Beruflich Dokumente
Kultur Dokumente
Robin Britton
Robin Britton
iSmithers
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
A catalogue record for this book is available from the British Library.
Every effort has been made to contact copyright holders of any material
reproduced within the text and the authors and publishers apologise if
any have been overlooked.
ISBN: 978-1-84735-406-8
1. Introduction ......................................................................... 1
iii
Update on Mouldable Particle Foams
iv
Contents
v
Update on Mouldable Particle Foams
vi
P
reface
This Update has been written for technologists active in the mouldable
particle foam industry, who require an up-to-date account of the
status of the field, including areas with which they may not be so
familiar. It is also written for those who may have only recently come
into the industry, and though acquainted with polymer technology,
are not yet fully immersed in the specifics of particle foams.
I must first acknowledge the help and advice I have received from
my colleagues in the Synbra Group, especially Jan Noordegraaf and
Jürgen de Jong at Synbra Technology bv, who have been very helpful
in reviewing the text and suggesting improvements. I have to thank
all those within this industry who have helped me to explore what,
less than ten years ago, was to me an esoteric branch of polymer
vii
Update on Mouldable Particle Foams
Robin Britton,
Spring 2009
viii
1
Introduction
1
Update on Mouldable Particle Foams
Surveys of the market for EPS suggest that 2007 saw worldwide
consumption of some 5 million tonnes [3, 4], compared with only
35,000 tonnes in 1960 [5]. Growth continues to be strong, especially
in Asia, which now produces around half the world total, the majority
for protective packaging. The second largest market is in Europe,
where construction (principally insulation) takes more than 70%,
while NAFTA countries are the major users of EPS for drinking cups.
The strength of manufacturing of consumer goods in Asia is clearly
the reason for the high proportion used for packaging there (and the
low proportion in Europe).
2
Introduction
3
Update on Mouldable Particle Foams
4
Introduction
The references are up to date at the time of writing (early 2009), but,
as always, some may already have been superseded – new publications
may be on the way, or further patent grants or refusals. It is worth
the effort to follow up any point that is of interest and check for new
information – the field does not stand still, and this is particularly
true of the materials of Chapter 4, where significant progress can be
expected in the coming years.
References
1. Handbook of Polymer Foams, Ed., D. Eaves, Rapra
Technology, Shawbury, Shrewsbury, UK, 2004.
5
Update on Mouldable Particle Foams
6
2
Expandable Polystyrene (EPS) –
A Mature Technology?
7
Update on Mouldable Particle Foams
8
Expandable Polystyrene (EPS) – A Mature Technology?
Moulding is also effected with steam – the prepuff beads are blown
into an aluminium mould and steam applied through a number of
small vents. This softens the beads and expands them further, using the
residual blowing agent which remains in them after the prefoaming
and ageing steps, in order to fuse adjacent beads together. Vacuum
may be applied to the mould in the later stages, to help create a well-
fused surface on the moulding. The distribution of steam between
the mould halves can be adjusted to optimise the moulding process,
prevent distortion, etc. Cooling follows before the moulding can be
ejected and allowed to dry. Moulding cycles are much longer than,
for example, those of injection moulding, as the insulating properties
of the foam dictate long heating and cooling times, although section
thicknesses are also generally much larger than can be achieved in
injection mouldings. Tolerances on product dimensions are usually
quite wide – p1.5 mm is not unusual – as these are rarely critical in
the end application.
Key features of the standard EPS process give the material some key
strengths and weaknesses, summarised (not exhaustively) next:
9
Update on Mouldable Particle Foams
Strengths
10
Expandable Polystyrene (EPS) – A Mature Technology?
Weaknesses
• Both polystyrene and the blowing agent are flammable, and fire
retardation is required in many applications. This is particularly
important for construction insulation products. Almost all EPS
products for construction include brominated hydrocarbon
fire retardants often with peroxide synergists. Brominated fire
retardants are coming under increasing scrutiny as potential
persistent organic pollutants, and although the compound most
commonly used in EPS, hexabromocyclododecane (HBCD), has
not as yet been so designated, it is now proposed that it should be
considered under the European REACH legislation as a Substance
of Very High Concern. This issue is potentially very serious for
the EPS construction market, and much work has been done to
try to find solutions, without dramatic success to date.
11
Update on Mouldable Particle Foams
12
Expandable Polystyrene (EPS) – A Mature Technology?
The four BASF patents all cover the use of phosphorus compounds
(always claiming for a list of such compounds, although some are
obviously more effective than others) but in combination with other
additives to improve the material performance. The first patent [16]
describes a combination of expandable graphite with a phosphorus
compound. The examples mention 5% of either red phosphorus
or dimethylphenylphosphonate (DMPP), with 15% of expandable
graphite – red phosphorus is preferred for an extrusion process. The
13
Update on Mouldable Particle Foams
second patent [17], which was filed in 1997 but only granted in 2004,
takes a different approach, mixing the phosphorus compound with
a water-releasing metal hydroxide (such as magnesium hydroxide
or alumina trihydrate) at a combined addition rate of greater
than 12%. The best-performing examples have 10% TPP and 5
or 10% magnesium hydroxide. The third patent [18-21], which
is actually a family of four patents filed in different jurisdictions,
brings another phosphorus compound into play, 9,10-dihydro-9-
oxa-10-phosphaphenanthrene 10-oxide (DOPP), in combination
with a peroxide such as dicumyl peroxide or di-tert-butyl peroxide.
