DE2355813A1 - Acrylic (co)polymer dispersions contg silicone prod or emulsion - give films with improved water-proofness - Google Patents

Abstract

Main Patent DT 1745360, 1st Patent of addn. DT 2348585 and 2nd Patent of addn. DT 2349602, describe a process for prepn. of dispersions contg. monomer-free polymers or copolymers in an aq. medium, by polymerisation of Bu acrylate, Et acrylate or Me acrylate, or copolymerisation of monomers contg. at least acrylic and/or methacrylic acid or their esters, by emulsion polymerisation in the presence of water, emulsifiers, water-soluble redox systems at pH 2-6 and opt. organic peroxides. In present Patent of addn., the finished dispersion is admixed with 2-5 wt. % water-soluble silicon prod. or a silicon resin emulsion. Prods. are pref. as binders for prodn. of pigmented external- and/or internal coating media. Water-proofness of films is improved.

Description

Process for the preparation of dispersions, the monomer-free polymers or copolymers in aqueous Medium included.

The subject of the main patent (patent application 17 45360.0) is a process for the production of low-odor dispersions containing monomer-free polymers or copolymers in an aqueous medium by polymerizing butyl acrylate, ethyl acrylate or methyl acrylate or copolymers of monomeric compounds
which are at least acrylic acid and / or methacrylic acid or their esters, by means of emulsion polymerization in the presence of water, emulsifiers, water-soluble redox systems at pH values between 2 and 6

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organic peroxides, characterized in that the reaction mixture at the latest when the residual monomer content has a constant low value of 0.2 to 1 wt -.% has reached, as additional percompound Oji relative to 3 gene .-% ₃ on the total monomer content, of a perester of the general formula

R ₁ -COOR ₃

a tertiary butyl group in which R and IL an aromatic or an unsaturated aliphatic primary _s secondary or tertiary hydrocarbon group having 1 to 20 carbon atoms, and / or a Perketals of formula

I ³ . I ³

H-C - C - CHp - CHp - C ■ "

0 CH, 0

I 1 ³ I.

0 C 0

added and polymerized by maintaining the polymerization temperature until the residual monomer content is negligible is j and, if appropriate, after the polymerization, excess perester or perketal by addition

eliminated by reducing agents.

A special embodiment of the method according to the The main patent is characterized in that the

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Use of perester or perketal with decomposition temperatures above 30 C.
case of the same used.

temperatures above 30 C a stimulant for the decomposition

A further training of the procedure after the main pa € ent is described in the first additional patent (additional patent application P 23 48 585.O). It is about a process for the production of low-odor dispersions, the monomer-free polymers or copolymers contained in the aqueous medium by polymerizing butyl acrylate, ethyl acrylate or methyl acrylate or copolymers of monomeric compounds, among which at least acrylic acid and / or methacrylic acid or their esters are located by means of emulsion polymerization in the presence of water, emulsifiers, water-soluble Redox systems at pH values between 2 to 6 and organic peroxides, according to the main patent (patent application P 17 ^ 5 36O.O), characterized in that the Polymerization is initiated by adding inorganic peroxy compounds and by adding a water-soluble one Redox system continues the polymerization.

Furthermore, the first additional patent relates to the use of the produced dispersions as binders for the production of pigmented exterior and / or interior paints with improved water resistance.

Submission of the 2nd additional patent application P 23 49- 602 ■. 8 is to improve such dispersions of the type described in the main patent or first additional patent in their water resistance. In this case, the dispersions prepared according to the main patent or first additional patent should preferably be used. However, for the procedure of the 2nd additional patent application after other

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Process produced dispersions cannot be excluded.

Water resistance is understood to mean the property that the film applied from the dispersion shows a pale bluish color after film formation at room temperature or at 50 ° C. when covered with water. In the case of particularly poor film quality, this discoloration turns into an opaque white haze. The film then no longer has any mechanical strength at this point. The time between the completed overlaying of the film with water and a clearly perceptible blue coloration of the film is a measure of the water resistance. In the case of the films _a which can be produced with dispersions which have been obtained according to the main patent, the time for the water resistance is about 30 seconds, while water resistance is achieved by the modification of the production process according to the present invention which in most cases is 3 minutes at room temperature or 14 minutes at 50 ° C ₃ dried films.

