DE2858784C2 - Copolymer soln. for use in reaction and stoving lacquers - Google Patents

Abstract

Copolymer soln. contains (A) an inert organic solvent with b.pt. 75-200 degrees C, (B) the addn. prod. of an alpha,beta-unsatd. mono-carboxylic acid and a glycidyl cpd., opt.contg. unreacted components or by-prods. and (C) >=1 further vinyl cpd.Used in reaction lacquers by crosslinking with polisocyanates, or in storing lacquers by crosslinking with amino resins. The solns are colourless and clear, giving films which are speck-free and do not yellow even in presence of catalyst. Prepn. is relatively insensitive to reaction conditions and unwanted side reactions are avoided.Reaction time is reduced and the process can be carried out in a single vessel. Films obtd. are non-tacky, water-resistant and elastic

Description

The invention relates to a Intermediate solution which is an addition product of an α, β-unsaturated Monocarboxylic acid with a monoglycidyl compound, optionally including minor amounts of unreacted α, β-unsaturated monocarboxylic acid and / or monoglycidyl compound and formed by-products, as it is in Claim 1 is characterized.

In DE-PS 10 38 754 is a process for the preparation of esterified polyhydroxy copolymers described. This known Method is characterized in that simultaneously and in the presence of an epoxy-carboxy catalyst and a Catalyst for vinyl polymerization to be implemented: (a) a short chain α, β-unsaturated monocarboxylic acid, (b) a Vinyl monomer with only one active, for the addition polymerization capable, terminal CH₂ = C group and (c) a monoepoxide, the one, optionally alkyl-substituted, alkylene oxide, an ether or ester with only one tripartite epoxide substituent otherwise, the monoepoxide is not a reactive one Group has. This must always be simultaneously in the presence an epoxy-carboxy catalyst and a catalyst for the Be implemented vinyl polymerization. How to rework the there have shown examples provide the known copolymers  yellow to brownish colored solutions. The result produced paint films show after evaporation of the solvent an undesirable yellow to brown color, so this Products can only find a very limited application.

In FR-PS 13 90 572 is also a process for the preparation of esterified polyhydroxy copolymers, the addition reaction between the epoxy and carboxy group occurs during or after the copolymerization. The application This method is described in the following patents DE-OS 20 54 231, CH-PS 5 23 961, DE-OS 20 21 141, DE-PS 26 26 900, DE-AS 26 03 259, DE-AS 26 59 853, CH-PS 5 19 532, DE-OS 25 15 705, DE-OS 26 03 624, DE-OS 26 18 809, DE-OS 20 65 770.

The disadvantage of these known processes on a production scale is that for the full implementation, namely Esterification and copolymerization, relatively long reaction times (12 to 15 hours) are required. This will find unwanted Side reactions take place because the carboxyl group of the α, β-unsaturated Monocarboxylic acid before and after their copolymerization with the other monomers with reactive groups, eg. B. with the Hydroxyl groups and / or glycidyl groups with ester formation, and the glycidyl groups with each other or with the hydroxyl groups under ether binding structures. Such reaction approaches are therefore contrary to the reaction conditions very sensitive, so that it is required on an industrial scale is to follow the reaction parameters very closely to copolymers with the desired properties in comparable To produce quality safely. It also takes place very carefully Reaction always a certain gel particle formation with particle diameters of about 5 to 25 microns instead, the by the paint expert in the paint films produced therefrom Be referred to as "specking" and not achieving a high performance finish allow.

In DE-OS 16 68 510 is also a process for the preparation of esterified polyhydroxy copolymers, however, the addition reaction between the epoxy and carboxy Groups before, after or during the copolymerization becomes. In the embodiment in which the esterification  during or after the copolymerization, apply the versions of the already explained above type with the indicated disadvantages. In the embodiment in which two Reaction components, namely the α, β-unsaturated monocarboxylic acid with the epoxy compound containing a glycidyl ester of a tertiary aliphatic monocarboxylic acid, first alone in the absence of esterification catalysts to a precursor are processed as esters (as in the DE-PS 27 09 782 and 27 09 784), the results Disadvantage that the Copolymerisatlösungen incurred clouded and the varnish films made therefrom are also clouded. Further can easily encounter further difficulties because of the α, β-unsaturated carboxylic acid for polymerization with itself also tends to cause the homopolymers formed thereby Cause cloudiness. Such findings will also by the information in DE-PS 10 38 754 column 9, lines 43rd to column 10, line 8 and in DE-AS 26 26 900 column 10, Lines 1 to 39 confirmed.

In DE-AS 16 69 009, especially Example 1, is already a Solution of inert organic solvents, an addition product an α, β-unsaturated monocarboxylic acid (acrylic acid) with a monoglycidic compound (glycidyl ester of acids with 9 bis 11 carbon atoms) and other vinyl compounds. The there obtained intermediate solution is obtained by the Glycidyl ester with methacrylic acid in the presence of ethyl acetate is esterified by heating at 100 to 110 ° C for 6 hours. While heating at 100 to 110 ° C to form the addition product is no further vinyl compound in the reaction mixture contain. Only after esterification is acrylic acid added. As already explained above, such a manufactured Intermediate solution clouded solutions in the copolymerization.

In DE-OS 25 15 705 is a copolymer solution consisting out

• A) 20 to 30 wt .-% in the paint industry usual organic solvents
• B) 70 to 80 wt .-% of copolymers obtained by heating to 160 to 200 ° C in a mixture of an inert solvent and the component to be esterified
  • a) 25 to 30 wt .-% glycidyl esters of α-Alkylalkanmonocarbonsäuren and / or of α, α-Dialkylalkanmonocarbonsäuren following empirical formula C _12-14 H _20-26 O₃ and slowly uniform addition of
  • b) 10 to 18% by weight of hydroxyethyl acrylate and / or hydroxyethyl methacrylate,
  • c) 7 to 9% by weight of acrylic acid,
  • d₁) 20 to 30 wt .-% of styrene and / or methyl methacrylate and
  • d₂) 13 to 40 wt .-% butyl acrylate and / or ethyl acrylate, wherein the components a, b, c, d₁ and d₂ have been used in amounts such that their sum is 100 wt .-%, in the presence of peroxide mixtures as polymerization initiators have been prepared described.

