DE4315207A1 - Oxime compounds as crosslinkers for copolymers - Google Patents

Description

The invention relates to a compound of the formula

wherein R¹ and R² independently of one another for a C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₀-C₁₀ cycloalkyl or a C₅-C₁₀ aryl radical, which also 1 to 3 non-adjacent nitrogen, oxygen or sulfur atoms contained as heteroatoms in the carbon chain or carbon ring and may be substituted by 1 to 3 C₁-C₄-alkyl or alkoxy groups, R¹ or R² can represent a hydrogen atom, or R¹ and R² together can be a bridge of 2 to 14 Form carbon atoms, and some of the carbon atoms can also be part of an aromatic ring system,
A and B represent an n- or m-valent organic radical, X the meaning of a linear or branched hydrocarbon chain of 2 to 12 carbon atoms, which may be represented by 1 to 3 non-adjacent oxygen atoms, sulfur atoms or nitrogen atoms or a C₅-C₁₀- Cycloalkylene or a C₅-C₁₀ arylene ring can be interrupted, and n or m represent an integer greater than 1.

The invention further relates to dispersions or solutions of radical polymers, polycondensates or polyadducts, which contain compounds of formula I, II or III.

In the case of copolymers which are used in coating compositions or adhesives fabrics are used, it is often networked viable copolymers. Through networking, e.g. B. Protective covers or adhesive coatings with good elastic Properties, high cohesion, d. H. inner strength, high che resistance to chemicals and solvents can be obtained.

For crosslinking, the copolymers are generally a Ver added wetting agent with functional groups in the copo lymerisat reacts.

Possible crosslinking agents are e.g. B. polyisocyanates, which with Hydroxyl or amino groups react.

From DE-A-35 21 618 there are corresponding aqueous adhesive accessories Horse riding known, in which dispersed in water Polyisocya nate aqueous dispersions of radical polymerized copolyme risate be added as a crosslinking agent. Similar adhesive Substance preparations are also in US-A 4,396,738 and DE-A-31 12 117.

However, the disadvantage of these aqueous preparations is that current storage stability. The polyisocyanate must therefore only be brief before its use as a crosslinking aid in water dis pergiert and mixed with the copolymer.

An increased storage stability can be achieved by reacting the isocyanate groups with blocking agents, e.g. B. oximes, caprolactam, pheno len, maleic dialkyl esters can be achieved. The received So-called blocked polyisocyanates hydrolyze in an aqueous dispersion sion only to a minor extent.

The subject of DE-A-38 07 555 is one that blocks with oximes tes diisocyanate, which is dispersed in water and itself suitable as an additive for polymers dispersed in water.

Crosslinking reactions, however, only occur after the Blocking agent at temperatures above approx. 130 ° C.  

Previously known aqueous adhesive preparations with polyiso Cyanates as crosslinking aids are therefore either not stable in storage and can therefore only be used as a 2-component system find or network only at high temperatures.

Storage stable, at room temperature after removing the solvent Crosslinking aqueous dispersions are known from EP-A-3516 knows. These dispersions contain polyhydrazides, which with in Copolymer copolymerized monomers with carbonyl groups react.

In EP-A-516 074 aminooxy derivatives are used as crosslinking agents for keto or Copolymers containing aldehyde groups are described. In EP-A-522 306 are polyisocyanates blocked with oximes Crosslinker for polymers containing carbonyl groups ben. Subject of the German patent applications P 42 19 385.0 and P 42 19 384.2 also contain crosslinkers for carbonyl groups polymers.

Basically there is a need for more at room temperature crosslinking dispersions to find alternatives to polyhydrazidever to be able to provide networking. Furthermore, these should Dispersions have good application properties, e.g. Legs good adhesion, especially wet grip on various Substrates.

The object of the present invention was therefore storage-stable dis persions or solutions of crosslinkable copolymers, which contain a crosslinking agent and can be crosslinked at room temperature are.

Accordingly, the compounds defined above, as well as Disper ions or solutions containing these compounds the.

The compounds of formula I, II or III are suitable as Vernet agent or adhesion promoter in dispersions or solutions of radical polymers, polycondensates or polyadducts ten.

The crosslinking of radicals containing keto or aldehyde groups Mix polymers, polycondensates or polyadducts with Ver wetting agents of formula I, II or III occurs when removed the liquid phase of the dispersion or solution.  

