5
Field of the invention
The present invention relates to thermoplastic
elastomers (TPE), and notably engineering polymers of
10 high added value used in various sectors, such as
electronics, automobiles or sports. The present
invention relates more particularly to a thermoplastic
elastomer dc rived from renewabl-e raw materia 1 s. The
invention also relates to a method of making said
15 thermoplastic elastomer derived from renewable
materials.
In conventional thermoplastic elastomers, we
essentially find ingredients of petro1eu.m origin or of
20 synthetic origin. Their methods of production are
sometimes regarded as causing environmental pollution.
In fact, the raw materials used for synthesis of these
ingredients are obtained by steam kracking or catalytic
cracking of petroleum fractions, Use of these materials
25 contributes to the increase in the greenhouse effect.
With decreas i tlg world petroleum reserves, the ::ources
of these rdw materials are gradually being exhausted.
Rag materials derived from biomass are from a renewable
30 source and have a reduced irnpact on the environment.
They do not require all the energy-consuming refining
stages of petroleum products, Production of C02 is
reduced, so that they contribute less to global
warming, '
It therefore appears necessary to have methods of
synthesis that are not dependent on raw materials of
fossil origin, but instead use raw materials of
renewable origin,
Nowadays, manufacturers who use TPEs are increasingly
adopting an eco-design approach and are searching for
plastics of high added value of vegetable origin.
Moreover, in competitive markets such as sports or the
car industry, manufacturers must neet consumers '
demands for polymer materials combining technical and
environmental performance. Now, said perf orrnance
10 depends both on the raw materials and on the processes
used.
The prcseint inveiltion ther~ofr e has the + I i 111 o i
providing TPEs that meet these requirements, both in
15 terms of mechanical properties, chemical resistance or
resistance to aging, and in terms of ecological ethics.
Prior art
20 Thermoplastic elastomer (TPE) means a bloclt copolymer
comprising alternating blocks or segments that are
callkd hard or rigid (rather with thermoplastic
behavior) and blocks or segments that are pliable or
flexible (rather with elastomeric behavior),
25
A block is sL~id to be "pliable" if it has a luw glass
transition temperature (Tg). Low glass transition
temperature means a glass transition temperature Tg of
less than 15"~, preferably less than OOc,
30 advantageously less than - 1 5 " ~ ~ even more
advantageously less than -30°C, and optionally less
than -50"~-
The flexible bloclts are generally based on polyethers
35 (PE) selected from poly (ethylene glycol) (PEG),
poly(1,2-propylene glycol) (PPG), poly(l,3-propylene
glycol) (P03G) , poly (tetramethylene glycol) (PTMG) , and
copolymers or blends thereof. The rigid blocks are
generally based on polyamide, polyurethane, polyester
or a mixture of these polymers,
As examples of copolymers ~iitzh rigid bloclts and with
flexible bloclts, we may mention respectively (a)
5 copolymers with polyester bloclts and polyether bloclts
(also called COPE or copolyetheresters) , (b) copolymers
with polyurethane blocks and polyether blocks (also
called TPU, abbreviation o f thermoplastic
polyurethanes) and (c) copolymers with polyamide blocks
10 and polyether blocks (also called PEBA according to
IUPAC) .
111 t . 1 7 ~ f i e l d of thermop1ac;tic c l a s t o n ~ e r s such T'PU or
COPE, products manufactured partially from raw
15 materials of renewable origin have recently been
marketed, As an example, the TPUs marketed under the
brand name Pearlthane@ ECO-D12T95 by Merquinsa claim a
proportion of renewable carbon of 38% according to
ASTM-D6866, We may also mention the COPE range marketed
20 under the brand name HytrelO RS by Uupont. This COPE
comprises a P03G derived from renewable resources that
repl, dces petrochemical polyols,
As for the PEBAs, they are mainly obtained from raw
25 materials of fossil origin, as only these n~alte it
possible to achieve the cost/performance coirq~romise
required for certain applications.
--
In fact, the PEBAs or Polyether-Block-Amides, such as
30 those marlteted by the company Arkema under the name
PebaxB, are plasticizer-free thermoplastic elastomers
which belong to the class of engineering polymers, They
can be processed easily by injection molding and
,
extrusion of shapes or films. They can also be used in
35 the form of filaments, threads and fibers for woven
fabrics and nonwovens, They are used in applications of
high added value and in particular:
- high-level sport, notably as elements of soles of
foo-twear for sprinting, football, rugby, tennis,
basket-ball, running, Alpine or Nordic sltiing, as well
as i-ri golf balls, and in many other sports articles;
5 - in industry, notably as conveyor belts, as breathable
rainwear or as antistatic additive;
- in the medical field, notably as catheters,
angioplasty balloons, peristaltic band;
10
- automobile, notably as synthetic leather, skin
panels, instrument panels, airbag components, etc.
They make it possible to combine, j.n a single polymer,
15 unequalled mechanical properties and very good
resistance to thermal or UV aging, as well as low
density. They thus make it possible to produce
lightweight components. In particular, at equivalent
hardness, they dissipate less energy than other
20 materials, which endows them with very good resistance
to dynamic stresses in bending or tension, and they
have exceptional properties of elastic springback,
The PEBAs comprising polyamide blocks a.nd PEG bloclts
25 also have well-known permanent antistatic properties
and provide the films with breathable w~11c:rproof
properties and leakproof properties, as described in
patents EP 1046675 and - EP 0737709.
30 Since 2007, the "PebaxB Rnew" range marketed by Arkema
is the 'only one to offer a range of engineering-grade
thermoplastic elastomers in which the proportion of
carbon of renewable origin varies from about 20% to
I
95%, depending on the content of polyamide of renewable
35 origin in the thermoplastic elastomer. In fact the
classical PEBA is a thermoplastic elastomer obtained
from polyamide 12 (or from polyamide 6) for the rigid
bloclc and from polyether for the flexible block, these
two blocks being made from materials of fossil origin,
For the rigid block, a first move towards developing
renewable raw materials consis-ted of selecting a
polyamide made from raw materials of vegetable origin,
5 such as amino-11-undecanoic acid. In fact, amino-11-
undecanoic acid is obtained from the processing of
castor oil, extracted from the plant of the same name
(Ricinus communis, the castor-oil plant), from the
seeds of the castor-oil plant. Replacement of PA 12
10 with PA 11, obtained by polycondensation of amino-11-
undecanoic acid, in the manufacture of PEBA provides,
in addition to a reduced environmental impact, a
material €01- kdhi~h certain properties are sup( I ior to
those of the material of fossil origin. In particular,
the PEBAs manufactured on the basis of PA 11 no longer
have a plasticity threshold when submitted to stress,
giving an improvement not only in low-temperature
impact strength, but also in bending fatigue strength.
The heat resistance is also improved, along with
increased stiffness at low temperature.
How,ever, for the polyether flexible bloclc there is at
present no renewable alternative cther than the P03G
polyether blocks recently put on the market by Dupont
25 under the brand name CerenolB, or else the flexible
polyesters, Ibdsed on dimerized fatty acid, mall oted by
Uniqema under the brand name PriplastB. However, use of
POJG polyether blocks alone or PriplastB polyester
blocks alone for making PEBAs does not allow the same
30 performance to be achieved as with PEG bloclts, in terms
of derisity, take-up of water and/or mechanical
properties, antistatic properties, breathable
waterproof propert.ies and leakproof proper ties,
(
Moreover, the use of these P03G or polyester bloclts
35 does not make it possible to readily modulate both the
mechanical and antistatic properties of the block
copolymer. Furthermore, the use of these P03G bloclts
does not allow the same performances to be achieved as
with PPG blocks, in terms of low take-up of moisture,
and in particular in terms of stability of the
mechanical properties with respect to ambient moisture.
The present invention therefore has the aim of devising
5 a novel TPE that is of renewable origin and offers high
performance. The present invention notably has the aim
of supplying a TPE of renewable origin, but with
performance at least equivalent to those of the
conventional TPEs of fossil origin.
10
The present invention also has the aim of supplying a
method of manufacture of said TPE that is simple, easy
to apply, railid (hrith the fewest possible stag(>+), and
that does not involve chemical or technological
15 manipulations that are arduous, energy-consuming or
polluting, so as to have the srna1.lest possible
environmental impact. In particular, the present
invention has the aim of providing such a method that
is easy to modulate, i.e. that is easy to adapt
20 according to the desired antistatic, antiperspirant and
mechanical properties.
Armed with its expertise in the :manufacture of highperformance
bioresourced polymers, the applicant was
25 now able to clemonstrate that it is possible to produce
a TPE:
- - in which the polyether flexible blocks are of
recewable origin, owing to the use of ethylene oxide
30 and/or propylene oxide containing 14c, notably owing to
the use of PEG and/or PPG blocks made from biomass, and
- whose performance is at least identical to that of
the ~orre~~ondiTnPgE s whose polyether bloclts are of
35 fossil origin.
Summary of the invention
The invention relates to a bloclt copolymer derived from
at least one ethylene oxide and/or propylene oxide
monomer containing 14c. Advantageously, said copolymer
comprises at least one polyether block derived at least
partially from ethylene oxide and/or propylene oxide
5 containing 14c,
Advantageously, the block copolymer according to the
invention comprises:
10 - from 1 to 99% of at least one polyether flexible
bloclc derived at least partially from ethylene oxide
and/or propylene oxide containing 14c , and
- from 1 to 99% of at least one rigid block selected
15 from: polyamide blocks, polyurethane blocks, polyester
blocks, and mixtures thereof,
Advantageously, said at least one polyether flexible
bloclc comprises at least one polyethylene glycol. (PEG)
20 and/or polypropylene glycol (PPG) derived at least
partially from renewable materials. Advantageously, the
proportion by mass of said at least one flexible block
represents from 5 to 95%, preferably from 5 Co 85%, and
the proportion by mass of said at least one rigid block
25 represents from 5 to 95%, preferably from 15 to 95% of
the total mass of the copolymer.
Adv-a ntageously, said at least one rigid bloclc is
derived at least partially from renewable raw
30 materials.
Advantageously, said at least one polyether block
and/or said at least one rigid. bloclc is/are derived
(
totally from renewable materials,
35
Advantageously, the copolymer according to the
invention has a biocarbon content of at least 1%, which
corresponds to a 14 c/'~c_ isotope ratio of at least
1. 2x10-l4 Advantageously, the copolymer according to
the invention has a biocarbon conten-t above 5%,
preferably above 10% , preferably above 25%, preferably
above 50%, preferably above 75%, preferably above 90%,
preferably above 95%, preferably above 98%, preferably
5 above 99%, advantageously roughly equal to loo%, which
corresponds to a 14c/12c isotope ratio of 1,2x10-~~,
Advantageously, the copolymer according to the
invention comprises at least one polyamide block.