According to the information there (page 20, last paragraph) is the glycidyl ester in solvent heated to 175 to 180 ° C and in this heated mixture, the monomer mixtures and the peroxide mixtures added slowly. As in addition to the esterification always a copolymerization, the inventive monomeric intermediate solution can not be obtained.

As far as the intermediate product according to the invention for the manufacture of copolymers based on known or new monomeric Composition finds use, are the copolymers in significantly improved form before.

The object of the invention is that described above Disadvantages of the known and sometimes large-scale carried out procedures of the type described above substantially to improve, namely:

• 1. The copolymer solutions should be colorless and bright. This means that the paint films produced with it also "speck-free" or very stippenarm should be and despite the presence of the catalyst does not yellow.
• 2. The manufacturing process is also against factory scale the reaction conditions are relatively insensitive, so that after determination of the optimal reaction parameters also at small deviations from the reaction conditions always usable, high performance copolymers are obtained and unwanted side reactions are also due to the Catalyst in the copolymerization and in use the copolymers are largely avoided.
• 3. The manufacturing process should be especially in the implementation on a factory scale with a much shorter implementation time be carried out in a one-pot process, so by the significantly shortened boiler occupancy time productivity significantly increase the production plant and thus to reduce production costs.
• 4. The manufacturing process should allow it, further improved Copolymers based on known or newer Produce monomer composition.
• 5. The copolymers prepared by the process are intended non-stick, waterproof and elastic films on the various substrates or as a binder for pigments, Opaque colors and nonwovens be suitable, and as a binder component be usable, wherein the coatings produced therewith or fabrics in various directions advantageous Have properties.

The solution of the above objects is in the characterizing part of claim 1. It can be seen that a Intermediate solution is provided which is the addition product an α, β-unsaturated monocarboxylic acid having a Contains monoglycidyl compound. From a theoretical view From this perspective, it is possible that small amounts of  By-products, eg. B. by etherification of the monoglycidyl compound with itself and possibly minor polymerization the polymerizable α, β-unsaturated monocarboxylic acid or their derivatives may be included in the intermediate solution. It is essential, however, that the new intermediate product solution when used for the preparation of copolymers such as a solution of monomeric compounds behaves and in surprising Way allows copolymer solutions by copolymerization produce, which are completely cloudless.

The object of the invention and the use is specified in claims 1 to 8.

As α, β-ethylenically unsaturated monocarboxylic acids are acrylic acid, Methacrylic acid and / or crotonic acid, individually or in admixture, used. These include half esters of maleic and fumaric acid with saturated alcohols containing 1 to 10 carbon atoms.

The monoepoxides include substituted alkyl compounds as well Ether and ester, provided the one three-membered epoxy ring contain.

Examples of alkyl-substituted monoepoxides are propylene oxide Butene-2-oxide, hexene-2-oxide, octene-2-oxide and styrene oxide.

Examples of substituted ether monoepoxides are butyl glycidyl ether Hexyl glycidyl ether, octyl glycidyl ether and phenyl glycidyl ether.

Examples of ester monoepoxides are the glycidyl esters of the following Acids: acetic acid, propionic acid, butyric acid, caproic acid, Caprylic acid, 2-ethylhexanoic acid, isononanoic acid, α, α-dialkylalkane monocarboxylic acids, in which in α-position to the carboxyl group the hydrogen atoms of alkane monocarboxylic acid by alkyl radicals substituted so that a tertiary carbon atom is present, with the formula  

wherein R¹, R² and R³ are alkyl groups and the total the carbon atoms of all alkyl groups is 3 to 25. Prefers are the glycidyl esters of α, α-Dialkylalkanmonocarbonsäuren with 9 C to 13 C atoms in the alkyl group radical.

The most preferred glycidyl ester of an α, α-dialkylalkane monocarboxylic acid has the empirical formula C₁₃H₂₄O₃.

As vinyl compounds, the aromatic vinyl compounds, z. As styrene, vinyl toluene, α-methyl styrene and halogenated styrene used which, except the vinyl group, will not react with possess the carboxyl group capable group.

As vinyl compounds are the esters of acrylic, methacrylic and Crotonic acid with saturated alcohols containing 1 to 10 carbon atoms contained in the alcohol residue, such as. Methyl, ethyl, propyl, Isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Amyl, hexyl, heptyl, octyl, nonyl and decyl radicals, individually or in admixture, usable.

Examples of vinyl esters which may be used are vinyl esters of α, α-dialkylalkane monocarboxylic acids having the formula

wherein R¹, R² and R³ are alkyl groups, and the sum total of the carbon atoms of all the alkyl groups is 3 to 25, and of these, vinyl esters having the following molecular formula
C₉H₁₉-CO-O-CH = CH₂ preferred. As vinyl esters, vinyl acetate and vinyl propionate are also useful.

As hydroxyl-bearing α, β-ethylenically unsaturated compounds may be hydroxyethyl methacrylate, hydroxyethyl acrylate, Hydroxypropyl acrylate, hydroxypropyl methacrylate and butanediol monoacrylate and / or butanediol monomethacrylate, alone or in admixture, be used. Furthermore, hydroxyl groups are also Ether esters, such as polypropylene glycol monomethacrylate and / or Polyethylene glycol monomethacrylate with average molecular weights between about 175 to about 390, usable.

As epoxy-carboxy catalysts based on an alkali metal compound can all sodium, lithium, potassium, rubidium and cesium compounds - used singly or in admixture be in the reaction mixture of α, β-unsaturated monocarboxylic acid, Monoglycidyl compound and at least one other Vinyl compound are soluble or at least during the addition and / or at the holder of the reaction mixture to reaction temperature go into solution, but the alkali compound used should be free of such components, which in the further processing of the addition product representing an ester, can have an unfavorable effect.

Useful are, for example, the carbonates, bicarbonates, formates and the hydroxides of the aforementioned alkali metals.

At factory scale, lithium hydroxide and potassium hydroxide are best - individually or in mixture - proven.

