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V. A. Fomin and V. V.

Guzeev

Biodegradable Polymers, Their Present State and


Future Prospects

V.A. Fomin and V.V. Guzeev


FGUP “NII polimerov”, Dzerzhinsk, Russia

At the end of the 20th century the worldwide production of synthetic


plastics reached 130 million t/year(1, 2). One of the rapidly growing areas
for use of plastics is packaging. Since as early as 1975, polymers
occupied third place after glass, paper and cardboard, in usage for
packaging(3).
Out of total plastics production, 41% is used in packaging, and 47%
of this quantity is used in the packaging of foodstuffs(4, 5). Convenience and
safety, low price and good aesthetic qualities are the conditions determining
rapid growth in the use of plastics for manufacture of packaging.
Whereas glass containers, as a rule, are reused, and paper packaging
undergoes decomposition in natural conditions, packaging made of
synthetic polymers, amounting to 40% of domestic refuse, is practically
“eternal” – it does not readily decompose, and the question of what to do
with plastics refuse is becoming a global environmental problem(6-9). The
world’s ecological situation and apparently the rates and directions for
development of the production of synthetic plastics in the 21st century
will largely depend on solving the problem of plastics wastes. Otherwise
we shall be buried in plastics refuse.
Two main approaches are now being developed actively for keeping
the environment free from plastics wastes:

- burial (storage of wastes at landfill sites);


- utilisation.

Disposal of plastics wastes in landfill is a time bomb, with today’s


problems being shifted onto the shoulders of future generations.
Utilisation is a more benign approach, which can be divided into a
number of main trends:

- incineration;
- pyrolysis;
- recycling (by reprocessing).

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Biodegradable Polymers, Their Present State and Future Prospects

However, neither incineration nor pyrolysis of waste containers and


packaging, and of plastics in general, improves the environmental
situation in any fundamental way(10). Recycling solves the problem to
some extent, but even so it requires considerable expenditure of labour
and energy: removal of plastic containers and packaging from domestic
refuse, separation according to types of plastics, washing, drying,
grinding and, only then, reprocessing to the final article.
To promote the recycling of waste plastics, especially from containers
and packaging, many countries are adopting regulations making the
collection and recycling of plastics containers and packaging a legal
requirement(11, 12). Thus, European directives call for the use of 15% of
secondary plastics in the manufacture of plastics packaging, whereas in
Germany the quota is 50% but is set to increase to 60%. Experts consider
that this is technically impossible, because the use of up to 25% of
secondary plastics is only possible for non-food and transport packaging,
but not for the packaging of food products(13).
It should be pointed out that collection and reprocessing of polymer
containers and packaging, makes the packaging more expensive and the
quality of the recycled polymer is also lower than that of the material
produced directly by the primary manufacturer(14). Furthermore, not
every consumer is agreeable to using packaging from recycled polymer.
Even if we assume that a considerable proportion of containers and
packaging will be recycled, there is still the question of how many times
recycling is permissible, after which the time comes for disposal in landfill
or, if possible, by incineration; in either case, the ecological problems
affecting the environment will be intensified(7).
A radical solution to the problem of “polymer waste”, according to the
experts, is the development and adoption of an extensive range of
polymers that will, in suitable conditions, biodegrade to components that
are harmless to the environment and the life it sustains(9,15-23).
Biodegradability of high molecular compounds should be given priority,
as this will obviate many of the problems of “plastics waste”, resulting
from the use of polymer containers and other articles made of polymers(24).
An assessment of the current situation in the development and
application of biodegradable plastics reveals three main trends in research
and development in this area(6,25,26):

- polyesters of hydroxycarboxylic acids;


- plastics based on reproducible natural polymers;
- imparting biodegradability to industrial high-molecular synthetic
materials.

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V. A. Fomin and V. V. Guzeev

BIODEGRADABLE POLYESTERS

Analysis of the literature on the development of biodegradable polymers


in recent years points to the active development of the production of
polymers based on hydroxycarboxylic acids(27). Such enthusiasm for this
class of compounds arises from the fact that, as long ago as 1925, it was
established that polyhydroxybutyric acid is a nutrient and a medium for
sustaining various species of microorganisms. Under their action, a
polymer based on hydroxybutyric acid decomposes to carbon dioxide and
water(28-30). Polyesters based on other hydroxycarboxylic acids: glycolic,
lactic, valeric or caproic, exhibit similar behaviour (31-33).
Production of the corresponding polyesters of the above acids is based on
the use of their dimeric derivatives – glycolides and lactides in the case of
glycolic and lactic acids, or β-, γ- or ε-lactones for the other acids mentioned(34).
Currently one of the most promising biodegradable plastics for use in
packaging is polylactide – a condensation product of lactic acid(21,35-39).
This is mainly because the lactide and polylactide are obtained both by
synthetic routes, and by fermentation of sugar dextrose or of maltose,
grain wort or potato wort, which are renewable raw materials of
biological origin(34).
Polylactide biodegrades in compost in a month, and is assimilated by
microbes in sea water(40,41).
An important advantage of polylactide is that it is a transparent,
colourless thermoplastic polymer that can be processed by all the
methods used for processing known thermoplastics. Trays and plates can
be thermoformed from sheet, and it is possible to produce film, fibre,
packaging for food products, and implants for use in medicine(39). With
appropriate plasticisation, polylactide becomes elastic and resembles
polyethylene, plasticised poly(vinyl chloride) or polypropylene(40,42,43).
The service life of the polymer increases with decrease of monomer in its
composition, as well as after orientation, which increases its strength,
elastic modulus and thermal stability(44). Despite all these advantages of
polylactide its wide application as a polymer for everyday and industrial
uses has until recently been held back by the small production volumes,
low productivity of the production lines and, in consequence, high price
of the product.
Accordingly, developers of polyesters are now paying particular
attention to problems of lowering the price of biodegradable products by
creating highly productive manufacturing processes(45-47). The American
company Cargill Inc. is active in the area of improving the technology for
manufacture of lactic acid(40,48). On the basis of lactic acid, it developed the

