FI116844B - Reactive film formers - Google Patents

Description

I. REACTIVE FILM FORMERS

I REACTIVITY FILMFORMARE

FIELD OF THE INVENTION The present invention relates to reactive film-forming epoxides containing polar groups and their use in substrates, in particular in coatings containing organic compounds. The invention also relates to threads for accelerating curing of the composition.

One of the Prior Art I 2 I One of the objectives of the development of film-forming agents is to import replacement film-forming agents which do not belong to VOC I. However, many commonly used non-volatile or Hita I components have the disadvantage of providing a softener property that will slow the hardness and soft film. Indeed, N> I is concerned with reactive film-forming agents, which at I forming temperature, but also react partially as coating I emissions are minimized.

Of the structure I of reactive compounds known in the art, the effect of lowering the film-forming temperature is often very low I for normal volatiles or so-called. no-VOC film makers. In order to achieve the required well formation temperatures required for operation, hurry up; In addition to the compounds I use conventional film former.

I 15 I In water-based coating compositions, mold growth is also typically added. The fungicides used are often compounds that are harmful to health.

OBJECTIVE OF THE INVENTION The object of the invention is to introduce new polar groups, preferably a barrier * * ·· * · Epoxides.

• * • · · # ♦ #. It is also an object of the invention to provide polar groups, preferably an ester: • · * • * · 3

It is a further object of the invention to provide a process for the preparation of epoxides containing polar groups, preferably groups.

It is also an object of the invention to provide a method of accelerating the coating composition ke 5.

The preparation features of the polar group-containing epoxides of the invention, the film-forming agents thereof, the surfaces comprising them, and the polar group-containing epoxides of the process are disclosed in the claims.

Summary of the Invention

According to the invention, the film forming of aqueous or solvent based coating compositions utilizes an ester of 2 to 20 carbons of ethylenically unsaturated or saturated alcohol and ethylenically unsaturated or carboxylic acid, wherein all or at least part of the ester. of the doxes have been oxidized to epoxy groups. More particularly, the chemical composition is as defined in claim 1 as a cycloaliphatic epoxy ♦ · ·: V 20 as a film-forming agent in coating compositions and in claim 1. A coating composition containing cycloaliphatic epoxide.

DETAILED DESCRIPTION OF THE INVENTION It has surprisingly been found that prior art solutions must be avoided or at least substantially reduced to 4,4 mers of the invention. This is particularly affected by the appropriate molecular size. high boiling point above 200 ° C.

According to the invention, the film forming agent of the aqueous or scintillator coating compositions is an ester of one or more 2 to 20 carbons of an unsaturated or saturated alcohol and an ethylenically saturated alcohol or carboxylic acid, all or double bonds of which are oxidized to epoxy groups. Such compounds can wholly or partially replace the current film number 10 of coating compositions, particularly reactive film formers. They can be used to help cure the coating film.

The invention will now be examined in more detail with the aid of the following, and finally with a few examples.

15

According to the present invention, cycloaliphatic epoxide compounds containing one epoxy group are used as the film composition of the coating compositions. In cycloaliphatic epoxide esters, alcohols are derived from straight or branched monovalent alcohols containing from 2 to 20 carbon atoms. The alcohol moiety may also be derived from an oligo- or polyether formed by a ketol, man.

• · 4 4 lit 4 4 «4 · * · 'The carboxylic acid residue of the cycloaliphatic epoxide esters is from the Diels-Alder sequence between the * 4 * ·' and the dienophile containing the carboxyl group) The 25 alkaliphatic epoxide esters may contain 1-4 epoxy groups which c« 4 · • * 4 5 OOO g

M 1 R

L-lk where R 7 is -O-, -CH 2 -, or -CH 2 CH 2 -; 5

R 8 is either hydrogen, straight or branched, C 2 -C 20 ethylenically saturated hydrocarbon which may contain one of epoxy groups and / or ether groups, preferably a group of hydrocarbons, particularly preferably R 8 is C 2 -C 6 hydrocarbon 10 R 9 is either hydrogen or methyl; and k = 0 or 1.

The cycloaliphatic epoxide esters of the invention include arylene glycolide (5,6-epoxy-2-norbomanecarboxylate) and neo-N-di (5,6-epoxy-2-norbomanecarboxylate).

