DE2851615C2 - Process for the preparation of copolymers containing hydroxyl groups which are soluble in organic solvents and their use - Google Patents

Description

a) 20 to 32% by weight styrene and / or vinyl toluene,

b) 16 to 26 wt .-% methyl methacrylate, _χ

c) 26 to 16% by weight of hydroxyethyl methacrylate. of which, if appropriate, up to 7% by weight of hydroxyethyl methacrylate by polypropylene glycol monomethacrylate with the formula

CH ₃

CH ₃

CH ₂ = C-COO (CH ₂ CHO) _n -H
are replaced

where η denotes numbers from 5 to 6 and the average molecular weight is about 350 to 387,

d) 6 to 9% by weight of acrylic acid and / or methacrylic acid and

e) 20 to 30% by weight of glycidyl esters of aliphatic saturated monocarboxylic acids having 9 to 15 carbon atoms are produced, the components a. b, c. d and e are selected so that that these add up to 100% by weight.

4. The method according to claim 1, characterized in that copolymers from

ίι) IO to 29 wt .- ^. Styrene and / or vinyl toluene,

b) 18 to 26% by weight of methyl methacrylate.

c) 16 to 26 percent by weight, hydroxyethyl methacrylate.

d) 7 to 12% by weight of acrylic acid and / or methacrylic acid and

e) 36 to 20% by weight of glycidyl esters of aliphatic saturated monocarboxylic acids with 9 to 15 carbon atoms are produced, the Components a. b. c, d around. e are selected so that they add up to 100 wt .- 'v.

5. The method according to claim I, characterized in that that copolymers from

a) 27 to 32 λ by weight, styrene and / or vinyl toluene.

b) IS to wt. ",. Methylmeihacrylal.

40

50

55

60 Ci) 16 to 18 wt .-% hydroxyethyl methacrylate,
C ₂ ) 2 to 6% by weight of polypropylene glycol monomethacrylate with the formula

CH ₃ CH ₃

I.

CH ₂ = C - COO- (CH ₂ CHO) _n -H,

where η denotes numbers from 5 to 6 and the average molecular weight is about 350 to 387,

d) 6 to 7% by weight acrylic acid and / or methacrylic acid and

e) 23 to 25% by weight of glycidyl esters of aliphatic saturated monocarboxylic acids having 9 to 15 carbon atoms be prepared, the components a, b, c, d and 3 are selected so that that these add up to 100% by weight.

6. The method according to claim 1, characterized in that that copolymers from

up to 40% by weight s) styrene and / or vinyitoluoi and / or b) methyl methacrylate, up to 40% by weight b,) acrylic acid ester and / or Methacrylic acid esters of aliphatic saturated monoalcohols with 2 to 12 carbon atoms,

up to 30 % by weight c) hydroxyethyl acrylate and / or hydroxyethyl methacrylate. Polypropylene glycol monomethacrylate with the formula

CH ₃ CH ₃

! I.

CH ₂ = C-COO- (CH ₂ CHO) _n -H,

where η denotes numbers from 5 to 6 and the average molecular weight is about 350 to 387,

up to 12% by weight n d) acrylic acid and / or methacrylic acid and

be manufactured% glycidyl esters of aliphatic saturated monocarboxylic acids having 9 to 15 carbon atoms, wherein the components abc d and e are selected such that these up to 100 wt .- 'i - to 15 wt.. add to.

7. Use of the copolymers obtainable according to Claims 1 to 6 based on vinyl compounds. jr, / J-unsaturated monocarboxylic acids and monoglycidyl compounds, polyisocyanates, inert organic solvents and, if necessary, other additives customary in reactive lacquers in Quantities of (A) 60 to 95% by weight as a component in reactive lacquers.

8. Use of the copolymers obtainable according to claims 1 to 6 in amounts of (A) 70 bis % By weight in stoving enamels.

65 In DE-PS 1038 754 a process / ur production of esterified polyhydroxy copolymers is described. This known method is thereby

characterized in that at the same time and in the presence of an epoxy-carboxy catalyst and a catalyst for vinyl polymerization are reacted: (a) a short-chain a, /? - unsaturated monocarboxylic acid, (b) a vinyl monomer with only one active terminal capable of addition polymerization CH ₂ = C <group and (c) a monoepoxide which is an optionally alkyl-substituted alkylene oxide, an ether or ester with only one three-membered epoxide substituent, the monoepoxide otherwise having no reactive group. The reaction must always be carried out simultaneously in the presence of an epoxy-carboxy catalyst and a catalyst for the vinyl polymerization. As reworking of the examples there has shown, these known copolymers give yellow to brownish colored solutions. The paint films produced therefrom show an undesirable yellow to brown coloration after the solvent has evaporated, so that these products can only be used to a very limited extent.