In the preparation of compounds I, II or III one can choose from go from oxime ether alcohols of the formula

The production of oxime ether alcohols is known and z. B. in G.B. Bachmann et al. T. Hokama, J. Am. Chem. Soc. 81: 4223 (1959) wrote.

R¹, R² and X have the meaning given above.

The variable X is preferably a linear one or branched hydrocarbon chain from 2 to 12, in particular 2 to 8 carbon atoms, which are optionally represented by 1 to 3, in particular 1 to 2 non-adjacent oxygen atoms or one C₅-C₁₀ cycloalkylene or a C₅-C₁₀ arylene ring may be interrupted can. It is particularly preferably a linear or branched hydrocarbon chain of 2 to 8 carbon atoms.

R¹ and R² are preferably independently water substance atom, a C₁ to C₆ alkyl group, C₁ to C₆ alkoxy group or a C₅-C₁₀ aryl radical, in particular a phenyl ring. in the In the case of the hydrogen atom, only one of the two radicals R² and R³ be a hydrogen atom.

The oxime ether alcohols can be added to polyisocyanates to compounds I (urethane formation of the hydroxyl group in IV with Isocyanate) or by transesterification with polycarboxylic acid esters or Carbonic acid esters to compounds II and III who implemented the.

The reaction of the oxime ether alcohols with polyisocyanates can after usual methods for the production of urethanes or polyurethane NEN done. In general, the reaction takes place at a tem temperature between 20 and 160 ° C, especially between 40 and 100 ° C. The reaction can not be reacted with isocyanate tive solvents or without solvents. Prefers no solvents are used. To speed up the re action of the isocyanates, the usual catalysts such. B. Dibutyltin dilaurate, stannous octoate or diazabicyclo- (2,2,2) -oc tan can also be used.  

Suitable polyisocyanates are organic compounds, the min have at least two free isocyanate groups. Preferably be Diisocyanates (X (NCO) ₂ used, where X is an aliphatic Koh hydrogen radical with 4 to 12 carbon atoms, a cycloa lipatic hydrocarbon residue with 6 to 15 carbon atoms men, an aromatic hydrocarbon residue with 6 to 15 Koh or an araliphatic hydrocarbon residue with 7 to 15 carbon atoms.

Examples of such diisocyanates are tetramethylene diisocyanate, Hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanate nato-cyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethyl- cyclohexane (IPDI), 4,4'-diisocyanatodicyclohexylmethane (HMDI), 4,4'-diisocyanato-dicyclohexylpropane- (2,2), 1,4-diisocyanatoben zole, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diiso cyanato-diphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate and mixtures consisting of these compounds. It it is also possible to use the known higher-functionality poly isocyanates or modified, known per se, for example wise carbodiimide, allophanate isocyanurate, urethane and / or To use polyisocyanates containing biuret groups. Called be z. B. polyisocyanate containing isocyanurate or biuret groups cyanates, especially those based on 1,6-diisocyanatohexane and / or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcy clohexane or reaction products of polyisocyanates with more term, especially 2- to 5-valent alcohols. Are preferred aliphatic alcohols with a total of 2 to 8 carbon atoms, such as ethyl lenglycol, 1,4-butanediol, 1,2-propanediol, glycerin, trimethylol propane or pentaerythritol.

Hydrophilically modified polyisocyanates are also suitable. These are self-dispersible in water, so that for dispersion tion on emulsifiers and dispersing aids largely ver can be waived. Self-dispersible polyiso are known cyanates with non-ionic groups, in particular reaction pro products of polyisocyanates with polyalkylene ether alcohols such as e.g. B. are described in EP-A-206 059. Also by installing ionic groups or convertible ionic groups Groups become self-dispersible polyisocyanates. The latter are e.g. B. from DE-A-41 13 160 or DE-A-40 01 783 known.

Hexamethylene diisocyanate, IPDI, HMDI, 2,4-diiso are preferred cyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphe nylmethane and mixtures thereof are used.  

The radical A in formula I is accordingly preferably derived from egg from the polyisocyanates mentioned.

The transesterification of the polycarboxylic acid esters or the carbonic acid esters with the oxime ether alcohols in the temperature range of 70 to 150 ° C, preferably at 100 to 130 ° C, where as Catalysts e.g. B. the above-mentioned tin salts or titanium acid can use ester.