When used on a factory scale, this is due to the Price and the excellent catalyst properties the potassium hydroxide used particularly advantageous. expedient is the alkali metal hydroxide used or the alkali compound or mixtures thereof in the α, β-unsaturated to be esterified Monocarboxylic acid dissolved. But you can also from the alkali compound,  z. The alkali hydroxides, alkali carbonates or alkali bicarbonates, and the α, β-unsaturated monocarboxylic acid first you Alkali salt as a catalyst and then can the alkali metal salt the α, β-unsaturated carboxylic acid in the reaction mixture solve or in the implementation of the addition reaction by heating bring in solution.

In general, it is sufficient from about 0.005 wt .-% to about 0.5 wt .-% alkali metal compound of the type already mentioned, wherein the wt .-% based on the alkali metal content of Relate connection, based on the weight of the ester-forming components, for the Add addition reaction. However, an additive is preferred from about 0.01% to about 0.3% by weight of alkali metal compound.

The preferred range for the additive is about 0.02% by weight. to about 0.1% by weight of alkali metal compounds, wherein the alkali metal compounds then potassium and lithium compounds find particularly advantageous use.

In the execution of the addition reaction is as above worked, however, becomes an inert organic Solvent or a mixture of inert organic solvents co-used, wherein the addition reaction preferably in Temperature range of 100 to 180 ° C is performed. As inert Solvents are those that are not active hydrogens contain, usable, for. As toluene, xylene or other aromatics having a boiling range of about 100 ° C to about 180 ° C, Butyl acetate, monoglycol ether acetates, e.g. For example, ethyl glycol acetate, or mixtures of monoglycol acetate and xylene, being used as monoglycol acetates for example, methyl glycol acetate, ethyl glycol acetate, Called isopropyl glycol acetate or n-butyl glycol acetate become. In carrying out this embodiment The inert organic solvents can be in the double up to four times the weight, based on the weight of Monoepoxydverbindung be used.  

The above statements show that the selection conditions on the type and amount of other vinyl compounds in the implementation the addition reaction (before the copolymerization) and the presence or absence of chain regulators a considerable Influence on the properties of the in the subsequent copolymerization step exert copolymers to be prepared. A Such control of the properties already in the Addition reaction for the subsequent copolymerization is for the question in question monomer mixtures not previously known and thus allows copolymers with known or new monomer composition with improved properties manufacture.

After the addition product of the α, β-unsaturated monocarboxylic acid and the monoepoxide compound in the presence of at least a vinyl compound has been prepared, optionally after adjustment of the monomer composition or by feed of other monomers and polymerization initiators, optionally Chain regulators, the copolymerization take place.

In a preferred embodiment, the above-explained Addition product in the presence of an inert solvent or solvent mixture (eg xylene and ethyl glycol acetate) in the presence of several (eg four) other monomeric vinyl compounds and a chain regulator at reflux within 3 hours. The polymerization reaction can thereby be carried out that the approach of the addition product with the present vinyl compounds is further refluxed and a mixture of the required additional amount of vinyl monomers and polymerization initiators in the course of 3 to Is added in small portions for 5 hours and copolymerized.

Optionally, for example octylmercaptan, Decylmercaptan, laurylmercaptan and the branched dodecylmercaptan used. The proportion of chain regulators, based on the total proportion of ethylenically unsaturated monomers including the esterified monoepoxides is 0 to 2.5 wt .-%.  

The processing capabilities of the intermediate solutions are described in detail in DE-OS 28 51 616 as a parent application and these are represented by the examples 1 to 7, 9, 11, 13 to 18, 20, 22, 24, 26 to 27 illustrates.

The production of paints from the on the intermediate solutions based copolymer solutions is also detailed there and examples 8, 10, 14, 21 and 23 (stoving enamels), 12, 19 and 25 (reaction lacquers) occupied. The surprising Properties of the reaction coatings described are compared to the best on the Market competitive products in terms of pot life been proven. Further, on the other Information in DE-OS 28 51 616 to the local application examples 20 to 29 (paints) and the results of the comparative studies 1 to 4 pointed out.  

Example 1

In a equipped with stirrer, reflux condenser and thermometer reaction vessel under reflux at 140 to 146 ° C, a mixture consisting of
294 g of xylene,
150 g of ethyl glycol acetate,
155 g glycidyl ester of an α, α-Dialkylalkanmonocarbonsäure the following empirical formula C₁₃H₂₄O₃ having an epoxide equivalent of 245 to 253 (boiling range 5% to 90% at 57 N · m ^-2 251 ° to 278 ° C) (= 23.5 wt .-%, = 0.627 epoxide equivalent). (The glycidyl ester is described in "Shell Chemicals Technical Bulletin RES / CAX / 1" entitled "Shell Resin Intermediates Cardura E 10" whose structure can be represented by the following formula, which is based on a synthetic saturated, highly branched Monocarboxylic acid based on 10 carbon atoms,

wherein R₁, R₂ and R₃ represent straight-chain alkyl groups, at least one of which always represents the methyl group),
45.0 g of acrylic acid (= 6.9% by weight, = 0.625 equivalent),
3.0 g of polypropylene glycol monomethacrylate having an average molecular weight of 350 to 387 and a hydroxyl number of 145 to 160 (= 2.6 wt .-%). The product can be represented by the following formula:

where n is the numerical value 5 or 6,
9.6 g of hydroxyethyl methacrylate (= 8.3% by weight),
15.0 g of styrene (= 12.07% by weight),
15.0 g of methyl methacrylate (= 12 wt .-%) and
7.4 g of dodecylmercaptan
was refluxed for three hours to reach the acid number 21 to form the addition product. In this reaction, about 6.6 g of unreacted acrylic acid are present. The acid number, refers to the amount of monomers used, in the present case to 35.4 wt .-%.

