DE2312221B2 - Polymerization catalyst, process for its preparation and its use - Google Patents

Description

R- [X- (R ') J "-Y-R"

wherein X and Y, which can be the same or different, are SO or SO ₂ groups; R and R "methyl, alkyl groups with 2 to 10 carbon atoms, cycloalkyl, aryl, arylalkyl, alkylcyclo-

4 (i are alkyl groups or divalent radicals with each other can react to form a ring; R 'is a divalent arylene, cycloalkylene, alkylarylene, Alkylcycloalkylene radical or a methylene chain with a number of carbon atoms from 0 to 20

4-) represents; is chosen between 0 and I and is an integer which can be 1, 2 or 3, in a ratio between 10 and 0.3 in the presence of aliphatic or aromatic hydrocarbons, tetrahydrofuran, dioxane, hexamelhylphosphoramide

«Or liquid ammonia as a solvent for a Temperature between -80 "C and f 80" C produced has been.

The Mctallkoniponenle of the polymerization catalyst is derived from the groups IA, EIA and <. \ INA des

v, Periodic Table of the Elements awesome! "Handbook of Chemistry and Physics" of the Chemical Rubber Publishing Co. (39th edition) selected.

Examples of metals or their derivatives which are particularly suitable for the invention are Li,

w) Na, K, LiH, CaH ₁ , NaH, ZnH ₂ , LiR, ZnR ₂ , MgR ₂ , AIH ₁ U, AIR. ,, LiNH ₂ , Mg, (NII,), i \ m \ Mg (NH, ) ,, where B is a Lewis base.

The following may be mentioned as examples of the compounds of the formula I:

CH, - SO - (CH ₂ I ₄ SO - CH,

CH ₁ -SO - <

-SO - CH,

Φ - SO - (CH ₂ ) ,, - SO - Φ (Φ = phenyl)

CH ₃ -> Ο, - (CH ₂ U - SOj - CHj

etc.

κι

In the preparation of the catalyst of the invention is preferably in a ratio of 1: 1 between melal-supplying agent and the compound of formula I worked.

The catalysts according to the invention can be used for Polymerization processes are used that are in polar solvents or in mixtures thereof at temperatures in the range of -4 () "C to + I (K)" C and preferably from -20 ° C to +40 ° C. The concentration of the Catalyst between 0, (X) I% and 5%, based on the fed moles of the monomers and preferably between 0.01% and 1%. Various compounds can be selected as monomers, such as, for example Episulphides, among which may be mentioned in particular: ethylene sulphide, propylene sulphide, l.sobiilcnepi.siilfid, .Styrolepisul / id, Vinyfcyelohexeriepisullid, Allyloxy-2, vcpithiopropane and butadiene nionocpisuliide. However, other monomers can also be used, such as monomers from vinyl glyph, Lucion-type monomers and monomers tics Dimelhylkcten- or of the aldehyde type. The monomers mentioned can be made using the invention Polymerization catalysts processed into homopolymers, copolymers and terpolynes will. Particularly interesting results were found in the formation of: homopolymers of named monomers, random and Ulock copolymers von Episullidmonoinercn, Fcrpolyniereu of Episullidnionomercn, static and Bloek copolymers of vinyl and episullide monomers, copolymers of vinyl monomers and statistical and block copolymers of EpisiiUidmoiumieren, achieved.

Example I.

Production of
OO

Il Il

CU., - S - (CH ₂ ) ,, - S - CH.,

and the corresponding reaction product
with Li-Butyl (Catalyst A)

A three-necked flask equipped with a stirrer, dropping funnel and thermometer is all in one Argon flow 4.6 g (170 mmol) NaH introduced, and 100ecm dimethyl sulfoxide slowly graze Stir added dropwise. The whole is stirred for 6 hours at + 40 ° C. and then filtered and titrated. The reaction mixture, which is 95 mmol

Il

Na ^ CH ₂ -S-CH,
contains, is with 48 mmol

Br - CH ₂ - CH ₂ - CH ₂ - CH ₂ - Br

diluted with IO ecm DMSO, implemented. The reaction b-> runs slightly exothermic. The reaction is held at 60 ° C. for 8 hours, DMSO is distilled by vacuum removed, ether is added, and then the whole thing is filtered and cold with 50 ecm THF washed.