The preferred polycarboxylic acid used for the transesterification esters and carbonic acid esters are with lower alcohols such as metha nol or ethanol esterified.

The oximes can be used to prepare compounds II and III theralkohole IV also with the corresponding polycarboxylic acid ride or react with phosgene. In this way, the Reaction temperatures to values lower than room temperature drop.

Preferred polycarboxylic acid esters for the reaction are diesters, in particular C₄-C₁₂-alkanedioic acid ester or benzene or naphthol dicarboxylic acid esters.

In formula II, m is therefore preferably 2. For the radicals R¹, R² and X applies to what has been said above. The rest of B in Formula II conducts preferably from one of the polycarboxylic acid esters mentioned.

The dispersion or solution preferably contains which compound gene I or II are added as a crosslinking agent, a polymer risat, polycondensate or polyadduct containing 0.001 to 20% by weight, preferably 0.01 to 10% by weight and very particularly preferably 0.05 up to 4% by weight of aldehyde groups -CHO- or keto groups -CO- be stands.

It can be z. B. a radical polymerized Copolymer, a polyester as a polycondensate or a poly act urethane as a polyadduct.

In the case of the radically polymerized copolymers, these are Aldehyde or keto groups, preferably by ethylenically unsaturated Compounds containing these groups are polymerized siert.

These are preferably ethylenically unsaturated compounds having one or two aldehyde or keto groups or one aldehyde and one keto group and a free-radically polymerizable olefinic double bond (hereinafter referred to as monomer a))
In the case of a polyester z. B. monoalcohols, diols, monocarboxylic acids or dicarboxylic acids, in the case of a poly urethane it can be, for. B. are mono-, diisocyanates or also monoalcohols or diols which contain aldehyde or keto groups.

As mono alcohols such. B. hydroxyacetone, hydroxybenzal dehyde, acetoin and benzoin.

Suitable monocarboxylic acids are e.g. B. ketocarboxylic acids such as Brenz grape acid or levulinic acid.

Polyurethane dispersions containing keto groups are known, for. B. from DE-A-38 37 519, EP-A-332 326 and EP-A-442 652.

Furthermore, compounds with aldehyde or keto groups in the Polymers, polycondensates or polyadducts not only as loading part of the main chain, but also through implementation with reak tive groups in the main polymer chain to the polymers, poly condensates or polyadducts are bound.

A free-radically polymerized copolymer is preferred ches from the monomers a), which ent aldehyde or keto groups hold, and monomers b) and c).

As monomers a) come, for. B. acrolein, methacrolein, vinyl alkyl clays with 1 to 20, preferably 1 to 10 carbon atoms in Alkyl radical, formylstyrene, (meth) acrylic acid alkyl ester with one or two keto or aldehyde, or one aldehyde and one keto group in the alkyl radical, the alkyl radical preferably totaling 3 comprises up to 10 carbon atoms, e.g. B. (meth) acryloxyalkyl propa nale, as described in DE-A-27 22 097. The white tere are also N-oxoalkyl (meth) acrylamides such as z. B. from US-A-4 226 007, DE-A-20 61 213 or DE-A-22 07 209 are known.

Acetoacetyl (meth) acrylate and acetoacetoxye are particularly preferred thyl (meth) acrylate and especially diacetone acrylamide.

The main monomers b) are in particular in the copolymer 20 to 99.99, preferably 60 to 99.9 and particularly preferably 80 up to 99.5% by weight, based on the copolymer.  

Monomers b) are esters of acrylic or methacrylic acid from 1 up to 20 C-containing alkyl alcohols in question. As such Alcohols may be mentioned methanol, ethanol, n- or i-propanol, n-, s- and t-butanol, n-pentanol, isoamyl alcohol, n-hexanol, octanol, 2-ethylhexanol, lauryl and stearyl alcohol.

Good results are obtained with (meth) acrylic acid alkyl esters with a C₁-C₁₀ alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyla crylate, ethyl acrylate and 2-ethylhexyl acrylate.

In particular, mixtures of the (meth) acrylic acid alkyl esters suitable.

