DE102022114642A1 - HIGH MOLECULAR WEIGHT POLYMER DISPERSIONS PRODUCED UNDER CONTROLLED ADIABATIC CONDITIONS - Google Patents

Abstract

The invention relates to processes for producing a polymer dispersion, to polymer dispersions and their use. The methods for preparing the polymer dispersion include the steps of providing a reaction mixture in an aqueous medium comprising a polymeric dispersant and a monomer composition comprising radically polymerizable monomers, and subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer, to form the polymer dispersion, the step of subjecting the monomer composition to being carried out under controlled adiabatic conditions. These polymer dispersions are referred to as water-in-water (w/w) polymer dispersions.

Description

The invention relates to processes for producing a polymer dispersion, to polymer dispersions and their use. The methods for preparing the polymer dispersion include the steps of providing a reaction mixture in an aqueous medium comprising a polymeric dispersant and a monomer composition comprising radically polymerizable monomers, and subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer, to form the polymer dispersion, the step of subjecting the monomer composition to being carried out under controlled adiabatic conditions. These polymer dispersions are referred to as water-in-water (w/w) polymer dispersions.

The water-in-water polymer dispersions are useful as flocculants, drainage aids and retention aids in papermaking and other technical areas. To produce paper, an aqueous slurry of cellulose fibers is first produced that has a water content of more than 95% by weight. The finished paper sheet has a water content of less than 5 percent by weight. Drainage and retention are crucial steps in papermaking and are important for an efficient papermaking process. High-performance w/w polymer dispersions are a key factor in the papermaking process.

A known flocculant is a w/w polymer dispersion prepared by copolymerizing ethylenically unsaturated monomers in an aqueous system containing a polymeric dispersant, thereby forming a dispersion containing the polymeric dispersant and the synthesized copolymer. The US8476391B2 and the US7323510B2 are early publications of such w/w polymer dispersions. It is well known in this technical field that the addition of separately synthesized copolymers on the one hand and polymeric dispersants on the other hand results in products which have completely different properties than the w/w polymer dispersions disclosed in the above-mentioned patent documents. Copolymerization in a system containing the polymeric dispersant is necessary to obtain high performance flocculant products, for example for papermaking.

These circumstances make the production of the w/w polymer dispersions a multi-parameter system. The type of ethylenically unsaturated monomers, their ratio and the type of polymer dispersant are just a few parameters that influence the properties of the w/w polymer dispersion. Improving the properties of the end product of the w/w polymer dispersion has been the subject of countless research and development attempts.

The person skilled in the art knows how to radically polymerize monomers in a reaction mixture. The person skilled in the art generally knows how to modify the amount and type of initiator in order to change the properties of the resulting polymer product, particularly with regard to the molecular weight and molecular weight distribution of the synthesized polymer.

However, there is still a need to find those parameters that have a positive effect on complex polymer systems and provide the opportunity to improve their properties. There is still a need to improve long-term stability and ensure a long shelf life under unfavorable conditions such as. B. to ensure changing temperatures. In addition, the handling of the W/W polymer dispersion needs to be improved. In particular, the w/w polymer dispersions must have a tailored viscosity to enable better handling for downstream applications.

In addition to the properties of the end product of the w/w polymer dispersion, there is also a need to improve the process itself. In this regard, it is desirable to shorten the duration of the process for obtaining the final product of the w/w polymer dispersion. Reducing the process time increases the amount of product over time because a larger number of batches can be produced. However, such a reduction in the time for producing the final product should not be associated with a loss in the quality of the final product. In particular, the reduction in time should not be associated with a deterioration in viscosity, i.e. a deterioration in handling.

The object underlying the invention is to overcome the disadvantages of the prior art. In particular, the invention is based on the object of providing a process for producing a w/w polymer dispersion which leads to a product which has improved handling guaranteed. Furthermore, the invention is based on the object of providing a method for producing a w/w polymer dispersion which has a high degree of stability during the manufacturing process and a high durability under unfavorable conditions, such as. B. changing temperatures. Furthermore, the invention is based on the object of providing a process for producing a w/w polymer dispersion in which the time for carrying out the process is reduced without loss of quality of the w/w polymer dispersion.

The problems underlying the invention are solved by the subject matter of claim 1. Thus, according to a first aspect, the invention relates to a method for producing a polymer dispersion, comprising the steps A) providing a reaction mixture in an aqueous medium, comprising a) a polymeric dispersant and b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more of a nonionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; and B) subjecting the monomer composition to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion, wherein step B) is carried out under controlled adiabatic conditions.

The process includes providing a reaction mixture containing the monomers to be copolymerized and a polymeric dispersant. The monomers are polymerized in an aqueous medium in the presence of the polymeric dispersant. According to the prior art, a polymer dispersion obtained by the process according to the invention cannot be obtained by subjecting the monomer composition to copolymerization and then adding the polymeric dispersant after the copolymerization. By using the process according to the invention, the polymer dispersion is given unique properties, the polymer dispersion representing the end product which comprises the copolymer obtained from the free-radically polymerizable monomers together with the polymeric dispersant.

It was surprisingly found that carrying out the process under controlled adiabatic conditions leads to overcoming the problems underlying the invention. It is known to those skilled in the art to carry out particularly exothermic reactions under adiabatic conditions. The person skilled in the art understands the term “adiabatic conditions” to mean conditions that essentially do not allow heat exchange with the environment of the reaction vessel.

What is essential to the present invention is that the process is carried out under “controlled” adiabatic conditions. In the context of the present application, this term is understood to mean that measures are applied that affect thermal management. Process measures are applied so that the reaction occurs in such a way that the heat increases more or less slowly or more quickly.

In a preferred embodiment of the invention, the catalyst is used in such a way that the reaction proceeds in the desired manner. Therefore, according to a preferred embodiment, the method is characterized in that step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system. Preferably the redox initiator system comprises an oxidizing agent and a reducing agent.

The process step of adding the initiator system means that control over the reaction is taken. In other words, the addition of the initiator system is tailor-made for controlling the reaction.

Controlling the adiabatic conditions also means that the heat generation is determined depending on the redox initiator system.

Normally, polymerization reactions are carried out in the presence of one or more polymerization initiators. Radicals can be formed by thermally induced or photochemically induced homolysis of single bonds or redox reactions. In the following, the term “initiator” includes all compounds and combinations of compounds that are capable of generating radicals through thermal and/or photochemical induction and/or through redox reactions.

According to a preferred embodiment, the type of initiator system controls the process for producing the w/w polymer dispersion. In a first preferred embodiment, the method is characterized in that step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system. The redox initiator system preferably comprises an oxidizing agent and a reducing agent.

According to a preferred embodiment, the method is characterized in that the oxidizing agent has a redox potential of 0.6 to 2.0 V. Preferred oxidants used in the redox initiator system to control adiabatic conditions are peroxydiphosphates; hydrogen peroxide (1.14 V); alkyl hydroperoxides, preferably t-butyl hydroperoxide; or aryl hydroperoxides, preferably cumene hydroperoxide. According to a particularly preferred embodiment, the process is characterized in that the oxidizing agent is selected from alkyl hydroperoxides, in particular t-butyl hydroperoxide, or aryl hydroperoxides, in particular cumene hydroperoxide.

Persulfates can also be used as agents in an initiator system. However, it has been found that persulfates with a redox potential of 2.01 V do not have such a large influence on the manufacturing process that it can meet the requirement that the process is carried out under controlled adiabatic conditions. If persulfates are used as initiators in the present process, another oxidizing agent which has a potential of 2 V or less and 0.6 V or more is used in the redox initiator system. In a preferred embodiment, however, the redox initiator system is free of a persulfate salt.

In a preferred embodiment, the method is characterized in that the reducing agent has a redox potential of -2 to 0.3 V. Preferred reducing agents are selected from sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite (-1.12 V), potassium sulfite, ammonium sulfite, a hydrogen sulfite (-0.08 V); a thiosulphate (-.017 V); an amine; an acid, preferably ascorbic acid (0.127 V) or erythorbic acid (0.127 V). Further preferred reducing agents are bisulfites, in particular sodium bisulfite, potassium bisulfite or ammonium bisulfite.

The redox potential is determined using standard methods known to those skilled in the art.

In a particularly preferred embodiment, the redox initiator system comprises an alkyl/aryl hydroperoxide together with a bisulfite.

In a preferred embodiment, more oxidizing agent is used than reducing agent by weight. According to a preferred embodiment, the method is characterized in that the weight ratio between the reducing agent and the oxidizing agent is below 35:1 and above 2:1, preferably below 15:1 and above 3:1, more preferably below 9:1 and above 4: 1 lies.

The controlled adiabatic state feature and the preferred features related to the controlled adiabatic state feature are associated with an improvement in the process for producing the w/w polymer dispersion as such. These features improve the process according to the invention in that the time for copolymerization (step B) is shortened. In a preferred embodiment, step B is carried out in a time frame of less than 40 minutes. The time frame begins with the addition of a first portion of an initiator and ends with reaching the maximum temperature (Tmax). According to a preferred embodiment, the next step is carried out at Tmax, i.e. H. the step of reducing the residual monomer content.

1. (i) wasserlösliche und wasserunlösliche Azoverbindungen wie 2,2'-Azobis(2-amidinopropan)dihydrochlorid (Vazo 56 oder V-50), 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitril) (Vazo 33), 2, 2'-Azobis(2,4-dimethylvaleronitril) (Vazo 52), 2,2'-Azobis(isobutyronitril) (Vazo 64), 2,2'-Azobis-2-methylbutyronitril (Vazo 67), 1,1-Azobis(1-Cyclohexancarbonitril) (Vazo 88), 2, 2'-Azobis[2-(2-imidazolin-2-yl)propan]dihydrochlorid (VA-044), 2,2'-Azobis(2-cyclopropylpropionitril) und 2,2'-Azobis(methylisobutyrat) (V-601), 2,2'-Azobis[2-(2-imidazolin-2-yl)propan] (VA-61), 2, 2'-Azobis{2-[1-(2-Hydroxyethyl)-2-imidazolin-2-yl]propan}dihydrochlorid (V-60) und 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamid] (VA-086) (die von DuPont oder Wako Pure Chemical Industries Ltd. ); 2,2'-Azobis(methylisobutyrat), 4,4'-Azobis-(4-cyanopentansäure), Dimethyl-2,2'-azobisisobutyrat, 2,2'-Azobis(isobutyramid)-Dihydrat, 2-Phenylazo-2,4-dimethyl-4-methoxyvaleronitril, 2-(Carbamoylazo)isobutyronitril, 2,2'-Azobis(2,4,4-trimethylpentan), 2, 2'-Azobis(2-methylpropan), 2,2'-Azobis(N,N'-dimethylenisobutyramidin) in Form der freien Base oder des Hydrochlorids, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamid}, und 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamid; worauf besonders bevorzugt wird; und
2. (ii) wasserlösliche und wasserunlösliche organische Peroxide, wie t-Butylhydroperoxid, Dit-Butylperoxid, t-Butylperoxypivalat, t-Butylperoxyisopropylcarbonat, Benzoylperoxid, Dibenzoylperoxid, 2, 4-Dichlorbenzoylperoxid, Benzoylhydroperoxid, 2,5-Dimethylhexyne-2,5-di-t-butylperoxid, 2,5-Dimethylhexan-2,5-di-t-butylperoxid, Di-tert-amylperoxid, Dicumylperoxid, Cumolhydroperoxid, Isopropylbenzolperoxid, Acetylperoxid, Diacetylperoxid, t-Butylperacetat, Isopropylperoxycarbonat, Diisopropylperoxydicarbonat, Lauroylperoxid, Dilaurylperoxid, Decanoylperoxid, Diisononanoylperoxid, Didecanoylperoxid, Dioctanoylperoxid, Dicetylperoxydicarbonat, Di(4-t-butylcyclohexyl)peroxydicarbonat (Perkadox 16S erhältlich von Akzo Nobel), Di(2-ethylhexyl)peroxydicarbonat, t-Butylperoxypivalat (Lupersol 11 erhältlich von Elf Atochem), t-Butylperoxy-2-ethylhexanoat (Trigonox 21-C50 erhältlich von Akzo Nobel), Acetylcyclohexansulfonylperoxid, t-Amylperneodecanoat, t-Butylperneodecanoat, t-Butylperpivalat, t-Amylperpivalat, Bis(2,4-dichlorbenzoyl)peroxid, Bis-(4-chlorbenzoyl)-peroxid, Bis-(2-methylbenzoyl)-peroxid, Disuccinsäureperoxid, t-Butylperisobutyrat, t-Butylpermaleinat, 1,1-Bis-(t-butylperoxy)3,5,5-trimethylcyclohexan, 1,1-Bis-(t-butylperoxy)cyclohexan, t-Butylperisononaoat, 2,5-Dimethylhexan-2,5-dibenzoat, t-Amylperbenzoat, t-Butylperbenzoat, 2,2-Bis(t-butylperoxy)butan, 2,2-Bis(t-butylperoxy)propan, 3-t-Butylperoxy-3-phenylphthalid, α, α'-Bis(t-butylperoxyisopropyl)benzol, 3,5-Bis(t-butylperoxy)3,5-dimethyl-1,2-dioxolan, 3,3,6,6,9,9-Hexamethyl-1,2,4,5-tetraoxa-cyclononan, p-Menthanhydroperoxid, Pinanhydroperoxid und Diisopropylbenzolmono-α-hydroperoxid;