/
10 Advantageously, said polyamide comprises a copolyamide.
~dvantageously, the copolymer according to the
invention compris3s at least one polyamide block
comprising a1 least one of the following mol~~cules
amino-11-undecanoic acid, n-heptylamino-11-undecanoic
15 acid, succinic acid, azelaic acid, sebacic acid,
dodecanedioic acid, myristic acid, tetradecanedi-oic
acid, hexadecanedioic acid, octadecanedioic acid,
butanediamine, pentanediamine, decamethylenediamine,
fatty diacid(s), fatty acid dimer(s) and mixtures
20 thereof, Advantageously, said at least one polyamide
block comprises at least one monomer selected from the
following polyamide monomers: 11, 5,4, 5.9, 5,10, 5.12,
5.13, 5.14, 5.16, 5.18, 5.36, 6:4, 6,9, 6-10, 6.12,
6.13, 6.14, 6-16, 6.18, 6.36, 10,4, 10.9, 10,10, 10.12,
25 10.13, 10.14, 10.16, 10.18, 10.36, 10.T, 12.4, 12.9,
12.10, 12.12, 12.13, 12.14, 12.16, 12.18, 1 2 I , 12.T
and blends or copolymers thereof. Advantageously, the
blnck copolymer according to the invention is a
co~olymer with polyether blocks and polyamide bloclts
30 (abbreviated: PEBA) .
Advantageously, said PEBA is based on PA11-PEG,
PA10,10-PEG, PA10.12-PEG, PA10.14-PEG, PA6,lO-PEG,
(
PA6.12-PEG, PA6.18-PEG, PA11.-PPG, PAlO. 10-PPG, PAIO. 12.-
35 PPG, PA10.14-PPG, PA6.10- PPG, PA6.12-PPG, PA6.18-PPG,
~~11-PEC/PPG, ~~10.10-PEG/PPG, PA10.12-PEG/PPG,
PA10.14-PEG/PPG, PA6.10-PEIG/PPG, PA6.1.2-PEG/PPG, and/or
PA6.18-PEG/PPG, preferably based on PAl1-PEG, PA11-PPG
or PA11-PEG/PPG,
Advantageously, the copolymer according to the
invention comprises at least one polyester bloclc.
Advantageously, said polyester comprises a copolymer.
5 Advar~tageously, said at least one polyester bloclc
comprises at least one of the following molecules:
ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 10-
decanediol, dimerized fatty acid reduced to obtain the
corresponding diol, 2,s--fu randicarboxylic acid,
10 succinic acid, azelaic acid, sebacic acid,
dodecanedioic acid, myristic acid, tetradecanedioic
acid, hexadecanedioic acid, octadecanedioic acid,
and/or dirnerj ;led fatty acids,
15 Advantageously, said copolymer according to the
invention id a polyetherester,
Advantageously, the copolymer according to the
invention comprises at least one polyurethane bloclc.
20 Advantageously, said polyurethane comprises a
copolymer, i.e. a copolyuretliane. Advantageously, said
at ,l east one polyurethane bloclc is made from at least
one polyol of renewable origin, selected from th2
following polyols: polyols derived from starch;
25 erythritol; sorbitol; maltitol; mannitol; polyols
derived from sugars, sucrose; isomalt; xylitol; }~olyols
derived from maize, soya, cotton, colza, sunflower or
peanut; glycerol; propylene glycol; ethylene glycol;
regction coproducts from biodiesel production;
30 polyethylene glycol (PEG) , poly (1,2--propylene glycol)
(PPG), ' poly (l,3-propylene glycol) (P03G) I
polytetramethylene glycol (PTMG),
Advantageously, said copolymer according to the
I
invention is a polyetherurethane.
35
Advantageously, said at least one polyether block
additionally comprises polyethers other than PEG and/or
PPG, such as P03G, PTMG, poly(3-methyltetrahydrofuran)
of renewable origin or of fossil origin and/or PEG or
PPG of fossil origin
Advantageously, the copolymer according to the
invention is a segmented block copolymer comprising
5 three different types of bloclts (called tribloclt
hereinafter), said triblock being selected from
copolyetheresteramicles, copolyetheramideurethanes,
copolyetheresterurethanes, in which:
10 - the percentage by mass of polyether flexible block
is above 20%;
- the perci.litage by mass of polyamicle riqid 1)loclc is
above 10%;
15
of the total mass of triblock.
The present invention also relates to a method for
preparing block copolymer as defined previously,
20 comprising the stage of supplying polyether derived at
least partially from ethylene oxide and/or propylene
oxid& containing 14c and conversion by synthesis to
block copolymer. Advantageously, said polyether
comprises polyethylene glycol and/or polypropylene
25 glycol having a biocarbon content of at least 1%
Advantageously, the supply stage comprises a stage of
praduction of polyether from ethylene - oxide and/or
propylene oxide having a biocarbon content of at least
30 1%. Advantageously, the supply stage comprises a stage
of production of said ethylene oxide and/or propylene
oxide respectively from ethylene and/or propylene.
Advantageously, the supply stage comprises a staae of
productio; of said ethylene and/or propylene from plant
35 biomass. Advantageously, said ethylene and/or propylene
is produced by dehydration of bioethanol and/or
isopropanol.
The present invention also relates to the use of the
block copolymer as defined previo~~sly, in the
automobile industry, textiles, woven fabrics,
nonwovens, clothing, shoes, sports articles, leisure
articles, electronics, c:omputer equipment, health
5 equipment, industrial additives, pacltaging and/or
household products.
Advantageously, the bloclc copolymer according to the
invention is used in instrument panels, airbags, soles
10 of sports shoes, golf balls, tubes for medical use,
catheters, angioplasty balloons, peristaltic bands,
conveyor belts, breathable waterproof rainwear,
anti static ;itlditives, skin panels,. synthetic I clathcr,
thermoplastic films and/or packaging films.
Advantageously, the block copolymer of the invention is
used alone or mixed, said copolymer representing by
mass from 5 to loo%, preferably from 5 to 70%,
preferably from 5 to 30%,
20
Detailed description of the invention:
The invention uses products of natural. origin as
starting products for making thermoplastic elastomers,
2 5
1 The carbon of a biomaterial comes t ~ o ~ uth e
photosynthesis of plants and therefore from atmospheric
COz-. The degradation (degradation will also be used with
the meaning of combustion/incineration at the end of
30 life) of these materials to C02 therefore does not
contribhte to global warming since there is no increase
in carbon discharged into the atmosphere. The C02
balance of biomaterials is therefore much better and
contributes to a reduction of the carbon footprint of
35 the products obtained (only the energy for manufacture
has to be talten into account). In contrast, when a
material of fossil origin also degrades to C02 it will
contribute to the increase in the proportion of C02 and
therefore to global warming. The compounds according to
the invention will therefore have a better carbon
footprint than that of compounds obtained from a fossil
source. The invention therefore also improves the
ecological balance during manufacture of TPEs.
5
The term "biocarbon" indicates that the carbon is of
renewable origin, or of natural origin and. is from a
biomaterial, as indicated bel-ow. The biocarbon content,
the 14c content and the content of biomaterial are
10 expressions denoting the same value.
A material of renewable origin, or biomaterial, is an
organic matei ial in whiclh the carbon comes I I om C02
fixed recently (on the human scale) by photosynthesis
15 from the atmosphere. On land, this C02 is captured or
fixed by pl-ants. In the sea, the C02 is captured or
fixed by bacteria or by plankton carrying out
photosynthesis. A biomaterial (100% carbon of natural
origin) has a 14c/12c isotope ratio greater than 10-12,
20 typically of the order of 1.2 x lo-'', whereas a fossil
material has a ratio of zero. In fact, the isotope
I
forms in the atmosphere and is then integrated by
photosynthesis, on a time scale of some decades at
most. The half-life of 14c is 5730 years. Therefore
25 materials derived from photosynthesis, namely plants in
general, necessarily have a maximum content 01 i-sotope
14c e
#
The presence of' I4c, the content of biomaterial, the
30 content of biocarbon or the content of organic carbon
1
of renewable origin of a material is determined on the
basis of standards ASTM D 6866 (ASTM D 6866-06) and
ASTM D 70, 26 (ASTM D 7026-04). Standard ASTM D 6866
relates tb "Determining the Biobased Content of Natural
35 Range Materials Using Radiocarbon and Isotope Ratio
Mass Spectrometry Analysis", whereas standard ASTM D
7026 relates to "Sampling and Reporting of Results for
Determination of Biobased Content of Materials via
Carbon Isotope Analysis", The second standard refers in
its first paragraph to the first standard, The first
standard describes a test for measuring the 14c/12C ratio
of a sample and compares it with the 14c/12C ratio of a
reference sample of 100% renewable origin, to give a
5 relative percentage of C of renewable origin in the
sample. The standard is based on the same concepts as
14c dating, but without applying dating equations, The
ratio thus calculated is designated as "pMC" (percent
Modern Carbon). If the material to be analyzed is a
10 mixture of biomaterial and fossil material (without
radioactive isotope), then the value of pMC obtained is
directly correlated with the amount of biomaterial
present i l l Ciie sample. The reference value ilc)c.d for
dating with 14c is a value dating from the 1950s. This
15 year was chosen because there were nuclear tests in the
atmosphere, which introduced large amounts of isotopes
into the atmosphere after this date. The reference 1950
corresponds to a pMC value of 100. Taking into account
the thermonuclear tests, the present value to be
20 adopted is about 107-5 (which corresponds to a
correction factor of 0.93), The radioactive carbon
sign:?ture of a plant today is therefore 107.5. H
signature of 54 pMC and one of 99 pMC therefore
correspond to an amount of biomaterial in the sample of
25 50% and 93%, respectively.
The standard ASTM D 6866 proposes three methods of
measuring the content of isotope 14C:
30 - LSC (Liquid Scintillation Counting) liquid
scintiliation spectrometry. This technique consists of
counting Beta particles resulting from the
disintegration of 14c. The Beta radiation from a sample
1
of ltnown mass (Itnown number of C atoms) is measured
35 over a certain time. This "radioactivity" is
proportional to the number of 14c atomsf which can thus
be determined. ,The 14C present in the sample emits P
rays, which on contact with the scintillation fluid
(scintillator) give rise to photons, These pl-lotons have
- 14 -
different energies (be'cween 0 and 156 IteV) and form
what is called a 14C spectrum. According to two variants
of this method, the analysis relates either to the C02
previously produced by the carbon-containing sample in
5 a suitable absorbent solution, or to benzene after
prior conversion of the carbon-containing sample to
benzene. Standard ASTM D 6866 therefore gives two
methods A and C, based on this LSC method.
