WO2016062655A1

WO2016062655A1 - Method for producing an aqueous polymer dispersion

Info

Publication number: WO2016062655A1
Application number: PCT/EP2015/074115
Authority: WO
Inventors: Gerhard Roessler; Valeria BEM; Rupert Konradi
Original assignee: Basf Se
Priority date: 2014-10-23
Filing date: 2015-10-19
Publication date: 2016-04-28
Also published as: AR103690A1

Abstract

The invention relates to a method for producing an aqueous polymer dispersion by radical polymerization of a monomer (M), which is contained in an emulsion and comprises a vinyl benzene entity and a secondary amino group, in the presence of a surfactant mixture, which contains at least one anionic surfactant and at least one nonionic surfactant.

Description

The present invention relates to a process for the preparation of an aqueous polymer dispersion by radical polymerization of an emulsion-containing monomer (M) comprising a vinylbenzene moiety and a secondary amino group in the presence of a surfactant mixture containing at least one anionic surfactant and at least one nonionic surfactant.

Various techniques have been described in the art for imparting antimicrobial properties to polymers. For example, the polymers may contain additives such as silver, zinc or copper and thereby have antimicrobial properties. Polymers which have antimicrobial properties by the addition of additives are often unsuitable for permanent use because they either show only low antimicrobial properties or their antimicrobial properties have only a limited lifespan, as the additives migrate out of the polymers, increasing their antimicrobial properties Properties are lost.

The prior art therefore also describes polymers which have intrinsically antimicrobial properties. Such polymers having intrinsically antimicrobial properties include, for example, quaternary ammonium or phosphonium compounds. These polymers are often hydrophilic and have high water compatibility so that they swell or dissolve upon contact with water. The applications of such polymers are therefore very limited.

Antimicrobial polymers which have intrinsically antimicrobial properties and at the same time a lower hydrophilicity are described, for example, in WO 2014/1 18339. The antimicrobial polymers described in WO 2014/1 18339 are prepared by the polymerization of a monomer comprising vinylbenzene units and a secondary amino group. The preparation of these antimicrobial polymers is preferably carried out by solution polymerization and subsequent precipitation of the polymer by the addition of water in order to completely liberate the antimicrobial polymer from the residual monomer.

With the method described in WO 2014/1 18339, the monomers are only partially reacted. It is usually achieved a turnover of less than 95%. Therefore, to obtain pure polymer, the polymer must be dissolved several times and reprecipitated by the addition of water. That in WO 2014/1 18339 described process for the preparation of antimicrobial polymers is therefore very time consuming and costly, since several purification steps are necessary.

It is an object of the present invention to provide a simpler process for the preparation of polymers having antimicrobial properties. The process should not or to a lesser extent have the disadvantages of the processes described in the prior art described above.

This object is achieved by a process for preparing an aqueous polymer dispersion comprising the steps i) providing an emulsion containing the components

(A) water,

(B) a surfactant mixture containing at least one anionic surfactant and at least one nonionic surfactant,

(C) at least one monomer (M) selected from the group consisting of monomers of the general formulas (I), (II) and

in which

R is a C 1 -C ₁₀ -alkyl, and optionally at least one further ethylenically unsaturated monomer (wM), ii) free-radical polymerization of the component (C) contained in the emulsion and optionally of component (D) to obtain the aqueous polymer dispersion. It has surprisingly been found that the at least one monomer (M) (component (C)) and optionally the component (D) can be polymerized in a free-radical emulsion, if a suitable surfactant mixture (component (B)) is present in the emulsion, and that thereby higher sales are achieved than with the methods described in the prior art. In addition, the polymer produced according to the invention shows a high purity, so that complex purification processes such as those described in the prior art can be avoided. It is also advantageous that the polymer is obtained as an aqueous polymer dispersion, since in many areas in which the polymer is used, aqueous polymer dispersions are used. The inventive method thus eliminates the solution polymerization described in the prior art thus also an additional step for producing such a polymer dispersion, since the polymer is already obtained as a polymer dispersion. The method according to the invention will be explained in more detail below.

Step i)

According to the invention, an emulsion is provided in step i). An emulsion is understood to mean a mixture of two liquids, the two liquids having a miscibility gap and therefore forming two phases.

The excess liquid is called the "continuous phase" or the "outer phase". The other liquid is distributed in the continuous phase in the form of droplets and is referred to as a "disperse phase" or as an "inner phase".

The emulsion according to the invention comprises water (component (A)) as the continuous phase and the at least one monomer (M) (component (C)) and optionally the at least one further ethylenically unsaturated monomer (wM) (component (D)) as the disperse phase. The emulsion is therefore also referred to as "oil-in-water emulsion".

The present invention therefore also provides a process in which component (A) forms a continuous phase and component (C) and optionally component (D) form a disperse phase of the emulsion. The diameter of the droplets of the at least one monomer (M) (component (C)) and optionally of the at least one further ethylenically unsaturated monomer (wM) (component (D)) in the emulsion is usually in the range from 0.01 to 1000 μηη, determined by light scattering, fraunhof diffraction or light microscopy.

According to the invention, the emulsion contains the following components:

(A) water,

(C) at least one monomer (M) selected from the group consisting of a monomer (I), a monomer (I I) and a monomer (II I) and

(D) optionally at least one further ethylenically unsaturated monomer (wM). In one embodiment of the process according to the invention, the emulsion contains in the range from 35 to 89% by weight of component (A), in the range from 0.005 to 9% by weight of component (B), in the range from 10 to 60% by weight. % of component (C) and in the range of 0 to 30 wt .-% of component (D), each based on the sum of the weight percent of components (A) to (D), preferably based on the total weight of the emulsion.