The subject of the second additional patent application is a process for the production of dispersions, the monomer-free polymers or copolymers in aqueous Contain medium, by polymerization of butyl acrylate, ethyl acrylate or methyl acrylate or ·. Copolymerization of monomeric compounds, including at least acrylic acid and / or methacrylic acid or their esters, by means of emulsion polymerization in the presence of water, emulsifiers, water-soluble redox systems at pH values between 2 and 6 and optionally organic Peroxides, in particular according to the main patent (patent application P 17 45 36O.O) and the first additional application,

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characterized in that at the latest after completion of polymerization, about 1 to 10 wt. ~ _t% based on the monomers used _s aliphatic, cycloaliphatic and / or aromatic hydrocarbons, individually or in mixture, with
are set.

Mixture j with a boiling point of about 50 - 350 ° C draws'

A particular embodiment of this modified method is characterized in that the hydrocarbons are partly during and after the polymerization can be added to the approach.

For example, provides the best results when using the test gasoline as aliphatic hydrocarbons, when etx \ ra 6 wt .-% ₃ based on the total, adding to the batch during the polymerization and about 2 wt -.% Of white spirit to the batch after completion of the Polymerization admits.

The invention relates to a process for the preparation of dispersions which contain monomer-free polymers or copolymers in an aqueous medium, by polymerizing butyl acrylate _? Ethyl acrylate or methyl acrylate or copolymers of monomeric compounds, including at least acrylic acid and / or methacrylic acid or their esters, by means of emulsion polymerization in the presence of water, emulsifiers, water-soluble redox systems at pH values between 2 and 6 and, if necessary, organic peroxides _? in particular according to patent (patent application P 17 45 3 β 0.0 and first additional application and second additional application ⁺⁺ ) ₃ characterized in that 2 to 5% by weight of a water-soluble silicone product or a silicone resin emulsion are added to the finished dispersion.

+) P 23 48 585.O + ■ * / p 22M9 '-502.8

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A water-soluble silicone product can be used which contains sodium methyl siliconate3 as the active ingredient a sodium salt of methyl silicic acid. This connection corresponds roughly to the following Formula:

OH

i CH, - Si ■ ONa

OH

Already by weak acids, the water-soluble Natriummethylsilikonate be to give the free acid methyl silicone _s decomposed rapidly to a water-insoluble hydrophobic methyl silicone condensed. Even the carbonic acid of the air is able to bring about this reaction.

A useful commercial product has the following properties:

Aqueous, non-flammable liquid

Pest body content 30 ± 1.0 % Methyl silicone (CH ₃ SiO _{1 r} ) 20 + 0.5 %

Na ₂ O ³ 10 +. 1.0 %

NapCO, 1.5 % max.

NaCI 1.5 % max.

Viscosity at 20 ° C 10-16 c.P

Density at 20 ° C 1.23 - 1.26

Freezing point below -10 C

pH 13

Colorless to yellowish in color

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The following can be used as a silicone resin emulsion:

An emulsion of 25 parts by weight of a silicone resin in 25 parts by weight of an organic solvent mixture , which consists mainly of xylene in addition to small amounts of toluene and butanol and 40 parts by weight

Water with the addition of 2 % non-ionic emulsifiers

-1 with a specific gravity of 1.01 + _ 0.01 g / ccm and an expiry time of a maximum of 35 seconds. (DIN 3 mm nozzle)

The addition of water-soluble silicone product or Silicone resin emulsion is made in amounts of 2 to 5 percent by weight, with the pesticide content of the silicone products is based on the solids weight of the dispersion to be treated.

The range of 3 to 3.5 percent by weight of that to be added Silicone product is preferred.

