DE1767557C - Process for the production of polyethers - Google Patents

Description

[767

In the polymerization or interpolymerization of three-membered cyclic ethers is the use A catalyst prepared from an organoaluminum compound and water is known. Under However, only polyether of relatively low molecular weight can be used with a catalyst of this type getting produced.

The object of the invention is to improve this known method and to provide a method create, can be obtained by the polyether with high molecular weight ι.

This object according to the invention can be achieved by using (a) one of an organoaluminum compound and a catalyst prepared from an organic monocarboxylic acid ester, or (b) one of a Organ mluminum compound, an organic monocarboxylic acid ester and water prepared catalyst for polymerization or copolymerization the tripartite cyclic ethers are dissolved.

The invention relates to a process for the production of polyethers by polymerization of a monoepoxide or by copolymerization with at least one other monoepoxide in the presence a catalyst at a temperature of - 50 to 2 (Ml'C and a pressure of 1 to 200 atmospheres, which is characterized in that one of an organoaluminum compound of the general formula

AIX _n R,. "

wherein R is an alkyl group with 1 to 1? Carbon atoms, X represents a halogen or hydrogen atom and π represents a number from 0 to 2, and an organic one Monocarboxylic acid ester of one of the formulas

R ₁ COO

20th

AiX _n R ₁ "

where R is an alkyl group having I Hi-, 12 carbon atoms, X is a halogen or hydrogen atom and η is a number from () to 2. Particular examples are triethylaluminum, triisobutylaluminum, tridodecylaluminum, ethylisobutylaluminum chloride, diethylaluminum fluoride, diethylaluminum chloride, diethylaluminum iodide, diisohutylaluminum hydride, dihydric aluminum chloride, and isobutylaluminum dihydric chloride, isobutylaluminum chloride. Furthermore, the organoaluminum compounds of the invention naturally also include the various alkylaluminum halide mixtures which are obtained either by the reaction of metallic aluminum and alkyl halides or the reaction of alkylaluminum and aluminum halides. In addition, it is also possible to use the compounds obtained by modifying the above organoaluminum compounds with compounds such as methanol, ethanol, cresol, ethylene glycol, propylene glycol and pyrocatechol. or the compounds obtained by coordinating the above organoaluminum compounds with a Lewis base such as ethyl ether, dioxane, tetrahydrofuran. Thiophene, pyridine and tertiary amines, or the complexes obtained by reacting the above organoaluminum compounds with a complexing agent of the formula MY _n,. wherein M is a metal of groups I or II of the periodic table and Y is hydrogen, fluorine. Represents bromine or iodine and is in the valence of the metal M, can be obtained.

The organic monocarboxylic acid ester, the other

Component of the catalyst according to the invention

(hereinafter referred to as an organic ester because of the choice

oezcichnet) is either a chain or a cyclic one

Monoesters of the formulas

R ₁ C

where R ₁ and R ₂ each represent the same or different saturated aliphatic hydrocarbon radical, halogen-substituted saturated aliphatic hydrocarbon radical, unsaturated aliphatic hydrocarbon radical, alicyclic hydrocarbon radical or aromatic hydrocarbon radical and Rj is an alkylene radical with 2 to 15 carbon atoms, optionally with the addition of water , the organic monocarboxylic acid ester in a range from 0.02 to 20 mol, the water in a range from ob to 10 mol per mol of the organoaluminum compound

is used.

Among the organoaluminium compound, one of the components of the catalyst according to the invention is a compound from the group of Aluminiumall ^ l.Aluminiumalky halide! UndAluminiumalkyl-

or

fto wherein R 1 and R _{2 are} each the same or different saturated aliphatic hydrocarbon radical. halogen-substituted saturated aliphatic hydrocarbon residue, unsaturated aliphatic hydrocarbon residue, alicyclic hydrocarbon residue

Represent <> 5 or aromatic hydrocarbon radical and Rj is an alkylene radical having 2 to 15 carbon atoms is. Examples of these organic esters are ethyl acetate, t-butyl propionate, 2-ethylbutyl acetate,

Ueihylpulmilal, vinyl acetate, Meihylacrylal, Meihylnethacrylat, 2-Acelo. \ Y-1-Propane, Methyl-3-penio-KUiI, Allyhicrylal, Methyl-2-Octoal, Meihylhen / oal, IMienyliicelat, I'lienylacrylal, Äihes'lzimls ,. In addition, the above organic esters include the lactones, ie intramolecular lister such as / i-propioluetone,; -Butyro- _lü lactone and Λ-valerolacion.

