PARWEZ and FEDTKE: Formation of oligomers by free radical polymerization of 2,3-epoxy propyl allyl ether (allyl glycidyl ether)

Acta Polymerica 36 (1985) Nr. 7

397

0,6 1 46 08 1,O 1.2 t 4 16 1.8 2,O

lgrII.4 P H C . 2. 3aBHCHMOCTb CKOPOCTH I I O J I H M e p H 3 a q H H 1 B BOHHOM ( I , 2 , 3 ) A MeTaHOJIbHOM ( 4 , 5 , 6) p a C T B O p e OT K O H q e H T p a q H H H H H q H a T o p a IICA ( 1 , 2, 3, 4 , 5) AAEC ( 6 ) : 1 - [MI = 0,2 MOJIb/JI; 2 - [Mi = 1,o MOJIb/JI; 3 - [MI = 3,O MOJIb/JI; 4 - [MI = 0,5 MOJIb/JI; .i - [MI = 2,0 MOJIb/JI; 6 -

[MI = 2,0 MOJIb/JI

P H C . 3. 3aBHCHMOCTb CKOPOCTH I I O J l H M e p H 3 a q H H I OT KOH- q e H T p a q P r H M O H O M e p a B BOAHbIX ( I ) H M e T a H O n b H b I X (2)

p a C T B O p a X : [ITCA] = 5 . MOJIblJI , 60°C

Summary

Radical polymerization of a new monomer - N,N-diallyl-N- methyl-N-carbisopropyloxymethylammonium chloride - in water and methanol solutions was investigated a t 35 to 6OOC. Polymerization had the order 0.5 with respect to initiator con- centration in the interval 5 . to 5 - lo4 mol/l (PSA, AIBN). The rate of polymerization increases sharply and non-linearly with initial concentration of the monomer. There is no degra- dation transfer to the monomer reaction under the choosen conditions in the investigated systems.

Jumepamypa [I] E A B A E B , H. A , : ~ 6 . 11 Bcecolo3~ol K O H @ e p e H q H H MOJIO-

A H X YYeHbIX IIO @H3HYeCKO8 XHMHH, M O C K B a , (10-14 O K T R ~ ~ H 1983) 6.

Acta Polymerica 30 (1979) 113-115.

91 -95.

[2] JAEOER, W., WANDREY, CH., REINISCH, G., LINOW, K.-J.:

[3] BARTLETT, P. D., TATE, P. A.: J. Amer. Chem. SOC. 75 (1953)

H. A. B A 6 A E B t, A. m. MAPTHHEHKO, a. A. TOIIYHEB, B. A. K A 6 A H O B AH CCCP, UHCTHTYT H e @ T e x H M m e c K o r o C H H T ~ ~ ~

CH. WANDREY, M. HAHN, W. JAEOER und G. REINISCH Akademie der Wissenschaften der DDR, Institut fur Polymerenchemie ,,Eric11 Correns", DDR-1530 Teltow-Seehof

H M . A. B. T o n w e B a , 117912 rCn M O C K B a B-'Il/CCCP

IlocmynuJca B per9aqulo 13 Mapma 1.984

Formation of oligomers by free radical polymerization of 2,3-epoxy propyl allyl ether (allyl glycidyl ether)

1. Introduction

Though the modifications of epoxy resins, specially of bis- phenol A type and of cycloaliphatic and nitrogen containing compounds, are of great importance in fundamental research work as well as for the industrial use, it is interesting, too, to synthesize and study polymers with epoxy groups. Due to the presence of epoxy groups such polymers can be used for further chemical reactions, e.g., modification reaction or net-work formation. The modified products often have better high-

temperature and chemical stabilities. These products can also be applied as diluting agents in the epoxy resin proces- sing.

I t is a well known fact that the radical polymerization of allyl compounds is difficult, as the formed allyl radicals during the reaction are not active enough to continue the chaingrowth. They undergo preferably the termination reaction [l]. This paper describes the synthesis and mechanism of formation of 2,3-epoxy propyl allyl ether (allyl glycidyl ether) by free radical polymerization in bulk.

Acta Polymerica 36 (1985) Nr. 7

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1 2 3

PARWEZ and FEDTKE: Formation of oligomers by free radical polymerization of 2,3-epoxy propyl allyl ether (allyl glycidyl ether)

CH,= 4.96 negligible =CH- 4.08 negligible -CHZ-O-CHS- 3.10 quite large

3.09

2. Experimental

10 g of monomer and 0.013 g (0.1 mole-% of total monomer) of initiator, di-tert.-butyl peroxide, were put in a glass ampule and the ampule was attached to a vacuum line. The oxygen present in the system was removed through a freeze-defreeze- cycle. The polymerization was carried out a t 413 K, maintained by an oil bath.

