DE1495157A1 - Process for the production of crosslinkable macromolecular polyethers - Google Patents

Description

Process for the production of crosslinkable macromolecular Polyethers

The invention relates to a method for producing ver wettable macromolecular polyethers.

It has been found that monoglycidic ethers containing hydroxyl groups can be obtained the general formula

RR RR 0 _s

I HO-O- (O) _n-1 -CG- (G) _n-1 -CO-CH ₂ -GH-CH ₂ or RR RR

RR / R R 0

II () (

RRRR

Macromolecular crosslinkable polyethers are obtained if they are obtained at temperatures between -50 and +150 ⁰ C in the presence of 0.001 to 5 percent by weight, preferably 0.1 to 1 percent by weight, of halogen-containing Friedel grafts compounds and / or alkyl derivatives of an element of the 3rd Main group or the 4th group of the periodic table.

The compounds of the formulas I and II, the preparation of which is not the subject of the present invention, become simpler Way obtained by adding doubly or triply unsaturated

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T495157

Reacts diols with epichlorohydrin in a molar ratio of 1 % 1 at temperatures between about -10 and +10 ⁰ C with boron trifluoride dietherate and then converted in the usual manner with alkali, advantageously with sodium etherate * with elimination of hydrogen chloride into the corresponding epoxy compound. In the formula, this is demonstrated using the example of butenediol as follows: HO-CH ₀ -CH = CH-Ch ₀ -OH + CH ₀ -CH-CH ₀ -Cl —- *

HO-CH ₀ -CH = Ch-CH ₀ -O-CH ₀ -CH-CH ₀ - * HO-CH ₀ -CH = CH-CH ₀ -O-Ch ₀ -CH-CH ₅

OH Cl ^Hül ^ O

From the corresponding hexynediol compound is obtained

> CC = CCO-CH ₀ -CH-CH
OH CH ₅ ^ O

The epoxy compound thus obtained is now according to the invention in Presence of from 0.001 to 5 percent by weight, preferably from 0.1 to 1 percent by weight, of a Priedel-Crafts catalyst and / or reacted in the presence of alkyl compounds, wherein as Friedel-Crafts catalysts the halogen compounds and as alkyl compounds the alkyl derivatives of elements of the 3rd main group or the 4th group of the Periodic Table in question come »in particular boron trifluoride and its addition compounds, Titanium-IV-chloride, tin-IY-chloride or aluminum chloride, also aluminum triethyl, titanium tetrabutyl or zirconium oxychloride.

The reaction is carried out at temperatures between -50 and + 15O ⁰ C, preferably wiping -10 and -, + 5O ⁰ G - made, and in the presence or absence of inert Yerdünnungsmitteln.

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\ J »ti *

The epoxy compounds of the general formulas I or II are; liquid to solid compounds, the simplest epoxy compounds being liquids that can be distilled, rend the triple unsaturated epoxy compounds at lamb temperature are present in crystallized form in the presence of indifferent diluents work. As indifferent diluents come above all Saturated aliphatic things that are liquid under the reaction conditions and cycloaliphatic and aromatic hydrocarbons ^ substances in question, such as petroleum ether, pentanes, hexanes, octanes, Cyclonexane, benzene, toluene or cumene.

The degree of polyaddition of the polyethers obtained can be regulated within a wide range both by the selection of the catalysts and by the amount in which the catalysts are used. For the production of relatively low molecular weight foly ethers of the type mentioned, boron trifluoride and its addition products, such as etherates, alcoholates, of hydrates, are particularly suitable, while with tin tetrachloride, for example, polyethers with high molecular weights and high polyaddition rates are obtained in an often very violent reaction . More generally lie MolekulaiigeWieihte achieved between about 4-0000 and 250 OOOV'l-n special cases can also be relatively low molecular weight products with PolymeirlB ^ ^ ationsgiiadein wiped about hens make 2000 luad 10,000.

As starting connections for the polymerisation of the type I

- 4 - O.Z. 22 857.

857 ■

or II are, for example, the reaction products of butenediol, Hexenediols and octenediols, as well as the corresponding triunsaturated compounds with epichlorohydrin, are suitable.

It is possible, up to about $ 10 for the corresponding reaction products of saturated diols, such as butanediol, hexanediol or octanediol, to be used in the manufacture of the polyethers.

The new polyethers obtained contain double mouths. and can therefore be networked in the usual way. The high molecular weight products are rubbery and can for example with the processing machines customary in rubber technology, z-.B. processed on calenders or co-kneaders and are crosslinked or vulcanized. The crosslinking is carried out, for example, with sulfur, optionally in the presence of the usual Vulcanizing agents, such as mercaptans or thiazoles and the like, made.

The new crosslinkable compounds are particularly suitable for the production of aging-resistant rubbers.