In the FR-PS 1J90 572 is also a method for Production of esterified polyhydroxy copolymers described, the addition reaction between the epoxy and carboxy group takes place during or after the copolymerization. The application of this procedural principle has been described in the following publications: 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 this known method on a factory scale is that for the complete Conversions, namely esterification and copolymerization, relatively long conversion times (12 to 15 hours) required are. Unwanted side reactions take place here, since the carboxyl group is the ar, /? - unsaturated Monocarboxylic acid before and after its copolymerization with the other monomers with reactive groups, z. B. with the hydroxyl groups and / or glycidyl groups with ester formation, and the glycidyl groups ίο react with each other or with the hydroxyl groups under ether bond structures. Such reactions are therefore very sensitive to the reaction conditions, so that it is on an industrial scale Scale is required to adhere to the reaction parameters very precisely in order to produce copolymers with the to reliably produce the desired properties in a comparable quality. It also takes place very carefully Reaction always carried out a certain amount of gel particle formation with particle diameters of about 5 up to 25 lacquer films produced are marked as "slips" b2 and no high-performance lacquer is achieved allow.

In DE-OS 16 68 510 isi also a method for « Production of esterified polyhydroxy copolymers described, but the acldition reaction between the epoxy and carboxy groups is carried out before, after or during the copolymerization. at of the embodiment in which the esterification is carried out during or after the copolymerization the designs of the type already explained above with the stated disadvantages. In the embodiment. in the case of two reaction components, namely the ^. / (- unsaturated monocarboxylic acid with the epoxy compound, which is a glycidyl ester of a tertiary aliphatic monocarboxylic acid, first;: alone in the absence from esterification chewy lysmors to a preliminary product are processed as esters (as is also done in DE-PS 27 09 784 and 27 09 782), the result is A surprising disadvantage is that the copolymer solutions and the paint films produced from them are cloudy are also tarnished. Furthermore, further difficulties can easily arise because the ^ -unsaturated carboxylic acid tends to polymerize with itself, as a result of which the homopolymers formed in the process also Cause clouding. Such findings are also supported by the information in DE-PS 10 38 754 Column 9, lines 43 to column 10, line 8 and in DE-PS 26 26 900 column 19, lines 1 to 39 are confirmed.

The object of the invention is to overcome the above-described disadvantages of the known and in some cases on an industrial scale to significantly improve the method of the type explained above, namely:

1. The copolymer solutions should be colorless and bright. This means that the manufactured with it Varnish films should also be "free of specks" or very "low-fat" and despite the presence of the The catalyst does not yellow.

2. The manufacturing process should also be relative to the reaction conditions on a factory scale be insensitive, so that after determining the optimal reaction parameters even with small Deviations from the reaction conditions always usable, high-performance copolymers are obtained and undesirable side reactions are also due to the catalyst in the Copolymerization and largely avoided when using the copolymers.

3. The manufacturing process is said to be particularly significant when carried out on a factory scale The shortened implementation time can be carried out in one-pot process, all the more so due to the considerably shortened Boiler occupancy time to significantly increase the productivity of the manufacturing plant and thus lowering production costs.

4. The manufacturing process should allow, furthermore improved copolymers based on known or new monomer compositions to manufacture.

5. The copolymers produced by the process should be non-adhesive, waterproof and elastic Produce films on a wide variety of substrates or as binders for pigments. Opaque colors and nonwovens be suitable, as well as be usable as a binder component, the produced therewith Coatings or flat structures have advantageous properties in different directions.

The object of the invention was achieved in that the esterification stage with simultaneous copolymerization in the presence of selected epoxy-carboxy catalysts was carried out.

The invention relates to a method for production of soluble in organic solvents hydroxyl-containing copolymers on the Based on vinyl compounds from the group of aromatic vinyl compounds, acrylates and methacrylates with 1 to 12 carbon atoms in the alcohol radical, the Esters of crotonic acid with saturated alcohols containing 1 to 10 carbon atoms in the alcohol residue, the Vinyl ester and hydroxyl group-bearing jr./i-ethylenic unsaturated compounds on the one hand and unsaturated compounds Monocarboxylic acids and monoglycidyl compounds, on the other hand, by heating with esterification

in the presence of an epoxy catalyst and at the same time Copolymerization by means of polymerization initiators in inert organic solvents and optionally Chain terminators, characterized in that at least one epoxy-carboxy catalyst Alkali compound is used.

As esterification catalysts based on an alkali metal compound, all sodium, lithium, Potassium, rubidium and cesium compounds - individually or in a mixture - are used, which in the reaction mixture of (/, ^ - unsaturated monocarboxylic acid, Monoglycidyl compound and at least two other vinyl compounds are soluble and at least in the Addition and / or while keeping the reaction mixture at the reaction temperature for the purpose of esterification by addition go into solution with simultaneous copolymerization, but the alkali compound used is free of should be such constituents that are used in the copolymerization of the addition product, which is an ester, can have an adverse effect.

