Colloids and Surfaces, 17 (1986) Elsevier Science Publishers B.V.

67-78 Amsterdam

Printed

in The Netherlands

67

THE PREPARATION IN NON-AQUEOUS

OF POLY(METHYL MEDIA*

METHACRYLATE)

LATICES

L. ANTL**, J.W. GOODWIN, R.D. SM. OWENS? and S. PAPWORTH School J.A. of Chemistry, University

HILL,

R.H.

OTTEWILL***, BS8 ITS (United Kingdom)

ofBristol,

Bristol

WATERS Chemical 4 April Industries 1985; PLC, Paints Division, in final form Slough SLZ 5DS (United Kingdom)

Imperial (Received

accepted

12 June

1985)

ABSTRACT A single-stage method is described for preparing monodisperse poly(methy1 methacrylate) latices stabilised by poly( 12-hydroxy-stearic acid) in hydrocarbon media. By variation of solvency conditions, it was possible to obtain a variation in particle size. At high monomer concentrations, a range of particle diameters between 178 nm and 2.6 pm was obtained with a small coefficient of variation on the number average size. At low monomer concentrations, stable latices were obtained with diameters of -80 nm. Some suggestions are made for the mechanism of particle formation and growth in non-aqueous latices.

INTRODUCTION

Over the last two decades knowledge of the behaviour of colloidal dispersions has advanced rapidly, particularly in aqueous dispersions, due to the synthesis of monodisperse polymer particles and their ready availability as latices for use as model colloidal dispersions [l-3]. Nowhere near as much attention has been given to dispersions in media of low relative permittivity, although during the same time period there has been a steady growth in work on non-aqueous polymer colloids. One of the first attempts to prepare a non-aqueous polymer latex was that by Osmond and Thompson [4] using methyl methacrylate (MM) as the monomer in a hydrocarbon solution of degraded rubber with benzoyl peroxide as the initiator; in this preparation an amphipathic graft copolymer was formed in situ. This approach led to a rapid growth of the technology for preparing latices by various techniques with lipophilic layers and their utilisation in industry. This is well described
*Dedicated to the memory of M.W. Thompson. **Present address: Barvy and Laky, Prague, Czechoslovakia. ***To whom correspondence should be addressed. *Present address: Dulux Australia Limited, Clayton, Victoria,

Australia.

0166-6622/86/$03.50

0 1986

Elsevier

Science

Publishers

B.V.

68

in the book by Barrett [5] to which a notable contribution was made by Morice Thompson [6]. Since the stability of these latices was based on steric stabilisation, knowledge in this area has also grown rapidly [ 71. Although a number of papers for the preparation of polymer colloids in non-aqueous media have appeared [ 8-121 the straightforward preparation of such systems has not been well covered. However, in an earlier paper we described the preparation of poly(methy1 methacrylate) (PMM) latices by a seeded-growth method [9]. This type of latex has been used for studies of particle-particle interactions [7, 9, 131, small-angle neutron scattering [14], diffusion studies in concentrated dispersions by quasi-elastic scattering [ 1416] and rheology [12,17]. The advantages of latices of PMM with a covalently surface-linked stabiliser moiety of poly(12-hydroxy-stearic acid) (PHS) for fundamental studies have been demonstrated by this work. Consequently, it has become clear that straightforward single-stage polymerisation methods for preparing latices in non-aqueous media were needed. In this contribution we describe methods for the preparation of monodisperse PMM latices, in a range of sizes from 178 nm to 2.60 pm, in hydrocarbon media.
EXPERIMENTAL

