DE1151375B - Process for the production of molded parts or coatings - Google Patents

Description

According to an older proposal (German Auslegeschrift 1 099 163), moldings or coatings are obtained from soluble, linear polyether acetals and α-substituted monomeric compounds which can be polymerized onto them and have the grouping CH ₂ = Cc, S. The linear polyether acetals in the presence of acidic catalysts by addition of esters containing hydroxyl groups, / S-unsaturated dicarboxylic acids to diallylidenepentaerythritol. j ο

However, a disadvantage of the products obtained according to this proposal is a certain sensitivity to Atmospheric oxygen, which prevents complete hardening at the interface between the molding compound and air so that the surface of the molded parts or coatings produced is not scratch-resistant.

It has now been found that air-drying moldings and coatings can be used in a simple manner can get a high-gloss surface. '

The invention relates to a process for producing molded parts or coatings by curing molding compositions which contain monomeric, partially polymerizable, unsaturated compounds, peroxides, optionally accelerators and optionally basic inorganic or organic compounds; bonds as well as soluble, linear, optionally silicon-modified polyether acetals, which are made up of hydroxyl-containing esters of ", / 9-unsaturated dicarboxylic acids, which can be replaced up to half by those dicarboxylic acids which do not contain ¹ aliphatic multiple bond, and. Diallylidenepentaerythritol have been obtained in the presence of acidic catalysts. The process is characterized in that masses are cured which contain polyether acetals into which about 5 to 15% allyl alcohol - based on the hydroxyl group-containing ester - have been condensed.

The esters used to produce the polyether acetals are made from 1 to 2 moles of, for example, saturated aliphatic alcohols such as ethylene, diethylene, triethylene glycol, 1,2-propylene glycol, glycerol, trimethylolpropane, and 1 mole, ^ - unsaturated dicarboxylic acids such as maleic , Fumaric, itaconic or citraconic acid, with the dicarboxylic acid component still being up to half of those dicarboxylic acids that do not contain an aliphatic multiple bond, such as adipic acid, succinic acid, phthalic acid. For example, the molar ratio of the unsaturated dicarboxylic acid to the other dicarboxylic acid can be 3: 1. The esters can also be used together with polyhydric alcohols, ζ. B. the mentioned or polynuclear diphenols, a process for the production of molded parts
or coatings

i- applicant:

Chemical works Albert,
Wiesbaden-Biebrich, Albertstr. 10-14

Dr. Alfred English, Opladen-Lützenkirchen,

and Dr. Rolf Zimmermann, Wiesbaden-Biebrieh,

have been named as inventors

preferably ρ, ρ'-dihydroxydiphenylpropane or whose Dioxyäthyläther are used.

The addition of the free hydroxyl groups of the esters or the alcohols and diphenols is in the presence of acids or Lewis catalysts in a ratio of 0.5 to. 2 moles of ester per mole of diallylidenepentaerythritol carried out, with ether bridges being formed. The temperatures are in general between 20 and 110 ° C, preferably at 50 to 70 ⁰ C. Suitable catalysts are, for. B. suitable: phosphoric acid, sulfuric acid, p-toluenesulfonic acid, glacial acetic acid, haloacetic acids, aluminum chloride, tin tetrachloride, boron trifluoride, especially boron trifluoride etherate.

The addition products thus obtained, still containing the acidic catalyst, can be obtained by the Addition of small amounts of basic inorganic or organic compounds and stabilized by polymerization inhibitors such as substituted catechols, hydroquinones and the like so that the mixtures with -substituted ethylene compounds remain stable and stable in storage. Suitable basic substances are, for example, alkali metal hydroxide, alkali metal alcoholate or organic ones Bases such as piperidine, morpholine, ethylenediamine or pyrrolidine. The addition of these substances also causes a lightening of the addition products.

. By dissolving the polyether acetals in «-substituted ethylene compounds, z. B. vinyl toluene, vinyl pyrrolidone, Vinyl acetate, diallyl maleate, diallyl phthalate, acrylic acid esters, acrylonitrile, but preferably in Styrene or methacrylic acid esters, as well as the addition of peroxides and, if appropriate, accelerators one curable molding compounds. The amount of ethylene

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monomers can be varied depending on the intended use together with 0.29 parts of boron trifluoride etherate for 4 hours - 30 to 50% by weight at 70 ° C. have proven favorable. After adding 0.11 part percent, based on the mass, sodium methylate is dissolved in 70 parts of styrene and, depending on the molecular weight achieved, with 8 parts of cyclohexanone peroxide (50% in Dide's addition product of diallylidene pentaerythritol 5 methyl phthalate) and 4 parts Cobalt octoate solution and the ester. The more advanced the addition polymerizes. Thinly applied films are already, the better the miscibility; preferably hard after 4 hours at room temperature and the OH number of the adducts should be less than 100. tack free.
If the addition progresses too far, Beistnel takes 3