The ignitability test used to assess the samples is, in contrast to the
other patents that use the DIN 4102-1 B1 or B2 rating [12], a very
ad hoc horizontal burning test with a very short application of the
flame, and it is not clear how well any of these formulations would
perform in national or international standard test methods. BASF’s
most recent patent [22] for non-halogen compositions combines
the first two approaches mentioned above [16-21], claiming for
recipes which include a filler (chalk in the examples, but metal
hydroxides are also claimed), expandable graphite and a phosphorus
compound (red phosphorus, TPP and DOPP are all mentioned in
the examples), plus optionally carbon black or laminar graphite to
improve the insulation performance (see Section 2.3). Clearly the use
of phosphorus compounds is not an easy route to fire retardation –
the mechanism by which these agents operate, char formation, is less
effective in EPS than the flame quenching and shrinking mechanism
of the HBCD/peroxide system, and the amounts of additive used are
far higher – in a typical current recipe HBCD is present at less than
1% and the peroxide even less, where all of these patents describe
recipes with more than 10% of additive, sometimes much more. Such
a volume of ‘dead’ (non-expandable) filler can only be detrimental
to expandability, mechanical properties, etc.
One aspect that is not much discussed in the BASF patents, but is
relevant to the GE Plastics documents, is the strong tendency of
phosphate compounds to lower Tg of the polystyrene, reducing the
heat resistance of the foam. To overcome this, two patents [23, 24]
describe compositions which combine a phosphate such as resorcinol
14
Expandable Polystyrene (EPS) – A Mature Technology?
Dow Global has pursued a slightly different track with their recently
granted patent [25], which employs a modified multifunctional epoxy
compound together with a phosphate such as DOPP. This patent
is not aimed specifically at EPS as the other are, but at polystyrene
applications in general, and mentions extruded foamed sheet (XPS)
products but not expandable beads. There is, however, no obvious
reason why this system could not be used in bead products.
There have recently been patents for a quite different approach to the
challenge of improving the fire performance of EPS for construction
applications. Rather than incorporate a fire retardant package in the
beads, both BASF [27] and Ertecee, part of the Dutch Synbra Group
[28], have taken the route of applying a fire-resistant coating to pre-
expanded beads of EPS, then moulding the coated beads into slabs
or other shapes. The common feature to both is the use of sodium
silicate (waterglass), but the coatings are otherwise quite different.
BASF’s method bonds the waterglass to the beads with an aqueous
dispersion of an acrylate adhesive, which can then be used to fuse
the beads together in the moulding step, while Ertecee’s process for
Xire reacts the waterglass to form a coating on the beads which
becomes insoluble after moulding. In both cases the weight of the
coating is much greater than that of the EPS – the moulded products
have densities of 80–100 kg/m3 or more, with the beads contributing
less than 20 kg/m3 – but the fire performance is in a different league
from that of a more conventionally retarded EPS. The panels are more
15
Update on Mouldable Particle Foams
16
Expandable Polystyrene (EPS) – A Mature Technology?
17
Update on Mouldable Particle Foams
18
Expandable Polystyrene (EPS) – A Mature Technology?
19
Update on Mouldable Particle Foams
20
Expandable Polystyrene (EPS) – A Mature Technology?
21
Update on Mouldable Particle Foams
22
Expandable Polystyrene (EPS) – A Mature Technology?
23
Update on Mouldable Particle Foams
24
Expandable Polystyrene (EPS) – A Mature Technology?
25
Update on Mouldable Particle Foams
26
Expandable Polystyrene (EPS) – A Mature Technology?
Pentane and other blowing agents commonly used in EPS are very
effective but they are nowadays seen to have an environmental
downside. When EPS beads are produced, stored, pre-expanded,
moulded and post-aged, some blowing agent is vented to the
atmosphere at each stage (particularly during pre-expansion and
moulding). Typically beads are produced with some 5–6% of blowing
agent, so that the 5 million tonnes of EPS produced in 2007 released
250,000–300,000 tonnes of volatile organic compounds (VOC) to the
27
Update on Mouldable Particle Foams
Various methods exist and have been tried for plasticising the
polystyrene, and development work continues. There are probably
rather more proprietary formulations than are to be found in the
patent literature, as not all manufacturers are willing to publish
their findings in this way – or they use obscure wording so that their
patents are hard for competitors to find. A number of patents have
been found and are discussed next.
28
Expandable Polystyrene (EPS) – A Mature Technology?
The first patents in this area were filed by BASF, which has a family of
US patents dating to the early 1990s. One from 1992 [72] is a typical
example, and claims a bead with a pentane level of 2.0–4.4%. The
key to its improved expandability is stated to be the precise control of
molecular weight distribution and limited branching. The molecular
weight should be between 180,000 and 300,000, with polydispersity
below 2.5 and less than 5% branching. Even so, a series of expansion
stages, with the beads allowed to mature between them, is required
in order to reach commercially useful (20 kg/m3 or less) product
densities. More recent patents appear to contradict this prescription,
but that was the state of development at that time.
29
Update on Mouldable Particle Foams
These are said to expand well, but to produce foamed beads that
are hard and tough.
BASF has taken a slightly different path with another 2008 patent
[79, 80] which demonstrates development since the early 1990s. Now
a broad, even multimodal molecular weight distribution is seen as
essential, and the ‘best’ examples are blends using a low-molecular
weight terpolymer (Joncryl ADF1300) of styrene, acrylic acid and
A-methylstyrene at up to 10% addition to polystyrene with molecular
weight of 280,000 and polydispersity of 2.8. Another example
has a 1:1 blend of two polystyrenes with molecular weight values
of 195,000 and 280,000 and no low-molecular weight polymer –
30
Expandable Polystyrene (EPS) – A Mature Technology?
31
Update on Mouldable Particle Foams
32
Expandable Polystyrene (EPS) – A Mature Technology?
A later paper [86], the final one in a series of four from Eindhoven
University of Technology, takes a different approach. The polystyrene
is first prepolymerised in a bulk polymerisation process, and the water
is dispersed in it as a water-in-oil emulsion during this stage. Sodium
chloride in the water is used to control its droplet size and dispersion
and the polymer viscosity is sufficient to preserve the emulsion
through the second stage. The prepolymer with its dispersed water
is then finished in a normal free radical suspension polymerisation.