10 - AMS/IRMS (Accelerated Mass Spectrometry coupled
with Isotope Radio Mass Spectrometry). This technique
is based on mass spectrometry. The sample is reduced to
graphite or to gaseous C02, analyzed in 1 mass
spectrometer. This technique uses an accelerator and a
15 mass spectrometer to separate the 14C from the 12c ions
and thus determine the ratio of the two isotopes.
The compounds according to the i-nvention come at least
partly Lrorn biomaterial and therefore have a corltent of
biomaterial of at least I%, which corresponds to a
content of 14c of at leasr 1.2 x 10-14. This content is
advantageously higher, notably up to loo%, which
corresponds to a content of 14c : of 1.2 x 10-12s The
compounds according to the invention can therefore
comprise 100% of biocarbon or in contrast result from a
mixture with ZI fossil origin
The compounds according to the invention are, as
mentioned above, thermoplastic elastomers (TPE) derived
30 at least partially from raw materials of renewable
I
origin.
More precisely, the present invention relates to
!
thermoplastic elastomers (TPE), block copolymers,
35 comprising at least one polyether block derived from at
least Gne ethylene oxide and/or propylene oxide monomer
containing C.
As polyethers that can be made from ethylene oxide
conkaining 14c, we may melltion poly (ethylene oxiide) ,
also called polyoxyethylene glycol or more commonly
called poly(ethy1ene glycol) or polyethylene glycol
(abbreviated to PEG). As polyethers that can be made
5 from propylene oxide containing 14C , we may mention
poly (propylene oxide) , also called polyoxypropylene
glycol or more commonly called poly(l,2-propylene
glycol) or polypropylene glycol (abbreviated to PPG) .
10 The polyether bloclts of the TPEs according to the
invention are obtained at least partially from raw
materials of renewable origin and comprising at least
one unit 0- (CH2) 2- and/or at least ot,( uni t
-0-CHCH3--( CHz)- -,i n which the carbons are biocarbons.
Polyether bloclts (hereinafter abbreviated to PE) mean,
in the sense of the invention, pol-yalkylene ether
polyols, notably polyalkylene ether diols, Said at
least one PE bloclc of the copolymer of the invention
20 comprises at least poly(ethy1ene glycol) (PEG) and/or
polypropylene glycol (PPG) of at leas t parti ally
renewable origin, but the PE bloclt(s) of the copolymer
of the invention can additionally comprise other PEs of
renewable origin or of fossil origin, selected from
25 poly (ethylene glycol) (PEG) and/or polypropylene glycol
(PPG) of 11oll-renewable origin, poly (1, 2-1) I opylene
glycol) (PPG), polytetramethylene ether glycol (PTMG),
polyhexamethylene glycol, poly (1,3-propylene glycol)
( ~ 6 3,~ )po ly (3-alkyl tetrahydrofuran) in particular
30 poly(3-methyltetrahydrofuran (poly (3MeTHF) ) , and
mixture,k thereof. A PE block of the bloclc or random
"copolyether" type containing a chain of at least two
types of PE mentioned above can also be envisaged.
!
35 The polyether bloclts can also comprise bloclts obtained
by ethoxylation of bisphenols, for example bisphenol A.
These last--menti-oned products are described in patent
EP 613 919. The polyether blocks can also comprise
ethoxylated primary amines. Advantageously these blocks
are also used, As examples of ethoxylated primary
amines we may mention the products of formula:
5
in which m and n are between 1 and 20 and x is between
8 and 18. These products are available commercially
under the brand name NORAMOXB from the company CECA and
under tlhe /)rand liame GENAMING? f;om tlie (40nipci~ly
10 CLARIANT.
Thus, the chain ends of the PE bloclcs can be diOH,
diNH2, diisocyanate or diacid depending on their method
of synthesis, The PE blocks with NH2 chain ends can be
15 obtained by cyanoacetylation of aliphatic
dihydroxylated alpha-omega polyoxyalkylene sequences
called polyether diols such as JeffaminesB D300, D400,
D2000, ED-600, ED-900, ED2003, the ElastaminesB RP-409,
RP-2009, RT-1000, RE-600, RE-900, 1>,E:-20OOr HT-1700, HE-
180 from the company Huntsman. Said blocks are
described in patents JP 2004346274, JP 2004353794 and
Aceording #- to one embodiment, said at least one
25 polyether, for example PEG, is derived from at least
one ethylene oxide monomer containing 14c, which is
8
synthes~zed from ethylene which is itself synthesized
from ethanol (bioethanol) or from a mixture of alcohols
comprising ethanol. These alcohols are derived froa the
f
30 fermentation of renewable raw materials, in particular
vegetable raw materials selected from sugar cane and
sugar beet, maple, date palm, sugar palm, sorghum,
American agave, corn, wheat, barley, sorghum, soft
wheat, rice, potato, cassava, sweet potato and algae.
According to a second embodiment, said at least one
polyether, for example PPG, is derived from at least
one propylene oxide monomer (PPG) contai-ning 14c, which
is synthesized from propylene which is itself
5 synthesized from an alcohol or from a mixture of
alcohols, said alcohol or mixture of alcohols
comprising at least isopropanol and/or at least a
mixture of ethanol and of I-butanol. These alcohols are
themselves derivatives of renewable raw materials and
10 are derived from the fermentation of vegetable
materials selected from sugar cane and sugar beet,
maple, date palm, sugar palm, sorghurn, American agave,
corin, wheat, lisrley, sorqhurn, soft wheat, r i~oiato,
cassava, sweet potato, and materials comprising
15 cellulose or hemicellulose, such as wood, straw or
paper.
These two embodiments of the invention are alternatives
or can be combined, such that the polyether block
20 comprises both PEG and PPG containing 14c, according to
standard ASTM D6866.
I
The thermoplastic elastomers (TPE) according to the
invention can additionally contain other flexible
25 blocks that are not polyether-based, We may notably
mention blocks based on polyesters s ~ 1 c . 1 1 as
poly(capro1actone) or polyesters of the PriplastB type,
based on polydimethylsiloxane or PDMS, based on
/-
aliphatic polycarbonate, based on polyolefin such as
30 polybutadiene, polyisobutylene etc,
Moreover, the thermoplasti-c elastomers (TPE) according
to the invention comprise at least one rigid block
f
selected from polyamide bl-ocks, polyurethane bloclts,
35 polyester bloclts, and mixtures thereof in the form of
block or random copolymers.
The rigid bloclts can be derived from renewable
materials and/or from materials of fossil origin.
Advantageously, said rigid bloclts are also derived at
least partially from renewable materials, According to
a particularly advantageous embodiment of the present
invention, the polyether blocks and/or the polyamide
5 bloclts and/or the polyurethane bloclts and/or the
polyester blocks are derived totally from renewable
materials.
Thus, depending on the choice of components of the
10 flexible and rigid blocks, the biocarbon content of the
copolymer of the invention is at least 1%, which
corresponds to a 14c/12c isotope ratio of at least
3 .2~10-'T~h[~_ I~iocarbonc o n t e ~ to f t h ~co polymel of thp
invention is preferably above 5%, preferably above lo%,
15 preferably above 25%, preferably above 50%, preferably
above 75%, preferably above 90%, preferably above 95%,
preferably above 98%, preferably above 99%. It is
advantageously rouyhly equal to loo%, which corresponds
to a 14c/12c isotope ratio of at least 1.2~10-12.
20
According to a preferred embodiment, the block
copojymer of the present invention comprises at least
one polyether flexible block derivkd at least partially
from ethylene oxide and/or propylene oxide containing
25 14c, preferably at least one PEG and/or PPG obtained at
least in part from raw materials of renewable origin,
and polyamide blocks.
-
Polyamide means, in the sense of the invention,
30 homopolyamides and copolyamides; i.e. products of
condensation of lactams, amino acids or diacids with
diamines and, as a general rule, any polymer formed by
units joined together by amide groups,
I
35 Polya-mi.de of totally renewable origin that can be
included in the copolymer according to the invention
means:
- aliphatic polyamides obtained from lactains or from
amino acids (for example PA 11 obtained. by
polycondensation of amino--11-undecanoic acid);
- the products of condensation of a dicarboxylic
5 acid with a diamine (for example PA 10.10, the
condensation product of decanediamine with sebacic
acid, or PA 10.12, the condensation product of
decanediamine with dodecanedjoic acid, or PA
10,36, the condensation product of decanediamine
10 with a fatty acid dimer);
- the copolyamides resulting from the polymerization
of var i o u s mo~)iorners, such as thosc r n r s t ~it oned
above, for example the following copolyamides : PA
15 11/10.10, PA 11/10.12, PA 10.10/10.12, PA
11/10,36, PA 10.1.2/10.36, PA 10.10/10.36, the
amino-11-undecanoic/n-heptyl-11-aminoundecanoic
copolyamide, etc, Copolyamides of renewable
origin, which comprise at least two monomers, are
20 more particularly described in French patent
application No,: 07.53319,
The term "monomer" in the present desc~iption of
copolyamides must be understood in the sense of
25 "repeating urit", In fact, a particular case is when a
repeating ui1i.L of PA is constituted of a combi~~~rl~oifo n
a diacid with a diamine. It is considered that it is
the- combination of a diamine and of a diacid, i.e. the
diamine.diacid couple (in equimolar amount), that
30 corresponds to the monomer. This is explained by the
fact tdat indiviclually, the diacid or the diamine is
only one structural unit, which in itself is not
sufficient to polymerize.
I
35 As examples of amino acids of renewable origin, we may
mention: 11-aminoundecanoic acid produced for example
from castor oil, 10--aminodecanoic acid produced for
example from decylenic acid obtained by metathesis of
oleic acid, 9-aminononanoic acid produced for example
from oleic acid,
As examples of diacids of renewable origin, we may
mention, according to t.he number x of carbons in the
5 molecule (Cx) :
- C4: succinic acid from glucose for example;
- C6: adipic acid from glucose for example;
10
- C7: heptanedioic acid from castor oil;
- C9: azela i ( acid from oleic acid (ozonoly::i s ) for
example;
15
- C10: sebacic acid from castor oil for example;
- C11: undecanedioic acid from castor oil;
20 - C12: dodecanedioic acid from biofermentation of
dodecanoic acid = lauric acid (rich oil: cabbage palm
oil and coconut oil) for example;
- C13 : brassylic acid from erucic acid (ozonolysis)
25 which occurs i.n colza for example;
- C14: tetradecanedioic acid by biofermentation of
myr- istic acid (rich oil: cabbage palm oil and coconut
oil) for example;
30
- C16: hexadecanedioic acid by biofermentation of
palmitic acid (mainly palm oil) for example;
I
- C18: octadecanedioic acid obtained by biofermentation
35 of stearic acid (a little in all vegetable oils but
chiefly in animal fats) for example;
- C20: eicosanedioic acid obtained by biofermentation
of arachidic acid (mainly in colza oil) for example;
- C22: clocosanedjo_ic acid obtained by metathesis of
unclecylenic acid (castor oil) for example;
5 - C36: fatty acid dimer derived principally from oleic
and linoleic acids.