The manufacture of the catalytic converter can also be used. in which the organoaluminium compound, the organic ester and water are used! are in mutual relation to each other largely va- _IS be defined. That is, the organic esters can be used in a range of 0.02 to 20 moles, preferably 0.05 to 5 moles, per mole of the organoaluminum compound. On the other hand, the water is used in a range of 0 to 10 moles, and preferably 0.3 to 2 moles, per mole of the organoaluminum compound. When the two components of the organoaluminum compound and the organic ester or the three components of the organoaluminum compound, the organic ester and water are appropriately mixed in accordance with the above molar ratios, a new KiSalysatorsystem is formed, the activity of which is very high, although its structure is not completely clear is.

The mixing of the organoaluminum compound and the organic ester or the organoaluminum compound, the organic ester and water can be added by adding the components in any Order to be executed. A particularly preferred order of addition is one in which the organoaluminum compound, the organic ester and water are added in the order given will. Furthermore, the catalyst can be prepared in the presence of the monoepoxide, or the catalyst, the preparation of which is bcendei, can be added to the monocpoxide. The one in the making of the catalyst applied temperature, as in conventional processes, within one in a wide range from -78 to 200 ° C. The amount of this catalyst used can, as with the 45, usual practice, can be varied within a wide range, with a suitable application being calculated as an organo-aluminum compound, in customary amounts in the range from 0.1 to 10 mol percent or occasionally in a larger amount, based on the monomer, is possible ..

As monoepoxides which can be polymerized by the method according to the invention, come Alkylene oxides, such as ethylene oxide, propyl oxide, 1-butene oxide, 2-butene oxide, isobutyl oxide and 1-hexene oxide, substituted alkylene oxides, such as cyclohexene oxide, styrene oxide and glycidyl ethers of phenol and Bisphenol, halogen-containing monoepoxides, such as epiehlorohydrin, epibromohydrin, epifluorohydrin, trifluoromethylethylene oxide, Perfluoropropylene oxide and perfluoroethylene oxide into consideration. Also belong to the Monoepoxydcp of the process according to the invention, the monoepoxides with a content of an unsaturated Bond, such as vinyl cyclohexene monoxide, allyl glycidyl ether, glycidyl methacrylate, butadiene monoxide and 2-methyl-5,6-epoxyhexetvl. The unsaturated bond-containing monocpoxides can with the above saturated monoepoxydcn / in creating polymers with an olefinically unsaturated one Binding are mischpolymerisierl, furthermore The mono-epoxy powder must necessarily be of a single kind, but they can be a mixture of two or more of the ethers mentioned.

While a diluent or diluent is not necessarily used in the process of the invention, it is also possible to use such as long as it does not have significant effects on the catalyst and the polymerization system according to the invention. Preferably, a solvent is used to obtain polymers with a high degree of polymerization. Conveniently, the aliphatic, aromatic, and acyclic hydrocarbons, such as η-hexane, benzene and C'yelohexan.die halides aliphatic hydrocarbons, for example methylene dichloride, chlorobenzene and cyclohexyl ODC ^r cyclic or chain ether such as dioxane or ethyl ether is used. However, the organic esters, one of the components of the catalyst, such as ethyl acetate, cannot be used as diluents.

While the polymerization process can be carried out within a wide temperature and pressure range, as in the case of conventional processes, a polymerization temperature in the range between -50 and i 200 (while the polymerization pressure used in the range from I to 2 (K) is used. Atmospheres.

The catalyst used in the process according to the invention has in practice a very large one Advantage, as can be seen from the figure, because the molecular weight and crystallinity of the resulting Polymers by changing the nature of the organoaluminum compound and the organic Esters and the proportion in which they are used can be regulated. That is, the polymers or Copolymers of the monoepoxides have different physical properties depending on of their crystallinity. and consequently, their resistance to oil and their tensile strength when used, for example, as a rubber or rubber in a suitable manner by varying their crystallinity can be varied.

