DE1644782A1 - Organopolysiloxane-based coating compositions - Google Patents

Description

'. Passport, lawyerL in Gen. VolIIm. (HL-No. 52/64) from DOW CORNING Corp. Midland / Me. (UNITED STATES)

Munich, June 1st, 1967 Dr.Wg./ku

DC 1273-1364 / 805

Coating compositions based on organopolysiloxane

The present invention relates to coating compositions based on organopolysiloxanes and other conventional additives, which are characterized in that they are the organopolysiloxanes in the form of

(1) Copolymers consisting essentially of 25 to 90 wt. Ji Aorylates and 10 to 75 wt .- ^ organopolysiloxanes consist, the organopolysiloxanes consisting essentially of 40 to 100 MoIJi RgSiO units and 0 to 60 MoIJi RSiO, / g units are, wherein R is monovalent, unsubstituted or substituted carbon hydrogen radicals, or

(2) Mixtures consisting essentially of 25 to 90% weight aorylates and 10 to 75 parts by weight of organopolysiloxanes consist, wherein

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the organopolysiloxanes are composed essentially of 40 to 100 mol #RgSiO units and O. to 60 mol £ RSiO, / _£ units, where R has the meaning given,

contain.

Optionally, the invention usable mixing W can be polymers and mixtures in the form of aqueous emulsions.

With the coating compositions according to the invention, any Materials are coated; The coating compounds include Lacquers, compounds for roof coverings and in particular latex paints.

In the coating compositions according to the invention, both for the copolymers (1) and any organic acrylates can be used as acrylates for the mixtures (2), such as Acrylic acid and methacrylic acid or their derivatives, such as esters, Nitriles and amides; esters are preferably used. Examples are methyl acrylate, ethyl acrylate, amyl aorylate, cyclohexyl acrylate, Vinyl acrylate, ß-methallyl acrylate, methyl c <-chloroacrylate, Benzyl acrylate, p-chlorobensyl aorylate, hydroxyethyl aorylate, Ethyl w-hydroxymethyl acrylate, ethyl yanoaorylate, perfluoro-ethyl acrylate, Xethylene glycol diaorylate, glyceryl trlaorylate, ethyl metheorylate, Ethylene glycol dimethacrylate and methyl ethacrylate.

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It should be noted that in a known manner both a single acrylate, as well as any combination of different acrylates used for the production of the copolymers can be. The special selection of the acrylate reaction component is determined by the intended use of the copolymer. For example, methyl methacrylate tends to even to deliver hard and somewhat brittle products that are suitable for the manufacture of car paints, while xfchyl acrylate itself, soft and somewhat sticky products supplies that are not suitable for car paints, but in other areas of application, such as for textile treatment or for Manufacture of adhesives can be used. If, on the other hand, properties are desired that are roughly between the mentioned mixtures of methyl methaorylate and ethyl acrylate can be used be used. Products are obtained that have the special degree of hardness in connection with the required Have flexibility «which are suitable for wood coverings. Generally In other words, it is advantageous to use acrylate mixtures to produce the copolymers, since it is only used in exceptional cases it is possible to find a single compound, the products with optimal properties for the desired purpose supplies.

The organs that can be used for the production of the copolymers

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1644732

Nanopolyeiloxanes are preferably composed of 45 to 65 mol # R SiO units and 55 to 55 mol # RSiO ₃ / g units.

The unsubstituted or substituted hydrocarbon radicals R can be alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, alkaryl or aralkyl radicals, which are optionally substituted by halogen or cyano groups, or ether, thioethers, esters or May contain thioester bonds. Of course, there may be no groups in the radicals of the organopolysiloxanes which can react with the mixtures or copolymers. Examples of radicals R are methyl, ethyl, propyl, butyl, amyl, dodecyl, octadecyl, myricyl, vinyl, allyl, hexenyl, ethynyl, propargyl, cyclobutyl, cyclohexyl, Cyolohexenyl, phenyl, naphthyl, xenyl, tolyl, xylyl, mesityl, tert. Butylphenyl, benzyl, 2-phenylethyl, 2-phenylpropyl, J-chloropropyl, 3,3,3-trifluoropropyl, perfluorovinyl, chloroyclohexyl, bromophenyl, dichlorophenyl, «, o (,-trifluorotolyl -, mercaptoethyl, mercaptopropyl, mercaptododeoyl, cyanoethyl, cyanopropyl, hydroxypropyl radicals or radicals of the formulas - (CHg) ₃ OOCCH-CH ₂ , - (CH ₂ J ₅ OOCC (CH ₃ ) -CHg,

/ Ov

- (CHg) ₃ OCH ₃ , - (CHg) ₃ OC ₂ H ₅ , - (CHg) ₃ COOC ₂ H ₅ , - (CHg) ₃ CH ^ CH ₂ , -C ₆ H ^ OCH ₃ , - (CHg) ₃ C ₆ H ^ OCgH ₅ and - (CHg) ₂ SCgH ₅ . R preferably contains fewer than 10 carbon atoms; particularly preferred radicals R are methyl, ethyl, vinyl, phenyl and 3,3,5-trifluoropropyl radicals.

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Preferred types of copolymers which can be used according to the invention are those which have been produced by vinyl melt polymerization. In this type of copolymers it is essential that some of the radicals R contain double bonds of the vinyl type, which is to be understood as meaning that these structures of the formula CHg »C _v contain as part of the radical. Examples of such groups are listed under the radicals mentioned above. The number of radicals R with vinyl structure must be chosen so that the ratio of radicals with vinyl structure to the Si atoms in the organopolysiloxanes is in the range from 0.02: 1 to 0.3 5 1 and preferably in the range from 0.02: 1 to 0.1: 1. In general terms: 'The more residues with a vinyl structure there are in the siloxanes, the less flexible the product and vice versa. The ratio of the radicals with a vinyl structure used in the mixed polymers to the Si atoms is of course determined by the desired properties of the end product.