Materials

Hexane (aromatic free), dodecane and 40/60 petroleum ether were BDH materials. A high boiling hydrocarbon fraction (HBPH), which was low in aromatics (-l%), and boiled in the range 230-250C was obtained from Carless, Cape1 and Leonard. Octyl mercaptan (Honeywill and Stain) and diethanolamine (Shell Chemicals) were both technical grade materials obtained via ICI PLC. Azo-bis-isobutyronitrile (ADIB) was obtained from BDH Ltd. It was recrystallised at a low temperature from acetone before use. Methyl methacrylate and methacrylic acid (MA) were obtained from ICI PLC. Before use each monomer was distilled under nitrogen at a low pressure at 40C and condensed in a container surrounded by solid carbon dioxide and methanol. 12-Hydroxy-stearic acid (HS) was obtained from Prices Ltd. Glycidyl methacrylate was obtained via ICI PLC. It was found essential to use this material in a fresh state.
Preparation of the stabiliser acid)

I. Poly(l2-hydroxy-stearic

12-Hydroxy-stearic acid (47.9 g), 8.52 g toluene and 0.1 g methane sulphonic acid (catalyst) were refluxed (<150 ) for about 2 days. The water produced by the condensation reaction was removed by azeotropic distilla-

69

tion. The reaction was continued until the acid value determined by titration with alcoholic potassium hydroxide (using phenolphthalein as the indicator) was 32.2 mg KOH per g polymer. End-group analysis gave a molecular weight of 1740. Examination by gel permeation chromatography gave the ratio M&M, as 2.14; the latter value was based on a calibration using polystyrene fractions.
II. Poly(l2-hydroxy-stearic acid) macromonomer

To the toluene solution of PHS (reaction I) was added 2.13 g paraffinic hydrocarbon (SBPG) - an 83% aliphatic material supplied by Esso Petroleum Company Ltd - 5.16 g glycidyl methacrylate, 0.19 g Armeen DMCD - a fatty secondary amine supplied by Armour Hess Chemicals - and 0.05 g tbutyl catechol. The latter material acted as a free-radical inhibitor and the amine as a ring-opening catalyst. The mixture was maintained under reflux conditions until an acid value of 0.3 mg KOH per g polymer was obtained. A further 35.9 g SBP6 was added to the warm mixture in order to maintain fluidity on cooling. At this stage the solution then contained 50.5% solids as the PHS-glycidyl methacrylate adduct (Fig. 1). This will simply be termed PHSA.
CH200C-iPHS) &OH IH~o-CO-C=Cti2 ;H3

Fig. 1. Glycerol l-poly( 12-hydroxyoctadecanoate)-3-methacrylate. methacrylate adduct (PHSA).

The PHS-glycidyl

III. The %omb stabiliser

The stabiliser was prepared by forming a graft copolymer of PHSA with MM. A 49.15 g aliquot of a 50.5% solution of PHSA in SBP6 from stage II was added to 22.4 g MM, 2.49 g glycidyl methacrylate and 0.375 g ADIB. This mixture was metered continuously over a period of approximately 3h into a refluxing mixture comprised of 17.1 g ethyl acetate and 8.5 g butyl acetate. Reflux conditions were maintained for a further 6 h during which time two small additions of ADIB, 0.17 g each, were made at intervals of 2 h. Conversion of monomer to polymer was >95%. The final mixture was diluted with further ethyl acetate/butyl acetate mixture until the system contained 40% of the stabiliser (solution C). The weight average and number average molecular weights of the stabiliser were 65,800 and 14,600, respectively, as determined by gel permeation calibration. chromatography, giving M, IM, = 4.50, based on a polystyrene

70

Preparation Method 1

0 f la tices

The preparation of PMM latices, stabilised latex has been described previously [9] .
Method 2

by PHSA, by growth of a seed

In the present work, latices were prepared by a single-stage process in closed systems. In this method, which was used to screen a large number of preparations for particle size, a 150-cm3 Ehrlenmeyer flask closed with a B14 stopper, was used. The ADIB, monomer and stabiliser as solution C were weighed into the flask. The hydrocarbon medium (hexane/HBPH in the ratio 0.675) and octyl mercaptan were then also weighed into the flask. It was found important to leave room in the flask for refluxing to occur and, in general, the volume of material added did not exceed 50 cm3. The lightly stoppered flask was submerged in a water bath at 80C for a period of 2 h; these systems were not stirred. The monomer used was composed of 98 parts of MM and 2 parts of MA by weight.
Method 3