Beads with up to 4% of finely dispersed water can be achieved in this
way. In order to increase the melt strength and temperature resistance
of the polystyrene so that it is more robust during the expansion and
moulding processes, a proportion of PPE/PPO is added to the reaction
mixture. The optimum recipe yields beads with up to 8% water (the
PPE also increases the amount of water which can be held in the
beads) and Tg around 108 °C. This paper does not report or discuss
the expansion and moulding processes for these beads, simply stating
that molecular weight is important, and that the PPE is expected to
improve the processing window.
33
Update on Mouldable Particle Foams
sufficient expansion power to fuse well in the mould. The process may
be applied to solid beads (which can be polystyrene, polyethylene,
polypropylene or even other polymers) and allows the elimination
of the volatile blowing agents normally used, as well as the large
storage bags needed for the maturing step and the emissions that arise
during it. It is, however, advantageous to ‘pre-nucleate’ the beads by
carrying out a mild pre-expansion (e.g., from a bulk density of more
than 600 kg/m3 to 400 kg/m3 or so) which creates the structure of
foam nuclei for the later expansion and for which a (low) pentane
content is very useful. This process may allow the elimination of the
storage bags for maturing, but it does instead require equipment
for the impregnation of the beads under high gas pressures. As this
does not seem to be a great advance on the well-known PAT system
for expanded polypropylene/polyethylene (see Chapter 3), in which
prepressurisation of the prepuff beads gives them enough internal
pressure to expand during moulding, it might not appear to be very
inventive, and it is possible that the application will be revised and
narrowed before it is granted.
The first of these papers [90] describes how an XPS process using
carbon dioxide alone is difficult to control because of its poor
solubility in the polymer (maximum around 4 wt%), but the
addition of a similar level of ethanol (boiling point of 78 °C, so
potentially useful in steam expansion) gives better plasticisation and
expandability. The paper concludes that combining the two blowing
34
Expandable Polystyrene (EPS) – A Mature Technology?
The second paper [91] describes the use of water and n-butane together
to produce ‘bi-cellular’ foam – a sheet with two cell size populations
which reportedly improves the insulation performance of the sheet.
The polystyrene also included a low percentage of precipitated silica
which, by adsorbing water onto its hydrophilic surface, helped the
dispersion of the water and also acted as a nucleation agent for the
foam. With 5% butane, 2% water and 3% silica, the expansion
ratio reached 35:1 (corresponding to a foam density around 30 kg/
m3) with a well-defined two-peak distribution of cell sizes. Clearly
this technique still relies on a volatile hydrocarbon, but exemplifies
some advantages of combining two blowing agents.
Another approach that may have potential for the future is the use of
Expancel expandable microspheres [93]. These have a diameter in
the range 10–40 Mm and have a polymeric shell enclosing a volatile
fluid such as a blowing agent. Once incorporated in a polymer matrix
and heated above the softening point of the shell, the microspheres
release their volatile contents to expand the matrix (although clearly
this must also have been softened by the heat) and expansion ratios of
up to 60 times are claimed. Although the microspheres are expensive,
this approach may have potential in allowing the use of blowing
agents that are not soluble in polystyrene.
35
Update on Mouldable Particle Foams
36
Expandable Polystyrene (EPS) – A Mature Technology?
via static mixers and melt pumps) and any desired additives
compounded into it. Blowing agent can be pumped into the (sealed)
extruder barrel and mixed into the polymer in a mixing zone, then
the melt fed (sometimes via a ‘cooling extruder’ which can be a
single-screw type, or directly via a melt pump – either ensures a
steady flow of melt at a consistent pressure) to the inlet of the
micropelletiser. This has a die with a large number of very fine
holes arranged in clusters round an annular face, and fed through
a number of ‘pots’ which pass through the heated body of the
die. A multi-knife cutting head rotates against the die face at high
speed under a flow of pressurised cooling water. To illustrate the
challenges, a bead of 1 mm diameter has a mass of around 0.5 mg,
so that a process running 300 kg/h must cut that throughput into
some 10 million beads every minute. Die design is a critical part of
a reliable process, and although there is much commercial secrecy,
some approaches have been described [97-99]. The beads that result
are egg-shaped rather than spherical, but close enough to be able
to be processed in the same way as beads made by conventional
suspension polymerisation.
37
Update on Mouldable Particle Foams
38
Expandable Polystyrene (EPS) – A Mature Technology?
into or over metal parts [104]. Techniques have also been devised
(or in one case, borrowed from the brick-making industry [104]) to
increase production rates by use of multiple moulds which can be
the same or different from one another, allowing several parts to be
produced in parallel. Automation of pre-expanders and moulding
machines is likely to become ever more sophisticated, as demand
for process efficiency and consistent quality continues to grow.
An interesting study into the relationships between EPS molecular
weight and density and the quality of ‘lost foam’ castings [105]
shows that demand for efficiency applies to all EPS processes – it
was found that the molecular weight of the EPS controlled the rate
of volatilisation, but that mould filling time also depended on the
density of the foam.
Recycling of EPS is well established and the industry has long met
and exceeded its recycling targets under EC packaging directives.
The most common method of recycling is to grind waste foam
back to its constituent expanded beads, then add a proportion
of them into virgin pre-expanded beads to mould new products
– if the beads are clean they often have very little effect on the
product properties. Waste foam can also be densified by crushing,
allowing relatively economic transportation (a standard 12 m
freight container holds less than 1 tonne of scrap EPS, whereas,
if the foam can be densified to around 300 kg/m3, the same
container will hold 12 tonnes or more). It can then be melted and
reprocessed to a general-purpose polystyrene or modified to have
greater added value. The economics of melt reprocessing are very
sensitive to the price of oil, which not only controls the price of
prime polymer (hence a ceiling on the price of recyclates) but also
the cost of transportation of the scrap material from where it is
generated to where it is recycled – an operation that is profitable
today can become unprofitable tomorrow irrespective of the best
efforts of the recycler.
39
Update on Mouldable Particle Foams
40
Expandable Polystyrene (EPS) – A Mature Technology?
References
1. R-D. Klodt and B. Gougeon in Modern Styrenic Polymers:
Polystyrene and Styrenic Copolymers, Ed., J. Schiers and D.B.