Solubility or miscibility decreases again. ok

Catalysts for curing are the usual a) 56 parts of diallylidene pentaerythritol, 50 parts of one

organic peroxides, e.g. B. benzoyl, cyclohexanone, mixed maleic fumaric acid glycol ester, based on methyl ethyl ketone, methyl isobutyl ketone and cumene 4 moles of ethylene glycol, 1 mole of maleic acid and 1 mole of hydroperoxide and also tert. Butyl perbenzoate contains fumaric acid, 6 parts allyl alcohol and 0.43 parts are suitable. With the addition of accelerators such as boron trifluoride etherate dimethyl-15 for 6 hours at 6O ⁰ C reaanilin, Kobaltoetoat, lauryl mercaptan may be left in yaw. The highly viscous, brownish polynormal temperature to be cured. ätheracetyl is then mixed with 0.17 part of sodium. The hardening leads to even the thinnest layers of methylate, with a strong lightening after a few hours to non-tacky, pale yellow after room temperature, and after cooling on products with a high-gloss surface, so that at 20 Room temperature in 77 parts of styrene containing 0.02 parts of the corresponding procedure no after-treatment of hydroquinone, dissolved. After adding more is needed. Even the untreated surfaces of methyl ethyl ketone peroxide and cobalt octoate solution are characterized by high scratch resistance and the molding compound begins to shine at room temperature. Although machining usually takes about 10 minutes to harden. A thin layer is not required, the lacquer films can be given the film dries in 5 hours hard and tack-free, if also sanded and polished. From these through.

The reasons are the b) to be cured according to the invention. The same batch gives after addition of a

Molding compounds are good paint raw materials. Flow-promoting agent (eg., 2 parts of a / ^s oig 1 °

The masses can also contain inorganic fillers (styrenic solution of a silicone oil) after Aufwie Asbestos, lime, chalk, ground glass or 30 wear thin layers within a few hours Silicon carbide, or organic dyes, or pig- a film of great smoothness and glossy surface contain. These additives do not interfere. The area.

Moldings or coatings obtained according to the invention Example 4

are characterized by good chemical resistance

- especially against alkalis and acids. The 35 35 parts of maleic acid glycol ester, 3.5 parts of maleic properties of the moldings and coatings are acid diethylene glycol esters, 28 parts of diallylidene penta also of the type and amount of addition erythritol used and 3 parts of allyl alcohol are catalyst ^ and the reaction conditions from 0.27 after addition Share boron trifluoride ether for 7 hours when pending. 6O ⁰ C stirred. The highly viscous, brownish poly-

Finally, it is also possible to obtain the ether acetal according to the invention with 0.11 part of sodium Modify moldings or coatings, add methylate and, after cooling, on Zimmerindem the Polyärtheacetale used, if temperature dissolved in 37 parts of styrene. After more thorough they have a hydroxyl number between 80 and 130, preferably mixing with 4 parts of methyl ethyl ketone peroxide between 100 and 120, with dihalogen solution and 2 parts cobalt octoate solution this becomes silanes, e.g. B. dichloromethylsilane, implemented. 45 solution applied thinly. After 15 minutes it occurs

In the following examples, parts are cure by weight, and after just 2 hours the parts are. On the described production of the coatings according to the invention tack-free and dry, according to contained in the molding or coating compositions
No protection is claimed here for polyether acetals. Example 5

Example 1 _It W _11n J ₆ initially an ester of acid number 28 and

117 parts of diallylidene pentaerythritol, 110 parts of Malein- the OH number 306 by melt flow condensation of

acid diglycol ester and 6 parts of allyl alcohol are 55.7 parts of fumaric acid, 32 parts of maleic anhydride

mixed well with 0.43 parts of boron trifluoride ether and drid, 70 parts of ethylene glycol and 12 parts of propylene hours stirred at 60 ° C. The obtained brownish, 55 glycol-1,2 produced. 120 parts of this ester and

highly viscous mass is then mixed with 0.17 parts of 20 parts of allyl alcohol to 115 parts of diallylidene

Sodium methylate is added and pentaerythritol in 125 parts of styrene in the presence of 1.35 parts of boron tri-

solved. 100 parts of this solution with 4 parts of fluoride butyl ether in a stream of carbon dioxide at a

Methyläthylketonperoxydlösung (adds 40% in dimethyl temperature of about 7O ⁰ C until the polyadduct phthalate) and 2 parts of cobalt octoate (1% ^6o the OH number of 100 and an acid number of 18 has.

Cobalt content) and stirred up in thin layers. Thereupon the highly viscous resin with 111 parts

Wood applied. The hardening starts at room temperature - styrene, 0.3 parts of solid caustic soda (dissolved in methanol)

temperature after about 8 minutes and results in 0.03 parts of hydroquinone added. After the fiI-

a hard, tack-free coating for a few hours. a clear, pale yellow color was obtained

_. . _{1 9} 65 solution with a solids content of about 70%

Example I _{100 parts of} this solution were mixed with 3 parts of a

60 parts of diglycol fumarate, 64 parts of diallyl 50% paste of benzoyl peroxide in dimethylidene pentaerythritol and 6 parts of allyl alcohol are added to phthalate and with 1.5 parts of para-dimethyltoluidine

solution (5% in dimethyl phthalate) added. Moldings made from this mixture with a thickness of about 20 mm cured even at room temperature with tack-free surfaces. Standard bars produced from these shaped bodies have a flexural strength of 1200 kg / cm ² .

Claims (1)

PATENT CLAIM: Process for the production of molded parts or coatings by curing molding compounds which contain monomeric, partially polymerizable, unsaturated compounds, peroxides, optionally accelerators and optionally basic inorganic or organic compounds as well as soluble, linear, optionally silicon-modified polyether acetals, which are derived from hydroxyl-containing esters of α, / 3- unsaturated dicarboxylic acids, up to half of which can be replaced by those dicarboxylic acids which do not contain an aliphatic multiple bond, and diallylidene pentaerythritol in the presence of acidic catalysts, characterized in that masses containing such polyether acetals are obtained in about 5 to 15 % Allyl alcohol, based on the hydroxyl-containing ester, have been condensed in. © 309 620/231 7.63