Vinyl esters of carboxylic acids with 1 to 20 carbon atoms also come such as vinyl laurate, stearate, vinyl propionate and vinyl acetate Consideration.

Coming as vinyl aromatic compounds with up to 20 carbon atoms Vinyl toluene, a- and p-styrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene. Examples for ethylenically unsaturated nitriles are acrylonitrile and meth acrylonitrile.

The vinyl halides are substituted with chlorine, fluorine or bromine ethylenically unsaturated compounds, preferably vinyl chloride and Vinylidene chloride.

As non-aromatic hydrocarbons with 2 to 8 carbon atoms and are at least two conjugated olefinic double bonds Called butadiene, isoprene and chloroprene.

The monomers b) can in particular also be used in a mixture be, above all, to desired glass transition temperatures of the Adjust copolymer.

As another, d. H. not copolymerized under a) and b) bare monomers c) come z. B. esters of acrylic and methacrylic acid of alcohols with 1 to 20 carbon atoms, which in addition to the oxygen atom contain at least one further heteroatom in the alcohol group and / or which contain an aliphatic or aromatic ring ten.

May be mentioned for. B. 2-ethoxyethyl acrylate, 2-butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylamino ethyl (meth) acrylate, (meth) acrylic acid aryl, alkaryl or cyclo alkyl esters, such as cyclohexyl (meth) acrylate, phenyl  ethyl (meth) acrylate, phenylpropyl (meth) acrylate or acrylic acid esters of heterocyclic alcohols such as furfuryl (meth) acrylate.

In addition, there are other comonomers such as (meth) acrylamide and their derivatives substituted on nitrogen with C₁-C₄-alkyl called.

Hydroxy-functional Comono are also of particular importance mere, e.g. B. (meth) acrylic acid-C₁-C₁₅ alkyl ester, which by a or two hydroxy groups are substituted. In particular from Be Interpretation as hydroxy-functional comonomers are (meth) acrylic acid re-C₁-C₈-hydroxyalkyl esters, such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl (meth) acrylate.

The use of comonomers with salt-forming groups emp is missing z. B. for the production of self-dispersible Copolymers which, for. B. suitable for aqueous secondary dispersions are not. Comonomers with salt-forming groups are special Itaconic acid, acrylic acid and methacrylic acid.

The proportion by weight of the other comonomers in the copolymer can in particular 0 to 50%, preferably 0 to 20% and very particularly which are preferably 0 to 10% by weight.

The proportions of the monomers a), b) and c) add up 100% by weight.

The proportion of the monomers a) is chosen so that the above specified content of aldehyde or keto groups in the copolymer is present.

The copolymer is generally prepared by radical polymerization. Suitable polymerization methods, such as bulk, solution, suspension or emulsion polymers tion are known to the expert.

The copolymer is preferably obtained by solution polymerization with subsequent dispersion in water or especially before produced by emulsion polymerization, the copoly merisat is obtained as an aqueous dispersion.

The comonomers can be used as usual in emulsion polymerization in the presence of a water-soluble initiator and an emulga tors are polymerized at preferably 30 to 95 ° C.  

Suitable initiators are e.g. B. sodium, potassium and ammonium persulfate, tert-butyl hydroperoxides, water-soluble azo compounds or redox initiators.

As emulsifiers z. B. Alkaline salts of longer chain fat acids, alkyl sulfates, alkyl sulfonates, alkylated aryl sulfonates or alkylated biphenyl ether sulfonates.

In addition, reaction products of alky come as emulsifiers lenoxides, especially ethylene or propylene oxide with fat alcohols, acids or phenol, or alkylphenols.

In the case of aqueous secondary dispersions, the copolymer first by solution polymerization in an organic solvent prepared and then with the addition of salt formers, e.g. B. from ammonia to carboxylic acid groups Copolymers, in water without the use of an emulsifier or Dispersing aid dispersed. The organic solvent can be distilled off. The production of aqueous secondary dispersions is known to the skilled worker and z. B. in DE-A-37 20 860 described.

To adjust the molecular weight in the Polymerisa tion controller can be used. Are suitable for. B. -SH containing Compounds such as mercaptoethanol, mercaptopropanol, thiophenol, Thioglycerin, thioglycolic acid ethyl ester, thioglycolic acid methyl ster and tert-dodecyl mercaptan.

