DE1273516B - Process for the production of low molecular weight halogenated epoxy ethers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C07d

C08g

German class: 12 ο - 5/05

12 ο-5/09

39C-6

Number: 1273 516

File number: P 12 73 516.9-42 (S 101596) Filing date: January 24, 1966
Opening day: July 25, 1968

The invention relates to a method of manufacture low molecular weight halogenated epoxy ether made from halogenated epoxies.

It is already known from US Pat. No. 3,058,921, polymers of halogen-substituted epoxyalkanes by contacting them with a catalyst in the presence of water. The proposed catalysts include substances such as hydrogen fluoride, sulfur, phosphorus and Hydroiodic acids, salts such as tin tetrachloride and boron trifluoride complexes, especially the diethyl ether complex.

The use of these catalysts, however, results in side reactions during the polymerization which apparently cause the formation of cyclic dimers of the halogen-substituted epoxyalkane and olefinic or allylic halide groups. These side reactions reduce the number of halohydrin end groups in the polymer that is formed and thereby lower the functionality of the polymer. According to the German Auslegeschrift 1076 657, polymers of epihalohydrins with compounds of metals of group II of the Periodic Table, in particular magnesium or zinc, are obtained, which, however, mainly consist of dimeric and trimeric epihalohydrins. The reaction is carried out at an elevated temperature of e.g. B. 100 to 200 ⁰ C carried out.

It has now been found that polymers of halogen-substituted epoxyalkanes with less By-product formed when a catalyst is used under special conditions Contains boron trifluoride.

The inventive method for the preparation of low molecular weight halogen-containing epoxy ethers from halogen-containing epoxides, in which the halogen atom is bonded to a carbon atom adjacent to the epoxy group, in the presence of water and a fluorine and boron-containing compound as a catalyst is characterized in that the catalyst used is boron trifluoride and the Implementation in two stages, working in the first stage with a molar ratio of epoxy compound to water between 2: 1 and 6: 1 and a reaction temperature between 50 and 9O ⁰ C, whereupon in the second stage at a reaction temperature below that of the first stage, the implementation with further halogen-containing! Epoxy leads to the end.

The epoxyhalogensubstituierte alkane is preferably a Fluorborsäurekatalysator at a temperature between 50 and 7O ⁰ C, A process for preparing low molecular weight
halogen-containing epoxy ether

Applicant:

Shell International Research

Maatschappij N.V., The Hague

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse
and Dipl.-Chem. Dr. E. Frhr. v. Bad luck man,
Patent Attorneys, 8000 Munich 9, Schweigerstr. 2

Named as inventor:

John David Hassall, Bryncoch, Glamorgan,

Wales (Great Britain)

Claimed priority:
Great Britain January 25, 1965 (3140),
dated October 14, 1965

in particular 60 and 70 ° C, brought into contact.

The reaction between the adduct of the epoxyhalogensubstituierten alkane and water and further epoxyhalogensubstituiertem alkane is preferably carried out at a temperature between 20 and 40 ⁰ C.

1,4-dichloro-2,37epoxybutane is an example of the epoxyhalosubstituted alkane in practice of the method according to the invention. Preferably the epoxyhalosubstituted alkane contains in its molecular structure no more than 8 carbon atoms and a vicinal epoxy group from which only one carbon atom is bonded directly to a halogen-bearing carbon atom. Epibromohydrin, 2-methylepichlorohydrin, 2-ethylepibromohydrin and 1-chloro-2,3-epoxypentane are examples of the preferred epoxyhalosubstituted alkane. From the point of view For reasons of availability, the preferred epoxyhalosubstituted alkane is epichlorohydrin.

The process according to the invention can most conveniently be carried out in the presence of an organic solvent be performed.

Examples of the organic solvents used to carry out the method according to the invention are dioxane and diethyl ether.

809 587/585

However, the preferred organic solvents are halogenated hydrocarbons, for example halogen-substituted ones Alkanes, e.g. B. methylene dichloride, ethylene dichloride and chloroform. While the amount of solvent suitably up to about 200 parts per 100 parts by weight of epoxyhalosubstituted Can be alkanes, it is preferred that the amount of solvent not greater than 100 parts per 100 parts by weight of epoxyhalosubstituted alkane

weight between 1500 and 2500 produced by reacting epichlorohydrin and water in the presence of a halogenated hydrocarbon in an amount of not more than 100 parts by weight per 5 100 parts by weight of epichlorohydrin, in the process of epichlorohydrin with a mixture of water, fluoroboric acid and not more than 50 ⁰ / o of the amount of halogenated hydrocarbon at a reaction ^{temperature between 50 and 7O 0} C to one

is, for example, between 30 and 50 parts per io adduct of epichlorohydrin and water with one 100 parts of epoxyhalosubstituted alkane. Weight increase in molecular weight between 203

The amount of fluoroboric acid can expediently and 298 are reacted, and then the adduct with more between about 0.1 about 5 ° / o of the comparable epichlorohydrin at a reaction temperature between agreed weight of water and the epoxy- 20 and 40 ⁰ C to an adduct of epichlorohydrin halogen-substituted alkane. If the polymer 15 and water with a weight increase in the molecular weight of the epoxyhalogen-substituted alkane converts a polymer weight between 750 and 1050, then to that of epichlorohydrin with a weight increase in the reaction mixture the remainder of the halogenated carbon molecular weight of 750 to 2250, the hydrogen is and then with a further amount of epichlor catalyst, preferably 0.1 to 0.5% of the hydrin at a reaction temperature between 20 and combined weight of water and epichloro 20 40 ⁰ C the adduct with an increase in weight of hydrin. Molecular weight between 750 and 1050 converts.