♦

• M

Diethylene glycolide (5s6-epoxy-2-norbomanocarboxylate) is a new ······················································································ </RTI> s♦ D D Edull Edull Edull Edull Edull Edull Edull Edull Edull 'Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull Edull In a second step, the Diels-Alder product is co-esterified with a single moiety to be hydrolyzed to a carboxylic acid group followed by dehydration of the acid chloride. In the third step, the acid chloride is introduced with an alcohol, such as diethylene glycol or neopentyl glycol, in the step, the double bonds in the ester are oxidized to the epoxy groups by m-chloroperbenzoic acid or peracetic acid.

The cycloaliphatic diesters of the invention can also be obtained by only 10 processes.

Cycloaliphatic diesters may be prepared by reacting the first of any of the above dienes with a di (meth) acrylate ester with ethylene glycol dimethacrylate, di (ethylene glycol) dimethacrylate or glycol) diacrylate, followed by a second step of oxidizing; the double bonds in the aliphatic ester into epoxy groups.

The coating used in the first step of the preferred embodiment is preferably aluminum chloride, lithium perchlorate or diethylaluminum chloride in a solvent, preferably toluene or dichloromethane. The reaction may (φ also be thermally free from catalyst. To the suspension is added acrylate ester * ··· * ... * methyl acrylate followed by diene dissolved in the reaction solvent, e ···; cracked cyclopentadiene. The reaction is allowed to proceed from -80 to +30 • * 0 At -20 ° C for at least 30 min, after which the catalyst is washed with water and the organic layer is separated and further evaporated, it can be surprisingly found that the ester layer has completely disappeared. acidifying the base solution with, for example, hydrochloric acid solution, separating the acidic layer, washing and evaporating to dryness, further acidifying the free acid in an organic solvent such as dichloromethane and adding oxalyl chloride and N, N-dimethylformamide yl chloride can be used to prepare the acid chloride. C for at least one hour until the acid chloride is 85% The product is recovered by evaporation of the excess of chloride in the reaction mixture. The amount of oxalyl chloride is preferably 3-7 times that of the reacting acid and the amount of Ν, Ν-dimethyl form relative to oxalyl chloride is 0-1.0 times.

In the third step, the mono- or diester is prepared by adding a mixture of a mono- or di-alcohol such as diethylene glycol and pyridine at 10-30 ° C for at least two hours until it is at least 90%, usually at least 95%. The product is then taken up in dichloromethane by washing the organic phase with evaporation to dryness. Preferably, both the pyridine and the alcohol have a molar equivalent of acid chloride.

* »I • · ♦ • · * 20» 1 «mll \ In the final step, the double bonds in the ester oxidize * · why. Preferably, the epoxidation is performed by reacting ethyl ester of ethyl ester with peracetic acid using dichloromethane as the N. The reaction is conveniently carried out at 10-35 ° C for at least 2; ·. 25 until the yield of the epoxide ester is at least 90%, typically at least »i» + * »···. Preferably, the molar ratio of peracid to double bonds in the reacting ester is 8

Suitable alcohols for the invention are the monoalcohols and diols listed below for the preparation of epoxide esters. Suitable branched or unbranched or ethylenically unsaturated monoalcohols and diols generally having 2 to 20 carbon atoms are suitable. Mono alcohols and diols were prepared by the cycloaliphatic epoxide esters. Suitable alcohols are e.g. m crotyl alcohol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, pentanol, isopentanol, 1-hexanol, 2-ethylhexanol, 2-ethyl-2-heptanol, 1-octanol, diols such as 2-ethyl-1 , 3-hexanediol, ethylene ethylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2- and 1,3-propa; 1,2-, 1,3- and 1,4-butanediol.

Suitable dienes for the preparation of the cycloaliphatic epoxide compounds of the invention are cyclopentadiene, ochran, and 1,3-cyclohexad.

Preferred dienophiles for the invention are methyl acrylate, ethyl butyl acrylate and 2-ethylhexyl acrylate, methyl methacrylate. crylate and butyl methacrylate.