The process can be carried out using additional initiators. In addition to the redox initiator system, the following can be used as additional initiators

1. (i) water-soluble and water-insoluble azo compounds such as 2,2'-azobis(2-amidinopropane) dihydrochloride (Vazo 56 or V-50), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (Vazo 33) , 2, 2'-Azobis(2,4-dimethylvaleronitrile) (Vazo 52), 2,2'-Azobis(isobutyronitrile) (Vazo 64), 2,2'-Azobis-2-methylbutyronitrile (Vazo 67), 1, 1-Azobis(1-Cyclohexanecarbonitrile) (Vazo 88), 2, 2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (VA-044), 2,2'-Azobis(2-cyclopropylpropionitrile ) and 2,2'-Azobis(methyl isobutyrate) (V-601), 2,2'-Azobis[2-(2-imidazolin-2-yl)propane] (VA-61), 2, 2'-Azobis{ 2-[1-(2-Hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride (V-60) and 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (VA -086) (those of DuPont or Wako Pure Chemical Industries Ltd. ); 2,2'-Azobis(methyl isobutyrate), 4,4'-azobis(4-cyanopentanoic acid), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis(isobutyramide) dihydrate, 2-phenylazo-2, 4-dimethyl-4-methoxyvaleronitrile, 2-(carbamoylazo)isobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2, 2'-azobis(2- methylpropane), 2,2'-azobis(N,N'-dimethyleneisobutyramidine) in the form of the free base or hydrochloride, 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl] propionamide}, and 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide; what is particularly preferred; and
2. (ii) water-soluble and water-insoluble organic peroxides such as t-butyl hydroperoxide, dit-butyl peroxide, t-butyl peroxypivalate, t-butyl peroxyisopropyl carbonate, benzoyl peroxide, dibenzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, benzoyl hydroperoxide, 2,5-dimethylhexyne-2,5-di- t-butyl peroxide, 2,5-dimethylhexane-2,5-di-t-butyl peroxide, di-tert-amyl peroxide, dicumyl peroxide, cumene hydroperoxide, isopropyl benzene peroxide, acetyl peroxide, diacetyl peroxide, t-butyl peracetate, isopropyl peroxycarbonate, diisopropyl peroxydicarbonate, lauroyl peroxide, dilauryl peroxide, decanoyl peroxide, Diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dicetyl peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16S available from Akzo Nobel), di(2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11 available from Elf Atochem), t-butyl peroxy- 2-ethylhexanoate (Trigonox 21-C50 available from Akzo Nobel), acetylcyclohexanesulfonyl peroxide, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amyl perpivalate, bis(2,4-dichlorobenzoyl) peroxide, bis-(4-chlorobenzoyl)- peroxide, bis-(2-methylbenzoyl) peroxide, disuccinic acid peroxide, t-butyl perisobutyrate, t-butyl permaleate, 1,1-bis-(t-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-bis-(t- butylperoxy)cyclohexane, t-butyl perisononaoate, 2,5-dimethylhexane-2,5-dibenzoate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy) propane, 3-t-butylperoxy-3-phenylphthalide, α, α'-bis(t-butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl-1,2-dioxolane, 3,3 ,6,6,9,9-hexamethyl-1,2,4,5-tetraoxa-cyclononane, p-menthane hydroperoxide, pinane hydroperoxide and diisopropylbenzene mono-α-hydroperoxide;

In a further preferred embodiment, the method is characterized in that step B is carried out by stirring while measuring the torque of a motor-driven agitator. Alternatively, the method is characterized in that step B is carried out by stirring and the torque of a motor-driven agitator is kept below 65 N/cm. When the torque is 65 N/cm or more, gel formation is observed, resulting in a final product that does not have the required flocculant properties.

1. i. ein nichtionisches Monomer der Formel (I)

, in der

• R¹ Wasserstoff oder Methyl bedeutet;
• R² und R³ sind unabhängig voneinander Wasserstoff, C1-C5-Alkyl oder C1-C5-Hydroxyalkyl, ii. ein kationisches Monomer der Formel (II)

, wobei

• R¹ Wasserstoff oder Methyl bedeutet;
• Z₁ O, NH oder NR⁴ ist, wobei R⁴ C1-C4-Alkyl, vorzugsweise Methyl, bedeutet, und Y eine der folgenden Bedeutungen hat

, wobei

• Y₀ und Y₁ sind eine C1-C6-Alkylengruppe, gegebenenfalls substituiert mit einer oder mehreren Hydroxygruppen, vorzugsweise Ethylen oder Propylen, gegebenenfalls substituiert mit einer Hydroxygruppe;
• Y₂, Y₃, Y₅, Y₆, Y₇ unabhängig voneinander jeweils C1-C6-Alkyl, vorzugsweise Methyl, bedeuten; und
• Z^- ein Gegenion ist, vorzugsweise ein Halogen, Pseudohalogen, Acetat oder SO₄CH₃ ^-; und iii. ein amphiphiles Monomer der Formeln (III) oder (IV)
  
  , wobei
• Z₁ O, NH, NR⁴ ist, wobei R⁴ C1-C4-Alkyl, vorzugsweise Methyl, bedeutet,
• R₁ Wasserstoff oder Methyl bedeutet,
• R₈ eine C1-C6-Alkylengruppe ist, vorzugsweise Ethylen oder Propylen,
• R₅ und R₆ unabhängig voneinander jeweils C1-C6-Alkyl sind, vorzugsweise Methyl,
• R₇ ein C8-C32-Alkyl ist, gegebenenfalls substituiert mit einer oder mehreren Hydroxygruppen, vorzugsweise C12-C20-Alkyl, gegebenenfalls substituiert mit einer Hydroxygruppe, und
• Z^- ein Gegenion ist, vorzugsweise ein Halogen, Pseudohalogen, Acetat oder SO₄CH₃ ^-; oder
  
  ist, wobei
• Z₁ O, NH, NR⁴ ist, wobei R⁴ C1-C4-Alkyl, vorzugsweise Methyl bedeutet,
• R₁ Wasserstoff oder Methyl bedeutet,
• R₁₀ Wasserstoff, C8-C32-Alkyl, C8-C32-Aryl und/oder C8-C32-Aralkyl, vorzugsweise C12-C20-Alkyl bedeutet,
• R₉ eine C1-C6-Alkylengruppe ist, vorzugsweise eine Ethylengruppe oder Propylengruppe, und n eine ganze Zahl zwischen 1 und 50, vorzugsweise zwischen 2 und 30, besonders bevorzugt zwischen 3 und 15, besonders bevorzugt zwischen 4 und 8 ist.

In a preferred process, the monomer composition comprises the radically polymerizable monomers selected from the group consisting of one or more of the following:

1. i. a nonionic monomer of the formula (I)

, in the

• R ¹ represents hydrogen or methyl;
• R ² and R ³ are independently hydrogen, C1-C5 alkyl or C1-C5 hydroxyalkyl, ii. a cationic monomer of the formula (II)

, where

• R ¹ represents hydrogen or methyl;
• Z ₁ is O, NH or NR ⁴ , where R ⁴ is C1-C4 alkyl, preferably methyl, and Y has one of the following meanings

, where

• Y ₀ and Y ₁ are a C1-C6 alkylene group, optionally substituted with one or more hydroxy groups, preferably ethylene or propylene, optionally substituted with a hydroxy group;
• Y ₂ , Y ₃ , Y ₅ , Y ₆ , Y ₇ each independently represent C1-C6 alkyl, preferably methyl; and
• Z ^- is a counterion, preferably a halogen, pseudohalogen, acetate or SO ₄ CH ₃ ^- ; and iii. an amphiphilic monomer of the formulas (III) or (IV)
  
  , where
• Z _{1 is} O, NH, NR ⁴ , where R ^{4 is} C1-C4 alkyl, preferably methyl,
• R ₁ means hydrogen or methyl,
• R ₈ is a C1-C6 alkylene group, preferably ethylene or propylene,
• R ₅ and R ₆ are each independently C1-C6 alkyl, preferably methyl,
• R ₇ is a C8-C32 alkyl, optionally substituted with one or more hydroxy groups, preferably C12-C20 alkyl, optionally substituted with a hydroxy group, and
• Z ^- is a counterion, preferably a halogen, pseudohalogen, acetate or SO ₄ CH ₃ ^- ; or
  
  is, where
• Z ₁ is O, NH, NR ⁴ , where R ^{4 is} C1-C4 alkyl, preferably methyl,
• R ₁ means hydrogen or methyl,
• R ₁₀ is hydrogen, C8-C32 alkyl, C8-C32 aryl and/or C8-C32 aralkyl, preferably C12-C20 alkyl,
• R ₉ is a C1-C6 alkylene group, preferably an ethylene group or propylene group, and n is an integer between 1 and 50, preferably between 2 and 30, particularly preferably between 3 and 15, particularly preferably between 4 and 8.

In the context of the present invention, a cationic monomer is a monomer that permanently carries a positive charge, or the monomer carries a positive charge through protonation.