Priddy, John Wiley & Sons, New York, NY, USA, 2003.
41
Update on Mouldable Particle Foams
42
Expandable Polystyrene (EPS) – A Mature Technology?
43
Update on Mouldable Particle Foams
44
Expandable Polystyrene (EPS) – A Mature Technology?
45
Update on Mouldable Particle Foams
46
Expandable Polystyrene (EPS) – A Mature Technology?
68. B.I. Chaudhary, L.S. Hood and R.P. Barry, inventors; Dow
Chemical Co., assignee; US2002/0111389A1, 2002.
72. W.H. Harclerode, W.E. Volz, J.V. Wiman, J.C. Voss, B.J.
Pekich and J.C. Knutsen, inventors; BASF Corporation,
assignee; US05110837, 1992.
75. D.C. Jung, M.C. Kim, S.R. Kim and G.I. Song, inventors;
Cheil Industries Inc., assignee; KR20010008871, 2001.
47
Update on Mouldable Particle Foams
91. K-M. Lee, E.K. Lee, S.G. Kim, C.B. Park and H.E. Naguib
in Proceedings of SPE ANTEC 2008, Milwaukee, WI, USA,
2008, p.1920.
92. J. Yang, S-K. Yeh, Z. Guo, Z. Cai, L.J. Lee, N-R. Chiou and
T. Daniel in Proceedings of SPE ANTEC 2008, Milwaukee,
WI, USA, 2008, 1013.
48
Expandable Polystyrene (EPS) – A Mature Technology?
49
Update on Mouldable Particle Foams
108. S.W. Lye, H.S. Aw and S.G. Lee, Journal of Applied Polymer
Science, 2002, 86, 456.
109. S.W. Lye and H.D. Aw, Plastics, Rubber and Composites,
2003, 32, 368.
50
3
Expanded Polyolefin Moulded
Foams (EPE and EPP) – Materials
with Growing Application
The features of the EPS process described in Chapter 2 are not easily
reproduced in other polymers, for reasons which will be explored
in this and the following chapter. Polyolefins are commodity
polymers that are produced in larger volumes than polystyrene, yet
expandable bead production is very much smaller. In contrast to
polystyrene, extrusion of expanded sheet from polyolefins is much
more widely practised than manufacture of mouldable beads, which
remain niche products for particular applications. This is a direct
result of the differences between these polymers and polystyrene
in relation to foaming and these differences must be considered in
order to understand the reasons for the way moulded polyolefin foam
technology has developed.
51
Update on Mouldable Particle Foams
The first key difference from EPS is that there are no blowing agents
that can be impregnated into the beads and held there at ambient
pressures for later expansion, in the way that pentane functions in
EPS. Instead, once impregnated with blowing agent, the beads must
be expanded immediately, or held under high pressure. Expanded
beads have a high bulk, so that transporting them (and the finished
products) is costly. Clearly, producing the beads on the same site as
moulding the finished products would eliminate that cost, but those
finished products could then require transporting over long distances
to the customer – small-scale production units for expandable
polyolefin beads are not economically attractive.
The third area of difference arises when the beads are expanded and
moulded. Polystyrene is amorphous with a Tg value around 100 °C,
while the polyolefins are semi-crystalline – their Tg values lie below
room temperature, but their crystalline melting points lie in the range
110–140 °C (polyethylenes) or 150–170 °C (polypropylenes). Because
of these higher melting/softening points, high steam temperatures
and pressures are needed for polyolefins, and the process window is
very narrow – a few degrees wide, just below the crystalline melting
point. Further, because of the slow crystallisation of polypropylene,
expanded polypropylene (EPP) products often require post-ageing
in an autoclave before they are fully stable. This all adds cost and
complexity to the process, and further handicaps these polyolefin
bead foams in the marketplace.
On the positive side, polyolefins are far more ductile than polystyrene,
so their foams are also much tougher and more resilient. This is
particularly useful for protection against repeated impacts, so the
automotive industry has long been a major area of application as
well as transport packaging.
52
Expanded Polyolefin Moulded Foams (EPE and EPP) –
Materials with Growing Application
53
Update on Mouldable Particle Foams
54
Expanded Polyolefin Moulded Foams (EPE and EPP) –
Materials with Growing Application
55
Update on Mouldable Particle Foams
Over time polymer manufacturers have seen the value of higher melt
strength (also very useful in thermoforming) and have developed
special grades to meet this need. The logical approach was to make
polypropylene with a degree of branching, and a paper presented at
ANTEC in 2001 [7] by workers from the University of Toronto and
Borealis GmbH reported significant improvements in foamability
by blending so-called ‘high melt strength’ (HMS) branched
polypropylene into linear polypropylene. Not only did the cell density
increase (showing less cell-wall breakage) with the proportion of
HMS polypropylene, but also the minimum foam density and the
temperature at which it was reached fell, although it was reported
that the crystallisation temperature did not change. This work was
56
Expanded Polyolefin Moulded Foams (EPE and EPP) –
Materials with Growing Application
done in a sheet extrusion process rather than beads, but the same
principles were clearly applicable to bead making.
57
Update on Mouldable Particle Foams
58
Expanded Polyolefin Moulded Foams (EPE and EPP) –
Materials with Growing Application
description of the prior art and the claims would require a translation
from Chinese.
59
Update on Mouldable Particle Foams
60
Expanded Polyolefin Moulded Foams (EPE and EPP) –
Materials with Growing Application
61
Update on Mouldable Particle Foams
62
Expanded Polyolefin Moulded Foams (EPE and EPP) –
Materials with Growing Application
A niche but potentially large future market area for EPP foam is as an
underlayer in synthetic sports surfaces [27] – a sheet of EPP provides
the necessary level of cushioning between the hard substrate and the
synthetic turf, while having sufficient toughness and resistance to
compression set to have an adequate service life.