: v: 20

The cycloaliphatic epoxide derivatives of the invention may be used in the preparation of crystalline compositions. For example, they may be added to dispersions based on water f which contain a binder and, as such, excipients. Aqueous dispersions are particularly preferably prepared. binders known from latex paints;

• ♦ * m> 9 diene, styrene, acrylonitrile, itaconic acid, maleic acid, fumaai acrylic and methacrylic acid and their branched or straight chain: esters, especially C2-C8 esters. Typical (meth) acrylic acid can not be used are methyl acrylate, methyl methacrylate, et; 5 ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexylmethyl acrylate, butyl methacrylate. The polymer may also comprise monomers which contain functional groups. Typical reactive groups include hydroxyl groups (e.g., hydroxyethyl (meth) acrylates, carbonyl groups (e.g., diacetone acrylate, diacetonacrylic anhydride, acetoacetoxyethyl methacrylate), urea groups, and epoxide groups dyl methacrylate). Other monomers may also be used, of which; examples include acrylamide and its derivatives methylol acrylamide and N-isobutoxymethyl acrylamide), and other than single double bonded compounds such as divinyl also use water-dispersible binders, such as various water soluble polymers such as polyvinyl .

In addition to the above, alkyd resins may be used as binders. These condensate products of 20 * divalent polyol and fatty acid or natural oil.

· «« • «

The epoxide compounds of the invention may be used in coatings, such as paint, varnish, grout, filler, plaster and adhesive, preferably in aqueous compositions and particularly preferably in compositions such as 1 * 1 * ♦. in paints with a binder which forms · 10 »m 10 reen-butyl acrylate latexes, Examples of preferred monomer; are styTeem-butyl (meth) acrylate (meth) acrylic acid, styrene-2-eth (meth) acrylate (meth) acrylic acid, methyl (meth) acrylate butyl (me (meth) acrylic acid and methyl (meth) acrylate butyl) (Meth) Acrylate-15L (Meth) Acrylate Example 2 below illustrates the use of keyless film former in combination with styrene-butyl acrylic acid and commercial styrene-acrylate latex (Dispersion A).

The amount of polymer is typically 20 to 80% of the dispersion, preferably 10 of the dispersion. Polymer dispersions typically contain the polymer and surfactant (s), preservatives, antifoaming pH adjusting agent, such as, for example, aqueous ammonia. Other: additives and excipients include dispersants and thickener The amount of reactive film-forming agents of the invention in the composition is about 0.01 to 20% by weight, preferably 0.1 to 15% by weight of the film-forming agent may consist solely of the epoxy compound, the mixture or epoxy a mixture of conventional detergents. In general, the epoxide compounds represent at least 20% by weight of the total amount of membrane s' ** · 20, preferably at least 5 m «« i «» 1 · «li *

In addition, it was found that some film-forming agents may also act as mold inhibitors in coatings used specifically on inert materials such as metal, glass or plastic, but also on wood and p 25 materials. This can avoid traditional fungicides at m * ψ ♦ · or at least significantly reduce their amount.

11

Table 1. Compounds with fungicidal activity | <Λχϊ

Diethylene glycolide (5,6-epoxy-2- [t] t, 3,4 -Epoxycyclohexyl norbomanyl carboxylate Epoxycyclohexanecarb

Preferably, the present epoxide derivatives are used in combination with known film formers or film formers having a boiling point of at least 250 ° C under normal atmospheric pressure. those film-forming agents include, for example, ethyleneglycol phenyl ethers, 2,2, 1,3-pentanediol monoisobutyrate (e.g., Texanol®), diethylene butyl ether acetate, and dipropylene glycol mono-n-butyl ether 10-ethylene glycol mono-n-butyl ether (D) and .

Alone or in combination with known film former, the present derivatives are capable of significantly accelerating the development of coating composition. According to the solvent resistance test, at least 90% k; This hardness can be achieved within 24 hours at room temperature at room temperature, even at a shorter time, when at least 20%, preferably at least 50%, of the composition of the composition consists of epoxide derivatives of the invention.

• Stability and Silica of the present Reactive Film Forms

The compounds of the invention may also be used in the preparation of 1-component component coatings, wherein the second component 1 is used prior to the use of the coating composition.

The present film-forming agents have been compared in commercial examples. The epoxide compound of Example 1 acts in the coating compositions to lower the anchoring temperature,

From the following Table 2 it can be stated that the prepared epoxy compound has an index of at least more than 1500, usually more than 2000, which makes the compound safer than conventional reactants due to its volatile volatility and is not classified as VOCs.

