Note: Descriptions are shown in the official language in which they were submitted.
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Stabilized moulding compositions of biologically degradable materials
The present invention relates to thermoplastic moulding compositions, which
are
stabilized against hydrolytic and microbial degradation, of biologically
degradable
polymers, a process for the preparation of concentrates based on thermoplastic
biologically degradable polymers, a process for the preparation of
thermoplastic
biologically degradable moulding compositions which are stabilized against
hydrolysis
and have an antimicrobial or microbistatic action, and the use of the moulding
compositions stabilized according to the invention as biologically degradable
materials
for the production of semi-finished products, films, injection mouldings, mono-
and
multifilaments, fibres, nonwovens and woven fabrics, and the shaped articles
or semi-
finished products, filins, injection mouldings, mono- and multifilaments,
fibres,
nonwovens and woven fabrics themselves produced therefrom.
Biologically degradable plastics are known (see, for example, EP-A 561 224, EP-
A
641 817). Hydrolysis stabilizers and microbicides and microbistatic active
compounds
are likewise known (see, for example, 9th corrected and improved edition of
Rompp
Chemie Lexikon on CD-ROM, version 1.0, Thieme Verlag, key words
"Stabilisatoren", "Mikrobizid", "Preventol ", "Carbodiimid").
Many biologically degradable materials are generally accessible to a
hydrolytic
degradation mechanism which proceeds not only in the presence of
microorganisms
living in the soil, water and compost, but also at a slow to moderate rate in
the
presence of moisture already during storage of the granules and during use of
the
products produced therefrom.
The object of the present invention is to control and in particular to slow
down this
premature degradation and loss of properties of the materials, without thereby
impairing the desired biological degradation of the finished components after
use to a
noticeable extent.
An object is fiuthermore to increase the storage stability and prolong the
usable life, in
particular under damp climate conditions, of the semi-finished products and
finished
components produced fiom the moulding compositions according to the invention.
It
has now been found that, by addition of additives and stabilizers to
biologically
degradable polymers, the start of the biological and hydrolytic degradation is
delayed
~z'/~ 32 ~~S
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such that long-term applications, e.g. in the building sector or in
landscaping, are
possible with these materials.
The invention provides thermoplastic biologically degradable moulding
compositions
S comprising biologically degradable polymers and at least one stabilizer
chosen from
group A 1 ) and A2)
Al) 0 to 50 wt.%, preferably 0.001 to 30 wt.%, and particularly preferably
0.05 to 5
wt.%, based on the total mixture, of stabilizers chosen from ax least one of
the
group consisting of hydrolysis stabilizers, such as e.g. aliphatic or aromatic
monomeric, oligomeric or polymeric carbodiimides, such as, for example,
urethanized carbodiimides, N,N'-dicyclohexylcarbodiimide, N-glycidyl-
phthalimide, 1,3-bis(1-methyl-1-isocyanato-ethyl)benzene with terminal
isocyanate-, urea- and/or urethane groups, bis(trimethylsilyl)-carbodiimide,
polyfunctional oxazolines, polyfunctional epoxides and polyfunctional
isocyanates, preferably chosen from the group consisting of polymeric or
polymer-bonded carbodiimides, which are obtainable, for example, from the
polymerization, which takes place by conventional catalysts with splitting off
of carbon dioxide, of aromatic or aliphatic isocyanates, such as, for example,
2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropyl-2,4-diisocyanatobenzene,
naphthalene 1,5-diisocyanate, 2,4-diisocyanato-3,5-diethyltoluene, 4,4'-
methylene-bis(2,6-diethylphenyl isocyanate), 4,4'-methylene-bis(2-ethyl-6-
methylphenyl isocyanate), 4,4'-methylene-bis(2-isopropyl-6-methylphenyl
isocyanate), 4,4'-methylene-bis(2,6-diisopropylphenyl isocyanate) and 4,4'-
methylene-bis(2-ethyl-6-methylcyclohexyl isocyanate) and
A2) 0 to 50 wt.%, preferably 0.001 to 30 wt.%, and particularly preferably
0.01 to 5
wt.%, based on the total mixture, of a stabilizer chosen from at least one of
the
group consisting of antimicrobial agents, for example thiurams,
thiophthalimides, sulfamides, urea derivatives, triazole derivatives,
triazoline
derivatives, benzimidazole derivatives, benzimidazolylcarbamic acid
derivatives, aryl sulfones, sulfenylsulfamides, phenols and phenolates,
thiobenzothiazole derivatives, amino alcohols, isothiazolinones,
benzothiazoles
and pyrethroids and
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B) 0 to 85 wt.%, based on the total mixture, of fillers and reinforcing
substances,
preferably naturally occurring mineral, synthetic inorganic or naturally
occurring organic substances based on renewable raw materials or synthetic
organic and metallic substances or a mixture of several of these constituents.