The figure is an X-ray diffraction spectrograph to display the difference in terms of crystallinity of the resulting polymer occurs due to the composition of the catalyst. The illustration is detailed in the following given examples.

Furthermore, in the case of the catalyst used in the process according to the invention, it is composed of an organoaluminum compound, an organic ester and water milder the reaction during its preparation than in the case of the known organoaluminum compound-water catalyst, and there is one uniform composition can easily be obtained, if it is used in the polymerization or interpolymerization reaction is used, the advantage that the reaction can be carried out with good reproducibility progresses.

The invention is explained in more detail using the following examples. Unless otherwise stated, The percentages and parts in the examples are based on weight.

5
Example I.

A carefully dried pressure-resistant glass polymerization vessel with a capacity of 100 ml is filled with dry nitrogen, whereupon 50 ml of benzene, carefully dried with calcium hydride, are stirred in. Then 0.397 g (0.0020 mol) of triisobutylaluminum and 0.540 g (0.0020 mol) of methyl palmitate are added, and then the mixture is left to stand at room temperature for 30 minutes. After further addition of O.O28R g (0.0016 mol) of water and 11.7 g (10 ml) of epichlorohydrin in the order given, the reaction mixture is stirred at 60 ° C. for 5 hours. The reaction is then stopped by adding methanol to the reaction mixture, followed by washing with normal aqueous hydrochloric acid solution to remove the polymerization catalyst. Then, the reaction product is neutralized with 1/2 normal aqueous sodium hydroxide solution, followed by washing with water and then freeze-drying to obtain a solid polymer whose elasticity is extremely large. is obtained in a yield of 54.4%. A 0.1% strength cyclohexane solution of this polymer was obtained by heating 0.0473 g of the polymer together with 50 ml of a 0.5% strength cyclohexane solution of 2.2 - methylene - bis - (4 - methyl-6-tert-butylphenol) for 2 hours made at 115C. The reduced specific viscosity f / _jp / C of this solution, measured at 50 ^r C, was 1.81 (unless otherwise stated, the reduced specific viscosity given below is> ( _Jp / C measured under these conditions). If 0.5 g of this polymer were extracted with acetone for 24 hours using the Soxhlet extractor, the acetone-insoluble content was 2.3%.

Examples 2 to 5

In the procedure of Example 1, the amounts of the catalyst used were unchanged of its composition varies. As can be seen from the following table. became epichlorohydrin polymers of high molecular weight obtained at yields about the amount used Are proportional to the catalyst.

■ mole

Example triisohutylaluminium in detail

Howl

0.0010 (0.19S)
0.0015 (0.297)
0.0030 (0.595)
0.0050 (0.990)

29.6
42.5
71.9
KHlO

Reduced
specific
viscosity

1.51
1.51
1.90
1.52

Examples 6 to 10

L game MnI
TriisnhiiUlaluminiutn Howl Rctlu / ierle
spe / ilischi.
Viscose silal IuI CnI ._.'':': .'1'.. 6th 0.0010 (0.19H) 18.6 7th 0.0015 (0.297) 28.9 8th 0.0020 (0.397) 35.6 9 0.0030 (0.595) 45.1 10 O. (X) 50 (0.990) 68.9 .34 .63 .65 .42 .45

Comparative Examples I to 5

The results obtained in the case where the organic Ester was not used, obtained in the procedures given in Examples I to 10 are listed in the following table:

Following the procedure of Example 1, ethyl acetate was obtained used in place of methyl palmitate, and the amount of catalyst used was without Change in the molar composition of the catalyst components varies. As from the following Table can be seen. became fluorohydrin polymers of high molecular weight obtained at yields roughly proportional to the amount of applied Catalyst are.