63
Update on Mouldable Particle Foams
EPP and polyurethane foams. The results are also compared against
a common constitutive foam model and show that, above around
1000/s, strain rate dependence becomes very marked. Another study
[30] explores the effect of multiple compression cycles on EPS and
EPE, and compares their performance against simulations using finite
element analysis. EPE (and EPP) is significantly more resilient to
multiple loadings than EPS – the deformation of EPS quickly leads to
breakage of the cell walls of the foam, as the matrix polymer is quite
brittle, while polyolefins have much greater ductility and ‘absorb’
deformation by flexing and yielding without breaking – the cell
structure therefore remains more or less intact and the cushioning
power of the air inside the cells is retained.
64
Expanded Polyolefin Moulded Foams (EPE and EPP) –
Materials with Growing Application
References
1. F. Statsny, R. Gaeth and G. Treischmann, inventors; BASF,
assignee; US3616365, 1971.
65
Update on Mouldable Particle Foams
19. J.B. Choi, M.J. Chung and J.S. Yoon, Industrial and
Engineering Chemistry Research, 2005, 44, 8, 2776.
66
Expanded Polyolefin Moulded Foams (EPE and EPP) –
Materials with Growing Application
67
Update on Mouldable Particle Foams
68
4
‘Sustainable’ Polymers –
The Future?
69
Update on Mouldable Particle Foams
was replaced by foam from renewable sources over the next 10 years,
volumes would become significant and require large investments in
polymer production capacity.
Over the past few years, a wide range of sustainable polymers has
been promoted as potential solutions to these issues, and it remains
unclear which of them will be among the winners and losers – some
may find specific niches while some may succeed on a larger scale
and others fall by the wayside [2]. Long-established materials such as
starch and cellulosic polymers have come under fresh consideration,
together with polyhydroxyalkanoates (PHA), polylactic acid (PLA)
and other more exotic polymers (Nylon 12, for example, is made from
castor oil). There has also been an announcement [3] that Braschem
SA of Brazil is to produce a fully renewable linear polyethylene
derived from sugar cane, although this is intended for packaging film
production at present. Producers and users of mouldable particle
foams are also keenly interested in this developing area – if, for
example, governments legislate (or large customers decree) to require
packaging to be sustainable or degradable then cost constraints that
presently apply may become much less important and the ability to
deliver a product that works much more critical.
70
‘Sustainable’ Polymers – The Future?
71
Update on Mouldable Particle Foams
72
‘Sustainable’ Polymers – The Future?
73
Update on Mouldable Particle Foams
and it will not be a surprise if the number of players in this field suffers
significant attrition in the next few years. What is more important
when considering the options for foams made from sustainable
polymers is the comparative costs of the candidates – here PLA and
starch-based materials have a clear advantage over polyalkanoates
and cellulosics. As will be seen below, PLA-based materials have seen
by far the greatest amount of effort in recent years.
Processes for EPS and EPO rely on steam as the medium for heat
transfer to the beads – it has a high heat capacity and can be controlled
in temperature over quite a wide range, by varying the pressure or
diluting with air. Existing equipment for expansion and moulding
has been developed and tuned for use with these types of beads – if
a new bead material requires a significant redesign of the process
equipment then that will add to its costs and make it less likely to
be adopted.
74
‘Sustainable’ Polymers – The Future?
75
Update on Mouldable Particle Foams
As lactic acid is a chiral molecule (see Figure 4.1), in which the methyl
group can be either on one side of the chain backbone (‘looking’ from
the double carbon–oxygen bond) or on the other, there are potentially
many types of ‘PLA’ which can be produced. By controlling the mix
of lactides (L–L, L–D, D–D) fed into the ring-opening polymerisation
process, polymers can be made with all L-lactic acid units in their
chains (PLLA) or with all D-lactic acid units (PDLA), or with the
chains comprising a random mixture sometimes referred to as P(DL)
LA. Most of the useful grades are strongly biased towards PLLA
76
‘Sustainable’ Polymers – The Future?
L-Lactic acid
D-Lactic acid
77
Update on Mouldable Particle Foams
78
‘Sustainable’ Polymers – The Future?
79
Update on Mouldable Particle Foams
80
‘Sustainable’ Polymers – The Future?
81
Update on Mouldable Particle Foams
82
‘Sustainable’ Polymers – The Future?
JSP’s first application dates back to 2003 [25] and claims an expanded
bead containing at least 50 mol% of lactic acid units (allowing for
83
Update on Mouldable Particle Foams
84
‘Sustainable’ Polymers – The Future?
85
Update on Mouldable Particle Foams
Following the storage period, the beads contain 8–12% CO2 and
can be expanded at a temperature in the range 50–70 °C – some of
the examples were expanded in hot water. The pre-expansion yields
a prepuff that can then be moulded immediately (no need for the
maturing process which is typical of EPS) or stored (again in a freezer)
for moulding at a later date. Moulding is carried out at temperatures
86
‘Sustainable’ Polymers – The Future?
up to 110 °C, although the claims cover both the case where the
moulding is effected at or above the pre-expansion temperature and
the case where it is done at or below the pre-expansion temperature,
and the examples are similarly various. What is made clear is that
the pre-expansion should not exhaust the expansion potential of the
beads, and that enough CO2 should remain to drive further expansion
during moulding.
87
Update on Mouldable Particle Foams
88
‘Sustainable’ Polymers – The Future?
abstract how much expansion is achieved at the die and how much
more during moulding, nor what blowing agents or other additives
are required.
89
Update on Mouldable Particle Foams
90
‘Sustainable’ Polymers – The Future?
91
Update on Mouldable Particle Foams
Amylose
Amylopectin
92
‘Sustainable’ Polymers – The Future?
Using water as the blowing agent for starch has the disadvantage that
the concentration of water must be tightly controlled before expansion,
as it affects the rheology of the material as well as providing the
driving force for the expansion. If the water concentration is too high,
the material may have insufficient melt strength to sustain a good
cell structure, too low and it may not be able to expand sufficiently.