Further preferred types of copolymers which can be used according to the invention are those that, using siloxanes, contain Si-bonded hydroxyl and / or alkoxyl groups (e.g. methoxyl, Ethoxyl, propoxyl or butoxyl groups), and Acrylates, which accordingly contain hydroxyalkyl groups, have been prepared. The siloxanes at least need to be used here

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0.5 wt .- #, preferably at least 2 wt .- # of hydroxyl and / or contain alkoxyl groups. Generally speaking, Je The greater the percentage of such groups in the siloxanes, the less flexible the product becomes and vice versa. Of the . exact percentage of hydroxyl and / or alkoxyl groups in the The siloxane used is of course determined by the desired properties of the copolymer. The one for the stiffening The acrylates used in these copolymers must contain 1 to 20 mol of a hydroxyalkyl aorylate. Of these are 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are preferred. If the copolymer is produced by emulsion polymerization, it is advantageous if the amount of hydroxy alkyl acrylates in the range from 1 to 10 Mo1 #.

Another method for producing those which can be used according to the invention Copolymers is the copolymerization of siloxanes, which contain meroaptoalkyl substituents, with acrylates. In addition, the copolymers which can be used according to the invention can also be produced by other known processes.

The siloxane-acrylate mixtures which can be used according to the invention are best obtained by polymerizing the siloxanes and acrylates separately and then in a simple way are mixed together.

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With regard to the relative amounts of RgSiO and RSiO, / g units in the organopolysyl oxanes, it should be pointed out that the exact proportions are in turn determined by the desired properties of the copolymer. The following applies as a guideline for the quantities that can be used: With increasing quantities of RgSlO units, the resulting acrylate-siloxane miso-polymers or mixtures become softer, more sticky and tend to absorb more dirt. On the other hand, with increasing amounts of RSiO -, / g units, the resulting acrylate-siloxane copolymers become harder, drier and more brittle. By using appropriate amounts of the two siloxane units, the copolymer can be given the properties desired in each case. It should be pointed out that the siloxanes can also contain small amounts of ^R 3 ^S10 i / 2 ~ ¹ ^ SiOg units, as long as these have no adverse effect on the final mixtures or copolymers.

Preferably, the copolymers useful in this invention contain 60 to 80 weight 56 acrylates and 20 to 40 wt -.% Organopolysiloxanes, with the precise proportions in turn depend on the required properties for the intended use of the mixture or the interpolymer.

So far known, the following procedure has been used

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Production of the copolymers best proven: First, the organopolysiloxanes are emulsion polymerized produced, the starting products preferably being the corresponding Alkoxysilanes are used. The siloxane emulsion thus obtainable then becomes a catalyst which forms free radicals added, and then the acrylate monomer or monomers are added and siloxanes and acrylates, advantageously under acidic conditions, copolymerized. Details of this best method of making more specific preferred Copolymers are described in the examples.

Any catalyst which accelerates the copolymerization of siloxanes and acrylates can be used as catalysts capital. Preferred compounds are catalysts and catalyst systems which form free radicals. Examples of such Catalysts are inorganic peroxides such as hydrogen peroxide, ammonium persulfate and potassium pereulfatej the various organic peroxy catalysts, such as dialkyl peroxide, ζ. B. Diethyl peroxide, Dllsopropylperoxid, DilaurylperoxId, Dioleyl peroxide, Disteeryl peroxide, Di (ter.-butyl) peroxide, Di- (tert-amyl) peroxide and dioumylperoxldj alkyl hydrogen hydroxides, such as tert-butyl hydroperoxide, tert. Amyl hydroperoxide, Cumene hydroperoxide, tetralin hydroperoxide and diisopropylbenzene

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hydroperoxide; symm. Diacyl peroxides, e.g. B. aoetyl peroxide, propionyl peroxide, Lauroyl peroxide, stearoyl peroxide, malonyl peroxide, Suocinoyl peroxide, phthaloyl peroxide, benzoyl peroxide; Ketone peroxides, such as methyl ethyl ketone peroxide and cyelohexanone peroxide; Fatty acid peroxides such as coconut oleic acid peroxides; unsymm. or mixed diacyl peroxides such as acetyl benzoyl peroxide and Propionyl benzoyl peroxide; Azo compounds, such as 2-aisobis (isobutyronitrile), 2-azobis (2-methylbutyronitrile), 1-azobis- (l-cyclohexanecarbonitrile) and other free radical forming catalysts such as disulfides.

example 1

In a 500 ml beaker was placed 254.4 g distilled water, 6 g of sodium dodecylbenzenesulfonate and 4 g of a 28% strength by weight ammonia solution and heated to 65.degree heated with stirring with an electric stirrer. Then within 10 minutes by means of a dropping device Mixture of 10 g vinyltrimethoxysilane, 90.4 g phenylmethyldimethoxysilane and 50 g of phenyltrimethoxysilane were added. Well The silane addition was completed again for 10 minutes with stirring heated. JOO g of the opalescent emulsion obtained were heated to the boil (86 ° C.-90 ° C.), with about 70 ml volatile Components distilled off (mainly methanol and

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Ammonia). It became a siloxane emulsion with a solids content of about 30% e-5i. and a pH value in the range of 7.5 to 8.0 obtained.