MnI Bulge Reilu / icrle ispiel Trüsi> hat \! Aluminum Cl specific
Viscous Ij!) 21.2 l '<. r <"l I. 0. (X) IO (0.198) 31.4 0.60 1 0. (X) 15 (0.297) 42.S 0.62 3 0.0020 (0.397) 55.5 0.63 4th 0.0030 (0.595) 78.2 0.62 5 0. (X) 50 (0.990) 0.61

If the results of the above Examples 1 to 10. in which an organic ester is used as one of the Components of the catalyst was used, with the results shown in the table above compared, it can be seen that there is a decrease in the yield in the case of the examples 6 to 10. in which ethyl acetate was used, while an increase was observed in the case of Examples 1 to 5 in which methyl palmitate was used has been found. However, the feature persists of the catalyst of Examples 1 to 10. which contain the organic ester. not in the fact that an increased yield is obtained, but rather that polymers with higher moles! alargcw ot be obtained. That is, in the case of the catalytic converter, which does not contain the organic ester. (Verglcichsbeispiele 1 to 5) can only polymers of low molecular weight unsuitable for use as a rubber or gum as shown by their reduced specific viscosity of 0.6 (corresponding to a molecular weight of 120 (K) O), whereas, for example, in the case of Example 4, a polymer with high Molecular weight can be obtained, as evidenced by a reduced specific viscosity of 1.90 (corresponding to a molecular weight of 720,000) shows.

Examples 11-15

Even if the catalyst components of Example I are in the one shown in the following table Order added were high molecular weight polymers, as in the table listed, received. To facilitate comparison, the results are from Example! also in the table atifueluhit.

13th
14th
15th

diluc ilcr

B «Λ · Ρ 'W» I!

B> Λ 'W · Ρ Ή

B · [·:> Λ · Ρ> VV

β · ι ·: «α · νν · ρ

I) 'Κ> Ρ' W »Λ

Howl

I ",. I

54.4

43.8
37.3
44.3

Rediizicrle -ixvitistlii-

(■ "■ ('ι

IS I
1.02
2.48
1.22
1.94

H: lleii / ol A rriisohiiiylaliiminiiini. P: Mellnlpalniilal W: water. l ^: .: Hpithlorhyilnn

Examples 16 to

The amount of triiso water and ethyl acetate used in Example 6 were varied with the iirbutyl aluminum was unchanged at 0.0010 mol result. that in all cases solid polymers, as in fol-Kl.l ^l ) 8 μ), were left, but the amounts used were shown in the gender table.

For ease of comparison, the results of Comparative Example I and Example f are also shown listed.

Hi-i-pii'l Mc.lM-rh.illMi- Athjlacclal
I rii-ohut>! Aluminum Moherhiillniv Wisher
TnisobuU! Aluminum Au-tx'iHi ¹
I ".. I Comparative
example 1
16 0.0
0.5 0.8
0.8 21.2
21.7 6th 1.0 0.8 18.6 17th 2.0 0.8 17.8 18th 3.0 0.8 20.7 19th 5.0 0.8 18.2 20th 1.0 0.0 9.0 21 1.0 0.4 12.5 22nd 1.0 0.6 12.5 23 1.0 1.0 13.2 24 1.0 1.2 5.1

Reduced specific viscosity

0.60

1.24 1.34 1.26 1.26 1.40

0.31 0.45 0.81 0.93 0.60

The crystallinity of the microfluoric polymers obtained in Examples 6 and 16 was investigated with the aid of X-ray diffraction. In the figure, curves 1 and B are each the X-ray diffraction patterns of the poles of -s in Examples 6 and 16. The measurement conditions were as follows:

Anticathode

Tilter

voltage

Tubular flow

Discharge speed

Regisli κι stivifcnueschw mdigkei

copper

nickel

40 KV 5 111Λ 1 min I cm min

Il 0.2 mm in the course of the polishing of example 6. obtained by means of a catalytic converter. in which the amount of organic ester used was large. the peak appeared at the inclination angle (2 <->) 19.5. What indicated the presence of a crystalline portion, after taking this fact into account, it is evident that the crystallinity can be adjusted to a greater degree by the amount of organic lister used.

