ° C. of approx. 3 to approx. 50 mPas). The protective colloid, in particular the PVAL, is used in a total amount of 0.5 to 15% by weight, preferably 3 to 10% by weight, based on the monomers which are liquid under the reaction conditions. If comonomers are additionally used which are known to stabilize dispersion (e.g. vinyl sulfonate), z. B. even the addition of about 1 to 3 wt .-% protective colloid provide very good results.
Es ist selbstverständlich möglich, Gemische unterschiedlicher Schutzkolloide zu verwenden, z. B. Gemische höher- und niedriger- viskoser, bzw. höher- und niedrigerverseifter PVAL's. Es können auch eines (oder einige) dieser Schutzkolloide eher und (ein) andere (s) später zugesetzt werden. Es sei auch daran erinnert, daß Polymerisate allgemein eine gewisse Bandbreite in ihrer Zusammensetzung aufweisen., also z. B. ein bestimmter PVAL, charakterisiert durch die obigen Merkmale, nicht nur einer einzigen Molekülspezies besteht.It is of course possible to use mixtures of different protective colloids, e.g. B. Mixtures of higher and lower viscosity, or higher and lower saponified PVAL's. There may also be one (or some) of these protective colloids rather and (another) others are added later. It should also be remembered that polymers generally have a certain range in their composition. B. a certain PVAL, characterized by the above characteristics, does not consist of only a single molecular species.
Die Polymerisation wird vorzugsweise mittels sogenannter Redoxinitiatorsysteme durchgeführt, die im allgemeinen aus einer Kombination mindestens einer peroxidischen Verbindung und*Reduktionsmittel bestehen. Eine dieser Komponenten kann ganz oder teilweise vorgelegt werden, die andere Komponente und gegebenenfalls der Rest der teilweise vorgelegten Komponente oder gegebenenfalls beide Komponenten werden dann im Verlaufe der Polymerisation dosiert. Beispielsweise kann die Oxydationskomponente vorgelegt werden, und man steuert die Polymerisation durch die Dosierung der Reduktionskomponente. Diese ist im allgemeinen die bevorzugte Ausführungsform. *mindestens einemThe polymerization is preferably carried out by means of so-called redox initiator systems, which generally consist of a combination of at least one peroxidic compound and * reducing agent. One or all of these components can be initially introduced, the other component and optionally the rest of the partially introduced component or optionally both components are then metered in during the polymerization. For example, the oxidation component can be introduced and the polymerization is controlled by metering in the reduction component. This is generally the preferred embodiment. * at least one
Im allgemeinen benötigt man ca. 0,01 bis ca. 0,5 Gew.-%, vorzugsweise 0,03 bis 0,3 Gew.-% an Reduktionskomponente und ca. 0,01 bis ca. 2 Gew . -% , vorzugsweise 0,03 bis 0,8 Gew.-% an Oxydationskomponente, wobei vielfach besonders gute Ergebnisse erhalten werden, wenn das Molverhältnis von Oxydations- zu Reduktionskomponente von 0,5 bis 4 beträgt. Obige %-Angaben beziehen sich jeweils auf das Gesamtgewicht der bei den Reaktionsbedingungen flüssigen Monomeren.In general, about 0.01 to about 0.5% by weight, preferably 0.03 to 0.3% by weight, of reduction component and about 0.01 to about 2% by weight are required. %, preferably 0.03 to 0.8% by weight of the oxidation component, with particularly good results being obtained in many cases if the molar ratio of the oxidation component to the reduction component is from 0.5 to 4. The above percentages relate to the total weight of the monomers liquid under the reaction conditions.
Bevorzugte Beispiele für die Oxydationskomponente sind folgende peroxidischen Verbindungen: Ammonium- und Kaliumpersulfat, -peroxodisulfat, Wasserstoffperoxid, Alkylhydroperoxide, wie tert . -Butyl-hydroperoxid, Perox-odiphosphate, wie Kalium-, Natrium- und Ammoniumperoxodiphosphat, sowie deren Gemische.The following peroxidic compounds are preferred examples of the oxidation component: Ammonium and potassium persulfate, -peroxodisulfate, hydrogen peroxide, alkyl hydroperoxides, such as tert. -Butyl hydroperoxide, peroxodiphosphates, such as potassium, sodium and ammonium peroxodiphosphate, and mixtures thereof.