For example, the carbonates, bicarbonates, formates and the hydroxides of the above are useful called alkali metals. On a factory scale, lithium hydroxide and potassium hydroxide are best used individually or in a mixture - proven.

When used on a factory scale, this is due to the cheap price and excellent The potassium hydroxide is used with particular preference as a catalyst. This is expediently used Alkali hydroxide or the alkali compound or mixtures thereof in the ^ -unsaturated to be esterified Dissolved monocarboxylic acid. But you can also from the alkali compound, z. B. alkali hydroxides, alkali carbonates or alkali bicarbonates, and the ar, / J-unsaturated Monocarboxylic acid first produces its alkali salt as a catalyst and can then use the alkali salt of the ar, /? - unsaturated Dissolve carboxylic acid in the reaction mixture or when carrying out the esterification and copolymerization Bring into solution by heating.

In general, it is sufficient to have from about 0.005 to about 0.5% by weight of the alkali metal compound mentioned type, based on the weight of the ester-forming components, to be added for the addition reaction. However, an addition of about 0.01 to about 0.3% by weight of the alkali metal compound is preferred.

The most preferred range for the addition is about 0.02 to about 0.1 wt% alkali metal compounds, Of the alkali metal compounds, potassium and lithium compounds are particularly advantageous Find use.

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

The monoepoxides include substituted alkyl compounds as well as ethers and esters, provided that the one is tripartite Contain epoxy ring, as well as styrene oxide.

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

Examples of substituted ether monoepoxides are butyl glycidyl ethers. Hexyl glycidyl ether. Octyl glycidyl ethers and phenyl glycidyl ether.

Examples of ester monoepoxides are the glycidyl esters of the following acids: acetic acid, propionic acid. Butyric acid, Caproic acid, Ca'rylic acid, 2-ethylhexanoic acid. Isononanoic acid, or.ar-dialkylalkane monocarboxylic acids. in those in -position to the carboxyl group substituted the hydrogen atoms of the alkane monocarboxylic acid by alkyl radicals are such that a tertiary carbon atom is present, with the formula

R '
R ² -C-COOH

R ³

wherein R ¹ , R ² and R ^{3 represent} alkyl groups and the total sum of the carbon atoms of all alkyl groups is 3 to 25. The glycidyl esters of the cr.jz-dialkylalkanemonocarboxylic acids with 9 to 13 carbon atoms in the alkyl group are preferred.
The most preferred glycidyl ester of an ar.z-dialkylalkanemonocarboxylic acid has the empirical formula ChHhC ,.

Examples of the aromatic ^v nylverbindungen are styrene, Vinyitoiuoi, ar-Methyisiyroi ·. nd shark styrofoam. which apart from the vinyl group have no group capable of reacting with the carboxyl group.

Examples of the esters of acrylic, methacrylic and crotonic acid are the esters with methyl, ethyl, propyl. Isopropyl, η-butyl, isobutyl, sec-butyl, ten-butyl, Amyl, hexyl, heptyl, octyl, nonyl and decyl alcohol.

Examples of vinyl esters that can be used are: vinyl esters of Zit-Dialkylalkanmonocarbor.säuren with the formula

R ¹
R ² —C — COOH

R ³

wherein R ¹ . R ² and R 'denote alkyl groups and the total sum of the carbon atoms of all alkyl groups is 3 to 25, and of these, vinyl esters with the sum formula CqHi ₉ -CO-O-CH-CH _{2 are} preferred. Vinyl acetate and vinyl propionate can also be used as vinyl esters.

As x / i-ethylenically unsaturated ones bearing hydroxyl groups Compounds can be Hydroxyäthylmethacrylat, Hydroxyäthylacrylai, Hydroxypropylacrylai, Hydroxypropylmethacrylat as well as butanediol monoacrylate and / or butanediol monon'.ethacrylate, individually or in a mixture, be used. Furthermore, ether esters bearing hydroxyl groups, such as polypropylene glycol monomolyte acrylate, are also used and / or polyethylene glycol monomethacrylate with average molecular weights between 175 to 390, usable.

In a preferred embodiment of the method is worked with a deficit of jr./i-unsaturated monocarboxylic acid "up to the equivalent, with the molar ratio of monoepoxide: ^. / '- unsaturated Monocarboxylic acid 1: 0.95 to 1 is. The copolymers should have acid numbers from 3 to 5. the The hydroxyl numbers of the copolymers should be 40 to 200 be.

A Ausführui.3sforrr> the method inspects the fact that for the implementation of 1 1 to 0.5 wt ^'1., Pr./i-ungesiitligtc carboxylic acid. 1.5 to 39% by weight, mnnoglycidyl compound

manure. 5Ii to 9X wt. of the other vinyl compounds are used, it being possible for the other vinyl compounds to contain up to / u 30% by weight ¹ · .. one or more vinyl compounds with a hydroxyl group in the molecule.