According to a preferred embodiment, one or more of the above under i. to iii. mentioned monomers are used as monomers in the monomer composition to be polymerized. A copolymer is preferably polymerized, ie two of the above under i. to iii. mentioned monomers are provided for the monomer composition to be polymerized. It is preferred that the monomer composition to be copolymerized is a monomer from point i. and a monomer from point ii. to be provided. In a preferred embodiment, the radically polymerizable monomers comprise a radically polymerizable nonionic monomer according to the general formula (I); and a radically polymerizable cationic monomer according to the general formula (II). These monomers are beneficial for solving the above-mentioned problems.

In a preferred embodiment, the process is characterized in that the monomer composition comprising the radically polymerizable monomers comprises at least the nonionic monomer of formula (I) selected from those in which R ₁ is hydrogen or methyl and R ₂ and R ₃ are both hydrogen, hydrogen and C1-C3 alkyl, hydrogen and hydroxyethyl or both are C1-C3 alkyl, and/or the cationic monomer of formula (II) selected from those in which R1 is hydrogen or methyl and Z ₁ is O, NH or NR ⁴ , where R ⁴ is methyl, Y ₁ is C2-C6 alkylene, preferably ethylene or propylene, Y ₅ , Y ₆ and Y ₇ are all methyl and Z ^- a halogen is.

In a preferred embodiment, the radically polymerizable monomers comprise a radically polymerizable nonionic monomer according to the general formula (I), which is selected from the group consisting of (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth )acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl-N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide and N-hydroxyethyl(meth)acrylamide.

In a further preferred embodiment, the radically polymerizable monomers comprise a radically polymerizable cationic monomer according to the general formula (II), which is selected from the group consisting of trimethylammonium C2-C6 alkyl (meth)acrylate halides and trimethylammonium C2-C6 alkyl (meth) acrylamide halides. In a particularly preferred embodiment, the monomer composition comprises a radically polymerizable monomer that is (meth)acrylamide, together with a radically polymerizable monomer selected from trimethylammonium C2-C6 alkyl (meth)acrylate halides, which is in particular it is an acryloyloxyethyltrimethylammonium halide.

Optionally, the monomer composition may further contain a crosslinker, preferably an ethylenically unsaturated crosslinker, and/or a hydrophobic monomer, preferably a hydrophobic (meth)acrylic acid C4-18 alkyl ester, and/or an ethylenically unsaturated monomer.

In a preferred embodiment, the process is characterized in that the radically polymerizable monomers are selected from the non-ionic monomer of the formula (I) and/or the cationic monomer of the formula (II), the amount of the radically polymerizable monomers being selected from the non-ionic monomer of the formula (I) and/or the cationic monomer of the formula (II) are selected, is between 80 and less than 100% by weight, preferably 85 and 99% by weight, most preferably 90 and 95% by weight, based on the total amount of radically polymerizable monomers, the remainder being selected from the group consisting of any other ethylenically polymerizable monomer, a monomer of formula (III), a monomer of formula (IV) and a bifunctional ethylenically polymerizable monomer.

The sum of the values in% by weight does not have to be 100% by weight, since the monomer composition, i.e. in the reaction mixture, may contain further ethylenically unsaturated monomers (e), which must be taken into account when determining the total amount of monomers . However, the monomer composition preferably consists of the monomers (a) and (b), so that the sum of the two values in% by weight is 100% by weight, i.e. no further monomers are present.

1. (a) mindestens 5 Gew.-%, vorzugsweise mindestens 20 Gew.-% eines radikalisch polymerisierbaren nichtionischen Monomers der allgemeinen Formel (I);
2. (b) mindestens 5 Gew.-%, vorzugsweise mindestens 15 Gew.-%, stärker bevorzugt mindestens 20 Gew.-% oder 25 Gew.-%; vorzugsweise 10 bis 30 Gew.-% oder 40 bis 60 Gew.-%, stärker bevorzugt 15 bis 25 Gew.-% oder 23 bis 32 Gew.-% oder 45 bis 55 Gew.-%, eines radikalisch polymerisierbaren kationischen Monomers gemäß der allgemeinen Formel (II);
3. (c) gegebenenfalls bis zu 1,25 Gew.-% eines vorzugsweise ethylenisch ungesättigten Vernetzers;
4. (d) gegebenenfalls bis zu 1,25 Gew.-% eines hydrophoben (Meth)acrylsäure-C4-18-Alkylesters; und
5. (e) gegebenenfalls weitere ethylenisch ungesättigte Monomere.

In a preferred embodiment, the monomer composition comprises

1. (a) at least 5% by weight, preferably at least 20% by weight, of a free-radically polymerizable nonionic monomer of the general formula (I);
2. (b) at least 5% by weight, preferably at least 15% by weight, more preferably at least 20% or 25% by weight; preferably 10 to 30% by weight or 40 to 60% by weight, more preferably 15 to 25% by weight or 23 to 32% by weight or 45 to 55% by weight, of a radically polymerizable cationic monomer according to general formula (II);
3. (c) optionally up to 1.25% by weight of a preferably ethylenically unsaturated crosslinker;
4. (d) optionally up to 1.25% by weight of a hydrophobic (meth)acrylic acid C4-18 alkyl ester; and
5. (e) optionally further ethylenically unsaturated monomers.

Here too, the sum of the values in% by weight does not have to be 100% by weight, since further ethylenically unsaturated monomers (e) can be contained in the monomer composition, i.e. in the reaction mixture, which are used when determining the total amount of monomers must be taken into account. However, the monomer composition preferably consists of the monomers (a) and (b), so that the sum of the two values in% by weight is 100% by weight, i.e. no further monomers are present.

In the present application, all percentages relating to the monomer composition refer to the total amount of monomers.

According to the invention, the copolymerization is carried out in the presence of a polymeric dispersant.

In a preferred embodiment, the process is characterized in that the polymeric dispersant is selected from the group consisting of a cellulose derivative, polyvinyl acetate, starch, starch derivative, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyamine, polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, Polyvinyl-1,3-oxazolidone-2, polyvinyl-2-methylimidazoline, itaconic acid, (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylic acid amide; preferably a (meth)acryloylamidoalkyltrialkylammonium halide or a (meth)acryloxy-alkyltrialkylammonium halide.

Preferably the polymeric dispersant is derived from one or more cationic monomers, most preferably from a single cationic monomer.

In a preferred embodiment, the polymeric dispersant is derived from one or more radically polymerizable, ethylenically unsaturated monomers.

ist, wobei

• R¹ Wasserstoff oder Methyl bedeutet;
• Z₁ O, NH oder NR⁴ ist, wobei R⁴ C1-C4-Alkyl, vorzugsweise Methyl, bedeutet, und Y ist eines von

ist, wobei

• Y₀ und Y₁ eine C1-C6-Alkylengruppe sind, gegebenenfalls substituiert mit einer oder mehreren Hydroxygruppen, vorzugsweise Ethylen oder Propylen, gegebenenfalls substituiert mit einer Hydroxygruppe;
• Y₂, Y₃, Y₅, Y₆, Y₇ unabhängig voneinander jeweils C1-C6-Alkyl, vorzugsweise Methyl, bedeuten; und
• Z^- ein Gegenion ist, vorzugsweise ein Halogen, Pseudohalogen, Acetat oder SO₄CH₃ ^-.

In a further preferred embodiment, the process is characterized in that the polymeric dispersant is a homopolymer consisting of the cationic monomer of the formula (II)

is, where

• R ¹ represents hydrogen or methyl;
• Z ₁ is O, NH or NR ⁴ , where R ⁴ is C1-C4 alkyl, preferably methyl, and Y is one of

is, where

• Y ₀ and Y ₁ are a C1-C6 alkylene group, optionally substituted with one or more hydroxy groups, preferably ethylene or propylene, optionally substituted with a hydroxy group;
• Y ₂ , Y ₃ , Y ₅ , Y ₆ , Y ₇ each independently represent C1-C6 alkyl, preferably methyl; and
• Z ^- is a counterion, preferably a halogen, pseudohalogen, acetate or SO ₄ CH ₃ ^- .

Preferably Y ₁ , Y ₂ and Y ₃ are identical, preferably methyl. In a preferred embodiment, Z ₁ is O or NH, Y ₀ is ethylene or propylene, R ¹ is hydrogen or methyl, and Y ₁ , Y ₂ and Y ₃ are methyl. The cationic monomer according to the general formula (II) can be an ester (Z ₁ = O), such as Trimethylammonium ethyl (meth)acrylate (ADAME quat.). However, the cationic monomer according to the general formula (I) is preferably an amide (Z ₁ =NH), in particular trimethylammoniumpropylacrylamide (DIMAPA quat.).

Preferred radically polymerizable cationic monomers according to the general formula (II) are quaternized dialkylaminoalkyl (meth)acrylates or dialkylaminoalkyl (meth)acrylamides with 1 to 3 carbon atoms in the alkyl or alkylene groups, particularly preferably the methyl chloride-quaternized ammonium salt of dimethylaminomethyl ( meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylamino-propyl (meth)-acrylate, diethylamino-methyl (meth)acrylate, diethylamino-ethyl (meth)acrylate, diethyl-amino-propyl (meth)acrylate, dimethylamino-methyl( meth)acrylamide, DimethylaminoEthyl(meth)acrylamide, Dimethylamino-propyl(meth)acrylamide, Diethylamino-methyl(meth)-acrylamide, Diethylamino-ethyl(meth)acrylamide, Diethylamino-propyl(meth)-acrylamide.

Quaternized dimethylaminoethyl acrylate and dimethylaminopropylacrylamide are particularly preferred. Quaternization can be done with dimethyl sulfate, diethyl sulfate, methyl chloride or ethyl chloride. In a preferred embodiment, the monomers are quaternized with methyl chloride.

In a preferred embodiment, the polymeric dispersant is a homopolymer of trimethylammonium propylacrylamide (DIMAPA quat).

Preferably, the polymeric dispersant is derived from a monomer composition containing a cationic monomer selected from the group consisting of (alk)acrylamidoalkyltrialkylammonium halides (e.g., trimethylammonium alkyl (meth)acrylamide halides), (alk)acryloyloxyalkyltrialkylammonium halides (e.g., trimethylammonium alkyl (meth)acrylate halides), alkenyltrialkylammonium halides and dialkenyldialkylammonium halides (e.g. diallyldialkylammonium halides). More preferably, the polymeric dispersant is a cationic polymer derived from a monomer composition containing a cationic monomer selected from the group consisting of trimethylammonium alkyl (meth)acrylate halides, trimethylammonium alkyl (meth)acrylamide halides and diallyldialkyl ammonium halides. Preferably, the aforementioned cationic monomers contain 6 to 25 carbon atoms, more preferably 7 to 20 carbon atoms, most preferably 7 to 15 carbon atoms and especially 8 to 12 carbon atoms.

In a preferred embodiment, the polymeric dispersant is derived from a dialkenyl dialkylammonium halide, preferably a diallyldimethyl ammonium halide (DADMAC).

According to a preferred embodiment, the process is characterized in that the polymeric dispersant is a homopolymer of a (meth)acryloylamidopropyltrimethylammonium salt or a (meth)acryloyloxyethyltrimethylammonium salt.

In this application, the halide may be any acceptable halide such as chloride, bromide or iodide; the counterions of the salts may be any acceptable counterions such as halides, methosulfate, sulfate or others.

According to a preferred embodiment, the process is characterized in that the polymeric dispersant has a weight average molecular weight Mw, determined by size exclusion chromatography, of 60,000 to 400,000 g/mol, preferably 70,000 to 350,000 g/mol, more preferably 80,000 to less than 230,000, most preferably 85,000 to less than 150,000 g/mol.

