Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR THE PREPARATION OF EP(D)M WITH A BRIDGED
PENTADIENYL-FLUORENYL TRANSITION METAL COMPLEX
The present invention relates to a process for the preparation of rubber-like
ethylene/propylene copolymers and ethylene/propylene/non-conjugated dime
terpolymers, and to the use of the polymers obtainable in this way for the
production
of all types of shaped articles.
Because of their saturated main chain, ethylene/propylene copolymers (EPM) and
ethylene/propylene/non-conjugated dime terpolymers (EPDM) are important
starting substances in industry. To obtain their final properties, the
polymers must
be crosslinked with peroxides, radiation or sulfur/sulfur agents. The content
of
unsaturated bonds in EPDM, which is adjusted via the content of non-conjugated
dime, is of importance precisely in the case of sulfur crosslinking. Many
catalysts
have been developed for tailor-making the composition and microstructure of
EPM
and EPDM.
It is prior art to prepare EPM and EPDM with catalysts based on Ziegler-Natta
systems. Vanadium-containing catalysts are usually employed for this. The
processes are carried out in solution, suspension or the gas phase.
It is prior art to prepare ethylene/propylene copolymers with bis-
cyclopentadienyl-
zirconium compounds (EP-B-129 368), but the degree of incorporation of non-
conjugated dime is usually unsatisfactory.
US-A-4.892.851 discloses a compound in which a cyclopentadienyl ligand (cp) is
linked with a fluorenyl ligand (flu) via a dimethylmethylene bridge.
The doctrine of EP-A2-512 554 is also bridged cp-flu compounds and the use
thereof as catalysts for the polymerization of olefins.
~7 33 36~
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The doctrine of US-A-x.158.920 is bridged cp-flu compounds and the use thereof
for
the preparation of stereo-specific polymers. Bridged cp-flu compounds are also
known from further documents, but all the documents have the common feature
that
the bridge member is a linear chain. However. the catalysts of this type show
weaknesses in the chain length of the EP(D)M obtained, so that oils or waxes,
which
cannot be used for the production of shaped articles. are often obtained.
There was thus the object of providing a process for the preparation of EPM
and
EPDM which does not have the disadvantages of the prior art.
This object is achieved according to the invention by a process for the
polymerization of ethylene, propylene and optionally a non-conjugated dime
employing a metallocene as the catalyst. characterized in that the metallocene
employed is a compound of the general formula (I)
IJ
Ra
R: LRs
R
R"
M ,.."... X
20 R3 R\ ~X (I)~
14
R ~ w~w~R
w ~ \ Rs
~~ w
w
R'3.-w~ ~R,o
~w
w ~ ~ R"
25 R'2
wherein
R' to R~' independently of one another represent H. C,-Ci2-alkyl, C~-C,Z-aryl
or C~-
C,Z-aralkyl radicals,
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X represents H, halogen or C,-C,z-alkyl radicals,
W represents a carbon atom or an optionally substituted atom of groups 13, 1 S
or 16,
Y represents C,-C,2-alkyl radicals or an optionally substituted atom of groups
14, 15 or 16 and
M represents a metal of group 4,
optionally in the presence of one or more co-catalysts.
C,-C,2-Alkyl is understood as meaning all the linear or branched alkyl
radicals
having 1 to 12 C atoms known to the expert, such as methyl, ethyl, n-propyl,
i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, neo-pentyl and hexyl,
which in
their turn can again be substituted. Possible substituents here are halogen or
also C,-
C,2-alkyl or -alkoxy, as well as C6 C,2-cycloalkyl or -aryl, such as benzoyl,
trimethylphenyl, ethylphenyl, chloromethyl and chloroethyl.
C,-C,2-Alkoxy is understood as meaning all the linear or branched alkoxy
radicals
having 1 to 12 C atoms known to the expert, such as methoxy, ethoxy, n-
propoxy,
i-propoxy, n-butoxy, i-butoxy, t-butoxy, n-pentoxy, i-pentoxy, neo-pentoxy and
hexoxy, which in their turn can again be substituted. Possible substituents
here are
halogen or also C,-C,2 alkyl or -alkoxy, as well as C6 C,2-cycloalkyl or -
aryl.