Another embodiment of the method of the invention provides that acrylic acid and / or methacrylic acid. Monoglycidyl esters or monoglycidyl ester mixtures of aliphatic saturated monocarboxylic acids with 2 to 19 carbon atoms. Styrene. Vinyl esters of saturated monocarboxylic acids or mixtures of such esters with 4 to 1 ⁽ ) carbon atoms in the carboxylic acid molecule. Athylaerylate. n-, iso-. sec.-, tert-butyl acrylate, methylaerylai, ethyl methacrylate. n-, iso-, sec.-. tert-Hutylmeihacrylai. Methyl methacrylate and llydroxyäthylacrylai. Hydroxy prop \ IacryUu. Butanediol monoacrylate. Hydroxy ethyl methacrylate. Hydroxypropyl methacrylal, Buiandiolmonomethacrylal are implemented.

A special embodiment of the method is uauun.ii gckcnri / ciLtitici. uaß 6 ui? » iz ucw.- ^r i. Aciyisäuie with 18 to 44 wt .- ",, glycidyl ester of a x. Jr-Dialkylalka ^ monocarboxylic acid with the sum formula ChHj ₄ Oi. De ^ jn structure about

R 'O

I Il / ^u \

I Il / \

R- -CCOC H ² -C HC H ²

R <

corresponds to where R ¹ . R ^: and R 'represent straight-chain alkyl groups, of which at least one is the methyl group Kt. The molar ratio of glycidyl ester to acrylic acid is 1: 0.98 to 1, and 15 to 30% by weight, styrene and / or vinyl toluene. 15 to 25% by weight methyl methyl acrylate. 15 to 25% by weight ¹ V, hydroxyethyl methacrylate. is implemented and the implementation until reaching. -w ~ * <hr C'Iaae ^ -S'tl-hl ¹ 1 l · * tf V Λ »-Γ / \ 1 rt» »ι η / -J SI ad iiirtnnisiart I -aiii _ ι 1

must add up to 100% by weight.

A special embodiment of the process is characterized in that 5 to 7% by weight of acrylic acid with 17 to 25% by weight of a glycidyl ester of a x, 7-dialkylalkane monocarboxylic acid with the empirical formula CnHj ₄ Oi

R ¹ O

.O,

R ^ CCO-CH ₂ -CH-CH ₂

i
R ^;

corresponds to where R '. R ^: and R 'represent straight-chain alkyl groups, at least one of which is the methyl group. where the MoKer ratio of glycidyl ester to acrylic acid is 1-0.98 to 1, and 25 to 30% by weight, styrene. 15 to 20% by weight, methyl methacrylate. 15 to 20 wt ^r '. Hydroxyethyl methacrylate, 2 to 6 wt + ^1. Polypropylene glycol monomethacrylate. its structure roughly the formula

CH-.

CH-,

₂ = C-COO- (CH ₂ CHO) _n -H

corresponds, where η denotes numbers from 5 to 6 and the average molecular weight is about 350 to 387 and 3 to 10 wt .- *, vinyl ester of a jr, z-Diaikyialkanmonocarbonsäure with about the formula C ₉ Hi ₅ -CO-O-CH = CH ₂ . where the grouping C ₅ H, ₉ largely has the structure

CII;

IC _: H, —C -

CMI ₁₁

aulwe:;, where the weight- ",, to 100 weight-" ,. add to must be copolymerized until acid numbers of 3 to 5 are present.

A special embodiment of the process of the invention is characterized in that for copolymers, which are intended for polyisocyanate crosslinking, the starting components are selected and are implemented that copolymers with a hydroxyl group content of about 2 to about 6 wt .- ",,. based on the weight of the starting monomers.

A more specific embodiment of the above Embodiment of the method is characterized in that the starting components are selected and are implemented as long as copolymers with acid numbers of 2 to 12, preferably 3 to 6 are obtained.

One embodiment of the process is characterized in that for copolymers which are used for crosslinking The starting components are determined with amino resins are selected and implemented so that copolymers with a hydroxyl group content from 2 to 4.5 wt .-% based on the weight of the starting monomers, and with an acid number of IO to 15 can be obtained.

Another preferred embodiment of the process consists in that as the organic solvent Xylene. Monoglycol ether acetates or mixtures of xylene and mono ether acetates are used, with as Polymerization initiator 0.8 to 1.5% by weight, di-tert.-

merkaptan can be used as a chain terminator, with the percentages by weight for the polymerization initiator and the chain terminator are based on the sum the weights of the monomers used to be converted.

The most preferred embodiment of the invention is characterized in that the solvent Xylene or the mixture of xylene and Äthylglykoiacetat heated with the glycidyl ester to 140 to 180'C, another Mixture consisting of acrylic acid in which the catalyst was dissolved, then with the other monomers Add vinyl compounds di-tert-butyl peroxide and dodecyl mercaptan evenly in 2 to 5 hours and Polymerized and condensed for a further 4 to 5 hours at constant temperature.