As examples of diamines of renewable origin, we may
mention, according to the number x of carbons in the
10 molecule (Cx) :
- C4: butanediamine obtained by amination of succinic
a c i d , by hi o f i>rmentation;
15 - C5 : pentamethylene dialnine (from lysine) ;
and so on for the diamines obtained by amination of the
diacids of renewable origin already discussed.
20 "Polyamide of partially renewable origin", i.. e . derived
only partly from renewable materials (called "mixed"
polyamide in this document) means:
(
- the products of condensation of a dicarboxylic
25 acid with a diamine, and in which only one of the
two (tllr> diacid or the diamine) is of I q.newable
origin, This applies for example to PA 6.10, since _ in the monomer 6.10, only the sebacic acid - is of
renewable origin, whereas the hexamethylene
diamine is obtained from petrochemistry.
- the copolyamides resulting from the polymerization
of various monomers (renewable, nonrenewable or
mixed) such as those mentioned above. This applies
for example to CoPA 6.6/10.10 in which the monomer
"6.6" is of nonrenewable origin whereas the
monomer "10.10" is of renewable origin. This also
applies to PA 11/10, T for example, which comprises
a monomer of renewable origin ("11") and a mixed
monomer of partially renewable origin ( " 1 . 0 , T W )
since only the clecanediamine is of renewable
origin, whereas the terephthalic acid (T) is not.
5 "Polyamide of fossil origin" means all the other
polyamides on the Earth that are not included in the
two categories mentioned above, i,e. that are not made
from renewable organic raw materials.
10 Advantageously, the block copolymer of the present
invention forms a polyether block amide, abbreviated to
PEBA.
The PEBAs according to the invention therefore include
15 any TPE compri-sing at least one polyether block, the
latter bei-nq derived at least partially from ethylene
14 oxide and/or propylene oxide containing C:, such as PEG
and/or PPG respectively derived at least partially from
renewable materials, and at least one PA block
20 (homopolyamide or copolyamide) derived from fossil
materials or else derived totally or partially (in the
case of mixed polyamides) from renewable raw materials.
The PEBAs result from the polycondensation of polyamide
25 blocks with reactive ends with polyether bloclcs with
reactive ends, such as, among others:
I)-- polyamide bloclts with diamine chain ends with
polyoxyalkylene blocks with dicarboxylic chain ends.
2) polyamide blocks with dicarboxylic chain ends with
polyoxyalkylene bl-ocks with diamine chain ends,
obtained by cyanoethylation and hydrogenation of
(
aliphatic dihydroxylated alpha-omega polyoxyalkylene
35 bloclts called polyetherdiols
3) polyamide blocks with dicarboxylic chain ends with
polyetherdiols, the products obtained being, in this
particular case, polyetheresteramides.
The polyamide blocks with dicarboxylic chain ends
result, for example, from the condensation of
precursors of polyamides in the presence of a chain-
5 limiting dicarboxylic acid.. The polyamide bloclts with
diamine chain ends are obtained for example from the
condensation of precursors of polyamides in the
presence of a chain-limiting diamine. The numberaverage
molecular weight Mn of the polyamide blocks is
10 in the range from 400 to 20 000 g/mol, preferably from
500 to 10 000 g/mol, and more preferably from 600 to
6000 g/mol,
The polymers with polyamide blocks and polyether blocks
15 can also comprise randomly distributed units.
The polyamide blocks can comprise homopolyamides or
copolyamides. Three types of polyamides can be present
in the composition of these PA blocks.
20
According to a first type, the polyamide blocks are
deriked from the condensation of at least one
dicarboxylic acid (aliphatic, cycloal iphatic or
aromatic) in particular those having from 4 to 36
25 carbon atoms, preferably those having from 6 to 18
carbon atoms and from at least one diamine (a1 rj~hatic,
cycloaliphatic or aromatic) selected in particular from
those having from 2 to 20 carbon atoms, preferably
those having from 6 to 15 carbon atoms. As examples of
30 aliphatic diacids, we may mention butanedioic, adipic,
suberic, azelaic, sebacic, dodecanedicarboxylic,
myristic, tetradecanedicarboxylic, hexadecanedicarboxylic,
octadecanedicarboxylic acids and the
I
dimerized fatty acids. As examples of cycloaliphatic
35 diacids, we may mention 1,4-cyclohexyldicarboxylic -
acid, F!s examples of aromatic diacids, we may mention
terephthalic acid (T) and isophthalic acid (I). As
examples of aliphatic diamines, we may mention
tetramethylenediamine, hexamethylenediamine, 1,lO-decame
tbylenediamine, dodecamethylenediamine, trimethylhexamethylenediamiiie.
As examples of cycloaliphatic
diamines, we may mentiorl the isomers of bis-(4-
aminocyclohexyl) -methane (BACM or PACM) , bis- (3-methyl-
5 4-aminocyclohexyl) -methane (BMACM or MACM) , and 2-2-
bis-(3-methyl-4-aminocyclohexy1)-propane (BMACP) ,
isophoronediamine (IPDA), 2,6-bis- (aminomethyl) -
norbornane (BAMN) and piperazine (Pip) .
10 Advantageously, the copolymer according to the
invention comprises at least one PA block based on PA
4.4, PA 4.6, PA 9 , PA 4.10, PA 4.12, PA 4.14, PA
4.16, f'A 4 PA 4.36, PA 6-4, PA 6.6, PA O 9 PA
6.10, PA 6.12, PA 6.13, PA 6.14, PA 6-16, PA 6-18, PA
15 6.36, PA 9.4, PA 9.6, PA 9,10, PA 9,12, PA 9.14, PA
9.18, PA 9.36, PA 10.4, PA 10.6, PA 10,9, PA 10,10, PA
10.12, PA 10.13, PA 10.14, PA 10.16, PA 10.18, PA
10.36, PA 30.T, PA BMACM.4, PA BMACM.6, BMACM.9, PA
BMACM.10, PA BMACM.12, PA BMACM,14, PA BMACM,16, PA
2 0 BMACM. 18, PA BMACM .3 6, PA PACM .4, PA PACM, 6, PA PACM. 9,
PA PACM. 10, PA PACM. 12, PA PACM -14, PA PACM. 16, PA
PACM'.1 8, PA PACM. 36, PA Pip,4 , PA Pip. 6, PA Pip.9 , PA
Pip.10, PA Pip.12, PA Pip.14, PA Pip.16f PA Pip.18
and/or PA Pip.36, and mixtures thereof.
25
According to a second type, polyamide block: result
from the condensation of one or more alpha-omega
aminocarboxylic acids and/or one or more lactams having
from 6 to 12 carbon atoms in the presence of a
30 dicarboxylic acid having from 4 to 12 carbon atoms or
of a diamine. As examples of lactams, we may mention
caprolactam, enantholactam and lauryllactam. As
examples of alpha-omega aminocarboxylic acid, we may
mention the aminocaproic, amino-7-heptanoic, amino-11-
35 undecanoic and amino-12-dodecanoic acids.
Advantageously, the polyamide blocks of the second type
are of polyamide 11, of polyamide 12 or of polyamide 6.
PA 11, PA 10,10, PA 10,12, PA 10,14, PA 10-18, PA 6-10,
PA 6,12, PA 6.14, PA 6.18 as principal components
(percentage by mass above 50% of the total mass of PA)
and PE blocks comprisirig PEG and/or PPG of renewable
5 origin as principal component (percentage by mass above
50% of the total mass of PE), and optionally P03G of
renewable origin as other components of the PE blocks
of the PEBA of the invention. Particularly preferred
bloclc copolymers of the invention are PA11-PEG,
10 PA10.10-PEG, PA10.12-PEG, PAIO. 14-PEG, PA6.10-PEG,
PA6.12-PEG, PA6.18-PEG, PA11-PPG, PAIO. 10-PPG, PA10.12-
PPG, PA10.14-PPG, PA6.10-PPG, PA6.12-PPG, PA6.18-PPG,
In particular, PA11-PEG, PA11-PPG or PA11-PEG/PPG
according to the invention, of totally renewable
origin, are preferred.
20
According to a second embodiment, the bloclc copolymer
of the present invention comprises at least one
polyether flexible block which cokprises at least one
PEG and/or PPG glycol obtained at least in part from
25 raw materials of renewable origin, and at least one
polyester blocvlc,
Pol-yester means, in the sense of the invention, the
pro>ucts of condensation of dicarboxylic acids with
30 diols, and as a general rule, any polymer whose
macromol'ecular backbone contains repeating units
containing the ester chemical function.
f
The polyester bloclts (abbreviated hereinafter as PES
35 blocks) are usually made by polycondensation between a
dicarboxylic acid and a diol, Suitable carboxylic acids
comprise those mentioned above used to form the
polyamide blocks. Suitable diols comprise linear
aliphatic diols such as ethylene glycol, 1,3-propylene
PA 6/6.6 in which 6 denotes caprolactam and 6-6
denotes a monomer resulting from the condensation of
hexamethylenediamine with adipic acid.
5
PA 6.6/Pip.10/3.2 in which 6.6 denotes a monomer
resulting from the condensation of hexamethylenediamine
with adipic acid. Pip. 10 denotes a monomer resulting
from the condensation of piperazine with sebacic acid.
10 12 denotes lauryllactam.
PA 6.6/6,10/11/12 in which 6.6 denotes a monomer
resulting fro111 tlle condensation of hexamethyl_e~ic>(liamine
with adipic acid. 6.10 denotes a monomer resulting from
15 the condensation of hexamethylenediamine with sebacic
acid, 11 denotes amino-11-undecanoic acid. 12 denotes
lauryllactam.
As examples, we may also mention PA 10.10/11, PA
20 6 1 0 1 PA10.12/11, PA 101@/11/12 PA 6,10/10.10/11,
PA 6.10/6.12/11, PA 6.10/6.12/10.10.
The polyether blocks can represent 1 to 99 wt.%, ai;d
preferably 5 to 90 wt,% of the copolymer with polyamide
and polyether blocks, The molar mass Mn of the
polyether bloclts is in the range from 100 to 6000 g/mol
and preferably from 200 to 3000 g/mol, even more
preferably from 250 to - 2000 g/mol.
The preparation of the copolymers with polyamide
block (sf) and polyether block (s) according to the
invention comprises any means for attaching the
polyamide bloclts (PA blocks) and polyether blocks (PE
I
blocks) according to the present invention. In
practice, essentially two processes are used: a twostage
process and a one-stage process, these two
processes being described in application FR0856752,
Advantageously, the PEBA copolymers comprise PA bloclts
comprising at least one of the following polyamides
According to a third type, the polyarnide bloclts resul-t
from the conclensatioi? of at least one monomer of the
first type with at least one monomer of the second
type. In other words, the polyamicle bloclts result from
5 the condensation of at least one alpha-omega
aminocarboxylic acid (or a lactam), with at least one
diamine and a dicarboxylic acid.
