KR20070047312A - Products resulting from polymer-analogous reactions - Google Patents

Abstract

The present invention relates to products resulting from polymer-like reactions comprising aldehydes and ketones and monomers that can be polymerized in free-radical reactions, methods for preparing them, and uses thereof.

Polymer-like reaction products.

Description

Product produced from polymer-like reactions {PRODUCTS RESULTING FROM POLYMER-ANALOGOUS REACTIONS}

The present invention relates to products of polymer-like reactions, methods for preparing the same and uses thereof.

EP 0 346 788, EP 0 377 199, and DE 102 06 987 disclose radiation-sensitive compounds, preferably containing polymer derivatives containing acetophenone as a sub-residue and / or containing acetophenone residues. have.

EP 0 346 788 describes ethylenically unsaturated, copolymerizable irritable organic compounds having at least one (meth) acrylic ester group. EP 0 377 199 describes UV-crosslinkable compositions based on (meth) acrylic ester copolymers. DE 102 06 987 describes vinyl ether derivatives.

None of these documents mention polymer-like reactions of ketone-aldehyde resins containing acetophenone by free-radical polymerization.

Ketone-aldehyde resins are used in coating materials, for example as additive resins, to improve certain properties such as gloss, hardness or scratch resistance.

Ketone-aldehyde resins generally have hydroxyl groups and can therefore be crosslinked only with, for example, polyisocyanates or amine resins. These crosslinking reactions are generally initiated or accelerated by heat. For example, additional functional groups, such as amino and / or carboxyl groups, can only be inserted through special monomers, which are difficult to obtain on an industrial scale (although actually obtainable).

Polymer-like reactions of cyclohexanone-formaldehyde resins with azo compounds are described in Die Angewandte Makromolekulare Chemie, 168 (1989), p. 129 ff. This method is expensive and inconvenient on an industrial scale. Since azo compounds are used, this manufacturing method is burdened with considerable safety problems. In addition, because azo compounds are thermally unstable, they are expensive and inconvenient for storage.

Journal of Applied Polymer Science, Vol. 72 (1999), p. 927 ff., Describe cyclohexanone- and acetophenone-formaldehyde resins that become photoactive by attachment of 10 mol% of benzoin or benzoin butyl ether. This synthesis method is carried out in two steps that take 16 hours or more, which is expensive and inconvenient. Full conversion is not guaranteed and volatile components may be present. In addition, low molecular weight mass fractions degrade the performance profile of higher coatings in terms of mechanical properties. In addition, only polymer-like reactions using styrene as monomers are described. The weathering properties of polymers containing styrene are known to be inadequate.

It is an object of the present invention to prepare products of ketone-aldehyde resins and unsaturated monomers which have additional functional groups in addition to carbonyl and hydroxyl groups and which are distinguished by different solubility compared to the original resin.

It is a further object of the present invention to develop a method for preparing the product which allows for various changes in the properties described above in a simple manner.

The product is suitable for use in coating materials, adhesives, inks including print inks, gelcoats, varnishes, glazes, pigment pastes, filler compounds, cosmetics, sealants and / or insulators.

Surprisingly, it has become possible according to the claims of the present invention through polymer-like reactions by UV light irradiation of ketone-aldehyde resins containing unsaturated monomers and derivatives of acetophenone and / or acetophenone.

Suitable ketone-aldehyde resins are polymer reaction products using aldehydes of the general formula (I) and ketones of the general formula (II) below and, if necessary, additional ketones.

Wherein R = H, unbranched or branched C1-C12 alkyl radicals, aryl radicals

In which R ₁ = Unbranched alkyl radical of 1 to 12 carbon atoms

R ₂ is

Wherein R ₃ to R ₇ = H, alkyl, OCH ₃ , OC ₂ H ₅ , Cl, F, COO (C ₁ -C ₃ alkyl).

In addition, R ₄ to R ₆ may be OH or SH.

Suitable unsaturated monomers are all kinds of unsaturated monomers that can be polymerized in free radical reactions.