190 g of the siloxane emulsion thus obtained, 6.4 g of a solution of an anionic surface-active agent (pesticide content 36% by weight) and an oemisoh of 34 g of distilled water

W and 0.95 g of acrylic acid were placed in a beaker and the pH was adjusted to 5.0 by adding 3 g of a 7% strength by weight sodium bicarbonate solution. This mixture was placed in a three-necked flask, purged with nitrogen and heated to 85 ° C; then 10% by weight of a mixture of 79 * 8 g of ethyl acrylate and 53.2 g of methyl methacrylate were added and then 25% by weight of a solution of 34.7 g of distilled water and 0.76 g of potassium persulfate. Within 45 minutes, the temperature to 85 ⁰ C were added with stirring and passage of nitrogen, the remaining amounts of the acrylate mixture and maintaining Persulfatlöaung. The persulfate solution was added in 3 portions of 25% by weight each (following the addition of 25, 50 and 75% by weight in each case of the aorylate mixture a. After the reaction had ended, the siloxane-acrylate misohypolymer mixture was cooled, the pH -Value adjusted to 8.6 with ammonium hydroxide and 20 g of distilled water added to adjust the viscosity to 262 oP.

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A copolymer film in the form of the emulsion prepared above was cast on a metal plate. The wetting of the plate by the emulsion was excellent and the interpolymer film obtained was completely clear. The film had a pencil hardness ^W B "and a smoothness of the OT radius.

Example 2

In a beaker with a capacity of 600 ml were 224.8 g of water, 4 g of ammonium hydroxide, 3 μ of an adduct of nonylphenol with 9 moles of ethylene oxide and 8.3 g of an anionic surfactant mixed and heated to 60 ° C. Then it became a mixture within several minutes from 25.8 g vinyltrimethoxysilane, 86.3 β phenyltrimethoxysilane, 20.6 g of diphenyldimethoxysilane and 59.2 g of dimethyldiraethoxyeilane added and after the addition was complete, heating was continued for about 10 minutes with stirring, with about 100 g of the volatile Components distilled off.

133 g of the siloxane emulsion thus obtained were 39.8 g Water, 0.77 g acrylic acid and 1.3 g sodium lauryl sulfate mixed and then the pH is adjusted to 5.0 by adding 1.3 g of a 7% strength by weight sodium bicarbonate solution. the obtained mixture was placed in a three-necked flask with

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Nitrogen flushed and heated to 85 ⁰ C and then 10 wt .- # were 8l g of a mixture of ethyl acrylate and 27 g of methyl methacrylate was added, and then 25 wt -.% Of a solution of 28.2 g of water and 0.62 g of potassium persulfate was added. The remaining acrylate solution and the persulfate solution were added over the course of 60 minutes in the same way as in the example previously described. The product obtained was an emulsion of the siloxane-acrylate misoh polymer.

Example 3

A mixture of 677t6 g distilled water, 11 g ammonium hydroxide, 14 g of an adduct of nonylphenol with 9 moles of ethylene oxide and 40.2 g of an anionic surfactant were placed in a beaker and heated to 60 ° C. The mixture was then stirred continuously for 10 minutes 41.8 grams of methyltrimethoxysilane, 214 grams of phenyltrimethoxysilane, 51 grams Diphenyldimethoxysilane, 148 g dimethyldinethoxysilane and 22.5 g Vinyltrimethoxysilane added. After the addition had ended, the temperature was kept at 60 ° C. for about 30 minutes with stirring and then 280 ml of the volatiles are distilled off.

g of the siloxane emulsion thus prepared were 1.27 g Acrylic acid, 3.24 g sodium dodeoylbenxene sulfonate and 80.77 g

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The mixture was mixed with water and the pH of the mixture obtained was adjusted to 5 by adding about 4 g of a 7% strength by weight sodium carbonate solution. A mixture of 75 g of ethyl acrylate and 50.5 g of methyl methacrylate and a solution of 30 g of water and 0.72 g of potassium persulfate, as described in Example 1, were added to this. The reaction was over after about an hour. The product obtained was an emulsion of the siloxane-acrylate copolymer. The copolymer was thermoplastic when hot. A film of the copolymer was poured onto a metal plate and cured at 150 ° C. for 15 minutes. He had a pencil ^{hardness of M} HB ⁿ and a suppleness of the OT radiue. Another film of the copolymer, which had been cured for 15 minutes at 205 ° C., had a pencil hardness of "JH * and a suppleness of" OT ".

Example 4

To 372 g of an aqueous emulsion of a Siloxanmisohpolymerieates from 95 moles of diphenyl liloxane contents and 5 moles of monovinylsiloxane units with a Slloxane solids content of about 35 wt .- #, 2.7 g of acrylic acid, 6.9 S sodium dodecylbenzenesulfonate and 173 S water are added and then the pH is adjusted by adding about 13 g of a 7% strength by weight sodium bicarbonate solution set to 5. The mixture obtained was heated to 85 ° C

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heated, then a mixture of 160 g of ethyl aorylate and 107 g Methyl methaorylate and a solution of 63 * 5 g of water and 1.5 g Potassium persulfate, as in the examples previously described, was added. The reaction was over after about 45 minutes. That The product obtained was an emulsion of the siloxane-acrylate copolymer . A 25.4 ^ thick coating (1 rail) was applied made of a metal plate and the resulting copolymer " film cured for 5 minutes at 150 ° C. The wetting of the plate by the emulsion was excellent and the film obtained transparent. The film had a "B" pencil hardness and a OT radius suppleness.