C6 C,2-Aryl is understood as meaning all the mono- or polynuclear aryl
radicals
having 6 to 12 C atoms known to the expert, such as phenyl and naphthyl, which
in
their turn can again be substituted. Possible substituents here are halogen,
nitro,
hydroxyl or also C,-C,Z-alkyl or -alkoxy, as well as C6 C,Z-cycloalkyl or -
aryl, such
as bromophenyl, chlorophenyl, toluyl and nitrophenyl.
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C,-C,2-Aralkyl is understood as meaning a combination of the above alkyls with
the
abovementioned aryls.
The radicals R' to R'z are preferably hydrogen, methyl, ethyl, propyl, t-
butyl,
methoxy, ethoxy, cyclohexyl, benzoyl, methoxy, ethoxy, phenyl, naphthyl,
chlorophenyl and toluyl.
If the radicals X represent halogen, this is understood by the expert as
meaning
fluorine, chlorine, bromine or iodine, and chlorine is preferred.
If Y represents an atom of groups 14, 1 S or 16, this is understood as meaning
preferably Si, Ge, Su, Pb, N, P, O and S. Si, N and P are particularly
preferred.
M represents Ti, Zr and Hf, and Zr is preferred.
Catalysts of the general formula (II)
R'
R~ c~
R 5«"","
R°
R (II)
3 R' M~'
Rrs \\ Rs
a
~~ R
~''L R,~ R:
wherein
R' to R'Z independently of one another represent H, C,-C,Z alkyl or C6 C,2-
aryl
radicals,
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X represents Cl or methyl and
M represents Ti or Zr
are preferably employed.
The catalyst of the formula (III)
"""", a
Zr .",~" CI
(EI)~
~ CI
is very particularly preferably employed.
The invention also provides the compounds of the formula (I), (II) and (III).
The compounds of the formula (I), (II) and (III) are often employed in
combination
with co-catalysts for the polymerization according to the invention. Possible
co-
catalysts are the co-catalysts known in the field of metallocenes, such as
polymeric
or oligomeric alumoxanes, Lewis acids and aluminates and borates. In this
connection reference is made in particular to Macromol. Symp. vol. 97, July
1995,
p. 1 - 246 (for alumoxanes) and to EP 277 003, EP 277 004, Organometallics
1997,
16, 842-857 (for borates) and EP 573 403 (for aluminates). Particularly
suitable co-
catalysts are methylalumoxane, methylalumoxane modified by
triisobutylaluminium
(TIBA) and diisobutylalumoxane, trialkylaluminium compounds, such as
trimethylaluminium, triethylaluminium, triisobutylaluminium and
triisooctylaluminium, and moreover dialkyaluminium compounds, such as
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diisobutylaluminium hydride and diethylaluminium chloride, substituted
triarylboron compounds, such as tris(pentafluorophenyl)borane, and ionic
compounds which contain tetrakis(pentafluorophenyl)borate as the anion, such
as
triphenylmethyl tetrakis(pentafluorophenyl)borate, trimethylammonium
tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis
(pentafluorophenyl)borate, substituted triaryaluminium compounds, such as
tris(pentafluorophenyl)aluminium, and ionic compounds which contain
tetrakis(pentafluorophenyl)aluminate as the anion, such as triphenylmethyl
tetrakis(pentafluorophenyl)aluminate and N,N-dimethylanilinium tetrakis
(pentafluorophenyl)aluminate.
It is of course possible to employ the co-catalysts as a mixture with one
another.
The most favourable mixture ratios in each case can be determined by suitable
preliminary experiments.
The polymerization according to the invention is carried out in the gas,
liquid or
slurry (suspension) phase. The temperature range for this extends from -
20°C to
+200°C, preferably 0°C to 160°C, particularly preferably
+20°C to +80°C; the
pressure range extends from 1 to 50 bar, preferably 3 to 30 bar.
Polymerization-inert
solvents which are co-used are, for example: saturated aliphatics or
(halogeno)aromatics, such as pentane, hexane, heptane, cyclohexane, petroleum
ether, petroleum, hydrogenated benzines, benzene, toluene, xylene,
ethylbenzene,
chlorobenzene and analogues or mixtures thereof. These reaction conditions for
the
polymerization are known in principle to the expert.