In this case, the PA blocks are prepared by
10 polycondensation:
- of aliphatic, cycloaliphatic or aromatic diamine(s)
having X rarl-)on atoms;
15 - of dicarboxylic acid(s) having Y carbon atoms; and
- of comonomer (s) {Z} selected from lactams and alphaomega
aminocarboxylic acids having Z carbon atoms;
20 - in the presence of a chain limiter selected from
dicarboxylic acids or diamines or an excess of diacid
or of diamine used as structural unit,
Advantageously, the chain limiter used is a
25 dicarboxylic acid having Y carbon atoms, which is
introduced iri excess relative to stoichiometry of the
diamine or diamines.
--
According to another embodiment, the polyamide bloclts
30 result from the condensation of at least two different
alpha-omega aminocarboxylic acids or of at least two
different lactams having from 6 to 12 carbon atoms or
of a lactam and an aminocarboxylic acid that does not
I
have the same number of carbon atoms optionally in the
35 presence of a chain limiter,
As examples of polyamicle blocks of the third type, we
may mention those formed by the following poly2mides
(copolyamides) :
glycol, 1,4-butylene glycol, 1,G-hexylene glycol,
branched diols such as neoper~tylylycol, 3-rnethylpentane
glycol, 1,2-propylene glycol, and cyclic diols such as
1,4-bis(hydroxymethyl)cyclohexane and 1,4-cyclohexane-
5 dimethanol,
Advantageously, the block copolymer of the present
invention forms a copolyetherester (abbreviation COPE),
i.e. a copolymer with polyester and polyether blocks.
10
The COPEs according to the invention therefore include
any TPE comprising at least one polyether block (PE)
derived at I east part] y from ethylene oxidc and/or
propylene oxide comprising 14C, preferably comprising
15 polyethylene glycol (or PEG) and/or polypropylene
glycol (or PPG) derived at least partially from
renewable materials, and at least one polyester block
PES (homopolymer or copolyester) derived from fossil
materials or else derived totally or partially (in the
20 case of mixed polyesters) from renewable raw materials,
The COPEs comprise polyether flexible bloclts derived
I
from polyetherdiols and polyester rigid bloclts, which
result from reaction of at least one dicarboxylic acid
25 with at least one chain-extending short diol unit. The
polyester bl oclts and polyether bloclts are jo i lned by
ester bonds resulting from the reaction of the acid
fu~ctions of the dicarboxylic acid with the OH
functions of the polyetherdiol. The chain-extending
30 short diol can be selected from the group comprising
neopentylglycol, cyclohexanedimethanol and aliphatic
glycols of formula HO(CH2),0H, in which n is an integer
from 2 to 10, The chain of polyethers and diacids forms
the flexiRle blocks, whereas the chain of glycol or of
35 butanediol with the diacids forms the rigid bloclts of
the cop~lyetherester,
Advantageously, the diacids are aromatic dicarboxylic
acids having from 8 to 14 carbon atoms. Up to 50 mol.%
of the aromatic dicarboxylic acid can be replaced with
at least one other aromatic dicarboxylic acid having
from 8 to 14 carbon atoms, and/or up to 20 mole% can be
replaced with an aliphatic dicarboxylic acid having
5 from 2 to 14 carbon atoms. As examples of aromatic
dicarboxylic acids, we may mention terephthalic acid,
isophthalic acid, dibenzoic acid, naphthalene
dicarboxylic acid, 4,4'-diphenylenedicarboxylic acid,
bis(p-carboxypheny1)methane acid, ethylene-bis-p-
10 benzoic acid, 1,4-tetramethylene-bis(p-oxybenzoic)
acid, ethylene-bis-(p-oxybenzoic) acid, 1,3-
trimethylene-bis-(p-oxybei~zoic) acid. As examples of
glycols, w~ may mention ethyl e r ~ e glycol, I, 3-
trimethylene glycol, 1,4-tetramethylene glycol, 1,6-
15 hexamethylene glycol, 1,3-propylene glycol, l,8-
octamethylene glycol, 1,10-decamethylene glycol and
1,4-cyclohexylene dimethanol.
The copolymers with polyester and polyether blocks are
20 copolymers having polyether units derived from
polyetherdiols as defined previously, for example
polyethylene glycol (PEG), polypropylene glycol (PPG),
polytrimethylene glycol (P03G) or polytetramethylene
glycol (PTMG), dicarboxylic acid units such as
25 terephthalic acid and glycol units (ethanediol) or 1,4-
butanediol. :;aid copolyetheresters are desc~ I bed in
patents EP402883 and EP405227, These polyetheresters
can also contain plasticizers and other additives that
are well known by a person skilled in the art,
30
According to a third embodiment, the block copolymer of
the present invention comprises at least one polyether
flekible block derived at least partially from ethylene
oxide and/or propylene oxide containing 14c, preferably
35 comprising at least one polyethylene glycol and/or one
polypropylene glycol obtained at least in part from raw
materials of renewable origin, and at least one
polyurethane rigid block,
Polyurethane (abbreviatioin PTi) means, in the sense 01
the invention, the products resulting from the reaction
of at least one diisocyanate which can be selected from
the aromatic diisocyanates (e.g. MDI, TDI) and/or the
5 aliphatic diisocyanates (e.g. HDI or
hexamethylenediisocyanate) with at least one short
diol. This chain-extending short diol can be selected
from the glycols mentioned above in the description of
the copolyetheresters. The polyurethanes included in
10 the composition of the copolymers according to the
invention can comprise all types of polyols, and in
particular those of renewable origin, such as polyols
derived from starch (erythritol, sorbitol , I I I , I I iitol,
mannitol), polyols derived from sugars such as sucrose
15 (isomalt, xylitol), polyols derived from maize, soya,
cotton, colza, sunflower or peanut (glycerol, propyl ene
glycol, ethylene glycol, coproduct of the reaction for
production of biodiesel) . As other examples of polyols
that can be included in the composition of these
20 polyurethanes, we may also mention polyethylene glycol
(PEG) , poly (l,2-propylene glycol) (PPG) , poly (l,3-
prop.yrlene glycol) (P03G), polytetramethylene glycol
(PTMG) , whether they are of petrochemical origin or
renewable origin. Advantageously, the PEG and/or PPG
25 produced from renewable materials will be used.
Advantageously, the block copolymer of the present
inyention forms a thermoplastic polyurethane
(abbreviation TPU) , i. e. a copolymer with polyurethane
30 and polyether bloclts, also called polyetherurethane,
I
The TPUs according to the invention therefore include
any TPE comprising polyether bloclts, the latter being
derived at least in part from ethylene oxide and/or
35 propylene oxide comprising 14cf including for example
PEG and/or PPG derived at least partially from
renewable materials; and PU blocks (homopolymer or
copolyurethane) derived from fossil materials or else
obtained totally or partially (in the case of mixed
polyurethanes) from renewable raw materials, ancl said
PU blocks can also be obtained from ethylene oxide
and/or propylene oxide compri.sing 14c, and comprise for
example PEG and/or PPG derived a-t least partially from
5 ren'ewable materials.
The polyetherurethanes result from the coliclensation of
polyether flexible blocks, which are polyetherdiols,
and of polyurethane rigid blocks. The polyurethane
10 bloclts and polyether blocks are joined together by
bonds resulting from the reaction of the isocyanate
functions of the polyurethane with the -OH functions of
the polyethe1 c l i o l .
If the block copolymers described above genera1l.y
comprise at least one polyether flexible bloclc and at
least one rigid block, it is evident that the present
invention in fact covers all the copolymers comprising
two, three, four (or even more) different bloclts
selected from those described in the present
description, if at least one of these blocks is derived
from at least one ethylene oxide and/or propylene oxide
monomer containing 14c.
25 Advantageously, the copolymer according to the
invention i:; a segmented block copolymer co~iiljrising
three diff-erent types of blocks (called "triblock" in
the present description of the invention), which result
frch the condensation of several of the blocks
30 described above. Said triblock is preferably selected
from co~olyetheresteramides, copolyetherarnideurethanes,
copolyetheresterurethanes, in which:
- the dercentage by mass of polyether flexible block
35 is above 20%;
- the percentage by mass of polyamide rigid block is
above 10%;
of the total mass of triblock,
The bloclc copolymer of the invention can also be used
alone or as a blend, said copolymer represen-tiny by
5 mass from 5 to loo%, preferably from 5 to 70%,
preferably from 5 to 30%, of the total mass of the
blend.
The copolymer according to the invention can have as
10 additives: stabilizers, plasticizers, lubricants,
natural or organic fillers, dyes, pigments, nacres,
antimicrobial age~ts, fireproofing agents, antistatic
agents, age~its modifyilly the viscosity o f the
copolymer, and/or any other additive well ltnown by a
15 person skilled in the art in the field of thermoplastic
polymers.
The present invention also relates to a method for
preparing a copolymer as defined above. The method
20 according to the invention comprises the stage of
supplying polyether (PE) derived at least partially
from ethylene oxide and/or propylene , oxide comprising
and conversion by synthesis t,; the block copolymer
according to the invention. Said conversion by
25 synthesis leads to a bloclc copolymer that comprises at
least one PI#:(-a;n d/or PPG block of at least 1)(1t1i ally
renewable origin. Preferably, said PE comprises PEG
and-f or PPG having a biocarbon content of at least I%,
30 In particular, the preparation of the copolymers with
polyamide block (s) and polyether block (s) according to
the invention comprises any means for attaching the
polyamide bloclts (PA bloclts) and polyether bloclts (PE
(
blocks) according to the present invention, In
35 practice, essentially two processes are used: a twostage
process and a one-stage process.
In the one-stage process, the polyamide precursors, the
chain limiter and the polyether are mixed together.
Thus, polyamide bloclss are also produced ir; the onestage
process, The simultaneous polycondensation of the
polyether blocks and of the precursors of the polyamide
blocks is preferably carried out at a temperature from
5 180 to 300"~. A polymer is then obtained having
essentially polyether blocks, polyamide blocks of very
variable length, but also the various reactants that
have reacted randomly, which are distributed
statistically (randomly) along the polymer chain.
10
Whether using a one-stage process or a two-stage
process, it is advantageous to work in the presence of
a catalyst . "Catalyst '' means ally proc1llc.r t 1 1 ~i1 can
facilitate bonding of the polyamide bloclts and of the
15 polyether blocks l~y esterificatioiz or by amidation, The
esterification catalyst is advantageously a derivative
of a metal selected from the group comprising titanium,
zirconium and hafnium or a strong acid such as
phosphoric acid or boric acid, The catalysts described
20 in the following patents can be used: US 4 331 786, US
, 4 115 475, US 4 195 015, US 4 839 441, US 4 864 014, US
4 230 838 and US 4 332 920, WO 04 037898, EP 1262527,
EP 1270211, EP 1136512, EP 1046~675, EP 1057870, EP
1155065, EP 506495 and EP 504058.