In Example 1, the reaction of 155 g of glycidyl ester and 45 g of acrylic acid to the addition product in the presence of 3 g Propylene glycol monomethacrylate, 9.6 g of hydroxyethyl methacrylate, 15 g of styrene and 15 g of methyl methacrylate made, the Ratio of addition product to the other vinyl monomers 85.8% by weight to 14.2 wt .-% is. In addition, the formation of the monomeric addition product in the presence of tert-Dodecylmerkaptan performed.

example 2

The procedure is as in Example 1, worked, but are used:
294.0 g of xylene,
150.0 g of ethyl glycol acetate,
155.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid of the type mentioned in Example 1, (= 23.5% by weight, = 0.627 epoxide equivalent),
45.0 g of acrylic acid (= 6.9% by weight, = 0.625 acid equivalent),
12.6 g of hydroxyethyl methacrylate (= 1.91% by weight),
15.0 g styrene (= 2.27 wt.%),
15.0 g of methyl methacrylate (= 2.27 wt .-%) and
0.7 g of dodecylmercaptan
are refluxed in about 3 hours at about 144 ° C to the acid number 18.5 to form the addition product. The acid number refers to the amount of monomers used, in the present case to 35.4 wt .-%.

In Example 2, in the first stage 200 g of monomeric Addition product of the glycidyl ester and acrylic acid in the presence of 12.6 g of hydroxyethyl methacrylate, 15 g of styrene and 15 g Methyl methacrylate produced. The ratio addition product to the other monomers is 82.44 wt .-% to 17.56 wt .-%. In the production of the addition product is a small amount Dodecyl mercaptan present.  

example 3

The procedure is as in Example 1, worked, but are used:
294.0 g of xylene,
150.0 g of ethyl glycol acetate,
155.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid (= 23.5% by weight, = 0.627 epoxide equivalent) of the type mentioned in Example 1,
45.0 g of acrylic acid (= 6.83% by weight, = 0.625 acid equivalent),
12.6 g of hydroxyethyl methacrylate (= 1.91% by weight),
15.0 g styrene (= 2.27 wt.%),
15.0 g of methyl methacrylate (= 2.27 wt .-%) and
26.2 g of vinyl ester of an α, α-dialkylalkane monocarboxylic acid having the formula C₉H₁₉-CO-O-CH = CH₂ (= 3.98 wt .-%), wherein the radical C₉H₁₉- largely by the following structure

can be marked. This mixture is 3 hours at about 145 ° C to the acid number 17 to the addition product - as described in Example 1, but here with 37.7 wt .-% calculated - implemented.

In this example, 200 g of monomeric addition product from the glycidyl ester and acrylic acid in the presence of 12.6 g Hydroxyethyl methacrylate, 15 g of styrene, 15 g of methyl methacrylate and 26.2 g vinyl ester prepared. The ratio addition product to the four other vinyl monomers is 74.4 wt .-% to 25.6 wt .-%. In the preparation of the addition product was in the absence worked from Dodecylmerkaptan.

example 4

The procedure is as in Example 1, worked, but are used:
294.0 g of xylene,
150.0 g of ethyl glycol acetate,
155.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid (= 23.5% by weight, = 0.627 epoxide equivalent) of the type described in Example 1,
45.0 g of acrylic acid (= 6.82% by weight, = 0.625 acid equivalent),
25.0 g of styrene (= 3.79% by weight),
1.7 g of dodecylmercaptan be for 3 hours at about 145 ° C to the acid number 20 to the addition product - as described in Example 1, but here calculated with 33.6 wt .-% - implemented.

In this example, 200 g of monomeric addition product from the glycidyl ester and acrylic acid in the presence of 25 g of styrene manufactured. The ratio of addition product to styrene is 88.88% by weight to 11.12% by weight. In the preparation of the addition product was worked in the presence of dodecyl mercaptan. In addition, the feed of the monomer mixture contained in the copolymerization Dodecylmercaptan.

example 5

The procedure is as in Example 1, worked, but are used:
400.0 g of xylene,
209.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid of the type mentioned in Example 1 (= 34.83% by weight, = 0.853 epoxy equivalent),
61.0 g of acrylic acid (= 10.16% by weight, = 0.847 acid equivalent),
50.0 g of styrene (= 5% by weight),
50.0 g of butyl acrylate (= 5 wt .-%) and
0.7 g of dodecylmercaptan.
The mixture was reacted for 3 hours at 142 ° C to the acid number of 15 to the addition product - as described in Example 1, but here calculated at 48 wt .-%.

In this example, 270 g addition product from the glycidyl ester and the acrylic acid in the presence of 50 g of styrene and 50 g of butyl acrylate produced. The ratio addition product to the styrene and butyl acrylate is 73% by weight to 27% by weight.  

example 6

The procedure is as in Example 1, worked, but are used:
294.0 g of xylene,
150.0 g of ethyl glycol acetate,
150.0 g of phenyl glycidyl ether (= 22.79% by weight, = 1 epoxide equivalent)
72.0 g of acrylic acid (= 10.93% by weight, = 1 acid equivalent),
60.0 g of styrene (= 9.12% by weight),
60.0 g of n-butyl acrylate (= 9.12 wt .-%) and
5.0 g of dodecylmercaptan.
The mixture was reacted at 146 ° C for 3 hours to the addition product with the acid number 97.

example 7

The procedure was as in Example 6, worked, but were instead of phenyl glycidyl ether, 130 g of n-butylglycidyl ether were used.

example 8

The procedure is as in Example 1, worked, but are used:
290 g of xylene,
150 g of ethyl glycol acetate,
178 g of benzoic acid glycidyl ester (= 27.04% by weight, = 1 epoxide equivalent),
72 g of acrylic acid (= 10.93% by weight, = 1 acid equivalent),
60 g of styrene (= 9.12% by weight),
60 g of n-butyl acrylate (= 9.12 wt .-%) and
4 g of dodecylmercaptan.
The mixture was reacted at 145 ° C for three hours to the addition product with the acid number 62.

example 9

The procedure was as in Example 8, worked, but instead of benzoic acid glycidyl ester, 128 g of octene-2-oxide used.  

example 10

In a equipped with stirrer, reflux condenser and thermometer reaction vessel under reflux at 140 to 146 ° C, a mixture consisting of
294 g of xylene,
150 g of ethyl glycol acetate,
160 g of glycidyl ester of an α, α-dialkylalkenemonocarboxylic acid of the following empirical formula C₁₃H₂₄O₃ having an epoxide equivalent of 245 to 253 (boiling range 5% to 90% at 57 N · m ^-2 Hg 251 ° to 278 ° C) (= 24.3% by weight) , = 0.64 epoxy equivalent),
0.1 g of potassium hydroxide dissolved in
46 g of acrylic acid (= 6.99% by weight, = 0.638 equivalent),
5 g of propylene glycol monomethacrylate having an average molecular weight of 350 to 387 and a hydroxyl number of 145 to 160 (= 0.76 wt .-%),
29 g of hydroxyethyl methacrylate (= 4.4% by weight),
47.6 styrene (= 7.23 wt.%),
31.5 g of methyl methacrylate (= 4.78 wt .-%) and
7.4 g of dodecylmercaptan
held for three hours to reach the acid number of 14.7 to form the addition product. The calculation results from the sum of the monomers used glycidyl ester, acrylic acid, polypropylene glycol monomethacrylate, hydroxyethyl methacrylate, styrene and methyl methacrylate to 41.8 wt .-%.

