The Effect of the Side Group upon the Properties of the Poly(epoxides)

The work described in this series of papers forms part of an investigation o/ polyethers of general formula [C~-IR--CH~--O]n, which was initiated in the Chemistry Department of the University of Manchester by Professor G. Gee. Early work, principally that of D. J. Marks, showed that polymers with R=H, CH3, CH:CH 2 or n-CaoHzl had similar melting points ca. 70 to 80C and glass transition temperatures ca. -70C. Here we report detailed investigations of the properties of two poly(epoxides) with much larger side groups, namely poly(t-butyl ethylene oxide) and poly(styrene oxide). We also report some useful properties of other poly(epoxides) which were not measured earlier.

I--The Preparation and Characterization of Poly(t-butyl ethylene oxide) and Poly(styrene oxide)
G. ALLEN, C. BOOTH and S. J. HORST*
In this paper the preparation and characterization of polymers of t-butyl ethylene oxide and styrene oxide are described. Mixtures of water and zinc diethyl, having ~t~ole ratios approaching unity, were used as catalysts, and dioxan was used as solvent. The poly(t-butyl ethylene oxide) was highly crystalline and had narrow distributions of both molecular weights and degrees of stereoregularity. The poly(styrene oxide) was slightly crystalline, had a wide molecular weight distribution, and contained molecules of widely different degrees of stereoregularity.

POLY(t-BUTYL E T H Y L E N E OXIDE) THE polymerization of t-butyl ethylene oxide (tBEO) was recently reported 1. Zinc diethyl and water (mole ratio 1 : 0"4) were used to initiate the polymerization and evidence was presented which showed that tBEO, in common with other alkyl substituted ethylene oxides, polymerized by a mechanism similar to that described for propylene oxideL Accordingly, in order to prepare high-molecular-weight crystalline poly(tBEO), we chose conditions similar to those which were used to produce corresponding samples of poly(propylene oxide)a, i.e. a mole ratio of zinc diethyl to water approaching unity.
PREPARATION

The polymerization was carried out at 60C in dioxan solution, by use of the high vacuum technique described earlier. The following concentrations of reagents were used: tBEO, 3.27 M; zinc diethyl, 0.28 M; water, 0.252 M. A slight precipitate was formed when the reagents were mixed; in the light of previous experience it was assumed that this would not seriously influence the course of polymerization2. Poly(tBEO) was precipitated during the reaction. Later it was found that poly(tBEO) was not completely soluble in dioxan at 80C.
*Present address: Stockport College for Further Education.

385

G. ALLEN, C. B O O T H a n d S. J. H U R S T

The reaction was terminated by dissolving the products in benzene at 80C and adding enough methanol to precipitate the catalyst. A hindered phenol antioxidant (1 wt % of polymer) was added and the products were dried under vacuum. Catalyst residues were removed before using the polymer. The results of the polymerization were as follows: conversion, 83 per cent in 310 h; intrinsic viscosity in toluene at 75C, 19"2 dl g-t; viscosity average molecular weight (estimated), 7 107. CHARACTERIZATION Viscometry Dilute solution viscosities were determined in toluene at 75C, by use of a Desreux-Bischoff viscometeP modified according to Kaufman and Solomon s. The maximum shear stress was 1-8 gcm -t see-2. The intrinsic viscosity/molecular weight relationship was not determined (though some fragmentary molecular weight data are presented in part II of this work).

Fractionation The poly(tBEO) separated from the reaction mixture was incompletely soluble at 25C in every solvent tried, including a representative selection of paraffins, aliphatic ethers, chlorinated hydrocarbons, aromatic hydrocarbons, ketones and alcohols. At 80C it was completely soluble in solvents which had solubility parameters in the range 8"6 to 9-5 (cal cm-3) ~ at 25C; e.g. toluene, benzene, carbon tetrachloride. Fractionation was achieved by dissolving the polymer in benzene at 80C (concentration 2 g/1.) and cooling the resulting solution. Precipitation of crystalline polymer occurred at a temperature just below 70C; such fractions were allowed to grow for a day or two before separating the precipitate by filtering the solution through a hot funnel packed with glass wool. Below 60C liquid phases precipitated, and these were separated in the usual way by allowing them to settle overnight and syphoning off the dilute phase. All fractions were dissolved in benzene and subsequently dried under vacuum for several days.
RESULTS