The solid is extracted with hot THF, the extract in tetrahydrofuran with anhydrous ether precipitated and then filtered and dried, 5.6 g (yield = 56%)

CH ₃ - S - (CH ₂ J ₅ - S - CH ₃

O O

contains.

Into a previously vented 250 cc three-necked flask, equipped with a condenser, dropping funnel and thermometer, 4.1 g r, (19.4 mmol)

CH., - S - (CH ₂ J ₆ - S - CHj

introduced, and then 2 (X) ecm of anhydrous dioxane are added (dehydration of the dioxane by LiAlH ₄ ). It is heated to 40 to 50 ° C. for complete dissolution, and 40 mmol of Li-butyl in hexane solution are slowly added / l.

A noticeable evolution of gas is observed and the temperature rises to +55 ° C. Against find the implementation, the formation of a white precipitate is observed. The mixture is stirred for 3 hours 50 C, nitrate the mixture, wash repeatedly with THF in the heat to remove excess Li-BuIyI and may not remove unigcsel / .tcs product and dries on the vacuum pump for 1 to 2 hours. The product dried in this way is dissolved in hexamelhylphosphoramide (HMPA) solved.

characterization
a) Electronic analysis

.κι calculated ... C 43, H 7.2, S 28, Li 6.4%:
found .... C 42, H 7.5, Li 6.4%.

b) with CjH ₅ Br

In a 100 cc three-necked flask that was previously enl- ■ r. Was vented and was equipped with a stirrer, dropper and thermometer, 0.2 g (0.90 mmol) of Catalyst A were introduced under argonal amplification, and 50 μm of THF were added, a white suspension being formed. _{6 mmol of CiII 5} Br were added and the mixture was stirred for a further 16 hours at 30 ° C. A clear solution was obtained which was evaporated to dryness with formation of a white hygroscopic solid which had a molecular weight of 266 in the mass spectrum, which is the sum of two C \ H ₅ clusters with catalyst Λ.

Example 2
Implementation of

CHj - S - (CHj) ₆ - S - CHj

O O

with NaNH, (catalyst B)

In a flask equipped with a fixed Quickfit glass stirrer and a dropping funnel

Jacket, 0.39 g (10 mmol) of NaNH _{2 are} introduced and dissolved in 40 ecm of liquid ammonia at -70 C. 5 mmoles

CH ₃ - S - (CHA - S - CH,

suspended in 40 ecm THI "are added. Es is stirred for a further 10 hours at -45 "C, MHj in is removed and the dry solid content is used for polymerization.

Characterization with BrAt is carried out on part of the solid as in Example 1. The product obtained turns out to be in the Massenspck-Irum in accordance with a structure similar to the previous one.

Example 3
Implementation of MgAt ₂ and

r>

CHj-S- (CH ₂ V ₁ -S-CH.,
(Catalyst C)

In one with magnetic stirrer, dropping funnel and Flask equipped with a condenser will add 0.5 g (2.4 mmol)

CH, - S - (CH ₂ ) ,, - S - CH,

introduced and dissolved with 70 ecm THF at +40 C. 4.8 mmol of MgAt _{2 dissolved} in 20 cm of tetrahydrofuran are then added. One observes the formation of a precipitate and the simultaneous evolution of a gas, which disappears after 30 minutes of aging.

The temperature of +40 C is maintained for 18 hours. The opalescent solution is concentrated and precipitated with hexane, filtered, washed with THI- '(tetrahydrofuran) and hexane to remove the unused Products washed and dried, and the precipitate becomes in the polymerization used.

Example 4

Implementation of ZN - (C ₂ H ₅ J ₂ and
CH., - S - (CH ₂ ) ,, - S - CH,

O O

(Catalyst D)

Following the procedure of Example 3, 0.75 mmol

CH, S - (CH ₂ ) ,, - S - CH,
OO

reacted with 0.75 mmol ZnAl ₂ in THI '.

Gas evolution occurs, and so does the solution opalized. The temperature is kept at t 50 C for 16 hours, the solution is concentrated and

quenched with hexane, washed with THF and hexane, dried, and the precipitate becomes in the polymerization used.

