Eect of interactions between stabilisers and silica used for antiblocking applications on UV and thermal stability of polyolen lm
1. Adsorption studies
C.M. Liauw a,*, A. Childs a, N.S. Allen a, M. Edge a, K.R. Franklin b, D.G. Collopy c
a
Department of Chemistry and Materials, The Manchester Metropolitan University, Chester Street, Manchester M1 5GD, UK
b
Unilever Research, Port Sunlight Laboratory, Quarry Road East, Bebington, Wirral L63 3JW, UK
c
Croseld Limited, Research and Development, PO Box 26, Warrington, Cheshire WA5 1AB, UK
Received 1 May 1998; accepted 7 June 1998
Abstract
Interactions between stabilisers and silicas, produced by both the gel process and by precipitation, have been studied using ow
micro-calorimetry (FMC) and diuse reectance Fourier transform infrared spectroscopy (DRIFTS). The silicas had approximately equivalent BET surface areas. By virtue of its greater pore volume and lower water content, the gel silica was shown to have
the greatest adsorption activity. For both the silicas, the adsorption activity of a stabiliser was related to its basicity and number of
adsorbing groups per molecule which gave rise to multi-point adsorption, hence polymeric hindered amine light stabilisers (HALS)
and large hindered phenols showed the strongest adsorption. Competitive adsorption of polymeric HALS versus hindered phenols
was also investigated. The data obtained has been very useful for predicting preferential adsorption of the stabilisers on to the
silicas from a linear low density polyethylene melt which in turn has been related to photo-oxidative and thermo-oxidative stability.
The latter investigation will be reported separately. # 1999 Elsevier Science Ltd. All rights reserved.
1. Introduction
In production of layat lm, self adhesion (blocking)
of the lm layers after bubble collapse is a serious problem which can be overcome by addition of very low
levels (i.e. 10002000 ppm) of a suitable ller to the
polymer, such additives are known as antiblocking
agents [1]. It is anticipated that the ller particles serve
to roughen the surface of the lm and hence reduce the
contact area thereby reducing the level of self adhesion
[1]. Antiblocking llers include calcium carbonate and
silica, which is the subject of this study.
The stabilisation of polymer lms is an important
issue due to their high surface area to volume ratio
which causes the mechanical properties to be highly
surface dependent. Adsorption of polymer additives on
to llers is an acknowledged problem, particularly in the
elastomer industry where measures have to be taken
against such eects [2]. In thermoplastics, the adsorption of stabilisers by llers is a recognised problem
which is solved by using additives which sacricially
* Corresponding author. Tel.: +44-161-247-3325; fax: +44-161247-6357; e-mail: c.m.liauw@mmu.ac.uk
0141-3910/99/$see front matter # 1999 Elsevier Science Ltd. All rights reserved
PII: S0141 -3 910(98)00119 -0
392
spectroscopy. Eects of these interactions on the stabilisation performance in linear low density polyethylene
will be reported separately.
2. Experimental
The stabilisers investigated were Irganox 1010, Chimassorb 944, Tinuvin 328 [all from Ciba, UK] and BHT
(2,6 Di-tert-butyl-4-methylphenol) (Aldrich), further
details are given in Table 1 and the structures are presented in Fig. 1. All other solvents/reagents were of
HPLC grade or 99%+ purity where appropriate. The
silicas used were supplied by Croselds Limited, Silica A
was produced by the gel process and Silica B produced
by precipitation. Other parameters are given in Table 2.
The FMC system used was that developed by Ashton
and Rothon [5] and consisted of a Microscal 3V
(upgraded to all PTFE uid path) FMC linked to a
Waters 410 dierential refractometer. The data outputs
were handled by PerkinElmer Nelson 900 Series data
stations which were in turn linked to a PC running
Nelson chromatography software. Experiments were
conducted using a cell temperature of 27 (1 C) and
an additive concentration of 0.30% w/v. The n-heptane
carrier ow rate was 6.6 cm3 hr1. n-Decane was used as
the non-adsorbing probe. Sample size was 24 mg (1
mg) and 45 mg (1 mg) for Silicas A and B, respectively. Before adsorption experiments were commenced
the sample bed was allowed to equilibrate for two hours
at a carrier ow rate of 6.6 cm3 hr1. Three separate
runs were carried out with each additive and the average
results reported. Competitive adsorption was investigated by rst attaining adsorption equilibrium with one
stabiliser and then switching to a solution of the other in
the same solvent. Any adsorption/displacement was
observed in the usual manner. The experiment was then
repeated on a fresh bed of silica, this time with the order
of stabiliser addition reversed. For a more comprehensive description of the FMC technique, the reader is
referred to a description by Ashton and Briggs [18].
Samples isolated from the FMC were air dried and
then examined using DRIFTS. Before analysis the
samples were diluted to 5% w/w with nely ground KBr
and then placed in a Spectra-Tech DRIFTS cell tted to
a Nicolet 510 FTIR spectrophotometer (DTGS detector). Spectra were made up of 150 scans with resolution
set to 4 cm1. All spectra shown are normalised to a
silica band at 800 cm1 which is not aected by silanol
type/concentration [13].
3. Results and discussion
The FMC data is represented in Figs. 2 and 3. It is
immediately evident that Silica A has a higher overall
393
Table 1
Stabilisers investigated
Trade name
(supplier in parentheses)
Additive type
Systematic name
Molar mass
AO
1178
BHT (Aldrich)
Chimassorb 944 (Ciba)
AO
LS
LS
Fig. 1. Structures of stabilisers used, (a) Irganox 1010, (b) BHT, (c)
Chimassorb 944, (d) Tinuvin 328.
218
ca. 3000
335
394
Table 2
Properties of silicas A and B
Silica Surface areaa
(m2 g1)
A
B
320
364
a
b
1.6
0.3
1.8
0.4
1.5
0.7
23
215
595
1600
Fig. 2. FMC data for Silica A (adsorption data is all exothermic, the
sign of the energy change has been reversed to facilitate comparison):
& adsorption, & desorption.
Fig. 3. FMC data for Silica B (adsorption data is all exothermic, the
sign of the energy change has been reversed to facilitate comparison):
& adsorption, & desorption.
receptive to both oxygen containing and nitrogen containing model compounds, with the more basic amine
probes, i.e. ethylamine, diethylamine and the substituted
piperidine, having the higher heats of adsorption. Silica
B presents a completely dierent picture; in this case the
overall amount of probe adsorption, particularly with
ketones and esters, is less than for Silica A, however, the
energies of adsorption per molecule and strengths of
adsorption for the more basic amine probes are signicantly higher. This shows that Silica B may possess a
greater number of Brnsted acid sites relative to Silica A.
These observations generally mirror those for the stabilisers and conrm that adsorption can occur via hydroxyl
groups, amine functionality and ester linkages.
Fig. 4. DRIFTS data for Silica A isolated from FMC cell: (a)
untreated silica; (b) Silica A after adsorption/desorption of Irganox
1010; (c) as (b) but substrate subtracted; (d) unbound Irganox 1010
(run as powder in KBr).
395
Fig. 5. FMC data for adsorption of model compounds: & adsorption, & desorption (4A2266T is 4-amino-2,2,6,6-tetramethylpiperidine).
396
Fig. 6. DRIFTS spectra showing OH stretching region of silicas treated at 95 C in vacuo for 16 h: (a) Silica A, (b) silica B.
Fig. 8. Raw FMC data showing adsorption of Chimassorb 944 followed by switch over to Irganox 1010 (at 120 min): (a) thermal signal,
(b) dierential refractometer signal.
397
4. Conclusions
Acknowledgements