The production, of the dispersion to be treated can be carried out by a known method, for example "Methoden der organischen Chemie" (Houben Weyl), Georg Thieme Verlag Stuttgart 1961, Volume XIV ₃ 1, page 186. However, the present process preferably in such dispersions which have been produced according to the main patent (patent application P 17 45 36O.O) or the first additional patent (patent application P 23 48 585.0).

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Due to the improved water resistance of the film obtained with the dispersions prepared according to the invention are used as binders for the production of pigmented exterior and / or interior paints particularly suitable.

Example 1 :

In a reactor equipped with a stirrer, thermometer, gas inlet tube and reflux condenser, and a reactor equipped with a reaction agent feed vessel, 16 g of a condensation product of p-nonyphenol, with 30 mol of ethylene oxide, 6.0 g of a condensation product of p- Dissolved nonylphenol with 4 moles of ethylene oxide and I ₃ 5 g of the sodium salt of a sulfated condensation product of p-nonylphenol with 3-4 Hol of ethylene oxide. The clear solution obtained is freed from atmospheric oxygen by supplying nitrogen. The vessel is kept under an inert gas atmosphere during the entire reaction time. At a temperature of about 30 C, O ₃ 45 g of potassium peroxydisulfate, dissolved in 37 g of deionized water, are added and stirred in. 130 g of this solution are removed from the reaction vessel and 176 g of styrene, 208 g of butyl acrylate, 16 g of methacrylic acid and 0.5 g of tert-butyl peroctoate are emulsified into it. The solution remaining in the reaction vessel is then heated to 60 ° C. and a solution of 0.3 g of potassium peroxydisulfate in 40 g of deionized water is added. Then start adding the aforementioned monomer emulsion while increasing the temperature to 70-75 ° C. As soon as the reaction has started, which is indicated by the formation of a bluish opalescent color of the reaction mixture ₃ but no later than 10 minutes after the start

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- Q -

of the emulsion feed3 begins the addition of a solution of 0.3 g sodium pyrosulfite in 38 g deionized water. The amounts added per unit of time are to be calculated as follows: that said pre-emulsion and the sodium pyrosulfite solution are added within 80 minutes.

60 minutes after the start of the continuous addition of the pre-emulsion, 0.1 g of sodium pyrosulfite ₃ dissolved in 9 g of deionized water is added. This addition has to be repeated three times at intervals of five minutes each time. From 15 minutes after completion of the continuous Zulaufe 0.1 g potassium _{peroxydisulfate}} are at intervals of five minutes each dissolved in 4 g of water, and a solution of O ₃ I g -Natriumpyrosulfit in H g water was added. Overall, in Reaktionsansat ζ of 8 zuzufüllen these additives. 2 g of hydrazine sulfate (24%) are added. The dispersion must then be kept at 70 ° C. after 90 minutes and then cooled. A dispersion is thus obtained which has a pest body content of approx. 50% by weight. has, with a viscosity of approx. 500 cP and an average particle size of less than 0j2 μ. Then 35 g of sodium methyl siliconate are added and homogeneously distributed in the dispersion by stirring.

One with a wet film thickness of 150 μ on a glass plate The applied film of the dispersion is dried at 20.degree. A drop of water is placed on the dried film. After 8 minutes, the wetted area begins to discolour as a result of the absorption of water, until it finally becomes milky-white Stain arises.

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ίο -

Example 2 :

The procedure described in Example 1 is followed. However, the O ₃ 5 g of tert-butyl peroctoate mentioned are not added until immediately before the hydrazine sulfate is added.

Example 3 :

(Production of an exterior paint using the polymer dispersion produced according to the invention)

30 parts by weight of water, 10 parts by weight of 10% sodium hexametaphosphate solution in water, 1 part by weight of 20% sodium hydroxide solution, 40 parts by weight of turpentine oil, 150 parts by weight of a 2% aqueous solution of low-viscosity methyl cellulose (e.g. Tylose MH 2000 K), 160 parts by weight of rutile, 260 parts by weight of ground Calcium carbonate and 50 parts by weight of talc are dispersed together. The white pigment paste thus obtained is mixed with 317 parts by weight of the polymer dispersion obtained according to Example 1. The emulsion paint has a pesticide content of approx. Oil % by weight with a pigment concentration of 50%. The viscosity is around 30,000 cP. The paints produced with the paint are extremely water-resistant and also have an abrasion resistance of more than 6600 double rubs (Gardner).