Example 5

Implementation of AlH ₁ N (CH ₃ J ₃ and
CH ₃ -S- (CH ₂ J ₆ -S-CH ₃

O O

(Catalyst E)

According to the procedure described in the previous example, 0.57 mmol

CH ₃ -S- (CHA-S-CH ₃

20 reacted with 0.57 mmol AIHjN (CHj) ₃ in 40 ecm toluene. The temperature of 60 "C is maintained for 1 hour, the precipitate is filtered, washed with THI" and toluene and dried and used in the polymerization.

Example 6

Precipitation of CH _{3 -SO 2} (CHA-SO ₂ -CH ₃ and reaction with Li-BuI (catalyst F)

In a flask equipped with a stirrer, Dropping tube and condenser, becomes I g (4.7 mmol)

CH ₃ -S- (CHA-S- CH ₃

introduced and dissolved in the smallest possible amount of glacial acetic acid. The mixture is heated to 70 ° C. and the necessary amount of H ₂ O ₂ is added dropwise. The reaction is held at 70 ° C. for 10 hours and then left to stand overnight. A white precipitate forms, which is crystallized from alcohol. The product is carefully dried in vacuo. 1.05 g (87%) of the desired product were obtained.

According to the procedure described in Example I, 1.05 g (4.1 mmol)

CH., SO, (CH ₂ ) ,, SO -CH ₃

implemented with 8.2 mmol of Li-but. The product was dried and dissolved in I IM PA.

Calculated
found .

characterization
a) Elementary analysis c

. C 38.0, H 6.2, S 25.2, Li 5.5%;
. C 37.5, H 6.0. Li 5.7%.

b) with UrAt

The implementation was described in detail in Example I. Analysis by mass spectrometry is consistent with a compound with a molecular weight of 2MX match.

-CH ₃

CH ₁ -S

'Il - ο ο

and conversion with Li-BuI (catalyst H)
The disulfone was by oxidation of

CH., - S - <Λ) / - S - CH.,

treated. After the NH _{3 had} been freed from water using metallic Na and distillation into the reaction vessel kept at -40 ° C., SmMoI of the disulfone and 16 mmol of NaNH _{2 were} added and the reaction was carried out for 4 hours.

At the end the NH _{3 was} completely evaporated, and the whole ^{thing was treated with 60 cm '1 of} a mixture of El ₂ O-HEMPA (5: 1), the catalyst being obtained, which was then used for the poly-

H) merization was used. Its structure was given by the _{product obtained by treatment with C 2} H ₅ Br, which, according to its MS and NMR data, has the following structure:

(Reports 1909. 42, pp. 2721-2731) Prepared with H ₂ O ₂ in acetic acid at 70 C for 7 hours. The product was isolated after treatment with water and crystallization from ethyl alcohol (melting point 195 197 C). The mass spectroscopy (MS) and nuclear magnetic resonance (NMR) Dalcn confirm the proposed structure.

The following data were obtained in the mass spectrum: m / e = 172 (1 (X)). 1 55 (72), 219 (41), M ⁴ x 234 (40), 76 (24), 50 (20). 63 (14). 75 (13), 109 (11). The data in brackets refer to the relative intensity.

In the NMR spectrum in CD., CN (TMS-Slandard) the following chemical shift was obtained in ppm: 8.4 7.S C / '. Multiples). 3.12 (CHj, singulctt).

8. OmMol of the disulfone were treated in 60cm ^{1 of} a mixture of 1: 1, O and Hcxumcthylphosphoramid (HIiMPA) (5: 1) with 16mMol Li-Butyl (LiBu) at room temperature for 4 hours. The catalyst was isolated on the linden tree, _{washed with Hl 2} O and dried. It was then dissolved in HI-MPA and used for polymerization.

Example 8

Production of
OO

ί i!

</ <- S- (CH ₂ US-Φ

O O

and reaction with NaNH ₂ (catalyst J)

The disulfone was by oxidation of
'/' - S (CH ₂ I ₄ - S - Φ

with H ₂ O ₂ in L.-iMg ^ aure. at Kl) C, produced for 4 hours.

The product was isolated by treatment with H ₂ O and crystallization from ethyl alcohol (melting point 115 116 C). The MS and NMR data confirm the proposed structure.

The following values were obtained in mass spectroscopy: m / e = 143 (100). 77 (86), 197 (68), 55 (66). 125 (20), 141 (16). 51 (16), 29 (15), M ⁺ -338 (1).