Als bevorzugte Beispiele für die Reduktionskomponente sind Verbindungen des Schwefels, in denen der Schwefel nicht in seiner formalen Oxydationsstufe +6 vorliegt, zu nennen. Insbesondere seien genannt : wasserlösliche Sulfite und Sulfoxylate wie Alkali-(Na-, K-) oder Ammoniumsulfit bzw. -hydrogensulfit oder Alkali- (Na-, K-) oder Zinkformaldehydsulfoxylat. Ebenso eignen sich Wasserstoff/Edelmetallkatalysatorkomponenten unter gleichzeitiger Verwendung geringer Mengen von Schwermetallsalzen als Aktivatoren.Compounds of sulfur in which the sulfur is not in its formal +6 oxidation state are to be mentioned as preferred examples of the reduction component. In particular, the following may be mentioned: water-soluble sulfites and sulfoxylates such as alkali (Na, K) or ammonium sulfite or hydrogen sulfite or alkali (Na, K) or zinc formaldehyde sulfoxylate. Hydrogen / noble metal catalyst components are also suitable as activators with the simultaneous use of small amounts of heavy metal salts.
Geeignete Initiatorsysteme werden u. a. "Fundamental Principles of Polymerization" G. F. Alelio, John Wiley and Sons Inc.,Suitable initiator systems are u. a. "Fundamental Principles of Polymerization" G.F. Alelio, John Wiley and Sons Inc.,
New York, 1952 auf den Seiten 333 ff. und in DE-B-11 33 130 beschrieben.New York, 1952 on pages 333 ff. And described in DE-B-11 33 130.
Grundsätzlich ist auch der Einsatz von Radikalinitiatoren, z. B. den Persulfaten oder Peroxodiphosphaten in Abwesenheit eines Reduktionsmittels möglich. Sowohl bei diesem System als auch bei den vorhergenannten werden vorzugsweise in an sich bekannter Weise Spuren von Salzen geeigneter Schwermetalle, z. B.- von Eisen oder Kupfer, zugegeben.The use of radical initiators, e.g. B. the persulfates or peroxodiphosphates in the absence of a reducing agent possible. Both in this system and in the aforementioned, traces of salts of suitable heavy metals, e.g. B.- of iron or copper added.
Nach der Polymerisation, allenfalls auch am Ende der Polymerisation*können, sofern dies gewünscht wird, auch anionische und/oder nichtionogene Emulgatoren in Mengen von 0 bis 4 Gew.-%, vorzugsweise bis 2 Gew.-%, bezogen auf den Festgehalt der Dispersion, zugesetzt werden. *, z. B. zur Nachpolymerisation, Als Beispiele werden genannt: Alkali- oder Erdalkalisalze von alkylierten Benzol- und Naphthalinsulfonsäuren, wie Natriumbenzylsulfonat, Alkalialkylsulfonate, wie z. B.Natriumlaurylsulfonat, Natriumdodecylsulfonat, Salze der Alkylschwefelsäuren, wie Natriumlaurylsulfat, ferner Natriumalkylsulfosuccinat bzw. Natriumalkylsulfosuccinatmono- und -diester, Natrium- oder Ammoniumsalze, von Sulfatestern von Alkylphenoxipoly (ethoxylen) äthanolen, wie Octyl- oder iso-Nonylphenoxipoly (ethoxylen) äthanolen, sowie deren ethoxylierte Produkte, Ethylenoxidaddukte von Alkylglycolen und Alkylphenolen, Blockcopolymere aus Ethylenoxid und Propylenoxid sowie sulfonierte Fettsäureamide, Fettalkoholoder Fettamin/Ethylenoxidadditionsprodukte.After the polymerization, if necessary also at the end of the polymerization *, if desired, anionic and / or nonionic emulsifiers in amounts of 0 to 4% by weight, preferably up to 2% by weight, based on the solids content of the dispersion , are added. *, e.g. B. for post-polymerization, Examples include: alkali or alkaline earth metal salts of alkylated benzene and naphthalenesulfonic acids, such as sodium benzyl sulfonate, alkali alkyl sulfonates, such as, for. B.Natriumlaurylsulfonat, sodium dodecyl sulfate, salts of alkylsulfuric acids, such as sodium lauryl sulfate, sodium alkyl sulfosuccinate or further Natriumalkylsulfosuccinatmono- and diesters, sodium or äthanolen of Sulfatestern of Alkylphenoxipoly (ethoxylene) ammonium salts, such as octyl or iso-Nonylphenoxipoly (ethoxylene) äthanolen and their ethoxylated products, ethylene oxide adducts of alkyl glycols and alkylphenols, block copolymers of ethylene oxide and propylene oxide, and sulfonated fatty acid amides, fatty alcohol or fatty amine / ethylene oxide addition products.