For larger scale preparations using a charge of 750 g, in which intermediate sampling could also be undertaken, an apparatus was used which was virtually identical to that described by Cairns et al. [9] . However, the stirrer was driven by a direct drive and an anchor-type stirrer was used. A solvent composition of hexane/HBPH in the ratio 2:l was also used. The system was continuously flushed with nitrogen. Samples were withdrawn by applying pressure to a side tube. After 2 h, the steam bath was switched off and the flask contents were cooled to room temperature under nitrogen. The percentage conversion was determined by drying samples to constant weight in a vacuum oven.
Locking stage

In all cases where the latices were to be used for further experiments, the stabiliser was covalently linked to the particle surface by a further reaction. This was carried out in the following manner: The condenser was changed to the horizontal position and the hexane removed by distillation in a nitrogen stream. A volume of HBPH equal to that of the hexane removed was added and the condenser returned to the reflux position. The steam bath was also replaced by an oil bath and the temperature in the flask, as measured by a thermometer with the bulb in the liquid, was raised to 120C. An amount of diethanolamine equal to 0.2% of the total weight of the system, was then added and the system allowed to reflux at 120 C. After -15 min of refluxing, a sample of approximately 5 g was removed.

71

After weighing, the sample was diluted to a known volume with a mixture of 3 parts of toluene and 1 part of methanol. The resultant solution was then titrated with alcoholic potassium hydroxide (0.02 mol dmm3), using phenolphthalein as the indicator. The titrations were carried out in a stirred system (magnetic stirrer) under nitrogen. The alcoholic potassium hydroxide was standardised using oxalic acid and the same indicator. The acid values were determined by this method at 30-min intervals until no further change in the value occurred. It was assumed at this stage that the reaction between the stabiliser epoxide groups and the -COOH groups on the latex was complete. After completion of the locking process the latex was filtered through glass-wool to remove any coagula which had formed during the preparation. It was found that the concentration of monomer left in solution at this stage was very low and that essentially 100% conversion of monomer to polymer had occurred. Procedure for cleaning the latices

After the locking procedure, the latices contained excess stabiliser in the solution phase. Therefore, it was necessary to remove the excess stabiliser and transfer the particles to a homogeneous dispersion medium. In order to separate the particles from the dispersion medium, centrifugation was used at 25C. For latices containing small particles (< 1 pm) centrifugation was carried out at 7000 rpm and for those containing larger particles (>l pm) at -2000 rpm for 1 h. After centrifugation the supernatant was removed and replaced by 40/60 petroleum ether; the particles were then resuspended and centrifuged. Infrared measurements at 1720 cm- were used to check the supernatants for the presence of > C = 0 groups. Experience showed that eight washings with petroleum ether were adequate for the larger particles and 10 for the smaller ones. In the case of large particles (>l pm), some new nucleation was observed after raising the temperature to 120C for locking purposes. The small particles formed (- 50 nm) were easily removed by several decantations of the five-times diluted dispersion in 40/60 petroleum ether. In general, the latices were used as dispersions in dodecane. Solvent replacement was achieved by centrifugation, removal of the supernatant and replacement of the latter with new solvent. For larger particle size dispersions, with concentrations in excess of 50%, it was found useful to maintain them in slow rotation during storage in order to prevent the formation of a cohesive sediment. Determination of latex concentration

This was obtained from density measurements using a pycknometer with a volume of -10 cm3. An independent determination of the weight of polymer present (dry weight) also enabled the density of the polymer to be ob-

72

tained. Samples were dried between 125 and 130C in a vacuum of at least 0.1 torr using small glass boats. It was found that, at 130C the sample retained its white opacity, whereas at 135C it became translucent. With a good vacuum at 13OC, 12 h was found to be adequate to ensure dry samples. Determination of particle size