25
In the two :, tage process, the polyamide blc,, Its are
produced rirst, then in a second stage the polyamide
blqcks and polyether blocks are attached. The
pol-yetherdiol blocks according to the invention are
30 either used as they are and copolycondensed with
polyamide blocks with carboxylic ends, or they are
aminated, being converted to polyether diamines and
condensed with polyamide blocks with carboxylic ends.
i The general method of two--stage preparation of PEBA
35 copolymers having ester bonds between the PA blocks and
the PE bloclts is known and is described, for example,
in French patent FR 2 846 332, The general method of
preparation of the PEBA copolymers of the invention
having amide bonds between the PA blocks aiid the PE
blocks is known and is described tor example in
European patent EP 1 482 011.
The reaction of formation of the PA block is usually
5 carried out between 180 and 3 0 0 " ~pr~e ferably from 200
to 290°c, the pressure in the reactor is set between 5
and 30 bars, and it is maintained for about 2 to 3
hours. The pressure is reduced slowly, exposing the
reactor to atmospheric pressure, then the excess water
10 is distilled, for example for an hour or two.
Once the polyamide with carboxylic acid ends has been
prepared, thr polyether and a catalyst are adtl('d., The
polyether can be added in one go or gradually,
15 simj-larly for the catalyst. According to an
advantageous embodiment, first some or all of the
polyether is added; reactio:? of the OH ends of the
polyether and of the COOH ends of the pqlyamide begins
with formation of ester bonds and elimination of water,
20 As much of the water as possible is removed from the
reaction mixture by distillation, then the catalyst is
introduced for bonding the polyamide bloclts and
polyether blocks, This second stage is carried out with
stirring, preferably under a vacuum of at most
25 100 mbar, preferably of at most 50 mbar, preferably of
at most 20 ~rlbar, preferably at most 10 mbd~, at a
temperature such that the reactants and the copolymers
obt-ained are in the molten state. As an example, this
tesperature can be between 100 and 300"~ and is
30 generally between 200 and 2 5 0 " ~T~h e reaction is
monitored by measurement of the torque exerted by the
molten polymer on the stirrer or by measurement of the
electric power consumed by the stirrer. The end of the
f, reaction 1s determined by the target value of the
35 torque or power,
It will also be possible to add during the synthesis,
at the moment judged to be the most suitable, one or
more molecules used as aintioxidant, for example
According to one embodiment of the rnethod of the
invention, the stage of supplying PE in the method of
5 the invention further comprises a prior stage of
production of PEG and/or PPG polyether respectively
from ethylene oxide (EO) and/or propylene oxide (PO)
having >a biocarbon content of at least 1%. Any known
method for the production of PEG and/or PPG
10 respectively from ethylene oxide (EO) and/or propylene
oxide (PO) can be used for the present invention,
Volume A21, page 583, of "Ullmann's Enclyopedia of
Industrial Cli~~mistry"d escribes these methods.
15 By way of example, low-molecular-weight polyethylene
glycol (molecular weight less than 20 000) is produced
by reacting ethylene oxide with water, ethylene glycol
or ethylene glycol oliyomers. The reaction is catalyzed
by acid or basic catalysts, such as metal oxides or
20 alkali metal oxides. Ethyl~ne glycol and oligomers
thereof are preferable to water as starting reactants,
since they make it possible to obtain a polymer with a
narrow molecular weight distribution (lod
polydispersity). The polymer chain length depends on
25 the ratio between the reactants,
~ccording to the type of catalyst, the polymerization
30 mechani'sm may be cationic or anionic. The anionic
mechanism is preferred since it maltes it possible to
obtain a PEG of low polydispersity, The polymerization
(polycondensation) of ethylene oxide is an exothermic
f process, I
35
High-,molecular-weight polyethylene oxide (greater than
20 000) is synthesized by suspension polymerization.
During the polycondensation process, it is necessary to
maintain the growing polymer chain in solution. This
rea-ction is catalyzed by organometallic magnesium,
aluminum or calcium compounds, for example. In order to
prevent coagulation of the polymer chains out of -the
solution, chelating adclitives such as dimethylglyoxime
5 are used.
Alkali metal catalysts, such as sodium hydroxide
(NaOH), potassium hydroxide (KOH) or sodium carbonate
(Na2C03), are used to prepare low-molecular-weight
10 polyethyl.ene glycol.
According to another advantageous embodiment of the
method of t l i c s invention, said stage of supply incj PE,
such as PEG and/or PPG, from respectively ethylene
15 oxide (EO) and/or propylene oxide (PO), in the methocl
of the invention further includes a prior stage of
production of said ethylene oxide from e tl~ylene and/or
a prior stage of productiorl of said propylene oxide
from propylene; the ethylene and/or the propylene being
20 derived from renewable raw materials.
The production of ethylene oxide from ethylene
generally involves the direct oxidation of the ethylerie
by air or oxygen. A method of direct oxidation of
25 ethylene by oxygen, in the presence of a catalyst
between 240 =~nd2 7 0 " ~an d at a pressure of 15 10 25 atm
(1.5 to 2.5 Mpa) is preferably used according to the
re-a ction: C2H4 + 1/2 O2 >- C2H40
30 There are two principal methods for obtaining propylene
oxide and propylene: the conventional ex-chlorohydrin
route and catalytic epoxiclation. In the conventional
ex-chlorohydrin route, the propylene reacts with
chlorine in an aqueous medium so as to give a
35 chlorohydrin which is dehydrochlorinated in the
presence of Ca(OH)2, In catalytic epoxidation, three
hydroperoxides have an industrial importance: that of
the tert-butyl, that of ethylbenzene and propylene
peroxide. By reacting with propylene, they produce
propylene oxide
According to yet another embodiment, said stage of
supplying PE (PEG and/or PPG) from ethylene and/or
5 propylene in the method of the invention further
comprises a prior stage of production of said ethylene
and/or of said propylene from renewable raw materials.
By way of example, the production of ethylene from
10 renewable raw materials comprises the following stages:
a) fermentation of renewable raw materials and,
optionally, purification in order to produce at
least orie alcol-iol sclected from ethanol ,rnd the
mixtures of alcohols comprising ethanol;
b) dehydration of the alcohol obtained in order to
produce, in a first reactor, at least one alltene
selected from ethylene and mixtures of alltenes
comprising ethylene, and, optionally,
purification of the alkene in order to obtain
ethylene.
As renewable raw materials for the production of
ethylene or propylene, use may be made of vegetable rav
materials, materials of animal origin or materials of
25 plant or animal origin which are derived from recovered
materials (~cbcycled materials). In the senst. of the
invention, the materials of vegetable origin contain at
least sugars and/or starches. The vegetable materials
co;taining sugars are essentially sugar cane and sugar
30 beet; mention may also be made of maple, date palm,
sugar balm, sorghum, American agave; the vegetable
materials containinq starches are essentially cereals
and legumes such as corn, wheat, barley, sorghum, soft
1
wheat, rice, potato, cassava, sweet potato, or else
35 algae. Among the materials derived from recovered
materials, mention may in particular be made of
vegetable waste or organic waste comprising sugars
and/or starches. Preferably, the renewable raw
materials are vegetable materials,
As renewable raw materials, ilse may also be made of
cellulose or hemicellulose, or even lignin, which, in
the presence of the appropriate microorganisms, can be
5 converted into materials comprising sugar. Among these
renewable materials are straw, wood and paper, which
can advantageously originate from recovered materials.
Pmong the materials derived from recovered materials,
mention may in particular be made of vegetable waste or
10 organic waste comprising sugars and/or polysaccharides.
The lists provided above are not limiting,
The ferrncl-ital ion of the renecvable materials is c~arri~cl
out in the presence of one or more appropriate
15 microorganisms; this microorganism may optionally have
been naturally modified by a chemical or physical
constraint, or genetically modified, and the term
mutant. is then used.
20 Conventionally, the microorganism used for the
production of ethylene is Saccharomyces cerevisiae or a
mutai1t thereof.
Preferably, the fermentation stage is followed by a
25 purification stage intended to separate the ethanol
from the otht~a~l cohols,
In -stage b) the alcohol (s) obtained is (are) dehydrated
#- in order to produce, in a first reactor, at least one
30 alltene selected from ethylene and mixtures of alkenes
comprising ethylene, the by-product of the dehydration
being water.
1
Generally, the dehydration is carried out using an
35 alpha-alumina-based catalyst, such as the catalyst sold
by Eurcsupport under the trade name ESM 1108 (undoped
trilobed alumina containing little -approximately
0.04%- residual Na20).
The operating conditions for the dehydration are part
of the general knowledge of those skilied in the art;
by way of indication, the dehydration is generally
carried out at a temperature of the order of 40O0c,
5
Another advantage of the method according to the
invention is its energy saving: the fermentation and
dehydration stages of the method according to the
invention are carried out at relatively low
10 temperatures, less than 50O0e, preferably less than
400°C. In comparison, the stage of cracking and steam
cracking of oil to give ethylene is carried out at a
temperature OF the order of 800"~.T his enercjy saving
is also accompanied by a decrease in the amount of C02
15 released into the atmosphere.
Preferably, a purification stage is carried out during
stage a) or during stage b). The optionai purification
stages (purification of alcohol (s) obtairied in
stage a), purification of alkene (s) obtained in
stage b)) are advantageously carried out by absorption
on conventional filters, such as molecular sieves,
zeolites, carbon black, etc. ) . If. the alcohol obtained
in stage a) has been purified so as to isolate the
ethanol, the alltene obtained in stage b) is ethylene.
If the alcolrol obtained in stage a) has r r o i been
purified, a mixture of alkenes comprising ethylene is
obtained at the end of stage b).
30 Advantageously, at least one purification stage is
carried' out during stage a) and/or stage b) in order to
obtain ethylene having a purity of greater than 85% by
weight, preferably than 95% by weight, preferably than
99% by wdight and most preferentially than 99.9% by
35 weight. Particularly preferably, the alcohol obtained
in stage a) is purified so as to isolate the ethanol;
the allcene obtained in stage b) is consecluently
ethylene ,
The principal impurities present in the ethylene
derived from the dehydration of ethanol are ethanol,
propane ancl acetaldehyde. Advantageously, the ethylene
will have to be purifie~d, i. e. the ethanol, the propane
5 and the acetaldehyde will have to be eliminated, in
order to be able to easily oxidize the ethylene. The
ethylene, the ethanol, the propane and the acetaldehyde
can be separated by carrying out one or more
distillations at low temperature. The boiling points of
10 these compounds are the following:
Compound Boiling point
I
I ethanol 1 75.5 1
propane
acetaldehvde IThe
ethylene, the ethanol, the propane and the
acetaldehyde are cooled to approximately - 1 0 5 " ~ ~
15 preferably --103.7"~a~nd then distilled in order to
-42.1
20.8
extract the ethylene.