Das erfindungsgemäße Verfahren wird vorzugsweise bei pH-Werten von 2,5 bis 7 durchgeführt. Dieser Bereich kann aber gegebenenfalls auch über- oder unterschritten werden. Zur Stabilisierung des pH können auch übliche Puffersubstanzen zugesetzt werden, z. B. Bicarbonate, Borate, Acetate, Citrate, Gemische primärer und sekundärer Phosphate der Alkalimetalle.The process according to the invention is preferably carried out at pH values from 2.5 to 7. However, this range can also be exceeded or undershot if necessary. To stabilize the pH, customary buffer substances can also be added, e.g. B. bicarbonates, borates, acetates, citrates, mixtures of primary and secondary phosphates of the alkali metals.
Das erfindungsgemäße Verfahren wird vorzugsweise nach dem Dosierverfahren hergestellt, jedoch kann die gesamte Monomerenmenge vorgelegt werden. Beim Dosierverfahren kann mindestens ein Monomeres ganz oder teilweise vorgelegt werden, während die anderen zur Gänze, sowie gegebenenfalls der Rest der teilweise vorgelegten Monomeren dosiert werden.The process according to the invention is preferably produced by the metering process, but the entire amount of monomers can be introduced. In the metering process, at least one monomer can be introduced in whole or in part, while the others are metered in whole, and optionally the rest of the partially introduced monomers.
Nachdem ümsatzmessungen in der Praxis vielfach schwierig sind, wird vorzugsweise mit dem Zusatz von Schutzkolloid frühestens bei einem (leicht zu ermittelnden) Festgehalt der Dispersion von 2 Gevt . -% , vorzugsweise 5 Gew.-%, und spätestens bei einem Festgehalt von 40 Gew.-%, besser von 30 Gew.-%, insbesondere von 20 Gew.-% begonnen.Since turnover measurements are often difficult in practice, the addition of protective colloid is preferred at the earliest when the (easy to determine) solid content of the dispersion of 2 units -%, preferably 5% by weight, and at the latest at a solids content of 40% by weight, more preferably 30% by weight, in particular 20% by weight.
Die nach dem erfindungsgemäßen Verfahren hergestellten Dispersionen eignen sich als Kleber, zum Beschichten von Papier, Geweben und Vliesen, aus Natur- oder Kunstfasern, Glasfasern, Holzfasern usw., als Zusatz oder als Bindemittel in Beton- und Mörtelmischungen.The dispersions produced by the process according to the invention are suitable as adhesives, for coating paper, fabrics and nonwovens, from natural or synthetic fibers, glass fibers, wood fibers, etc., as additives or as binders in concrete and mortar mixtures.
Die folgenden Beispiele dienen der Erläuterung der Erfindung. Die Ergebnisse der Beispiele und Vergleichsversuche sind in der beigefügten Tabelle aufgeführt. %-Angaben verstehen sich, soweit nicht anders angegeben, stets als Gewichtsprozente und beziehen sichThe following examples serve to illustrate the invention. The results of the examples and comparative tests are listed in the attached table. Unless stated otherwise, percentages are always percentages by weight and relate
(a) auf Gesamtgewicht der bei den Reaktionsbedingungen flüssigen Monomeren(a) on total weight of the monomers liquid under the reaction conditions
(b) auf den Festgehalt(b) on the fixed salary
(c) auf das Gesamtgewicht der Dispersion.(c) on the total weight of the dispersion.
Die Viskositäten der PVAL's in mPas wurden, wie vorstehend beschrieben, nach Höppler bestimmt, die der Dispersionen mit dem Epprecht-Rheometer, wobei die Meßeinheit jeweils in () angegeben ist.As described above, the viscosities of the PVALs in mPas were determined by Höppler, those of the dispersions using the Epprecht rheometer, the measuring unit being given in ().
Druckangaben erfolgten nur, wenn der Anfangsdruck höher lag als der Druck der umgebenden Atmosphäre. Allgemeine Versuchsbeschreibung der erfindungsgemäßen Beispiele (numeriert).Pressure information was only given if the initial pressure was higher than the pressure of the surrounding atmosphere. General experimental description of the examples according to the invention (numbered).