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Biodegradable Polymers, Their Present State and Future Prospects

production of Eco-Pla biodegradable polymer, sheets of which are


comparable to polystyrene in impact strength. Coatings and films are
characterised by great strength, transparency, gloss, an acceptable
extrusion temperature above 200°C, and they have a low coefficient of
friction. The film heat-seals well, and furthermore it can biodegrade when
composted.
Following the development work, Cargill Inc. commissioned plant for
production of polylactide by fermentation of corn (maize) dextrose with
capacity of up to 6000 t/year. Its future plans include expanding output
to 50 to 150 thousand t/year and lowering the price of polylactide from
250 to 2.2 $/kg.
The Dutch company CSMN is now ready to produce 34,000 t/year
of lactic acid, with a possible subsequent doubling of capacity. The
technology for production of the acid was developed and patented by the
combined company Purac-Gruppe, which supplies lactic acid to the
world market under the PURAC trademark.
With the aim of lowering the cost of polymer based on lactic acid, the
Japanese company Mitsui Toatsu commissioned pilot plant for single
stage production of polylactide(49). The resulting product is a heat resistant
polymer with properties better than those of the plastic obtained in the
two stage process. The price of the new material is 4.95 $/kg.
On the basis of this polylactide, the company Dai Nippon developed
rigid film, comparable in properties to polystyrene, and flexible film
comparable to polyethylene.
The Finnish company Neste, has been actively engaged in research
into technology for production of polymers based on polylactic acid since
1991. It has undertaken comprehensive investigations of the physico-
mechanical properties of polylactide with molecular weight of 5000 to
10000 and is developing applications for this polymer(50).
In addition to polylactide, among polyesters capable of biodegradation,
mixtures of hydroxycarboxylic acids find particularly wide application,
such as poly-3-oxybutyrate and copolymer of poly-2-oxybutyric acid with
poly-3-oxyvaleric acid, which are made by the British company Zeneca
Bioproducts PLC. In 1995 the company produced 75 tonnes of Biopol
biodegradable polymer at a price of 13.5 DM/kg, which is 5 to 7 times
dearer than polyethylene, polypropylene, polystyrene or PVC and 1.5 to
2 times dearer than polyamide(27,51-54).
As can be seen, current prices for biodegradable plastics are quite high,
especially when compared with large tonnage synthetic polymers, and
lowering the cost of biodegradable articles is still one of the most urgent
problems. It is the increase in output tonnage of these plastics that

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V. A. Fomin and V. V. Guzeev

accounts for the unremitting search for the most effective bacteria among
the enormous number currently available(55). Good results have already
been achieved, with removal of 50 to 60 kg of polymer per cubic metre
of fermentation volume per day.
With an optimum fermentation process, minimum costs of substrate,
optimum plant design and appropriate production volumes, the cost of
biodegradable polymer can be brought down to 3 DM/kg.
The fermentation substrates most commonly used are sugar, organic
acids, and alcohols.
In addition to polymers obtained on the basis of individual
hydroxycarboxylic acids, or their copolymers, possessing guaranteed
biodegradability, studies are actively in progress for using polyoxycarboxylic
acids together with various synthetic products(56-58) and natural polymers
as initiators of biodegradability of the entire composition. The latter
makes it possible to endow an article with properties of biodegradability,
lower its cost and ensure high physico-mechanical properties.
Studies are being pursued particularly actively for developing
biodegradable materials for packaging, films, fibres, products for gardens
and orchards, consisting of a principal biodegradable polymer and synthetic
polyesters based on industrial dicarboxylic acids and glycols(59-61). The basic
principle in compounding is to maintain acceptable proportions, which
provide both the utility properties and capacity for biodegradation during
composting of the used article.
Since the rate of enzymatic breakdown of a polylactide mixture largely
depends on the nature of the additive and its proportion in the composition,
and on the physical condition of the sample, selection of an optimum
composition requires investigation of all these parameters(62,63). This is
very evident from the example of film produced by extrusion from a
polylactide-polyvinylacetate mixture with proportions ranging from 100:0
and from 0:100 respectively. The rate of decomposition of the film
decreases sharply as the proportion of polyvinylacetate in its composition
is increased. There is 52% decomposition of polylactide film in 10 hours,
but on adding 5 to 10% of polyvinylacetate there is just 8% decomposition
in 60 hours, and when the mixture contains 30% polyvinylacetate there
is hardly any biodegradation of the film(64).
The dependence of the rate of biodegradation on the method of
production of the film is in the following order: film after relaxation >
oriented, extruded > fixed-annealed > annealed at 90°C for 9 minutes.
This order of variation in biodegradability can be explained by the
increased crystallinity and some degree of migration of polyvinylacetate
to the film surface during annealing.

