DE1520648C - Process for the production of polymers based on etherified aminoplast resins - Google Patents

Description

3 4

Acrylic acid, methacrylic acid, maleic acid, maleic product II acid anhydride and fumaric acid in question.

The polymers are prepared by the process according to the invention (fumaric acid and castor oil) in such a way that 1 mole of castor oil and 1 mole of fumaric acid are used to heat the etherified aminoplastic resins in a solution under CO ₂ protective gas at 215 ° C. for 9 hours , medium-dissolved with an unsaturated polymerisier- One obtains an ester with the acid number 64. Baren monomers and a half-ester of an unsaturated aliphatic dicarboxylic acid and a hydroxy fatty acid with 10 to 18 carbon atoms or castor oil

in the presence of a polymerization catalyst under io ■ (ltaconic acid and castor oil)

Heating to react. Depending on the 1 mole of castor oil and 1 mole of itaconic acid

applied temperature (40 to 200 ° C) ynter CO ₂ protective gas first 3V ₂ hours at 16O ⁰ C,

one different polymerization times; they lay . then heated to 200 ° C. for 3V for _{2 hours.} The light brown one

between a few minutes and 12 hours. Due to the viscous reaction product, the acid number is 50. The proportions of the components used can be 15

the properties of the end product, such as hardness product IV

and elasticity, largely affect it. On 100 ge / »,, · .. -, '■'. ·,,. ,,. _TT ,

parts by weight aminoplast resin can, for. B. 20 to 200 parts (maleic anhydride and 12-hydroxystearic acid)

Ie half esters and 40 to 300 parts of unsaturated poly- if 240.8 g of 12-hydroxystearic acid (0.75 mol)

merizable monomer are used. 2 ° with 73.5 g maleic anhydride (0.75 mol) under CO ₂ -

The reaction is preferably carried out in the presence of a protective gas for 1 hour at 140.degree. C., so one obtains a

normal amount, d. H. 0.1 to 2 percent by weight) of a clear, light brown, pasty product from the acid

Vinyl polymerization initiator carried out. Examples number 265 (theoretical acid number of the half-ester: 268). these include benzoyl pefoxide and di-tert-butyl peroxide

and cumene hydroperoxide. > 25 Product V

As a solvent for the etherified aminoplast- ,,,, ... t 1 ·,> ^ - · ... ^ resin, for example, toluene, xylene, homolo- \ · (maleic anhydride and castor oil) genraffinate, hydrogenated naphthalenes and Use monohydric 450 g castor oil (about V ₂ MoI) and 98 g maleic alcohols. It is most expedient to use sec-butanol as the solvent anhydride (1 mol) with stirring and with a CO _{2 solvent.} 3 ° shielding gas on. Heated from 140 to 150 ° C. After IV ₂ hours

The polymers produced according to the invention have reached the acid number 100, which is also far no longer changed in numerous solvents such as xylene, solvents heating for 30 minutes. Man naphtha and similar products commonly used for stoving enamels give a clear, yellow-colored, highly viscous product Solvents soluble. These paints can after all (theoretical acid number: 102). usual methods such as spraying, dipping, 35

flow or be applied by rolling. The product VI

Coatings are baked in in a known manner in order to, _ _{,, .. ..,,., 1Λ TT} , ... _x

to harden them and convert them to an insoluble form. (Maleic anhydride-10-hydroxycapric acid)

The coatings obtained are elastic, water-resistant and weather-resistant to 188 g of 10-hydroxy-capric acid (1 mol); They have a high heat resistance - with 98 g maleic anhydride (1 mol) under CO _{2 conditions} as well as good mechanical and chemical protective gas IV ₂ hours at 140 ° C and get a wax. The coatings are also characterized by a yellowish-like reaction product with an acid number of gloss and do not tend to form hairline cracks. In 188 (theoretical acid number of the expected half-ball common is the elasticity and the luster of the overester: 196). the better the more the polymer used for the production of the 45 B ice ρ ie 1 1 lacquer produced by the process according to the invention from unsaturated In a three-necked flask equipped with a stirrer, saturated dicarboxylic acids and hydroxy fatty acids, a reflux condenser and a thermometer, contains factory condensed. The 200 g of maleic acid half-ester of castor oil, 300 g of polymers prepared according to the invention can also be used as films, cast, spatula 5 ° styrene and 364 g of a 55% solution of the methylol or molding compound. melamine sec-butyl ether introduced into sec-butanol