The polymerization according to the invention is preferably carried out in the
presence of inert organic solvents. Possible inert organic solvents are, for
example:
aromatic, aliphatic and/or cycloaliphatic hydrocarbons, such as, preferably,
benzene,
toluene, hexane, pentane, heptane and/or cyclohexane or mixtures thereof. The
polymerization is preferably conducted as solution polymerization or in
suspension.
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In another preferred embodiment the process according to the invention is
carried
out in the gas phase. The polymerization of olefins in the gas phase was
realized
technologically for the first time in 1962 (US 3.023.203). Corresponding
fluidized
bed reactors have been prior art for a long time.
The organometallic compound of the formula (I), (II) or (III) and optionally
the co-
catalyst are also applied to an inorganic support and employed in
heterogenized form
when used in suspension or the gas phase. Suitable inert inorganic solids are,
in
particular, silica gels, clays, alumosilicates, talc, zeolites, carbon black,
inorganic
oxides, such as silicon dioxide, aluminium oxide, magnesium oxide or titanium
dioxide, or silicon carbide, preferably silica gels, zeolites and carbon
black. The
inert inorganic solids mentioned can be employed individually or as a mixture
with
one another. In another preferred embodiment organic supports are employed
individually or as a mixture with one another or with inorganic supports.
Examples
of organic supports are porous polystyrene, porous polypropylene or porous
polyethylene.
Possible non-conjugated dimes are all the dimes known to the expert in which
the
double bonds have different reactivities towards the catalyst system employed,
such
as 5-ethylidene-2-norbornene (END), 5-vinylnorbornene, 1,4-hexadiene, 7-methyl-
1,6-octadiene and dicyclopentadiene. 5-Ethylidene-2-norbornene and 1,4-
hexadiene
are preferred.
It may be advantageous to purify the starting substances to remove impurities,
such
as oxygen, water or polar substances. The polymerization is in general
conducted
under inert conditions.
The rubber-like EPM and EPDM which can be prepared according to the invention
are distinguished by a low crystalline content. The crystalline content is in
general
less than 30%, preferably less than 20%, particularly preferably less than
10%, very
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_g_
particularly preferably in the range from 0 to 10%. The crystalline content
can be
determined by measurements of the fusion enthalpy ratios and by the DSC
method.
The following factor has proved appropriate here:
crystallinity - fusion enthalpy J/g B100
J/g
The non-crosslinked EPM and EPDM are readily soluble in the usual solvents,
such
as hexane. heptane or toluene.
1 () The ethylene content is in the range from 5 to 95 wt.%. preferably 40 to
90 wt.%.
The propylene content is in the range from ~ to 95 wt.%, preferably 9.5 to
X9.5 wt.%.
1 ~ The content of non-conjugated dime is in the range from 0 to 20 wt.%.
preferably
0.5 to 12 wt.%.
It is commonplace that the individual contents of the monomers must add up to
100% and an expert will accordingly choose them appropriately from the
individual
w-t.% ranges.
It is a particular advantage of the process according to the invention that
the catalyst
can remain in the end product and causes no interference during further
processing
or use.
2J
The further processing of the EPM and EPDM which can be prepared according to
the invention usually comprises a crosslinking step with peroxides.
sulfur/sulfur
donors or high-energy radiation. This step is known to the expert. but
reference may
be made expressly at this point to "Handbuch fiir die Gummi-Industrie,
published by
Bayer AG, Leverkusen, 2nd edition. 1991; p. 231 et seq.". The EPM and EPDM can
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also be extended with oils, if this is desired.
The invention also provides the use of the rubber-like EPM and EPDM which can
be
prepared according to the invention for the production of all types of shaped
articles.
Shaped articles which may be mentioned are seals, O-rings, profiles, sheets,
coverings for other materials and damping elements.
For applications in the low temperature range. it may be advantageous to
employ
1 (> products with a crystallinity in the range from 0 to 5%.
It is of course possible also to employ the rubber-like EPM and EPDM according
to
the invention as a mixture with other polymers or rubbers, such as SBR, BR,
CR,
NBR; ABS. HNBR. polyethylene, polypropylene, polyethylene copolymers, LDPE,
I ~ LLDPE, HDPE. HMWPE, polysiloxanes, silicone rubbers and fluorinated
rubbers.
Corresponding mixtures are known to the expert and can be optimized by a few
experiments.