Preferably, the emulsion contains in the range of 55 to 84% by weight of component (A), in the range of 0.3 to 6% by weight of component (B), in the range of 1.5 to 45% by weight. of component (C) and in the range of 0 to 22.5 wt .-% of component (D), each based on the sum of the weight percent of components (A) to (D), preferably based on the total weight of the emulsion.

In a particularly preferred embodiment, the emulsion contains in the range from 60 to 79% by weight of component (A), in the range from 1 to 5% by weight of component (B), in the range from 20 to 40% by weight. of component (C) and in the range of 0 to 20 wt .-% of component (D), each based on the sum of the weight percent of components (A) to (D), preferably based on the total weight of the emulsion. The present invention thus also provides a process in which the emulsion provided in step i) comprises from 35 to 89% by weight of component (A), from 0.005 to 9% by weight of component (B), from 10 to 60% by weight of component (C) and from 0 to 30% by weight of component (D), based on the total weight of components (A) to (D).

In the event that component (D) is included as a compulsory component in the emulsion provided in step ii), the lower limit is 0.1% by weight, preferably 1% by weight and more preferably 5% by weight. -%, in each case based on the sum of the weight percent of components (A) to (D), preferably on the total weight of the emulsion. Usually, the wt .-% of components (A) to (D) add up to 100% by weight.

It goes without saying that the weight percentages for the components (A) to (D) contained in the emulsion relate to the emulsion before the start of the radical polymerization according to step ii). The person skilled in the art knows that the composition of the emulsion usually changes during step ii).

According to the invention contains the emulsion as component (A) water. Preferably, deionized and / or distilled water is used as component (A). Component (B)

According to the invention, a surfactant mixture which contains at least one anionic surfactant and at least one nonionic surfactant is used as component (B). For the purposes of the present invention, "at least one anionic surfactant" means both exactly one anionic surfactant and one mixture of two or more anionic surfactants.

The same applies to "at least one nonionic surfactant." In the present case, "at least one nonionic surfactant" is understood to mean both exactly one nonionic surfactant and one mixture of two or more nonionic surfactants.

In one embodiment, the weight ratio of the at least one anionic surfactant to the at least one nonionic surfactant of component (B) is in the range of 1: 7 to 5: 1, preferably in the range of 1: 1 to 1: 5, and most preferably in the range of 1: 2 to 1: 4.

The present invention thus also provides a process in which the weight ratio of the mindsetens an anionic surfactant to the at least one nonionic surfactant of component (B) in the range of 1: 7 to 5: 1. In the process according to the invention, it is possible to use all anionic and nonionic surfactants known to the person skilled in the art.

In one embodiment of the present invention, the at least one anionic surfactant of component (B) is a surfactant of general formula (IV):

in the

R ^{1 is} an unsubstituted or at least monosubstituted C ₅ -C ₅₀ alkyl, wherein the substituents are independently C ₁ -C ₂ o-alkyl; X ^{+ is} selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ and NH ₄ ⁺ .

The present invention thus also provides a process in which the at least one anionic surfactant of component (B) is a surfactant of the general formula (IV)

wherein R ^{1 is} an unsubstituted or at least monosubstituted C ₅ -C ₅₀ alkyl, wherein the substituents are independently C ₁ -C ₂ o-alkyl; X ^{+ is} selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ and NH ₄ ⁺ .

In a preferred embodiment, the at least one anionic surfactant of component (B) is a surfactant (IV), wherein the substituents have the following meaning: R ¹ is an unsubstituted C ₈ -C ₁₅ alkyl; X ⁺ is Na ⁺ or K

The present invention thus also provides a process in which the at least one anionic surfactant of component (B) is a surfactant (IV) in which

R ^{1 is} an unsubstituted C ₈ -C ₁₅ alkyl; X ⁺ Na ⁺ or K ⁺ is. In a particularly preferred embodiment of the process according to the invention, the at least one anionic surfactant of component (B) is selected from the group consisting of sodium n-decylbenzenesulfonate, sodium n-undecylbenzenesulfonate, sodium n-dodecylbenzenesulfonate and sodium n-tridecylbenzenesulfonate , Such anionic surfactants are known to the person skilled in the art and are commercially available, for example under the trade name Disponil LDBS 20 or Disponil LDBS 25 from BASF SE.

The at least one nonionic surfactant of component (B) in one embodiment of the present invention is a surfactant of general formula (V).

in the

R ^{2 is} an unsubstituted or at least monosubstituted C ₅ -C ₃₀ -alkyl or an unsubstituted or at least monosubstituted C ₅ -C ₃₀ -alkenyl, wherein the substituents are independently C ₁ -C ₂ 0-alkyl; n, x, y, z are independently an integer between 1 and 20,

where the sum of n, x, y, and z is an integer between 4 and 25. The present invention thus also provides a process in which the at least one nonionic surfactant of component (B) is a surfactant of general formula (V),

in the

where the sum of n, x, y, and z is an integer between 4 and 25.

In a preferred embodiment, the at least one nonionic surfactant of component (B) is a surfactant (V), wherein the substituents have the following meaning.

R ² is an unsubstituted C 1-10 -C 20 -alkyl or an unsubstituted C 1-10 -C 20 -alkenyl; n, x, y, z are independently an integer between 1 and 20,

where the sum of n, x, y, and z is an integer between 15 and 20.