Example * t :

20 g of a nonionic emulsifier are added to 200 g of water on the basis of ethoxylated p-Nony! phenols with a

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Content of 30 mol of ethylene oxide and 20 g of dioctylsulfosuccinic acid dissolved in a Witt'sehen pot. The reaction vessel (Witt's pot) is carefully flushed with nitrogen and thus freed from atmospheric oxygen. The entire polymerization takes place under this protective gas atmosphere. Then 0.5 g of potassium peroxydisulfate is dissolved in 65 ml of water and added to the Witt'sehen pot. 50 % of this solution are removed and referred to as batch I. The 50% of this mixture remaining in the pot are mixed in the reaction vessel with 0.3 g of peroxydisulfate dissolved in 35 ml, and O ₃ 3 g of sodium metabisulfite dissolved in 35 ml of water. The mixture is brought to 60 ° C. The batch I is mixed with 220 g of butyl acrylate, 16 g of acrylic acid, 190 g of styrene and 30 g of white spirit (boiling range 60-100 ° C) and converted into an emulsion by stirring. This pre-emulsion is added dropwise to the Witt'sehen pot at 65-70 ° G in about 90 minutes. Simultaneously O ₅ 5 g of sodium metabisulfite are added in 65 ml of water dropwise into the Witt'sehen pot. 15 minutes after the pre-emulsion feed has ended, 10 g of white spirit and 6 separate solutions of 0.15 g of potassium peroxydisulfate dissolved in 5 g of water and 0.15 g of sodium metabisulfite, dissolved in 5 g of water, are added 6 times at intervals of 20 minutes . 15 minutes after the last addition of potassium peroxydisulfate, the largely polymerized reaction mixture _5, in which the residual monomer content is still about 0.3 to 0.5 %, is mixed with 0.5 g of tert-butyl perisononate and 1 ml of a vanadyl p-toluenesulfonate solution in isopropyl alcohol / xylene with 1 % metal content. After a holding time of 90 minutes at 80 ° C. with stirring, the residual monomer content is then negligibly low, ie below Q.01 %. After cooling to 30.degree.-40.degree. C., 31 g of sodium monomethylsiliconate are added to the batch and stirred in evenly.

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The water resistance of the manufactured according to the invention Dispersion is 60 minutes. The same untreated dispersion shows 50 minutes.

example 5 -

You work as in example 4, but use instead White spirit here xylene. This achieves a water resistance of the dispersion of 45 minutes.

Example 6 :

The procedure described in Example 4 is followed. However, an additional 30 g of toluene and the After the monomer emulsion had been fed in, 10 g of toluene were added to the dispersion. It results in a water resistance the dispersion of 30 minutes ..

Example 7 :

One works as indicated in Example 4. To the mentioned However, an additional 30 g of hexane and the dispersion become emulsion after the monomer emulsion has been fed in 10 g of hexane were added. Discoloration only occurs after 20 minutes.

Example 8 :

The procedure described in Example 4 is followed. In the said However, an additional 30 g of cyclohexane are emulsified

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and the polymerized dispersion after the end 10 g of cyclohexane were added to the monomer emulsion feed. This makes the applied films water-resistant of 35 minutes received.

example 9 :