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Biodegradable Polymers, Their Present State and Future Prospects

It should be pointed out that in recent times there has been active
development of biodegradable (co)polymers not only for containers,
packaging and for medical uses(65-71), but also polymeric materials for a
great variety of applications: adhesives(72,73), paints(74), engine lubricants(75),
materials for fishing(29), in construction(6) and in agriculture(76,77). Both pure
polylactides, and copolymers of lactic acid with other derivatives from a
number of hydroxycarboxylic acids are used(78-83).
It can already be said that, because of their ability to biodegrade,
polyesters based on the aforementioned acids have tremendous potential
for capturing market share for containers, packaging, throw-away
utensils, healthcare products, and in agriculture.
This might all become reality in the near future, especially if, in addition
to comprehensive efforts to lower their prices, legislative measures are also
taken to restrict the use of non-biodegradable plastics for the purposes
mentioned above, which form the basis of the “polymer waste”(72,76).

BIODEGRADABLE PLASTICS BASED ON NATURAL


POLYMERS

Although biodegradable polyesters with the necessary commercial


properties can only be obtained on the basis of hydroxycarboxylic acids,
plastics whose composition includes starch, cellulose, chitosan or protein
are, as a rule, composite materials, containing a great variety of additives.
Priority must be given to solving the problem of the proportions of the
components, above all ensuring biodegradability of the system, high
physico-mechanical properties and an acceptable price.
Among the natural compounds, starch is used the most widely in
biodegradable packaging materials(84-92).
To obtain, from a mixture of starch and pectin, a water-soluble film that
can be broken down by bacteria, plasticisers (e.g. glycerol or
polyoxyethyleneglycol) are included in the composition. It has been
observed that the film becomes more brittle as the starch content is
increased(93).
Sheet extruded from a composition containing, in addition to starch,
amylose and a small amount of weak acids, is used for making packaging
products by blow moulding(94,95).
Compositions containing a mixture of high-amylose and ordinary
starch, plasticised with glycerol, urea and polyethyleneglycol with molecular
weight above 3000, are processed in a twin screw extruder(96). The
granules obtained are extruded into film in the form of tubing with blow-

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V. A. Fomin and V. V. Guzeev

up ratio of 3.0, shrinkage 14% and strength 10 MPa. The compostable,


biodegradable films produced are used in agriculture and for packaging.
In order to lower the cost of biodegradable materials for everyday
applications: packaging, agricultural film for mulching, and refuse sacks,
it is recommended to use unpurified starch, mixed with poly(vinyl alcoho)l
and talc(97) and other additives(98-101).
Foamed sheet and throw away utensils are produced from a composition
containing granulated starch and an aqueous solution of poly(vinyl
alcohol) (102). The best indices for strength, flexibility and water resistance
were obtained with compositions containing 10 to 30% poly(vinyl
alcohol). A respirometric study of the composition’s behaviour in soil
showed that the mixture rapidly biodegraded in one week.
There have also been proposals to produce foamed products for
packaging on the basis of two biodegradable components: starch and
polyester of hydroxycarboxylic acids(103,104).
As can be seen, even though starch itself is biodegradable, in order to
accelerate biodegradation and obtain articles with specified properties,
polymers based on polyester are included in the composition in addition
to starch(98,105-111). Film obtained from a mixture of starch and polylactide
decomposes in compost at 40°C in seven days(112).
Without impairing their biodegradability, water resistant compositions
are produced from a mixture of esters of starch and polyoxyalkyleneglycol,
in which some of the polyethyleneglycol is replaced by polyoxybutyrate
with molecular weight of 1000 to 10000(113). Biodegradable nappies and
sanitary pads with good absorbency for liquids are produced on the basis
of a hydrophilic composition containing degraded starch impregnated with
a copolymer of ethylene with vinyl alcohol and aliphatic polyesters(114-116).
Film based on this material possesses great strength, and retains its
properties when held at a temperature of 50°C for 3 months. This film
is used in agriculture for mulching and in the packaging of food products.
As well as carrying out scientific research into the development of
compositions and everyday applications of biodegradable plastics
containing starch(117-120), some companies have already embarked on
practical application of these materials.
On the basis of starch, the company Biotec GmbH manufactures
compostable plastics for various fields of application:

- a castable bioplastic in the form of granules for casting disposable articles;


- foamed materials for packaging food products;
- granules for making compostable flat films and tubing: Bioflex.

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These materials are promising for everyday application, as they are