Typical fractionation data are given iD Table 1. The melting points (T,~) quoted for the fractions were obtained by methods discussed in ref. 10. Some degradation of the polymer occurred; the weight-average intrinsic
Table I. Fractionation of poly(t-butyl othylene oxide) from benzene Fraction No. Precipitation temperature C Nature of precipitate
['0] (dl g-l) T,n oC

Wt %

1
2 3 4 5 6 7

67'4
65"0 62- 5 49-9 40"5 24.3 Residue

Crystalline
Crystalline C,-ystalline Liquid Liquid Liquid --

28"4
11 "2 11.6 27.0 3"6 8-3 10-0

17"I
17"9 20" 3 17"0 12"5 10"3 6-1

149
149 149 150 -149 149

386

EFFECT OF SIDE GROUP UPON PROPERTIES OF POLY(EPOXIDES) I

viscosity of the fractions is some 18 per cent lower than the intrinsic viscosity of the original polymer. Nevertheless the reduction in [~/] is remarkably small when one considers the high temperatures used and the very high molecular weights involved, and it reflects the stability of poly(tBEO) towards oxidative degradation.
DISCUSSION

All the fractions have the same melting point: 149+ I deg. C. It can be assumed that fractional crystallization would separate species of differing stereoregularity~, and we conclude that our specimen of poly(tBEO) is highly stereoregular with a narrow distribution of sequence lengths among the individual chains. The molecular weight distribution is more difficult to define from the limited data to hand; only the few fractions obtained by liquid phase separation are pertinent. However, it is clear that the distribution is fairly narrow, e.g. if we assume that the exponent of the Mark-Houwink equation for toluene at 75C (a good solvent) is > 0 . 7 , then the ratio 2~rw/~rn calculated from the fractionation data is ~ 1.4. Taking into account the degradation which occurred before and during the fractionation, we conelude that the original reaction product had a narrow molecular weight distribution, possibly monodisperse, but certainly very much narrower than those of poly(styrene oxide) and poly(propylene oxide)~ produced under similar conditions. As far as we can tell, the course of the polymerization of tBEO seems to be parallel to that of propylene oxide1. Nevertheless the polymers produced are quite different: poly(propylene oxide) prepared with the same zinc diethyl/water catalyst (mole ratio of 1:0.9) would consist of many stereoisomers and have a wide molecular weight distribution2,3. Of the reactions proposed z to explain the polymerization of propylene oxide, it seems that two do not occur with tBEO, i.e. the propagation reaction which results in the occurrence of syndiotactic or perhaps head to head placements, and the transfer reaction with polymer which results in random scission of the chain and causes the wide molecular weight distribution. These conclusions are understandable in terms of the severe steric interactions which occur in the poly(tBEO) chain due to the large bulk of the, t-butyl substituent group. For example it is impossible to construct a model of the syndiotactic poly(tBEO) chain (or indeed a syndiotactic, did, triad) without distorting bond angles and bond lengths. Thus we also conclude that our product is a polymer with an extremely high probability of isotactic placements. Furthermore, the reduced rate of the propagation reaction is readily explained in terms of these severe steric restrictions1. The narrow molecular weight distribution, rationalized in terms of a drastic reduction in~ the rate of the chain transfer reaction with polymer, also could be a direct consequence of steric factors. However, the insolubility of poly(tBEO) in the solvent used provides a possible alternative mechanism for producing a narrow molecular weight distribution. 387

G. ALLEN, C. BOOTH and S. J. HURST

POLY(STYRENE OXIDE)
Several accounts of the polymerization of styrene oxide have appeared 1"6.7, including polymerization by the zinc diethyl-water catalyst system1,~. It is clear from earlier work 1 that no direct analogy can be drawn between the polymerizations of styrene oxide and those of the alkyl substituted ethylene oxides. Accordingly we have investigated, to a limited extent, the effect of changing the water to zinc diethyl mole ratio. Polymerizations have been carried out by use of 'dry' zinc diethyl, and by use of a mole ratio of water to zinc diethyl of 0"8: 1. Polymerizations at a mole ratio of 0"4:1 have been reported earlier 1. Attempts to carry ,out a dry reaction at 50C resulted in a very slow reaction; the rate decreased as the drying technique was improved, e.g. a conversion of 23 per cent was obtained in 956 hours with styrene oxide (0.84 M) and zinc diethyl (0.093 lvi) in toluene at 50C. A similar, though somewhat faster, reaction (67 per cent conversion in 1 100 h) gave poly(styrene oxide) with an intrinsic viscosity in toluene at 25C of 3"8 dl/g, and a number-average molecular weight of 9508. Reactions carried out with a mole ratio of 0.8:1 were extremely rapid at 60C. Eventually we followed the reaction by dilatometry at lower temperatures: e.g. a conversion of 63 per cent was obtained in 72 h with styrene oxide (1-.09 M), zinc diethyl (0.142 M) and water (0-113 M) in dioxan at 40C, Representative data for differing water concentrations are compared in Figure 1. No attempt has been made to formulate a reaction mechanism consistent with these curves because of the few results available. They merely illustrate that the kinetics of polymerization are very different from
Time, h 50 I