In a reactor equipped with a stirrer, thermometer _s gas inlet tube and reflux condenser, 16 g of a condensation product of p-nonylphenol, with 30 mol of ethylene oxide and 6.0 g of a condensation product of p-nonylphenol are added to 155 g of deionized water 4 mol of ethylene oxide and 1.5 g of the sodium salt of a sulfated condensation product of p-nonylphenol with 3 - ■ 4 mol of ethylene oxide dissolved. The clear solution obtained is freed from atmospheric oxygen by feeding in nitrogen. The vessel is kept under an inert gas atmosphere during the entire reaction time. At a temperature of about 30 ° C, 0.45 g of potassium peroxydisulfate, dissolved in 37 g of deionized water, is added and stirred in. From this solution, 130 g of the reaction vessel are removed and in 176 g of styrene, 208 g butyl acrylate, 16 g methacrylic acid, ₅ 3O g of white spirit (boiling range 60-100 ° C) and 0.5 g tert emulsified Butylperisononat ~.. The solution remaining in the reaction vessel is then heated to 60 ° C. and a solution of 0.3 g of potassium peroxydisulfate in 40 g of deionized water is added. Then, one starts with the addition of the above-mentioned monomer emulsion, with simultaneous increase in temperature to 70-75 ° C. Once the reaction is jumped _s which is indicative of the formation of a bluish opalescent color of the reaction mixture, but not later than 10 minutes after the start of the emulsifier

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sion inflow, begins the addition of a solution of 0.3 g Natriurapyrosulfxt in 38 g deionized water. The added amounts per unit of time are to be calculated so that the aforementioned pre-emulsion and the sodium pyrosulfite solution are within of 80 minutes are added.

60 minutes after the start of the continuous addition of the pre-emulsion, 0.1 g of sodium pyrosulfite, dissolved in 9 g of deionized water, is added. This addition has to be repeated three times at intervals of five minutes each time. 15 minutes after the feed of the pre-emulsion has ended, 10 g of white spirit are added. From 15 minutes after the end of the continuous feed, 0.1 g of potassium peroxydisulfate, dissolved in 4 g of water, and a solution of O ₅ I g of sodium pyrosulfite in .4 g of water are added at intervals of five minutes. A total of 8 of these additives each have to be added to the reaction mixture. 2 g of hydrazine sulfate (24 % ± g) are added. The dispersion must then be kept at 70 ° C. after 90 minutes and then cooled. In this way a dispersion is obtained which has a pest body content of approx. 50% by weight, with a viscosity of approx. 500 cP and an average particle size of less than O ₃ 2 μ. After cooling to 30 ° C., 30 g of sodium monomethylsiliconate are added and distributed homogeneously in the dispersion. A film of the dispersion x drawn onto a glass plate with a wet film thickness of 150 µ is dried at 20 ° C. A drop of water is placed on the dried film. After 70 minutes, the wetted area begins to discolour as a result of the Viasser absorption, until a milky-white stain appears.

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Example 10 :

One works as indicated in Example 9. However, the same amount of toluene is added instead of white spirit. The water resistance is further improved compared to that mentioned in Example 6 with 45 minutes.

Example 11 :

One works as indicated in Example 9, but is used as organic solvent hexane. The film obtained from the dispersion has water resistance of 35 minutes.

Example 12 :

The procedure given in Example 9 is followed. For improvement Cyclohexane is added to the water resistance. The water resistance of the films obtained from the dispersion reaches 40 minutes.

Example 1? :

The procedure given in Example 9 is followed. For water repellency xylene is used instead of white spirit. Water resistance values of 40 minutes are determined.

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Example l4 :

The procedure given in Example 9 is followed. Instead of white spirit, a mixture of hydrocarbons with about 97 % alkylated aromatics with a boiling range of 177 to 206 ° C (for example Solvesso 150) is used. The films obtained from the dispersion have a water resistance of 35 minutes.

Example 15 :

The procedure given in Example 9 is followed. As a hydrocarbon additive, a mixture is used that consists of up to 86% ring-condensed aromatic and has a boiling range of 250 - 285 ° C (e.g. Solvent HRN). When stored in water, the films from the dispersion remain unchanged for 40 minutes.

Example 16 :

(Production of an exterior paint using the polymer dispersion produced according to the invention)

30 parts by weight of water, 10 parts by weight of 10% sodium hexametaphosphate solution in water, 1 part by weight of 20% sodium hydroxide solution, 40 parts by weight of turpentine oil, 150 parts by weight of a 2% aqueous solution of low-viscosity methyl cellulose (e.g. Tylose MH 2000 K) _s 160 parts by weight of rutile, 260 parts by weight of ground calcium carbonate and 50 parts by weight of talc are dispersed together. The white pigment paste thus obtained is 317 wt.