In this Example 10, the reaction of 160 g of glycidyl ester and 46 g of acrylic acid to the addition product in the presence of 5 g Propylene glycol monomethacrylate, 29 g hydroxyethyl methacrylate, 97.6 g of styrene and 31.5 g of methyl methacrylate made, the Ratio of addition product to the other vinyl monomers 64.55% by weight to 33.45 wt .-% is. In addition, the formation of the monomeric addition product in the presence of tert-Dodecylmerkaptan performed.

example 11

The procedure is as in Example 10, worked, but are used:
294.0 g of xylene,
150.0 g of ethyl glycol acetate,
160.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid of the type mentioned in Example 1, (= 24.35% by weight, = 0.64 epoxide equivalent),
0.3 g of lithium hydroxide dissolved in
45.0 g of acrylic acid (= 6.85% by weight, = 0.625 acid equivalent),
47.6 g of styrene (= 7.24% by weight),
31.5 g of methyl methacrylate (= 4.79 wt .-%) and
7.5 g of dodecylmercaptan be in about 3 hours at about 144 ° C to the acid number 11, as described in Example 10, but here calculated with 39 wt .-%, converted to the addition product.

In this Example 11, in the first stage, 205 g of monomeric Addition product of the glycidyl ester and acrylic acid in Presence of 47.6 g of styrene and 31.5 g of methyl methacrylate prepared. The ratio of addition product to the other monomers is 72.15 wt .-% to 27.85 wt .-%. In the production of the Addition product is a small amount Dodecylmerkaptan present.

example 12

The procedure is as in Example 10, worked, but are used
294.0 g of xylene,
150.0 g of ethylene glycol acetate,
160.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid (= 24.1% by weight, = 0.64 epoxide equivalent) of the type mentioned in Example 1,
0.3 g of lithium hydroxide dissolved in
46.0 g of acrylic acid (= 6.98% by weight, = 0.638 acid equivalent),
20.0 g of styrene (= 3.04% by weight),
12.0 g of methyl methacrylate (= 1.82 wt .-%) and
7.4 g of dodecylmercaptan are esterified in about 3 hours at 144 ° C to the acid number 14, as described in Example 1. Here, the determination of the acid number is calculated to a solids content of 34.9.

In this example, 206 g of monomeric addition product from the glycidyl ester and acrylic acid in the presence of 20 g Styrene and 12 g of methyl methacrylate produced. The relationship Addition product to the other four vinyl monomers is 86.55% by weight. to 13.45% by weight. In the preparation of the addition product was worked in the absence of dodecyl mercaptan.

example 13

The procedure is as in Example 10, worked, but are used
294.0 g of xylene,
150.0 g of ethyl glycol acetate,
155.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid (= 23.5% by weight, = 0.627 epoxide equivalent) of the type described in Example 1,
0.2 g of lithium hydroxide dissolved in
45.0 g of acrylic acid (6.82% by weight, = 0.625 acid equivalent),
12.0 g of methyl methacrylate,
25.0 g of styrene (= 3.79% by weight),
7.4 g of dodecylmercaptan be 3 hours at about 145 ° C to the acid number 11 to the addition product, as described in Example 1, implemented.

In this example, 200 g of monomeric addition product from the glycidyl ester and acrylic acid in the presence of 25 g Styrene and 12 g of methyl methacrylate produced. The relationship Addition product to styrene is 84.38 wt .-% to 15.62 wt .-%. In the preparation of the addition product was in the presence worked from Dodecylmerkaptan.

example 14

The procedure is as in Example 10, worked, but are used
400.0 g of xylene,
209.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid of the type mentioned in Example 1 (= 34.83% by weight, = 0.853 epoxy equivalent),
0.2 g of potassium hydroxide dissolved in
61.0 g of acrylic acid (= 10.16% by weight, = 0.847 acid equivalent),
40.0 g of styrene (= 6.66 wt.%),
40.0 g of butyl acrylate (= 6.66 wt .-%) and
0.7 g of dodecylmercaptan.
The mixture was reacted for 2 hours at 142 ° C to the acid number 6.0, as described in Example 1, to the addition product.

In this example, 270 g addition product from the glycidyl ester and the acrylic acid in the presence of 50 g of styrene and 50 g of Dutylacrylat produced. The ratio addition product to the styrene and butyl acrylate is 77.14 wt .-% to 22.86 wt .-%.

example 15

The procedure is as in Example 10, worked, but are used:
294.0 g of xylene,
150.0 g of ethyl glycol acetate,
150.0 g of phenylglycidyl ether (= 22.79% by weight, = 1 epoxide equivalent),
0.2 g of lithium hydroxide dissolved in
72.0 g of acrylic acid (= 10.93% by weight, = 1 acid equivalent),
60.0 g of styrene (= 9.12% by weight),
60.0 g of n-butyl acrylate (= 9.12 wt .-%) and
5.0 g of dodecylmercaptan.
The mixture was reacted at 146 ° C for 3 hours to the addition product with acid number 75.

example 16

The procedure was as in Example 15, worked, but were instead of phenyl glycidyl ether, 130 g of n-butylglycidyl ether were used.

example 17

The procedure is as in Example 10, worked, but are used:
290 g of xylene,
150 g of ethyl glycol acetate,
178 g of benzoic acid glycidyl ester (= 27.04% by weight, = 1 epoxide equivalent),
0.1 g of potassium hydroxide and
0.2 g of lithium hydroxide dissolved in
70 g of acrylic acid (= 10.85% by weight, = 0.97 acid equivalent),
60 g of styrene (= 9.12% by weight),
60 g of n-butyl acrylate (= 9.12 wt .-%) and
4 g of dodecylmercaptan.
The mixture was reacted at 145 ° C for three hours to the addition product with the acid number 48.