1oo

100

l
80
C O t~

2 3

~. 6o
C
u

8 ~4o
" 2c
0 500 Time, h

IuO0

Figure /--Polymerization of styrene oxide. Conversion versus time for: 1, 'dry' zinc diethyl in toluene at 50C; 2, mole ratio of water to zinc diethy! of 0"4 in dioxan at 60C; 3, mole ratio of water to zino diethyl of 0'8 in dioxan at 40C 388

E F F E C T O F SIDE G R O U P U P O N P R O P E R T I E S O F POLY(EPOXIDES) I

the kinetics of the propylene oxide system and so we have no useful guide to the best conditions for production of high-molecular-weight crystalline polymer.
PREPARATION

Styrene oxide was polymerized in dioxan at 60C under high vacuum, with the following reagent concentrations: styrene oxide, 4.31 M, zinc diethyl 0.143M, water 0.114M. A slight precipitate formed when the reagents were mixed. The reaction was terminated by dissolving the products in benzene and adding sufficient methanol to precipitate the catalyst. Insoluble residues were removed by centrifugation, a hindered phenol antioxidant (1 wt % of polymer) was added, and the polymer was recovered by freeze drying. The results of the polymerization were as follows: conversion, 91 per cent in 288 h; intrinsic viscosity in toluene at 25C, 1-94 dl/g; numberaverage molecular weight, 1 4508.
CHARACTERIZATION

Viscometry Dilute solution viscosities were measured in toluene at 25C by use of modified Desreux-Bischoff viscometers~. Maximum shear stress was 3.0 g cm -1 sec -2. Viscosity-average molecular weights were calculated by means of the relationship9
'[~7]= 6"79 10-sA~7e6

Fractionation The poly(styrene oxide) was very soluble at room temperature in such solvents as benzene, toluene, chloroform and carbon tetrachloride but largely insoluble in paraffins, acetone, methanol and methyl ethyl ketone. Fractionation was achieved by adding isooctane to a dilute solution of the polymer in benzene at 25C: isooctane was added until the solution became turbid, the temperature was raised until the precipitate dissolved, and the solution was then cooled slowly to 25C. Precipitates were separated by syphoning off the dilute phase through a glass wool plug. Early precipitates were crystalline solids, later ones were liquid gels. Fractions were recovered by dissolving in benzene and freeze drying. Maximum concentration of polymer during fractionation was 2 g 1-1.
RESULTS

Typical fractionation data are given in Table 2. Some degradation of the polymer occurred even at this low temperature and relatively low molecular weight; the weight-average intrinsic viscosity of the fractions is some 21 per cent lower than the intrinsic viscosity of the original polymer. The stability of poly(styrene oxide) is therefore much lower than that of poly(tBEO) towards oxidative degradation. No melting points are available for these fractions. However, subsequent work 1 showed that similar high molecular weight fractions had melting points in the range 150 to 160C, and that some separation into species of differing melting point occurred 389

G. ALLEN, C. BOOTH and S. J. HURST

Table 2. Fraetionation of poly(styrene oxide) from benzene--isooctane

mixtures at 25C

Fraction
No.