The size of the PMM core of the latex particles was determined by electron microscopy. For small particles (diameter < 0.5 pm) carbon replicas of the particles were prepared. 1,4-Dioxan was used as a solvent to dissolve the particles away from the carbon film. Larger particles were diluted with dodecane to a concentration of -lo9 per cm3 and deposited directly on to either carbon-coated or formvar-coated grids. A carbon replica of a diffraction grating was used to obtain the magnification of the electron microscope (an Hitachi HU 11B). A Zeiss TGZ 3 particle size analyser was used to measure -200 particles in order to obtain a particle size distribution and hence the number average particle size diameter.
RESULTS

Monomer

concentration

range 35-5072

Over this monomer concentration range successful preparations were carried out using the formulations listed in Table 1. In all the preparations the amount of stabiliser used was kept at a constant value of 5% by weight of
TABLE 1

Details of latex preparationsa Latex designation Monomer (wt%) Octyl mercaptan (wt%) s4 s7 S24 SPSOB S25 S18 LAS2134 SPSOl s19 LAS1129 s20 RS9/14 aADIB 5.0 5.0 35.0 35.0 37.5 40.0 42.0 42.5 45.0 46.5 47.5 50.0 in all preparations 0.025 0.025 0.175 0.175 0.188 0.200 0.210 0.210 0.225 0.233 0.238 0.250 0.39% by weight. High boiling hydrocarbon (wt%) 31.4 31.4 20.1 19.5 18.6 17.7 17.0 17.0 15.9 15.3 14.9 14.3 63.3 63.3 40.5 40.6 38.6 36.7 35.2 35.2 32.9 31.8 31.0 29.8 0.25 0.25 1.75 1.75 1.88 2.00 2.10 2.08 2.25 2.33 2.38 2.50 Hexane (wt%) Stabiliser (wt%)

73

the amount of monomer used. Preparations were carried out using both stirred (method 3) and unstirred (method 2) conditions and the results obtained are plotted in Fig. 2 as particle diameter against monomer concentration by weight in the mixture. As can be seen from the data presented stirring appeared to have no significant influence on the final diameters formed, at least in the small reaction volumes used. The particle diameters obtained varied from 173 nm using 35% monomer to 2.6 pm using 50% monomer. As shown in Table 2 the coefficient of variation on the number average particle diameter varied from 10.3 to 3.9%, i.e. monodisperse preparations were obtained.

Monomer

Concentration

w/w

Fig. 2. Particle size against monomer concentration Non-stirred preparations; (o), stirred preparations.

for systems

listed

in Table

1. (o),

Monomer

concentration

range 8.5-34%

Using the same methods as described in the above paragraph it was found that in the monomer concentration range 8.5-34% coagulation, or flocculation, of the latex occurred if the preparation was allowed to proceed for the full period of 2 h. In some cases the particles formed were redispersible on agitation, i.e. flocculation had occurred, whereas in other cases, the particles were not redispersible, i.e. coagulation had occurred. An investigation was therefore made of the time interval between the start of the reaction and the

74 TABLE Diameters Latex designation s4 s7 S24 SPSOB SPSO4 S25 S18 SPSOl LAS2134 SPSO5 s19 LAS1129 s20 RS9/14 aMethod 2 of particles in latex preparations Coefficient of variation (%) 10.3 7.7 8.6 7.4 6.9 5.4 4.9 3.9 Methoda

Number diameter 85 75 178 176 188 222 350 391 403 429 750 939 1200 2586 2 = not stirred;

average (nm)

2 2 2 2 3 2 2 2 3 3 2 3 2 3

method

3 = stirred.

moment that aggregation became visibly apparent. The results so obtained are shown in Fig. 3. The region in which flocculation occurred most rapidly was found to be at a monomer weight, of 24 + 2%. Hence, with the conditions used it was not possible to obtain monodisperse stable latices.

60 -

I I

I
Fig. 3. Time region.