Therefore, the present invention

A) an aldehyde of formula (I)

B) at least one ketone of formula II,

C) if necessary, additionally a CH-acidic ketone, and

D) Inks, including coating materials, adhesives, print inks, gelcoats, varnishes, glazes, pigment pastes, filler compounds, containing significant amounts of reaction products of one or more unsaturated monomers that can be polymerized in free radical reactions, Provided are polymer reaction products for use as main substrates or additives in cosmetics, sealants and / or insulators.

<Formula I>

Wherein R = H, unbranched or branched C1-C12 alkyl radicals, aryl radicals

<Formula II>

In which R ₁ = Unbranched alkyl radical of 1 to 12 carbon atoms

R ₂ is

Wherein R ₃ to R ₇ Is H, alkyl, OCH ₃ , OC ₂ H ₅ , Cl, F, COO (C ₁ -C ₃ alkyl).

In addition, R ₄ to R ₆ may be OH or SH.

Suitable aldehyde components A) of formula (I) are generally for example unbranched or branched aldehydes, for example formaldehyde, benzaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valerianaldehyde, And dodecanal. In general, it is possible to use all kinds of aldehydes mentioned in the literature as being suitable for the synthesis of ketone-aldehyde resins. However, it is preferable to use formaldehyde and benzaldehyde alone or in combination.

The required formaldehyde is generally used as an aqueous or alcohol (eg methanol or butanol) solution at a concentration of about 20% to 40% by weight. The use of other forms of formaldehyde, for example para-formaldehyde or trioxane, is also possible.

Examples of ketones B) of formula (II) are acetophenones and ring-substituted acetophenone derivatives such as hydroxy-, methyl-, ethyl-, tert-butyl-, and cyclohexyl-acetophenone.

In addition, in addition to component B), additional ketones C), for example, acetone, 4-tert-butyl methyl ketone, methyl naphthyl ketone, hydroxynaphthyl ketone, methyl ethyl ketone, heptane-2-one, pentane- 3-one, methyl isobutyl ketone, propiophenone, cyclopentanone, cyclododecanone, a mixture of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexa All kinds of alkyl-substituted cyclohexanones having a paddy and at least one alkyl radical containing a total of 1 to 8 hydrocarbon atoms may be present alone or in a mixture in a mixture. Examples that may be referred to as alkyl-substituted cyclohexanones include 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

Benzoin and / or alkyl ethers such as methyl, ethyl, propyl and isobutyl ethers of benzoin can be used in component C) in small amounts (up to 9.9 mol%) on the basis of ketone components.

However, it is possible to use all kinds of ketones, more generally all kinds of CH-acidic ketones mentioned in the literature as additional ketones C), which are generally suitable for ketone resin synthesis and ketone-aldehyde resin synthesis.

Formaldehyde and / or benzaldehyde and acetophenone, hydroxy-, methyl-, tert-butyl- and / or cyclohexyl-acetophenone and, if necessary, 4-tert-butyl methyl ketone, cyclohexanone, 4-tert-butylcyclo Preference is given to reaction products of hexanone, 3,3,5-trimethylcyclohexanone and / or heptanone.

Polymer synthesis from components A), B), and, if necessary, C), occurs in a condensation reaction in a basic medium in a manner known in the literature (Dieter Stoye, Werner Freitag, Lackharze, Chemie, Eigenschafen und Anwendungen, Carl Hanser Verlag, Munich , Vienna, 1996, p. 164 ff .; US-B 2 540 885; US-B 2 540 886; DE-C 11 55 909; DL-PS 12 433; DE-C 13 00 256; DE-C 12 56 898; DE 33 24 287; DE 103 38 580.0; EP 0 007 106; DE 12 65 415).

Reaction condition:

menstruum:

The reaction can be carried out using an auxiliary solvent. Examples that proved to be suitable include alcohols such as methanol or ethanol. It is also possible to use water soluble ketones such as methyl ethyl ketone or acetone as auxiliary solvents (they are subsequently introduced into the resin by reaction).

base:

The products of A), B) and also C), as described herein, are prepared using from 0.05 to 10 mol% (based on the ketone used) of one or more bases. Preferred are (metal) hydroxides, for example hydroxides of the cations NH ₄ , Li, Na and K. Particular preference is given to using potassium hydroxide and / or sodium hydroxide.