Another advantage of the method according to the
present invention concerns the impurities. The
20 impurities present in the ethylene derived from the
dehydration of ethanol are completely dif fert)t~ ~f rom
those present in the ethylene derived from cracking or
stsam cracking. In particular, among the impurities
present in the ethylene derived from cracking or steam
25 cracking are dihydrogen and methane, regardless of the
composition of the initial charge. Conventionally, the
separation of the dihydrogen and the methane is carried
o~lt after compression at 36 bar and coolin? to
I
approximately -120°C, Under these conditions, the
30 dihydrogen and the methane, which are liquid, are
separated in the demethanizer; then the ethylene is
recovered at 19 bar and - 3 3 " ~Th~e method according to
the present invention makes it possible to do away with
the stage for separating the dihydrogen and the
methane, and also makes it possible to cool the mixture
to -105"~ at atmospheric pressure instead of -120"~ at
36 bar. The cooling in this separation stage can also
be carried out under pressure in order to increase the
5 boiling point of the compounds to be separated (for
example around 20 bar and -35"~.) These differences
also contribute to making the method according to the
invention more economical (savings In terms 'of maserial
and energy, which is also accompanied by a decrease in
10 the amount of C02 released into the atmosphere).
Another advantage, is that the ethylene obtained in
stage b) of t he method according to the invent ion does
not comprise acetylene, unlike the ethylene obtained by
15 cracking or steam craclting. As it happens, acetylene is
very reactive and causes oligomerization sidereactions;
the obtaining of ethylene without acetylene
is therefore particularly advantageous,
20 Another advantage is that the method according to the
invention can be carried out in production units
located on the production site of the raw materials. In
addition, the size of the production units in the
method according to the invention is much smaller than
25 the size of a refinery: refineries are in fact large
plants whic11 are generally located far from I he raw
material production centers and are supplied by means
30 By way of example, the production of propylene from
renewable raw materials comprises the following stages:
a' ) fermentation of renewable raw materials, and,
optionally, purification, in order to produce an
alcohoi or a mixture of alcohols, said alcohol or
mixture of alcohols comprising at least isopropanol
and/~r at least one mixture of ethanol and/or
1-butanol,
b') dehydration of the alcohol or of the mixture of
alcohols obtained for the purpose of producing, in
at least one first reactor, an alltene or a mixture
of alkenes, said alkene or mixture of alkenes
comprising at least propylene, and, optionally,
purification of the mixture of alk.enes in order to
5 obtain propylene.
These stages a) and b) are in particular described in
application FR0858244.
10 As renewable raw materials, those already defined above
are used. In the case of polysaccharides, the vegetable
material used is generally in hydrolyzed form before
the fermentciI ion stage. This prel iminary hy(1 I 01 y s i s
stage thus allows for, for example, saccharif ication of
15 the starch in order to converc it to glucose, or
conversion of the sucrose to glucose.
The fermentation of the renewable materials is carried
out in the presence of one or more appropriate
20 microorganisms; this microorganism may optionally have
been naturally modified by a physical or chemical
constraint, or genetically modified, and the term
mutant is then used.
25 Advantageously, the microorganism used for the
production 01 propylene is Clostridium beijeriiictil-ii or
a mutant thereof, preferably immobilized on a support
of-the calcium or polymer fiber type. This fermentation
ma1;es it possible to obtain a mixture of alcohols
30 comprising ethanol, isopropanol and 1-butanol. The
alcohols obtained can be continuously extracted by
means of a pervaporation membrane; an advantage of the
use of this type of membrane is that of allowing better
preservatibn of the microorganisms, since the latter
35 are destroyed when their concentration becomes too
high,
Other microorganisms that can be used are Clostridium
aurantibutyricum or Clostridium butylicum, and also
mutants thereof. The fermentation of these raw
materials essentially results in the production of
isopropanol and/or butanols with possibly acetone.
5 According to a first variant, the alcohol obtaj-ned is
essentially isopropanol,
The fermentation stage is advantageously followed by a
purification stage, for example a distillation intended
10 to separate the isopropanol from the other alcohols.
According to this first variant, in stage b'), the
isopropanol i s dehydrated in order to produrc , in a
first reactor, at least propylene or a mixture of
15 alkenes comprising propylene, the by-product of the
dehydration being water.
Generally, the dehydration is carried out in the
presence of oxygen and water using an al-pha--alumina
20 catalyst, such as the catalyst sold by Eurosupport
under the trade name ESM 1100 (undoped trilobed alumina
containing little - approximately 0.04% - residual
Na20) .
25 The operatinq conditions for the dehydration are part
of the genel,il Itnowledge of those sltilled in I lie art;
by way oi indication, the dehydration is generally
carried out at a temperature of the order of 400"~.
*-
30 An advantage of this method according to the invention
is its knergy saving: the fermentation and dehydration
stages in the method according to the invention are
carried out at relatively low temperatures, less than
5 0 0 " ~p~rk ferably less than 400°C; in comparison, the
35 stage of craclting and steam craclting of oil to give
propylene is carried out at a temperature of the order
of 800°C.
This energy saving is also accompanied by a d3crease in
the amount of C02 released into the atmosphere,
According to a second variant, which can be implemented
following a fermentation by means of C l o s t r i d i ~ l m
5 beijerincltii or a mutant thereof, a mixture of alcohols
comprising at least. ethanol and 1-butanol is obtained.
Advantageously, the fermentation stage is followed by a
purification stage, for example a distillation intended
10 to separate the ethanol and the 1-butanol from the
other alcohols.
According to i 11is second variant, stare h" ) is ('arriccl
out by means of a series of reactors:
15 - in a first part of the series of reactors
(located at the inlet of the series of reactors in the
direction of the passage of the fluids) the ethanol and
the I-butanol are dehydrated for the purpose of
producing at least ethylene and 1-butene, this
20 dehydration being carried out under the same conditions
as the dehydration of isopropanol described above;
- in a second part of this first series of
reactors (located in the intermediate part of the
series of reactors) a reaction in which I-butene is
25 hydroisomerized to give 2-butene is carried out;
- in a Lllird part of this first series of ieactors
(located at the outlet of the series of reactors in the
di~ection of the passage of the fluids) metathesis of
the ethylene and of the 2-butene is carried out in
30 order to form propylene.
I
The details of the hydroisomerization and metathesis
rzactions are, for example, mentioned in patent
applicatidn FR 2 880 018.
35
The reaction in which I-butene is hydroisomerized to
give 2-butene is generally carried out usiny a
catalytic composition comprising a compound of a
group VIII transition metal, and more , particularly of
pal-ladium or of nicltel, The catalytic composition may
also comprise a. quaternary ammonium and/or phosphoniurn
salt, which makes it possible to carry out the reaction
at ,a relatively low temperature, in a closed, semi-
5 closed or continuous systerr~.
The metathesis reaction is carried out by bringing the
reactants into contact with a bed of catalyst; the
metathesis is generally carried out continuously and
10 comprises a reaction phase and a regeneration phase,
The catalysts used contain rhenium oxide on alumina or
an alumina-derived compound, for instance a silicaalumina
or a horon oxi de--alumina.
15 Preferably, the microorganism used is C l o s t r i d i u m
bei j e r i n c l c i i or a mutant thereof; this microorganism
can in fact be used to carry out the first variant and
the second variant, thus the method can be carried out
using isopropanol and/or the combination of ethanol and
20 1-butanol .
The optional purification stages (purification of
alcohol(s) obtained in stage a'), purification of
alltene (s) obtained in stage b' ) ) are advantageously
25 carried out by absorption on conventional filtei-s, such
as molecular sieves, zeolites, carbon black, el(
Adyantageously, at least one purification stage is
carried out during stage a') and/or stage bf ) in order
30 to obtain a propylene with a degree of purity
sufficibnt to form a polymerization or a
copolymerization. Propylene with a degree of purity of
greater than 85% by weight, preferably than 95% by
weight, ;referably than 99% by weight and most
35 preferentially than 99,9% by weight may preferably be
obtained. The principal impurities present in the
propylene derived from these dehydrations are acetone,
diisopropyl ether, acetaldehyde, 1-propanol and
hydrogen.
Advantageously, the propylene is purified, i. e. the
acetone, the diisopropyl ether, the acetaldehyde, the
1-propanol and the hydrogen will have to be eliminated,
5 The hydrogen, which has a boiling point much lower than
that of propylene, can be isolated by compressing the
gas and then cooling it slightly, for example at 19 bar
and -33°C.
10 The propylene, the acetone, the diisopropyl ether, the
acetaldehyde and the 1-propanol can be separated by
carrying out one or more distillations at low
temperature. 'J'11~ boiling points at atmospheric 1 ) I-cssure
of these compounds are the following:
Compound Boiling point ("c)
propylene -47.7
acetaldehyde 20,8
acetone 5 6
diisopropyl ether 68
1-propanol 97
The propylene, the acetone, the diisopropyl ether, the
acetaldehyde and the l-propanol are cooled, at
atmospheric pressure, to approximately -50°c,
preferably -47.7OC, and then distilled in order to
extract the 1, I-opylene. This distillation can ol~i ionally
be carried out under pressure in order to be able to
extract the propylene at a higher temperature,
Another advantage of the method according to the
present invention concerns the impurities. The
impurities present in the propylene derived from the
dehydration of the alcohols are completely different
f from those present in the propylene derived from
craclting or steam cracking. In particular, among the
impurities present in the propylene derived from
cracking or steam cracking are methylacetylene and
propadiene,
With the method according to the present invention,
methylacetylene and propadiene are also obtained, but
these compounds are then present in much lower amounts.
This difference makes it possible to limit the risks
5 , linked to the very reactive nature of methylacetylene
and also to limit the oligomerization side-reactions.
Another advantage is that the method according to the
invention can be carried out in production units
located on the raw material production site. In
10 addition, the size of the production units in the
method according to the invention is much smaller than
the size of a refinery: refineries are in fact large
plants which are generally located far from Ihe raw
material productj-on centers and are supplied by means
15 of pipelines. All these differences contribute to
making the method according to the invention more
economical (saving in terms of material and energy,
which is also accompanied by a decrease in the amount
of C02 released into the atmosphere) than the
20 corlventional methods for obtaining propylene.
