DE2200021C3 - ACRYLIC ACID ESTERS OR METHACRYLIC ACID ESTERS OF OH-GROUPED TRICYCLIC DECANOLS, METHOD FOR THE PRODUCTION AND USE THEREOF - Google Patents

Description

The present invention relates to diacrylic esters of

t]
decan or
3,9-di (hydroxymethyl) tricyclo- [5.2,1.0. ^2l> ] -

decan or
4,8-di (hydroxymethyl) tricyclo- [5.2.1.0. ^2IJ ] -

decane or

their mixtures, as well as dimethacrylic acid esters of

decan or

use. However, if you want to prepare the defined compounds, you first separate the isomeric diols and then carry out the implementation or transesterification by.

In the preparation of the acrylic or methacrylic acid esters of the above-mentioned di- (hydroxymethylj-tricyclodecanediols Polymerization inhibitors should be present. Suitable inhibitors are as Stabilizer for monomers known substances such as

ίο such as hydroquinone or dialkylated phenols. In In some cases, however, it is sufficient if one for an abundant supply of as a polymerization inhibitor active oxygen

For the preparation of acrylic acid esters according to the invention

Is or methacrylic acid esters can in principle all be used Ester formation useful reactions are used. In the simplest case, the tricyclic diol esterified with acrylic acid or methacrylic acid, in particular with the addition of catalysts, whereby one for example using organic solvents to distill off the water formed azeotropically can. Instead of the acrylic acids mentioned themselves, their anhydrides or acid halides can of course also be used can be used. Transesterification with, for example, the methyl esters or ethyl esters of the Acrylic acids are possible. In principle, of course, you can also use the tricyclic diols with a highly volatile one Esterify acid and then a transesterification with acrylic acid ester or methacrylic acid ester one easily volatile alcohol. However, this requires an additional process step, which is usually undesirable. If mixtures of the mentioned isomeric di-fhydroxymethylJ-tricyclodecanes are used as starting material, mixtures of isomers are obtained in this way. The refractive

j-5 dex of the purified acrylic acid ester is around 1,506, while that of the methacrylic acid ester is 1,502. The esters can be purified, for example, by washing them out their solutions in organic solvents or other known methods. One Distillation of liquids is not practical because of their decomposition at elevated temperatures possible.

The acrylic acid esters or methacrylic acid esters according to the invention are monomers that are known by means of Initiators can be converted into high molecular weight compounds. They can be used beneficially are used as a component of acrylic acid ester adhesives which harden in the absence of oxygen. Using the esters of the invention are special

in this way heat-resistant bonds are obtained. Especially with the Use of diacrylic esters or dimethacrylic esters of

decan or
4,8-di (hydroxymethyl) tricyclo- [5.2.1.0. ²⁶ ] - «

decane or

their mixtures, processes for their production and their use.

The starting material used for the preparation of the compounds ^{according to the invention is expediently h (1} moderately di- (hydroxymethyl) -decanes, as they are easily made in a manner known per se after the oxo synthesis by the addition of carbon monoxide and hydrogen to dicyclopentadiene in the presence of catalysts such as cobalt compounds and then Hydrogenation of the *> ^r > formed tricyclodecanedialdehyde. For practical reasons it is advantageous to convert the resulting mixture of isomeric di- (hydroxymethyl) -decanes to 3,8-di- (hydroxymethyl) -tricyclo- [5.2.1.0. ²⁶ ] -

decan or
3,9-di (hydroxymethyl) tricyclo- [5.2.1.0. ²⁶ ] -

decan or
4,8- Di- (hydroxy methyl I) -tricyclo- [5.2.1.0. ^{2 6} ] -

decan

than adhesives that harden with the exclusion of oxygen, optionally with the addition of further acrylic esters and Customary auxiliaries such as polymerization initiators, accelerators, stabilizers, dyes, thickeners heat-resistant adhesives are obtained. As accelerators are in particular tertiary amines and as Initiators effective in the absence of oxygen are hydroperoxides such as cumene hydroperoxide or the like useful.

20th

From DE-OS 19 20 83vi adhesives based on acrylic esters were already known which, although still producing good adhesive bonds even after exposure to heat, soon lose their strength themselves at higher temperatures. For example, the adhesives according to Examples 1 and 2 of DE-OS 19 20 830 only show 40 to 50% of the strength at room temperature ^{at 100 ° C., while at 150 °} C. the drop was 100 to 95%. This result must be surprising due to the otherwise similar composition of the adhesives.

example 1

In a 2 liter glass flask with a stirrer, thermometer, air inlet tube and a The distillation column was equipped with an attached water separator, a mixture of

784 g of di-ihydroxymethyO-tricyclo - ^. L.O. ^ - decane

(4 moles of isolation mixture)
648 g acrylic acid (9 mol)

23 g of p-toluenesulfonic acid

19.5 grams of hydroquinone
400 ml of benzene

^{slowly heated to 90-106 0} C sump temperature for 7 hours while passing in air. During this time, 141 ml of water separated out in the water separator.

