DE1180530B - Process for the production of high molecular weight epoxidized polyether acetals - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Boarding school Class: C 08 g

GERMAN

PATENT OFFICE

EDITORIAL

German AI .: 39 c - 30

Number:
File number:
Registration date:
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D 37711 IVd / 39 c
December 18, 1961
October 29, 1964

It is already known to epoxidize monomeric acetals and ketals, e.g. B. according to the USA patent 2,895,962 and Belgian patents 580 904, 580 905, 595 150 and 596 268. It is also known that OH groups under certain conditions with α, / 3-unsaturated acetals to so-called Ether acetals react (Angewandte Chemie, 62, p. 113 [1950]). A saturated polyether acetal is thereby formed.

It has now been found that high molecular weight epoxidized polyether acetals can be prepared by using acids to unsaturated aldehydes with activated double bonds with unsaturated dihydric alcohols, optionally with the addition of saturated polyhydric alcohols, in proportions such that an aldehyde group meets three to four hydroxyl groups at temperatures of 50 to 150 ⁰ C and treated the polyether acetals obtained in a manner known per se with epoxidizing agents.

As unsaturated dihydric alcohols according to the invention, open-chain or cyclic olefinic Connections such as B. butene-2-diol-l, 4, l, l-dimethylol-cyclohexene-3 and 6-methyl-l, l-dimethylol-cyclohexene-3, be used. The cycloolefinic compounds are preferably suitable last mentioned Art.

As unsaturated aldehydes which contain reactive double bonds are according to the invention especially «, ^ - unsaturated aldehydes understand and also aldehydes which contain a vinyl ether structure in the molecule, e.g. B. acrolein, Λ-methylacrolein, x-ethylacrolein, 2-formyl-2,3-dihydro-y-pyran, 3-formyl-5,6-dihydro-ix-pyran and homologues of this group of substances.

In the case of α, / 3-unsaturated aldehydes, pro Aldehyde group an amount of alcohol corresponding to about three OH groups, in the case of aldehydes with Vinyl ether structures in the molecule, e.g. B. with 2-formyl-2,3-dihydro-y-pyran, an amount of alcohol corresponding to about four OH groups per aldehyde group.

Optionally additionally usable polyhydric saturated alcohols are in particular to name: pentaerythritol, glycol, butanediol, glycerine and hexanetriol.

Crosslinking takes place during the production of the acetals by the process according to the invention by reaction of the additional OH groups with the activated double bonds of the aldehyde Formation of ether structures instead, so that polyether acetals are obtained as reaction products, their double bonds subsequently epoxidized process for the production of high molecular weight epoxidized polyether acetals

Applicant:

German gold and silver refinery

formerly Roessler,

Frankfurt / M., Weißfrauenstr. 9

Named as inventor:
Dipl.-Chem. Dr. Willibald Walk,
Rheinfelden (Bad.)

will. The desired epoxy content results from the ratio of unsaturated to saturated Polyol.

The condensation takes place in the presence of an acidic catalyst, carried out at temperatures between 50 and 15O ⁰ C. Temperatures between 75 and 100 ^° C. have proven useful. The water formed can either be removed from the reaction mixture directly, possibly under vacuum, or it can be towed away azeotropically. After completion of the reaction, the acid catalyst is neutralized and the polymeric acetal epoxidized in a known manner, conveniently with peracids such as peracetic acid, optionally in an organic solvent at 30 to 60 ⁰ C.

The epoxidized polyether acetals obtained in this way are colorless to yellowish colored resins.

They can be used to produce moldings that are particularly resistant to acids and alkalis.
According to US Pat. No. 2,895,962, unsaturated, low molecular weight acetals are obtained by reacting, unsaturated aldehydes and a polyhydric saturated alcohol in such a way that two hydroxyl groups are used for one aldehyde group. The acetals are then polymerized to macromolecules on the double bond of the aldehyde component by linking them via epoxy bridges.

By using unsaturated dihydric alcohols, in such amounts that on one Aldehyde group three to four hydroxyl groups come, according to the inventive method already obtained high molecular weight polyacetals. the

409 709/360

The carbonyl group and the double bond of the aldehyde are no longer free, but the double bond of the unsaturated alcohol, which is now being epoxidized. In this way arise a lot high molecular weight resins. They are much harder and more resistant to chemicals than the products of the USA patent 2,895,962. Since it is also possible according to the process according to the invention, in addition to unsaturated Use alcohols saturated alcohols, the degree of crosslinking by epoxidation and thus the hardness of the end products can be adjusted as desired.

example 1

a) 58.3 g of acrolein (96%; 1 mol) and 213 gl, l-dimethylol-cyclohexene-3 (1.5 mol) are mixed with 813 mg of p-toluenesulfonic acid (0.3 percent by weight), which in 2 ml H ₈ ^{O are dissolved, heated to 75 to 80 0} C for 3 hours with stirring in a stream of nitrogen. The water of reaction is then distilled off in vacuo at the same temperature and the residue is kept at this temperature for a further 20 hours.