The present invention thus also provides a process in which the at least one nonionic surfactant of component (B) is a surfactant (V) in which

R ² is an unsubstituted C ₁₀ -C ₂ o alkyl or an unsubstituted C ₁₀ -C ₂ o alkenyl; n, x, y, z are independently an integer between 1 and 17,

in which the sum of n, x, y, and z is an integer between 15 and 20.

"C ₁ -C ₂ o alkyl" refers to saturated hydrocarbons having a free valence (radical) and from 1 to 20 carbon atoms. The hydrocarbons can be linear, branched or cyclic, it is equally possible that they have a cyclic and a linear component Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl and cyclohexyl Corresponding statements also apply to C ₁ -C 10 -alkyl, for C ₄ -alkyl ₅ -C ₅₀ -alkyl, for C ₅ -C ₃₀ -alkyl and for C ₃ -C ₇ -alkyl.

"C ₅ -C ₃ o-Alkeny referred unsaturated hydrocarbons having a free valence (radical) and from 5 to 30 carbon atoms. The hydrocarbons may be monounsaturated or polyunsaturated. The hydrocarbons may also be linear, branched or cyclic. It is also possible that they contain a cyclic and a linear component. Examples of alkenyl groups are 1-pentenyl, 2-pentenyl, 1-hexenyl, 9-octadecenyl, 9-hexadecenyl and 1-eicosenyl. Corresponding statements apply to C ₁₀ -C ₂ o-alkenyl. In a particularly preferred embodiment, the at least one nonionic surfactant of component (B) is selected from the group consisting of polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate and polyoxyethylene (20 ) sorbitan monooleate. Such nonionic surfactants are known to the person skilled in the art and are commercially available, for example under the trade names Tween 20, Tween 40, Tween 60 and Tween 80.

The present invention thus also provides a process in which the at least one anionic surfactant of component (B) is selected from the group consisting of sodium n-decylbenzenesulfonate, sodium n-undecylbenzenesulfonate, sodium n-dodecylbenzenesulfonate and sodium n tridecylbenzenesulfonate and the at least one nonionic surfactant of component (B) is selected from the group consisting of polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate and polyoxyethylene (20) sorbitan.

Component (C) According to the invention, the emulsion contains as component (C) at least one monomer (M) selected from the group consisting of a monomer (I), a monomer (II) and a monomer (III). For the purposes of the present invention, "at least one monomer (M)" means both exactly one monomer (M) and one mixture of two or more monomers (M).

In one embodiment of the present process, the at least one monomer (M) is selected from the group consisting of a monomer (I), a monomer (I I) and a monomer (II I), where the substituent has the following meaning:

R is a C ₃ -C ₇ alkyl.

In a further preferred embodiment, R is selected from the group consisting of isopropyl, sec-butyl, isobutyl, tert-butyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 3 -Methyl-but-2-yl, 2-methylbut-2-yl, 2,2-dimethyl-propyl,

2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,3-dimethyl-butyl, 2,2-dimethyl-butyl and

3-ethyl-3-pentyl.

In a particularly preferred embodiment, R is selected from the group consisting of isopropyl, sec-butyl, isobutyl, tert-butyl, 3-methylbut-2-yl, 2-methylbut-2-yl, 2 Methyl-3-pentyl, 3-methyl-3-pentyl, 2,3-dimethyl-pentyl and 3-ethyl-3-pentyl, more preferably R is selected from tert -butyl, 2-methyl-but-2-yl , 3-methyl-3-pentyl and 3-ethyl-3-pentyl. In a further particularly preferred embodiment, component (C) is a monomer (I). For the substituent R, the previously described embodiments and preferences apply.

The present invention thus also provides a process in which component (C) is a monomer (I) in which

R is a C ₃ -C ₇ alkyl.

In a further preferred embodiment, component (C) is selected from the group consisting of p-tert-butylamino (methylvinylbenzene), m-tert-butylamino (methylvinylbenzene) and o-tert-butylamino (methylvinylbenzene).

In a further particularly preferred embodiment, component (C) is p-tert-butylamino (methylvinylbenzene).

The present invention thus also provides a process in which component (C) is p-tert-butylamino (methylvinylbenzene). Component (D)

According to the invention, the emulsion optionally contains at least one further ethylenically unsaturated monomer (wM) as component (D).

In one embodiment, the emulsion contains in the range of 0 to 30% by weight, preferably in the range of 0 to 22.5% by weight and more preferably in the range of 0 to 20% by weight of the at least one further ethylenically unsaturated monomer (wM), in each case based on the sum of the weight percent of components (A) to (D), preferably based on the total weight of the emulsion.

According to the invention, "at least one further ethylenically unsaturated monomer (wM)" is understood to mean both exactly one further ethylenically unsaturated monomer (wM) and a mixture of two or more further ethylenically unsaturated monomers (wM).

By "ethylenically unsaturated monomer" is meant a compound containing an ethenediyl group In other words, an ethylenically unsaturated monomer is a compound containing an unsaturated ethanediyl group Such compounds are known to those skilled in the art An example of another ethylenically unsaturated Monomer (wM) is styrene.

initiator

In one embodiment of the present invention, the free radical polymerization in process step ii) is initiated by at least one initiator.

The present invention thus also provides a process in which the free-radical polymerization in step ii) is initiated by at least one initiator.