Suitable solvents for the preparation of the new copolymers are those which are not active

"Contain hydrogen atoms like xylene, monoglycol ether acetates or mixtures of monoglycol ether acetate and xylene, with monoglycol ether acetates being exemplary Methyiglycolacetat, Äthylglykoiacetat, Isopropylglykolacetat or n-Butylglykolacetat can be mentioned.

As polymerization initiators, for example, diacyl peroxide, z. B. dibenzoyl peroxide, perester, e.g. B. tert-butyl peroctoate, and dialkyl peroxides, e.g. B. Di-tert-butyl peroxide, as well as all peroxides whose half-lives are in a temperature range of 50 to 150 ° C,

⁶ - can be used.

The peroxide part is 0.5 to 5% by weight, based on the total proportion of a:, / J-ethylenically unsaturated Monomers including the esterified monoepoxides.

Ociylmerkaptan, for example, are used as a ladle regulator. Decylmerkaptan, I.aurylnierkapian unt! that branched Dodecylmerkapian used. The proportion of chain rulers, based on the total proportion of ethylenic unsaturated monomers including the esterified monoepoxides amounts to 0 to 2.5 wt.

These copolymers can be used as a component in reactive lacquers together with a polyisocyanate component be used.

To use the copolymers prepared according to the invention, the mixtures are applied Solvent-containing hydroxy group-containing copolymers and polyisocyanate in the simplest possible way, for example after adding known oils. like leveling agent. Pigments or dyes, by spraying. Diving, pouring. Brushing or other suitable measures onto the appropriate documents and dry the sheet-like structures at room temperature; in With special fillings, the coatings can be baked in, which essentially depends on the type of material used Documents and the requirements imposed by practice on the coatings. Also the use of reactive melamine resins can be beneficial. The reactive melamine resins can be found in Add amounts of 1 to 10% by weight, based on the weight of the binder component, whereby in particular an increase in gloss can be observed in the fabric.

When the copolymers are used in the reactive lacquers already explained, the reaction takes place and applying the fabrics to the substrate in solution. Suitable solutions are e.g. B. acetic acid Ethyl ester, butyl ester, ether ester. Diethylglykoldiacelal as well as aromatics such as benzene, toluene or xylene. The concentration the solutions can vary within wide limits and is essentially based on the Solubility of the components. Solutions with a solid content of 20 to 80% by weight are preferably used.

When using the manufactured according to the invention Mixed polymers in reactive lacquers, the components are preferably used in the following amounts:

60 to 95% by weight of copolymers containing hydroxyl groups, produced according to the invention.
5 to 40% by weight organic polyisocyanate. which together numerical values of 100 wt ¹ V, must arise.

example 1

In a reaction vessel equipped with a stirrer, reflux condenser and thermometer, the mixture is refluxed at approx. 146 ° C a mixture consisting of

294.0 g xylene,

150.0 g ethyl glycol acetate,

144.5 g of glycidyl ester of an α, α-dialkylalkane monocarboxylic _{acid with the formula ΟπΗ 2} 4θ3 with an epoxy equivalent of 245 to 253 (boiling range 5 to 90% at 710 mmHG from 251 to 278 ° C) *). (0.59 epoxy equivalent, 21.72 = wt%.)

The following mixture, which is located at room temperature in a dropping funnel, consists of 26.2 g of vinyl ester of an x, ^ -dialkylalkanemonocarboxylic acid with the formula CIIlCO-O-CH = CHj (3. ¹ M wt. ¹ · ,,). the rest CoMi «largely due to the structure

C ₂ Ih-C-CH,

CH _n

can be marked.

116.1 g llydroxyüthylmethacrylat (17.45 wt ¹ ,,).

26, Og polypropylene glycol monomethacrylal with an average molecular weight of 350 to 387 and a hydroxyl number of 145 to 160 (3.9% by weight) ♦ *).
192.0 g styrene (28.85% by weight),

118.0 g of methyl methacrylate (17.7% by weight),
6.4 g of di-tert-butyl peroxide.
6 4g dodecyl mercaptan.

4: .0g acrylic acid (6.388 wt. ", And 0.583 acid equivalent),

0.3 g of potassium hydroxide, with the potassium hydroxide was first dissolved in the acrylic acid, added dropwise evenly over 4 hours and then copolymerized for a further 5 to 6 hours. The copolymer solution has a Solids content of 61.8%. The viscosity of the solution diluted to 50% with xylene gives a Flow time of 115 seconds, measured in Din cup with 4 mm nozzle. The acid number of the copolymer is 3.3.

The calculation of reaction batches for the production of copolymers with a certain hydroxyl group content is in DE-AS 26 03 259 in the chips 5 and 6 and in DE-AS 26 26 900 have been described.