Ratio of Ketones to Aldehyde Ingredients:

The sum of the ketone component (B) + C) and the aldehyde component A) can vary from 1: 0.9 to 1: 4. However, it is preferred that the ketone / aldehyde ratio is 1: 1 to 1: 2.5. The ketone component and the aldehyde component may be added in pure form or in a solvent or water soluble form as mentioned above. Particular preference is given to using water-soluble or alcohol formaldehyde solutions, trioxane and / or para-formaldehyde and / or benzaldehyde.

Ratio of ketones B) to component C) :

Based on the total amount of ketones B) and C) used, the ketone component B) may be present at 10 to 100 mol%, preferably 20 to 100 mol%, more preferably 25 to 100 mol%. Ketone component C) may be used at 0 to 90 mol%, preferably 0 to 80 mol%, more preferably 0 to 75 mol%.

Depending on the nature of the ingredient and its proportions to other ingredients, additional properties such as properties such as solubility in solvents of different polarities, compatibility with other raw materials, softening ranges, glass transition temperatures or OH groups in a simple manner It is possible to change the functional groups.

The reaction products of A), B) and, if necessary, C) react polymer-likely with component D) by irradiation with UV light.

Suitable component D) is generally all kinds of unsaturated monomers which can be polymerized in a free-radical reaction.

Maleic acid, fumaric acid, acrylic acid and / or methacrylic acid, C ₁ -C ₄₀ alkyl esters and / or cycloalkyl esters, hydroxyalkyl acrylates and / or hydroxyalkyl methacrylates of methacrylic acid and / or acrylic acid, Glycidyl methacrylate, glycidyl acrylate, 1,2-epoxybutyl acrylate, 1,2-epoxybutyl methacrylate, 2,3-epoxycyclopentyl acrylate, 2,3-epoxycyclopentyl meta Preference is given to using acrylates, acrylated polyethers alone or in mixtures, and also allowing the presence of styrene and / or derivatives thereof at low levels. Similar amides can also be used.

Additionally (meth) acryloyl chloride, (meth) acryloyl isocyanate, α, α-dimethyl with alkyl spacers having 1 to 12 carbon atoms, preferably 2 to 8, more preferably 2 to 6 carbon atoms 3-isopropenylbenzyl isocyanate, (meth) acryloylalkyl isocyanate such as methacryloylethyl isocyanate or methacryloylbutyl isocyanate are suitable.

It is also possible to use di-, tri- and / or tetraacrylate as component D), in which case a branched product is formed. Examples are dipropylene glycol diacrylate (DPGDA) or tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA) and trimethyllopropane triacrylate, which are suitable for free-radical reactions in the literature. All kinds of higher polyfunctional acrylates mentioned can be used.

The ratio of the reaction product of A), B) and, if necessary, C) to unsaturated monomers D) is 99% by mass: 1% by mass to 1% by mass: 99% by mass, preferably 99% by mass: 1% by mass to 20 % By mass: 80% by mass, more preferably 99% by mass: 1% by mass to 40% by mass: 60% by mass.

It is also possible to carry out polymer-like reactions of the different reaction products of A), B) and, if necessary, C) with unsaturated monomers D).