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parts of the polymer dispersion obtained according to Example 4 are mixed. The emulsion paint has a pesticide content of approx. 6% by weight with a pigment concentration of 50%. The viscosity is around 30,000 cP. The paints made with the paint are excellent waterproof and have good rub resistance.

Example 17 :

Preparation of a dispersion according to the prior art (Methods of organic chemistry, Houben-Weyl, Georg Thieme-Verlag, Stuttgart, 1961, Volume XIV, 1, Page 186).

25 parts by weight of sodium oleyl sulfonate and 25 parts by weight of a condensation product of stearyl alcohol with 20 mol of ethylene oxide are dissolved in 2500 g of H ₂ O. 50 parts by weight of acrylic acid are added and the pH is adjusted to 7 with ammonium hydroxide solution. Then 1375 parts by weight of vinyl acetate and 1375 parts by weight of butyl acrylate are added and, with stirring, converted into an emulsion, 20 % of which is placed in a reaction vessel under a nitrogen atmosphere. From a solution of 1.35 parts by weight of potassium peroxysulphate in 50 parts by weight of water, 20 % is added to the reaction mixture in the reaction vessel and the temperature is increased to 80 ° C. like the persulfate solution, on the other hand, was added over the course of 2 hours

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and then cooled to 30 ° C. A 90 y wet film thickness dried from the dispersion at room temperature begins to swell after 4 minutes of immersion in water with the onset of turbidity and to mechanical strength lose.

Example 18 :

The procedure is as in Example 17. After the dispersion has cooled down according to the invention, the addition of takes place at 30.degree 50 parts by weight of sodium methyl siliconate. A corresponding one The water resistance of the film is improved by 30 minutes compared to that which does not contain siliconate.

Example 19 :

20 g of a nonionic emulsifier based on ethoxylated p-nonylphenols with a content of 30 mol of ethylene oxide and 20 g of dioctylsulfosuccinic acid are dissolved in 200 g of water in a Witt's saucepan. The reaction vessel (Witt's pot) is carefully flushed with nitrogen and thus freed from atmospheric oxygen. The entire polymerization takes place under this protective gas atmosphere. Then 0.5 g of potassium peroxide sulfate is dissolved in 65 ml of water and put into the Witt'sehen pot. 50 % of this solution are removed and referred to as batch I. The 50% of this mixture remaining in the pot are mixed with O ₅ 3 g of peroxydisulfate dissolved in 35 ml of water in the reaction vessel. The mixture is brought to 60.degree. The batch I is mixed with 220 g of butyl acrylate, ₃ l6 g of acrylic acid and 190 g of styrene and stirred in

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transferred to an emulsion. This Vorermilsion is added dropwise in about 90 minutes at 65 ~ 70 ° C in the Witt'sehen pot. At the same time, 0.5 g of sodium metabisulphite, dissolved in 65 ml of water, is added dropwise to the Witt'sehen pot. 15 minutes after the pre-emulsion feed has ended, separate solutions of O _5, 15 g of potassium peroxysulfate dissolved in 5 g of water and 0.15 g of sodium metabisulfite, dissolved in 5 g of water, are added 6 times, each at 20 minute intervals. 15 minutes after the last addition of potassium peroxydisulfate, the largely polymerized reaction mixture, in which the residual monomer content is still about 0.3 to 0.5 %, is mixed with 0.5 g of tert-butyl perisonate and 1 ml of a vanadyl p-toluenesulfonate solution in Isopropyl alcohol / xylene with 1 % metal content. After a holding time of 90 minutes at 80 ° C. with stirring, the residual monomer content is then negligibly low, ie below 0.01 %. After cooling to 30 ° C., 35 g of sodium monomethyl siliconate are stirred in. This improves the water resistance from 30 seconds to β minutes.