Example

to 36

Even if the triisobunaluminum compound is replaced with other organoaluminum compounds in the procedure of Example I, solid polynes can be obtained as shown in the following table. However, in all of Examples 2 and 2S in ^{Figure 1, the time of PoKnicrisation was 22 hours}

(iru.mo.iluminiiiimcrbimluML ¹ Niisheuk- Rcilii / icrlc -pe / game I "" I Visknsiia Triethylaluminum 61.5 ! ', ". <I.
- 25th Tri-n-hydroxyl aluminum 75.5 1.88 26th Diethyl aluminum chloride 21.8 3.35 27 Ethyl aluminum chloride 21.4 1.34 28 Triisobutyl aluminum and tetrahydrofuran 69. i 1.42 29 (Molar ratio l / l) 3.68 Triisobutyl aluminum and dioxane 54.3 30th (Molar ratio l / l) 2.14 Triisobutyl aluminum and thiophene 44.8 31 (Molar ratio l / l) 1.81 Triisobutyl aluminum and pyridine 18.4 32 (Molar ratio 10/1) 3.52 Triisobutyl aluminum and ethyl alcohol 39.6 33 (Molar ratio 2/1) 0.88 Triisobutyl aluminum and ethyl alcohol 32.2 34 (Molar ratio 3/1) 0.94 Triisobutyl aluminum and potassium chloride 48.5 35 (Molar ratio l / l) 1.90 Triisobutyl aluminum and sodium fluoride 46.8 36 (Molar ratio l / l) 1.25

B e i s ρ i e I e 37 to 46

As shown in the following table, solid polymers were obtained even when the ethyl acetate was replaced by the other organic esters in the procedure of Example 6. To make things easier a comparison, the results of Examples and 6 are also shown.

Example organic liier

fi j ethyl acetate

2 'Melhylpalmital

37! n-butyl celate

38 phenyl acetal

39 Ethyl benzoate

40 C'ydohcxylacelal

41 vinyl acetate

42 methyl methacrylal

43; Eth) ld; chloroacetate

44 benzylchloroformal

45,; -Prnpiolactone

46 -Butyr <> lacl; in

yield

18.6 29.6 17.8 13.2 22.4 18.2 26.0 24.6 22.0 11.3 14.6 17.2

Reilu / i.rlc spe / ilis.: he viscous.al

1.34 1.51 0.99

11.6 ')! 1.86 0.81 1.73 1.13 1.25 0.70 1.43 1.61

• to

Examples 47 to 53

As shown in the table below, polymers were used obtained even if f> 5 when working Example I the methyl palmitate was exchanged for other organic esters and also none Water was used.

example

47
48
49
50
51
52
53

(! manic I.

Methyl methaenate, methyl acrylate

Ethylbenzon

Ethyl valerate ethyl trilluoroacetate ethyl dichloroacctate

Phenylacelate howling I "η I

17.7

14.7

18.5

10.7

9.2

7.8

16.8

Kcilii / icrlc specific viscosity

0.16 0.11 0.16 0.12 0.11 0.17 0.16

Examples 54 to 56

As shown in the following table, solid polymers even daiiii obtained if the polymerization temperature in the procedure of Example! 6 varies would. The results of Example 6 are also shown for ease of comparison.

lh MKTIs.llHMls- j

temperature j ^ 'shciiic

ICi S i ",. I

54 20 j 4.1

55 j 40 j 14.1 6! 60! 18.6

56 80 25.0

Kcilu / ierle spe / ilKche Viscousiiiii

not measured 1.69 1.34 1.01

Examples 57 to 60

In the procedure of Example I, after adding the methyl pulmitate, the reaction mixture was aged at 60 C for various periods of time. As a result, solid '' polymers. as in the following

Table shown. receive. To facilitate comparison the results of Example I are also applicable.

Kapa / iliil of 200 ml used. To make things easier Also the results of Example I are comparative specified.

example

Alleruiijjs-

I Cl

Room temperature
60
60
60
60

IhI

0.5

0.5,
1.0
3.0
5.0

yield

54.4

46.7
48.8
39.9
39.4

Rcdii / ierle
spe / ilisclie
Vi-lio-il.it

ι · ,,,, η
I.XI

1.13
J. 13
1.13
1.44

B e i s ρ i e I e 61 to 66

example

62

63
64
65
66

Used
Ueivolnieniic

10

30th

50

70

90

120

160

Howl

I "i.l

56.4
50.4
54.4
50.8
53.9
52.1
51.1

Kedu / icnc

-pC / Ü'lM'llC

Vi-ko-iiiii

0.38
1.00
1.81
1.88
2.11
2.37
2.32

"Venn the amount of ben / oil in the operation of Example I was varied, high molecular weight solid polymers were at a practically uniform The yield is shown in the table below. In Examples 64, 65 and 66, however, a pressure-resistant ilaspolymerization vessel with a Example e 64 to 74

In the procedures of either Example I or 8, other organic solvents were substituted used by benzene and solid polymers, as in the following Table shown received.