The parts mentioned in the examples are parts by weight. The K values were determined by the method of "ikentscher in" Cullulosechemie "JJ5" ^1932, page 58th

example 1
135 parts of butenediol monoglycid ether are mixed with 100 parts of petroleum

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ether was added and with vigorous tubes 0.5 ropes Bortrifluoriddiäthylätherat and 0.5 parts of tin tetrachloride dissolved in 10 parts of diethyl ether, were added dropwise in Yerlauf of 60 minutes while the dropwise addition maintaining the! temperature at ⁰ O, followed by 3 hour stirred at room temperature. After removing the solvent in vacuo, 102 parts of a sticky, viscous residue remain.

The product has a K value of 73 (0.5 $ solution in dioxane), the Mooney value MI 4 'is 38 (measured according THE 53 523) and the Defo value at 80 ⁰ G 400 (measured according to DIN 53 514). Subject vulcanization under standard conditions (40 minutes ,,, 142 ⁰ C, 3 a tu - for 100 parts of polymer: 50 parts of carbon black OK 3, 2-part stearic acid, 3 parts of zinc oxide, 5 parts of a mixture of higher molecular weight, partially , unsaturated hydrocarbons, as it is available under the trade name Faftolen ZD, 1.5 parts phenyl-ß-naphthylamine, 1.75 parts sulfur and 1 part ethylenediaminetetraacetic acid) has a strength of 105 (kg / cm) and an elongation of 330 $ > (both measured according to DIF 53 504) found.

Is worked as above, but with the addition of 15 parts Alkyl glycidyl ether, a product is obtained which is partially soluble and whose soluble fraction has a K value of 82 * (0.5% in tetrahydrofuran).

Subject to vulcanization - as above - a product with a strength of (155 kg / cm) is obtained.

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U'95157

Example 2

100 parts of hexynediol monoglycid ether are grounded with 100 parts of pentane added and with stirring 0.5 part of boron trifluoride diethyl etherate, dissolved in 10 parts of diethyl ether, and 0.2 parts of aluminum diethyl monoehlorid dissolved in 10 parts of isooctane in the course of Added dropwise separately for 30 minutes.

The reaction tempera door is held to +3 ⁰ C "at 0". After the solvent has been distilled off, 83 parts of a viscous, soluble product remain. The K value is 69 (0.5 $ solution in dioxane), the Mooney value ML 4 'is 52 and the Defo value at 80 ⁰ C 580th

After vulcanizing under standard conditions (compare Example 1), but with the addition of 3 parts of copper versenate, a hard product with a strength of 98 (kg / cm) and an elongation of 215 $ is found.

Example 3

The procedure is as described in Example 1, but instead of the butenediol monoglycide ether, octene diol monoglycid ether is now used and as a catalyst a mixture of 0.5 part of boron trifluoride diethyl etherate and 0.5 part of zirconium oxychloride used.

Bs become 89 parts of a product with a K value of 8, the Mooney value ML 4'29 and a Defo value of 390.

After vulcanization under standard conditions (compare Example 1), the. Pe ^ JJI ^ ft ^ l ^{18 k} s / cm ²⁾ and elongation of 335 Jt '-. 7 -

ORIGINAL INSPECTED

Example 4

..; in mixture of 50 parts and 30 Hexendiolmonoglvcidäther file Oktindiolmonoglyciaäther ether is dissolved in 100 parts of diethyl * 'and at -30 ⁰ C a .Gemisch of 0.1 part aluminum · miniumtriäthyl and 0.4 parts Titantetraßhlorid within 10 Minutes smdropped.

Then allowed to react for 60 minutes at 30 ⁰ G. If 0.5 part of Ehenyl-ß-naphthylamine is added, the solvent is stripped off

iöa 68 parts of a soluble copolymer with a K value of 81 ($ 0.5 in dioxane) obtained. The Mooney value H-j 4 * is 32 and the Defo value is 490

after vulcanizing under standard conditions (cf.

liäbeispiel 1) is a vulcanizate with a strength of 120 (kg / cm) and got an elongation of $ 325.

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Claims (1)

Claim Process for the production of crosslinkable macromolecular polyethers, characterized in that epoxy compounds of the general formula RR RRO _n I HO-C- (C) _n-1 -CC- (C) _n-1 -CO-CH ₂ -CH-CH ₂ or RR _m RR RR RR 0 II HO-C- (C) _n-1 -CsC- (C) _n-1 -CO-CH ₂ -CH-CH ₂
RR RR of the Periodic Table in the presence of 0.001 to 5 percent by weight · halogen-containing Friedel-Crafts compounds and / or alky! derivatives of elements of main group 3 or 4 "group, at temperatures between -50 and ⁰ C · +.150 BADISCHE AlTILIN & SODA FABRIK AG / 009820/1585