A pigment dispersion was made by mixing 1000 g of water, 31.6 g of an anionic surfactant, 815 g titanium dioxide, 136 g mica, 454 g calcium carbonate, 204 g Aluminum silicate, 68 g ethylene glycol, 9.1 g polyethylene glycol with a molecular weight of 1200, and 18.1 g of methyloellulose with a viscosity of 4000 cP. produced, the 3 last-mentioned Beatand parts had been premixed. These Mixture then turned to the desired shade of green with yellow Iron oxide and phthalocyanine colored green. 100 g of this pigment « The dispersion were thoroughly mixed with 100 g of the emulsion of the slloxane / aorylate copolymer prepared above and coated a metal plate with the obtained latex paint.

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The wetting was excellent and, after drying, the paint film had a pencil hardness "B" and a suppleness from the TDC radius.

Example 5

To 154 g of an aqueous emulsion of a siloxane bulk polymer composed of 5.2 moles of monovinylsiloxane units, 62.8 moles of phenylmethylsiloxane units and 32 moles of monophenylsiloxane units, with a siloxane solids content of about 35% by weight , there were added 127 g of acrylic acid , 1.2k g of sodium lauryl sulfate. 80.77 g of water are added and the pH is then adjusted to 5 by adding about 5 g of a 7% strength by weight sodium bicarbonate solution. The mixture obtained was heated to 85 ° C., then a mixture of 75 g of ethyl acetate and 50 g of methyl methacrylate and a solution of 30 g of water and 0.5 g of potassium persulfate, as in the examples described above, were added. The reaction was over after about an hour.

A film of the siloxane-acrylate copolymer was cast onto a metal plate from the copolymer emulsion prepared above. The wetting of the plate by the emulsion was excellent and the film obtained was transparent. The film was cured at 175 ° C for 5 minutes. He had a pencil hardness ^M B "and a suppleness of the OT radius.

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A latex paint was prepared by mixing 100 g of the above Siloxane-aorylate mixed polymer emulsion and 100 g of the pigment dispersion from Example 4 prepared. With this Paint was coated onto a metal plate and the coating was coated for 5 minutes cured at 175 ° C. The paint had excellent wettability and the cured film had pencil hardness "B" and a suppleness from TDC radius.

Example 6

To 134 of an aqueous emulsion g of a Siloxanmischpolymerisates from 10 MoIJi monomethylsiloxane units, 35 mole # monophenylsiloxane units, 5 mol £ Monovinylsiloxaneinheiten, 10 Mo1 # diphenylsiloxane units and 40 mol # Dlmethyleiloxaneinheiten, with a Siloxanfes ^ matter content of about 40 wt -.% In the emulsion, was a mixture of 93 S water, 1.27 6 acrylic acid and 9.3 β of an anionic surfactant was added. The pH was adjusted to 5 by adding a 7% strength by weight sodium bicarbonate solution and the mixture was then heated ^{to 83 ° C.} A mixture of 75.5 g of ethyl aylate, 44 g of methyl methacrylate and 6.3 g of hydroxypropyl methacrylate and a solution of 30 g of water and 0.5 g of potassium persulfate, as described in the preceding examples, were then added.

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The reaction was over after about 45 minutes. The received Emulsion contained about 46 weight percent Slloxane aorylate interpolymer solids and had a viscosity of 150 cP. A film of the copolymer was poured onto a metal plate and hardened. It had a pencil hardness of "HB" and a suppleness of the OT radius.

A good latex paint was made by mixing 100 g of the above-prepared siloxane-acrylate copolymer emulsion and 100 g of the pigment dispersion from Example 4 produced.

Example 7

To 1350 g of the siloxane emulsion from Example 6, 970 g of water, 10 g acrylic acid and 31 * 5 g of an anionic surface-active Admitted by means. This mixture was heated to about 85 ° C and then a mixture of 755 g xthylaorylate, 480 g of methyl methacrylate, 25 g of hydroxypropyl methacrylate and 26.7 g of acrylic acid, together with a solution of 300 g of water and 5 g of potassium persulfate, according to the examples described above, admitted. The reaction was over after about an hour. The emulsion was cooled to room temperature and 40 g Ammonium hydroxide added. The siloxane-acrylate mixed polymer emulsion had a viscosity of 1000 cP.

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Example 8

1,350 g of an aqueous Siloxanemulslon, with a Siloxanfeststoffgehalt of 40 wt -.% »Mol of IJ # MonomethyIsiloxaheinheiten, 35 MoIJi monophenylsiloxane, 2 M0I56 units of the formula CH ₂ -C (CH ₃₎ COO (CH ₂₎ SiO ₃ Z ₃ , 10 moles of diphenylsiloxane units and 40 moles of dimethylsiloxane units, 970 g of water, 10 g of acrylic acid, 31.5 g of an anionic surfactant were added and then the pH was adjusted by adding about 40 g of 7% by weight sodium carbonate. solution set between 5 and 6. The mixture was then heated to 85 ⁰ C and a Oemisch from 755 g ethyl acrylate, 505 g methyl methacrylate and 15.7 g acrylic acid, and a solution of 260 g water and 5 g of potassium persulfate, as added in the above described examples. The reaction was over after about an hour. The Sübxan aorylate mixed polymer mixture was cooled to room temperature and then 40 g of ammonium hydroxide were added.

Example 9

Were according to Examples 4 and 6 from one of the preceding Examples produced copolymers, paints produced and applied to aluminum or wood paneling, plastic

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plates or sheets of plywood having a size of 1.22 m 2.44 m χ χ 6,35 mm (4 ¹ χ 8 'χ 1/4 ") applied, prefabricated components were obtained, which can be used in interior and exterior.