The half esters used in the examples can and with 20 g of 50% benzoyl peroxide paste and 350 g

by known processes not claimed here, xylene is added as a diluent. While stirring

z. B. be prepared as follows: the mixture is heated and 40 minutes at

Leave 55 100 ° C. It is then cooled rapidly and

Product I ^m 't 165 g of solvent benzene' (homolog raffinate from

.. ,, ·. _, τ ,. . .., s boiling range 150 to 200 ° C) diluted in which

(Maleic acid and castor oil) 0.2 percent by weight tert-butyl-p ^ cresol dissolved

180 grams of castor oil (0.2 moles) and 23.2 grams of maleic acid are. The reaction product is physically mixed through a Seitz fil- (0.2 mol) and filtered under 60 ter (filter disc ν, οο). It has a protective gas (CO ₂ ) slowly heated to 160 ° C. With a content of 50%; this solution has a viscosity of this temperature, the mixture IV is left at 60 to 90 seconds (DIN beaker, 4 mm nozzle) for _{2 hours and then cooled.} The conversion to, is slightly yellowish in color and has a flame product is viscous and colored a little deeper yellow than point (according to Abel-Pensk y, DIN 53 213) of 24 ° C. the castor oil used. The acid numbers found 65 Baked on sheet metal V for ₂ hours at 150 ° C. gives between 65 and 75; Pendulum hardness 94 show ultrared spectroscopic investigations. announce, cross-cut 1, Erichsen value 5 mm. On off

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the physical mixture of the components manufactured has a 50 ° / ₀ solution of the binder having a imputed paint supplies to plate ¹ Z ₂ hours at 150 ° C switched on viscosity of 34 seconds. By _^half hours Eingebrannt a coating having strong interference surface, burn to sheet at 150 ° C produced a resilient, moderate water resistance, pendulum hardness 113 seconds, high-gloss coating with good water resistance, crosshatch 3. 5 a pendulum hardness of 100 seconds and a grid

Example ^cutL

• λ.,., ._ ..,., ·, Examples
• The batch quantities are the same as in the example. 1, just will

Instead of the methylolmelamine sec-butyl ether, a Me- In the reaction vessel described in Example 1

ethylene melamine isobutyl ether, 55% dissolved in isobutaio, 200 g of fumaric acid half-ester of castor oil,

nol, used. The reaction time in this is 150 g of diisopropyl fumarate, 150 g of styrene and

Case 70 minutes at 100 ° C. The viscosity of the 50 ° / ₀ % 364 g methylolmelamine sec-butyl ether (55% in

Dissolution of the binder takes 82 seconds. sec-butanol), 20 g benzoyl peroxide paste (50 ° / ₀ ig) and

. · Ι -i · 350 g of xylene introduced. The implementation takes place at

Example _{3 lg 100} ° c in 7 minutes. The reaction mixture will

The batch amounts are as in Example 1 and 2, depending on cooling with 1.4 g of tert-butyl-p-cresol stabilized

but now the methylol melamine isononyl ether, siert and with 165 g of benzene to 50% substance -

55 ° / _o ig set in sec-butanol, salary as aminoplast. The viscosity of the solution is

used. The response time is now 115Mi- 54 seconds. The paint solution is on iron sheets

grooves at 100.degree. C. A 50% solution of the 20 is obtained and baked at 150.degree. C. for 30 minutes.

Binder with a viscosity of 85 seconds. The result is an elastic, glossy coating of

_, ..,. . good water resistance. Pendulum hardness 100 seconds,

Example 4 Cross cut 1.

The batch amounts are as in Examples 1 bis 19
to 3, however, a methylol 25

melamine cyclohexyl ether, 55% in sec-butanol, one 200 g itaconic acid half-ester of castor oil, 300 g

set. The reaction time is 60 minutes with styrene and 364 g of a 55% solution of methylol

100 ° C. The 50% solution of the final product possesses. melamine-sec-butyl ether in sec-butanol, 20 g of 50 ° / ₀ sodium

a viscosity of 60 seconds. Benzoyl peroxide paste and 350 g of xylene are used as in

. . 30 Example 1, described, leave at 100 ° C. for 20 minutes.