For the purposes of the present invention, "at least one initiator" means both exactly one initiator and one mixture of two or more initiators, based on the total weight of the components (C) contained in the emulsion and, if appropriate, (D) being generally within the range from 0.5 to 15% by weight of initiator, preferably in the range from 1 to 10% by weight of initiator and particularly preferably in the range from 1 to 5% by weight of initiator. % of components (C) and optionally (D) are contained in the emulsion, from 0.5 to 15 wt .-%, preferably from 1 to 10 wt .-% and particularly preferably from 1 to 5 wt .-% initiator be used. If the emulsion contains, for example, 60% by weight of components (C) and optionally (D), then from 0.3 to 9% by weight, preferably from 0.6 to 6% by weight and especially preferably from 0, 6 to 3 wt .-% initiator used.

Suitable initiators are those which can initiate a radical polymerization. Such initiators are known in the art as such. For example, the at least one initiator is selected from the group consisting of peroxides, disulfides, tetracenes and azo compounds.

Examples of suitable peroxides are didecanoyl peroxide, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxydiethyl acetate, tert-butyl peroxydiethyl isobutyrate, methyl isobutyl ketone peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and sodium peroxodisulfate.

Suitable disulphides are, for example, 2-hydroxyethyl-2'-bromoisobutyrate, propargyl-2-bromoisobutyrate and bis [2- (2'-bromoisobutyryloxy) ethyl] disulphide.

Examples of suitable azo compounds are 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and azodi (cyclohexylcarbonitril).

Preferably, the at least one initiator is selected from the group consisting of peroxides and azo compounds. Particularly preferably, the at least one initiator is a peroxide.

In process step i), the emulsion is provided. Methods of providing the emulsion are known to those skilled in the art. For example, the emulsion may be provided by mixing components (A), (B), (C) and optionally (D) in a reactor. Suitable reactors are known to the person skilled in the art and, for example, stirred tank reactors. Usually, the reactors comprise a mixing device such as anchor stirrer, blade stirrer or propeller stirrer.

It is also possible to provide the emulsion by first mixing only two or three of the components (A), (B), (C) and optionally (D) in a reactor and then adding the remaining components optionally with stirring , For example, component (A) and component (B) may first be mixed with one another in a reactor, and then component (C) and optionally component (D) may be added with stirring, if appropriate. Step ii)

In step ii), the component (C) contained in the emulsion and optionally the component (D) are radically polymerized to give the aqueous polymer dispersion.

Radical polymerizations as such are known to those skilled in the art. The radical polymerization in step ii) can be initiated by all methods known to those skilled in the art. In one embodiment, the free radical polymerization is initiated by contacting component (C) and optionally component (D) with at least one initiator. In this embodiment, the radical polymerization is thus initiated by at least one initiator.

The initiation of a free-radical polymerization by at least one initiator is known to those skilled in the art. Usually, an initiator is used which, when exposed to heat or when exposed to radiation, in particular when exposed to UV radiation, forms free radicals and thus initiates the radical polymerization according to step ii). Such initiators are known to the person skilled in the art. Suitable initiators are, for example, those described above.

The free-radical polymerization of the component (C) and, if appropriate, component (D) contained in the emulsion is also referred to as "emulsion polymerization." Emulsion polymerization is known to the person skilled in the art in the emulsion polymerization is initially component (C) and optionally the component (D) usually in the form of droplets as the dispersed phase in component (A) Component (B) is present in component (A) in the form of micelles The component (C) emulsified in component (A) and optionally component (D) is then free-radically polymerized in the presence of component (B), wherein the polymerization is optionally initiated by at least one initiator which is soluble in component (A) During this polymerization, a polymer forms Polymer is present in component (A) in solid form, therefore, in the course of radical polymerization, that provided in step i) e emulsion converted into the polymer dispersion. The polymer usually diffuses into the micelles of component (B). In the radical polymerization of component (C) and optionally component (D), the polymer is formed, which contains components derived from component (C) and optionally from component (D). If the emulsion provided in step i) contains no component (D), then the polymer contains only structural units derived from component (C) and the polymer is a homopolymer of component (C). If the emulsion provided in step i) contains component (D), the polymer contains components derived from component (C) and from component (D) and the polymer is a copolymer of components (C) and ( D).

The free-radical polymerization of the component (C) contained in the emulsion and optionally component (D) in step ii) usually takes place at a temperature in the range from 30 to 150.degree. C., preferably in the range from 50 to 100.degree. C. and particularly preferably in the range of 60 to 100 ° C.

The present invention thus also provides a process in which the free-radical polymerization in step ii) is carried out at a temperature in the range from 30 to 150.degree. The conversion in step ii) is usually in the range of 95 to 100%, preferably in the range of 97 to 99.9999% and more preferably in the range of 98 to 99.99%.

By conversion is meant the proportion of component (C) and optionally component (D), which polymerizes radically to the polymer. A conversion of 100% means that the components (C) and optionally (D) polymerize completely free-radically to the polymer.

In the radical polymerization according to step ii), the aqueous polymer dispersion is obtained. The polymer is thus present in the aqueous polymer dispersion.

The term "aqueous polymer dispersion" as used herein means a dispersion in which the polymer is dispersed in solid form in water (component (A).) In the polymer dispersion, water (component (A)) is the dispersion medium The dispersion medium is also referred to as "dispersant The polymer is the disperse phase and is also referred to as the "dispersed phase". The polymer dispersion contains the polymer, component (B) and component (A). The polymer dispersion obtained in step ii) usually contains in the range of 10 to 60 wt .-% of the polymer, preferably in the range of 15 to 45 wt .-% and particularly preferably in the range of 20 to 40 wt .-%, based on the Total weight of the polymer dispersion.