Example 10

To 1000 g of an aqueous emulsion of a siloxane from 97 mol £ Dimethylsiloxane units and 3 MoISi methylvinylsiloxane units, with a siloxane solids content of about 30 percent by weight to the emulsion, 20 g of an anionic surfactant was added. The mixture was heated to 65 ° C and then JOO g of methyl methacrylate and 100 g of a 3 Oew.- Hydrogen peroxide solution was added. The addition of the acrylate and the peroxide was as described above Examples made. The reaction was over after about an hour and the product obtained was an emulsion of the siloxane-acrylate copolymer.

Example 11

Were 465 g of an aqueous siloxane emulsion from 30 moles of methyl Ethylslloxaneinhelten, 10 mol £ Methallylsiloxaneinheit, 5

Monocyclohexyleiloxane units, 40 Mo 1 # monomethylsiloxane

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units and 15 MoIJi monophenylsiloxane units, where the Emulsion had a siloxane solids content of about 30 wt. with 30 g of butyl ether, 30 g of methyl methacrylate and 5 g Azobisisobutyronitrile, mixed and reacted according to the method described above, was an emulsion of the siloxane-acrylate copolymer obtain.

Example 12

Were 100 g of an aqueous siloxane emulsion of 50 MolJi dimethylsiloxane units, 10 moles of octadecylmethylsiloxane units, 10 month! Methyl vinylsiloxane units, 10 mol # bromophenylmethylsiloxane units, 10 MoI ^ monobenzyleiloxane units and 10 MoI ^ Monovinylsiloxaneinhelten, the emulsion a Siloxane solids content of about 10% by weight, with 10 g of vinyl acrylate, 80 g ethyl methacrylate and 3.5 g benzoyl peroxide, according to the method described above, mixed and reacted, an emulsion of the siloxane-acrylate copolymer was obtained obtain.

Example 13

The procedure from Example 12 was repeated, but with the difference that the siloxane used was composed of 40 moles of dimethyl

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siloxane units, 5 Molji phenylmethylsiloxane units, 5 tolylmethylsiloxane units, 15 MoIJi monomethylsiloxane units, 30 MoIJi monovinylsiloxane units and 5 Molji units of the formula CgHcSCHgCH ₂ SiO, / g and as peroxide tert. Buty! Hydroperoxide was used, practically the same results were obtained.

Example 14

If 165 g of an aqueous siloxane emulsion of 40 mol £ dimethylsiloxane units, 10 mol # trifluoropropylmethylsiloxane units, 5 MoIJi mono vinylsiloxane units, 10 MoIJi monophenyliloxane units, 10 Mo1 # 3,3,3-trifluoropropylsiloxane units and 25 MoIJi monomethylsiloxane units, the emulsion had a siloxane solids content of about 50% by weight 200 g of methyl methacrylate, 135 g of perfluoroethylene aylate and 2 g Ammonium pereulfate, according to the procedure described above, mixed and implemented, was an emulsion of the siloxane-acrylate misoh polymer obtain.

Example 15

OemXe example 8 was a SiloMn-acrylate mixed polyiderisate-Snulslon produced, with the difference that the

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CHg-C (CHL) COO (CHg), SiO, / g units in the siloxane have been replaced by CHp-CHSiO ^ y ₂ units. This emulsion was used to bond two strips of cardboard that were about 1.27 cm (1/2 inch) overlap. After the adhesive had cured for various lengths of time, the strips were pulled apart at an angle of 180 ° to determine the force required to tear the bond apart. The results are shown in the table below, the required force being given in kg / cm (psi). For comparison, the same test was carried out with a commercially available glue (Craftsman), the results of which are also shown in the following table. The results proved that the Silcon acrylate melt polymer prepared above is a good adhesive.

Time in min. welder flax Silicone acrylate 3 4.64 (66) 4.08 (58) 4th 4.22 (60) 4.85 (69) 5 6.75 (96) 6.61 (94) 10 4.85 (69) 4.78 (68) 15th 8.15 (116) 7.03 (100) 20th 8.44 (120) 8.15 (116) 30th 9.77 (139) 12.42 (176) 60 10.69 (152) 9.56 (136)

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Example l6

The siloxane Aerylat copolymer emulsions of Examples 4 and 7 were grown to a copolymer solids content of 10 wt · - $ diluted with water.. These emulsions were
then applied to bleached hard paper. One part of the paper was air dried, while another part was two mi-. Nuts was dried at 121 ° C. For comparison, a
Part of the paper not dealt with. Then were 2.54 cm wide
Adhesive tape was applied to the papers, each adhesive strelfen having been rolled on 5 m * l with a 2.04 kg (4 1/2 pound) roller after application. The papers were placed in a wedge tester and the adhesive strip peeled off at an angle of 180 ° to the paper surface. the
The force required to separate the adhesive tape from the paper is measured in grams per band width. The results are
listed in the table below. These results indicate that these emulsions can be used as release coats.

Siloxane acrylate
Mixed polymer air dried dried 2 min
at 121 ° C Example 4 480 g 498 g Example 7 510 g 402 g none (for comparison) 796 g 796 g

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Example 17 Four mixtures were made from the following ingredients:

(A) 72 g dimethyldimethoxysilane, 79 g phenyltrimethoxysilane, 13 ^ 5 g ethyl acrylate, 78.3 g methyl methacrylate, 11.2 g 2-hydroxyethyl methacrylate and 2 g of acrylic acid.

(B) 258 g of water, 22 g of an anionic surfactant Means, 2.48 g acrylic acid and 5 g of a 7 wt .- # lgen sodium bicarbonate solution to adjust the pH of this mixture to about 4.

(C) 25 g of water and 1 g of potassium sulfate.

(D) 4 grams of ammonium hydroxide.