For work-up, the residue is taken up in chloroform, _{neutralized with solid NaHCO 3} , the filtrate is evaporated and dried on a boiling water bath at 12 mm vacuum with thorough stirring.

This gives 224 g of a yellowish, viscous oil having a reduced viscosity *) of 3.2 x 10 ~ ² (20 ⁰ C) and an iodine number of 159 (Wijs).

b) For epoxidation, 220 g of the polyether acetal are dissolved in 200 g of chloroform and, with stirring and cooling at about 30 ° C. _, 4-06 g of a 28.5% solution of peracetic acid in ethyl acetate are added in about one hour. The temperature is kept at 30 ^° C. for a further 6 hours and left to stand overnight. After that, the theoretical amount of peracetic acid has been used up.

The epoxidation solution is gradually introduced into boiling xylene under a weak vacuum. The more volatile components such as chloroform, ethyl acetate, acetic acid and excess distill Peracetic acid, along with some of the xylene. After removing the remaining xylene the residue is dried with thorough stirring in vacuo on a water bath.

222 g of a slightly yellowish, viscous soft resin with an oxirane oxygen content of 6.8%.

Example 2

a) A mixture of 58.3 g of acrolein (96%;

1 mol), 106.5g U-dimethylol-cyclohexene-S (0.75MoI) and 51 g of pentaerythritol (0.375 mol) is dissolved in 647 mg (0.3 percent by weight) of p-toluenesulfonic acid

2 ml of water, in a stream of nitrogen and with stirring

Heated to 75 to 80 ^° C. for 3 hours. After the water of reaction has been distilled off in vacuo, the mixture is heated for a further 20 hours. The reaction mixture is taken up with chloroform, _{neutralized with NaHCO 3} , filtered and the residue is dried on a boiling water bath at 12 mm with thorough stirring. This gives 143 g of a yellowish, viscous resin having the reduced viscosity of 4.0 x 10- ² (2O ⁰ C) and an iodine number of 119th

b) for the epoxidation, 140 g of the resin are dissolved in 200 g of chloroform and mixed with 193 g of a 28.3% strength ίο Peracetic acid treated in ethyl acetate according to Example 1. 142 g of a light, almost colorless, highly viscous resin with an oxirane oxygen content are obtained of 5.6%.

Example 3

A mixture of 58.3 g of acrolein (96%; 1 mol),

106.5 g of 1-dimethylol-cyclohexene-3 (0.75 mol) and 67.5 g of 1,4-butanediol (0.75 mol) are dissolved in 696 mg (0.3 percent by weight) of p-toluenesulfonic acid 2 ml H ₂ O, implemented according to Example 1.

This gives 186 g of a yellow, viscous oil having a reduced viscosity of 3.0 x 10- ² (20 ° C) and an iodine value of 97th

For the epoxidation 184 g of the oil obtained are dissolved in 200 g of chloroform and 207 g of one 28.5% peracetic acid in ethyl acetate, as indicated in Example 1, epoxidized. 192 g are obtained of a light-colored, thin-viscous soft resin with an oxirane oxygen content of 5.1%.

Example 4

a) 103 g of 2-formyl-2,3-dihydro-y-pyran (87%; 0.8 mol) and 170 gl, l-dimethylol-cyclohexene-3 (1.2 mol) are brought to 6O ^{0 with stirring} C. and 546 mg (0.2%) p-toluenesulfonic acid were added. An exothermic reaction occurs. The temperature is kept at 70 ^° C. by cooling. The mixture is then left to ^{stand at 70 °} C. for 1 hour, cooled and taken up in chloroform, washed neutral with soda and water and dried with Na ₂ SO ₄ . The chloroform is then distilled off and the residue is dried in vacuo on a boiling water bath while stirring. This gives 217 g of a brownish-colored soft resin having a reduced viscosity of 3.4 x 10- ² (2O ⁰ C) and an iodine number of 170th

b) The epoxidation is carried out according to Example 1. 195 g of the resin obtained are dissolved in 465 g of chloroform and treated with 382 g of a 28.5% strength peracetic acid in ethyl acetate as indicated there. This gives 199 g of a clear, pale yellow resin having a softening point of about 35 to 5O ⁰ C and an oxirane oxygen content of 5.8%.

B e i s ρ i e 1 5

a) 103 g of 87% 2-formyl-2,3-dihydro-y-pyran (0.8 mol) and 170 g of I, l-dimethylol-cyclohexene-S (1.2 mol) are with the same weight of benzene with 273 mg (0.1%) p-toluenesulfonic acid as

*) Measured in the Ostwald viscometer: capillary diameter 0.3 mm

For volume 3m!

Measuring volume 0.5 ml

t, - t, "

'L.M.