This makes the processing of the material inherently unstable and
unpredictable. Further, employing the conventional EPS processes,
using steam to expand and mould foamed TPS risks damage to the
foam structure (‘burning’ of the beads) as the temperature of the
steam will usually be above the softening point of the material. BASF
has addressed this issue by using more conventional blowing agents,
in beads made from starch-based blends [42] which have more heat
and moisture resistance. This patent claims blends of a biodegradable
copolyester with starch or a cellulose-derived polymer, expanded
using one of propane, butane, pentane, methanol, ethanol or propanol
as the blowing agent. The copolyester is the condensation product of
a C2–C12 alkanediol or a C5–C10 cycloalkanediol with a mixture of an
93
Update on Mouldable Particle Foams
94
‘Sustainable’ Polymers – The Future?
95
Update on Mouldable Particle Foams
96
‘Sustainable’ Polymers – The Future?
97
Update on Mouldable Particle Foams
The second Kaneka patent [49] follows much the same lines, but
additionally claims benefits from the addition of an isocyanate
compounded into the polymer (as a chain extender). A wider range
of blowing agents is also claimed, including isobutane and pentane.
There are no details of the bead-making process, and again the
moulding process is barely discussed. In the given, the temperature in
the impregnation vessel is 120–130 °C, close to the polymer melting
point, and the pressure is held at 2.5 MPa for an hour.
98
‘Sustainable’ Polymers – The Future?
99
Update on Mouldable Particle Foams
Cellulose
100
‘Sustainable’ Polymers – The Future?
The BASF patent [42] discussed in Section 4.3.2 also claims the
use, in expandable beads, of cellulosic polymers in a blend with a
biodegradable copolyester. This does not fully meet the need for
sustainability, as the copolyester is a synthetic polymer derived from
oil, and even if the product is practicable and economic, it may not
be easily accepted if full sustainability is mandated by governments
or customers.
101
Update on Mouldable Particle Foams
References
1. J.A. Brydson, Plastics Materials, 7th Edition, Butterworth
Heinemann, Oxford, UK, 1999.
102
‘Sustainable’ Polymers – The Future?
103
Update on Mouldable Particle Foams
104
‘Sustainable’ Polymers – The Future?
40. G.M. Glenn and D.W. Irving, Cereal Chemistry, 1995, 72,
155.
105
Update on Mouldable Particle Foams
106
5
Concluding Remarks – What
Forces Will Drive Development in
this Field?
107
Update on Mouldable Particle Foams
The most likely driver of change over the medium term will be the
increase in the price of crude oil as production peaks and begins to
decline, although it is almost inevitable that political and economic
instabilities will impose strong fluctuations on the rate of that
increase. Those instabilities and fluctuations will also have an impact
on the investment decisions made by the companies active in this
industry – some will be bold and perhaps lose their shirts, some
will be more cautious and maybe miss golden opportunities. It is,
however, possible to see where technological development effort could
be most usefully directed to give the industry the best options to face
the coming challenges (not forgetting that some of these challenges
will be new and unexpected).
The EPS industry faces the likelihood of increasing raw material and
energy costs, increased restrictions on its emissions and increasing
costs for transport both of its products and of the products for which
EPS is used as packaging. It is therefore likely that development which
enables further reduction of foam density (and therefore product
weight), while retaining or improving performance, will be fruitful, as
will reduction of volatile organic compounds (VOC) emissions during
manufacture and processing of EPS. Lower densities will of course
have an impact on the costs of recovery and recycling, activities which
may increasingly be mandatory. As alluded to above, fire performance
may become a critical issue for the insulation market – perhaps the
Xire technology (see Section 2.2) or something comparable to it will
108
Concluding Remarks – What Forces Will Drive
Development in This Field?
109
Update on Mouldable Particle Foams
The future will, therefore, present the particle foam technologist with
new challenges and opportunities. These may be similar to those
which have already been addressed, and for which the solutions have
been described in this update, or they may be completely new. Of one
thing we can be certain, there will always be a drive to fulfil existing
needs in a cheaper and ‘smarter’ fashion, and to meet new needs as
quickly and efficiently as possible. Without such progress, the industry
will be left behind and wither away, so there will continue to be ample
scope for the technologist who can invent, adapt and improve.