Depending on the nature of the components and the proportions to the other components, the reaction products of components A), B) and if necessary C) and also D) according to the invention

용융 범위가 0 내지 200℃, 바람직하게는 30 내지 150℃, 보다 바람직하게는 40 내지 125℃이고,

Melting range is 0-200 degreeC, Preferably it is 30-150 degreeC, More preferably, it is 40-125 degreeC,

평균 분자량이 300 내지 100,000, 바람직하게는 400 내지 10,000, 보다 바람직하게는 500 내지 5,000 g/mol이고,

The average molecular weight is 300 to 100,000, preferably 400 to 10,000, more preferably 500 to 5,000 g / mol,

색 지수(Gardner, 에틸 아세테이트 중 50%)가 7 미만, 바람직하게는 5 미만, 보다 바람직하게는 3 미만이고,

The color index (Gardner, 50% in ethyl acetate) is less than 7, preferably less than 5, more preferably less than 3,

OH 지수가 0 내지 250mg KOH/g, 바람직하게는 0 내지 200mg KOH/g이고,

The OH index is from 0 to 250 mg KOH / g, preferably from 0 to 200 mg KOH / g,

산 지수가 0 내지 250mg KOH/g, 바람직하게는 0 내지 200mg KOH/g이다.

The acid index is 0 to 250 mg KOH / g, preferably 0 to 200 mg KOH / g.

In addition, the present invention

A) an aldehyde of formula (I)

B) at least one ketone of formula II,

C) if necessary, additionally a CH-acidic ketone, and

D) contains a significant amount of the reaction product of at least one unsaturated monomer which can be polymerized in a free radical reaction, and the reaction products of A), B) and, if necessary, C) are mixed with component D), followed by UV light Irradiation provides a method for producing a polymer reaction product, in which the reaction preferably takes place in an inert gas atmosphere.

<Formula I>

Wherein R = H, unbranched or branched C1-C12 alkyl radicals, aryl radicals

<Formula II>

In which R ₁ = Unbranched alkyl radical of 1 to 12 carbon atoms

R ₂ =

Wherein R ₃ to R ₇ are H, alkyl, OCH ₃ , OC ₂ H ₅ , Cl, F, COO (C ₁ -C ₃ alkyl).

In addition, R ₄ to R ₆ may be OH or SH.

The preparation of the resins described herein takes place in a molten state or in a solution in a suitable organic solvent.

If necessary, a photosensitive catalyst such as tertiary amine can be added to accelerate the reaction.

In a preferred embodiment, component D) is added in the solution or melt of the reaction product of A), B) and if necessary C) in the presence of a suitable catalyst if necessary. Subsequently, it is preferably exposed to appropriate irradiation under an inert gas atmosphere.

If present, the solvent may be separated after completion of the reaction, if necessary, in which case generally a powder or melt of the product of the invention is obtained.

Using a polymerizable acid such as acrylic acid, methacrylic acid, fumaric acid and / or maleic acid, the polymer is obtained, which is then neutralized using a suitable neutralizing agent, which is non-hydrolyzable and can be diluted in water. It is a form. In addition, the property of dilution in water can be obtained after neutralization using a monomer having a polyether group, a sulfonate group and / or an amino group, for example, using a suitable neutralizing agent, if necessary.

In addition, the present invention is intended to be used as a main substrate or additive component in inks, gelcoats, varnishes, emulsions, pigment pastes, filler compounds, cosmetics, sealants and / or insulators, including coating materials, adhesives, print inks, and the like of the products of the invention. To provide.

A fraction of 5% by mass to 80% by mass, preferably 10% by mass to 70% by mass, more preferably 15% by mass to 60% by mass, based on the total formulation is preferred.

The products of the present invention are broadly compatible with different raw materials and are easy to incorporate.

Coating materials, adhesives, inks including print inks, gelcoats, varnishes, emulsions, pigment pastes, filler compounds, cosmetics, sealants and / or insulators may also be used as auxiliaries and adjuvants such as inhibitors, water and / or organics. Solvents, neutralizers, surface-active substances, oxygen scavengers and / or free-radical scavengers, catalysts, light stabilizers, color brighteners, thixotropic agents, anti-filming agents, antifoaming agents, antistatic agents, thickening agents, thermoplastic additives , Dyes, pigments, flame retardants, internal release agents, fillers and / or blowing agents.

The products of the present invention improve the gloss, flatness and hardness of inks, gelcoats, varnishes, emulsions, pigment pastes, filler compounds, cosmetics, sealants and / or insulators including coating materials, adhesives, print inks.

The following examples are intended to further illustrate the invention, but do not limit the scope of the invention.