extremely ecofriendly and have the ability to decompose in compost at
30°C in 2 months, with formation of decomposition products that are
favourable for plants.
Within the framework of a programme of environmental protection,
the Czech company Fatra, in collaboration with starch producers and a
polymer institute, developed the Ecofol grade of compostable packaging
film based on starch plus a polyolefin(121). By using inexpensive components
it was possible to obtain finished film at a price of 70 Czech crowns/kg.
In the conditions of composting, this film breaks down in 3 to 4 months.
Other polysaccharides: cellulose and chitin, cellulose and starch(122,123)
are being actively developed as a renewable natural biodegradable raw
material for manufacture of thermoplastics.
Polymers obtained by the interaction of cellulose with an epoxy
compound and anhydrides of dicarboxylic acids decompose completely
in compost in 4 weeks(124). They are used as the basis for the moulding
of bottles, disposable utensils, and film for mulching.
Multilayer packaging materials that are resistant to high and low
temperatures are produced from cellulose film adhesively bonded with
starch to greaseproof paper, which is permitted to be in contact with food
products(125). This packaging can be used when baking products in electric
or microwave ovens.
Binary and ternary mixtures, for moulding and casting a variety of
products: spectacle frames, handles for tools, toothbrushes, films and
fibres, are obtained from a cellulose ester, an aliphatic polyester and a
biodegrading additive of monocrystalline cellulose or starch in an amount
not exceeding 50% of the total mass(126).
To increase the biodegradability of materials based on cellulose esters,
it is recommended that the composition should include polyesters of citric
acid or cellulose acetate partially transesterified with 6-hydroxycaproic
acid(127-129).
Compostable materials obtained from a mixture of plant products and
natural raw materials, where the main component is cellulose or its
derivatives, are used as starting material for the manufacture of disposable
articles for packaging and essential goods(130,131).
However, biodegradable plastics are being developed using not only
cellulose, but other plant products as well, in particular lignin and lignin-
containing substances together with protein and other additives(132).
For making biodegradable polymeric materials for use in agriculture,
Japanese researchers(133) use thermomechanically treated wood pulp in

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V. A. Fomin and V. V. Guzeev

a composite with polyvinylacetate and glycerol.


Compositions containing chitosan and cellulose have recently been
attracting special attention from developers. These yield biodegradable
plastics, and film with good strength and water resistance, when the
mixture contains 10 to 20% chitosan(134). Thin films break down in the soil
in 2 months, dissolve completely and disappear.
A ternary composite of chitosan, microcellulose fibre and gelatine is
used for making films with increased strength, which can be broken down
by microorganisms when buried in the ground. They are used for
packaging and for the moulding of trays and films for mulching(135). The
semi-transparent film has dry strength of 133 N/mm2 and wet strength
of 21 N/mm2.
The company, Research Development (Japan), has introduced new
technology for production of biodegradable film(136). It is based on
macromolecules of chitosan, which is extracted from the shells of crabs,
prawns and molluscs, plus cellulose and starch. All three components are
mixed with acetic acid with heating, yielding a solution from which film
is obtained by casting; this film decomposes in the soil or in sea water in
a few months(137).
The biodegradability of film varies considerably depending on the
methods of treating the chitosan. Thus, film based on chitosan acylated
at the NH2 groups decomposes much faster, in an aerobic municipal
compost, than cellophane or poly(hydroxybutyrate)valerate films(138,139).
The ability of modified chitosan to speed up decomposition was utilised
in the production of film based on polyethylene with 10% chitosan,
which, according to the researchers, leads to complete decomposition of
the composition in 28 days.
Natural proteins are also attracting the attention of developers of
biodegradable plastics. A film based on zein, a hydrophobic protein, has
been developed for wrapping moist food and for making boxes for food
products(140).
Hardening of dried gelatine films in an atmosphere of formaldehyde
vapours has been used for making polymer films, which are also
plasticised with glycerol(141). Depending on the amount of glycerol added,
there is increase in elasticity and flexibility, elongation of the film and
absorbability of water vapour. It has been concluded that the
biodegradability of the film depends both on the glycerol content and on
the degree of crosslinking.
Methacrylated gelatine is also used in the production of biodegradable
material for packaging of food products, perfumery(142) and pharmaceuticals(143).
Production of thermoplastic biodegradable compositions with other types of

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Biodegradable Polymers, Their Present State and Future Prospects

protein has also been suggested: casein(144,145), derivatives of serine(146), and


keratin-containing natural products(147).
The company Showa (Japan) has developed a biodegradable polymer
for the outer casing of televisions and personal computers(148). The
polymer is a type of thermoset, obtained on heating an amine resin with
a protein, though the composition is not discussed in detail. The
proposed material has high heat resistance, strength and elasticity; it
decomposes in water and under the action of soil bacteria.
The use of natural polymers (e.g. polysaccharides, proteins) for
making biodegradable plastics is an interesting trend mainly because the
raw material resources are constantly renewable, and virtually unlimited.
The principal task facing researchers is to develop biodegradable
composites giving the required properties, similar to the multi-tonnage
synthetic polymers.

SYNTHETIC BIODEGRADABLE POLYMERS

Although, in the field of biodegradable polymers, there is active


development for production of polyesters based on hydroxycarboxylic
acids, as well as composites employing natural polymers, an important
area of research is the problem of imparting properties of biodegradability
to existing multi-tonnage industrial polymers: polyethylene, polypropylene,
poly(vinyl chloride), polystyrene and poly(ethylene terephthalate).
The above polymers and articles made from them can last “forever”
with disposal in landfill, so the problem of making them biodegradable is
especially urgent. Currently there are three directions of active
development:

- molecules whose composition includes functional groups that


promote accelerated photodegradation of the polymer are
incorporated in the structure of biodegradable polymers(149,150);
- compositions of multi-tonnage polymers are produced with
biodegradable natural additives, which are able in some degree to
initiate the breakdown of the principal polymer;
- directed synthesis of biodegradable plastics based on industrially
produced synthetic products.