Example 5 The mixture is rapidly cooled and with 165 g

The batch quantities correspond to Examples 1 diluted solvent benzene, in which 0.2 weight percent

to 4, but a percentage of tert-butyl-p-cresol will be dissolved as the aminoplast component. The Rea-

n-butanol etherified urea resin, 65 ° / _o solution in n-butanone tion product (through a Seitz-filter filter disc

nol, used. The reaction time is 35 minutes (35 ¹ U ₀₀ ) filtered. The resulting 50 ° / ₀ solution of

at .100 ° C. The 50 ° / ₀ solution of the final product has the binder has a viscosity of 100 seconds.

a viscosity of 3 minutes, 31 seconds.

• Examples '', example 10

In a reaction vessel, as described in Example 1, 4 ° 250 g of the half ester from maleic acid and 12-Hy-

200 g of fumaric acid half-ester of castor oil, droxystearic acid, 300 g of styrene, 364 g of methylol melamine

200 g of styrene, 364 g of methylolmelamine sec-butyl ether, min-sec-butyl ether (55% in sec-butanol) 400 g

(55% in sec-butanol), 16 g of benzoyl peroxide paste, xylene and 20 g of benzoyl peroxide paste (50%)

(50%) and 275 g of xylene introduced. With stirring as described in Example 1 for 2 hours and 25 minutes

the batch is heated up and heated to 100 ° C for 25 minutes at 80 ° C 45 th. The reaction mixture is after

left. The reaction mixture is cooled rapidly after cooling with 1.4 g of tert-butyl-p-cresol stabili-

and with 1.2 g of tert-butyl-p-cresol and 145 g of dissolved and diluted with 165 g of solvent benzene. The vis-

sungsbenzol added. After filtration through a Seitz the 50 ° / ₀ solution of the binder is viscosity by

. Filter (filter disk US) gives a clear 50 ° / ₀ ige 3 minutes, 26 seconds.

Solution of the binder with a viscosity of 5 °. .

73 seconds. The solution is drawn onto a sheet metal B e 1 s ρ 1 e 1 11

and ^{baked for 1} _1/2 hours at 150 ° C. A 300 g half ester of maleic acid and 10-hydroxy

elastic coating of high gloss and good capric acid, 300 g styrene and 364 g methylolmelamine

Water resistance. Pendulum hardness 93, cross-cut 1 to 2. Sec-butyl ether (55% in sec-butanol) is dissolved in

. 55 450 g of yylene, mixed with 21.1 g of benzoyl peroxide paste

B e 1 s ρ 1 e 1 7 (50%) and leaves 1110 minutes according to example

The batch amounts correspond to those of Example 6, react at 100.degree. After the cooling of the fumaric acid diisopropyl ester was used instead of styrene, the mixture is combined with 1.5 g of tert-butyl-p-cresol. The mixture was stabilized for 75 minutes at 100 ° C. and left at 50% with 186 g of solvent benzene. The reaction mixture was then adjusted to ^6o solids. The viscosity of the binder cools and is treated further as in Example 6. One redemption is 2 minutes, 8 seconds.

Claims (3)