After the epoxyhalosubstituted alkane has polymerized, the fluoroboric acid catalyst can with
concentrated aqueous ammonia or with a
Alkali carbonate or hydroxide are neutralized. 25th
The catalyst is preferably used at a reaction ^{temperature of from 20 to 40 °} C. with no more than 2 mol
Alkali carbonate neutralized per mole of fluoroboric acid.
In particular, the catalyst at a reaction temperature of 20 to 40 ⁰ C and not more than 30 is preheated. Epichlorohydrin is added at a 1.5 mol, eg about 1.0 mol, alkali metal carbonate per rate such that the reaction mole of fluoroboric acid is maintained at 60 ° C in the presence of no more than temperature. When the amount of 0.2% water, based on the total weight of the added epichlorohydrin, neutralizes 3 moles per mole of polymer. Corresponds to water, the addition of epichloride

The her- 35 hydrin terminated by the process according to the invention. The reaction mixture is made of epichlorohydrin polymers contain 15 minutes at 6O ⁰ C stirred. It is then terminated at 30 ° C. The polymers can be cooled and the remainder of epichlorohydrin added to the corresponding glycidyl ether according to any known method at such a rate that the reaction and suitable processes, for example treatment temperature, are kept at 30.degree. If the addition of the polymer with an excess, based on the 40 epichlorohydrin, is completed, the reaction chlorohydrin content of alkali hydroxide, converted to mixture, is stirred for about 1 hour at 30 ° C. to ensure a complete reaction of the epichlorohydrin

Particularly preferred polymers of epichlorohydrin afford.

produced by the process according to the invention, the reaction mixture is neutralized by

have a weight increase in molecular weight 45 addition of sodium carbonate and water and 1 to from 750 to 2500. You can e.g. B. stirred ^{at 3O 0} C for 6 hours. The reaction mixture can be used with polyurethanes. is filtered and the methylene dichloride through

In a preferred embodiment of the pre-heating under vacuum at 30 ° C removed,
The examples are summarized in the following table.

hydrins with an increase in weight in molecular 50.

Tabel

The present invention is illustrated by the following examples:

Examples

Epichlorohydrin slowly becomes a stirred mixture of an aqueous solution of fluoroboric acid and methylene dichloride added that to 60 ° C

2 example 3 4th 5 6th 1 1.88 1.88 2.40 2.06 0.86 3.60 118 118 198 188 119 196 0.2 0.2 0.2 0.2 0.2 0.2 48 48 80 80 48 80 14th 16 18th 19th 18th 13th 0.3 0.3 0.5 0.5 0.3 0.5 0.2 0.2 0.4 0.4 0.25 0.4 6th 6th 3 6th 6th 1

Respondents

Water, parts by weight

Epichlorohydrin, parts by weight .. fluoroboric acid, percent by weight. Methylene dichloride, parts by weight

Response time, hours

Neutralization

Sodium carbonate, parts by weight

Water, parts by weight

Stirring time, hour

Footnote at the end of the table.

I 273

Continuation of the table

ι 2 By S
3 fell
4th 5 6th 108 96 95 67 65 48 2.09 1.74 1.70 1.25 1.13 0.80 1040
955
nb 1170
1150
nb 1180
1175
1250 1675
1600
nb 1725
1770
1645 2340
2500
2055

Analysis results

Hydroxyl number, milligrams

Potassium hydroxide per gram
Chlorohydrin content, milliequivalents per gram
Molecular weight calculated from

Hydroxyl number

Chlorohydrin content

Molecular weight osmosis

nb = not determined.

Claims (4)

Patent claims: 1. A process for the preparation of low molecular weight halogen-containing epoxy ethers from halogen-containing epoxides, in which the halogen atom is bonded to a carbon atom adjacent to the epoxy group, in the presence of water and a compound containing fluorine and boron as a catalyst, characterized in that the catalyst used is boron trifluoride and the Implementation in two stages, one in the first stage with a molar ratio of epoxy compound to water between 2: 1 and 6: 1 and a reaction ^{temperature between 50 and 90 0} C, whereupon in the second stage at a reaction temperature below that of the first stage, the reaction with further halogen-containing epoxy leads to the end. 2. The method according to claim 1, characterized in that the halogen-containing epoxy Epichlorohydrin used. 3. Process according to Claim 1 to 2, characterized in that the second stage is carried out at a reaction temperature ^{between 20 and 40 ° C.} 4. The method according to claim 1 to 3, characterized in that the reaction is carried out in Presence of an organic solvent, preferably a halogenated hydrocarbon, in particular in an amount between 30 and 50 percent by weight of the halogen-containing used Epoxyds performs. Considered publications:
German Auslegeschrift No. 1076 651;
Belgian patent specification No. 576 728. 309 587/585 7.68 © Bundesdruckerei Berlin