In the NMR spectrum in CDCl ₃ (HMDS as standard), the following chemical shifts were obtained in ppm: 7.9-7.45 (0, multiple) 3.01 (CH ₂ *, multiple). 1.75 (CH ₂ /, ', multiples).

The disulfone was with NaNH ₂ in liquid NH ₃

O CH ₂ CH ₃ CH ₃ CH ₂ O

Φ - S - CH - CH ₂ - CH - S - Φ

O O

MS: m / e = 143 (1 (H)), 69 (80), 253 (57), 55 (57), 4 1 {38),

77 (36), 111 (29), 83 (19), M '■ 394 (3).

NMR in CDCI ₃ (HMDS): 7.9 7.4 [Φ, multiple), 2.76 (CH *, multiple), 1.95 1.35 (CH, / (, multi-2-3 plett), 0.84 (CH ₃ , triplet).

Example 9
Production of

O O

and reaction with NaNH ₂ (catalyst K)

The disulfone was obtained by oxidizing the cntspre-4 (i haste disulfide prepared under the same conditions as in the previous example. The product had a melting point of 197 C.

His MS data were: m / e = 127 (K) O), 128 (48), 193 (46), 55 (40), 247 (36), M ⁴ - 438 (34), 191 (22), 129 4-. (22), 175 (16).

NMR in CD ₂ CI ₂ + CF ₃ COOD (HMDS): 8.5 7.5 ('/ "Λ, multiple). 3.38 (CH ₂ λ. Multiple), 1.92 (CH ₂ /;, multiple).

It was metallized in the same way as described in bc-ίυ above. The structure of the catalyst was confirmed by treatment with C ₂ H ₅ Br. The structure was obtained from the MS and NMR analysis

O CH ₂ CH ₃ CH ₃ CH ₂ O
S CH (Cri2) 2 CH S
OO

bo MS: m / e = 128 (100), 127 (46), 193 (44), 303 (28), 69 (26), 55 (26), 129 (14), 41 (14), M ⁺ - 494 (4).

NMR in CDCl ₃ (HMDS): 8.4-7.3 (</ «/», multiple), 3.0 (CH, multiple), 1.8 (CH ₂ , multiple) 0.87 (CH ₃ , Triplet).

Application examples 1 to 6

The polymerization tests are carried out in a 250 cc vessel that has previously been vented and under argon

is held. First is the catalyst of Example I introduced with the solvent and then the monomer. The tests

are kept at 30 ° C in a thermostatic bath. The important dates are listed in Table I.

Tabel I. Monomers * lot Catalyst A l.osungsmillcl lot Around η. a. j ToI. 30 C To whom- change 2.24 DMFA " manic Type 60 mmol lot Art 25 ecm 0.29 ToI. " heispicl 63 mmoles 5 20 ecm 1%) i, 39 ■ No. Ethylene sulfide 63 mmoles 0.03 mmol HMPA 25 ecm KX) η. a. I. Propylene silicide HX) mmol 0.05 mmol HMPA-THF 30 ecm 100 ti. a. 2 Acrylonitrile 63 mmoles 0.1 mmol HMPA 25 ecm 84 3 Methyl acrylonitrile 63 mmoles 0.08 mmol HMPA 25 ecm 40 4th Methacrylonitrile 0.07 mmol HMPA 93 5 Pivalolaelon 0.07 mmol HMPA 95 6th

I IM PA = Oxaniclhylphosphoraniid.
THF = tetrahydrofuran.
I) MFA = dimethylformamide.

Applicable example 7

Following the procedure described above, 0.05 mmol of the reaction product of

CH ₃ - S - (CFU) ₆ - S - CH.,

with NaNH ₂ (designated as catalyst B) in 25 ecm THF under argon in a vented vessel. Then 63 mmol propylene sulfide are added. The experiment is carried out in a thermostatic bath at 30 ° C. 4.65 g (yield KX) Vo) of a polymer with a value for [<,] in toluene at 30 ° C. of 2.10 dl / g are obtained.