Example 20 :

The procedure is as in Example 19, but 30 minutes after the addition of the vanadyl salt solution, 1 g of a 25% aqueous hydrazine solution is added and the mixture is kept at 80.degree. 90 minutes after this addition, the residual monomer content is below 0.01 wt -% lower and reduces the unused tert-Butylperisononat.. The film shows a water resistance of 5 minutes.

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Example 21 :

The procedure is as in Example 19, but instead of tert-butyl perisononate, tert-butyl peroctoate is now used. Here, too, the residual monomer content is now below 0.01 %. The water resistance is 4-5 minutes.

Example 22 :

The procedure is as in Example 20, only instead of tert-butyl perisononate tert-butyl peroctoate is used. The residual monomers are now fully polymerized and the tert-butyl peroctoate destroyed. The water resistance is determined to be 3-4 minutes.

Example 2? :

The procedure is as in Example 19; Instead of tert-butyl perisononate, mono-tert-butyl permaleate will now be used. The residual monomer content is thus reduced to below O ₃ Ol % . The water resistance of the film is 5 minutes.

Example 24 :

You work as in example 19, but give differently the 0.5 g of tertiary butyl perisononate in the incoming pre-emulsion. When the pre-emulsion addition is complete, the corresponding Variady! Salt solution added. The residual monomer content after a holding time of 90 minutes

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75-80 C with stirring is negligible _s it is below ₅ O Ol%. Water resistance of the film: 4 minutes

Example 25 :

Work as indicated in Example 24. Instead of tert-butyl perisononate, the same amount of tert-butyl peroctoate is used. The percentage of unpolymerized monomers is less than 0.01 %. The water resistance is approx. 3 minutes.

Example 26 :. .

Proceed as in example 24. Instead of tert-butyl perisononate, mono-tert-butyl peracetate is used. The residual monomer content falls to below O ₃ Ol %. Water resistance: 4 minutes

Example 27 :

The procedure is as in Example 24 _s, but tert-butyl perbenzoate is used instead of tert-butyl perisononate. In this case too, the residual monomer is polymerized away _{up to an amount of less than O 3} Ol %. Water resistance: 3 minutes

Example 28 :

The procedure is as indicated in Example 24, but a cyclic perketal is used instead of tert-butyl perisononate

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the formula:

CH, 2 - CH ₂ - - C - CH, ³ I. Cf
j H * f 3 1
0
I. I.
-c I ·
O
j I.
O I.
-O

used. The content of unpolymerized monomers is now only x ^ less than 0.01 %. Water resistance: 5 minutes

Example 29 :

The procedure of Example 24 ₅ but after the addition of sodium metabisulfite, 1 g of 25% hydrazine hydrate was added. After a waiting time of 90 minutes at 75 - 80 ° C, the residual monomer content is below 0.01 % and the unused tert-butyl perisononate has disappeared. Water resistance: 3 minutes

Example 30 :

The procedure is as in Example 29, but instead of tert. Butyl perisononate is used as tert-butyl peroctoate. The residual monomer is now less than 0.01 % _t the tert-butyl peroctoate is completely reduced. Water resistance: 4 minutes

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Example 31 ?

The procedure is as described in Example 29, but instead of tert-butyl perisononate, tert-butyl peracetate is used. The residual monomer content is now below 0.01 % _s the tert-butyl peracetate is destroyed.
Water resistance of the film: _2½ 5 minutes

Example 32 :

The procedure described in Example 29 is followed. The tert-butyl perisononate is replaced by tert-butyl perbenzoate. The unpolymerized proportion of monomers is now below 0.01 % _s the tert-butyl perbenzoate is reduced. Water resistance: 3 minutes

Example 33 s

The procedure described in Example 29 is followed. Instead of the tert-butyl perisononate, a cyclic perketal is used Formula:

CH, CH,

I ³ ! ³

CH ₃ -C- CH ₂ - CH ₂ - C- CH ₃

0 CH, 0

II ³ I

0, C-0

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used. As a result, the residual monomer content was reduced to below 0.01% and the excess cyclic perketal was reductively destroyed. Water resistance: 3 minutes

Example 34 :