I
I

I
L

IO
Monomer to visible aggregation against

20

I
30 wwx I

Concentration monomer

concentration

showing

the unstable

75

Monomer

concentration

below 8.5%

Reactions carried out with monomer concentrations below 8.5% but maintaining the stabilizer concentration at 5% of the monomer led to stable latex preparations even if the reaction times were extended beyond 2 h. The conditions used (Table 1) gave final particle diameters of 75 and 85 nm.

Variation

of stabiliser

concentration

at constant

monomer

concentration

In view of the successful preparation of very monodisperse 2.6 pm diameter particles at a monomer concentration of 50%, with the presence of stabiliser at 5% based on monomer, some experiments were carried out in which the stabiliser concentration was changed from 5 to 20% of the weight of monomer. The results obtained are shown in Table 3. As can be seen, increasing the concentration of stabiliser had an adverse effect and the latices prepared became more polydisperse. The results also indicated that the choice of 5% was a very favourable one and provided very suitable conditions for the nucleation and growth of monodisperse particles.
TABLE Variation Latex designation RS9/14 Sll s12 s13 s14 3 of stabiliser concentration Number average diameter (wm) 2.59 2.80 2.77 0.5-10 0.2-8.5 Comments

Stabiliser as % of monomer 5.0 7.5 10.0 15.0 20.0

pm Mm

monodisperse fairly monodisperse fairly monodisperse very polydisperse very polydisperse

DISCUSSION

In the present work the preparation of PMM latices stabilised by an outer layer of covalently linked PHS has been explored using concentrations of monomer between 5 and 50%, with a stabiliser concentration of 5% by weight of the monomer. Octyl mercaptan was added as a chain-transfer agent at a concentration of 0.5% of monomer. The results obtained are summarised in Fig. 4 and, as can be seen, fall into three distinct regions. In the lower monomer concentration range, up to 8.5%, small stable particles were formed with a diameter of -80 nm. These particles were difficult to size by electron microscopy but were reasonably monodisperse. In the monomer concentration range from 8.5 to 34% difficulties were experienced in that coagulation or flocculation occurred before the reaction had gone to completion.

16 3c

Stable

2c E 2 a, N (I, aJ 0 .L LT

1c

20 Monomer Fig. 4. Particle size against regions of latex preparation.

40 Concentration concentration w/w %

60

monomer

showing

the

stable

and unstable

In the monomer range 35 to 50% very successful preparations were achieved. It proved possible to prepare monodisperse PMM latices in a hydrocarbon medium by a single-stage process and to vary the particle size from 178 nm to 2.6 pm. Electron micrographs of latices LAS2/34 and LAS2/29 are shown in Fig. 5 and demonstrate the good monodispersity of these systems. In the high monomer concentration range the mechanism of particle formation appears to be that suggested by Barrett and Thomas [18]. The high concentration of polar monomer initially present provides a good solvent for PMM. However, as the monomer is consumed the solvency decreases and reaches a stage where PMM becomes insoluble. Consequently, PMM particles are nucleated. Since there is stabiliser present in the solution phase with a PMM backbone, the latter is also in a medium of decreasing solvency and adsorbs on to the particles. The period of nucleation and formation of stable colloidal particles is probably comparatively short, leading to

Fig. 5. Electron LAS2129.

micrographs

of poly(methy1

methacrylate)

latices:

(a),

LAS2/34;

(b),

a constant number of particles (see previously, Ref. [19] ) which can then adsorb monomer by diffusion and grow over a longer time period to produce a monodisperse system. The mechanism of stabilisation in this system is undoubtedly due to steric interactions arising from the presence of the PHS chains [5, 9, 13, 201, At 35% monomer the final particle diameter was found to be 178 nm indicating that 1.2 X lOj particles crnm3 were formed with a surface area of 1.2 X 107cm2, whereas at 50% monomer 5.4 X 1012 particles cm-3 were formed with a surface area of 1.2 X lo6 cm. This would suggest that at the higher monomer concentration the particles grow to a larger size before adsorption of the polymer comb with its consequential colloidal particle stabilisation. It appears reasonable to conclude that in the high monomer concentrations (35-5076) the particle size is closely related to the solvency of the medium. However, it is not clear why increasing the stabilizer concentration at 50% monomer leads to an increase in polydispersity. One possibility is that the presence of butyl acetate in the stabilizer solution may have been a complicating factor since the increase in amount of solution would have increased the overall solvency of the medium and hence affected the precipitation of PMM. The mechanisms operating at low and intermediate monomer concentrations are also not completely clear. Below 8.5% monomer stable colloidal particles were obtained. The solvency in this region is poor for PMM and it seems possible that nucleation may have occurred before the polymer chains were complete leading to micellization of oligomers and the stabilizer. This would lead to high particle numbers and small particles. It is also pos-