Table 2. VOC index 15 of the compound prepared in Example 1

The name of the compound is VOC-im

Example 1. Diethylene glycolide (5,6-epoxy-2-norboro-2216 • · [ynanecarboxylate) • · · __ • * Reference substance: Butyldiglycol acetate (BDGA) 970

Reference substance: tetradecane 1000 • t «9 9999 9 99 9 9 9 9 99 9 I · —iii i I-i.1- - a VOC index R1 = 1000 * (ta / tci4) where it is the epoxy analyzed:. \ retention time and te14 is the rare standard for tetradecane used as internal standard M · 9 • 9 9 9 9 9 9 9 99 13

The invention provides considerable advantages. Thus, the film-forming agents of the invention provide a good dispersion of the coating composition, which appears to be due to a weakly polar ether bond or more of a p-bond. Surprisingly, several compounds also have an antifungal activity 5

In addition, due to the larger hydrocarbon group of the ester, the new film-forming compounds are better at forming film than the slides or epoxide compounds normally used.

10 Due to the low volatility of the compounds, they can be used in applications, especially when the compounds have a boiling point above 200

In addition, the reactive epoxy groups contained in the compounds enable the dosers to react as part of the coating film, thereby 15 and the hardness of the coating film develops favorably through the crosslinking holes. Furthermore, since most of the compounds are difunctional, cis-crosslinking is more effective than mono-functional ♦ ♦ · * 1

The compounds of the invention can accelerate the film hardness so that at least 70% of the final hardness is already achieved within about one µm. The present epoxide compounds can be used in combination with the propellants.

«· · Fr fr» fr a a »fr

The invention is illustrated by the following examples, in which:. 25, however, is not intended to be limited.

a · · • · »· · · •« 14

Example 1.

Preparation of diethylene glycolide (5,6-epoxy-2-norbomanycarboxylate)

I X 2 HC? H X

Il OMe. / ry Αία; iMe MCOCI); 0.510 mol (68.0 g) of anhydrous aluminum chloride were suspended in 660 ml of 0.600 mol (51.7 g) of methyl acrylate. Alloyed until all aluminum chloride dissolved. To the solution was added freshly cracked ethylene dissolved in 0.600 mol (39.7 g) of toluene (340 ml) for 45 min. The reaction mixture was stirred at room temperature for 90 min and poured into water. The toluene layer was washed with water, dried with water. um sulfate, filtered, and evaporated to dryness under reduced pressure. Yield m ·,;. norbomene-2-carboxylic acid methyl ester was purified by distillation. under pressure using a Vigreux column. The yield was 66.3 g (74%) and 15 (GC).

·· «♦ · I · · · | 5-Norbene-2-carboxylic acid was prepared by mixing 164 n-methyl ester with 10% NaOH solution (85 g) at 60 ° C, losing the layer. Further, the solution was cooled, washed with diethyl ether 15 132 mmol (18.2 g) acid dissolved in 480 mL dichloromethane, 2.66 mmol (0.205 mL) Ν, Ν-dimethylformamide was added dropwise; (57.0 mL) of oxalyl chloride over 1 hour. The mixture was stirred under reflux for 1.5 hours. The solvent and excess oxalyl chloride were evaporated to give a brownish oil residue. The yield was 18.1 g (88%).

The diester was prepared by adding 115 mmol (18.0 g) of the above Vail acid chloride to a mixture of diethylene glycol (57.5 mmol, 6.10 g) and pyridine 9.09 g) at room temperature. The mixture was stirred in my room for 10 h, after which 150 ml of dichloromethane was added and 100 l of the organic layer was further washed with water, sodium bicarbonate solution with acid solution and dried over anhydrous sodium sulfate. Seo; and evaporated to dryness to give a yellow oil residue. S a g (95%). 1 H and 13 C NMR spectra indicated that the product was predominantly di 15

Diethylene glycolide (5,6-epoxy-2-norbomanycarboxylate) was prepared by the preparation of 54.5 mmol (18.9 g) of the diester obtained in the preceding step with chloromethane. Further, 15.3 mmol (2.08 g) of sodium acetate trihydride; * * was added to 39% acetic acid in peracetic acid (153 mmol, 244 µl) was added dropwise to the diester solution over 30 min. The reaction mixture was stirred at room temperature. After stirring, the reaction mixture was washed with water and sodium hydroxide solution. The organic phase was dried over anhydrous sodium sulfate and evaporated to give a pale white diethylene glycol (5,6-epoxy-2-norbomannicarboxylate): 19.8 g (96%) and 94% purity. (GC).