Photodegradable polymers include copolymers of ethylene with carbon


monoxide(151). Photoinitiators of the decomposition of basic polymer of
polyethylene or polystyrene are vinylketone monomers(152). By adding
them as a copolymer to ethylene or styrene at the rate of 2 to 5%, plastics

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V. A. Fomin and V. V. Guzeev

can be obtained with properties similar to polyethylene or polystyrene,


but which can undergo photodegradation under the action of ultraviolet
radiation in the range 290 to 320 nm.
Films that are convenient for mulching are obtained from polyolefins
by incorporating light-sensitive additives in the composition:
dithiocarbamate of iron and nickel(149) or the corresponding peroxides(153).
To speed up the photo- and biodegradation of films based on
polyethylene for agriculture, polypropylene or poly(ethylene terephthalate),
cellulose pulp, alkyl ketones or fragments containing carbonyl groups are
added to them(154). The films obtained last for 8 to 12 weeks, before they
start to photo- and biodegrade. The film residues disappear completely
during harrowing and ploughing, serving as soil conditioners, until they
are destroyed completely(155).
An anticipated and obvious technique for imparting biodegradability to
widely used synthetic polymers is, at first glance, compounding them with
known biodegradable components.
As a rule(156), starch, polyesters and other biodegradable additives(9,157-162)
are used as sources of nutrients for microorganisms in composites
consisting of industrial polymers that are widely used in everyday
applications, especially for containers and packaging. However, even
though these composites, especially with polyethylene, are conventionally
classed as biodegradable(157), in reality they are not, because during
composting there is rapid decomposition of the starch, but in the majority
of cases the synthetic polymer does not undergo biodegradation(4,163,164).
It should be pointed out that recently the way of solving the problem
of biodegradability of synthetic polymers by including natural components
in their composition has begun to stagnate, as witnessed by the decrease
in number of publications on this subject.
The main trend in the production of biodegradable synthetic plastics
is now the synthesis of appropriate polyesters and polyester amides(165-168).
The two chemical giants BASF and Bayer AG are especially active in this
area(3,169-172).
Degradable copolyesters are obtained on the basis of aliphatic diols
and organic dicarboxylic acids. It has been established that their
susceptibility to biodegradation depends on the amount of terephthalic
acid in the polyester relative to the aliphatic acid, and is 30 to 55 mol.%.
With this ratio of the acid fragments, the polyester maintains
biodegradability and possesses physico-mechanical characteristics suitable
for practical application of the polymer(173,174).
On the basis of a polyester of this kind, in 1995 the company BASF
began producing the completely biodegradable plastic Ecoflex F, used in

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Biodegradable Polymers, Their Present State and Future Prospects

the manufacture of bags, agricultural film, healthcare film and for


laminating paper(175). In mechanical properties, Ecoflex F is comparable
to low density polyethylene. It is used for making film with high tearing
strength, flexibility, water resistance and permeability to water vapour. It
is processed by extrusion with blowing and cooling on the rolls, like low
density polyethylene, its deformability makes it possible to obtain thin
films (less than 20 mm), which do not require special treatment. Film from
Ecoflex F heat seals well, and can be printed on ordinary equipment(176).
Because the company uses its own raw material and production
facilities, it is able to produce granules of the synthetic polyester at a price
of 6.5-8.0 DM/kg, depending on grade. Composites containing
copolyester as the principal component, with high viscosity, are used for
making biodegradable foamed plastics for packaging.
BASF has also started making biodegradable plastics based on polyesters
and starch.
Since the second half of the 1990s, the company Bayer AG has been
manufacturing new thermoplastics BAK-1095 and BAK-2195(176,177),
based on polyester amide; these are compostable and biodegradable in
aerobic conditions. The proposed material has high adhesion to paper,
so it can be widely used for making moisture proof and weather proof
packaging, for use in the food industry and in agriculture(178,179). In
compost, with suitable moistening, bags made of BAK-1095 break down
in 10 days into biomass, carbon dioxide and water.
The other aliphatic polyester amide BAK-2195(180) can easily be
processed by injection moulding. It can contain fillers: cellulose, wood
flour, and starch, which give it sufficient rigidity and strength. The melting
point of the polyester amide is 175°C. The recommended applications
are flower vases and baskets, disposable utensils, and healthcare articles.
After use, these products are rapidly biodegraded in soil in a moist
environment, under the action of bacteria, fungi and moulds.
To lower the cost of materials based on polyesters and polyamides, the
companies are producing them using existing spare production capacity,
taking products already in regular industrial production as their raw
materials. Processing of these composites into the end products is carried
out in standard equipment. This approach enables the manufacture of
new ecofriendly polymers to be achieved with short lead times, and
largely solves the problem of lowering the price of biodegradable plastics,
thereby greatly reducing the problem of polymer waste from used
containers and packaging, with less disposal of polymers in landfill.
According to BASF, the potential West European market for
compostable, biodegradable materials made from poly(ester-amides),

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V. A. Fomin and V. V. Guzeev

copolyesters and their mixtures with starch is 200,000 tonnes/year.


Polyester film with structure similar to poly(butylene succinate), and
properties similar to those of polyethylene or polypropylene film, has
been developed by the Korean company Sun Kyong Ind.(181). This
biodegradable polymeric material combines adequate short term strength
in the finished article with its subsequent utilisation after use. Polymer film
of the Skyprene grade made from material of the above composition
decomposes in 60 days in soil, fresh water or sea water, with formation
of carbon dioxide and water.
A transparent, biodegradable copolyester with good formability, for
production of film and sheet, is synthesised by polymerisation with ring
opening and transesterification of a lactide with aromatic polyesters
based on tere(iso)phthalic acid and aliphatic diols(182).
It should be noted that recently there has been active development of
biodegradable compositions containing both poly(ester amide) groups(183-189),
and urethane groups(190-193), carbonate groups(194,195) or especially fragments of
hydroxycarboxylic acids(196-198), which can be used as a basis for making a wide
range of compostable articles(199,200), possessing high physico-mechanical
properties and an acceptable price.