Carbodiimides which are approved for contact with foodstuffs or a mixture
thereof are
particularly preferred.
The invention also provides additive concentrates based on the biologically
degradable
polymers themselves. Concentrates to date, which are based, for example, on
polyethylene or polyesters, do not meet the requirement of complete biological
degradation. Moreover, the melting ranges of conventional concentrates, for
example
based on aromatic polyesters, and the biologically degradable, usually
aliphatic or only
partly aromatic, plastics differ widely, so that a homogeneous incorporation
of the
conventional known concentrates into biologically degradable polymers is made
difficult. The concentrates based on biologically degradable plastics have the
advantage of good compatibility of the materials and the associated
homogeneous
distribution of the additives in the particular matrix. The concentrates in
general
comprise up to 40 wt.%, preferably 1 to 30 wt.%, in particular 5 to 20 wt.%
stabilizer,
based on the total mixture.
Suitable biologically degradable polymers are, for example, aliphatic
polyesters or
copolyesters, aromatic polyesters or copolyesters, aromatic-aliphatic
copolyesters,
polycarbonates, polyester-carbonates, aliphatic or partly aromatic polyester-
urethanes,
polyester-amides, polyether-amides, polyether-ester-amides,~cellulose ethers,
cellulose
ether-esters, thermoplastic starch, starch derivatives or copolymers or a
mixture of
these components.
The following polymers are preferably suitable:
Aliphatic or partly aromatic polyesters from
A) aliphatic bifimctional alcohols, preferably linear C2 to Cto dialcohols,
such as,
for example, ethanediol, butanediol or hexanediol, particularly preferably
butanediol, and/or optionally cycloaliphatic bifimctional alcohols, preferably
having 5 or 6 C atoms in the cycloaliphatic ring, such as, for example,
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cyclohexanedimethanol, and/or, instead of some or all of the diols, monomeric
or oligomeric polyols based on ethylene glycol, propylene glycol or
tetrahydrofuran or copolymers thereof having molecular weights of up to
8,000, preferably up to 4,000, and/or optionally small amounts of branched
bifunctional alcohols, preferably C,-C,Z alkyldiols, such as, for example,
neopentylglycol, and additionally optionally small amounts of alcohols of
higher functionality, .such as, for example, 1,2,3-propanetriol or
trimethylolpropane, and from aliphatic bifunctional acids, preferably CZ C,2
alkyldicarboxylic acids, such as, for example and preferably, succinic acid or
adipic acid, and/or optionally aromatic bifunctional acids, such as, for
example,
terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid, and
additionally optionally small amounts of acids of higher functionality, such
as,
for example, trimellitic acid, or
B) building blocks with acid and alcohol functional groups, preferably having
2 to
12 C atoms in the alkyl chain, for example hydroxybutyric acid,
hydroxyvaleric acid or lactic acid, or derivatives thereof, for example E-
caprolactone or dilactide, or a mixture and/or a copolymer of A and B, the
aromatic acids making up a content of not more than 50 wt.%, based on all the
acids;
Aliphatic or partly aromatic polyester-urethanes from
C) aliphatic bifunctional alcohols, preferably finear CZ to C,°-
dialcohols, such as,
for example, ethanediol, butanediol or hexanediol, particularly preferably
butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably
with a CS or C6 cycloaliphatic ring, such as, for example, cyclohexane-
dimethanol, and/or, instead of some or all of the diols, monomeric or
oligomeric polyols based on ethylene glycol, propylene glycol or
tetrahydrofuran or copolymers thereof having molecular weights of up to
4,000, preferably up to 1,000, and/or optionally small amounts of branched
bifunctional alcohols, preferably C3 C,2-allcyldiols, such as, for example,
neopentylglycol, and additionally optionally small amounts of alcohols of
higher functionality, preferably C3 C,Z alkylpolyols, such as, for example,
