DE908397C - Paints or plastics - Google Patents

Description

Paints or plastics It is known by catalytic High-pressure hydrogenation of terpene phenols to produce products that are sandalwood-like as a result of their Their own odor and their high boiling point as fixators in odorant compositions can be used advantageously. It was also known that such compounds Significantly improved odor through subsequent oxidation or dehydration can be. The high optical refractive index and the colorlessness of the perhydroterpene phenols Incidentally, they also make them useful as aids for optical purposes.

It has now been found that esterification of the perhydroterpene phenols with organic acids results in high-boiling esters which are suitable as plasticizers for plastics and paint raw materials, in particular nitrocellulose, chlorinated rubber and polyvinyl chloride. To prepare these esters, any phenols with terpene hydrocarbons in the presence of catalytically active substances, such as. B. boron fluoride glacial acetic acid, and after removal of the catalyst of high pressure hydrogenation with Raney nickel at r8o to aoo ° and a hydrogen pressure of 80 to a50 atm and then esterify. For industrial use, it is advantageous to use the product purified by washing out the excess acid and distilling off water and any unreacted terpenes. The pure monoterpene cyclohexyl esters can be obtained from this by fractional distillation. They are colorless to slightly colored oily substances. which are easily soluble in white spirit, benzene, toluene, chlorinated hydrocarbons such as carbon tetrachloride or trichlorethylene, acetone, alcohol, esters and ethers. They have low volatility and good lightfastness. They are perfectly compatible with other plasticizers, e.g. B. with chlorodiphenyl, dibutyl phthalate, tricresyl phosphate; They are also compatible with linseed oils and other oils commonly used in the construction of paints. In the production of paints or plastic combinations, the plasticizers mentioned are added in the usual way, ie if solvents are used, the plasticizers are added together with them, while for solvent-free combinations Heat occurs.

The production, which is not claimed here, and use are to be demonstrated in the following by a few examples. Example i A mixture of 750 g of camphene and 55o g of cresol is added to 15 g of boron fluoride egg @ sess, ig, the temperature being kept below 80 ° by cooling. To end the reaction, the mixture is stirred for a further 8 hours at this temperature and a small amount of unreacted cresol is driven off with steam. After neutralizing and washing, it is dried. The light brown soft resin weighs 1237 g and has an O H content of 5.3%. This resin is subjected to distillation at a pressure of 3 to 5 mm, and a fraction which is transferred at 175 to 190 ° and consists of Bornvlkresol is obtained.

Zoo parts of this fraction are treated with: 20 g of highly active nickel catalyst for several hours at 180 ° and a pressure of 150 to Zoo at with hydrogen. The catalyst is then filtered off and distilled. ', Ulan receives approx. 951 / o of the perhydro compound with a boiling point of 133 to 14.7 ° under 1 mm pressure as a colorless liquid. 380 g of this distillate, consisting of bornylinethylcyclohexanol, are mixed with 130 g of acetic anhydride and an acidic catalyst, e.g. B. 3 g boron fluoride glacial acetic acid, heated on a water bath. After cooling, the excess acid is removed by washing out with water and with sodium bicarbonate solution. The product is dried and distilled. A colorless ester which passes over at from 1 to 150 ° / 1 mm H is obtained in good yield. This borylmethylcyclohexyl acetate is a good plasticizer for commercially available nitrocellulose. The following solution, which is suitable as a paint, is prepared: if desired, with pigments, e.g. ß. 25o / o titanium white, can be added: 15 parts of commercially available nitro wool, moist butanol, 3o parts of butyl acetate, 10 parts of butanol, 15 parts of ethyl glycol, 20 parts of ethyl acetate, 10 parts of toluene, 10 parts of plasticizer, Bornylmethylcyclahexylacet.at.

After the solvents have evaporated, a completely clear, smooth, glossy @, r break-proof film with good lightfastness, the tear resistance of 79kg / cm2 and the elongation 15 to 20%. Examples By conversion of o-cresol with camphene, subsequent hydrogenation and distillation, as indicated in example i., one receives bornyl-o-methylcyclohexanol, which at i mm pressure, at 144 to 155 ° as colorless liquid passes over.

.40o g of this compound with 30o g of trichloro i @ gic acid anhydriid and heated for a few hours on a water bath with 2 g of boron fluoride glacial acetic acid. After this Washing is obtained by distillation: the trichloroacetate from bp ",, r50 to i so '. The property and use of this colorless oily plasticizer is one similar to example i z. B. it is particularly suitable for chlorinated rubber. 3o parts of commercially available chlorinated rubber, 3o parts of toluene, 3o parts of xylo.110 parts White spirit, 15 parts plasticizer.

250% pigments can also be incorporated into this solution. After the solvents have evaporated, a film with a tensile strength of 40.5 remains kg / cm2 and. the elongation i2o%. Example 3 The plasticizer specified in Example 2 @ is also suitable for commercially available polyvinyl chloride (post-chlorinated): 2o parts Polyvinylchloride (post-chlorinated), 10 parts of ethyl acetate, 20 parts of butyl acetate, d.o. Parts xylene, 20 parts plasticizer. Tear strength 17.5 kg / cm2, elongation 2800/0.

Claims (1)

PATENTANSPRU-G-H: paints or plastics. -ekeniizeichnet through .the content of perhydroterpene phenyl esters, in particular of acetates or halogen acetates ! des Bornylmethylcyclobexano, ls as a plasticizer.