CONCLUSIONS

Analysis of research in the development of biodegradable plastics


indicates that some progress has been made in this area. With the
increasing consumption of polymers for containers and packaging, and
other disposable everyday articles, the problem of plastics waste and its
threat to the environment will continue to grow. In this connection, the
anticipated tightening up of legal requirements to restrict the use of
nonbiodegradable plastics as containers and packaging will be an even
greater incentive for developing a wide range of biodegradable
thermoplastics with the required properties and at a reasonable price.
In Europe, the involvement of government agencies along with large
chemical manufacturers to tackle the problem of biodegradable plastics
is proving successful for solving this complex problem. In addition to an
expansion of research in the area of known biodegradable plastics,
probably there will be new approaches to the problem of endowing large
tonnage synthetic polymers with bio- and photo-degradability.
Unfortunately, the problems of the development and practical
application of biodegradable plastics are not receiving sufficient attention
in the Russian Federation.

198 Progress in Rubber and Plastics Technology, Vol. 17, No. 3, 2001
Biodegradable Polymers, Their Present State and Future Prospects

REFERENCES

1. V. Glukhov: Khimiya i biznes, 1997, No. 25, p. 34-35


2. G.E. Zaikov et al.: Polym. News, 1996, Vol. 21, No. 9, p. 323-324
3. R. Hinterwaldner et al.: Coating, 1995, Vol. 28, No. 10, p. 364,
366-367, 370
4. N. Niessner: Kunststoffe, 1998, Vol. 88, No. 6, p. 874-876, 878-
880
5. A. Ckapelle: Kunststoffe, 1995, Vol. 85, No. 10, p. 1636, 1638-
1640
6. J. Otake: Kinzoku = Metals and Technol., 1996, Vol. 66, No. 1, p.
64-65
7. M. Nishiyama: Kino Dzaire = Funct. and Mater., 1990, Vol. 10, No.
1, p. 181
8. C.E. Carraher: Polym. News, 1996, Vol. 21, No. 7, p. 238-241
9. W. Bednarski et al.: Przem. spoz., 1997, Vol. 51, No. 2, p. 33-35
10. W. Kaminsky: Adv. Polym. Technol., 1995, Vol. 14, No. 4, p. 337-
344
11. S. Apotheker: Resour. Recycl., 1995, Vol. 14, No. 5, p. 35-40
12. Kunststoffe, 1996, Vol. 86, No. 10, p. 1424
13. Kunststoffe, 1996, Vol. 86, No. 4, p. 463
14. G. Menges: Polimeri, 1995, Vol. 16, No. 3, p. 95-101
15. V.A. Vasnev: Vysokomolek. soed. seriya B. 1997, Vol. 39, No. 12,
p. 2073-2086
16. S. Moore: Mod. Plast. Int., 1999, Vol. 29, No. 5, p. 38-39
17. L.P. Schreiber: Technica (Suisse), 1995, Vol. 44, No. 25-26, p. 20-
22
18. A.B. Zezin: Soros. obraz. zh., 1996, No. 2, p. 57-64
19. R. Hinterwaldner: Coating, 1997, Vol. 30, No. 5, p. 180-182
20. Mod. Plast. Int., 1999, Vol. 29, No. 6, p. 14
21. R.G. Sinclair: J. Macromol. Sci. A., 1996, Vol. 33, No. 5, p. 703
22. Y. Yoshikuni: Sen-i gakkaishi = Fiber, 1996, Vol. 52, No. 6, p. 237-
241
23. Vestnik khimicheskoi promyshlennosti, 1998, No. 4(8), p. 59-60
24. A.V. Makarevich et al.: Plast. massy, 1996, No. 1, p. 34-36
25. D. Hunkeler et al.: Polym. News, 1998, Vol. 23, No. 3, p. 93-94
26. Petorotekku = Petrotech., 1997, Vol. 20, No. 8, p. 651-656
27. Mod. Plast. Int., 1996, Vol. 26, No. 3, p. 86
28. K. Nakasaki et al.: Kagaku Kogaku = Chem. Eng. Jap., 1995, Vol.
59, No. 7, p. 496-497
29. T. Ikejima: Kagaku to Kogyo = Chem. and Chem. Ind., 1997, Vol.

Progress in Rubber and Plastics Technology, Vol. 17, No. 3, 2001 199
V. A. Fomin and V. V. Guzeev