Application example 8

One works in the usual way in a vented vessel under argon, but using 0.05 mmol des from

CH ₁ -SO ₂ - (CHj) ₁₁ -SO ₂ -CH.,

Catalyst prepared with Li-But (catalyst F) in 25 ecm solvent (5 ecm HMPA +20 ecm THF). 63 mmoles of propylene sulfide are added and the experiment is carried out in a thermostatic bath at 30 ° C carried out.

4.65 g (yield I (X)%) of polymer with a value for [,,] = 1.84 dl / g at 30 ° C. in toluene are obtained.

Application example 9

Using the procedure described, 25 mg of the reaction product of MgAt and

O O

Il Il

CH ₃ -S- (CH ₂ J ₆ - S - CH ₃

(Catalyst C) placed under argon in a vented vessel, whereupon they are dissolved in 30 ecm HMPA and 63 mmoles of propylene sulfide are added. The polymerization is carried out at 30 "C, whereby 4.4 g (yield 98%) of a polymer with a value for [„] = 1.32 dl / g in toluene at 30 ° C. are obtained.

Application example IO

Using the procedures described above, under argon, in a small vessel H), 05 mmol of the by reaction of Zn (C ₂ H ₅ ) ₂ and

CH ₃ -S- (CH ₂ I _n -S -CH,
OO

(Catalyst D) introduced precipitate and dissolved in HMPA, whereupon 76 mmol propylene sulfide can be added. The polymerization is carried out at 30 ° C.; 3.4 g (61% bulge) are obtained Polymers with a value for [;,] = 1.86 dl / g in

4 ^r ) toluene at 30 "C.

Application example 11

Using the procedures described above, 0.05 mmol of the by conversion of AlH ₁ N (CH,)., And

CH ₃ - S - (CH ₂ ) ,, - S - CH ₃
OO

product obtained (catalyst E) introduced into a vented and kept under argon vessel. she are suspended in 20 ecm HMPA and 57 mmol propylene sulfide are added. The polymerization is carried out at 30''C, whereby 3 g (yield 70%) of a polymer with a value for [<,] = 1.80 dl / g in toluene at 30 "C.

Application example c 12-18

The copolymerization and terpolymerization experiments were carried out in a 250 ccm vessel.

which has been previously vented and kept under argon. First, the catalyst A. introduced with the solvent and then

Table Il

the mixture of monomers. The experiments were carried out in a thermostatic bath at 30 ° C. The data are given in Table II.

Monomers *
Art

Propylene sulfide

Propylene sulphide

Propylene sulfide

Propylene sulfide

Propylene sulfide

Propylene sulfide

lot

45 mmol
63 mmoles
63 mmoles

63 mmoles

76 mmol
67 mmol

Cnmonomcrcs Tcrmonomcres Catalyst Λ Solvent

ArI amount type amount amount

Ethylene- 19 mmoles

sullid

Acrylonitrile 10 mmol 0.0128 mmol HMPA 20 ecm 0.015 mmol DMSO 20 ecm 0.033 mmol DMSO 20 ecm

Acrylonitrile 50 mmol

Table II (continued)

Allyloxy - 3.15 mmol

2,3-epithio-

propane

Ethylene- 24mmol allyloxy- 6.14mmol 0.015mmol HMPA 20 ecm

sullid 2,3-epilhio-

propane

Methacrylic 11 mmoles 0.037 mmoles DMSO 25 ecm

nilril
Acrylonitrile 3 mmoles allyloxy 4 mmoles 0.25 mmoles DMSO 40 ecm

2,3-cpithio-

propane

Methyl 50 mmol 0.1 mmol HMPA 15 ecm

acryhit

Collaboration / iiMg Ethylene sulphide 20% I ,,] il Ι / μ 30th C. Around- Acrylonitrile 25% 30th C. warning 12th Propylene sulphide 80% Allyloxy 5% 1.89 toluene 80 C. 98 13th Propylene sulphide 75% 2,3-epithio- 2.17 CHCl., KX) 14th Propylene sulfide 95% - propane 2.20 toluene 100 Ethylene sulphide 33% 30th C. Methacrylic 17% 30th C. 15th Propylene sulphide 60% nitrile 1.15 toluene 97 16 Propylene sulfide 83% Acrylonitrile 19% ATE 6% 0.46 DMFA 30th C. 65 Methyl- 40% 17th Propylene sulfide 74% methacrylate 0.7 CHCI., 76 18th Acrylonitrile 60% - i.a. 70 DMSO = Dimethyl sulfoxide. IAIIyltiraii> lälcr |. DMFA = Dimethylformamide. ATl-: = Allyliixy-i.Vepilhio-priipan