example 18

The procedure was as in Example 17, worked, but instead of benzoic acid glycidyl ester, 128 g of octene-2-oxide used.

example 19

The procedure is as in Example 10, worked, but are used:
400.0 g of xylene,
209.0 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic acid of the type mentioned in Example 1 (= 34.83% by weight, = 0.853 epoxy equivalent),
61.0 g of acrylic acid (= 10.16% by weight, = 0.847 acid equivalent),
50.0 g of styrene (= 5% by weight)
The mixture was reacted for 3 hours at 142 ° C to the acid number of 15 to the addition product - as described in Example 1, but here calculated at 48 wt .-%.

In this example, 270 g addition product from the Glycidylester and the acrylic acid in the presence of 50 g of styrene and 50 g of butyl acrylate. The ratio addition product to the styrene and butyl acrylate is 73 wt .-% to 27% by weight.

In this example, no chain controllers were used.  

Example 20 (later) Studies on the storage stability of the intermediate solutions

According to the information in Examples 1 to 15 were intermediate solutions prepared according to the present invention. The obtained Intermediate solutions were filled into glass bottles and stored at room temperature for 4 months. The content of Glass bottles were completely transparent after this four-month storage period and free from cloudiness.

The 4 months stored intermediate solutions were then determined according to the information in DE-OS 28 51 616 copolymerized. The 4 months stored intermediate solutions prepared copolymer solutions were completely transparent and free from cloudiness. Furthermore, these showed - within analytical limits - the same acid numbers and viscosity values on like those copolymer solutions that immediately are copolymerized after preparation of the intermediate solution.

These special studies show that the intermediate solutions storage stable and thus commercially utilizable are.

Preparation of copolymer solutions from intermediate product solutions of the invention, further processing of the copolymer solutions to reaction lacquers and detection of the surprisingly advantageous properties of the reaction lacquers and the reaction lacquer coatings Example 21

The intermediate solution obtained in Example 2 is refluxed by heating to 140 to 146 ° C. Then, the following mixture, which is at room temperature, consisting of
130.0 g of hydroxyethyl methacrylate (= 19.72% by weight),
143.2 g of styrene (= 21.73% by weight),
143.2 g of methyl methacrylate (= 21.73% by weight),
6.7 g of dodecylmercaptan and
7.4 g of di-tert-butyl peroxide is added dropwise in 4 hours uniformly in the still at 140 to 146 ° C reaction mixture of the finished addition product with heating to reflux. After complete addition of the monomer feed, copolymerization is then continued for 3 hours at the same temperature.

The resulting copolymer solution has a solids content of 62.5% by weight and an acid number of 6.2. The viscosity the previously diluted to 50 wt .-% with xylene copolymer solution has a flow time of 195 seconds at 20 ° C, measured in a 4 mm flow cup Diameter of the outlet nozzle.

In the copolymerization is also contain dodecylmercaptan in the monomeric feed.

Example 22 Preparation of a reaction varnish

100 parts by weight of copolymer solution from Examples 21 and 40 Parts by weight of a 75% solution of a in xylene / Äthylglykolacetats logo CNRS logo INIST 1: 1 dissolved biuret aliphatic Triisocyanate, by reaction of 3 moles of hexamethylene diisocyanate and one mole of water has been obtained with an NCO content of 21% by weight, are mixed with a solvent mixture, consisting of xylene and butyl acetate = 1: 1 to one Viscosity of 18 seconds flow time, measured in a DIN cup with a 4 mm outlet nozzle at 20 ° C.  

Investigations of the reaction solution obtained according to Example 22 1. Determination of pot life, d. H. the durability of the two-component paint at 20 ° C. Outflow time in seconds (outlet nozzle 4 mm) beginning 18 after 24 hours 19 after 48 hours 22 after 50 hours 24 after 72 hours 42 after 96 hours 250 after 100 hours gelled

This result shows that these paints a surprisingly long Have pot life. Given the usual processing conditions in practice Increase of the viscosity by twice the Initial viscosity, d. H. maximum 36 seconds flow time - basis, this paint has a processing time of more than 60 hours. In addition, paint residues that are 96 hours old are diluted by adding freshly applied lacquer solutions be and still be processed well.

2. Determination of the curing time of the paint films This produced two-component lacquer solution is applied to a glass plate, so that a dry film thickness of about 40 microns results. 2a) Determination of pendulum hardness according to König at 20 ° C after a day 30 seconds after two days 80 seconds after three days 150 seconds after four days 188 seconds after seven days 200 seconds after ten days 201 seconds

It is surprising that the clearcoat already after 4 days Curing at 20 ° C its almost complete film hardness over Reached 188 sec. If you put this result in relation  four days of open pot life, d. H. that no gelling of the Lacquer solution occurs during this time, this result was surprising and unpredictable.

2b) Determination of king pendulum hardness after stoving 80 ° C and 30 minutes stoving time 80 ° C 30 minutes 55 seconds after one day at 20 ° C 95 seconds after two days at 20 ° C 165 seconds after three days at 20 ° C 189 seconds after seven days at 20 ° C 201 seconds after ten days at 20 ° C 200 seconds

The drying time of 30 minutes at 80 ° C is obtained After just another three days drying at 20 ° C the almost full film hardness of 189 seconds pendulum hardness.

The resulting paint films are very hard to the surface and can not be hurt with the fingernail sample. also These coatings are characterized by a very good light fastness and resistance to solvents such as xylene, toluene or acetone, out. After 1½ years Floridabewitterung at 5 ° C designed to the south sample sheets show these paint films no cracking and only a 10% reduced gloss compared to the initial gloss, which measured 110% DIN 67530 is.  

Example 23

The intermediate product solution obtained in Example 13, the 200 g addition product contains, is heated to 146 ° C.