It may also be advantageous to add fillers, such as carbon black. silica,
talc, silicic
?0 acids and metal oxides. These fillers and their use are known to the
expert, but
reference may be made expressly to the Encyclopaedia of Polymer Science and
Engineering, vol. 4, p. 66 et seq.
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Examples
All work up to the working up of the polymer was carned out in an inert gas
atmosphere using Schlenk, spraying and glovebox techniques. Argon from Linde
with a purity of >_99.996%, which was after-purified by means of an Oxisorb
cartridge from Messer-Griesheim, DE, was used as the inert gas. The toluene
used
for polymerizations and for preparation of catalyst and co-catalyst stock
solutions
was obtained from Riedel-de-Haen, DE, with a purity of >_99.5%. It was
predried
over potassium hydroxide for several days, degassed, heated under reflux over
a
sodium/potassium alloy for at least one week and finally distilled for use.
Example 1: Preparation of 1,3,3-trimethyl-2,3-dihydropentalene
600 ml methanol, 50 ml (0.61 mol) freshly distilled cyclopentadiene and 75 ml
(0.61 mol) diacetone alcohol are placed under argon in a 1 1 NZ flask. After
controlling the temperature of the mixture to 0°C, 80 ml freshly
distilled pyrrolidine
are added. After warming to room temperature the mixture is stirred for 18
hours.
The intensely yellow-coloured solution is concentrated to 200 ml and distilled
over a
30 cm Vigreux column. 16.9 g of a yellow-orange, viscous oil (distillation
temperature 64 to 70°C) are isolated under an oil pump vacuum at an oil
bath
temperature of 130 to 160°C. This fraction is distilled over a mirrored
25 cm
cracking tube column. 2.1 g (14 mmol) of the desired product are obtained
under
11 mbar at a distillation temperature of 66 to 69°C and at an oil bath
temperature of
150°C. The 'H-NMR spectrum shows a product to 6,6-dimethylfulvene ratio
of 5
to 1.
'H-NMR (100 MHz, CDC13, J [Hz], TMS):
8 [ppm]: 6.72 (1 H, d, 3J = 5.0, olefin. Cp proton)
6.06 (2 H, dd,'J = 5.0, 4J = 0.8, olefin. Cp protons)
2.82 (2 H, s, methylene protons)
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2.14 (3 H, s, methyl protons)
1.26 (6 H, s, methyl protons)
Example 2: Preparation of 1-fluorenyl-1,3,3-trimethyl-1,2,3,6-
tetrahydropentalene
9.56 ml (15.3 mmol) of a 1.6 N solution of n-butyllithium in hexane are added
dropwise to a mixture of 2.54 g (15.3 mmol) fluorene in 50 ml THF in a 250 ml
Nz
flask with a dropping funnel and reflux condenser at -50°C in the
course of 30
minutes. A$er warming to room temperature the solution is stirred for a
further
eight hours and then heated briefly at the boiling point. After cooling to -
50°C
1.68 g (11.5 mmol) 1,3,3-trimethyl-2,3-dihydropentalene in 20 ml THF are added
dropwise in the course of two hours and the mixture is stirred overnight at
room
temperature. After boiling up briefly, 20 ml half concentrated hydrochloride
acid
are added. The low aqueous phase is saturated with NaCI and extracted with
diethyl
ether. The combined organic phases are washed twice with 20 ml saturated NaCI
solution each time. They are then dried over NazS04. After all the solvent has
been
condensed off in a rotary evaporator, 5.0 g of crude product are obtained as
an
orange-yellow, viscous oil. The ligand is purified by column chromatography
(silica
gel 60; particle size 0.015-0.040 mm; petroleum ether 60/70). Yield: 1.10 g
(3.5 mmol; 30%, based on the pentalene)
'H-NMR (100 MHz, CDCI3, TMS):
8 [ppm]: 7.83-6.97 (8 H, m, arom. protons)
6.65-6.32 (2 H, m, olefin. Cp proton)
4.05 (1 H, s, aliph. fluorene proton)
3.40, 3.02, 2.72 (2 H, m, aliph. Cp protons)
1.73. 1.69 (3 H, s, methyl protons, 2 isomers)
1.34-1.18 (2 H, m, methylene protons)
0.98 (3 H, s, methyl protons)
0.30 (3 H, s, methyl protons)
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Mass spectrum: m/z 312 (molecular peak)
Example 3: Preparation of [1-(rls-fluorenyl)-1,3,3-trimethyl-rls-tetrahydro-
pentalenyl]-zirconium dichloride
4.4 ml (8.0 mmol) of a 1.8 molar solution of n-butyllithium in hexane are
added
dropwise to a mixture of 1.1 g (3.2 mmol) 1-fluorenyl-1,3,3-trimethyl-1,2,3,6-
tetrahydropentalene in 25 ml THF at room temperature. After four days the
mixture
is heated briefly at the boiling point. After complete condensation of the
solvent the
precipitate formed is washed twice with 10 ml pentane each time. After
decanting
the pentane 0.75 g (3.2 mmol) zirconium tetrachloride and, at -60°C, 35
ml pentane
are added. The mixture is stirred at room temperature for three and a half
days.