110
A
bbreviations for Mouldable
Particle Foam
111
Update on Mouldable Particle Foams
112
A
uthor Index
A
Abe, T 43
Ajioka, M 103
Allen, R B 49
Allmendinger, M 42, 45, 47, 48, 49
Andreas, W 49
Angelopoulou, A G 104
Anlas, G 67
Aoyama, T 106
Araya, A 43
Arduini-Schuster, M 44
Aw, H D 50
Aw, H S 50
B
Barry, R P 47
Bastioli, C 103
Batscheider, K-H 44
Berghmans, H 48
Berghmans, M 43, 48, 67
Berrios, J 105
Biglione, G 49
Bleijenberg, K 43, 48
Bleijenberg, K C 48, 67
Boukami, S 42
Braun, F 43, 44, 105
Brydson, J A 102
Buijk, C M G 43
113
Update on Mouldable Particle Foams
C
Cai, Z 48
Carlier, C 47
Casalini, A 45, 46, 49
Champagne, M F 48
Chaudhary, B I 47
Chen, L 66
Chen, N 65
Chiellini, E 105
Chiou, B-S 105
Chiou, N-R 48
Choi, J B 66
Chung, M J 66
Cigna, G 49
Cinelli, P 105
Cink, K 103
Cronin, D 67
Culkova, A 47
D
Daniel, T 48
Datko, A 45, 49
Daum, M 46
Day, M 104
de Grave, I 66
de Mink, P 65
de Swart, H J 43
Dehnert, P 47
Delaviz, Y 48
Der Hovanesian, M 105
Dietzen, F-J 42, 43, 45, 47, 48, 49, 66
Douay, D 47
Duan, S 66
114
Author Index
E
Eaves, D 5, 41, 50, 65, 66
Eberstellar, R 44
Ehrmann, G 42, 45, 47, 48, 49, 66
Enamoto, K 103
Erbay, E 46
Ezdesir, A 46
F
Favis, B D 103
Feil, H 105
Felisari, R 45, 46
Fiordelisi, F 103
Fischer, J 43, 44
Folland, R 65, 66
Ford, T M 103
Francis, T 43, 46
Frigiero, G 45
Fuminobu, H 106
G
Gaeth, R 65
Galewski, J-M 47
Gan, J 43
Gendron, R 48
Ghidoni, D 45, 46
Gilchrist, A 67
Gilead, D 105
Glenn, G M 105
Glenz, W 5
Gluck, G 42, 43, 44, 48, 105
Gougeon, B 41
Grave, D de 66
Green, J R 49
Guo, Z 48
Gupta, A P 103
115
Update on Mouldable Particle Foams
H
Hahn, K 42, 43, 44, 45, 47, 48, 49, 66
Hall, T 66
Haraguchi, K 104
Harclerode, W H 47
Hayashi, T 47
Henn, R 43, 44
Hesse, A 65
Hirokado, N 104
Hirosawa, K 65
Hirose, K 106
Hiroshi, N 103
Hiroyuki, M 106
Hohwiller, F 43, 44
Holoch, J 45, 47, 48, 49
Holtman, K M 105
Hood, L S 47
Hu, X 104
Huang, Z 105
Huneault, M A 103
Husemann, W 44
I
Imam, S H 105
Inoue, Y 106
Irving, D W 105
Isao, K 46
J
Jager, J 45
Jönsson, L 49
Jung, D C 47
K
Kabamba, E T 66
Kaempfer, K 44
116
Author Index
Kannah, K 47
Katsunori, N 104
Keisuke, O 105
Keitaro, S 105
Keller, A 43
Kelusky, E C 46
Kemperman, W P T 43
Keppeler, V 66
Keulen, G 43
Kim, M C 47
Kim, S G 48
Kim, S R 47
King, B 43
Kitahara, Y 103
Klamczynski, A K 105
Klement, E 5
Klempner, D 65
Klodt, R-D 41
Knutsen, J C 47
Kono, K 47
Kovarik, J 47
Krist, J 66
Krupinski, S M 47
Kuhn, J 44
Kumar, V 103
Kurcharikova, I 47
L
Lamprecht, J 43, 44
Landa, A 43
Lanfredi, R 45
Lanzani, F 103
Laun, M 45, 49
Lauzon, M 102
Lawton, J W 105
Lee, E K 48, 65
Lee, K-M 48
117
Update on Mouldable Particle Foams
Lee, L J 48
Lee, S G 50
Lemstra, P 48
Leung, S N 49
Levchik, S V 41
Li, H 103
Li, K 66
Lia, X 104
Liu, T 66
Liu, Y 105
Lopez, P 46
Lu, M 66
Lu, Y 66
Lye, S W 50
M
Makoto, Y 106
Maletzko, C 66
Masamichi, K 46
Mat, J Z 47
Matsumoto, T 104
Matsuoka, F 104
Metsaars, A C G 67
Michimiro, H 104
Mihai, M 103
Mills, N J 67
Miyagawa, T 106
Moore, G F102
Moreira, A 46
Movilli, W 103
Mronga, N 44
Muhlbach, K 49
Munakata, Y 65
N
Naegele, D 43, 44
Naguib, H E 48, 65, 104
118
Author Index
Naioki, N 105
Nakai, S 67
Namikawa, H 47
Nangeroni, J 103
Nawaby, A V 104
Nehls, B 43
Nelissen, L 48
Noordegraaf, J 43, 45
O
Ohara, H 47
Ohshima, M 67
Ohta, H 104
Oogi, Y 104
Orts, W J 105
Ouellet, S 67
Ozturk, U E 67
P
Pallay, J 48
Panayiotou, C 104
Panzer, U 65
Paquet, A N 41
Park, C B 48, 49, 65, 66
Pavlicek, J 47
Pekich, B J 47
Pinkert, R 47
Pirgov, W 66
Platt, D K 105
Polasky, M E 48
Ponticiello, A 45, 46
Priddy, D B 41
R
Randall, J R 103
Rathbun, M 43
119
Update on Mouldable Particle Foams
Rego, J M 43
Reichelt, N 65
Reiger, J 46
Rensen, P F M 43
Riethues, M 5, 43, 49
Rinaldi, R 49
Rodrigue, D 66
Roesch, J 44
Ruch, J 42, 45, 47, 48, 49
S
Sandler, J 43
Sands, M 50
Sanford, F L 49
Sasaki, H 104
Saunders, S M 102
Schellenberg, J 47
Schennink, G G J 105
Scherzer, D 42, 43, 44
Schiers, J 41
Schmeid, B 42, 43, 45, 47, 48, 49
Schouren, P W M 43
Schueneman, H H 46
Schuler, P 46
Schut, J 103
Schut, J H 49, 67
Scott, G 105
Sei, Y 103
Senda, K 65, 106
Sendijarevic, V 65
Sengupta, P 66
Shah, S 104
Shao, J 66
Shey, J 105
Shi, X 105
Shimida, S 65
Shinichi, F 104
120
Author Index
Shinko, Y 103
Shinohara, M 104
Shiv Kumar, S 50
Simonelli, A 45, 46
Smeets, E P W 43
Smith, J C 103
Snijders, E 48
Song, G I 47
Sopher, S R 65
Spinu, M 103
Stadlbauer, M 65, 66
Statsny, F 65
Sterzel, H-J 103
Suh, K W 41
Sunal, G 46
Suzuki, K 103
T
Takaaki, H 104
Takayoshi, K 103
Taki, K 66, 67
Taskiran, I 46
Tetsuo, K 104