The type and amount of the comonomers is conveniently so chosen that the copolymer obtained has a glass transition temperature temperature between preferably -60 and + 140 ° C. Depending on whether hard or Soft coatings are desired by choosing the mono high or low glass transition temperatures. The Glass transition temperature of the copolymer can be done according to the usual methods such as differential thermal analysis or differential Scanning calorimetry (see e.g. ASTM 3418/82, so-called "midpoint tem perature ").

The dispersion or solution contains as an adhesion promoter or as a crosslinking agent a compound of formula I or II.

The solids content of the dispersion or solution according to the invention is preferably between 20 and 90% by weight, in particular between 30 and 70 wt%.  

The dispersions or solutions according to the invention are suitable as Coating agent for different substrates with art fabric, wood or metal surfaces or z. B. for textiles, Nonwoven fabrics, leather or paper. They are also suitable for An Applications in construction chemistry, e.g. B. as adhesives, sealants, Binder or the like. With the coatings it can be e.g. B. to paint, protective coatings or adhesive coatings act.

In particular, an aqueous dis persion of a radically polymerized, especially one Copolymer containing keto and / or aldehyde groups is suitable.

The aqueous dispersion can also be organic, preferably with Contain water-miscible solvents as auxiliary solvents.

The dispersion or solution according to the invention can, depending on the use for the intended purpose contain auxiliary agents and additives. For this ge fillers such as quartz flour, quartz sand, for example, hear high disperse silica, heavy spar, calcium carbonate, chalk, dolo with or talcum, often together with suitable wetting agents such as e.g. B. polyphosphates such as sodium hexamethaphosphate, naphthalenesul fonic acid, ammonium or sodium polyacrylic acid salts used , the wetting agents generally from 0.2 to 0.6% by weight, based on the filler.

If desired, fungicides for preservation are generally used NEN in amounts of 0.02 to 1 wt .-%, based on the total dis persions or solution used. Suitable fungicides are included for example phenol or cresol derivatives or organotin Links.

The dispersions or solvents according to the invention are particularly suitable solutions, especially as an aqueous dispersion of a radical Copolymer, as a sealant or adhesive, especially z. B. as laminating adhesive for the production of composite films and Glossy films. As an adhesive, the dispersions can be used in addition to the above called additives still special, in adhesive technology Contain usual auxiliaries and additives. These include at for example thickeners, plasticizers or sticky Resins such as. B. natural resins or modified resins such as Ko rosin esters or synthetic resins such as phthalate resins.  

Dispersions that are used as an adhesive contain particularly preferably alkyl (meth) acrylates as monomers b) im Copolymer.

The glass transition temperature of the copolymers is Ver Use as an adhesive preparation preferably to values between 0 and set at -40 ° C.

When used as an adhesive, the dispersions show an outstanding amount very good adhesion, especially wet grip.

The pH of the dispersion is preferably between 2 and 9 set because the crosslinking reaction with the Copoly merisates can be catalyzed with acid.

The dispersions or solutions according to the invention, which Verbin containing formulas I are stable in storage. The networking reaction, e.g. B. with keto and / or aldehyde groups already occurs Room temperature when removing the liquid phase, e.g. B. Cursed water.

By increasing the temperature z. B. at 30 to 100 ° C can the cursing water accelerated.

In principle, it is also possible when coating substrates Lich, a dispersion or solution of the polymer, polycondensation sats or polyadducts, which the compounds of formula I, II or III not included to be applied to a surface the connections previously in a separate operation of the formula I, II or III were applied.

In this case, the compounds act as so-called primers.

After application of the dispersion or solution, crosslinking occurs or an improvement in liability is evident.  

Examples I. Production of crosslinkers V1-V4

1. succinic acid bis- [O- (2-hydroxyethyl) acetone oxime ester] (V1):

A mixture of 292 g (2.00 mol) dimethyl succinate, 515 g (4.40 mol) of O- (2-hydroxyethyl) acetone oxime and 16.0 g of tetra Isopropyl orthotitanate (catalyst) was raised to 120 to 5 hours Heated to 128 ° C. During this time, the methanol formed over a 15 cm packed column (stainless steel nets) with falling Vacuum (700 to 50 mbar) distilled off. Then distilled the excess oxime ether alcohol in a vacuum. from 0.1 mbar. The distillation residue was evaporated in a Sambay evaporator at 0.3 mbar and with a heater liquid temperature of 168 ° C 525 g (83% yield) product won.