The solution (B) was placed in a three-shark flask, under Passing nitrogen through, heated feuf 80 ° C and then 25 wt .- ^ (C) were added. Then it was stirred within of 2 hours (A) and the remaining amount of (C) into the Misohung entered, the addition of (C) being carried out in three portions after the addition of respective amounts (A) became. When the reaction was complete, (D) was added to neutralize the emulsion. The product obtained was an excellent emulsion containing about 38.3 wt .- ^ of the siloxane aorylate Mlsohpolymerisates contained.

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Example 18 Four mixtures were made from the following ingredients:

(A) 302, j5 g ethyl aorylate, 176.5 g methyl methacrylate, 25.2 g 2-hydroxyethyl methacrylate and 7 * 55 g acrylic acid.

(B) 616 g of an aqueous emulsion, the 35 Qew.- £ of an emulsion " Polytnerized siloxane copolymer contained “that

from 60 mol (CH,) ₂ SiO units and 40

Consisted units and at least 0.5 wt -.% Hydroxyl and / or methoxyl groups contained, 9.36 g of an anionic surfactant, 310.32 g of distilled water, 10 g of a 7 wt £ aqueous Natriumbioarbonatlösung and 15 drops of sulfuric acid , the pH of this mixture being about 5.5.

(C) 100 g water and 2 g potassium persulfate.

(D) 16 grams of ammonium hydroxide.

The solution (B) was placed in a three-necked flask, under Passing nitrogen through, heated to about 85 ° C and then 25 wt .- ^ (C) were added. Then it was stirring, inside of about 2 hours (A) and the remaining amount (C) entered into the mixture, the addition of (C) in three por-

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after adding the corresponding amounts (A) was made. When the reaction was complete, (D) became the Neutralizing the emulsion added. The product obtained was an excellent emulsion containing about 46 parts by weight of the siloxane-acrylate copolymer contained.

Example 19

260 g of an aqueous siloxane emulsion of 30 MoIJi Methyläthylsiloxaneinheiten, 10 MoIJi Methallylsiloxaneinheiten, 5 MoIJi Monocyclohexylslloxaneinheiten, 40 MoIJi monomethylsiloxane units and 15 MoIJi monophenylsiloxane, wherein the emulsion has a Siloxanfeststoffgehalt of about 30 wt -% had (with about 2 parts by weight Ji hydroxyl groups). , adjusted with methacrylic acid to a pH of about 4.5 and then mixed and reacted with 3 S butyl acrylate, 1 g of 2-hydroxypropylmethyl methacrylate, 29 g of methyl methacrylate and 5 g of azobislsobutyronitrll according to the method described above, an emulsion of the siloxane acrylate was mixed -Mischpolymerisates obtained.

Example 20

Were 100 g of an aqueous siloxane emulsion of 50 mol of dimethylsiloxane units, 10 MoIJi ootamethyldecylsiloxane units

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th, 10 molj methylvinylsiloxane units, 10 molj bromophenylmethylsiloxane units, 10 moljt monobenzylslloxane units and 10 molj6 monovinylsiloxane units, the emulsion having a siloxane solids content of about 10 wt .-% (with at least 0.5 wt .- % hydroxyl groups), with hydrochloric acid. A value of about 5 was set and then mixed and reacted with 40 g of 2-ethylhexyl acrylate, 49 g of ethyl methacrylate, 1 g of hydroxyethyl acrylate and 3.5 S benzoyl peroxide, according to the method of the last three examples, an emulsion of the slloxane acrylate was Copolymer obtained.

Example 21

Were 485 g of an aqueous siloxane emulsion composed of 40 mol of dimethylsiloxane units, 10 mol of trifluoropropylmethylsiloxane units, 10 mol of monophenylsiloxane units, 10 mol of 5,3,3-trifluoropropylsiloxane units, the emulsion having a solid siloxane content of 30 mol of mono-propylsiloxane units as J) O weight jC (with about 5 parts by weight Ji hydroxyl groups) was adjusted with sulfuric acid to a pH of about 4 and then with 200 g of methyl methacrylate, 100 g Perfluoräthylaerylat, 35 g and 2 g Hydroxypropylaorylat Amrooniumpersulfat, mixed and reacted according to the last four examples, an emulsion of the siloxane-acrylate copolymer was obtained.

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example 22nd

Were 1000 g of an aqueous emulsion containing about JO wt -.% Of siloxane-containing, consisting essentially of dimethylsiloxane units and about 5 wt -.% Hydroxyl and / or ethoxyl contained with 20 g of dodecylbenzenesulfonic acid were mixed and the resultant mixture with 273 g of methyl methacrylate , 27 g of 2-hydroxy thyme methacrylate and 100 g of a 3% strength by weight hydrogen peroxide solution reacted according to the method of the above example, an emulsion of the siloxane-acrylate copolymer was obtained.

Example 23

Five mixtures were made from the following ingredients:

(A) 3 ^ 2 g of toluene

(B) 200 g of ethyl acrylate, 225 g of methyl methacrylate, 75 g of hydroxyethyl methacrylate, 10 g cumene hydroperoxide, and 5 g tert. Dodeoyl mercaptan.

(C) 250 grams of phenylmethylsiloxane resin containing about 10% by weight methoxyl groups Contained 166 g of cellosolve acetate and 0.76 g of tetrapropyl titanate.

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(D) 215 g cellosolve acetate

(E) 25 g of butanol

The solvent (A) was placed in a three-necked flask having a capacity of 2 liters and heated under reflux. Then were 25 wt .- # of the catalyzed acrylate monomer (B) was added and the mixture reacted under reflux (110 ° C.) for one hour. The remaining amount of the acrylate monomers was added in three portions, with each addition first for one hour was implemented. This was followed by the siloxane resin and catalyst (C) added, the solution heated under reflux and reacted further until the compatibility of the resin achieved and the viscosity, measured as the test cup flow number (DS cup), was about 8 seconds. Then the solvent (D) was added and when the temperature had reached 80 ° C, (E) was added. The product obtained was a solution which contained about 50% by weight of the siloxane-acrylate copolymer.