In dem evakuierten und N2-gespülten Autoklaven wurden ein Teil des Wassers, eine Spur Eisenammoniumsulfat und ein Teil der gegebenenfalls vorgemischten flüssigen Monomeren (siehe Tabelle) unter Rühren vorgelegt und auf die gewünschte Temperatur erwärmt. Dann wurde gegebenenfalls Ethylen bis zu dem in der Tabelle angegebenen Anf angsdruck aufgedrückt und die Polymerisation durch Zudosieren der Katalysatorlösungen gestartet. Bei den in der Tabelle angegebenen Versuchen wurden jeweils gleiche Volumina wäßriger Lösungen von Ammonium-(oder Kalium-) persulfat und Natrium-Formaldehydsulfoxylat verwendet. Die Konzentration der Persulfatlösungen war doppelt so hoch wie die des Sulfoxylats. Der pH wurde durch Zudosieren von Ammoniak auf 2,5 bis 5 gehalten. Die Dosierung der Polyvinylalkohollösungen wurde ca. 30 Minuten nach Reaktionsbeginn bei Festgehalten von ca. 2 bis ca. 20 Gew.-% gestartet. Weitere 30 bis 45 Minuten später wurde die Monomerdosierung eingefahren.In the evacuated and N 2 -flushed autoclave, part of the water, a trace of iron ammonium sulfate and part of the optionally premixed liquid monomers (see table) were introduced with stirring and heated to the desired temperature. Then ethylene was optionally pressed up to the initial pressure given in the table and the polymerization was started by metering in the catalyst solutions. In the experiments given in the table, the same volumes of aqueous solutions of ammonium (or potassium) persulfate and sodium formaldehyde sulfoxylate were used. The concentration of the persulfate solutions was twice that of the sulfoxylate. The pH was kept at 2.5 to 5 by metering in ammonia. The metering of the polyvinyl alcohol solutions was started approx. 30 minutes after the start of the reaction with a holding of approx. 2 to approx. 20% by weight. A further 30 to 45 minutes later the monomer metering was started.
Nach Erreichen des maximalen Festgehalts, in der Regel 1 h nach Dosierende, wurde noch 2 h nachpolymerisiert, falls erwünscht der pH z . B. auf 7 gestellt und die Dispersion gegebenenfalls entspannt und schließlich vom Restmonomeren durch Evakuieren befreit. Gegebenenfalls wurde nach Ende der Polymerisation Emulgator zugesetzt. Allgemeine Versuchsvorschrift für die Vergleichsversuche (mit Buchstaben bezeichnet).After reaching the maximum solids content, usually 1 h after the end of metering, polymerization was continued for a further 2 h, if desired the pH, for. B. set to 7 and the dispersion optionally relaxed and finally freed of residual monomers by evacuation. If necessary, emulsifier was added after the end of the polymerization. General test instructions for the comparative tests (labeled with letters).
In dem evakuierten und N2-gespülten Autoklaven wurde ein Teil des Wassers, eine Spur Eisenammoniumsulfat etwas Kaliumpersulfat, der Polyvinylalkohol und gegebenenfalls der Emulgator (siehe Tabelle) vorgelegt und auf die in der Tabelle angegebenen Temperaturen erwärmt. Dann wurde unter Rühren ein Teil der Monomeren (siehe Tabelle) vorgelegt, gegebenenfalls Ethylen bis zum gewünschten Druck aufgepreßt und die Polymerisation durch Zugabe von gleichen Volumina wäßriger Lösungen von Ammonium- (oder Kalium- ) persulfat und Natrium-Formaldehydsulfoxylat gestartet. Die Konzentration der Persulfatlösung war doppelt so hoch wie die der Reduktionsmittellösung.A part of the water, a trace of iron ammonium sulfate, some potassium persulfate, the polyvinyl alcohol and, if appropriate, the emulsifier (see table) were placed in the evacuated and N 2 -flushed autoclave and heated to the temperatures given in the table. Then part of the monomers (see table) was introduced with stirring, ethylene was optionally injected to the desired pressure and the polymerization was started by adding equal volumes of aqueous solutions of ammonium (or potassium) persulfate and sodium formaldehyde sulfoxylate. The concentration of the persulfate solution was twice that of the reducing agent solution.
Der pH wurde durch Zudosieren von Ammoniak bzw. Ameisensäure auf 2,5 bis 5 gehalten. Die Dosierung der restlichen Monomermengen erfolgte analog der vorhergehenden Vorschrift kontinuierlich.The pH was kept at 2.5 to 5 by metering in ammonia or formic acid. The remaining amounts of monomer were metered in continuously as in the previous procedure.
Nach Erreichen des maximalen Festgehaltes, in der Regel 3 bis 9 h nach Dosierende, wurde noch 2 h nachpolymerisiert, falls erforderlich der pH z . B. auf 7 eingestellt und die Dispersion gegebenenfalls entspannt und durch Evakuieren von Restmonomeren befreit. After the maximum solids content had been reached, as a rule 3 to 9 h after the end of the metering, polymerization was continued for a further 2 h. B. set to 7 and the dispersion optionally relaxed and freed of residual monomers by evacuation.