1 2 of the patent specification specified conditions the three claims · components do not polymerize to a homogeneous resin. The inhomogeneous reaction mixtures obtained were in the solvents indicated 1. Process for the preparation of polymers 5 insoluble or not completely soluble. There was always an in-up based on etherified amino resins, homogeneous mixture. characterized in that it has now been found that polymers can be used Aminoplast resins whose methylol groups are obtained with one of the basis of etherified aminoplast resins which high-quality saturated alcohols are etherified, excellent for stoving enamels, films, casting, dissolved in a solvent, with half-esters from io fillers and molding compounds are suitable if one uses amino unsaturated dicarboxylic acids and hydroxy fatty plastic resins, the methylol groups of which with monovalent acids with 10 to 18 carbon atoms or castor oil, saturated alcohols are etherified, in a solution as with styrene and / or esters of fumaric acid medium dissolved, with half-esters of unsaturated di- with secondary alcohols or optionally carboxylic acids and hydroxy fatty acids with 10 to 18 C- Divinylbenzenes and their substitution products, »s atoms or castor oil, as well as with styrene and / or Vinyl esters, vinyl ethers, vinyl halides, acrylic esters of fumaric acid with secondary alcohols nitrile, α, / 3-unsaturated carboxylic acids and ma- or optionally divinylbenzenes and their sub- linic anhydride in the presence of 0.1 to 2 constitution products, vinyl esters, vinyl ethers, vinyl weight percent of a vinyl polymerization initiator halides, acrylonitrile, α, / 3-unsaturated carbon at a temperature of 40 to 200 ⁰ C to react 20 acids and maleic anhydride in the presence of 0.1 tion brings. . up to 2 percent by weight of a vinyl polymer 2. The method according to claim 1, characterized in that at a temperature of 40 to 200 ⁰ C, the aminoplast resins are reacted. Valuable saturated alcohols etherified melamine - Compounds which form aminoplasts come or urea-formaldehyde resins are used. 25 Urea and its substitution products, also 3. The method according to claim 1 and 2, characterized in aminotriazines containing at least two amino groups characterized in that one contains a melamine ether resin, such as melamine, ammeline and thioammeline used to react, the melamine from one part, in question. The most common aldehyde is formaldehyde-2,5 up to 6 parts of formaldehyde and 1.5 to 5.5 parts of hyd. The condensation products are more common a monohydric saturated alcohol formed 3 ° manner with elimination of water, removal of the has been. Water from the neutral or weakly alkaline Reaction mixture and etherification made with a monohydric saturated alcohol. Suitable Alcohols are e.g. B. propanol, isopropanol, butanol, 35 sec-butanol, isobutanol, isononanol and cyclohexanol. Even if the condensation products out It is known that etherified melamine-formaldehyde aminoplast formers, aldehyde and monovalent ge or urea-formaldehyde resins with alcohols saturated with alkyd resins from any amounts of the to implement. These condensation products are called components, so it can be formed Stoving enamels are used (German patent 748 820; 4 ° in the case of using melamine it is considered to be French patent 1 086 826). Proven to be particularly favorable, melamine with Formal-Furthermore it is known to dehydrate air-drying paints and a monohydric saturated alcohol in the based on methylolaminotriazinallyl ether ratio 1: 2.5 to 6: 1.5 to 5.5 in reaction to to manufacture. For this purpose, methylolamino- will bring. triazinallyl ethers with monoesters of α, / 9-unsaturated 45 The half-esters of unsaturated aliphatic di-dicarboxylic acids, such as maleic, fumaric, mesaconic, carboxylic acids and a hydroxy fatty acid with 10 to citraconic or itaconic acid, preferably with 18 carbon atoms in the molecule, such as B. 12-hydroxystea-saturated monohydric alcohols, such as allyl alcohol, saric acid and 10-hydroxycapric acid, or castor oil, such as those caused to react with styrene (Dr. Kittel, are produced in a known manner, e.g. by Er-progress report, Deutsche Farbenzeitschrift 1958, 5 ° heat their mixtures under normal pressure on p. 167 to 169; especially p. 168). To get a good temperatures up to 200 ⁰ C. As the unsaturated alipha-drying the diagram dicarboxylic acids produced from these paint resins include, for example maleic films at an ordinary temperature to obtain, is acid, fumaric acid, itaconic acid, mesaconic acid and the addition of Metallsikkativen such as cobalt oleate, Citraconic acid for use,
recommended. 55 The production of the aforementioned etherified ami-es has also been described, carbamine resins, noplastharze and the half-esters from unsaturated di-like etherified urea-formaldehyde or melamine-carboxylic acids and hydroxy fatty acids, which in the er-formaldehyde resins, e.g. a butyl alcohol inventive method serve as starting materials, ethereal urea-formaldehyde resin, with unsaturated takes place in a manner known per se. The production of th short-chain polyesters, e.g. B. from maleic an- 60 of these starting materials is not claimed here as an invention behydrid and ethylene glycol, and unsaturated poly-. '. merizable monomers, such as vinyl, acrylic or the preferred to be used according to the invention Methacrylic compounds, to condense, where syruping polymerizable monomers are styrene, like resins are to arise, which directly or fumaric acid diisopropyl ester and fumaric acid di-sec. after dilution with a solvent to give 65 butyl ester. There are also divinylbenzenes - and Impregnation of textiles should be used for their substitution products, as well as vinyl compounds, (French patent specification 1 030 158). The after-like vinyl esters, vinyl ethers and vinyl halides, furthermore Examination showed that with strict adherence to the in acrylonitrile and α, / 3-unsaturated carboxylic acids, such as