5

In addition, the polymer dispersion obtained in step ii) usually contains in the range of 35 to 89 wt .-%, preferably in the range of 50 to 84 wt .-% and particularly preferably in the range of 60 to 79 wt .-% of component (A ) and in the range of 0.005 to 9 wt .-%, preferably in the range of 0.3 to 6 wt .-% and 10 particularly preferably in the range of 1 to 5 wt .-% of component (B), each based on the Total weight of the polymer dispersion.

In one embodiment of the present invention, the proportion of solids in the polymer dispersion is in the range from 10 to 65 wt.%, Preferably in the range from 15 to 15 50 wt.% And particularly preferably in the range from 20 to 45 wt. , based on the total weight of the polymer dispersion.

By "solid" in the polymer dispersion is meant the polymer, component (D) and the decomposition products of the at least one initiator. Expressed differently, "solid" is understood to mean that part of the polymer dispersion which remains when the polymer dispersion is completely evaporated.

As described above, the polymer is in solid form, as particles, in the polymer dispersion. The particle diameters of the polymer are usually in the range of from 100 to 1000 nm, preferably in the range of from 100 to 500 nm, and more preferably in the range of from 100 to 300 nm, determined by light scattering, Fraunhof diffraction or Lichmicroscopy.

In one embodiment of the present invention, in addition to the polymer, component (A) and component (B), polymer dispersion 30 also contains traces of component (C) and optionally component (D).

"Traces of the component (C) and optionally the component (D)" are in the range of 0 to 1 wt .-%, preferably in the range of 0 to 0.5 wt .-% and 35 particularly preferably in the range of 0 to 0.1 wt .-% of component (C) and optionally component (D) understood, each based on the total weight of the polymer dispersion.

The polymer dispersion prepared according to the invention can be used without further work-up, for example for coating or for producing molded parts. In one embodiment of the present invention, the polymer dispersion prepared according to the invention is purified before it is used. Processes for this are known to the person skilled in the art. For example, the polymer dispersion can be purified to remove the traces of component (C) and optionally component (D). Processes for this are known to the person skilled in the art. For example, the traces of component (C) and optionally component (D) can be removed by chemical or physical deodorization. Processes for this are known to the person skilled in the art. In addition, the polymer can be separated from the polymer dispersion after step ii). Processes for this are known to the person skilled in the art. For example, the polymer can be separated from the polymer dispersion by spray drying.

The separated polymer can then be processed further. Processes for this are known to the person skilled in the art.

The polymer produced according to the invention has intrinsically antimicrobial properties and is therefore suitable, for example, for the production of aseptic packaging.

In one embodiment of the present invention, the process for preparing the aqueous polymer dispersion comprises the following steps: a) providing the emulsion in a first feed tank,

b) providing a first solution containing the component (A) and at least one initiator in a second storage container,

c) providing a second solution containing the components (A) and (B) in a reaction vessel,

d) adding a first portion of the emulsion from the first feed tank into the reaction vessel,

e) adding at least one initiator to the reaction vessel to initiate radical polymerization,

f) Continuously adding the remainder of the emulsion and the first solution from the first and second feed containers to the reaction vessel to obtain the aqueous polymer dispersion.

The present invention thus also provides a process comprising the following steps: a) providing the emulsion in a first storage container,

b) providing a first solution containing component (A) and at least one initiator in a second reservoir, c) providing a second solution containing the components (A) and (B) in a reaction vessel,

In step a), the emulsion is provided in the first storage container. Step a) thus corresponds to step i).

For the emulsion, the previously described embodiments and preferences apply. As a first storage container all known to the expert storage containers are. Preferably, the first storage container comprises a mixing device. Suitable mixing devices are known to those skilled in the art. Suitable mixers are static and dynamic mixers, with dynamic mixers being preferred. Dynamic mixers are, for example, stirrers such as anchor stirrers, blade stirrers, magnetic stirrers or propeller stirrers.

For example, the emulsion may be provided by mixing components (A), (B), (C), and optionally (D) in the first receiver. It is also possible to mix at least part of the components (A), (B), (C) and, if appropriate, (D) outside the first storage container and then to feed them to the storage container. The components (A) and (B) are preferably first mixed with one another and then the components (C) and optionally (D) are added, if appropriate with stirring, to obtain the emulsion.

In step b), the first solution containing the component (A) and the at least one initiator is provided in a second feed tank.

For the second storage tank, the same previously described designs and preferences apply as for the first storage tank.

For the component (A) and the at least one initiator, the previously described embodiments and preferences apply. The first solution can be provided in step b) by all methods known to those skilled in the art. For example, the component (A) and the at least one initiator optionally with stirring directly in the second storage container be mixed. It is also possible to mix the component (A) and the at least one initiator outside the second storage container and only then to supply the second storage container. In step c), a second solution containing the components (A) and (B) is provided in the reaction vessel.

For the components (A) and (B), the previously described designs and preferences apply.

Suitable reaction vessels are known to those skilled in the art. Suitable reaction vessels are, for example, reactors, such as stirred reactors or tube reactors. Stirred reactors are preferred as reaction vessels. Preferably, the reaction vessel comprises a mixing device. Preferred mixing devices are stirring, such as anchor stirrer propeller stirrer, magnetic stirrer or blade stirrer.

The second solution can be provided in step c) by all methods known to those skilled in the art. For example, components (A) and (B) may optionally be mixed with stirring directly in the reaction vessel. It is also possible to mix the components (A) and (B) outside the reaction vessel and only then to supply the reaction vessel.

In step d), a first portion of the emulsion from the first feed tank is added to the reaction vessel.