Example  1: Preparation of reaction product

600 g of acetophenone, 108 ml of methanol, 200 g of carbazole W 7M (methylated β-cyclodextrin derivative, walker, burghausen (Germany)) and 180 g of formalin (30% concentration in aqueous solution) were added to a three neck flask. Filled and heated to 50 ° C. under nitrogen while stirring. 16 g of 25% sodium hydroxide solution was added and the reaction mixture was heated to 70 ° C. After adding 330 g formalin (30% concentration in aqueous solution) for 90 minutes, the reaction mixture was heated to 95 ° C and then refluxed for 5 hours.

The aqueous phase was separated from the resin phase, the resin was neutralized by washing with water at 100 ° C. and heated to 150 ° C. under reduced pressure to remove volatiles.

This process produced a yellow clear, brittle, 50% solubility in methyl ethyl ketone, acetone, ethyl acetate and xylene, with a softening point of 48 ° C. The Gardner color index of the 50% strength solution in ethyl acetate was 2.2. The OH index was less than 10 mg KOH / g.

The prepared resin was mixed with hydroxy ethyl acrylate and methyl methacrylate in a ratio of 1: 4 in a ratio of 1: 4. Removing a result of irradiation, and then volatile materials under an inert gas atmosphere, and the average molecular weight increased from about 700g · mol ^-1 · mol ^-1 to about 2250g. OH index was 137 mg KOH / g.

Application example

10 g of the reaction product from Example 1 was dissolved in 10 ml of butyl acetate and 5 g of Vestanat IPDI (Degussa AG) and 0.1 g of dibutyltin dilaurate were added.

The solution was applied onto a glass plate using a drawing frame and stored at 120 ° C. for 60 minutes. The film that was previously soluble no longer dissolved in butyl acetate.

Claims (21)

A) an aldehyde of formula (I) B) at least one ketone of formula II, C) if necessary, additional CH-acidic ketones, and D) A product of a polymer-like reaction, comprising a polymer reaction product made from one or more unsaturated monomers that can be polymerized in a free radical reaction. <Formula I>

Wherein R = H, unbranched or branched C1-C12 alkyl radicals, aryl radicals <Formula II>

In which R ₁ = Unbranched alkyl radical of 1 to 12 carbon atoms R ₂ =

Wherein R ₃ to R ₇ = H, alkyl, OCH ₃ , OC ₂ H ₅ , Cl, F, COO (C ₁ -C ₃ alkyl) In addition, R ₄ to R ₆ may be OH or SH. The product according to claim 1, wherein formaldehyde, benzaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valerianaldehyde and dodecanal, alone or in combination, are used as aldehyde component A). . The product according to claim 1, wherein the acetophenone and the ring-substituted acetophenone derivatives are used alone or in combination as ketone component B). 4. A product according to claim 3, wherein hydroxy-, methyl-, ethyl-, tert-butyl- or cyclohexyl-acetophenone, alone or in combination, is used as a ring-substituted acetophenone derivative. Acetone, 4-tert-butyl methyl ketone, methyl naphthyl ketone, hydroxyl cinaphthyl ketone, methyl ethyl ketone, heptane-2-one, pentan-3-one, methyl isobutyl ketone, propiope N, cyclopentanone, cyclododecanone, a mixture of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone, cyclooctanone, cyclohexanone and a total of 1 to 8 hydrocarbon atoms All kinds of alkyl-substituted cyclohexanones having one or more alkyl radicals, alone or in combination, are used as additional CH-acidic ketone component C). The compound of claim 5, wherein 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3 , 3,5-trimethylcyclohexanone, alone or in combination, used as an alkyl-substituted cyclohexanone. 7. The method of any one of claims 1, 5 and 6, having a maximum of 9.9. up to mol%, wherein the CH-acidic ketone component C) can be substituted with benzoin or an alkyl ether of benzoin. 8. The product according to claim 1, wherein an unsaturated monomer which can be polymerized in a free-radical reaction is used as component D). 9. The cycloalkyl ester according to any one of claims 1 to 8, wherein maleic acid, fumaric acid, acrylic acid and / or methacrylic acid, C ₁ -C ₄₀ alkyl esters and / or cycloalkyl esters of methacrylic acid and / or acrylic acid, Hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate, glycidyl methacrylate, glycidyl acrylate, 1,2-epoxybutyl acrylate, 1,2-epoxybutyl methacrylate, 2,3 Epoxycyclopentyl acrylate, 2,3-epoxycyclopentyl methacrylate, acrylated polyethers are used alone or in mixtures as component D), and also styrene and / or derivatives thereof and similar amides are used. Product. The (meth) acryloyl chloride, (meth) acryloyl isocyanate, α, α-dimethyl-3-iso, according to any one of claims 1 to 9, having an alkyl spacer having 1 to 12 carbon atoms. A product characterized in that propenylbenzyl isocyanate, (meth) acryloylalkyl isocyanates such as methacryloylethyl isocyanate and methacryloylbutyl isocyanate are used alone or in mixtures as component D). The product according to claim 1, wherein di-, tri- and / or tetraacrylate is used as component D). The method of claim 1, wherein the dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA) or trimethylpropane triacrylate Product is used as component D). The reaction product according to any one of claims 1 to 12, wherein the ratio of the reaction products of A), B) and, if necessary, C) to unsaturated monomers D) is from 99% by mass to 1% by mass to 1% by mass: 99% by mass. Product, characterized in that%. The reaction product according to any one of claims 1 to 13, wherein the reaction products of components A), B) and if necessary C) and also D)