After decanting the pentane the residue is extracted with a total of 60 ml
methylene
chloride. After concentrating the solution 1.94 g of crude product are
obtained.
After renewed recrystallization from methylene chloride 150 mg (0.3 mmol, 10%
based on the zirconium tetrachloride) of the product are obtained as a
crystalline,
red, photosensitive solid. (X-ray structural analysis: fig. 3)
Mass spectrum: m/z 472 (molecular peak)
Polymerization:
Methylaluminoxane from Witco was used as the co-catalyst. This was employed as
a solution in toluene with a concentration of 100 mg/ml.
The gaseous monomers ethene (Linde) and propene (Gerling, Holz & Co.) used
have
parities of >_99.8%. Before introduction into the reactor they were passed
through
two purification columns in each case in order to remove traces of oxygen and
sulfur. The two columns had dimensions of 3 ~ 300 cm3, an operating pressure
of
8.5 bar and an operating temperature of 25°C and ensured a volume flow
of approx.
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1/min. 'The first column in each case was filled with Cu catalyst (BASF R3-11)
and the second in each case with a molecular sieve ( 10 ~).
The 5-ethylidene-2-norbornene (ENB) was obtained as a mixture of the endo and
5 exo form with a purity of >_99% from Aldrich, degassed, stirred with
n-tributylaluminium (Witco, 20 ml per 1 1 ENB) for one week and condensed off.
Procedure
The apparatus was first tested for leaks, during which both a vacuum applied
and an
10 argon pressure introduced of 4 bar had to remain constant for several
minutes. Only.
then was the apparatus heated thoroughly for one hour at 95°C under an
oil pump
vacuum. The reactor was then brought to the reaction temperature of 30 or
60°C and
charged. The temperature was maintained with an accuracy of ~ 1 °C
during the
reaction.
For the terpolymerizations 500 ml toluene and 10 ml MAO solution were
initially
introduced in counter-current with argon and the particular amount of the
liquid
monomer (ENB) required was then added. The solution was saturated first with
propene and then with ethene. When saturation was reached, the polymerization
was started by spraying in the metallocene solution. The ethene was topped up
during the reaction so that the overall pressure remained constant during the
reaction, but the monomer composition of the batch changed constantly. The
reactions were therefore interrupted at low conversions. The reaction was
ended by
destroying the catalyst by spraying in 5 ml ethanol and the gaseous monomers
were
let down carefully in a fume cupboard.
A 1.0 ~ 10-3 molar stock solution of the particular catalyst compound in
toluene was
employed for the polymerization.
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Experiment 4 to 9:
The product from example 3 in a homogeneous form was employed as the catalyst
compound.
The monomer composition of the experiment, the partial pressures of the
individual
monomers and the reaction temperatures are shown in table 1.
Experiment 10 (comparison experiment):
(CH3)ZC cp flu ZrCI, in a homogeneous form was employed as the catalyst
compound.
The monomer composition of the experiment, the partial pressures of the
individual
monomers and the reaction temperatures are shown in table 1.
Table 1: Compositions of the batches
Ex- XetheneXpropcneXENB petheneppropenevENB vttal CtW T
peri- mn.
ment
[bar][bar] [ml] [ml] [mol/I][C]
4 0.3 0.6 0.1 2.57 1.00 6.75 S 17 1 30
S 0.3 0.6 0.1 3.68 1.93 6.75 517 1 60
6 0.2 0.8 - 1.72 1.28 - S 10 1 30
7 0.2 0.8 - 2.45 2.53 - 510 1 60
8 0.4 0.6 - 3.42 1.00 - S 10 1 30
9 0.4 0.6 - 3.92 1.57 - 510 0.8 60
10 0.3 0.6 0.1 2.57 1.00 6.75 517 1 30
The polymer solutions in toluene from experiment 4-10 were removed from the
reactor and stirred overnight with 200 ml aqueous 5% hydrochloric acid. The
toluene phase was separated off, neutralized with SO ml saturated sodium
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bicarbonate solution and washed three times with 100 ml dist. water each time.