The copolymers comprising PEG blocks obtained according
to the method of the invention have good properties ia
terms of density, uptake of water and/or mechanical
25 properties, antistatic properties, breathable
waterproof pi operties and lealctight properti c ::. The
copolymers comprising PPG blocks obtained according to
thc method of the invention have good properties, in
ter%s of low uptake of moisture, and in terms of
30 stability of the mechanical properties with respect to
ambient'moisture. The copolymers comprising both PEG
and PPG blocks of the invention have a combination of
these advantageous properties, The method of the
I invention ,makes it possible to readily modulate these
35 properties by varying the PEG/PPG ratio,
Finally, the method according to the invention makes it
possible to obtain a block copolymer from ethylene
oxide and/or propylene oxide of renewable origi~n, ancl
with performance that is identical (or even better)
than that of the corresponding copolymers (same
chemical formula) but of fossil origin. Finally, the
method of manufacture of block copolymers of the
5 inverltio~l makes it possible to reduce, or even
completely eliminate the consumption of raw materials
of petroleum origin, and use raw materials obtained
from the growing of plants, Furthermore, it makes it
possible to reduce emissions of greenhouse gases.

1- A block copolymer derived from at least one ethylene
oxide aiid/or propylene oxide monomer containing 14c
5 determined in accordance with standard ASTM D6866.
2- The copolymer as clain~ed in claim if comprising at
least one polyether block derived at least! partially
from ethylene oxide and/or propylene oxide containing
3- The block copolymer as claimed in claim 1 or 2,
compri sing:
- from 1 to 99% of at least one polyether I-lexible
15 block derived at least partially from ethylene oxide
and/or propylene oxide containing 14C , and
- from 1 to 99% of at least one rigid block selected
from: polyamide blocks, polyurethane blocks, polyester
blocks, and mixtures thereof.
20
4- The block copolymer as claimed in any one of
claims 1 to 3, characterized in that said at least one
polyether block comprises at least one polyethylen2
glycol (PEG) and/or polypropylene glycol (PPG) derived
25 at least partially from renewable materials.
5- The copolymer as claimed in either of claims 3 and
4, - characterized in that:
- rile proportion by mass of said at least one flexible
30 bloclc represents from 5 to 95%, preferably from 5 to
85%,
- the proportion by mass of said at least one rigid
block represents from 5 to 95%, preferably from 15 to
95%, I
35 of the total mass of the copolymer.
6- The copolymer as claimed in any one of claims 3 to
5, characterizecl in that saicl at least one rigid bloclc
is derived at least partially from renewable raw
materials
7- The copolymer as claimed in any one of claims 3 to
6, characterj-zed in that said at least one polyether
5 bloclc and/or said at least one rigid block is/are
derived totally from renewable materials.
8- The copolymer as claimed in any one of the preceding
claims, comprising a content of biocarbon of at least
10 1%, which corresponds to a 14~/12c isotope ratio of at
least l.2xl0-~~.
9- The copolymer as claimed in any one of the pi c.cedinq
claims, comprising a content of biocarbon above 5%,
15 preferably above lo%, preferably above 25%, preferably
above 50%, preferably above 75%, preferably above 90%,
preferably above 95%, preferably above 98%, preferably
above 99%, advantageously roughly equal t.o loo%,
20 10- The copolymer as claimed in any one of the
preceding claiims, characterized in that it comprises at
least one polyamide bloclc,
11- The copolymer as claimed in claim 10, characterized
25 in that the polyarnide comprises a copolyamide.
12- The copolymer as claimed in claim 10 or 11,
ch-a-r acterized in that said at least one polyamide block
cofiprises at least one of the following molecules:
30 amino-11-undecanoic acid, n-heptylamino-11-undecanoic
acid, 'succinic acid, azelaic acid, sebacic acid,
dodecanedioic acid, myristic acicl, tetradecanedioic
acid, hexadecanedioic acid, octadecanedioic acid,
butanediardine, psntanediamine, decamethylenediamine,
35 fatty diacid(s), fatty acid dimer(s) and mixtures
thereof
13- The copolymer as claimed in any one of claims 10 to
12, characterized in that said at least one polyamide
block comprises at least one monomer selected from the
fol.lowiny polyamide monomers: 11., 5,4, 5.9, 5,10, 5-12,
5.13, 5.14, 5.16, 5.18, 5,36, 6.4, 6.9, 6,10, 6.12,
and mixtures thereof.
14- The copolymer as claimed in any one of the
10 preceding claims, characterized in that said copolymer
is a copolymer comprising polyether blocks and
polyamide blocks (PEBA) .
15- The copolymer as claimed in any one of the
15 preceding claims, characterized in that said copolymer
comprises at least one polyester block.
16- The copolymer as claimed in claim 15, characterized
in that the polyester comprises a copolyester.
2 0
17- The copolymer as clai~ned in claim 15 or 16,
characterized in that said at least one polyester block
comprises at least one of the 'following molecules:
ethylene glycol, 1,3-propanediol, 1,4-but-anediol, 1,10-
25 decanediol, 2,5-furandicarboxylic acid, succinic acid,
azelaic aci ( I , sebacic acid, dodecanedioi c acid,
myristic dcid, tetradecanedioic acid, hexadecanedioic
aci- d, octadecanedioic acid, fatty diacid, dimerized
fafty acid.
30
18- The copolymer as claimed in any one of claims 15 to
17, characterized in that said copolymer is a
polyetherester,
(
35 19- The copolymer as claimed in any one of the
preceding claims, characterized in that said copolymer
comprises at least one polyurethane block.
20- The copolymer as claimed in claim 19, characterized
in that the polyurethane cori~prises a copolyurethane,
21- The copolymer as claimed in claim 19 or 20,
characterized in that said at least one polyurethane
5 bloclc is manufactured from at least one polyo1 of
renewable origin, selected from the following polyols:
polyols derlved from starch; erythritol; sorbitol;
maltitol; mannitol; polyols derived from sugars,
sucrose; isomalt; xylitol; polyols derived from maize,
10 soya, cotton, colza, sunflower or peanut; glycerol;
propylene glycol; ethylene glycol; coproducts of the
reaction for production of biodiesel; polyethylene
glycol (PEG) , poly (I, 2-propyle~~e gl yc(o1) (PPG),
poly(l,3-propylene glycol) (P03G), polytetrarnethylene
15 glycol (PTMG) .
22- The copolymer as claimed in any one of claims 19 to
21, characterized in that said copolymer is a
polyetherurethane.
20
23- The copolymer as claimed in any one of claims 4 to
22, characterized in that said at least one polyether
bloclc additionally comprises polyethers other than PEG
,
and/or PPG, such as P03G, PTMG, P O ~(Y3 -
25 methyltetrahydrofuran) of renewable origin or of fossil
origin and/or PEG or PPG of fossil origin.
24- The copolymer as claimed in any one of the *
preceding claims, characterized in that said copolymer
30 is a tribloclc comprising three different bloclts, said
triblock being selected from copolyetheresteramides,
copolyetheramideurethanes, copolyetheresterurethanes,
characterized in that:
- the pkrcentage by mass of polyether flexible block
35 is above 20%;
- the percentage by mass of polyamide rigid block is
above 10%;
of the total mass of triblock,
25- A method for preparing the bloclc copolymer as
claimed in any one of the preceding claims, comprising
the stage of supplying polyether derived at least
partially from ethylene oxide and/or propylene oxide
containing 14c and conversion by synthesis to a bloclt
copolymer.
26- The method as claimed in claim 25, characterized in
that said polyether comprises polyethylene glycol
and/or polypropylene glycol having a biocarbon content
of at least 1%.
27- The me1 hod as claimer1 in c1-aim 25 or 26,
characterized in that the supply stage comprises a
stage of production of polyether from ethylene oxide
and/or propylene oxide having a biocarhon content of at
least 1%.
28- The method as claimed in claim 27, characterized in
that the supply stage comprises a stage of production
of said ethylene oxide and/or propylene oxide
respectively from ethylene and/or propylene,
29- The method as claimed in claim 23, characterized i.n
that the supply stage comprises a stage of production
of said ethy l (\lie and/or propylene from plant bioi~i~lss,
30- The method as claimed in claim 29, - characterized in
thgt the production of ethylene from renewable raw
materials comprises the following stages:
a) fermentation of renewable raw materials and,
optionally, purification in order to produce at
least one alcohol selected from ethanol and
mix?ures of alcohols comprising ethanol;
b) dehydration of the alcohol obtained in order to
produce, in a first reactor, at least one alkene
selected from ethylene and mixtures of alltenes
comprising ethylene, and, optionally,
purification of the alltene in order to obtain
ethylene.
31- The method as claimed in claim 28, characterized in
that the production of propylene from renewable raw
5 materials comprises the following stages:
a') fermentation of renewable raw materials, and,
optionally, purification in order to produce an
alcohol or a mixture of alcol.iols, said alcohol or
mixture of alcohols comprising at least isopropanol
10 and/or at least one mixture of ethanol and
1-butanol,
b') dehydration of the alcohol or of the mixture of
alcoliols ohtaincd for the purpose of produr i ng, in
at least one first reactor, an alkene or a mixture
of alkenes, said allcene or mixture of alkenes
comprising at least propylene, and, optionally,
purification of the mixture of alkenes in order to
obtain propylene.
20 32- Use of the bloclc copolymer as claimed in any one of
claims 1 to 24, in automobiles, textiles, woven
fabrics, nonwovens, clothing, shoes, sports articles,
leisure articles, electronics, computer equipment,
health equipment, industrial additives, packaging
25 and/or household products.
33- The use as claimed in claim 32, characterized in
that the block copolymer as claimed in any one of
claims 1 to 24 is used in instrument panels, airbags,
30 soles of sports shoes, golf balls, tubes for medical
use, catheters, angioplasty balloons, peristaltic
bands, conveyor belts, breathable waterproof rainwear,
antistatic additives, skin panels, and/or synthetic
leather, thermoplastic films, packaging films,
35
34- The use as claimed in claim 32 or 33, characterized
in that the bloclc copolymer as claimed in any one of
claims 1 to 24 is usecl alone or mixed, saicl copolymer
representing by mass from 5 to loo%, preferably from 5
to 70%, p r e f e r a b l y from 5 to SO%,
35- The copolymer as claimed in claim 14, characterized
in that said PEBA is based on PA11-PEG, PA10,lO-PEG,
5 PA10.12-PEG, PA10,14--PEG, PA6 10-PEG, PA6,12-PEG,
PA6.18-PEG, PA11-PPG, PA10.10-PPG, PA10.12--PPG,
PA10.14-PPG, PA6.10-PPG, PA6.12-PPG, PA6.18-PPG, PA11-
PEG/PPG, PA10. ~O-PEG/PPG, PA10. 13-PEG/PPG, PA2.0.14-
PEG/PPG, PA6. 10-PEG/PPG, PA^. 12-PEG/'PPG, and/or 'PA6.18-
10 PEG/PPG, preferably based on PA11-PEG, PA11-PPG or PA11-PEG/PPG.