The following mixture, which is at room temperature, consisting of
142.6 g of hydroxyethyl methacrylate (= 21.63% by weight),
133.2 g of styrene (= 20.21% by weight),
146.2 g of methyl methacrylate (= 24% by weight),
6.7 g of di-tert-butyl peroxide and
2.0 g of dodecylmercaptan is uniformly added in 3 hours at about 146 ° C and then copolymerized for a further 2.5 hours at the same temperature.

The copolymer solution has a solids content of 60.5% and an acid number of 4.5. The viscosity of previously with xylene on 50% by weight diluted solution is 150 seconds flow time, measured in the outlet cup with 4 mm outlet nozzle at 20 ° C.

Example 24 Preparation of a reaction varnish

100 parts by weight of copolymer solution from Examples 23 and 40 Parts by weight of a 75% solution of a in xylene / Äthylglykolacetats = 1: 1 dissolved biuret-containing aliphatic Triisocyanate, by reaction of 3 moles of hexamethylene diisocyanate and one mole of water has been obtained with an NCO content of 21% by weight, are mixed with a solvent mixture, consisting of xylene and butyl acetate = 1: 1 to one Viscosity of 18 seconds flow time, measured in a DIN cup with a 4 mm outlet nozzle at 20 ° C.  

Investigations of the reaction solution obtained according to Example 24 1. Determination of pot life, d. H. the durability of the two-component paint at 20 ° C. Outflow time in seconds (outlet nozzle 4 mm) beginning 18 after 24 hours 27 after 48 hours 70 after 50 hours 90

This result shows that these paints a surprisingly long Have pot life. Given the usual processing conditions in practice Increase of the viscosity by twice the Initial viscosity, d. H. maximum 36 seconds flow time - basis, this paint has a processing time of more than 60 hours. In addition, paint residues that are 96 hours old are diluted by adding freshly applied lacquer solutions be and still be processed well.

2. Determination of the curing time of the paint films

This produced two-component lacquer solution is applied to a Mounted glass plate, so that a dry film thickness of about 40 microns results

2a) Determination of pendulum hardness according to König at 20 ° C after a day 78 seconds after two days 120 seconds after three days 200 seconds

It is surprising that the clearcoat already after 3 days Curing time at 20 ° C its almost complete film hardness of has reached over 200 seconds. If you put this result in relation  to two days of open pot life, d. H. that no gelling of the Lacquer solution occurs during this time, this result was surprising and unpredictable.

2b) Determination of pendulum hardness according to König after firing at 80 ° C and 30 minutes burn-in time 80 ° C 30 minutes 120 seconds after one day at 20 ° C 150 seconds after two days at 20 ° C 200 seconds

The drying time of 30 minutes at 80 ° C is obtained after only two more days drying at 20 ° C the full film hardness of 200 seconds pendulum hardness.

The resulting paint films are very hard to the surface and can not be hurt with the fingernail sample. also These coatings are characterized by a very good light fastness and resistance to solvents such as xylene, toluene or acetone, out. After 1½ years Floridabewitterung at 5 ° C designed to the south sample sheets show these paint films no cracking and only a 10% reduced gloss compared to the initial gloss, the 110% - measured according to DIN 67 530 is.  

1. comparative study

Compared to products on the market in terms of pot life

To determine the "pot life" (pot life) were in the table above listed produced copolymers compared to on the market Products containing the aliphatic triisocyanate, by Reaction obtained from 3 moles of hexamethylene diisocyanate and 1 mole of water been mixed. The mixing ratios of the copolymers with the polyisocyanate, based on the solids content 70% by weight of copolymer: 30% by weight of polyisocyanate. The mixtures were mixed with a solvent mixture from xylene-butyl acetate in a weight ratio of 1: 1 to a viscosity of 18 seconds flow time, measured in a DIN cup with a 4 mm outlet, diluted and the viscosity increase was determined as a function of time at 20 ° C. How out the above table are the Copolymers prepared according to the known copolymers according to DE-AS 26 03 259 and DE-AS 26 26 900 clearly superior. The Copolymers prepared have a more favorable "pot life" in terms of slower viscosity increase or gelation. This allows for a much cheaper processing close the reaction lacquers.  

2nd comparative study

Compared to products on the market in terms of pot life

To determine the "pot life" (pot life) were in the table above listed produced copolymers compared to on the market Products containing the aliphatic triisocyanate, by Reaction obtained from 3 moles of hexamethylene diisocyanate and 1 mole of water been mixed. The mixing ratios of the copolymers with the polyisocyanate, based on the solids content 70% by weight of copolymer: 30% by weight of polyisocyanate. The mixtures were mixed with a solvent mixture from xylene-butyl acetate in a weight ratio of 1: 1 to a viscosity of 18 seconds flow time, measured in a DIN cup with a 4 mm outlet, diluted and the viscosity increase was determined as a function of time at 20 ° C. How out the above table are the Copolymers prepared according to the known copolymers according to DE-AS 26 03 259 and DE-AS 26 26 900 very similar.  

3. Comparison experiment a) Operation according to the prior art (later) Preparation of the addition product

400 g of Cardura E 10 glycidyl ester (according to Example 1 of the present description).
117.5 g of acrylic acid,
345 g of xylene
are held at 145 ° C for 1.5 hours under reflux. The acid number of the reaction product is 11.9.

Processing of the addition product

In a reaction flask with attached water separator 152 g of xylene and 140 g of ethyl glycol acetate filled. The solvent mixture is used for Boil heated (about 142 ° C).

The following mixture is added dropwise in the course of 5 hours with further heating in the solvent mixture:
345 g addition product (207 g reaction product),
190.4 g of styrene,
126.0 g of methyl methacrylate,
19.6 g of polypropylene glycol monomethacrylate (molecular weight: 350 to 387),
116.2 g of hydroxyethyl methacrylate,
6.4 g of di-tert-butyl peroxide,
7.4 g of dodecylmercaptan.
Rinse with 4 g of xylene and 10 g of ethyl glycol acetate. It is kept for 3 hours at circulation temperature (142 to 143 ° C).
The resulting copolymer solution is very cloudy.

b) Operation according to the invention Preparation of the addition product

In a reaction flask with attached water separator are
290 g of xylene,
140 g of ethyl glycol acetate,
160 g Cardura E 10,
47 g of acrylic acid,
190.4 g of styrene,
126 g of methyl methacrylate,
19.6 g of polypropylene glycol monomethacrylate (molecular weight: 350 to 370),
116.2 g of hydroxyethyl methacrylate
Heated to boiling for 1.5 hours. Thereafter, the acid number of the reaction product is 17.