According to a preferred embodiment, the ratio of the polymeric dispersant to the dispersed polymer in the polymer dispersion is in the range from 0.45:1 to 1:0.9, preferably in the range from 0.5:1 to 1:1, more preferably in the range from 0.55:1 to less than 1:1, even more preferably in the range of 0.6:1 to 0.99:1, in particular in the range of 0.65:1 to 0.9:1.

The invention is particularly efficient if the process is characterized in that the total weight of the polymeric dispersant, based on the total weight of the polymer dispersion, is in the range from 10 to 28% by weight, preferably 12 to 26% by weight, more preferably 14 to 24% by weight, even more preferably 16 to 22% by weight.

According to a further embodiment, the process is characterized in that the total weight of the polymeric dispersant, based on the total weight of the polymer dispersion, is between 18 and 26% by weight, preferably 19 to 25% by weight.

According to a preferred embodiment, the method comprises step C) reducing the residual monomer content by adding an initiator to the reaction mixture at approximately the time when the maximum temperature (Tmax) is reached. In an even more preferred embodiment, step C) is carried out isothermally, even more preferably step C is carried out by maintaining the temperature during step C at a level above 55°C and below 80°C, most preferably above 60°C and below 70°C , is held.

The initiator used to reduce the residual monomer content can be any of the additional initiators mentioned above. However, it is preferred that the initiator is selected from a peroxide or an azo compound, more preferably from the group consisting of a hydroperoxide, a dialkyl peroxide, a diacyl peroxide and an azo compound substituted by tertiary carbon atoms, preferably alkyl groups, nitrile groups and/or or carry ester groups. The initiator used in step C is in particular 2,2'-azobis(2-amidinopropane) dihydrochloride (V-50).

1. a) ein polymeres Dispergiermittel und
2. b) ein dispergiertes Polymer, das von einer Monomerzusammensetzung abgeleitet ist, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nicht-ionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht; wobei das polymere Dispergiermittel ein gewichtsmittleres Molekulargewicht Mw, bestimmt durch Größenausschlusschromatographie, von 40.000 bis weniger als 150.000 g/mol, bevorzugt 50.000 bis 140.000 g/mol, noch bevorzugter 60.000 bis 130.000, am meisten bevorzugt 85.000 bis 120. 000 g/mol; und/oder wobei die Polymerdispersion eine Volumenviskosität unter 6.700 mPas, vorzugsweise unter 6.000 mPas, bevorzugter unter 5.500 mPas, am meisten bevorzugt unter 5.000 mPas, gemessen bei 20°C mit einem Brookfield-Viskosimeter mit Spindel 4 und einer Geschwindigkeit von 10 U/min, aufweist.

The problems on which the invention is based are further solved by the subject matter of claim 13. Thus, according to a second aspect, the invention relates to a polymer dispersion comprising

1. a) a polymeric dispersant and
2. b) a dispersed polymer derived from a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; wherein the polymeric dispersant has a weight average molecular weight Mw, determined by size exclusion chromatography, of 40,000 to less than 150,000 g/mol, preferably 50,000 to 140,000 g/mol, more preferably 60,000 to 130,000, most preferably 85,000 to 120,000 g/mol; and/or wherein the polymer dispersion has a volume viscosity below 6,700 mPas, preferably below 6,000 mPas, more preferably below 5,500 mPas, most preferably below 5,000 mPas, measured at 20 ° C with a Brookfield viscometer with spindle 4 and a speed of 10 rpm , having.

It has surprisingly been found that the invention leads to a more stable product, which is reflected in a constant viscosity over time. In addition, it has surprisingly been shown that the bulk material viscosity is in a range that facilitates handling in downstream applications. The term “bulk viscosity” refers to the viscosity immediately after recovery of the cooled product.

1. a) ein polymeres Dispergiermittel und
2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
3. B) Unterziehen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
4. wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durchgeführt wird;
5. wobei das polymere Dispergiermittel ein gewichtsmittleres Molekulargewicht Mw, bestimmt durch Größenausschlusschromatographie, von 40.000 bis weniger als 150.000 g/mol, bevorzugt 50.000 bis 140.000 g/mol, weiter bevorzugt 60.000 bis 130.000, am meisten bevorzugt 85.000 bis 120. 000 g/mol; und/oder wobei die Polymerdispersion eine Volumenviskosität unter 6.700 mPas, vorzugsweise unter 6.000 mPas, bevorzugter unter 5.500 mPas, am meisten bevorzugt unter 5.000 mPas, gemessen bei 20°C mit einem Brookfield-Viskosimeter mit Spindel 4 und einer Geschwindigkeit von 10 U/min, aufweist.

The problems on which the invention is based are further solved by the subject matter of claim 14. Thus, according to a third aspect, the invention relates to a polymer dispersion which is obtained by a process for producing the polymer dispersion according to the invention, which comprises the following steps: A) providing a reaction mixture in an aqueous medium

1. a) a polymeric dispersant and
2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
3. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
4. wherein step B) is carried out under controlled adiabatic conditions;
5. wherein the polymeric dispersant has a weight average molecular weight Mw, determined by size exclusion chromatography, of 40,000 to less than 150,000 g/mol, preferably 50,000 to 140,000 g/mol, more preferably 60,000 to 130,000, most preferably 85,000 to 120,000 g/mol; and/or wherein the polymer dispersion has a volume viscosity below 6,700 mPas, preferably below 6,000 mPas, more preferably below 5,500 mPas, most preferably below 5,000 mPas, measured at 20 ° C with a Brookfield viscometer with spindle 4 and a speed of 10 rpm , having.

It has surprisingly been found that the invention leads to a more stable product, which is reflected in a constant viscosity over time. In addition, it has surprisingly been found that the bulk material viscosity is in a range that facilitates handling in downstream applications. The term “bulk viscosity” refers to the viscosity immediately after recovery of the cooled product.

• b. als Flockungsmittel bei der Sedimentation, Flotation oder Filtration von Feststoffen,
• c. als Verdickungsmittel,
• d. zur Kontrolle von Verunreinigungen,
• e. als Trockenfestigkeitsmittel, Retentionsmittel oder Entwässerungshilfe bei der Papierherstellung.

The problems on which the invention is based are further solved by the subject matter of claim 15. According to a second aspect, the invention relates to the use of the polymer dispersion according to the invention

• b. as a flocculant in the sedimentation, flotation or filtration of solids,
• c. as a thickener,
• d. to control contamination,
• e. as a dry strength agent, retention agent or drainage aid in paper production.

Features that relate to preferred embodiments of the first aspect of the present invention and that are disclosed solely with respect to the first aspect of the invention also represent preferred embodiments of the second and third embodiments.

Embodiments (A) to (L), which represent particularly preferred embodiments, are disclosed below by way of example.

(A)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
   3. B) Unterziehen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
2. wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durchgeführt wird; wobei die Monomerzusammensetzung, die die radikalisch polymerisierbaren Monomere umfasst, mindestens das nicht-ionische Monomer der Formel (I) umfasst, das aus denjenigen ausgewählt ist, in denen R¹ Wasserstoff oder Methyl bedeutet und R² und R³ beide Wasserstoff, Wasserstoff und C1-C3-Alkyl, Wasserstoff und Hydroxyethyl sind, oder beide C1-C3-Alkyl sind, und/oder das kationische Monomer der Formel (II), das aus denjenigen ausgewählt ist, in denen R1 Wasserstoff oder Methyl bedeutet und Z₁ O, NH oder NR⁴ ist, wobei R⁴ Methyl bedeutet, Y₁ C2-C6-Alkylen, vorzugsweise Ethylen oder Propylen ist, Y₅, Y₆ und Y₇ alle Methyl sind und Z^- ein Halogen ist.

Process for producing a polymer dispersion, comprising the steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
   3. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
2. wherein step B) is carried out under controlled adiabatic conditions; wherein the monomer composition comprising the radically polymerizable monomers comprises at least the non-ionic monomer of formula (I) selected from those in which R ¹ is hydrogen or methyl and R ² and R ³ are both hydrogen, hydrogen and C1 -C3-alkyl, hydrogen and hydroxyethyl, or both are C1-C3-alkyl, and/or the cationic monomer of formula (II) selected from those in which R1 is hydrogen or methyl and Z ₁ is O, NH or NR ⁴ , where R ⁴ is methyl, Y ₁ is C2-C6 alkylene, preferably ethylene or propylene, Y ₅ , Y ₆ and Y ₇ are all methyl and Z ^- is a halogen.

(B)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nicht-ionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
   3. B) Unterwerfen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
2. wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch aufeinanderfolgende oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem vorzugsweise ein Oxidationsmittel und ein Reduktionsmittel umfasst; wobei die Monomerzusammensetzung, die die radikalisch polymerisierbaren Monomere umfaßt, mindestens das nichtionische Monomer der Formel (I) umfaßt, das aus denjenigen ausgewählt ist, in denen R¹ Wasserstoff oder Methyl bedeutet und R² und R³ beide Wasserstoff, Wasserstoff und C1-C3-Alkyl, Wasserstoff und Hydroxyethyl sind, oder beide C1-C3-Alkyl sind, und/oder das kationische Monomer der Formel (II) ausgewählt ist aus denen, in denen R¹ Wasserstoff oder Methyl bedeutet und Z₁ O, NH oder NR⁴ ist, wobei R⁴ Methyl bedeutet, Y₁ C2-C6-Alkylen, vorzugsweise Ethylen oder Propylen ist, Y₅, Y₆ und Y₇ alle Methyl sind und Z^- ein Halogen ist,
3. und wobei das polymere Dispergiermittel ausgewählt ist aus der Gruppe bestehend aus einem Cellulosederivat, Polyvinylacetat, Stärke, Stärkederivat, Dextran, Polyvinylpyrrolidon, Polyvinylpyridin, Polyethylenimin, Polyamin, Polyvinylimidazol, Polyvinylsuccinimid, Polyvinyl-2-methylsuccinimid, Polyvinyl-1,3-oxazolidon-2, Polyvinyl-2-methylimidazolin, Itaconsäure, (Meth)acrylsäure, (Meth)acrylsäureester, (Meth)acrylsäureamid; vorzugsweise ein (Meth)acryloylamidoalkyltrialkylammoniumhalogenid oder ein (Meth)acryloxyalkyltrialkylammoniumhalogenid.

Process for producing a polymer dispersion, comprising the steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
   3. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
2. wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system preferably comprising an oxidizing agent and a reducing agent; wherein the monomer composition comprising the radically polymerizable monomers comprises at least the nonionic monomer of formula (I) selected from those in which R ¹ is hydrogen or methyl and R ² and R ³ are both hydrogen, hydrogen and C1-C3 -alkyl, hydrogen and hydroxyethyl, or both are C1-C3-alkyl, and/or the cationic monomer of formula (II) is selected from those in which R ¹ is hydrogen or methyl and Z _{1 is} O, NH or NR ⁴ is, where R ⁴ is methyl, Y ₁ is C2-C6-alkylene, preferably ethylene or propylene, Y ₅ , Y ₆ and Y ₇ are all methyl and Z ^- is a halogen,
3. and wherein the polymeric dispersant is selected from the group consisting of a cellulose derivative, polyvinyl acetate, starch, starch derivative, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyamine, polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, polyvinyl-1,3-oxazolidone-2 , polyvinyl-2-methylimidazoline, itaconic acid, (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylic acid amide; preferably a (meth)acryloylamidoalkyltrialkylammonium halide or a (meth)acryloxyalkyltrialkylammonium halide.