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung von durch Schutzkolloid stabilisierten wäßrigen Polymerdispersionen mit Festgehalten von1. Process for the preparation of aqueous polymer dispersions stabilized by protective colloid with a retention of
20 bis 75 Gew.-%, bezogen auf Gesamtgewicht, durch einstufige Polymerisation von Vinylhalogeniden und/oder Vinylalkanoaten, gegebenenfalls zusammen mit höchstens 50 Gew.-%, bezogen auf Gesamtgewicht der bei den Reaktionsbedingungen flüssigen Monomeren, anderen damit copolymerisierbaren ethylenisch ungesättigten Verbindungen bei Temperaturen von 0 bis 120°C und Drücken bis 200 bar mittels zumindest teilweise wasserlöslicher Radikalinitiatorsysteme, gegebenenfalls in Gegenwart üblicher Zusatzstoffe, d a d u r c h g e k e n n z e i c h n e t , daß mit der Dosierung von Schutzkolloid als erstem Dispergierhilfsstoff erst nach einem Umsatz von 1 bis 60 Gew.-%, bezogen auf Gesamtgewicht der bei den Reaktionsbedingungen flüssigen Monomeren, begonnen wird.20 to 75% by weight, based on the total weight, by single-stage polymerization of vinyl halides and / or vinyl alkanoates, optionally together with at most 50% by weight, based on the total weight of the monomers liquid under the reaction conditions, of other ethylenically unsaturated compounds copolymerizable therewith at temperatures from 0 to 120 ° C and pressures up to 200 bar by means of at least partially water-soluble radical initiator systems, optionally in the presence of customary additives, characterized in that with the addition of protective colloid as the first dispersing aid only after a conversion of 1 to 60% by weight, based on the total weight of the monomers liquid under the reaction conditions is started.
2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t , daß als Schutzkolloid mindestens ein Polyvinylalkohol mit einem Hydrolysegrad von 70 bis 99,8 mol-% und mittlerem Polymerisationsgrad von 200 bis 3000 eingesetzt wird.2. The method of claim 1, d a d u r c h g e k e n n z e i c h n e t that at least one polyvinyl alcohol with a degree of hydrolysis of 70 to 99.8 mol% and average degree of polymerization of 200 to 3000 is used as the protective colloid.
3. Verfahren nach Anspruch 1 oder 2, d a d u r c h g ek e n n z e i c h n e t , daß Schutzkolloid in Mengen von 0,5 bis I5 Gew.-%, bezogen auf die bei den Reaktionsbedingungen flüssigen Monomeren, eingesetzt wird. 3. The method according to claim 1 or 2, dadurchg ek indicates that protective colloid in amounts of 0.5 to I5 wt .-%, based on the monomers liquid under the reaction conditions, is used.
4. Verfahren nach einem der vorangehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , daß 1 bis4. The method according to any one of the preceding claims, d a d u r c h g e k e n n z e i c h n e t that 1 to
40 Gew . -% der bei den Reaktionsbedingungen flüssigen Monomeren vorgelegt und der Rest dosiert wird.40 wt. % of the monomers which are liquid under the reaction conditions are introduced and the remainder is metered in.
5. Verfahren nach einem der vorangehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , daß höchstens5. The method according to any one of the preceding claims, d a d u r c h g e k e n n z e i c h n e t that at most
20 Gew.-% weiterer bei den Reaktionsbedingungen flüssige Comonomere mitverwendet werden.20% by weight of other comonomers which are liquid under the reaction conditions can also be used.
6. Verfahren nach einem der vorangehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , daß darüber hinaus Ethylen als Comonomeres vorzugsweise bei Partialdrucken bis zu 80 bar eingesetzt wird.6. The method according to any one of the preceding claims, d a d u r c h g e k e n n z e i c h n e t that, in addition, ethylene is preferably used as a comonomer at partial pressures up to 80 bar.
7. Verwendung der gemäß einem der vorstehenden Ansprüche hergestellten Dispersionen zur Herstellung redispergierbarer Pulver. 7. Use of the dispersions prepared according to one of the preceding claims for the production of redispersible powders.
EP83901919A 1982-07-20 1983-06-09 Method for the preparation of polymer dispersions and utilization thereof Pending EP0114834A1 (en)

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DE3227090A1 (en) 1984-01-26
WO1984000369A1 (en) 1984-02-02
EP0099463A1 (en) 1984-02-01
JPH0347281B2 (en) 1991-07-18
DE3366242D1 (en) 1986-10-23
JPS59501363A (en) 1984-08-02
EP0099463B1 (en) 1986-09-17

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