·) The glycidyl ester is in the Technical Bulletin RES / CAX / 1 of Shell Chemicals with the title: »Shell Resin Intermediates Cardura E 10 ". described. Its structure can be represented by the following formula are based on a synthetic saturated, highly branched Monocarboxylic acid with 10 carbon atoms is based

R ¹ O _n

R ^: -C-C-O-CH; -CH-CH ;.

i.

wherein R ¹ . R ² and R ^! represent straight alkyl groups, at least one of which always represents the methyl group.

**) The above product can be represented by the following formula:

CH ₃ CHj

i I

CH ₂ = C-COO- (CH, -CHO), -H.
where η denotes the numerical values 5 to 6.

11 12

Table I. Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Examples 2 to 7 294 g 294 g 294 g 294 g 294 g 294 g 220 g xylene and 111g Solvesso 100 Item 1 xylene 150 g 150 g 150 g 150 g 150 g 150 g 111g butyl acetate 160 g 160 g 145 g 145 g 155 g 155 g 155 g Pos. 2 ethyl glycol acetate Pos. 3 glycidyl ester from 46 g 46 g 42 g 42 g 45 g 45 g 45 g Example 1 19.6 g 19.6 g 26 g 26 g 33 g 33 g 33 g Pos. 4 acrylic acid Item 5 polypropylene glycol monomethacrylate 190.4 g 190.4 g 198 g 198 g 197.7 g 158.2 g 159.2 g Example 1 126 g 126 g 112g 100 g 118.6 g 158.2 g 158.2 g Item 6 styrene 116.2 g 116.2 g 116.1 g 116g 10V.6 g HU g HU g Pos. 7 methyl methacrylate Item 8 hydroxyethyl meth- - - 21 g 26 g - - - acrylate Pos. 9 vinyl ester one α, α-dialkylalkane mono- 0.3 g - - - 0.1 g 0.1 g 0.1 g carboxylic acid - 0.1 g 0.1 g 0.1 g 0.1 g - - Pos. 10 potassium hydroxide 7.4 g 7.4 g 6.4 g 6.4 g - 7.4 g - Pos. 11 lithium hydroxide 6.4 g 6.4 g 6.4 g 6.4 g 6.4 g 6.4 g 6.4 g Pos. 12 dodecyl mercaptan 4 hours 4 hours 4 hours 4 hours 2 hours. 4 hours 4 hours Item 13 Di-tert-butyl peroxide 5 hours 6 hours 6 hours 4 hours 5 hours 5 hours 5 hours Inflow time of items 4 to 13 Copolymerization time after 109 sec. 98 sec. 95 sec. 98 sec. 382 sec. 98 sec. 192 sec. DIN 4 *) Incoming end Din 4 Din 4 Din 4 Din 4 Din 4 Din 4 Expiry time of 50% 4.0 4.2 4.0 4.3 4.8 4.8 4.6 diluted solution 62% 61.3% 61.3% 60.8% 62.8% 62.4% 62.5% Acid number Solids content

Iodine color number according to DIN 6162 <1 <1 <1 <1 <1 <1 <1

In Examples 2 to 7, the solvents and the glycidyl ester are, as described in Example 1, to 144 to 148.degree heated and the monomers and the catalyst dissolved therein, which were kept at room temperature, in the kept boiling Mixture added evenly and then copolymerized.

*) diluted to 50% by weight copolymer solids with ethylglycol acetate.

Comparative examinations to prove 50 makes borrowed. As soon as the exothermic reaction subsides, the differences essential to the invention is heated again so that the mixture continues under

compared to the procedure according to DE-PS 10 38 754 reflux boils until an acid value of 11.0 is reached

_Attempt (about 8 hours).

(according to Example 1, DE-PS 10 38 754) _v . ^D , ^{ie so} . ^^ ⁵ ^ ¹ ^^^, ⁰¹ ^ ⁶¹ ? ⁵³¹¹ ^ "? ^Bes j ^{LZT that}

⁶ 55 viscosity of 10 200 centipoise at 20 ° C and one

535.0 g of methyl isobutyl ketone were poured into a solids content of 52.1% by weight (2 hours Stirrer, thermometer and reflux condenser equipped at 150 ° C).

Filled in th 2-liter flask. The reactants become this solvent

the 178.5 g propylene oxide, 221.6 g acrylic acid and the theoretical solids content is 58.8% by weight 96.

400.0 g of styrene are added. In addition to the 178.5 g Pro-60

pylene oxide is a 10% excess (17.9 g) used ",.

det that compensates for a loss due to volatility, _ " _D. . ^ f ¹¹¹ L ₁ - _nc . ",,. ,,.

target. 16.0 g of ... ^{ & ™ * Be.sp.el 1, DE-PS 10 38 754

Benzoylperoxvd and 22.9 g of a 35% solution of ^{but with Katai} y ^{sator of the} present invention)

Benzyltrimethylammonium hydroxide in methanol was used as in Experiment 1 above. The flask inhalation is brought to reflux temperature (75 degrees, but with the modification that the benzyitribis 80 ° C) heated, with an exothermic reaction of a methylammonium hydroxide by potassium hydroxide sets that an interruption of the heat supply has been replaced.