Example 2 »

The procedure from Example 23 was repeated, with the difference that that instead of the hydroxyalkyl acrylate used there, 2-hydroxypropyl methacrylate was used. It got practical get the same results.

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Example 25 ^%

Four blends containing the following ingredients were made manufactured:

(A) 1225 grams of toluene

(B) 375 g ethyl aorylate, 687 g methyl methaorylate, 187.5 g profe pylene glycol monoacrylate, 25 g cumene hydroperoxide and 12.5 g

tert. Dodecyl mereaptane.

(C) 625 g of a phenylmethylsiloxane resin, which is about 10% by weight Contained methoxyl groups, and 9.5 g of maleic anhydride.

(D) 403 g cellosolve acetate and 200 g propylene glycol methyl ether.

The solvent (A) was placed in a three-necked flask having a capacity of 2 liters and heated under reflux. Then, 25 wt were -.% Dee catalyzed acrylate monomers (B) was added and the mixture was reacted for one hour under Rüokfluß (110 ° C). The remaining amount of the acrylate monomers was added in three portions, each addition being reacted first for one hour. The siloxane resin and the catalyst (C) were then added, the solution was heated under reflux and reacted further until the compatibility of the resin was reached and the viscosity, measured as the test cup flow number (DS cup), was about

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- 31 -

Was 8 seconds. Then the solvent (D) was added. The product obtained was a solution that was about 50 Qew .- # des Contained siloxane acrylate misoh polymer.

Example 26

A ball mill was charged with 51.25 grams of aluminum silicate, 57 grams of calcium carbonates 17.25 g mica (325 mesh), 1 * 25 g phthalocyanine green, 4.1 g yellow iron oxide, 47 g titanium dioxide (rutile), 6.25 grams of an anionic surfactant and 350 grams one of the siloxane-acrylate mixed polymer emulsions of the examples 17-22, with a mixed polymer solids content of about 30-40 parts by weight, loaded, a mixture of 3.75 β succinic acid-ditpheny / mercury) dodecyleeter , 5 S ethylene glycol, 3.2 g of an organic de-foaming agent and 0.85 8 a silicone defoamer, and these ingredients are ground for 16 hours, creating latex paints with good hardness and flexible properties were obtained.

Were the colors described above on metal and aluminum siding When applied or coated on coils and cured at 204 ° C for about 15 minutes, excellent coatings were made obtain.

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Were the colors listed above with 12.4 g of a 50% strength by weight aqueous solution of hexamethoxymethylmelamine and 0.85 g a 50% strength by weight aqueous solution of ammonium toluenesulfonate mixed together, we obtained coating compounds, which are good primers for wood paneling and other building materials which require a low curing temperature. These coating masses can be reached in about 5 minutes at 149 ° C hardened.

Example 27

If the copolymers of Examples 23 and 24 were on metal plates, When applied to coils or aluminum cladding, excellent coatings were obtained. By adding pigments these coating compounds are good paints for cars and aluminum panels.

Example 28

A three-necked flask equipped with a stirrer, condenser, thermometer, nitrogen inlet tube and dropper and had a capacity of 500 ml, 100 g of anhydrous toluene was charged. The toluene was about 30 Mlnu-

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2 0 9 8 11/13 2 7

th heated under reflux, then a mixture of 70 g of methyl methaorylate, 20 g of ethyl acrylate, 13 g of hydroxypropyl methacrylate, 3 # 4 g of benzoyl peroxide and 1 g of tert. Dodecylneroaptan was added, the mixture being refluxed for 45 minutes after each addition. After the final reflux, the polyacrylate solution was cooled to about 50 ° C. Then 36 g of trifluoropropylmethyldlmethoxysilane were quickly added, the mixture was stirred for 20 minutes, and then 21 g of phenyltrimethoxysilane and 41 g of trifluoropropyltrimethoxysilane were quickly added and the mixture was again stirred for 20 minutes. Thereafter, within 20 minutes 6.2 g of water was slowly added in 15 g of methanol, and the resulting mixture is about (about 7o ° C) for one hour under RÜokfluS and then to a Peststoffgehalt of about 45 wt, the volatile components -.% Deducted .

A small sample of the resulting solution of the siloxane-acrylate melt polymer was placed in an aluminum dish, then left to stand in the air for two hours and then put in Heated in an oven at 150 ° C for an hour. The copolymer cured to a dry, hard, transparent film.

Example 29 Practically the same results were obtained when in the

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Procedure from Example 28, the following changes were carried out: Instead of toluene, benzene was used as the solvent, and azobisisobutyronitrile instead of benzoyl peroxide as a catalyst; trifluoropropyltrlmethoxysilane was also used used instead of the phenyltrimethoxyailane and only 5.4 g of water .

Example 30 )

308 g of an aqueous emulsion (while passing nitrogen) "with a Siloxanfeststoffgehalt of about 36 parts by weight ji, containing about 60 MoIJi (CH) ₂ units and about 40 MoIJ * CGH ₅ SiO _{/ ß} units were used for setting the pH value to about 2 with n-dodecylbenzenesulfonic acid in sufficient quantity. Then 0.2563 g of the silane of the formula HSCHgCHgCHg-S1 (OCH,) were added and the mixture was left to equilibrate for four hours.