50, No. 7, p. 1024


30. Wang Jing et al.: Huanjing kexue = Chin. J. Environ. Sci., 1998,
Vol. 19, No. 5, p. 52-5
31. C. Lefevre et al.: Chim. nouv., 1998, Vol. 16, No. 62, p. 1921-
1922
32. H. Eya et al.: Kobunshi ronbunshu = Jap. J. Polym. Sci. and
Technol., 1997, Vol. 54, No. 8, p. 463-470
33. J.-P. Tailleur: Usine nouv., 1998. Hors serie nov. p. 76-77
34. J. Still (Ed.): Monomers for polycondensation. Izd. Mir, Moscow,
1976, p. 253
35. Japanese Patent 2725870, publ. 1998
36. R. Schlicht: Kunststoffe, 1998, Vol. 88, No. 6, p. 888-890
37. West German patent application 4239781, publ. 1994
38. US Patent 5443780, publ. 1995
39. G. Bruce: Chem. Week, 1997, Vol. 159, No. 15, p. 32
40. M.H. Naitove: Plast. Technol., 1995, Vol. 41, No. 3, p. 15, 17
41. US Patent 5409751, publ. 1995
42. R.G. Sinclair: J. Macromol. Sci. A, 1996, Vol. 33, No. 5, p. 585-
597
43. US Patent 5424346, publ. 1995
44. US Patent 5585191, publ. 1996
45. US Patent 5821299, publ. 1998
46. US Patent 5563239, publ. 1996
47. US Patent 5444113, publ. 1995
48. Plasty a kauc., 1997, Vol. 34, No. 2, p. 59-60
49. Plasty a kauc., 1996, Vol. 33, No. 8, p. 246
50. J.F. Selin, M. Skog: Kemia-Kemi, 1997, Vol. 24, No. 9-10, p. 770-
773
51. M. Menner et al.: Chem. Ind., 1996, Vol. 119, No. 12, p. 16-17
52. Z. Gan et al.: Yingyong huaxue = Chin. J. Appl. Chem., 1997, Vol.
14, No. 2, p. 84-86
53. US Patent 5475063, publ. 1995
54. German application 19600095, publ. 1997
55. J. Yin et al.: Huagong xuebao = J. Chem. Ind. and Eng. (China),
1998, Vol. 49, No. 3, p. 353-357
56. International application 9801493, publ. 1998
57. German application 19706621, publ. 1998
58. US Patent 5567435, publ. 1996
59. Japanese Patent 2746525, publ. 1998
60. Japanese Patent 2704330, publ. 1998
61. European Patent 829503, publ. 1998

200 Progress in Rubber and Plastics Technology, Vol. 17, No. 3, 2001
Biodegradable Polymers, Their Present State and Future Prospects

62. W. Mizuno et al.: Kobunshi ronbunshu = Jap. J. Polym. Sci. and


Technol., 1996, Vol. 53, No. 9, p. 513-521
63. US Patent 5409772, publ. 1995
64. A.M. Gajria et al.: Polymer, 1996, Vol. 37, No. 3, p. 437-444
65. Patent RF 2144047, publ. 2000
66. European application 0736563, publ. 1996
67. US Patent 5747633, publ. 1998
68. US Patent 5733994, publ. 1998
69. US Patent 5489470, publ. 1996
70. G.E. Zaikov et al.: Plast. massy, 1999, No. 9, p. 43-46; 2000, No.
1, p. 31-36; 2000, No. 2, p. 28-33
71. G. Rafler et al.: Drugs made Ger., 1997, Vol. 40, No. 3, p. 94-98
72. R. Hinterwaldner: Coating, 1997, Vol. 30, No. 8, p. 274, 275,
278-282
73. German application 19703980, publ. 1998
74. German application 19541757, publ. 1997
75. US Patent 5658863, publ. 1997
76. Kunststoffe, 1998, Vol. 88, No. 4, p. 466
77. European Patent 816430, publ. 1998
78. US Patent 5536564, publ. 1996
79. US Patent 5824751, publ. 1998
80. US Patent 5618855, publ. 1997
81. Y. Kimura: Kagaku to kogyo = Chem. and Chem. Ind., 1998, Vol.
51, No. 5, p. 732-735
82. French application 2765228, publ. 1998
83. US Patent 5498692, publ. 1996
84. A.I. Suvorova et al.: Uspekhi khimii, 2000, Vol. 69, No. 5, p. 494-
503
85. Japanese Patent 2741476, publ. 1998
86. German application 19721460, publ. 1998
87. German application 19633474, publ. 1998
88. Japanese Patent 2749918, publ. 1998
89. Japanese Patent 2813470, publ. 1998
90. US Patent 5459258, publ. 1995
91. Japanese Patent 2739775, publ. 1998
92. European Patent 850988, publ. 1998
93. US Patent 5451673, publ. 1995
94. European application 0669369, publ. 1995
95. West German application 4418678, publ. 1995
96. German application 19512252, publ. 1996
97. US Patent 5322866, publ. 1994

Progress in Rubber and Plastics Technology, Vol. 17, No. 3, 2001 201
V. A. Fomin and V. V. Guzeev

98. Application RF 97121172, publ. 1999


99. European Patent 877773, publ. 1998
100.International application 9820073, publ. 1998
101.West German application 19520093, publ. 1996
102.R.L. Shorgen et al.: J. Appl. Polym. Sci., 1998, Vol. 68, No. 13,
p. 2129-2140
103.US Patent 5437924, publ. 1995
104.US Patent 5736586, publ. 1998
105.US Patent 5679421, publ. 1997
106.US Patent 5401778, publ. 1995
107.Application RF 97115455, publ. 1999
108.US Patent 5462983, publ. 1995
109.US Patent 5665786, publ. 1997
110.Japanese Patent 2742630, publ. 1998
111.Application RF 92016573, publ. 1997
112.US Patent 5444107, publ. 1995
113.West German application 4424415, publ. 1996
114.US Patent 5422387, publ. 1995
115.US Patent 5393804, publ. 1995
116.US Patent 5384187, publ. 1995
117.H. Schmidt: Allg. Pap.-Rdsch., 1996, Vol. 120, No. 1, p. 354-356
118.German application 19633476, publ. 1998
119.German application 19705376, publ. 1998
120.International application 9807782, publ. 1998
121.J. Janostik: Plasty a kauc., 1997, Vol. 34, No. 1, p. 27
122.Patent RF 2117016, publ. 1998
123.German application 19706642, publ. 1998
124.West German application 4404840, publ. 1996
125.Swiss Patent 688856, publ. 1998
126.US Patent 5580911, publ. 1996
127.US Patent 5556905, publ. 1996
128.US Patent 5720803, publ. 1998
129.West German application 4428211, publ. 1996
130.German application 19637565, publ. 1998
131.US Patent 5741875, publ. 1998
132.International application 9806785, publ. 1998
133.T. Iwanami et al.: Sen-I gakkaishi = Fiber, 1996, Vol. 52, No. 2, p.
50-56
134.M. Nashiyama: Kamipa gikyoshi, 1995, Vol. 49, No. 4, p. 671-685
135.Japanese application 4-59830, publ. 1992
136.STA Today, 1996, Vol. 8, No. 9, p. 9