Elemental analysis:
Calculated:
C 53.15; H 7.65; N 8.86; O 30.34;
Found:
C 53.0; H 7.8; N 8.8; O 30.4.

The structure of the compound is consistent with the 1 H-NMR spectrum sound.

2. Carbonic acid bis- [O- (2-hydroxyethyl) acetone oxime ester] (V2):

A mixture of 291 g (2.49 mol) of O- (2-hydroxyethyl) acetone oxime, 147 g (1.24 mol) of diethyl carbonate and 10 g of tetraisopropyl orthoti Tanate was heated to 125 to 130 ° C for 6 hours and distilled in during this time, the ethanol produced over a 60 cm packed body lonne (stainless steel networks) at 500 to 50 mbar. The reaction ge was mixed by fractional vacuum distillation with a  10 cm packed column cleaned: yield 167 g, Bp = 117-120 ° C / 0.3 mbar.

Elemental analysis:
Calculated:
C 50.76; H 7.75; N 10.76; O 30.73;
Found:
C 50.7; H 7.8; N 10.6; O 30.8.

The 1 H-NMR spectrum of the substance is in agreement with the structure sound.

3. Oxime urethane from hexamethylene diisocyanate (V3):

168 g (1.0 mol) of hexamethylene diisocyanate were introduced. At 50 ° C 234 g (2.0 mol) of O- (2-hydroxyethylacetone oxime) were added within Added dropwise for 60 min.

After cooling to 20 ° C., a crystalline solid was obtained.

4. Oximurethane based on a hydrophilically modified polyiso cyanate (V4):
300 g of a hydrophilically modified trimer made from hexamethylene diisocyanate (1.25 mol NCO) were initially introduced. 146 g (1.25 mol) of O- (2-hydroxyethylacetone oxime) were added dropwise at 50 ° C. in the course of 60 minutes, giving a viscous oil.

II. Preparation of dispersions D1 to D3 Dispersion D1

In a reaction vessel with a stirrer and two inlet vessels (Zu Run 1 and feed 2) were 200 g of demineralized water, 37 g of the Zu Run 1 (see below) and 20 g of feed 2 and opened Heated to 85 ° C. After 15 minutes it became uniform within 2 hours feed 1 and feed 2 evenly within 2.5 h added to the reaction vessel. After the last addition of initiator (Feed 2), the dispersion was stirred at 85 ° C. for a further hour.  

Feed 1: (this feed is stirred during the polymerization)

107.5 g of demineralized water
400 g of ethyl acrylate
90 g methyl methacrylate
50 g of 20% by weight aqueous diacetone acrylamide solution
50 g 20% by weight solution of the sodium salt of p-dodecyl diphenyl ether disulfonate in water (emulsifier)
50 g 20% by weight solution of the reaction product of p-isononylphenol with approx. 50 mol ethylene oxide in water (emulsifier)

Inlet 2:
100 g of demineralized water
3 g sodium persulfate.

The dispersions D2 to D3 were prepared in a corresponding manner poses. The composition of the respective copolymers is in Table 1 given.

Production of dispersions D4 and D5

In a reaction vessel with a stirrer and two inlet vessels (Zu Run 1 and feed 2) 400 g of demineralized water, 150 g of the Feed 1 (see below), 25 g of a 20% by weight aqueous solution a fatty alcohol etherified with 18 ethylene oxide units (C₁₆ / C₁₈), 5 g of a 20 wt .-% aqueous solution of disodium salt of p-dodecyldiphenyl ether disulfonate and 50 g of zu Run 2 submitted and heated to 85 ° C. After 15 minutes it would be in feed 1 evenly within 2 h and within 2.25 h, feed 2 was uniformly added to the reaction vessel. After the complete addition of initiator (feed 2), the dis persion stirred for a further 2 h at 85 ° C.  

Feed 1: (is stirred during the polymerization)

368 g of demineralized water
50 g 20% by weight aqueous solution of a fatty alcohol etherified with 18 ethylene oxide units (C₁₆ / C₁₈) (emulsifier)
75 g 20% by weight aqueous solution of the disodium salt of dodecyl diphenyl ether disulfonate (emulsifier)
38 g 2- (acetoacetoxy) ethyl methacrylate (AAEM)
30 g 50% by weight aqueous solution of acrylamide
27 g methacrylic acid
300 g methyl methacrylate
700 g of n-butyl acrylate

Inlet 2:
200 g of demineralized water
5 g sodium persulfate.