A example (Iru.iiii-chc- I o-uim-mitlcl Organic l -.- ler 67 toluene Methyl palmitate 68 Dioxane Methyl palmitate 69 *) Tetrahydrofuran Methyl palmitate 70 Furan Methyl palmitut 71 Ethyl ether Ethyl acetate 72 Methylene dichloride Ethyl acetate 73 n'-hexane Ethyl acetate 74 Chlorobenzene Ethyl acetate

\ u-hculc Kctlu / icric spc / ilisirliL viscosity Γ'Ό ι., "η 51.1 1.35 13.9 0.72 18.5 0.53 58.7 3.7 27.6 1.76 30.2 1.93 27.8 0.34 25.9 1.58

* 1 t); i iki- product die-c- Hci-picK. «I was found with the help of a l-lenientaranah-e who was a Misthpei | \ niere- .in- XA.1 Moipro / ent TcIr.iliulrofiiran and I \ S Molpro / ent t.pichWirhulrin. was tl.i- (iewichl-verallni- l'oKmercn / u ileni <■ -.initueWiiht by l-.pichlorh \ d: in and Tctr.ihulroiuran ills Ausheule iinucnommcn.

In Examples 67 to 74 the reaction mixture After the reaction has ended, washed in normal aqueous hydrochloric acid solution to remove the polymerization catalyst to remove, then with ', -normal aqueous sodium hydroxide solution neutralized. whereupon it was washed with water and then the Layer d *: s organic solvent in vacuo has been dried to remove the solvent, whereupon the solid polymer was obtained.

Examples 75 to 77

Other types of tripartite cyclic ethers were used in the procedure of Example 6 in place \ on epichlorohydrin was used and the results listed in the table below were obtained. The inherent Viscosity. as si: is used here is an in Benzene measured value at 30 ° C.

example

monomeric bumps

Propylene oxide

Ethylene oxide

I.2-butene oxide

14.4
22.4
38.6

Inh.ircnlc

Vlsko-Ilill

1.02
2.14
1.13

fiO

Example 7S

If, in the procedure of Example I, 0.282 g (0.0010 minor tri-n-hexylaluminium. 0.1M18S g KUK) IO mol) Ethylacelat and 0.0144 g KUXX) X Mof] water were used as a catalyst and a (a mixture of 11.8 g (0.128 mol) of epichloride in it and 1.0 g (0.017 mol) propylene oxide used as monoepoxy was, a mixed polymer with a reduced specific viscosity of 1.50 at a Yield of 4i "n obtained.

The result of the chlorine attack was. that the Cieh.il .in epichlorohydrin in the mixed polymer 87.1 mol prozenl hetrug

Examples 79 to 80

If, in the procedure of Example 78, a C ic mixture of li.8g (0.128 mol) of tpichlorohydrin and I an unsaturated monoepoxuls with a double bond as shown in the following table solid polymers were retained in both cases.

The presence of an olefinically unsaturated double bond was found in the infrared absorption « spectra of these polymers observed.

79
HO

I ιιμί ">. ΙΙΙιμ <ι"> Mnnniilc
, ■ "" η ,, ρρι-ΙΙιιικΙιιημ

Allyl glyeidyl ether
Vinyl cyclohexane monoxide

He i S ρ ι e I Sl

Ul'iI | I / Il- | U ■

1.19

2.39

77th K.
95.0

The carefully dried pressure-resistant glass vaporization vessel is filled with a capacity of 3 liters of dry nitrogen, whereupon 1.5 liters of calcium hydride, carefully dried henol is poured into the vessel, followed by 23Og 12.49 mol) of iipichlorohulrin and 52 g (1.18 Moll of alyleno). Separately, a carefully dried 100 ml glass vessel for the production of a catalyst was filled with hot nitrogen, whereupon 50 ml hen / ol, carefully dried with calcium hydride, K.47 g * | 0.0300 mol) Tri-n -hexylaluminum. 2.16 g (0.0300 moles) of tetrahydrofuran. 2.64 g (0.0300 mol) of allyl acetate and 0.432 g (0.0240 mol) of water were added in the order shown to thereby prepare the catalyst. The catalyst prepared in this way is divided into four equal proportions and added to the above-described polymerization vessel in 30 minutes, where there :. The reaction mixture was stirred at 60 ° C. for 3 hours. The reaction was then stopped by adding methanol containing a small amount of 2,6-di-t-butyl cresol. After removing the solvent, unreacted monomer and methanol by blowing in steam, the reaction product was dried with hot air.