1,2,3-propanetriol or trimethylolpropane, and from aliphatic bifunctional
acids,
preferably C2 C,2-alkyldicarboxylic acids, such as, for example and
preferably,
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succinic acid or adipic acid, andlor optionally aromatic bifimctional acids,
such
as, for example, terephthalic acid, isophthalic acid or
naphthalenedicarboxylic
acid, and additionally optionally small amounts of acids of higher
functionality, such as, for example, trimellitic acid, or
D) building blocks with acid and alcohol fiuictional groups, preferably having
2 to
12 C atoms, for example hydroxybutyric acid, hydroxyvaleric acid or lactic
acid, or derivatives thereof, for example s-caprolactone or dilactide, or a
mixture and/or a copolymer of C and D,
the aromatic acids making up a content of not more than 50 wt.%, based on all
the acids;
E) the reaction product of C and/or D with aliphatic and/or cycloaliphatic
bifunctional isocyanates and additionally optionally isocyanates of higher
functionality, having preferably 1 to 12 C atoms, or 5 to 8 C atoms in the
case
of cycloaliphatic isocyanates, e.g. tetramethylene diisocyanate, hexamethylene
diisocyanate or isophorone diisocyanate, optionally additionally with linear
and/or branched and/or cycloaliphatic bifunctional alcohols and/or alcohols of
higher functionality, preferably C3 C,2-alkyldi- or -polyols, or 5 to 8 C
atoms in
the case of cycloaliphatic alcohols, e.g. ethanediol, hexanediol, butanediol
or
cyclohexanedimethanol, and/or optionally additionally with linear and/or
branched and/or cycloaliphatic bifunctional amines and/or amino alcohols
and/or amines and/or amino alcohols of higher fimctionality, having preferably
2 to 12 C atoms in the alkyl chain, e.g. ethylenediamine or aminoethanol,
and/or optionally fiuther modified amines or alcohols, such as, for example,
ethylenediaminoethane-sulfonic acid, as the free acid or as a salt,
the ester content C) and/or D) being at least 75 wt.%, based on the sum of C),
D) and E).
Aliphatic or aliphatic-aromatic polyester-carbonates fi-om
F) aliphatic bifimctional alcohols, preferably linear C2 to C,°-
dialcohols, such as,
for example, ethanediol, butanediol or hexanediol, particularly preferably
butanediol, and/or optionally cycloaliphadc bifunctional alcohols, preferably
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having 5 to 8 C atoms in the cycloaliphatic ring, such as, for example,
cyclohexanedimethanol, and/or, instead of some or all of the diols, monomeric
or oligomeric polyols based on ethylene glycol, propylene glycol or
tetrahydrofuran or copolymers thereof having molecular weights of up to
4,000, preferably up to 1,000, and/or optionally small amounts of branched
bifunctional alcohols, preferably with CZ C,Z alkyldicarboxylic acids, such
as,
for example, neopentylglycol, and additionally optionally small amounts of
alcohols of higher functionality, such as, for example, 1,2,3-propanetriol or
trimethylolpropane, and from aliphatic bifunctional acids, such as, for
example
and preferably, succinic acid or adipic acid, and/or optionally aromatic
bifunctional acids, such as, for example, terephthalic acid, isophthalic acid
or
naphthalenedicarboxylic acid, and additionally optionally small amounts of
acids of higher functionality, such as, for example, trimellitic acid, or
1 S G) building blocks with acid and alcohol functional groups, preferably
having 2 to
12 C atoms in the alkyl chain, for example hydroxybutyric acid,
hydroxyvaleric acid or lactic acid, or derivatives thereof, for example E-
caprolactone or dilactide, or a mixture and/or a copolymer of F) and G),
the aromatic acids making up a content of not more than 50 wt.%, based on all
the acids;
H) a carbonate content which is prepared from aromatic bifunctional phenols,
preferably bisphenol A, and carbonate donors, for example phosgene, or a
carbonate content which is prepared from aliphatic carbonic acid esters or
derivatives thereof, such as, for example, chlorocarbonic acid esters, or
aliphatic carboxylic acids or derivatives thereof, such as, for example, salts
and
carbonate donors, for example phosgene,