Thus, in step d), a first portion of the emulsion from the first storage tank is added to the second solution in the reactor.

The addition of the first part of the emulsion into the reaction vessel can be carried out by all methods known to the person skilled in the art. For example, the first part of the emulsion may be added by dropping it into the first reaction vessel, and it is also possible to add the first part of the emulsion by pumping into the first reaction vessel. After step d), the reaction vessel thus contains a second emulsion containing the components (A), (B), (C) and optionally (D).

In step e), at least one initiator is added to the reaction vessel to initiate radical polymerization. In other words, in step e) at least one initiator is added to the second emulsion obtained in step d) in the reaction vessel to initiate the radical polymerization. In one embodiment, the at least one initiator is added to the reaction vessel as a solution in component (A) to the reaction vessel.

The at least one initiator can be added to the reaction vessel by the same methods as the first part of the emulsion. Therefore, the same designs and preferences apply as previously described.

In step e), the radical polymerization is initiated. Usually, the free-radical polymerization is initiated by the at least one initiator. In general, the initiator initiates free-radical polymerization by forming free radicals. The radical formation of the initiator takes place, for example, by the action of heat or of radiation, in particular of UV radiation on the initiator, preferably by the action of heat. The mechanisms for this are known to the person skilled in the art.

In one embodiment of the method, the reaction vessel is therefore heated before step e), in particular directly before step e) and / or during step e) and / or after step e) and before step f). In a preferred embodiment, the reaction vessel is heated to a temperature in the range of 30 to 150 ° C, preferably in the range of 50 to 100 ° C and particularly preferably in the range of 60 to 100 ° C. Without limiting the invention to this, it is conceivable that, during step e), the polymerization of the component (C) contained in the second emulsion and optionally also the component (D) begins and thus forms a prepolymer having a low number average molecular weight. In step f), the remainder of the emulsion and the first solution from the first and second feed containers are continuously added to the reaction vessel in the reaction vessel to obtain the aqueous polymer dispersion.

The term "remainder of the emulsion" is understood to mean that part of the emulsion which is still present in the first feed container at the beginning of step f), ie the part which was not added to the reaction vessel as the first part of the emulsion in process step d).

For the purposes of the present invention, "continuous addition" means that the addition takes place over a period in the range from 0.5 to 24 hours, preferably in the range from 0.5 to 10 hours and in particular in the range from 1 to 3 hours Addition may be carried out by all methods known to those skilled in the art For example, the remainder of the emulsion and the first solution may be added dropwise. For the aqueous polymer dispersion obtained in step f), the above-described embodiments and preferences apply. In a preferred embodiment of the present invention, step ii) of the process according to the invention comprises steps e) and f).

The method according to the invention is explained in more detail below by the examples, without, however, limiting it to them.

Examples

In the examples, the following components were used: (A) demineralized water,

(B1) Tween-80 (CAS No. 9005-65-6; polyoxyethylene (20) sorbitan monooleate)

(B2) 20% solution of Disponil LDBS 20 in water (sodium n-alkyl (C ₁₀ -C ₁₃ ) benzenesulfonate)

(C) tert -butylamino (methylvinylbenzene) (TBAMS)

(D) Styrene (CAS No. 100-43-5)

Initiator 1 sodium peroxodisulfate (CAS No. 7775-27-1)

Initiator 2 Wako V 59 (2,2'-azodile (2-methylbutyronitrile), CAS No. 13472-08-7) Initiator 3 tert-butyl peroxypivalate CAS-No. 927-07-1)

The content of TBAMS was determined by gas chromatography. For this purpose, 100 mg of sample were mixed with 1 ml of standard solution (3 mg of butylbenzene in 1 ml of dioxane) and 9 ml of dioxane. A dimethylpolysiloxane (DBI) separation column having a length of 30 m and an internal diameter of 0.25 mm was used. Nitrogen was used as the carrier gas.

Example 1 In a first receiver, an emulsion containing 304 g of component (A), 15 g of component (B1), 25 g of component (B2) and 215 g of component (C) was provided. In a second receiver, a first solution containing 4 g of initiator 1 and 154 g of component (A) was provided.

In a 2 liter reactor with anchor stirrer and reflux condenser, a second solution was prepared containing 386 g of component (A), 2.1 g of component (B1) and 3.6 g of component (B2).

4 g of the emulsion was added to the second solution and heated with stirring. When reaching a temperature of 70 ° C, 2 g of the initiator 1 in 14 g of component (A) were added and then further heated until a temperature of 100 ° C was reached.

Five minutes after the end of the addition of initiator 1, the remainder of the emulsion was added over 15 of 1.5 hours and at the same time 106 g of the first solution were added over 1.75 hours. The remainder of the first solution (52 g) was then added over two hours.

After completion of the addition, the mixture was left for another two hours with stirring at 20 100 ° C, then added a further 3.1 g of the initiator 1 and left for another two hours with stirring at 100 ° C to give the polymer dispersion.

After cooling to room temperature, the resulting polymer dispersion was filtered through a 150 m filter.

25

TBAMS content (GC analysis): 0.28 g per 100 g reaction mixture

This corresponds to 1, 5% of the amount of TBAMS used and a conversion of 98.5%.

Example 2

30

In a first receiver, an emulsion containing 386 g of component (A), 24 g of component (B1), 39 g of component (B2) and 337 g of component (C) was provided.

In a second receiver, a first solution containing 6.3 g of initiator 1 and 151.7 g of component (A) was provided.