The bulge on the copolymer was 23.2%. and its reduced specific viscosity is hot 2.67. If this mixed polymer was extracted for 24 hours with water using the Soxhlet Hxtraklors, the water soluble portion of 0.8 V was ¹ The results of chlorine analysis showed that this mixed polymers of 69.5 Molprozenl Lpichlorhydrin and 30.5 Molprozenl ethylene oxide was composed.

H e i s ρ i e I 82

Pressure-resistant rust-free material that has been carefully dried Steel polymerization vessel with a capacity of 501 was filled with dry nitrogen, whereupon 29.6 kg benzene carefully dried with a molecular sieve and 7.9 kg (85.5 moles) kpichlorohydrin were poured and then 11.5 g (0.64 () mol) of water were added.

A carefully dried glass jar was used separately. Preparation of the catalyst is filled with dry nitrogen, after which 500 ml of benzene carefully dried with a molecular sieve are placed in the reaction vessel. 159 g (0.800 mol) of triisobutylaluminum and 70.4 g (0.800 mol) of ethyl acetate were added to prepare the catalyst.

This catalyst is poured into the above-described pressure-resistant, rust-free steel polymerization vessel, after which the mixture was stirred at 60 ° C. for 5 hours. The polymerization reaction was then terminated by adding acetone in a small amount of 2.6-1) il-biylk / u to the reaction mixture. To

Removal of the solvent. unreacted monomers and acetone by Linhlasen of steam was dried mil Heaklioiisprodukt the hot air.

Hs became a Kauischukarliges polymer with a reduced specific viscosity of 1.46 for one Howl of 29 ",, obtained. When 0.5 g of this polymer Extracted with 150 ml acetone for 24 hours using the Soxhlet extractor, the accton-insoluble fraction was 10.2%.

Part by weight of the rubbery polymer thus obtained was made with the following ingredients mixed.

FHl - "- carbon black 50

Zinkslear.il '

Lead oxide 5

Nickel dibutyldilhiocarbamai 2

2-mercaploimida / olin 1.5

The resulting mixture was then milled on rollers heated at 80 ° C. for 10 minutes and then milled Hot-pressed for 30 minutes at 160 ° C. The physical properties of the emerging vulcanized rubber were as follows:

Tensile strength 130 to 160 kg cnr

3M% module 70 to 140 kg cnr

Elongation 660 to 400%

Hardness (JlS) 65 to 57

Claims (1)

Claim: Process for the production of polyethers by polymerizing a monoepoxide or by Mixed polymerization with at least one other monoepoxide in the presence of a catalyst at a temperature of -50 to 200 C and a pressure of 1 to 200 atmospheres, that is through marked that one off an organoaluminum compound of the general formula AIX _n R., " wherein R is an alkyl group having from 1 to 12 carbon atoms. N is a halogen or hydrogen atom and / ι a number from π to 2, and an organic one Monocarboxylic acid ester of one of the formulas or R, CO
O wherein R ₁ and R, each have the same or preferably saturated aliphatic carbohydrates 767 557 sersiolTresi. halogenated saturated aliphatic Hydrogen carbon, uiiycsälliytcn uliphalic hydrocarbon fresl, alicycüschen Hydrocarbon residues or iromalous hydrocarbon residues and R <is an alkylene radical having 2 to 15 carbon atoms, if appropriate with the addition of water produced catalyst ρini ... is the organic M.mo-SiiurSer in a range of 0.02 _> his V, mol, the water in a Mere.ch vM (bs? () Mol'per mol der Organnaluminiumverhindu, ^ is used. 1 sheet of drawings