After substantial removal of the toluene and liquid monomer on a rotary
evaporator
at 30°C under 40 mbar, it was attempted to precipitate the polymer by
addition of
100 ml ethanol. If this was successful, the polymer was removed from the
solution
S and dried; if the polymer remained a highly viscous liquid, the residual
toluene and
monomer and the ethanol were stripped off on a rotary evaporator and the
polymer
was then dried. Drying was carried out overnight at 60°C under an oil
pump
vacuum.
Analysis of the polymer:
An Ubbelohde viscometer (capillary Oa, K = 0.005) temperature-controlled at
135°C
was used for the measurements of the weight-average viscosity M,,.
Decahydronaphthalene (Decalin), provided with 1 g/1 2,6-di-rerrbutyl-4-
methylphenol as a stabilizer, was used as the solvent. The flow-through times
were
measured with a Viskoboy 2.
To prepare the polymer solution, 50 ml decahydronaphthalene were added to 50
mg
of the polymer, the solid was dissolved overnight in a closed flask at
135°C, without
stirring, and the solution was filtered hot before measurement. To clean the
capillary, this was flushed twice with polymer solution. The measurements were
repeated until constant values were established or until there was a number of
measurement values sufficient to obtain a mean.
The molecular weights Mn for the EPM and the EPDM were calculated with the
Mark-Houwink constant for PE: k = 4.75 ~ 10~, a = 0.725.
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Table 2: Activities and molecular weights Mn
Experiment Activity Molecular weight M,, with Scholte
M,, correction [g/mol]
[g/mol]
4 1,600 72,400 no correction
1,700 45,600 no correction
6 550 75,100 95,400
7 1,900 49,200 58,900
8 1,100 110,000 128,100
9 2,700 77,800 87,800
6,700 11,500 no correction
To be able to compare the molecular weights of the EP with comparison values
for
5 dimethylmethylene-bridged cp flu ZrCl2 (M. Arndt, W. Kaminsky, A.-M.
Schauwienold, U. Weingarten; Macromol. Chem. Phys. 199 1135 (1988)), the
correction proposed by Scholte (T. G. Scholte, N. L. J. Meijerink, H. M.
Schoffeleers, A. M. G. Brands; J. Appl. Polym. Sci. 29 (1984) 3763) was made.
The
comparisons are shown in graph form in figure 1 and figure 2.
Significantly higher molecular weights compared with the literature values are
to be
found when the process according to the invention (4-9) is employed.
The various degrees of incorporation are shown in table 3:
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Table 3: Composition of the products
Experiment Incorporation Incorporation Incorporation
of of of
ethene propene ENB
(wt.%~ (wt.%] (wt.%]
4 38.4 52.6 9.0
53.9 34.5 11.6
6 36.2 63.8 -
7 50.7 49.3 -
8 57.7 42.3 -
9 65.9 34.1 -
50 40 10
A significantly better incorporation of propene is to be found in experiment 4
than in
experiment 10.
5
The DSC measurements for determination of the melting range Tm, fusion
enthalpy
~Hm and glass transition temperature Tg were carried out with a DSC 821e from
Mettler-Toledo. Calibration was carried out with indium (Tm = 156.6°C).
For the
measurement 5-20 mg substance were weighed into aluminium pans and measured
10 in the temperature range from -100°C to 200°C at a heating up
rate of 20°C/min. Of
the data obtained by heating up twice with intermediate cooling (-
20°C/min), those
of the second heating up were used.
The values are summarized in table 4:
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Table 4: DSC values of the products
Experiment Glass transitionMelting range Fusion enthalpy
(2nd heating) (2nd heating) (2nd heating)
[C] [C] [J/g]
4 -36 78 3.2
5 -42 106 2.0
6 -42 80 4.8
7 -52 100 10.3
8 -52 107 11.7
9 -49 113 7.5
10 -42 - -