Πί; ', ο Mischpolymerisailösung prepared has the viscosity of 49 200 centipoises at 20 "C after diluting with methyl isobutyl ketone to a solids content of 56.3 wt ^1.,.

The solid substance content (before dilution) is 59.7% by weight. When the The theoretical solids content is 60% by weight of the reaction partner.

Attempt 3

(according to example 1. DE-PS 1038 754.
but without a catalyst)

It was worked as in the above experiment 1, but with the change that the Benzyltrimeihylammoniumhydroxyd was omitted.

The viscosity and the solids content of the mixed polymer solution produced in this way could not be determined because insoluble components were present. The säu ^r Ewert was ^l> 5th This shows an insufficient

Discussion of experiments 1 to 3

Experiments 1 to 3 above show that the reaction cannot be carried out on an industrial scale without a catalyst. In the Experiment 1 (prior art) 6.7 wt take ¹ V of the reactants in the reaction does not participate so that (in the implementation on an industrial scale in a special process stage as well as in DE-PS 10 38 754. Column 5th line 70 to column 6th line 5), the unreacted reactants must be separated in order to avoid inadmissible environmental pollution.

In the procedure according to the invention, the reactants are practically completely implemented, so that the theoretical yield is achieved and thus no separation operations are required to avoid environmental pollution to avoid.

5.3. The iodine larb number according to DIN gave a value of 2 and thus a strong yellowish CopoU merisailosu.ig. while those with TiCl; pigmented films ·: yellowing exhibited.

In contrast, the copolymers according to the invention were colorless and the _{films pigmented with TiO:} did not show any yellowing either.

Further comparative studies ίο (taking into account DE-AS 26 26 TOG

as proof of technical progress)

Production of the copolymer 1 according to DE-AS 26 26 TOO

325 grams of xylene. 155 g Ath> IgK kolacetal and 214 g glycidyl ester \ on x. jr-Dialk> lai. \ anmonocarhonsäuren following empirical formula C,; H.-jOi -.ml "14" C are heated under reflux and a mixture consisting of 145 g of methyl methacrylate. 135 g of hydroxyethyl methacrylate. 2 g of tert-dodee yimer kaptan. 160 g of St> ro 1. 63 g of acrylic acid and 7 g of di.-ierl.-Buiylperowd added uniformly in 1 hour and polymerized and condensed for about 6 hours at 140 to 145 ° C. The product results in a solids content of 60 Geu.-. The solution diluted to 50 "solids with xylene gives viscosities of 350 seconds, measured in a DIN beaker with a 4 mm outlet opening at 20 ° C. The acidity of the copolymer has a value of 8.0. Further refluxing of the batch no longer changed the acid number.

Comparison copolymer according to the invention

The procedure was as described in Example 1 of DE-AS 26 26 TOO, but with the difference. i.e.! 3 the addition of 0.32 g lithium hydroxide previously dissolved in the acrylic acid and with the other compounds of the feed mixture was mixed.

The course of implementation was determined by the the acid number, based on the copolymer.

Further comparative studies
as proof of technical progress

Attempt 4

The procedure was as in Example 1, but based on the type and amount of solvents and monomers from Example 2 for the purpose of the comparative investigations. An extremely small amount was churned out as a catalyst in order to keep the yellowing of the resin solution as low as possible, since with larger amounts of catalyst already strong brown discoloration occurs. It was therefore used 0.3 g of triethylamine. The product had a solids content of 62% by weight and, after dilution to 5 (K with xylene, a viscosity of 88 seconds flow time, measured in a Din beaker with a 4 mm nozzle at 20 ° C. The acid number was 5.8 The iodine color number according to DIN gave a value of 2 to 3 and thus a strongly yellowish copolymer solution The pigmented films obtained _{with TiO 2 also showed yellowing.}

Attempt 5

The procedure was as in Experiment 4, but 1 g of a 4OtIgCn methanolic solution of benzyltrimethylammonium hydroxide was used instead of triethylmine. The product gave a solids content of 61.6 weight ^a o, and a flow time of 117 seconds as measured as 50 ° OIGE solution in xylene, and determines an acid number of.

One hour after the end of the feed acid number S. ^l)

Two hours after the end of the acid number .5

Three hours after the end of the addition, the acid number was 5.6

Four hours after the end of the acidity, 4.5

Five hours after the end of the acid number 4.0

Six hours after the end of the acid number 4.0

Further comparative studies

(taking into account DE-AS 26 03 259 as proof of technical progress)

Production of the copolymer 2 according to DE-AS 26 03 259

705 grams of xylene. 337 g of ethyl glycol acetate and 403 g of glycidyl ester of jr.jr-Dialkyla'kanmonocarbonsäuren the following empirical formula CoH ^ Oi are heated to 138 "C under reflux and a mixture consisting of 124 g of acrylic acid. 293 g of hydroxyethyl methacrylate. 423 g of styrofoam. 315 g of methyl methacrylate, 15.2 Tu-tert-butyl peroxide and 17 g of dodecyl mercaptan added uniformly and polymerized for about 6 hours at 135 ^C C together and condensed. the Feststoffgehali is 61 wt ⁰ O. the viscosity of the xylene to 50 wt .- '\, Solids diluted solution is 140 seconds, measured in a DIN beaker with a 4 mm outlet opening at 23 "C. The acid number is 8.2. based on the copolymer.