the ester content F) and/or G) being at least 70 wt.%, based on the sum of F),
G) and H);
Aliphatic or partly aromatic polyester-amides or polyetherester-amides from
1] aliphatic bifunctional alcohols, preferably linear Cz to C,a dialcohols,
such as,
for example, ethanediol, butanediol or hexanediol, particularly preferably
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butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably
having 5 to 8 C atoms, such as, for example, cyclohexanedimethanol, and/ or,
instead of some or all of the diols, monomeric or oligomeric polyols based on
ethylene glycol, propylene glycol or tetrahydrofuran or copolymers thereof
having molecular weights of up to 10,000, preferably up to 8,000, particularly
preferably up to 5,000, and/or optionally small amounts of branched
bifunctional alcohols, preferably C; C,Z alkyldiols, such as, for example,
neopentylglycol, and additionally optionally small amounts of alcohols of
higher functionality, preferably C3 C,2 allcylpolyols, such as, for example,
1,2,3-propanetriol or trimethylolpropane, and from aliphatic bifunctional
acids,
preferably having 2 to 12 C atoms in the alkyl chain, such as, for example and
preferably, succinic acid or adipic acid, and/or optionally aromatic
bifunctional
acids, such as, for example, terephthalic acid, isophthalic acid or
naphthalenedicarboxylic acid, and additionally optionally small amounts of
acids of higher functionality, such as, for example, trimellitic acid, or
K) building blocks with acid and alcohol functional groups, preferably having
2 to
12 C atoms in the carbon chain, for example hydroxybutyric acid,
hydroxyvaleric acid or lactic acid, or derivatives thereof, for example E-
caprolactone or dilactide,
or a mixture and/or a copolymer of 17 and K), the aromatic acids making up a
content of not more than 50 wt.%, based on all the acids,
L) an amide content from aliphatic and/or cycloaliphatic bifunctional and/or
optionally small amounts of branched bifunctional amines, preferred
compounds being linear aliphatic CZ to C,°-diamines, and additionally
optionally small amounts of amines of higher functionality, and among the
amines preferably hexamethylenediamine or isophoronediamine, and
particularly preferably hexamethylenediamine, and from linear and/or
cycloaliphatic bifunctional acids, preferably having 2 to 12 C atoms in the
alkyl chain, or CS or C6 ring in the case of cycloaliphatic acids, preferably
adipic acid, and/or optionally small amounts of branched bifunctional and/or
optionally aromatic bifuncdonal acids, such as, for example, terephthalic
acid,
isophthalic acid or naphthalenedicarboxylic acid, and additionally optionally
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small amounts of acids of higher functionality, preferably having 2 to 10 C
atoms, or
1V~ an amide content of building blocks with acid and amine functional groups,
preferably having 4 to 20 C atoms in the cycloaliphatic chain, preferably w-
lauryllactam or E-caprolactam, particularly preferably s-caprolactam,
or a mixture of L) and 1V~ as the amide content, the ester content 17 and/or
K)
being at least 30 wt.%, based on the sum of n, K), L) and IVn, and preferably
the weight content of the ester structures is 30 to 70 wt.% and the content of
the amide structures is 70 to 30 wt.%.
The polyether-ester-amides are built up, in particular, from the following
monomers:
oligomeric polyols comprising polyethylene glycols, polypropylene glycols,
polyglycols, built up randomly or in block form, from mixtures of ethylene
oxide or
propylene oxide, or polytetrahydrofurans having molecular weights (weight-
average)
of between 100 and 10,000 and
monomeric diols, preferably CZ C,2-alkyl-diols, in particular CZ-C6
alkyldiols, for
example ethylene glycol, 1,4-butanediol, 1,3-propanediol or 1,6-hexanediol,
and at
least one monomer chosen from the group consisting of
dicarboxylic acids, preferably CZ-C,z , particularly preferably CZ-C6-alkyl-
dicarboxylic
acids, for example oxalic acid, succinic acid or adipic acid, also in the form
of their
particular ethers (methyl, ethyl etc.)