78

sible that some micellization of the stabilizer itself occurred in the presence of the monomer and this is now being investigated [21]. This in itself could lead to a different mechanism of initiation at low monomer concentration. Hence, in the central region, there is the likelihood of nucleation and growth mechanisms both competing for stabiliser with consequent formation of unstable systems.
ACKNOWLEDGEMENTS

We wish to express our appreciation to SERC and ICI PLC, Paints Division for support of this work. We are also very grateful to Mr D.W.J. Osmond and Mr D.J. Waldbridge for many stimulating and helpful discussions.

REFERENCES 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 R.M. Fitch (Ed.), Polymer Colloids, Vol. I, Plenum Press, New York, NY, 1971. R.M. Fitch (Ed.), Polymer Colloids, Vol. II, Plenum Press, New York, NY, 1980. G.W. Poehlein, R.H. Ottewill and J.W. Goodwin (Eds), Science and Technology of Polymer Colloids, Vols I and II, Nijhoff, The Hague, 1983. D.W.J. Osmond and H.H. Thompson, British Patent 893,429. K.E.J. Barrett (Ed.), Dispersion Polymerization in Organic Media, Wiley, London, 1975. M.W. Thompson, ibid., Chapter 7, Applications of Polymer Dispersions Prepared in Organic Media. D.H. Napper, Polymeric Stabilisation of Colloidal Dispersions, Academic Press, London, 1983. R.M. Fitch and Y.K. Kamath, J. Indian Chem. Sot., 49 (1972), 1209; J. Colloid Interface Sci., 54 (1976) 6. R.J.R. Cairns, R.H. Ottewill, D.W.J. Osmond and I. Wagstaff, J. Colloid Interface Sci., 54 (1976) 45. D.H. Everett and J.F. Stageman, Faraday Discuss. Chem. Sot., 65 (1978) 230. J.V. Dawkins and G. Taylor, Polymer, 20 (1979) 599; Macromol. Chem., 180 (1979) 1737. M.D. Croucher and T.H. Milkie, Faraday Discuss. Chem. Sot., 76 (1983) 261. A. Doroszkowski and R. Lambourne, J. Polym. Sci., C34 (1971) 253; J. Colloid Interface Sci., 43 (1973) 97. D.J. Cebula, J.W. Goodwin, R.H. Ottewill, G. Jenkin and J. Tabony, Colloid Polym. Sci., 261 (1983) 555. P.N. Pusey and W. van Megen, J. Phys. Paris, 44 (1983) 285. W. van Megen, R.H. Ottewill, S.M. Owens and P.N. Pusey, J. Chem. Phys., 82 (1985) 508. S.G. Barsted, L.J. Nowakowska, I. Wagstaff and D.J. Walbridge, Trans. Faraday Sot., 67 (1971) 3598. K.E.J. Barrett and H.R. Thomas, Kinetics and Mechanism of Dispersion Polymerization, in K.E.J. Barrett (Ed.), Dispersion Polymerization in Organic Media, Wiley, London, 1975, Ch. 4. J.W. Goodwin, J. Hearn, C.C. Ho and R.H. Ottewill, Brit. Polym. J., 5 (1973) 347. R.J.R. Cairns, W. van Megen and R.H. Ottewill, J. Colloid Interface Sci., 79 (1981) 511. R.H. Ottewill and S. Papworth, to be published.

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