LM = trichlorethylene
C = 1g / 100mi

Catalyst dewatered azeotropically with a water separator. About 9.3 ml of water have separated out after 45 minutes. For work-up, it is neutralized with solid soda, filtered and the filtrate is evaporated as usual in vacuo and dried. This gives 245 g of a pale yellow, high-viscosity resin having a reduced viscosity of 3.1 · 10 ^-2 and an iodine number of 173 °.

b) The epoxidation is carried out as in Example 1 with 230 g of resin dissolved in 300 g of chloroform and 450 g of 29.3% peracetic acid in ethyl acetate. This gives 196 g of a clear, pale yellow resin having a softening point of about 49 to 60 ⁰ C and an oxirane oxygen content of 5.4%.

Example 6

a) 77 g 87% ig ^e s 2-formyl-2,3-dihydro-y-pyran (0.6 mol), 170 gl, l-dimethylol-cyclohexen-3 (1.2 mol) are dissolved in 247 g of benzene reacted with 247 mg (0.1%) p-toluenesulfonic acid as a catalyst according to Example 5. After 45 minutes, 10.4 ml of water have separated out. After working up, 225 g of a viscous resin with a softening point of 29 to 60 ^° C. and an iodine number of 184 are obtained.

b) for epoxidation, 205 g of resin are dissolved in 300 g of chloroform and mixed with 437 g of a 28.5% igeri Treated peracetic acid in ethyl acetate according to Example 1. 204 g of a clear, slightly yellowish color are obtained Resin with a softening point of 35 to 55 ° C and an oxirane oxygen content of 6.8%

Example 7

a) 103 g of 87% 2-formyl-2,3-dihydro-y-pyran (0.8 mol) are dissolved in 105.6 g of butene-2-diol-1,4 (1.2 mol). After the exothermic reaction has subsided, the same amount by weight (208 g) of benzene and 208 mg (0.1%) of p-toluenesulfonic acid are added and the mixture is heated to the boil for 45 minutes on a water separator. 11.5 ml of water separate out. After neutralization with sodium carbonate, filtering, distilling off the benzene and drying under vacuum with vigorous stirring on a boiling water bath to obtain 180 g of a brownish, viscous resin having a reduced viscosity of 3.7 x 10- ² (20 ⁰ C) and an iodine number of 263.

b) For epoxidation 165 g of this resin are dissolved in 200 g of chloroform and 500 g of a 28.5% peracetic acid in ethyl acetate, as indicated in Example 1, treated. 177 g of one are obtained clear, slightly yellow, sticky soft resin with an oxirane oxygen content of 7.4%

Example 8

a) 77.3 g of 87% 2-formyl-2,3-dihydro-y-pyran (0.6 mol), 105.6 g of butene-2-diol-1,4 (1.2 mol) are in the same amount by weight (182 g) of benzene with 182 mg (0.1%) of p-toluenesulfonic acid according to Example 7 heated on a water separator for 45 minutes. 11 ml of water are separated out in the process. After working up, 165 g of a brown, thin viscous resin having a reduced viscosity of 3.2 · 10 ^-2 (20 ⁰ C) and an iodine number of 252nd

b) For epoxidation, 144 g of resin are added with 405 g of 29.5% peracetic acid in ethyl acetate Example 1 treated. 132 g of a clear, slightly yellowish, sticky soft resin are obtained an oxirane oxygen content of 8.6%

Example 9

a) A mixture of 142 g (1 mol) 1,1-dimethylolcyclohexene-3, 45 g (0.5 mol) 1,4-butanediol and 129 g 2-formyl-2,3-dihydro-y-pyran (87 %; 1 mol) in 316 g of benzene is heated with 316 mg (0.1%) of p-toluenesulfonic acid as a catalyst for 45 minutes on a water separator. In the process, 12.5 ml of water separate out. Is obtained after work-up 281 g of a brownish, highly viscous resin with a reduced viscosity of 3.7 x 10- ² (20 ⁰ C) and an iodine value of 154. b) The epoxidation of 275 g of resin are dissolved in 300 g of chloroform, and with 475 g of a 29.5% peracetic acid in ethyl acetate treated according to Example 1. 265 g of a slightly yellow-colored soft resin with an oxirane oxygen content of 4.3% are obtained.

Claims (3)

Patent claims: 1. A process for the preparation of high molecular weight epoxidized polyether acetals, characterized in that unsaturated aldehydes with activated double bonds with unsaturated dihydric alcohols, optionally with the addition of saturated polyhydric alcohols, in such proportions that three to four hydroxyl groups meet an aldehyde group, by means of acids Reacts temperatures of 50 to 150 ⁰ C and treated the polyether acetals obtained in a manner known per se with epoxidizing agents. 2. The method according to claim 1, characterized in that the unsaturated aldehyde Acrolein or formyldihydropyran or their homologues are used. 3. The method according to claim 1, characterized in that the unsaturated polyvalent Alcohols l, l-dimethylol-cyclohexene-3 or butene-2-diol-1,4 or their homologues are used. References considered: U.S. Patent No. 2895,962. 409 709/360 10.64 & Bundesdruckerei Berlin