C2 C,z-alkylhydroxycarboxylic acids and lactones, such as caprolactone, inter
alia,
amino alcohols having 2 to 12 carbon atoms in the alkyl chain, for example
ethanolamine or propanolamine
cyclic lactams having 5 to 12, preferably 6 to 11 C atoms, such as E-
caprolactam or
lauryllactam etc.
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cu-aminocarboxylic acids having 6 to 12 C atoms in the alkyl chain, such as
aminocaproic acid etc.
mixtures (1:1 salts) of CZ C,~-alkyldicarboxylic acids, for example adipic
acid or
succinic acid, and CZ-C,Z alkyldiamines, for example hexamethylenediamine or
diaminobutane.
Polyesters having either hydroxyl or acid end groups and molecular weights of
between 300 and 10,000 can also be employed as the ester-forming component.
The proportion of the ether and ester contents in the polymer is in general S
to 85
wt.%, based on the total polymer.
The polyether-ester-amides according to the invention in general have an
average
molecular weight (Mw determined by gel chromatography in cresol against
polystyrene standard) of 10,000 to 300,000, preferably 15,000 to 150,000, in
particular
15,000 to 100,000.
All the acids can also be employed in the form of derivatives, such as, for
example,
acid chlorides or esters, both as monomeric and as oligomeric esters.
The synthesis of the biologically degradable polyester-amides according to the
invention can be carried out both by the "polyamide method" by stoichiometric
mixing
of the starting components, if appropriate with the addition of water, and
subsequent
removal of water from the reaction mixture, and by the "polyester method" by
stoichiometric mixing of the starting components and addition of an excess of
diol,
with esterification of the acid groups and subsequent transesterification or
transamidation of these esters. In this second case, in addition to water, the
excess diol
is also distilled off again. The synthesis by the "polyester method" described
is
preferred.
The polycondensation can furthermore be accelerated by using known catalysts.
Both
the known phosphorus compounds which accelerate polyamide synthesis and acid
or
organometallic catalysts for esterification and also combinations of the two
are
possible for acceleration of the polycondensation.
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It should be ensured that the catalysts adversely influence neither the
biological
degradability or compostability nor the quality of the resulting compost. The
polycondensation to give polyester-amides can furthermore be influenced by
using
lysine, lysine derivatives or other products which branch by amide formation,
such as,
for example, aminoethylaminoethanol, which both accelerate the condensation
and
lead to branched products (see, for example, DE-A 38 31 709).
The preparation of polyesters, polyester-carbonates and polyester-urethanes is
generally known or is carried out analogously to known processes (cf. e.g. EP-
A 304
787, WO 95/12629, WO 93/13154, EP-A 682 054 and EP-A 593 975).
The polyesters, polyester-urethanes, polyester-carbonates or polyester-amides
according to the invention can furthermore comprise 0.1 to 5 wt.%, preferably
0.1 to 1
wt.%, of branching agents (cf. also the description of the polymers). These
branching
agents can be e.g. trifunctional alcohols, such as trimethylolpropane or
glycerol,
tetrafunctional alcohols, such as pentaerythritol, or trifunctional carboxylic
acids, such
as citric acid. The branching agents increase the melt viscosity of the
polyester-amides
according to the invention to the extent that extrusion blow moulding with
these
polymers becomes possible. The biological degradation of these materials is
not
impeded as a result.
The biologically degradable/compostable polyester-urethanes, polyesters,
polyester-
carbonates and polyester-amides as a rule have a molecular weight of at least
10,000
g/mole, and in general have a random distribution of the starting substances
in the
polymer. In the polyurethane-typical polymer build-up optionally of C) and D)
and of
E), a completely random distribution of the monomer building blocks is not
always to
be expected.
A particularly preferred polycarbodiimide is the aromatic polycarbodiimide
which is
substituted with isopropyl groups in the o-position relative to the
carbodiimide groups,
i.e. in the 2,6- or 2,4,6-position on the benzene nucleus. The
polycarbodiimides
present preferably have an average molecular weight of 1,500 to 15,000, but in
particular 9,000 to 12,000. In particular, by addition of small amounts of
aromatic
and/or aliphatic (polyxarbodiimides, it is possible to increase the
thermooxidative
stability such that the end group contents of the biologically degradable
plastics are
reduced and a hydrolytic stability of the biologically degradable plastics is
achieved.