202 Progress in Rubber and Plastics Technology, Vol. 17, No. 3, 2001
Biodegradable Polymers, Their Present State and Future Prospects

137.Atoms Jap., 1996, Vol. 40, No. 10, p. 19


138.Xu Jin et al.: Macromolecules, 1996, Vol. 29, No. 10, p. 3436-
3440
139.West German application 4427667, publ. 1996
140.US Patent 5585060, publ. 1996
141. T. Maeda et al.: Jap. J. Polym. Sci. and Technol., 1996, Vol. 53,
No. 8, p. 506-508
142.R. Hinterwaldner: Coating, 1996, Vol. 29, No. 10, p. 366, 368,
369
143.Plasty a kauc., 1997, Vol. 34, No. 1, p. 23
144.International application 9849237, publ. 1998
145.Japanese Patent 2819199, publ. 1998
146.Japanese Patent 2720424, publ. 1998
147.International application 9803591, publ. 1997
148.Techno Jap., 1996, Vol. 29, No. 6, p. 96
149.B.-H. Chang: Polym. News, 1997, Vol. 22, No. 9, p. 307-314
150.Application RF 94023952, publ. 1997
151.Polish Patent 173504, publ. 1998
152.S. Writer: Techno Jap., 1995, Vol. 28, No. 4, p. 10-32
153.US Patent 5763518, publ. 1998
154.Japanese Patent 2729214, publ. 1998
155.US Patent 5532298, publ. 1996
156.US Patent 5346929, publ. 1994
157.L. Contat-Rodrigo et al.: J. Non-Cryst. Solids, 1998, Vol. 235-237,
p. 670-676
158.US Patent 5853848, publ. 1998
159.US Patent 5446078, publ. 1996
160.US Patent 5496895, publ. 1996
161.A.A. Ol’khov et al.: Plast. massy, 2000, No. 4, p. 18-21
162.US Patent 5449708, publ. 1995
163.M. Poulicek: Bull Soc. roy. sci. Liege, 1995, Vol. 64, No. 6, p. 327-
343
164.H. Haschke et al.: Monatsh. Chem., 1998, Vol. 129, No. 3, p. 253-
279
165.German application 19615899, publ. 1997
166.International application 9812245, publ. 1998
167.German application 19645919, publ. 1998
168.German application 19640032, publ. 1998
169.R. Colvin: Mod. Plast. Int., 1995, Vol. 25, No. 9, p. 49
170.German application 19638488, publ. 1998
171.German application 4440850, publ. 1996

Progress in Rubber and Plastics Technology, Vol. 17, No. 3, 2001 203
V. A. Fomin and V. V. Guzeev

172.German application 19624641, publ. 1998


173.German application 4440837, publ. 1996
174.Gordian. 1996, Vol. 96, No. 4, p. 48
175.U. Seeliger: Plast. South. Afr., 1998, Vol. 27, No. 1, p. 18, 20
176.P. Mapleston: Mod. Plast. Int., 1998, Vol. 28, No. 5, p. 125
177.Galvanotechnik, 1996, Vol. 87, No. 6, p. 1995
178.Polym. News, 1998, Vol. 23, No. 4, p. 129-130
179.E. Grigat et al. Plast. South. Afr., 1997, Vol. 27, No. 4, p. 24, 26,
28
180.Osterr. Kunstst. Z., 1997, Vol. 28, No. 9-10, p. 239
181.Mod. Plast. Int., 1996, Vol. 26, No. 4, p. 98
182.US Patent 5403897, publ. 1995
183.Techno Jap., 1996, Vol. 29, No. 10, p. 107
184.US Patent 5661193, publ. 1997
185.German application 19535715, publ. 1997
186.Japanese Patent 2777243, publ. 1998
187.Japanese Patent 2760739, publ. 1998
188.Japanese Patent 2713108, publ. 1998
189.US Patent 5731402, publ. 1998
190.German application 19652037, publ. 1998
191.West German application 19517185, publ. 1996
192.German application 19645663, publ. 1998
193.International application 9855527, publ. 1998
194.German application 19547636, publ. 1997
195.International application 9812243, publ. 1998
196.German application 4440858, publ. 1996
197.Japanese Patent 2794353, publ. 1998
198.German application 19601912, publ. 1997
199.German application 19630232, publ. 1998
200.German application 19630233, publ. 1998

204 Progress in Rubber and Plastics Technology, Vol. 17, No. 3, 2001

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