After cooling, benzene and acrylic acid were finally drawn off in vacuo. The oily residue was dissolved in 2 l of ether and with 5% sodium chloride solution, with 2% sodium hydroxide solution and again with Washed 5% sodium chloride solution. The ethereal solution was then poured over anhydrous sodium sulfate dried. The ether was drawn off, residues in a vacuum.

1159 g of the diacrylic acid ester of di- (hydroxymethyl) -tricyclo-decane fell on, corresponding to a yield of about 95% of theory. The refractive index of the reaction product was π = 1,506.

Molecular Formula C18H24O4 (304)
Calcd. C 71.05 H 7.90 O 21.05
found C 70.74 H 7.63 O 21.81

45 Example 2

Using the same procedure as described above, a mixture of di (hydroxymethyl) tricyclodecane was used esterified, but with 774 g of methacrylic acid instead of acrylic acid.

After work-up, 1195 g of the methacrylic acid ester were obtained obtained from di-ihydroxymethylJ-tricyclo-decane, which were an oily liquid with a refractive index of π = 1,502.

Molecular formula CmH ₂ SO ₄ (332)
Calcd. C 72-9 H 8.44 019.27
found C 71.65 H 838 O 1936

Example 3

In a reaction vessel equipped as in the previous example, but with a capacity of 500 ml, became a mixture of

98 g of di (hydroxymethyl) tricyclo- [5.2.1.0. ^: "'] decan

(1/2 mol isomer mixture)
150 g of methyl methacrylate
9.8 g of p-toluenesulfonic acid
9 g hydroquinone

slowly for five hours to 150 ⁰ C bottom temperature heated Practice: head was subtracted, a mixture at a temperature of 64-67 ° C, which consisted of an excess of methyl methacrylate and 35 ml of methanol.

Work-up and purification were carried out as described in Example 2. 147 g of the methacrylic acid ester of di- (hydroxymethyl) -tricyclo- [5.2.1.0. ²⁶ ] decane, corresponding to 88.5% of theory.

Example 4

To produce an adhesive that hardens in the absence of oxygen, the following were mixed together:

44.5 g of acrylic acid ester according to Example 1
44.5 g reaction product of diglycidyldiphenylolpropane with methacrylic acid (molar ratio 1: 2)

5.0 g acrylic acid

5.0 g of 70% cumene hydroperoxide in cumene

1.0 g of tributylamine

The adhesive was stable for weeks in the presence of air.

There were rust-free and grease-free bearing shafts (steel; diameter 24.90 mm) with cylinder rings (chrome steel; Bore 25.00 mm. Height 10 mm) glued to it.

After storage for 30 minutes at 120 ^° C., the test specimens were cooled to room temperature and the compressive shear strength of three pieces was found to be an average of 215 kp / cm ² .

Test specimens produced in the same way were then ^{heated to 150 °} C. and the compressive shear strength was then measured at this temperature. It was 170 kgf / cm ² . This means a drop in the compressive shear strength of only approx. 20% compared to the value at room temperature.

Claims (3)

Patent claims: 1. Diacrylic acid ester of
3,8-di- (hydroxymethyl) -tricyclo- [5.2.1.0. ²ⁱ ] - decan or
3,9-Di-ihydroxymeiiiyO-tricyclo-rji.Zl.O. ² *] - decan or
4,8-di (hydroxymethyl) tricyclo- [5.2.1.0. ⁱ⁶ ] - decane or mixtures thereof, as well as dimethacrylic acid esters of
3,8-di- (hydroxymethyl) -tricydo- [5.2.1.0. ²⁶ ] - decan or
3,9-di (hydroxymethyl) tricyclo- [5.2.1.0. ^is ] - decan or
4,8-di- (hydroxymethyl) -tricyclo- [5.2.1 .0. "] - decane or
their mixtures. 2. Process for the preparation of the compounds or the mixtures according to claim 1, characterized in that di- (hydroxymethyl) -tricyclo- [52.i.0. ^z6 ] -decanes with hydroxymethyl groups in the 3,8- or 3 ^ - or 4,8-position or mixtures thereof in a manner known per se with acrylic acid or methacrylic acid, their acid halides or anhydrides or their esters of low molecular weight alcohols, or that the esters of the di- (hydroxymethyl) -decanes mentioned of volatile acids are transesterified in a manner known per se either with acrylic acid or methacrylic acid or their esters of low molecular weight alcohols. 3. Use of the compounds or the mixtures according to claim 1 as a component of in Acrylic ester adhesives that harden with the exclusion of oxygen.