The following are the technological characteristics of those manufactured in Application Bcispicleii 14, 15 and 17 Polymers listed after vulcanization using the following recipe:

Polvmeres 100 parts of 2,2'-methylene-bis- <4-methyl- i part

6-tert-butylphenol)

Stearic acid 1 part

Carbon black *) 50 parts ZnO 5 parts

Mercaptobenzlhiazole 0.5 parts

Tetramethyhhiuramdisulfkl I part

Sulfur 2 parts

*) (Obtained by burning natural gas or vaporized aromatic hydrocarbon oil with 30% of the required air and cooling with spray water.) The vulcanization was carried out at 145 ° C. Reference example 14

Mi-module kg / cm ²
lines

100% 2 (X)% 300% kg / cm-

60

65

7th 34 69 15th 52 112 30th 58 124 45 61 - 60 59

103

147 142 124 121 114

Ar *

505 260 205 190 180

Permanent deformation

20 8 4 2 ι

♦) Cr = breaking strength.
**) Ar = elongation at break.

Minutes

15th
30th

45
60

Minutes

7th
15th

13th

Application example 15

Module kg / cm ² Cr Ar

200% 300% kg / cm ² %

132 -

51

62
66

72

145

125 118

135 175 160 145

Application example 17

Module kg / cm ² Cr Ar

I (X)% 200% 300% kg / cm ² % 41

19th

51

32
96

48 115

445

285

Permanent deformation

Permanent deformation

Minulen

30th
45
60

Module kg / cm "'

KMI ",,, 2 (10% 300 '/

63
55
66

101

Cr Ar Permanent
Ver
forming kg / cm ' % % 119 195 4th 128 295 6th KK) 160 0

Application examples 19 to 22

The polymerization experiments for the production of block copolymers were carried out in a 250 ccm Rcaktor carried out, which was previously vented and was allowed to run under argon.

First the catalyst A was introduced with the solvent and then the monomer I. When the polymerization of the first monomer has ended after 5-8 hours, the resulting polymer becomes with 50 ecm THF "is dissolved, and the second monomer is added, the reaction taking place at the temperature of 30 C.

The data are listed in Table Ml.

Table III

19th
20th

21
22nd

Monomcrcs 1 Art

Propylene sulfide Propylene sulfide Propylene sulfide Propylene sulfide

lot

63 mmol 63 mmol 63 mmol 63 mmol Monomcrcs 2
Art

Ethylene sulfide
Acrylonitrile
Methacrylonitrile
Pivalolactone

catalyst lot Art Λ 40 mmol 0.064 mmol 35 mmol 0.04 mmol 10 mmol 0.015 mmol 10 mmol 0.015 mmol

Table III (continued)

Solvent composition

19th HMPA 20 ecm 20th HMPA 20 ecm 21 HMPA 20 ecm 22nd HMPA 20 ecm V Melting temperature. Tk Glass passage lcmpcraliir. PS Propylene sulfide. IiS Ethyl sulphide. ACN = Acrylonitrile. MACN = Methacrylonitrile. 1 PVL = Pivalolactone.

PS 65% ES 35%

PS 70% ACN 30%

PS 90% MACN 10%

PS 90% PVL 10%

conversion '' K C; 200 C. (Tj 90% -42 ' C; 95 C. 90% -39 ' 90% n.d. C; 172 C. (Tf 90% -39

In addition to the data listed in Table III, pylene sulfide (PS) with 0.025 mmol of the catalyst H

the polymeric nature of the products obtained was polymerized t> o. After 4 hours at room temperature

proven by fractional extraction experiments, 4.6 g of a polymer with a value for are obtained

whereby the presence of mechanical mixtures- [,,]] ₀ ^ol _c = 1.61 dl / g.
gene of the two homopolymers is excluded.