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The following carbodiimides may be mentioned as examples:
(CH3)2 CH(CH3)2
CH(CH3)2
c:NlrH 1
(1)
CH(CH ) ~ J~~ CH(CH3)2 CH(CH3)z
3 2
/\ ~ /\
N-C=N \ N=C=N (2)
L
CH(CH3)Z P CH(CH3)2
CH(CH3)z
CH(CH3)z
CH(CH3)2
N=C=N ~
CH(CH3)z
P
wherein
p is determined by the molecular weight.
The carbodiimides can be prepared by processes known per se (e.g. DE-AS 25 37
685,
DE-AS 11 56 401, DE-AS 2419 968 and FR 1 180 307).
Fillers and reinforcing substances which are suitable according to the
invention can be
minerals, such as, for example, kaolin, chalk, gypsum, mica, lime or talc, or
naturally
occurring substances, such as, for example, starch or modified starch,
cellulose or
cellulose derivatives or cellulose products, wood flour or natural fibres,
such as, for
example, hemp, flax, sisal, rape or ramie. Metallic fillers which can
furthermore be
employed are iron powder, iron oxides, iron alloys (e.g. ferrotitanium,
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ferromolybdenum, ferromanganese), tungsten, tungsten carbide, ferrotungsten,
molybdenum, manganese, cobalt, copper, zinc, tin or bismuth or combinations
thereof.
The biologically degradablelcompletely compostable polyester-urethanes,
polyesters,
polyester-carbonates and polyester-amides according to the invention can be
equipped
with conventional additives. It is thus possible to use modifying agents
and/or
processing auxiliaries, such as, for example, nucleating agents, plasticizers,
mould
release auxiliaries, flameproofing agents, impact modifiers, stabilizers, for
example for
stability to heat, stability to oxidation and stability to UV and light,
colour-imparting
agents (e.g. pigments) or other additives which are usual in the
thermoplastics field,
but it should be ensured that complete compostability is not impaired or that
the
substances which remain, for example mineral auxiliaries, are harmless in the
compost.
The additives are in general added in an amount of up to 15 wt.%, based on the
total
mixture.
The moulding compositions according to the invention are biologically
degradable,
preferably completely degradable. Those moulding compositions which can be
classified as completely degradable in accordance with DIN 54 900 are
particularly
preferred.
The biologically degradable/completely compostable polyester-urethanes,
polyesters,
polyester-carbonates and polyester-amides according to the invention can also
be
mixed with further blend partners, e.g. thermoplastic starch, but it should be
ensured
that complete compostability is not impaired or that the substances which
remain, for
example mineral auxiliaries, are harmless in the compost.
Further blend partners which can be employed for fiuther fields of use in
which
biological degradability is not necessary are:
polyethylene, modified polyethylenes, such as, for example, an LDPE modified
with
malefic anhydride, a fluorine thermoplastic, such as, for example,
polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer,
tetra-
fluoroethylene/perfluoroalkoxyvinyl ether copolymer, ethylene/-
tetrafluoroethylene
copolymer, polychlorotrifluoroethylene, ethyleneJ-chlorotrifluoroethylene
copolymer,
polyvinylidene fluoride, polyvinyl fluoride, polyfluoroalkoxyalkane,
tetrafluoroethylenelhexafluoropropyleneJvinylidene fluoride copolymer,
amorphous
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perfluorinated polymers, polyvinyl chloride, polyvinylidene chloride, a poly-
propylene, a polyvinyl alcohol, a polyvinyl acetate, a partly hydrolysed
polyvinyl
acetate, a polyvinyl ether, a polyether, a polyacrylate, an aliphatic
polyester or
copolyester, an aromatic polyester or copolyester, an ammatio-aliphatic
copolyester, a
polycarbonate, a polyester-carbonate, a partly aromatic polyurethane, an
aliphatic
polyurethane, a polyester-urethane, a polyamide, a polyester-amide, a
polyether-amide,
a polyether-ester-amide, a cellulose ether, a cellulose ether-ester, a starch
derivative or
a copolymer or a mixture of several of those mentioned.
The blend partners can be employed up to a content of 99 wt.%, preferably up
to
70 wt.%, based on the total amount of the moulding composition.