(C)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nicht-ionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
2. B) Unterziehen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
   • wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch aufeinanderfolgende oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem vorzugsweise ein Oxidationsmittel und ein Reduktionsmittel umfasst; wobei die radikalisch polymerisierbaren Monomere ein radikalisch polymerisierbares nichtionisches Monomer gemäß der allgemeinen Formel (I) umfassen, das ausgewählt ist aus der Gruppe bestehend aus (Meth)acrylamid, N-Methyl(meth)acrylamid, N,N-Dimethyl(meth)acrylamid, N-Ethyl(meth)acrylamid, N,N-Diethyl(meth)acrylamid, N-Methyl-N-ethyl(meth)acrylamid, N-Isopropyl(meth)acrylamid und N-Hydroxyethyl(meth)acrylamid und ein radikalisch polymerisierbares kationisches Monomer gemäß der allgemeinen Formel (II), das ausgewählt ist aus der Gruppe bestehend aus Trimethylammonium-C2-C6-alkyl(meth)acrylathalogeniden und Trimethylammonium-C2-C6-alkyl(meth)acrylamidhalogeniden,
   • und wobei das polymere Dispergiermittel ein Homopolymer aus einem (Meth)acryloylamidopropyl-Trimethylammoniumsalz oder einem (Meth)acryloyl-Oxyethyl-Trimethylammoniumsalz ist.

Process for producing a polymer dispersion, comprising the steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
2. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
   • wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system preferably comprising an oxidizing agent and a reducing agent; wherein the radically polymerizable monomers comprise a radically polymerizable nonionic monomer according to the general formula (I), which is selected from the group consisting of (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide and a radically polymerizable cationic Monomer according to the general formula (II), which is selected from the group consisting of trimethylammonium C2-C6 alkyl (meth) acrylate halides and trimethyl ammonium C2-C6 alkyl (meth) acrylamide halides,
   • and wherein the polymeric dispersant is a homopolymer of a (meth)acryloylamidopropyl trimethyl ammonium salt or a (meth)acryloyl oxyethyl trimethyl ammonium salt.

(D)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
   3. B) Unterziehen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
   wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch aufeinanderfolgende oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem vorzugsweise ein Oxidationsmittel und ein Reduktionsmittel umfasst; wobei die Monomerzusammensetzung ein radikalisch polymerisierbares Monomer, bei dem es sich um (Meth)acrylamid handelt, zusammen mit einem radikalisch polymerisierbaren Monomer umfasst, das aus Trimethylammonium-C2-C6-alkyl(meth)acrylathalogeniden ausgewählt ist, wobei es sich vorzugsweise um ein Acryloyloxyethyltrimethylammoniumhalogenid handelt, und wobei das polymere Dispergiermittel ein Homopolymer aus einem (Meth)acryloylamidopropyltrimethylammoniumsalz oder einem (Meth)acryloyloxyethyltrimethylammoniumsalz ist.

A process for producing a polymer dispersion, comprising the following steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
   3. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
   wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system preferably comprising an oxidizing agent and a reducing agent; wherein the monomer composition comprises a radically polymerizable monomer which is (meth)acrylamide together with a radically polymerizable monomer selected from trimethylammonium C2-C6 alkyl (meth)acrylate halides, which is preferably an acryloyloxyethyltrimethylammonium halide and wherein the polymeric dispersant is a homopolymer of a (meth)acryloylamidopropyltrimethylammonium salt or a (meth)acryloyloxyethyltrimethylammonium salt.

(E)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
2. B) Unterwerfen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
   • wobei Schritt B) unter kontrollierten adiabatischen Bedingungen innerhalb eines Zeitrahmens von weniger als 40 min und durch sequentielle oder gleichzeitige Zugabe eines Redoxinitiatorsystems durchgeführt wird, wobei das Redoxinitiatorsystem vorzugsweise ein Oxidationsmittel und ein Reduktionsmittel umfasst;
   • wobei die radikalisch polymerisierbaren Monomere ein radikalisch polymerisierbares nichtionisches Monomer gemäß der allgemeinen Formel (I) umfassen, das ausgewählt ist aus der Gruppe bestehend aus (Meth)acrylamid, N-Methyl(meth)acrylamid, N,N-Dimethyl(meth)acrylamid, N-Ethyl(meth)acrylamid, N,N-Diethyl(meth)acrylamid, N-Methyl-N-ethyl(meth)acrylamid, N-Isopropyl(meth)acrylamid und N-Hydroxyethyl(meth)acrylamid und ein radikalisch polymerisierbares kationisches Monomer gemäß der allgemeinen Formel (II), das ausgewählt ist aus der Gruppe bestehend aus Trimethylammonium-C2-C6-alkyl(meth)acrylathalogeniden und Trimethylammonium-C2-C6-alkyl(meth)acrylamidhalogeniden,
   • und wobei das polymere Dispergiermittel ein Homopolymer aus einem (Meth)acryloylamidopropyl-Trimethylammoniumsalz oder einem (Meth)acryloyl-Oxyethyl-Trimethylammoniumsalz ist.

Process for producing a polymer dispersion, comprising the steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
2. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
   • wherein step B) is carried out under controlled adiabatic conditions within a time frame of less than 40 minutes and by sequential or simultaneous addition of a redox initiator system, the redox initiator system preferably comprising an oxidizing agent and a reducing agent;
   • wherein the radically polymerizable monomers comprise a radically polymerizable nonionic monomer according to the general formula (I), which is selected from the group consisting of (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide and a radically polymerizable cationic Monomer according to the general formula (II), which is selected from the group consisting of trimethylammonium C2-C6 alkyl (meth) acrylate halides and trimethyl ammonium C2-C6 alkyl (meth) acrylamide halides,
   • and wherein the polymeric dispersant is a homopolymer of a (meth)acryloylamidopropyl trimethyl ammonium salt or a (meth)acryloyl oxyethyl trimethyl ammonium salt.

(F)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
2. B) Unterziehen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
   • wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch aufeinanderfolgende oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem ein Oxidationsmittel und ein Reduktionsmittel umfasst,
   • wobei das Gewichtsverhältnis zwischen dem Reduktionsmittel und dem Oxidationsmittel unter 35:1 und über 2:1, vorzugsweise unter 15:1 und über 3:1, noch bevorzugter unter 9:1 und über 4:1 liegt.

A process for producing a polymer dispersion, comprising the following steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
2. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
   • wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system comprising an oxidizing agent and a reducing agent,
   • wherein the weight ratio between the reducing agent and the oxidizing agent is less than 35:1 and more than 2:1, preferably less than 15:1 and more than 3:1, more preferably less than 9:1 and more than 4:1.

(G)

• A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
  1. a) ein polymeres Dispersionsmittel und
  2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
• B) Unterziehen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
  • wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch aufeinanderfolgende oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem ein Oxidationsmittel und ein Reduktionsmittel umfasst,
  • wobei das Oxidationsmittel ein Redoxpotential von 0,6 bis 2,0 V hat und/oder das Reduktionsmittel ein Redoxpotential von -2 bis 0,3 V hat,
  • wobei das Gewichtsverhältnis zwischen dem Reduktionsmittel und dem Oxidationsmittel unter 35 : 1 und über 2 : 1, vorzugsweise unter 15 : 1 und über 3 : 1, noch bevorzugter unter 9 : 1 und über 4 : 1 liegt.

Process for producing a polymer dispersion, comprising the steps

• A) Providing a reaction mixture in an aqueous medium, comprising
  1. a) a polymeric dispersant and
  2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
• B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
  • wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system comprising an oxidizing agent and a reducing agent,
  • where the oxidizing agent has a redox potential of 0.6 to 2.0 V and/or the reducing agent has a redox potential of -2 to 0.3 V,
  • wherein the weight ratio between the reducing agent and the oxidizing agent is below 35:1 and above 2:1, preferably below 15:1 and above 3:1, more preferably below 9:1 and above 4:1.

(H)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
2. B) Unterwerfen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
   • wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch aufeinanderfolgende oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem ein Oxidationsmittel und ein Reduktionsmittel umfasst,
   • wobei das Oxidationsmittel ein Peroxydiphosphat, Wasserstoffperoxid, ein Alkylhydroperoxid, bevorzugter t-Butylhydroperoxid, oder ein Arylhydroperoxid, bevorzugter Cumolhydroperoxid, umfasst und das Reduktionsmittel Natriumbisulfit, Kaliumbisulfit, Ammoniumbisulfit, Natriumsulfit, Kaliumsulfit, Ammoniumsulfit, ein Hydrogensulfit; ein Thiosulfat; ein Amin; eine Säure, bevorzugter Ascorbinsäure oder Erythorbinsäure, umfasst;
   • wobei das Gewichtsverhältnis zwischen dem Reduktionsmittel und dem Oxidationsmittel unter 35 : 1 und über 2 : 1, vorzugsweise unter 15 : 1 und über 3 : 1, noch bevorzugter unter 9 : 1 und über 4 : 1 liegt.

Process for producing a polymer dispersion, comprising the steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
2. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
   • wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system comprising an oxidizing agent and a reducing agent,
   • wherein the oxidizing agent comprises a peroxydiphosphate, hydrogen peroxide, an alkyl hydroperoxide, more preferably t-butyl hydroperoxide, or an aryl hydroperoxide, more preferably cumene hydroperoxide, and the reducing agent comprises sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite, a hydrogen sulfite; a thiosulphate; an amine; an acid, preferably ascorbic acid or erythorbic acid;
   • wherein the weight ratio between the reducing agent and the oxidizing agent is below 35:1 and above 2:1, preferably below 15:1 and above 3:1, more preferably below 9:1 and above 4:1.

(I)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, enthaltend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
   3. B) Unterwerfen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
   wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch sequentielle oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem ein Oxidationsmittel und ein Reduktionsmittel umfasst; wobei das Oxidationsmittel ein Redoxpotential von 0,6 bis 2,0 V hat und das Reduktionsmittel ein Redoxpotential von -2 bis 0,3 V hat; wobei die radikalisch polymerisierbaren Monomere ein radikalisch polymerisierbares nichtionisches Monomer gemäß der allgemeinen Formel (I) umfassen, das ausgewählt ist aus der Gruppe bestehend aus (Meth)acrylamid, N-Methyl(meth)acrylamid, N,N-Dimethyl(meth)acrylamid, N-Ethyl(meth)acrylamid, N,N-Diethyl(meth)acrylamid, N-Methyl-N-ethyl(meth)acrylamid, N-Isopropyl(meth)acrylamid und N-Hydroxyethyl(meth)acrylamid und ein radikalisch polymerisierbares kationisches Monomer gemäß der allgemeinen Formel (II), das ausgewählt ist aus der Gruppe bestehend aus Trimethylammonium-C2-C6-alkyl-(meth)acrylathalogeniden und Trimethylammonium-C2-C6-alkyl(meth)acrylamidhalogeniden, und wobei das polymere Dispergiermittel ein Homopolymer aus einem (Meth)acryloylamidopropyl-Trimethylammoniumsalz oder einem (Meth)acryloyl-Oxyethyl-Trimethylammoniumsalz ist.