The melting range is from 0 to 200 ° C,

Average molecular weight is 300 to 100,000 g / mol,

Color index (Gardner, 50% in ethyl acetate) is less than 7,

OH index is 0-250 mg KOH / g,

Product characterized in that the acid index is 0 to 250 mg KOH / g. The product according to any one of claims 1 to 14, wherein the ratio of the sum of ketone components (B) and C) to the aldehyde component is from 1: 0.9 to 1: 4. The product according to claim 1, wherein the ketone component B) is from 10 to 100 mol%, based on the total amount of total ketone components (B) and C) used. A) an aldehyde of formula (I) B) at least one ketone of formula II, C) if necessary, additional CH-acidic ketones, and D) contains a significant amount of the reaction product of at least one unsaturated monomer which can be polymerized in a free radical reaction, and the reaction products of A), B) and, if necessary, C) are mixed with component D), followed by UV light The method of producing a polymer reaction product, preferably by irradiation, wherein the reaction takes place in the presence of a suitable catalyst, if necessary, in an inert gas fraction. <Formula I>

Wherein R = H, unbranched or branched C1-C12 alkyl radicals, aryl radicals <Formula II>

In which R ₁ = Unbranched alkyl radical of 1 to 12 carbon atoms R ₂ =

R ₃ to R ₇ Is H, alkyl, OCH ₃ , OC ₂ H ₅ , Cl, F, COO (C ₁ -C ₃ alkyl) In addition, R ₄ to R ₆ may be OH or SH. 18. The process according to claim 17, wherein the reaction products of A), B) and if necessary C) are prepared in the presence of a base. Process according to claim 17 or 18, characterized in that the reaction products of A), B) and, if necessary, C) react with component D) in a melt or solution in a suitable solvent. 20. The ink according to any one of claims 1 to 19 in coating materials, adhesives, inks including print inks, gelcoats, varnishes, emulsions, pigment pastes, filler compounds, cosmetics, sealants and / or insulators. Use of the polymer reaction product as the main substrate or additive. The method of claim 20, wherein the one or more adjuvants and adjuvants, inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen scavengers and / or free-radical scavengers, catalysts, light stabilizers, collars Brighteners, thixotropic agents, anti-filming agents, antifoaming agents, antistatic agents, thickening agents, thermoplastic additives, dyes, pigments, flame retardants, internal release agents, fillers and / or blowing agents, may be additionally present alone or in combination in addition to polymer reaction products. Usage.