The invention also provides a process for the preparation of the moulding
compositions according to the invention, characterized in that the individual
components and optionally fiutller additives (conventional additives) are
mixed in a
known manner and the mixture is subjected to melt compounding and melt
extrusion
at elevated temperatures, preferably of 150 to 300°C, in conventional
units, such as
internal kneaders, extruders and twin-screw extruders.
The invention also provides a process for the preparation of the moulding
compositions according to claims 1 to 15, wherein the biologically degradable
polymer
is mixed with a concentrate of biologically degradable polymer and at least
one
stabilizer A1) or A2) and optionally component B) and additives, and the
mixture is
subjected to melt compounding and melt extrusion at elevated temperature.
Extruders which can be employed are, for example:
a densely combing twin-screw extruder with screws which interlock completely,
a
single-screw extruder for high-performance extrusion which operates by the
stator-
rotor principle (e.g. Staromix~ fi-om Reifenhauser), a triple-screw extruder,
a
continuously/discontinuously operating CO kneader and a continuous dispersion
kneader with a slow-running rotor-stator combination (e.g. KEX, Drais,
Mannheim).
The invention also provides the use of the moulding compositions according to
the
invention for the production of semi-finished products, films, in particular
hygiene
films, rubbish bags, roof underlining webs and films as a constituent of
clothing,
injection mouldings, in particular plant pots, plant clamps and plant binders,
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multifilaments, monofilaments, fibres, in particular cut fibres and fibres for
coating
heat-sealable filter papers, nonwovens and woven fabrics, in particular
geotextiles,
protective works clothing and automobile interior lining, and the articles
themselves.
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Examples
Example 1
A polyester-amide (e.g. BAKE 1095 from Bayer AG) was melted with an aromatic
polycarbodiimide (e.g. Stabaxol~ P100 from Rhein Chemie Rheinau GmbI~ at
170°C
to 190°C on a twin-screw extruder of the type ZSK from Wemer &
Pfleiderer,
Stuttgart, with an LID ratio of >35 and special kneading elements, with at
least the first
cooled intake zone. The strands extruded in this way were cooled in a water
bath,
granulated and dried.
BAK~1095 is a polyester-amid of adipic acid, butanediol and caprolactam having
an
ester/amide weight ratio of 70/30, randomly copolycondensed with a relative
solution
viscosity of 2.78, measured on a 1 wt.% solution in meta-cresol at
20°C.
BAK~2195 is a polyester-amide of 32.3 wt.% adipic acid, 11.7 wt.% 1,4-
butanediol,
15.0 wt.% diethylene glycol, 41 wt.% AH salt, randomly copoly-condensed with a
relative solution viscosity of 2.8, measured on a 1 wt.% solution in m-cresol
at 20°C.
Table 1
Concentrates with hydrolysis stabilizer (the numerical data of the composition
designate wt.%)
Concentrate A B C D E
BAK~ 1095 90 90
BAK~ 2195 90 90 90
Stabaxol~ P 10 10
Stabaxol~ P100 10 10
Stabaxol~ P200 10
Rel. solution viscosity 2.78 2.72 3.91 3.27 2.66
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Example 2
BAK~2195 is injection moulded to test bars (80*10*4 mm) as a mixture with a
concentrate prepared according to example 1. The bars are stored at
60°C in water, to
which 0.02 wt.% sodium azide is added as a biocide to maintain sterility. The
results
are shown in table 2.
Table 2: Results of the storage in water at 60°C
Storage BAK 2195 BAK 2195 + BAK 2195 + BAK 2195 +
timeld unstabitized10% 10% 10%
concentrate concentrate concentrate
B D from
from example from example example 1
1 1 (corresponds
(corresponds (corresponds to
to to 1 % Stabaxol
1 % Stabaxol 1 % Stabaxol P200)
P) P100)
0 2.66 2.67 2.75 2.76
24 2.76 2.54 2.66 2.82
48 2.33 2.47 2.49 2.85
70 2.42 2.48
72 - 2.71
144 2.15
168 2.1 S 2.32 2.40 2.47
336 2.06 2.08 2.13
504 1.71 1.80
648 1.59
672 1.63
816 1.59 1.61
840
1.47