In a 2 liter reactor with anchor stirrer and reflux condenser, a second solution was prepared containing 304 g of component (A), 3.3 g of component (B1) and 5.5 g of component 40 (B2). 6 g of the emulsion was added to the second solution and heated with stirring. Upon reaching a temperature of 70 ° C, 3.1 g of the initiator 1 in 14 g of component (A) were added and then further heated until a temperature of 100 ° C was reached.

Five minutes after the end of the addition of the initiator 1, the remainder of the emulsion was added over 1.5 hours and, at the same time, 106 g of the first solution were added over 1.75 hours. The remainder of the first solution (52 g) was then added over two hours.

After completion of the addition, the mixture was left for another two hours with stirring at 100 ° C, then added a further 3.1 g of the initiator 1 and left for another two hours with stirring at 100 ° C to give the polymer dispersion. After cooling to room temperature, the resulting polymer dispersion was filtered through a 150 m filter.

TBAMS content (GC analysis): 0.77 g per 100 g reaction mixture

This corresponds to 2.9% of the TBAMS quantity used and a turnover of 97.1%.

Example 3

In a first reactor, an emulsion containing 386 g of component (A), 24 g of component (B1), 39 g of component (B2), 320.1 g of component (C) and 16.9 g of component ( D).

In a second reactor, a first solution containing 6.3 g of initiator 1 and 151.7 g of component (A) was provided.

In a 2 liter reactor with anchor stirrer and reflux condenser, a second solution was prepared containing 304 g of component (A), 3.3 g of component (B1) and 5.5 g of component (B2). 6 g of the emulsion was added to the second solution and heated with stirring. Upon reaching a temperature of 70 ° C, 3.1 g of the initiator 1 in 14 g of the component (A) were added and further heated until a temperature of 100 ° C was reached.

Five minutes after the end of the addition of the initiator 1, the remainder of the emulsion was added over 1.5 hours and at the same time 106 g of the first solution within 1, 75 hours added. The remainder of the first solution (52 g) was then added over two hours.

After completion of the addition, the emulsion was left for another two hours with stirring at 5 100 ° C, then added a further 3.1 g of the initiator 1 and left for another two hours with stirring at 100 ° C to give the polymer dispersion.

0

TBAMS content (GC analysis): 0.39 g per 100 g reaction mixture

This corresponds to 1, 6% of the amount of TBAMS used and a conversion of 98.4%. 5 Comparative Example 1

In a first receiver, 50 g of ethanol and 47.3 g of component (C) were provided. 0 A solution of 1.04 g of the initiator 2 in 20 g of ethanol was provided in a second receiver.

A solution of 5.3 g of component (C) and 0.01 g of initiator 2 in 230 g of ethanol was placed in a 2-liter reactor with anchor stirrer and reflux condenser.

5

The 2 liter reactor was heated to 75 ° C with stirring. At this temperature, 0.01 g of initiator 2 dissolved in 1 g of ethanol was added.

Ten minutes after the completion of the addition, the contents of the first receiver 0 were added within 2 hours, and at the same time, the contents of the second receiver were added within 3 hours.

After completion of the addition, the mixture was stirred for a further 24 hours at 75 ° C and then cooled to room temperature.

5

TBAMS content (GC analysis): 2.7 g per 100 g reaction mixture

This corresponds to 18, 1% of the amount of TBAMS used (81, 9% conversion) 0 Comparative Example 2 In a first receiver, 50 g of 2-propanol and 47.3 g of component (C) were provided.

In a second storage tank, a solution of 1.04 g of the initiator 2 in 20 g of 2-propanol was provided.

A solution of 5.3 g of component (C) and 0.01 g of initiator 2 in 230 g of 2-propanol was placed in a 2-liter reactor with anchor stirrer and reflux condenser. The 2 liter reactor was heated to 80 ° C with stirring. At this temperature, 0.01 g of initiator 2 dissolved in 1 g of 2-propanol was added.

Ten minutes after the completion of the addition, the contents of the first receiver were added within 2 hours, and at the same time, the contents of the second receiver were added within 3 hours.

After completion of the addition, the mixture was stirred for a further 24 hours at 80 ° C and then cooled to room temperature. TBAMS content (GC analysis): 2.7 g per 100 g reaction mixture

This corresponds to 18, 1% of the amount of TBAMS used (81, 9% conversion)

Comparative Example 3

In a first receiver, 50 g of ethanol and 47.3 g of component (C) were provided.

In a second receiver, a solution of 1.4 g of initiator 3 in 20 g of ethanol was provided.

A solution of 5.3 g of component (C) and 0.01 g of initiator 3 in 230 g of ethanol was placed in a 2-liter reactor with anchor stirrer and reflux condenser. The 2 liter reactor was heated to 75 ° C with stirring. At this temperature, 0.01 g of initiator 3 dissolved in 1 g of ethanol was added.

Ten minutes after the completion of the addition, the contents of the first receiver were added within 2 hours, and at the same time, the contents of the second receiver were added within 3 hours. After completion of the addition, the mixture was stirred for a further 24 hours at 75 ° C and then cooled to room temperature.

TBAMS content (GC analysis): 10.3 g per 100 g reaction mixture

This corresponds to 69, 1% of the amount of TBAMS used (30.9% sales)

Comparative Example 4 In a first receiver, 50 g of 2-propanol and 47.3 g of component (C) were provided.

In a second receiver, a solution of 1.4 g of initiator 3 in 20 g of 2-propanol was provided.

A solution of 5.3 g of component (C) and 0.01 g of initiator 3 in 230 g of 2-propanol was placed in a 2-liter reactor with anchor stirrer and reflux condenser.