The product was isolated after destilling over the rest mono- mer under reduced pressure. The number average molecular weight was determined with the help of a “302 B vapour pres- sure osmometer Hewlett-Packard” a t 316 K in toluene. The epoxy number of monomer and oligomers was evaluated with the help of titration method with bromic acid and glacial acetic acid mixture [2]. For the studies of IR- and 13C-NMR spec- troscopy “IR-Specord 71 Carl-Zeiss Jena” and “NMR-Spectro- meter HX 90-R Brauer”, respectively, were used.

3. Results and discussion

The bulk polymerization of 2,3-epoxy propyl allyl ether (allyl glycidyl ether) with different initiators was carried out in order to obtain polymers or prepolymers of low molecular weight and containing reactive glycidyl groups. 2,2‘-Azobisiso- butyronitrile, dibenzoyl peroxide and di-tert.-butyl peroxide were used as radical supplying compounds. In the case of the first two initiators no product was formed after 8 h of reaction a t 363 and 413 K, respectively. In opposition to this a monomer conversion of 16% was obtained, if di-tert.-butyl peroxide was used as an initiator for the polymerization.

The product obtained was a viscous liquid of amber colour. The number average molecular weight determined by vapour pressure osmosis was 464 g - mol-l. It was found that 16% of the theoretical value of the epoxy content were consumed during the polymerization reaction. The reasons for the decrease of epoxy content might he assumed as follows: 1) a radical attack on the epoxy group a t high temperatures [3, 41; 2) an intermolecular reaction of epoxy groups during the polymeri- zation as it has been described by BEDNAR et al. [5].

In the second part of this work attempts were made to eluci- date the mechanism of formation of oligomers. MUSTAFAEV et. al. [6] studied this system and proposed the following struc- ture of the oligomers formed by the reaction:

CH2=CH-CH-O-CHz-CH-CHz

I ‘0’ CH,=CH - C -0 -CH,-CH-CH,

I ‘o/ CHz=CH-C-O-CH2-CH-CH,

\O’

According t o this mechanism the formed monomer radical splits off a hydrogen atom from the next following monomer molecule, whereas the carbon-carbon double bond remains conserved. Our IR- and W-NMR spectroscopic results did not verify this mechanism. In the IR-spectrum of oligomers the typical band for carbon-carbon double bond a t 1650 cm-’ was not present and in contrast to this the bands for epoxy groups a t 845 and 910 cm-l were clearly visible. In 13C-NMR spectrum no signal for a quarternary carbon atom was observed. The signals for carbon-carbon double bond were present in a negli- gible concentration (Table 1).

The results obtained by our studies indicate that the poly- merization takes place preferably via the carbon-carbon double bond and suggest the following mechanism:

Initiator decomposition

(CH,), - C - 0 - 0 - C - (CH,), % 2 (CH,), -CO‘ (1)

Table 1. Data obtained from 13C-NMR spectrum

1 2 3 4 L-

CHz=CH- CH2-O -CH2- CH-CH2 \,/‘

Ally1 glycidyl ether

6 estimaed I ppm I quantity No. I Group

quite large -CH-CH,

Start reaction

(CH,),-CO‘ + CH,=CH--CH,-O-CH,-CH-CH,

\O/

+ (CH,),-C-OH + CHz=CH-CH-O-CHz-CH----- CH,

\O/

+ CH, - CH = CH -0 -CH,-- CH-CH, (2) ‘O/

‘0’

Propagation reaction

CH,=CH-CH-O-CH2-CH-CHz

c+ CHz=CH-CH-0- CH,-CH-CH,

I \O’ CH2-CH-CHz-O-CHz-CH-CH2

I \(f’

CH,-CH-CH,-O-CH,-CH-CH,

‘0’

(3)

The termination reaction occurs specially through degradative chain transfer.

From the results obtained i t can be concluded that allyl glycidyl ether is not a suitable bifunctional monomer for the synthesis of polymers containing reactive glycidyl groups, since by the radical polymerization a t the highest tetramers can be obtained in a low yield.

References

[l] LAIBLE, R. C.: Chem. Rev. 58 (1958) 807. [2] BUDIAK, N. F., ZILBERSTEIN, F. S., and OOIENKO, R. A.:

r31 GRITTER, R. J.: J. Ore. Chem. 26 (1961) 282. Plast. Massy 5 (1950) 259.

- 1

[4] HAUPTSCHEIN, M., ana LESSER, J.‘M.: J. Amer. Chem. SOC. 78 (1956) 676.

[5] BEDNAR; B., MRKVICKOV~, L., JANCA, J., DUSEE, K., and K ~ L A L , J.: Scientific papers of the Prague Institute of chemical Technology 53 (1980) 241.

[6] MUSTAFAEV, R. I., MAMEDOV, R. I., SAIDE-SADE, S. I., and AYOBOV, G. M.: Plast. Massy 6 (1973) 18.

M. Q. PARWEZ and M. FEDTKE Technical University ,,Carl-Schorlemmer“ Leuna-Merseburg, Otto-Nuschke-Str., DDR-4200 Mersehurg

Received December 11, 1984