«I * 14« «* · 4 • · 1 4« 16

Example 2.

Use of the Prepared Epoxide Derivative as a Reactive Film Form in Aqueous Compositions The performance of the film forming agent prepared in Example 1 was ground by preparing commercial styrene acrylate latex (Dispei mixed with 6 wt.% Epoxide esters. for film-forming agents, but) 10 acetate (BDGA) and butyl glycol (BG) are shown below in 1 Dispersion A MFFT = 16 ° C. Reactive Film Forming Added The lowest film forming temperature (MFFT) was measured according to ASTM on a Coesfeld Gradient Plate-Thermostair.

15 May Lock 3. Lowest Membrane Temperature (MFFT)

Compound M1 999 9 9 _____ '··; * Example 1. Diethylene glycolide (5,6-epoxy-2-norbomanyl-carboxylate) 999

Comparative sample: Butyl Diglycol Acetate (BDGA) 0 »999 9 ____________

Comparative sample: Butyl Glycol (BG) 0 · · ··· • i • · »• * 9 · * · 9 99 9 9 9 9 9 999

Claims (13)

Use of one or more cycloaliphatic epoxy ester as release compositions, characterized in that the cycloal distem is a cycloaliphatic epoxide ester of the general formula (II) in which R7 is -O-, -CH2-, or -CH2CH2-; R8 is either hydrogen, a straight or branched, ethylenic or C2-C20 hydrocarbon, which may contain one or more ethers R 9 is either hydrogen or a methyl group; and · 1 «» 1 • 4 · · 1 ·! k = 0 or 1. «1 · • 1 • ·» 1 2. Use according to Claim 1, characterized in that in C 1 -C 18 hydrocarbon, preferably R 8 is a C 2 -C 6 hydrocarbon. Use according to claim 1 or 2, characterized in that ;; • · Φ ll | The lifatic enoxide ester of the formula II is diethyl carbonyl 11 Use according to the claims of claims 1-4, characterized in that the coating composition is a paint, varnish, grout, fill or glue composition, advantageously a water-based san and especially advantageously a latex-based composition. 5 Coating composition, characterized in that the coating composition is aqueous or solvent-based and the one 20% by weight, advantageously 0.1-15% by weight of one or more cycloaliphatic, which is a cycloaliphatic epoxy ester of the general formula II L (II) in which R7 is -O-, -CH2-, or -CH2CH2-; • ft ft * 0 • · • ft * ** *: V R8 is either hydrogen, a straight or branched, ethylenic enamel • ** —2 to C2-C20 hydrocarbon, which may contain one or more ether ··· • · • * ·· · »** 9 * ·· [20 R9 is either hydrogen or a methyl group; and in*· . . k = 0 or L ft · i ft · 0 ftftft * ftftft • 0 • t · * · T5 t «» | - 1 r _ The coating composition of claim 6 or claim 7, wherein the cycloaliphatic epoxide ester is diethylene glycolide norbomane carboxylate) or neopentylglycolide (5,6-epoxy-2-norbomane). Coating composition according to any of claims 6 - 8, k thereof, that the coating composition also contains known films. Coating composition according to any of claims 6-9. assuming that the pH of the coating composition is less than circ; 10 currently below 8.0. Coating composition according to any of claims 6-10, wherein the coating composition is a paint, varnish, paint, mortar or adhesive composition, advantageously a composition and especially advantageously a latex-based composition. 12. Diethylene glycolide (5,6-epoxy-2-norbomane carboxylate). 13. A process for the preparation of a compound according to claim 12, wherein a diene is allowed to react with a (meth) acrylate ester in a first step of the product esterified in an estergr · · · · ··· * carboxylic acid group, after which an acid is produced from an acid, in a tri IM **, the acid chloride is reacted with an alcohol and in one final step oxidize 9 «9» bonds which the ester contains to epoxy groups, or cycloaliphide is prepared by allowing a diene in a first step to react with the di (meth) acrylate ester and then in a second step by oxidizing Λ *