Process for producing a polymer dispersion, comprising the steps

1. A) Providing a reaction mixture in an aqueous medium containing
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
   3. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
   wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system comprising an oxidant and a reducing agent; wherein the oxidizing agent has a redox potential of 0.6 to 2.0 V and the reducing agent has a redox potential of -2 to 0.3 V; wherein the radically polymerizable monomers comprise a radically polymerizable nonionic monomer according to the general formula (I), which is selected from the group consisting of (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide and a radically polymerizable cationic Monomer according to the general formula (II), which is selected from the group consisting of trimethylammonium C2-C6 alkyl (meth)acrylate halides and trimethylammonium C2-C6 alkyl (meth)acrylamide halides, and wherein the polymeric dispersant is a homopolymer a (meth)acryloylamidopropyl trimethyl ammonium salt or a (meth)acryloyl oxyethyl trimethyl ammonium salt.

(J)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
   3. B) Unterziehen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
   wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch aufeinanderfolgende oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem ein Oxidationsmittel und ein Reduktionsmittel umfasst, wobei das Oxidationsmittel ein Peroxydiphosphat, Wasserstoffperoxid, ein Alkylhydroperoxid, bevorzugter t-Butylhydroperoxid, oder ein Arylhydroperoxid, bevorzugter Cumolhydroperoxid, umfasst und das Reduktionsmittel Natriumbisulfit, Kaliumbisulfit, Ammoniumbisulfit, Natriumsulfit, Kaliumsulfit, Ammoniumsulfit, ein Hydrogensulfit; ein Thiosulfat; ein Amin; eine Säure, bevorzugter Ascorbinsäure oder Erythorbinsäure, umfasst; wobei die radikalisch polymerisierbaren Monomere ein radikalisch polymerisierbares nichtionisches Monomer gemäß der allgemeinen Formel (I) umfassen, das ausgewählt ist aus der Gruppe bestehend aus (Meth)acrylamid, N-Methyl(meth)acrylamid, N,N-Dimethyl(meth)acrylamid, N-Ethyl(meth)acrylamid, N,N-Diethyl(meth)acrylamid, N-Methyl-N-ethyl(meth)acrylamid, N-Isopropyl(meth)acrylamid und N-Hydroxyethyl(meth)acrylamid und ein radikalisch polymerisierbares kationisches Monomer gemäß der allgemeinen Formel (II), das ausgewählt ist aus der Gruppe bestehend aus Trimethylammonium-C2-C6-alkyl(meth)acrylathalogeniden und Trimethylammonium-C2-C6-alkyl(meth)acrylamidhalogeniden, und wobei das polymere Dispergiermittel ein Homopolymer aus einem (Meth)acryloylamidopropyl-Trimethylammoniumsalz oder einem (Meth)acryloyl-Oxyethyl-Trimethylammoniumsalz ist.

Process for producing a polymer dispersion, comprising the steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
   3. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
   wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system comprising an oxidizing agent and a reducing agent, the oxidizing agent being a peroxydiphosphate, hydrogen peroxide, an alkyl hydroperoxide, more preferably t-butyl hydroperoxide, or a Aryl hydroperoxide, preferably cumene hydroperoxide, and the reducing agent includes sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite, a hydrogen sulfite; a thiosulphate; an amine; an acid, preferably ascorbic acid or erythorbic acid; wherein the radically polymerizable monomers comprise a radically polymerizable nonionic monomer according to the general formula (I), which is selected from the group consisting of (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide and a radically polymerizable cationic Monomer according to the general formula (II), which is selected from the group consisting of trimethylammonium-C2-C6-alkyl (meth)acrylate halides and trimethylammonium-C2-C6-alkyl (meth)acrylamide halides, and wherein the polymeric dispersant is a homopolymer of one (Meth) acryloylamidopropyl trimethyl ammonium salt or a (meth) acryloyl oxyethyl trimethyl ammonium salt.

(K)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
2. B) Unterziehen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
   • wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch aufeinanderfolgende oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem ein Oxidationsmittel und ein Reduktionsmittel umfasst,
   • wobei das Gewichtsverhältnis zwischen dem Reduktionsmittel und dem Oxidationsmittel unter 35:1 und über 2:1, vorzugsweise unter 15:1 und über 3:1, noch bevorzugter unter 9:1 und über 4:1 liegt;
   • wobei die radikalisch polymerisierbaren Monomere ein radikalisch polymerisierbares nichtionisches Monomer gemäß der allgemeinen Formel (I) umfassen, das ausgewählt ist aus der Gruppe bestehend aus (Meth)acrylamid, N-Methyl(meth)acrylamid, N,N-Dimethyl(meth)acrylamid, N-Ethyl(meth)acrylamid, N,N-Diethyl(meth)acrylamid, N-Methyl-N-ethyl(meth)acrylamid, N-Isopropyl(meth)acrylamid und N-Hydroxyethyl(meth)acrylamid und ein radikalisch polymerisierbares kationisches Monomer gemäß der allgemeinen Formel (II), das ausgewählt ist aus der Gruppe bestehend aus Trimethylammonium-C2-C6-alkyl(meth)acrylathalogeniden und Trimethylammonium-C2-C6-alkyl(meth)acrylamidhalogeniden,
   • und wobei das polymere Dispergiermittel ein Homopolymer aus einem (Meth)acryloylamidopropyl-Trimethylammoniumsalz oder einem (Meth)acryloyl-Oxyethyl-Trimethylammoniumsalz ist.

A process for producing a polymer dispersion, comprising the following steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
2. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
   • wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system comprising an oxidizing agent and a reducing agent,
   • wherein the weight ratio between the reducing agent and the oxidizing agent is less than 35:1 and more than 2:1, preferably less than 15:1 and more than 3:1, more preferably less than 9:1 and more than 4:1;
   • wherein the radically polymerizable monomers comprise a radically polymerizable nonionic monomer according to the general formula (I), which is selected from the group consisting of (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide and a radically polymerizable cationic Monomer according to the general formula (II), which is selected from the group consisting of trimethylammonium C2-C6 alkyl (meth) acrylate halides and trimethyl ammonium C2-C6 alkyl (meth) acrylamide halides,
   • and wherein the polymeric dispersant is a homopolymer of a (meth)acryloylamidopropyl trimethyl ammonium salt or a (meth)acryloyl oxyethyl trimethyl ammonium salt.

(L)

1. A) Bereitstellen einer Reaktionsmischung in einem wässrigen Medium, umfassend
   1. a) ein polymeres Dispersionsmittel und
   2. b) eine Monomerzusammensetzung, die radikalisch polymerisierbare Monomere umfasst, wobei die radikalisch polymerisierbaren Monomere aus der Gruppe ausgewählt sind, die aus einem oder mehreren nichtionischen ethylenisch ungesättigten Monomeren, einem kationischen ethylenisch ungesättigten Monomer und einem amphiphilen ethylenisch ungesättigten Monomer besteht;
2. B) Unterwerfen der Monomerzusammensetzung in der Reaktionsmischung einer radikalischen Polymerisation, um ein dispergiertes Polymer zu synthetisieren und die Polymerdispersion zu bilden,
   • wobei Schritt B) unter kontrollierten adiabatischen Bedingungen durch aufeinanderfolgende oder gleichzeitige Zugabe eines Redox-Initiatorsystems durchgeführt wird, wobei das Redox-Initiatorsystem ein Oxidationsmittel und ein Reduktionsmittel umfasst,
   • wobei das Oxidationsmittel ein Peroxydiphosphat, Wasserstoffperoxid, ein Alkylhydroperoxid, bevorzugter t-Butylhydroperoxid, oder ein Arylhydroperoxid, bevorzugter Cumolhydroperoxid, umfasst und das Reduktionsmittel Natriumbisulfit, Kaliumbisulfit, Ammoniumbisulfit, Natriumsulfit, Kaliumsulfit, Ammoniumsulfit, ein Hydrogensulfit; ein Thiosulfat; ein Amin; eine Säure, bevorzugter Ascorbinsäure oder Erythorbinsäure, umfasst
   • wobei das Gewichtsverhältnis zwischen dem Reduktionsmittel und dem Oxidationsmittel unter 35:1 und über 2:1, vorzugsweise unter 15:1 und über 3:1, noch bevorzugter unter 9:1 und über 4:1 liegt,
   • wobei die radikalisch polymerisierbaren Monomere ein radikalisch polymerisierbares nichtionisches Monomer gemäß der allgemeinen Formel (I) umfassen, das ausgewählt ist aus der Gruppe bestehend aus (Meth)acrylamid, N-Methyl(meth)acrylamid, N,N-Dimethyl(meth)acrylamid, N-Ethyl(meth)acrylamid, N,N-Diethyl(meth)acrylamid, N-Methyl-N-ethyl(meth)acrylamid, N-Isopropyl(meth)acrylamid und N-Hydroxyethyl(meth)acrylamid und ein radikalisch polymerisierbares kationisches Monomer gemäß der allgemeinen Formel (II), das ausgewählt ist aus der Gruppe bestehend aus Trimethylammonium-C2-C6-alkyl(meth)acrylathalogeniden und Trimethylammonium-C2-C6-alkyl(meth)acrylamidhalogeniden,
   • und wobei das polymere Dispergiermittel ein Homopolymer aus einem (Meth)acryloylamidopropyl-Trimethylammoniumsalz oder einem (Meth)acryloyl-Oxyethyl-Trimethylammoniumsalz ist.

A process for producing a polymer dispersion, comprising the following steps

1. A) Providing a reaction mixture in an aqueous medium, comprising
   1. a) a polymeric dispersant and
   2. b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer;
2. B) subjecting the monomer composition in the reaction mixture to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion,
   • wherein step B) is carried out under controlled adiabatic conditions by sequential or simultaneous addition of a redox initiator system, the redox initiator system comprising an oxidizing agent and a reducing agent,
   • wherein the oxidizing agent comprises a peroxydiphosphate, hydrogen peroxide, an alkyl hydroperoxide, more preferably t-butyl hydroperoxide, or an aryl hydroperoxide, more preferably cumene hydroperoxide, and the reducing agent comprises sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite, a hydrogen sulfite; a thiosulphate; an amine; an acid, preferably ascorbic acid or erythorbic acid
   • wherein the weight ratio between the reducing agent and the oxidizing agent is below 35:1 and above 2:1, preferably below 15:1 and above 3:1, more preferably below 9:1 and above 4:1,
   • wherein the radically polymerizable monomers comprise a radically polymerizable nonionic monomer according to the general formula (I), which is selected from the group consisting of (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide and a radically polymerizable cationic Monomer according to the general formula (II), which is selected from the group consisting of trimethylammonium C2-C6 alkyl (meth) acrylate halides and trimethyl ammonium C2-C6 alkyl (meth) acrylamide halides,
   • and wherein the polymeric dispersant is a homopolymer of a (meth)acryloylamidopropyl trimethyl ammonium salt or a (meth)acryloyl oxyethyl trimethyl ammonium salt.

EXAMPLES

• Die Volumenviskosität wird wie folgt gemessen:
  • Man verwendet das Produkt direkt für die Messung. Die Spindel Nr. 4 wird langsam in das Produkt eingetaucht und die Viskosität mit einem Brookfield RVT-Viskosimeter bei 10 U/min bestimmt. Die Messung wird beendet, wenn der Messwert über einen Zeitraum von 30 Sekunden konstant bleibt.