The preparation of the copolymer dispersion D5 corresponds to that of D4, with 38 g of acetoacetoxyethyl methacrylate in feed 1 (AAEM) against an equimolar amount (30 g) of diacetone acrylamide (DAA) were exchanged.

Networkability (testing by swelling behavior and determination of the extractable parts)

The dispersions were the amounts given in Table 2 added to crosslinker. 10 g of the dispersions were filmed and the films dried at room temperature for 1 week. Subsequently was the swelling behavior as a measure of the degree of crosslinking water films in tetrahydrofuran examined by approx. 1 g of ver filmed samples in tetrahydrofuran stored for 24 hours and the sol was measured in% by weight (results in Tab. 2).

In the case of cross-linked polymers, it occurs through the absorption of solvents swelling. With increasing degree of crosslinking, the source less because less solvent from the closely cross-linked poly can always be included. Polymers that are not or hardly crosslinked are largely dissolved or swollen by solvents in the presence of a small number of networking points overly strong.

The extractables were determined by reweighing Room temperature after drying in a drying cabinet at 80 ° C during 4 h.  

In the tests according to Table 3, the drying time was Movies only 4 days instead of a week.

Table 1: Composition of the copolymers D1-D3

Table 2: Test results D1-D3

Table 3: Test results D4-D5

Claims (9)

1. Compound of the formula wherein R¹ and R² independently of one another for a C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₅-C₁₀ cycloalkyl or a C₅-C₁₀ aryl radical, which also 1 to 3 non-adjacent nitrogen, oxygen or sulfur atoms contain as heteroatoms in the carbon chain or carbon ring and can be substituted by 1 to 3 C₁-C₄-alkyl or alkoxy groups, R¹ or R² can represent a hydrogen atom, or R¹ and R² together a bridge of 2 to 14 carbon form atoms, where some of the carbon atoms can also be part of an aromatic ring system,
A and B represent an n- or m-valent organic radical, X the meaning of a linear or branched hydrocarbon chain of 2 to 12 carbon atoms, which, if appropriate, by 1 to 3 non-adjacent oxygen atoms, sulfur atoms or nitrogen atoms or a C₅- C₁₀-cycloalkylene or a C₅-C₁₀ arylene ring can be interrupted, and n and m represent an integer greater than 1. 2. Dispersion or solution of a radical polymer, Po lykondensats or polyadducts containing a compound of Formula I, II or III. 3. Dispersion or solution of a radical polymer, Po lycondensate or polyadduct, which is 0.001 to 20 wt .-% consists of aldehyde groups - CHO - or keto groups - CO -, containing a compound of formula I, II or III. 4. Dispersion or solution according to claim 2 or 3, containing as a radical polymer copolymers with a glass transition temperature between -60 and + 140 ° C, wherein the copolymer

• a) at least one comonomer with at least one aldehyde or keto group,
• b) 20 to 99.99 wt .-% of at least one C₁- to C₂₀-alkyl (meth) acrylate, a vinyl ester of 1 to 20 carbon atoms containing carboxylic acids, a vinyl aromatic with up to 20 carbon atoms, an ethylenically unsaturated nitrile with 3 to 6 carbon atoms, a vinyl halide or a non-aromatic hydrocarbon with 4 to 8 carbon atoms and at least 2 conjugated double bonds, and
• c) there is 0 to 50% by weight of at least one further ethylenically unsaturated monomer,

wherein the content of the monomer a) is chosen so that the Copolymer from 0.001 to 20 wt .-% of carbonyl groups -CHO- or keto groups -CO- and the monomers a), b) and c) add up to 100% by weight. 5. Use of a dispersion or solution according to one of the An Proverbs 2 to 4 as a coating agent. 6. Use of a dispersion or solution according to one of the An say 2 to 4 as an adhesive. 7. Coated substrates available using a Dispersion or solution according to one of Claims 2 to 4. 8. Gluing, available using a dispersion or Solution according to one of claims 2 to 4.