To 308.2563 g of the above-prepared siloxane emulsion, which now also contained HSCHgCH ₂ CH ₂ SiO, g units, 4.68 g of a nonionic surfactant and 154.72 g of deionized water were added. This diluted emulsion was then mixed with 15 g of ethyl acrylate, 88.4 g of methyl methacrylate, 2.52 g of methacrylic acid and 1.26 g of acrylic acid. Which he"

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The emulsion held was introduced through a dropper into a three-necked flask which contained 50 g of deionized water and 1 g of potassium persulfate. After introducing about 20 wt -.% Of the emulsion of the flask contents at 70 ° C was heated (under Durohleiten of Stiokstoff). Then, while maintaining the temperature and with stirring, the remaining amount of the emulsion prepared above was added, which took about an hour. After the addition had ended, the contents of the flask were again heated to 90 ° C. for 30 minutes with stirring and then the pH was adjusted to 9.5 by neutralization with ammonium hydroxide.

Two latex paints were produced, one by adding pigment to a commercially available aorylate latex emulsion (Rohm Haas AC-34) and the other by adding pigment to the siloxane aerylate emulsion prepared above. The only difference between the two colors was the presence of the polymer. Two coatings were made on cedar wood panels Applied from these colors, each coating was left to dry, then the panels were placed in a weatherometer placed, which contained an unfiltered charcoal loan sheet. The plates became during different periods of time for their gloss retention (60 ° Gardner glass) and visually

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assessed with regard to chalk and shrinkage according to the following scales

Chalk shrinkage

10 no failure 10 no failure

9-8 tracks 9 tracks

7-6 easy 8-6 easy

5-3 medium 5-3 medium

2-0 strong 2-0 strong

The results of the weathering test are shown in the table below listed:

Mixed polymer gloss (hours) chalking (hours) shrinkage (hours)

ur
jump
lich 100 300 100 300 100 ; 5oo customary '*' 4th 2 1 5 4th 4th 3 Silicone aorylate 3 4th 4th 9 * 5 9.5 6th 6th ⁺ for comparison Example 31

A siloxane emulsion with a solids content of 35% by weight

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was made by emulsion polymerization of methoxysilanes * where the siloxanes are 40 mol # dimethylsiloxane units, 10 Mo 1 # diphenylsiloxane units, 15 mol £ monomethylsiloxane units and contained 35 MoIJi monophenylsiloxane units.

The emulsion prepared above was mixed cold with a commercially available standard acrylate paint emulsion, which had a solids content of 46% by weight, in order to produce various weight ratios of siloxane and acrylate. All colors were münzgrün pigmented, while achieving a Pigmentvolumgehaltes of 35 wt -.%, Two coatings of this color, each of which was air dried, were applied to plates which had been prepared from a phenolic resin impregnated paper with darüberllegenden plywood layers. No primer was used. These panels were placed in a weathering apparatus with a non-hard carbon arc. After various periods of time, the plates were assessed for their gloss resistance, as well as for chalk and shrinkage, as in the previous example. The results of the siloxane-acrylate mixtures and the weathering test are given in the following table:

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Weight "

Gloss (hrs.)

Chalks (hours) Shrinkage (hours)

Siloxane

Acrylate

0 100 ^ 00 j [00 1000 100? 00 700 1000 100 300 700 1000

10O

6th

25th 75 50 50 75 25th

6th

6th

5.5

10 10 10

10 10 10

10 10 10

⁺ For comparison

Claims (5)

Patent claims: 1. Coating compounds based on organopolysyl oxanes and other common additives, characterized in that that they the OrganopoIysiloxane in the form of (1) Copolymers consisting essentially of 25 to 90 Weight aorylates and 10 to 75 weight organopolyslloxanes consist, the organopolysiloxanes consisting essentially of 40 to 100 Mo1 $ RgSiÖ units and 0 to 60 MoIJi RSiO / g units are built up, where R is monovalent, means unsubstituted or substituted hydrocarbon radicals, or (2) Mixtures consisting essentially of 25 to 90 wt Consist of aorylates and 10 to 75 percent by weight of organopolyslloxanes, the organopolysiloxanes consisting essentially of 40 to 100 mol RgSiO units and from 0 to 60 mol * RSiO Units are built up, in which R has the meaning given, contain. _4o 20981 1/1327 2. Coating materials naoh claim 1 «characterized in that the copolymers (1) used are those which consist of 60 to 80 wt. Acrylic acid, methacrylic acid and / or their esters and 20 to 40 wt Organopolyelloxanes are composed of 43 to 63 MoIJ * RgSlO units and 33 to 33 MoIjG RSlO, ^ ₂ units, where R is methyl, ethyl, vinyl, phenyl or 3 * 3 # 3-trifluoropropyl radicals and the ratio of Vinyl radicals to Si atoms in the siloxanes is in the range from 0.02 to 0.3: 1. 3. Besohierungsinassen according to claim 1 and 2, characterized in that the copolymers (1) used are those consisting of 60 to 80 wt 20 mol £ Hydroxyalkylaorylaten are built up, and 20 to 40 Gew.-Jf organopolysiloxanes are composed of 43 to 63 MoIJi RgSiO units and 33 to 33 mol £ RSiO / _g units, where R has the meaning given in claim 2 and the siloxanes contain at least 0.3 wt. Ji Sl-bonded hydroxyl and / or alkoxy 1 groups. - 41 - 209811/1327 4. Beachiohtungsmaseen according to claims 1 to 5, d a d u r o h marked that the copolymers (1) can be used in the form of an aqueous emulsion. 5. Beechiohtungsmaseen according to claim 1, characterized in » that the Qemisohe (2) are used in the form of an aqueous emulsion. 209811/1327