The test methods used are described in detail below:

• The bulk viscosity is measured as follows:
  • The product is used directly for measurement. The No. 4 spindle is slowly immersed in the product and the viscosity is determined using a Brookfield RVT viscometer at 10 rpm. The measurement is stopped when the measured value remains constant over a period of 30 seconds.

• Es wird eine Lösung von 5 Gew.-% in Wasser hergestellt. In ein 400-ml-Becherglas werden 323,0 ± 0,1 g demineralisiertes Wasser eingewogen. Dann werden 17,0 ± 0,1 g des Produkts unter Rühren bei 300 U/min zugegeben (22 ± 3°C). Die Auflösungszeit beträgt 60 Minuten bei 300 ± 10 U/min. Danach muss die Lösung 5 min ruhen. Nun wird die Spindel Nr. 2 langsam eingetaucht und die Viskosität mit einem Brookfield-RFT-Viskosimeter bei 10 U/min bestimmt. Die Messung wird beendet, wenn der Messwert 30 Sekunden lang konstant bleibt.

The viscosity of the solution is measured in DI water and determined as follows:

• A solution of 5% by weight in water is prepared. 323.0 ± 0.1 g of demineralized water are weighed into a 400 ml beaker. Then 17.0 ± 0.1 g of the product are added while stirring at 300 rpm (22 ± 3 ° C). The dissolution time is 60 minutes at 300 ± 10 rpm. The solution must then rest for 5 minutes. Now spindle No. 2 is slowly immersed and the viscosity is determined with a Brookfield RFT viscometer at 10 rpm. The measurement will stop when the reading remains constant for 30 seconds.

• In ein 400-ml-Becherglas werden 289,0 ± 0,1 g demineralisiertes Wasser eingewogen. Dann werden 17,0 ± 0,1 g des Produkts unter Rühren bei 300 U/min zugegeben (22 ± 3°C). Die Auflösungszeit beträgt 45 Minuten bei 300 ± 10 U/min. und dann werden 34,0 ± 0,1 g NaCl zugegeben. Die Lösung wird weitere 15 min gerührt. Danach muss die Lösung 5 min ruhen. Nun wird die Spindel Nr. 1 langsam eingetaucht und die Viskosität mit einem Brookfield RVT-Viskosimeter bei 10 U/min bestimmt. Die Messung wird beendet, wenn der Messwert über einen Zeitraum von 30 Sekunden konstant bleibt.

The salt viscosity is measured in a 10% NaCl solution and determined as follows:

• 289.0 ± 0.1 g of demineralized water are weighed into a 400 ml beaker. Then 17.0 ± 0.1 g of the product are added while stirring at 300 rpm (22 ± 3 ° C). The dissolution time is 45 minutes at 300 ± 10 rpm. and then 34.0 ± 0.1 g of NaCl are added. The solution is stirred for another 15 minutes. The solution must then rest for 5 minutes. Now spindle No. 1 is slowly immersed and the viscosity is determined with a Brookfield RVT viscometer at 10 rpm. The measurement is stopped when the measured value remains constant over a period of 30 seconds.

1. (a) 100 ± 0,1 g der Dispersion werden in ein Zentrifugationsröhrchen eingewogen. Das Röhrchen wird in eine Laborzentrifuge (Hermle Z300) gestellt und 1 Stunde lang bei 4000 U/min zentrifugiert. Anschließend wird der flüssige Teil der Probe innerhalb von 3 Minuten ausgephast und das Sediment im Zentrifugenröhrchen wird gewogen. Ein höheres Sediment bedeutet eine geringere Phasenstabilität.
2. (b) Die Probe wird 3 Tage lang bei 40°C im Trockenschrank gelagert. Das Aussehen wird visuell kontrolliert.

Stability is determined using two different methods: (a) centrifugation and (b) oven test. The tests are carried out as follows:

1. (a) 100 ± 0.1 g of the dispersion are weighed into a centrifugation tube. The tube is placed in a laboratory centrifuge (Hermle Z300) and centrifuged at 4000 rpm for 1 hour. The liquid part of the sample is then phased out within 3 minutes and the sediment in the centrifuge tube is weighed. Higher sediment means lower phase stability.
2. (b) The sample is stored in a drying cabinet at 40°C for 3 days. The appearance is checked visually.

The molar mass is measured using gel permeation chromatography (GPC or SEC). The measurement is carried out in particular to determine the molecular weight of the dispersant.

Molecular weights are characterized by aqueous SEC using pullulan standards for calibration.

Sample preparation:

The samples are diluted with the eluent (polymer make-down in a volumetric flask) and filtered through a 1µm filter (M&N) (using a syringe) before injection.

If the device is equipped with an autosampler, the solution is filtered through a 1µm filter into a vial.

Parameters used: Device: SEC (Agilent) Pillar: Novema 3000 (PSS) Detector: R.I Eluent: 1.5% by weight formic acid in water Flow rate: 1 ml/min Calibration standards: Pullulan with different M _w

The following examples further illustrate the invention but are not to be construed as limiting its scope.

Example 1: Synthesis of the polymeric dispersant:

First, 294.06 g of water, 666.7 g of acryloylamidopropyltrimethylammonium chloride (DIMAPA quat.) (60% by weight) and sulfuric acid (50% by weight) were added to adjust the pH to 5.0 ± 0.2 Weighed out 2 liter container. The monomer solution was then purged with nitrogen while stirring for 30 minutes. The aqueous solution was then heated to 65 °C and 2-mercaptoethanol and V-50 (2,2'-azobis(2-amidinopropane) dihydrochloride) were added. After reaching Tmax, the vessel is cooled to ≤ 80 °C.

Two additional portions of initiator (V-50) were then added to the product at 10 min intervals to burn off the residual monomer. The product was stirred at 70°C for 1 hour. The aqueous final product was cooled to 30°C. The dispersants were provided in 40% by weight aqueous solutions.

• - Viskosität des Produkts [mPas]: 110 - 180
• - pH-Wert (unverdünnt): 4,9 - 5,3
• - Gesamtfeststoffgehalt [%]: 40 - 43
• - M_wSEC [g/mol]: 70000 - 110000

Specifications:

• - Product viscosity [mPas]: 110 - 180
• - pH value (undiluted): 4.9 - 5.3
• - Total solids content [%]: 40 - 43
• - M _w SEC [g/mol]: 70000 - 110000

Example 2: Synthesis of a polymer dispersion (charge density 15 mol%)

In a batch process (batch size 1,000 kg), acrylamide and acryloyl-oxyethyl-trimethylammonium chloride (ADAME quat.) were polymerized in an aqueous solution in the presence of homopolyacryloyl-amidopropyl-trimethylammonium chloride (polymeric dispersant). The water phase was prepared at 200 rpm.

First, 206.90 kg of soft water, 261.80 kg of bio-acrylamide (49% by weight), 77.20 kg of acryloyl-oxyethyl-trimethylammonium chloride (ADAME quat) (80% by weight), 412.50 kg of polymers Dispersant from Example 1, 10.00 kg of ammonium sulfate and 0.20 kg of Trilon C were added to the reaction container. The pH was adjusted to pH 5.0±0.2 with approximately 0.10 kg of sulfuric acid (50%). The vessel was evacuated five times before venting with nitrogen. The initiator composition was added at a negative pressure of 0.5 bar and maximum stirrer speed. Initiation began at 22±1°C with the addition of 0.34 kg V-50 in 3.05 kg soft water, 0.025 kg sodium persulfate in 0.47 kg soft water, 0.014 kg sodium bisulfite in 0.27 kg soft water and 0.003 kg t-butyl hydroperoxide (70%) in 1 kg soft water. The vessel was then ventilated again with nitrogen. After reaching the maximum temperature, a solution of 0.17 kg V-50 in 1.53 kg soft water was added to reduce the monomer content. After a one-hour post-reaction time, the product was cooled to a temperature below 40 °C. Then 8.30 kg of citric acid and 0.82 kg of the biocide Acticide SPX were added and the product was cooled to a temperature of below 30 ° C.

• ◯ V-50 (2,2'-Azobis(2-amidinopropan)-Dihydrochlorid)
• ◯ Natriumpersulfat
• ◯ Natriumbisulfit
• ◯ t-BHP (tert.-Butylhydroperoxid), t-BHP setzt die Polymerisation bei 1 Minute in Gang.

A typical reaction profile of a w/w polymer dispersion is shown in 1 shown. After adding the initiators, the reaction begins and the temperature develops as shown in Table 1. The initiation starts at room temperature (here 22 °C). The initiator package is added to the monomer solution in the following order:

• ◯ V-50 (2,2'-Azobis(2-amidinopropane) dihydrochloride)
• ◯ Sodium persulfate
• ◯ Sodium bisulfite
• ◯ t-BHP (tert-butyl hydroperoxide), t-BHP initiates polymerization at 1 minute.

At the maximum temperature (Tmax) of 57.3°C, another initiator is added to remove the monomer residues. Especially at Tmax, a heating bath at 70°C is placed under the flask to ensure the so-called burnout phase above 60°C as in the production system. V-50 acts as a burnout initiator. After a 60-minute burnout phase, a cooling step begins. Tab. 1: Temperature profile during step B time [min] Temperature [°C] 0 22.2 1 22.2 2 31.9 3 34.1 4 34.8 5 35.4 10 38.2 20 49.1 35 57.3

The effect of the initiators will be examined below. The initiators control the reaction in the sense of the invention.

• a 20°C, Spindel 4, Drehzahl 10
• b 20°C, Spindel 2, Drehzahl 10, 5 Gew.-% in vorliegender Form
• c 20°C, Spindel 1, Drehzahl 10, 5 Gew.-% wie vorgegeben in 10%iger NaCl-Lösung
• d 20°C, Laborzentrifuge Hermle Z300, 1 h @ 4000 rpm
• e Drehmoment am Labormischer IKA Power Control, max. 65 N/cm

The concentrations of the initiators in the starter pack were varied both individually and together to understand the effects on polymerization. The following table and graphs summarize our results. Table 2: Variation of the t-BHP content, the entire initiator package and the bisulfite content Batch V-50 [ppm] Sodium persulfate [ppm] Sodium bisulfite [ppm] t-BHP [ppm] Torque reaction [N/cm] ^e Time to Tmax [min] Mass viscosity [mPas] ^a Solution viscosity [mPas] ^b Salt viscosity [mPas] ^c Sediment centrifuge [%] ^d Storage 40°C #1 375 27.3 16.0 3.00 29 25 3,840 1490 540 21% OK #2 375 27.3 16.0 2.35 28 35 3,880 1800s 650 15% OK #3 375 27.3 16.0 1.80 29 40 4,160 2190 725 17% OK #4 375 27.3 16.0 1.20 41 45 3,240 2590 865 12% OK #5 413 30.0 17.5 2.60 26 30 4,920 1660 570 15% OK #2 375 27.3 16.0 2.35 28 35 3,880 1800s 650 15% OK #6 337 24.5 14.5 2.12 27 40 5,280 2200 740 17% OK #7 375 27.3 25.0 2.35 30.2 40 6,720 1760 630 30% Post-thickening #2 375 27.3 16.0 2.35 28 35 3,880 1800s 650 15% OK #8th 375 27.3 12.5 2.35 29 30 3,760 1780 620 17% OK #9 375 27.3 7.5 2.35 29 25 3,440 1970 750 16% OK #10 413 0.0 17.5 2.60 25 35 5,000 1650 580 23% OK #11 413 60.0 17.5 2.60 25 35 4,500 1650 570 18% OK

• a 20°C, spindle 4, speed 10
• b 20 ° C, spindle 2, speed 10, 5% by weight in the present form
• c 20°C, spindle 1, speed 10, 5% by weight as specified in 10% NaCl solution
• d 20°C, laboratory centrifuge Hermle Z300, 1 h @ 4000 rpm
• e Torque on the laboratory mixer IKA Power Control, max. 65 N/cm

The results can be summarized as follows, i.e. H. the variation of the initiator quantities shows the following result. As a first result, batch #2 performs best overall.