Application example 23

According to the procedure described in the examples of the registration documents, 63 mmol per

Application example 24

6.3 mmoles of PS were combined with 0.0315 mmoles of the catalyst J polymerizes. After 1 hour at room temperature

15 16

temperature was obtained 4.6 g of a polymer with a value

for [-,] JS'c = 3.38 dl / g. Application example 26

The reactor was filled with 50 cm ^{3 of} TH

Application example 25 ^H ^ ι ⁴⁵ _x ^mM °! ^E S (ethylene sulfide). 551

5 and 0.023 mmol of the catalyst J bescl

63 mmol of PS were obtained with 0.0315 mmol of the catalyst for 2 hours at room temperature

sators K. polymerized. After 1 hour with spatial yields of 55 mol% ES un

temperature was obtained 4.6 e of a polymer with PS formed copolymer with a

a value for [,,] ™ _c = 3.83 dl / g. '[»,] Gi ^ = 3.18 <ll / g.

Claims (3)

Patent claims: 1 - polymerization catalyst, characterized that by reacting a metal from groups 1Λ, Ι1Λ and ΙΙΙΛ des Periodic Table of the Elements or its hydride, alkyl or amido derivatives with compounds the formula R - [X- (R ¹ LL- Y -R " wherein X and Y, which can be the same or different, are SO or SO ₂ groups; R and R "are methyl, alkyl groups with 2 to 10 carbon atoms, cycloalkyl, aryl, arylalkyl, alkylcycloalkyl groups or divalent radicals which can react with one another to form a ring; R 'is a divalent arylene, cycloalkylene, alkylarylene , Alkylcycloalkylene radical or a Melhylei? Ketle with a CoMensloffutom number from 0 to 20; in is chosen between 0 and I and η is an integer which can be i, 2 or 3, in a ratio between 10 and 0.3 in Presence of aliphatic or aromatic hydrocarbons, tetrahydrofuran, dioxane, hexamethylphosphoramide or liquid ammonia as a solvent at a temperature between -80 C and + SO C. 2. Process for the preparation of the polymerization catalyst according to claim I, characterized marked, dal.i a metal of groups IA, MA and INA of the periodic table or his Hydride, alkyl or amido derivatives with compounds of the formula R - [X - (R ') J "-Y-R" wherein X and Y, which can be the same or different, are SO or SO ₂ groups; R and R "are methyl, alkyl groups containing 2 to 10 carbon atoms, cycloalkyl, aryl, arylalkyl, alkylcycloalkyl groups or divalent radicals which can react with one another to form a ring; R 'is a divalent arylene, cycloalkylene, Alkylarylene, alkylcycloalkylene radical or a methylene chain with a carbon number of 0 to 20; m is chosen between 0 and I and η is an integer which can be I, 2 or 3, in a ratio between 10 and 0.3 in aliphatic or aromatic hydrocarbons, tetrahydrofuran, dioxane, hexamethylphosphoramide or liquid ammonia as a solvent, at a temperature between -80 'C and ¹ + 80C. 3. Use of the polymerization catalyst according to claim I for homo- or copolymerization of episulfides. In Dutch laid-open specifications 430 and 68 17932 and in US patent specification 17,489 describes the polymerization of episulphides. It is necessary in all cases to use reactive solutions or suspensions of different to use reactive components as polymerization aids. Such polymerization aids come as such for example solutions of diethyl magnesium in diethyl ether with water and ammonia or resorcinol, Mixtures of DimelhyLsulfo.xide with aii- ί ionic initiators or mixtures of alkali metals with acetone in question. The use of such polymerization aids brings in comparison with the The possibility of using a prefabricated catalyst has several disadvantages. The most important K) part can be seen in the secondary rcaklions that run through the various constituents forming the polymerisation aids can take place. For example, this is how in the reaction of sodium with Dinic'hylsulfoxid mixtures of hydrocarbons and r> dimethyl silide; the need arises more comprehensively Cleaning work processes on the polymers obtained. It has now been found a polymerization catalyst for the homo- and copolymerization of Episulfidcn is suitable and before the Polymcrisalionsreaklion can be prepared whereby polymerizations of the anionic type are carried out and end products with high purity can be obtained, since no small reactions occur 2 ^r > different components of polymerization aids have to be accepted. The invention therefore relates to a polymerization catalyst which is characterized by conversion of a metal of the groups ίο IA, HA and III Λ of the Periodic Table of the Elements or its hydride, alkyl or amido derivatives with compounds of the formula