The 2 liter reactor was heated to 80 ° C with stirring. At this temperature, 0.01 g of initiator 3 dissolved in 1 g of 2-propanol was added.

After completion of the addition, the mixture was stirred for a further 24 hours at 80 ° C and then cooled to room temperature.

TBAMS content (GC analysis): 7.5 g per 100 g reaction mixture

This corresponds to 50.3% of the amount of TBAMS used (49.7% sales)

Comparative Example 5 In a first receiver, 50 g of 2-propanol and 47.3 g of component (C) were provided.

In a second receiver, a solution of 2 g of the initiator 2 in 30 g of 2-propanol was provided.

In a third receiver, a solution of 1 g of the initiator 2 in 20 g of 2-propanol was provided. A solution of 5.3 g of component (C) and 0.6 g of initiator 2 in 200 g of 2-propanol was placed in a 2 liter reactor with anchor stirrer and reflux condenser. The 2 liter reactor was heated to 80 ° C with stirring. At this temperature, 0.6 g of initiator 2 dissolved in 2 g of 2-propanol was added.

After completion of the addition, the mixture was stirred for a further 2 hours at 80 ° C.

The contents of the third receiver were added within one hour.

After completion of the addition, the mixture was stirred for a further 18 hours at 80 ° C and then cooled to room temperature.

TBAMS content (GC analysis): 0.9 g per 100 g reaction mixture

This corresponds to 6.1% of the amount of TBAMS used (93.9% sales)

Claims

claims

A process for the preparation of an aqueous polymer dispersion comprising the steps

i) providing an emulsion containing the components

Water,

a surfactant mixture containing at least one anionic surfactant and at least one nonionic surfactant,

at least one monomer (M) selected from the group

Monomers of the general formulas (I), (II) and (III)

in which

R is a C 1 -C ₁₀ -alkyl, and optionally at least one further ethylenically unsaturated monomer (wM), ii) free-radical polymerization of the component (C) contained in the emulsion and optionally of component (D) to obtain the aqueous polymer dispersion. A method according to claim 1, characterized in that the emulsion provided in step i) of 35 to 89 wt .-% of component (A), from 0.005 to 9 wt .-% of component (B), from 10 to 60 wt. -% of component (C) and from 0 to 30 wt .-% of component (D), based on the total weight of components (A) to (D).

A method according to claim 1 or 2, characterized in that the free radical polymerization in step ii) is initiated by at least one initiator.

A method according to any one of claims 1 to 3, characterized in that the weight ratio of the mindsetens an anionic surfactant to the at least one nonionic surfactant of component (B) in the range of 1: 7 to 5: 1.

A process according to any one of claims 1 to 4, characterized in that the at least one anionic surfactant of component (B) is a surfactant of general formula (IV)

R ^{1 is} an unsubstituted or at least monosubstituted C ₅ -C ₅₀ alkyl, wherein the substituents are independently C ₁ -C ₂ o-alkyl;

X ^{+ is} selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ and NH ₄ ⁺ .

6. The method according to any one of claims 1 to 5, characterized in that the at least one nonionic surfactant of component (B) is a surfactant of the general formula (V),

in the

R ² is un substituted or at least monosubsituiertes C ₅ -C ₃₀ alkyl or an unsubstituted or at least mono-substituted C ₅ -C ₃₀ - alkenyl, wherein the substituents -C ₂ o alkyl independently of one another; n, x, y, z are independently an integer between 1 and 20, where the sum of n, x, y, and z is an integer between 4 and 25.

Process according to any one of Claims 1 to 6, characterized in that the at least one anionic surfactant of component (B) is a surfactant (IV) in which

R ^{1 is} an unsubstituted C ₈ -C ₁₅ alkyl; X ⁺ Na ⁺ or K ⁺ is.

Process according to any one of Claims 1 to 7, characterized in that the at least one nonionic surfactant of component (B) is a surfactant (V) in which

R ² is an unsubstituted C ₁₀ -C ₂ o alkyl or an unsubstituted C ₁₀ -C ₂ o alkenyl; n, x, y, z are independently an integer between 1 and 17, where the sum of n, x, y, and z is an integer between 15 and 20.

9. The method according to any one of claims 1 to 8, characterized in that the at least one anionic surfactant of component (B) is selected from the group consisting of sodium n-decylbenzenesulfonate, sodium n-undecylbenzolsulfonat, sodium n-dodecylbenzenesulfonate and Sodium n-tridecylbenzenesulfonate and the at least one nonionic surfactant of component (B) is selected from the group consisting of polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate and polyoxyethylene - (20) sorbitan monooleate.

10

10. The method according to any one of claims 1 to 9, characterized in that the free-radical polymerization in step ii) is carried out at a temperature in the range of 30 to 150 ° C.

15 1 1. Process according to any one of Claims 1 to 10, characterized in that component (C) is a monomer (I) in which

R is a C ₃ -C ₇ alkyl.

12. The method according to any one of claims 1 to 1 1, characterized in that the component (C) is p-tert-butylamino (methylvinylbenzene).

13. The method according to any one of claims 1 to 13, characterized in that it comprises the following steps:

25

a) providing the emulsion in a first storage container,

b) providing a first solution containing component (A) and at least one initiator in a second reservoir,

c) providing a second solution containing the components (A) and (B) 30 in a reaction vessel,

35 f) Continuously adding the remainder of the emulsion and the first solution from the first and second feed containers to the reaction vessel to obtain the aqueous polymer dispersion.