2 shows the properties of salt viscosity, reaction time and torque depending on the level of tert-butyl hydroperoxide concentration, while the other initiator amounts are kept constant (batch #1 to #4). A lower t-BHP concentration results in a higher salt viscosity (M _w of the polymer) and a longer reaction time. The torque during polymerization is fairly constant except at the lowest t-BHP concentration. The reason for this is the higher molecular weight.

3 shows the effect of varying the entire initiator package (batches #5, #2, #6). The lower amounts of initiator in turn lead to a higher salt viscosity (M _w of the polymer) and a longer reaction time. The torque during polymerization is relatively constant.

4 shows the effects of varying the sodium bisulfite concentration while keeping the other initiator amounts constant (Lots #7, #2, #8, #9). A lower bisulfite concentration results in a shorter response time while torque and salt viscosity remain relatively constant. The effect of this initiator is a surprise. Batch #7 in particular showed unacceptable stability and a bulk viscosity that was too high. As can be seen, the salt viscosity (Mw) was increased at the lowest bisulfite content, but the final dispersion was post-thickened after the stability test.

Even large variations in the sodium persulfate content with constant amounts of other initiators (batches #10 and #11) do not show any positive effects in terms of stability. All parameters are kept fairly constant.

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 8476391 B2 [0003]
• US 7323510 B2 [0003]

Claims (15)

Process for producing a polymer dispersion, comprising the steps A) Providing a reaction mixture in an aqueous medium containing a) a polymeric dispersant and b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; B) subjecting the monomer composition to radical polymerization to synthesize a dispersed polymer and to form the polymer dispersion, wherein step B) is carried out under controlled adiabatic conditions. Procedure according to Claim 1 , characterized in that step B) is carried out under controlled adiabatic conditions by successive or simultaneous addition of a redox initiator system, the redox initiator system preferably comprising an oxidizing agent and a reducing agent. Procedure according to Claim 1 or Claim 2 , characterized in that the oxidizing agent has a redox potential of 0.6 to 2.0 V, preferably wherein the oxidizing agent is a peroxydiphosphate; hydrogen peroxide; an alkyl hydroperoxide, more preferably t-butyl hydroperoxide; or an aryl hydroperoxide, more preferably cumene hydroperoxide; and/or the reducing agent has a redox potential of -2 to 0.3 V, the reducing agent preferably being sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite, a hydrogen sulfite, a thiosulfate, an amine, an acid, preferably ascorbic acid or erythorbic acid, includes. Procedure according to one of the Claims 1 until 3 , characterized in that the weight ratio between the reducing agent and the oxidizing agent is below 35:1 and above 2:1, preferably below 15:1 and above 3:1, particularly preferably below 9:1 and above 4:1. Procedure according to one of the Claims 1 until 4 , characterized in that the monomer composition comprising the radically polymerizable monomers is selected from the group consisting of one or more of the following: i. a nonionic monomer of the formula (I)

, in which R ¹ represents hydrogen or methyl; R ² and R ³ are independently hydrogen, C1-C5 alkyl or C1-C5 hydroxyalkyl, ii. a cationic monomer of the formula (II)

, where R ¹ represents hydrogen or methyl; Z ₁ is O, NH or NR ⁴ , where R ⁴ is C1-C4 alkyl, preferably methyl, and Y has one of the following meanings

, where Y ₀ and Y ₁ are a C1-C6 alkylene group, optionally substituted with one or more hydroxy groups, preferably ethylene or propylene, optionally substituted with a hydroxy group; Y ₂ , Y ₃ , Y ₅ , Y ₆ , Y ₇ each independently represent C1-C6 alkyl, preferably methyl; and Z ^- is a counterion, preferably a halogen, pseudohalogen, acetate or SO ₄ CH ₃ ^- ; and iii. an amphiphilic monomer of the formulas (III) or (IV)

, where Z ₁ is O, NH, NR ⁴ , where R ⁴ is C1-C4 alkyl, preferably methyl, R ₁ is hydrogen or methyl, R ₈ is a C1-C6 alkylene group, preferably ethylene or propylene, R ₅ and R ₆ are each independently C1-C6 alkyl, preferably methyl, R ₇ is a C8-C32 alkyl, optionally substituted with one or more hydroxy groups, preferably C12-C20 alkyl, optionally substituted with a hydroxy group, and Z ^- is a counterion, preferably a halogen, pseudohalogen, acetate or SO ₄ CH ₃ ^- ; or

is, where Z ₁ is O, NH, NR ⁴ , where R ⁴ is C1-C4 alkyl, preferably methyl, R ₁ is hydrogen or methyl, R ₁₀ is hydrogen, C8-C32 alkyl, C8-C32 aryl and/ or C8-C32 aralkyl, preferably C12-C20 alkyl, R ₉ is a C1-C6 alkylene group, preferably an ethylene group or propylene group, and n is an integer between 1 and 50, preferably between 2 and 30, particularly preferably between 3 and 15, particularly preferably between 4 and 8. Procedure according to one of the Claims 1 until 5 , characterized in that the monomer composition containing the radically polymerizable monomers contains at least the nonionic monomer of formula (I) selected from those in which R ¹ is hydrogen or methyl and R ² and R ³ are both hydrogen, hydrogen and are C1-C3 alkyl, hydrogen and hydroxyethyl or both are C1-C3 alkyl, and/or the cationic monomer of formula (II) selected from those in which R ¹ is hydrogen or methyl and Z ₁ is O , NH or NR ⁴ , where R ⁴ is methyl, Y ₁ is C2-C6 alkylene, preferably ethylene or propylene, Y ₅ , Y ₆ and Y ₇ are all methyl and Z ^- is a halogen; wherein the monomer composition comprising the radically polymerizable monomers most preferably at least the nonionic monomer of formula (I), which is (meth)acrylamide, and the cationic monomer of formula (II), which is (meth)acryloylamidopropyltrimethylammonium chloride or (meth) acryloyloxyethyltrimethylammonium chloride is included. Procedure according to one of the Claims 1 until 6 , characterized in that the free-radically polymerizable monomers are selected from the non-ionic monomer of the formula (I) and/or the cationic monomer of the formula (II), the amount of the free-radically polymerizable monomers being selected from the non-ionic monomer of the formula ( I) and/or the cationic monomer of the formula (II), is between 80 and less than 100% by weight, preferably 85 and 99% by weight, most preferably 90 and 95% by weight, based on the total amount of radically polymerizable monomers, the remainder being selected from the group consisting of any other ethylenically polymerizable monomer, a monomer of formula (III), a monomer of formula (IV) and a difunctional ethylenically polymerizable monomer. Procedure according to one of the Claims 1 until 7 , characterized in that the polymeric dispersant is a homopolymer consisting of the cationic monomer of formula (II)

is, where R ¹ represents hydrogen or methyl; Z ₁ is O, NH or NR ⁴ , where R ⁴ is C1-C4 alkyl, preferably methyl, and Y is one of

is, where Y ₀ and Y ₁ are a C1-C6 alkylene group, optionally substituted with one or more hydroxy groups, preferably ethylene or propylene, optionally substituted with a hydroxy group; Y ₂ , Y ₃ , Y ₅ , Y ₆ , Y ₇ each independently represent C1-C6 alkyl, preferably methyl; and Z ^- is a counterion, preferably a halogen, pseudohalogen, acetate or SO ₄ CH ₃ ^- . Procedure according to one of the Claims 1 until 8th , characterized in that the polymeric dispersant is a homopolymer of a (meth)acryloylamidopropyltrimethylammonium salt or a (meth)acryloyloxyethyltrimethylammonium salt. Procedure according to one of the Claims 1 until 9 , characterized in that the ratio of the polymeric dispersant to the dispersed polymer in the polymer dispersion is in the range from 0.45: 1 to 1: 0.9, preferably in the range from 0.5: 1 to 1: 1, even more preferably in the range from 0.55:1 to less than 1:1, more preferably in the range of 0.6:1 to 0.99:1, especially in the range of 0.65:1 to 0.9:1. Procedure according to one of the Claims 1 until 10 , characterized in that the method comprises the step C) reducing the residual monomer content by adding an initiator to the reaction mixture at approximately the time of reaching the maximum temperature (Tmax), and preferably maintaining the temperature during step C at a level above 55 ° C and below 80°C, more preferably above 60°C and below 70°C. Procedure according to Claim 11 , characterized in that the initiator is selected from a peroxide or an azo compound, preferably selected from the group consisting of a hydro peroxide, a dialkyl peroxide, a diacyl peroxide and an azo compound which is substituted by tertiary carbon atoms and preferably carries alkyl groups, nitrile groups and/or ester groups. Polymer dispersion comprising a) a polymeric dispersant and b) a dispersed polymer derived from a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more nonionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; where the polymeric dispersant has a weight-average molecular weight Mw, determined by size exclusion chromatography, from 40,000 to less than 150,000 g/mol, preferably 50,000 to 140,000 g/mol, more preferably 60,000 to 130,000, most preferably 85,000 to 120,000 g/mol; and/or wherein the polymer dispersion has a volume viscosity below 6,700 mPas, preferably below 6,000 mPas, more preferably below 5,500 mPas, most preferably below 5,000 mPas, measured at 20 ° C with a Brookfield viscometer with spindle 4 and a speed of 10 rpm , having. Polymer dispersion obtained by a process for producing the polymer dispersion according to one of Claims 1 until 11 , comprising the steps A) providing a reaction mixture in an aqueous medium, comprising a) a polymeric dispersant and b) a monomer composition which comprises radically polymerizable monomers, the radically polymerizable monomers being selected from the group consisting of one or more non- ionic ethylenically unsaturated monomers, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; B) subjecting the monomer composition to radical polymerization to synthesize a dispersed polymer and form the polymer dispersion, wherein step B) is carried out under controlled adiabatic conditions; wherein the polymeric dispersant has a weight average molecular weight Mw, determined by size exclusion chromatography, of 40,000 to less than 150,000 g/mol, preferably 50,000 to 140,000 g/mol, more preferably 60,000 to 130,000, most preferably 85,000 to 120,000 g/mol; and/or wherein the polymer dispersion has a volume viscosity below 6,700 mPas, preferably below 6,000 mPas, more preferably below 5,500 mPas, most preferably below 5,000 mPas, measured at 20 ° C with a Brookfield viscometer with spindle 4 and a speed of 10 rpm , having. Use of the polymer dispersion after Claim 12 or Claim 13 a. as a flocculant in the sedimentation, flotation or filtration of solids, b. as a thickener, c. to control contamination, i.e. as a dry strength agent, retention agent or drainage aid in paper production.

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