Nature of
precipitate Wt %

[~/]
(dl g - l )

T=
oC

1 2 3 4 5 6 7 8 9 10

Crystalline Crystalline Translucent liquid Liquid Liquid Liquid Liquid Liquid Liquid Residue

1"8 24.3 18.2 9"6 5"7 4"4 6'0 4"1 3"6 22.2

5"54 4"13 1"35 0"528 0"347 0"272 0"195 0"151 0"109 0"051

(162) (152) (150) ------

during the fractional crystallization. The data in Table 2 are the melting points of corresponding fractions taken from ref. 10.
DISCUSSION

Some separation of species differing in crystallizability takes place during the fractional crystallization. In contrast to the fractional crystallization of poly(propy!ene oxide)~,S the molecular weight varies between the fractions. This may reflect the fact that polymer of high molecular weight has a higher degree of structural regularity; or it may be due to a hybrid fractionation of the type discussed elsewhere n. The molecular weight distribution of the poly(styrene oxide) is very wide

~o/~

> 450

I f the effects of crystallization are neglected, all the data of Table 2 can be used to construct a molecular weight distribution in the conventional way. This distribution is shown in reduced form in Figure 2, where it is compared with similar curves calculated for high molecular weight

,00[

~801
_c _ 6,~_~

~
/ //, ,,

|///
If/

!40~/ / / ~// 2 o
2 3 Reduced molecular weight

cular weight distribution of poly(epoxides) prepared using a mole ratio of water to zinc diethyl approaching unity. Cumulative weight per cent versus reduced weight (-M. of fraction divided by Me of whole polymer) for: 1, poly(styrene oxide); 2, poly(propylene oxide); 3, po!y(t-butyl ethylene oxide)
I 1

Figure 2--Representative mole-

4 390

I,.

EFFECT OF SIDE GROUP UPON PROPERTIES OF POLY(EPOXIDES) II poly(propylene oxide) ~'3 and poly(tBEO) (Table 1). The distribution of molecular weights of poly(styrene oxide) is seen to be m u c h wider than that of poly(propylene oxide), which in turn is wider than that of poly(tBEO). Unfortunately use of these results to discuss the mechanism of polymerization of styrene oxide is precluded b y the fragmentary nature o f the data which are available. T h e primary aim of the work was to produce p o l y m e r fractions for studies of physical properties.

We acknowledge with thanks the practical assistance of Miss C. J. S. Guthrie and M r s J. /t. Hurst, and the helpful discussions with Dr J. M. Bruce. Department of Chemistry, University of Manchester (Received November 1966)

REFERENCES I BRUCE,J. M. and HURST, S. J. Polymer, Lend. 1966, 7, l 2 B o o ~ , C., HI~,m~soN, W. C. E. and POWELL,E. Polymer, Lend. 1964, 5, 479 s~ , G., BOOTH,C. and JONES, M. N. Polymer, Lend. 1964, 5, 257 DESREUX,V. and BISCHOFF,J. Bull. Soc. chim. Belg. 1950, 59, 93 KAUFM,L~q,H. S. and SOLOMON,E. lndustr. Engng Chem. (tndustr.) 1953, 45, 1779 e See, for example, C~LCLOUOH,R. O., Gr., G., HIGGINSON,W. C. E., JACKSON,J. B. and Lrrr, M. 1. Polym. Sci. 1959, 34, 171; VAr~rOENBERG, E. J. 1. Polym. Sci. 1960, 41, 486; KXMBAgA,S. and TAKAnASm,A. MakromoL Chem. 1963, 63, 89 See, for example, KEmq, R. J. Makromol. Chem. 1965, 81, 261 s Model 301A Vapour Pressure Osmometer, Mechrolab. Inc. 9 ~A~T~q, G., BOOTrL C., HURST, S. J., JONES, M. N. and PRICE, C. Polymer, Lend. 1967, $, 391 IOALL~, G., BOOTH, C., HUgST, S. J., PRICE, C., VERNON, F. and WARREN, R. F. Polymer, Lend. 1967, g, 406 u BOOTh, C. and PRICE,C. Polymer, Lend. !966, 7, 167

II--Intrinsic Viscosity and Light Scattering Measurements on Poly(ethylene oxide), Poly(styrene oxide) and Poly(t-butyl ethylene oxide)
G. ALLEN, C. BOOTH, S. J. HURST*, M. N. JONES and C. PRICE

Intrinsic viscosity and light scattering data are reported for fractions of the poly(styrene oxide) and for fractions of a commercial sample of poly(ethylene oxide). A few results obtained for fractions of the poly(t-butyl ethylene oxide) are also included. The following intrinsic viscosity/molecular weight relationships are obtained: poly(ethylene oxide) [,/] (benzene at 25 C) = 3"97 10-4 M ~'686
poly(styrene oxide) [7] (toluene at 25 C)= 6-79 10-s M ' 766 v 391
*Present a d d r e s s : John Dalton ColIeRe of Technology, Manchester 1.