Processing of the intermediate solution to the copolymer

The above-obtained intermediate solution is maintained at reflux temperature (140 to 141 ° C).
In the course of one hour, slowly let a mixture consisting of
6.4 g of di-tert-butyl peroxide,
7.4 g of dodecylmercaptan,
4.0 g of xylene,
10.0 g of ethyl glycol acetate
drip into the boiling intermediate solution. It is then further polymerized for 3 hours in the same temperature range.

It becomes a bright, clear solution with the acid number 9.3 (related to the solid) receive.

Summary

In the processing of the intermediate product (addition product solution) according to The prior art gives a turbid copolymer solution.

In the processing of the intermediate solution according to the invention to a Copolymerisatlösung with the same composition is a clear haze-free Solution received.

Comparative experiment (later) a) Preparation of a Methacrylsäureeaktionsproduktes according to Example 1 of DE-AS 16 69 009

300 g glycidyl ester of an α, α-Dialkylalkanmonocarbonsäure the Molecular formula C₁₃H₂₄O₃ with an epoxide equivalent of 245th to 253 (boiling range 5% to 90% at 760 mm Hg 251 to 278 ° C), 155 g Methacrylic acid, 0.08 g of hydroquinone and 50 g of ethyl acetate were in a Reaction vessel introduced, in which case no acrylic acid was added. The reaction mixture was added to complete the reaction for 6 hours with stirring Heated to 100 to 110 ° C. The acid number of the product obtained after the reaction (based on the solution) was 69.9.

b) Preparation of the copolymer solution

The following substances were introduced into a 2 liter flask:
60 g of 2-hydroxyethyl methacrylate,
5.2 g of methacrylic acid,
200 g of styrene,
200 g of ethyl acrylate,
150 g of methacrylic acid reaction product, according to a).
120 g of butyl acetate and
224 g of xylene.

The mixture was gradually heated to about 100 to 110 ° C. Then a solvent mixture of 3.6 g azobis was added. Isobutyrnitril and 120 g of toluene uniformly and dropwise added with stirring over 90 minutes, the Mixture was kept at the specified temperature. To  to the dropwise addition, the mixture became an additional 90 minutes long left in this state. Then a solution mixture from 3.6 g of azobisisobutyrnitrile and 120 g of toluene dropwise in the same way as described above, added. After that, another 2 hours to complete the reaction stirred.

The copolymer solution obtained is both in the heat and cold cloudy. The content of non-volatile matter was 49.0 wt .-%. The acid number, based on the solids was 24.5 and based on the solution 12th The viscosity, measured according to Gardner, was "Y".

Claims (8)

An intermediate product comprising an addition product of an α, β-unsaturated monocarboxylic acid with a monoglycidyl compound, optionally including minor amounts of unreacted α, β-unsaturated monocarboxylic acid and / or monoglycidyl compound and by-products formed, obtainable by:

• a) in an inert organic solvent having a boiling point between 75 and 200 ° C,
• b) 50 to 95 wt .-% equivalent amounts - with a molar ratio of monoepoxide to unsaturated monocarboxylic acid of 1: 0.98 to 1 - an α, β-unsaturated monocarboxylic acid and a Monglycidylverbindung, with
• c) 5 to 50 wt .-% of one or more monomeric vinyl compounds have been reacted, wherein the mixture of a) and b) with the further vinyl compound c) optionally in the presence of inhibitors and / or chain regulators by heating to 80 to 185 ° C. has been held until the α, β-unsaturated monocarboxylic acid and the monoglycidyl compound to 95 to 100 wt .-% reacted.

2. Solution according to claim 1, characterized in that this up to Contains 2.5 wt .-% chain regulator. 3. Solution according to claim 1 or 2, characterized in that this contains at least one epoxy-carboxy catalyst. 4. Solution according to one of claims 1 to 3, characterized that the addition product as added α, β-unsaturated Monocarboxylic acid acrylic acid, methacrylic acid and / or crotonic acid contains singly or in a mixture. 5. Solution according to one of claims 1 to 4, characterized that the addition product substituted as added monoepoxide Alkyl compounds, ethers and esters which have a threefold Epoxy ring included, individually or in mixture contains. 6. A solution according to claim 5, characterized in that this as added ester monoepoxides glycidyl esters of aliphatic monocarboxylic acids from the group consisting of acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, 2-Äthylhexansäure, isononanoic acid, α, α-Dialkylalkanmonocarbonsäuren in which in α Position to the carboxyl group, the hydrogen atoms of the alkane monocarboxylic acid are substituted by alkyl radicals, so that a tertiary carbon atom is present, having the formula (1) wherein R¹, R² and R³ are alkyl groups and the total of the carbon atoms of all alkyl groups is 3 to 25 contains. 7. Solution according to one of claims 1 to 6, characterized that as other vinyl compound styrene, vinyltoluene, α-methylstyrene and halostyrene; Esters of acrylic, methacrylic and crotonic acid with saturated alcohols having 1 to 10 carbon atoms in the alcohol radical, such as methyl, ethyl, Propyl, isopropyl, n-butyl, isobutyl, sec., Tert-butyl, Amyl, hexyl, heptyl, octyl, nonyl and decyl radicals; Vinylester of α, α-dialkylalkane monocarboxylic acids of the above formula (1); Vinyl acetate, vinyl propionate, singly or in admixture; hydroxyl-bearing α, β-ethylenically unsaturated compounds from the group hydroxyethyl methacrylate, hydroxyethyl acrylate, Hydroxypropyl acrylate, hydroxypropyl methacrylate, butanediol monoacrylate and / or butanediol monomethacrylate, hydroxyl group-bearing Ether ester, polypropylene glycol monomethacrylate and / or polyethylene glycol monomethacrylate having average molecular weights between about 175 to about 390. 8. Use of the intermediate solutions mentioned in claims 1 to 7 for the preparation of in organic solvents soluble, haze-free copolymer solutions.