Comparative copolymers according to the invention

It was, as in Example 2 of DE-AS 26 03 259 described, worked, but with the difference that the addition of 0.71 g of lithium hydroxide previously dissolved in the acrylic acid and with the other compounds of the feed mixture% 'was mixed.

The course of the reaction was determined by determining the acid number, based on the copolymer. determined.

One hour after the end of the feed acid number 9

Two hours after the end of the addition, the acid number was 7.2

Three hours after the end of the addition, the acid number was 5.8

Four hours after the end of the feed acid number 4.6

Five hours after the end of the acid number 3.9

Six hours after the end of the addition, the acid number was 3.9

The comparative tests show that the copolymers obtained according to the invention have acid numbers with the desired lower values, so that the incorporation of the glycidyl ester is more complete than in the methods according to the state of the art.

If one compares the conversion as a function of the time after the end of the feed of the monomers, it can be seen that that lower acid numbers are already obtained 2 hours after the end of the addition of the monomers, while the products obtained by the prior art process, at least 6 hours Require reaction time after the end of the feed of the monomers in order to give approximately the acid numbers.

The main areas of application for the copolymers are - in combination with aliphatic and aromatic polyisocyanates or their mixtures - air- and oven-drying metal, wood and plastic paintwork. Such two-component paints are preferably used, if properties are expected from the air-dried or force-dried paints that are usually present only offer stoving enamels.

These new reaction paints are used as binders Used in particular for the automotive refinish sector as well as for bus and truck painting.

In combination with aliphatic polyisocyanates you get full-bodied. non-yellowing paintwork with excellent weather resistance and gloss retention ;.

Example for the production of a reactive lacquer

100 g copolymer solution, obtained according to Example 2, and 20 g of a 75% solution of a xylene / ethyl glycol acetal = 1: 1 dissolved, biuret group-containing aliphatic triisocyanates, which by reaction from three moles of hexamethylene diisocyanate and one mole Water was obtained with an NCO content of 21% by weight. become mixed with a solvent. existing from xylene / butyl acetate = 1: 1 to spray viscosity set and coated steel sheets with a dry film thickness of 45 μm and 10 days at room temperature hardened. The films had excellent gloss and good resistance to xylene

t5 on.

A particularly preferred reaction varnish contains:

(A) 63 to 68% by weight of produced hydroxyl groups Copolymers and

, ₀ (B) 32 to 37% by weight, organic triisocyanate, which was obtained by reacting 3 mol of hexamethylene diisocyanate and 1 mol of water, (A) and (B) having to give numerical values of 100% by weight.

For the production of a stoving enamel 70 to 95 wt .-% hydroxyl-containing copolymers produced according to the invention with 5 to 30 parts by weight ¹ *., Will find use aminoplast resins, wherein the UEW .- "b-add up to 100 wt. - "b must complete. as

Hi amino Herein, all amino resins are used which are compatible with Acrylaicopolymerisatharzen and are in large numbers in the trade and are often based on urea and / or melamine-formaldehyde base and with lower alkanols

^r > are present in etherified form.

The solution of the finished copolymer is cooled and the aminoplast solution is introduced, wherein the solvent content is adjusted so that the desired concentration is achieved. Then can

^{4 (1} pigments are added

After stoving at 90 to 180 ° C, the stoving enamels produce films with excellent resistance properties to chemicals of all kinds such as Solvents. Acids and bases as well as super fuels.

308 132/187

Claims (3)

Patent claims: 1. Process for the production of in organic. Solvent-soluble hydroxyl groups Copolymers based on vinyl compounds from the group of aromatic vinyl compounds, the acrylates or methacrylates with 1 to 12 carbon atoms in the alcohol residue, the esters of crotonic acid with saturated alcohols that! Contains up to 10 carbon atoms in the alcohol residue, the vinyl ester and α, / ϊ-ethylenically unsaturated ones that carry hydroxyl groups Compounds on the one hand and ^ -unsaturated monocarboxylic acids and monoglycidyl compounds on the other hand by heating with esterification in the presence of an epoxy-carboxy catalyst and with simultaneous copolymerization by means of polymerization initiators in inert organic solvents and optionally chain terminators, thereby characterized in that at least one alkali compound is used as the epoxy-carboxy catalyst will. 2. The method according to claim 1, characterized in that the copolymerization with addition of a chain regulator. 3. The method according to claim 1, characterized in that copolymers from