The procedure is as in Example 2k, but using instead of 0.5 g of tert-Butylperisononat a mixture consisting of 0.25 g of tert-Butylperisononat and O _s 25 g of a cyclic Perketals, of the formula as indicated in example 15 °. This reduces the residual monomer content to below 0.01 %. Water resistance: 3, 5 mins

Example 35 :

The procedure is as in Example 20, but instead of the monomer mixture used there, a single monomer is used to produce a homopolymer, namely 400 g of butyl acrylate. The residual monomer content of butyl acrylate is when the procedure to below 0.01 - dropped.%. Water resistance: 5 minutes

Example 36 :

The procedure is as in _E Example 19, except that, instead of the monomer mixture used there is another mono Raeren mixture for the preparation of a polymer, consisting of 200 g of ethyl acrylate, 200 g styrene and 20 g of acrylic acid. The residual monomer content is also below 0.01 wt .- ^. Water resistance: 4 minutes

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Example 37 -

The procedure is as in Example "5S ₃ , but the ethyl acrylate in the monomer mixture is replaced by methyl acrylate. Even now the residual monomer content is below O ₃₁ 01% by weight . Water resistance: k 1/2 minutes

Example 38 :

The procedure is as in Example 20 _3, but a mixture consisting of monomers is used

200 g butyl acrylate 180 g styrene

20 g of acrylamide and

20 g acrylic acid

used.

The residual monomer content of each individual component is below

0.01% by weight . Water resistance: 5 minutes

Example 39 :

The procedure is as indicated in Example 38, but the acrylamide in the monomer mixture is replaced by 20 g of acrylonitrile. The residual monomer content of each individual component is less than O ₃ OI by weight.
Water resistance: k minutes

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Example 4P ;

The procedure described in Example 20 is followed. The monomers used are, however, a mixture consisting of

190 g butyl acrylate, 190 g methyl acrylate, 20 g methacrylic acid.

The residual monomer content at the end of the process is below 0.01% by weight for each individual component . Water resistance: 6 minutes

Example 4l :

The procedure is as in Example 20, but instead of 16 g of acrylic acid, 16 g of methacrylic acid are used in the monomer mixture. The residual monomer content sinks to below 0.01 % with a water resistance of the film of 6.5 minutes.

Comparative studies on the way in which technical progress is made

To prove the technical port step, comparative polymerizations were carried out according to the known procedure. The procedure was as described in Example 6, but in each case the perester by the equivalent amount of Replaced specified peroxides or azoisobutyric acid dinitrile. As the following table shows, none of the If the residual monomer content is completely polymerized.

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TABEL

Dispersion after

example

method

DOS 1 7 ^ 5 3βθ State of the art

0.5 min.

cn ο co 00 to

ο -j co

Patent application P 25 48 585.Ο (application as first additional patent)

Patent application P 23 49 602.8 (application as second additional patent)

of the present invention

present invention thermally initiated

5, min.

like first additional patent
(P 23 48 585.Ο)
+ White spirit,

50, min.

like second additional patent

(P 23 49 602.8)

+ Silicone emulsion

= like first additional patent

(P 23 48 585.Ο) + white spirit

+ Silicone emulsion

60 min,

like first additional patent

(P 23 48 585.Ο) + white spirit 70 + siliconate

Min.

Claims (2)

Claims 1. A process for the preparation of dispersions containing monomer-free polymers or copolymers in aqueous medium by polymerizing butyl acrylate, ethyl acrylate or methyl acrylate or copolymerization of monomer compounds, which includes at least acrylic acid and / or methacrylic acid or esters thereof are, by means of emulsion in the presence of water, emulsifiers, water-soluble redox systems at pH values between 2 to 6 and optionally organic peroxides, in particular according to patent (patent application P 17 4 5 360.0 and first additional application P 23 48 585-0) and second additional application P 23 ^ 9 602.8), characterized in that the finished dispersion 2 to 5 weight -% of a water-soluble silicone product or a silicone resin emulsion are added.. 2. Use of the dispersions prepared according to claim 1 as binders for the production of pigmented Exterior and / or interior paints with improved water resistance. 509824/0739