Tetsuya, O 104
Teubert, J 48, 67
Tokiwa, T 104
Toshiyuki, I 104
Treischmann, G 65
Trivedi, Y 66
Trn, N J 47
Troitzsch, J 42
Tsujimura, I 67
Tsunahiro, N 103
Tzivintzelis, I 104
121
Update on Mouldable Particle Foams
U
Ueda, K 104
Uyanik, N 46
V
Van Leuven, R A H 105
Vannini, C 103
Vink, D 103
Vo, C V 42
Volz, W E 47
Voss, J C 47
W
Wagner, F 45
Walter, B 106
Wang, J 66
Wang, X 66
Warzelhan, V 43
Wassmer, K-H 43, 44
Wassner, E 43, 46
Watanabe, T 103
Weil, E D 41
Wiman, J V 47
Witt, M R J 104
Wong, A 49
Wood, D 105
Worswick, M 67
X
Xu, F 105
Xu, J X 65
Y
Yamaguchi, A 103
Yang, J 48
122
Author Index
Yeh, S-K 48
Yin, H 66
Yoon, J S 66
Yoshihito, Y 104
Youngson, C G 43
Yu, S 105
Yukikage, M 106
Z
Zach, J 47
Zamperlin, L 45
Zavodska, V 47
Zhang, H 66
Zhang, L 66
Zhang, S 66
Zhang, W 66
Zhang, X 65
Zhu, Z 65
123
Update on Mouldable Particle Foams
124
S
ubject Index
A
Ageing 9, 62
Agglomeration 7
Amylopectin, structure of 92
Amylose, structure of 92
Antistatic mouldings 88
B
Bead foam moulding 99
Bead-making process 36, 98
Biodegradability 71
Blow moulding 88, 99
Blowing agents 31
C
Cellulose 109
Cellulosic polymers 99, 100, 101
Chlorofluorocarbons 11
Coating, hydrophobicising 18
Copolymerisation 22, 58
Crystallisation 61, 78, 83, 84, 85, 97, 98
Cold 84
Cushioning performance 23, 24
D
Dewatering 7
Differential scanning calorimetry 61, 99
125
Update on Mouldable Particle Foams
Dimethylphenylphosphonate 13
Dihydro-oxa-phosphaphenanthrene oxide 14, 15
E
Ethylene vinyl alcohol 95
Ethylene-bis-stearamide wax 78
Ethylene-vinyl acetate 55
Expanded polyethylene 55, 64, 109
Mouldable beads 53
Expanded polyolefin 62, 63, 65, 74
Bead products 62
Moulded foams 51
Expanded polypropylene 52, 55, 56, 61, 63, 80, 98, 109
Expanded polystyrene 2-4, 7, 10-17, 19, 21, 23, 25-28, 31, 32,
38, 40, 52, 54, 55, 59, 60, 62, 64, 65, 69, 74, 86, 90, 93, 94,
108, 110
Beads 7, 23, 36
Blowing agents 27
Industry 28, 60, 108
Low-pentane developments 28
Moulding 38, 39
Packaging 23
Unexpanded beads 7
Extruded foamed sheet 15, 34
Extruded polystyrene process 35, 36
Extrusion 8, 13, 17-21, 31, 37, 51, 58, 99
F
Fibre spinning 99
Fire retardation 12
Foam moulding 9, 101
Foam nucleation 38
Foam products 10
Foaming 1, 31
Assisting agent 29
In-mould 89
126
Subject Index
G
Gas impregnation process 87
Gelatinising 91
Ground stabilisation 1
H
Hexabromocyclododecane 11, 13, 14, 17
High melt strength 56
Hydrochlorofluorocarbon 11, 53
Hydrolysis 76, 90
Hygroscopic 91
I
Impregnation 34, 59, 84, 85, 86, 98
Injection moulding 9, 26, 88, 99
J
Japan Styrene Paper Process 53
K
Knudsen Effect 20
L
Life cycle analysis 69
Linear low-density polyethylene 55
Lost wax process 3
Low-density polyethylene 55, 58
M
Macroinitiator 23
Melt process 72, 98
Melt rheology 52
Metal casting 3
Micropelletisation 31, 37, 60
Mouldable bead foams 3
127
Update on Mouldable Particle Foams
O
Olefinic oligomer 19
Olefinic polymer 26
P
Particle foam industry 1
Pelletiser 36, 60
Polylactic acid 76, 81, 83
Recycling 90
Plasticisation 29, 30, 32, 34, 83
Plasticisers 80
Plastics foam industry 1
Plastics packaging 69
Plastics processing 9
Polybutylene succinate 80
Polycaprolactone 80, 102
Polydimethylsiloxane prepolymer 22, 23
Polyethylene bead foam processes 53
Polyethylene terephthalate 76
Amorphous 77
Polyhydroxyalkanoates 70, 96
Polyhydroxybutyrate 97
Polyhydroxybutyrate-co-hydroxyvalerate 97
Polyhydroxyvalerate 97
Polylactic acid 70, 109
Polymeric matrix 20
Polymers, sustainable 96, 109
Polymerisation 7, 8, 10, 18, 21, 25, 27, 31, 33, 36, 37, 76
Suspension 7, 8, 18, 19, 31, 35, 36, 37
128
Subject Index
R
Recycling 40, 69, 71, 96
Resorcinol 14
Resorcinol diphosphate 15
S
Self-nucleation 61
Sheet extrusion foaming 57, 81
Styrene-maleic anhydride 23
T
Thermal insulation 1
Thermoforming 56
Thermoplastic polymers 1
Thermoplastic starch 81, 90
Triphenyl phosphate 13, 14
V
Volatile organic compounds 27, 28, 108
129
Update on Mouldable Particle Foams
W
Waste packaging 109
Z
Ziegler-natta catalysts 57
130
Published by iSmithers, 2009
This update summarises the present status of particle foam technology and
how specific challenges have already driven its development. This includes
the potential threats to the fire retardants and blowing agents which have
been used for many years.
The potential for particle foams made from ‘renewable’ polymers such as
starch, polylactic acid, polyhydroxyalkanoates and cellulosics is also covered.
For each of these, existing technology is reviewed, together with the issues
for research and development.