Note: Descriptions are shown in the official language in which they were submitted.
~ ~3~7
This inven-tion relates to a process for hydrogenat-
ing olefinic compounds.
~ number of different ways of hydrogenatiny unsatur-
ated aliphatic substrates have been described, by employing:
a) stoichiometrical reagents e.~. alkyl aluminium
hydrides, diimidesi and
b) catalysts
b.l heterogeneous catalysts, such as Ni on kieselguhr
b.2 homogeneous catalysts, based on derivatives of
-10 transition metals.
Of all these, the homogeneous catalysts afford the
advantage of being active under comparatively low hydrogen pres-
sures and temperatures. In addition, low levels of catalysts
are employed. In the particular case of the hydro~enation of
polymeric substrates, the blanc reaction conditions offset side
reaction of degradation of the polymer and the low levels of
catalyst make the purification of the end products easier.
More particularly, starting from the year 1963, there
have been acquired homogeneous catalysts deriving from the
~0 combination of compounds of transition metals, preferably with
organic ligands, with:
c~ aluminium alkyls, more particularly aluminium trialkyls
d) Grignard compounds ~-
e) lithium alkyls.
The systems under c) and e) ha~e been applied to the
hydrogenation of diolefine polymers such as polybutadiene, pol~-
isoprene, soloprenes, in order to obtain novel polymeric
materials.
Is is par-ticularly interesting to be afforded
the possibility of obtainin~ saturated -thermoelastomers by
hydrogenation of unsaturated copolymers, such as
styrene/ butadiene/ styrene in such _
i~J~
~3 . . - 1 -
~ ~ 7
a way that the poly~utadiene unsaturated ~lastomeric sequenccs
are replaced by saturated co-ethylene-butene-l elastomeric
sequences.
This application is nonlimiting since it is possible, by
hydrogenation~ to prepare~ as a general rule~ polymers having
properties ~hich are radically different from those of the start-
ing polymer, an~ also polymers which cannot be obtained otherwise.
The.homogeneous catalyst systems which are the subject
matter of the present invention, are o~tained by the combination
of :
. - a derivative.of aluminium hydride: for example there can
be indicated AlH3.xB (wherein B is a Lewis base and 1 ~ x C 3;
AlHY2.xB (wherei.n Y is a halogen atom); AlH2Y.xB, AlH2NRlR2
wherein Rl and R2 are aliphatic~ cycloaliphatic, aromatic radicals
equal or different); Al~l(NRlR2)(NR3R4), A1~120R, AlH(ORl)~OR~)3
(~1 Al NR) (4 ~ n ~ 40)
: - a deriva-tive oE the transition mctals~ p~eferably with .
organic ligands~ such as Co(acetylacetonate)2, Co(2-ethylhexa-
. noate)2, Ni(acetylacetonate)2, Ni(2-ethylhexanoate)2, Ti(cyclo-
20 pentadienyl)2C12, Ti (alcoholate)~ Fe(acetylacetonate)3~ Fe(acetyl
acetonate)2, VO(alcoholate)3~ V(dialkylamide~4.
: Inor~anic compounds of transition metals (for example hali-
~ des) can also be employeda either alone or in the form of com-
: plexes with Lewis bases (amines, pho~phines).
Amon~ the olefine substrates towards which -the aforementioned
: catalyst systems are active~ there can be indicated :
a~ olefines : alpha olefines~ olefines having the internal bond
; ~ariously substituted, cyclo-olefines, aryl olefinesOb) conjugated or non conjugated diolefines~ and~ in general~
3 polyolefines capable of being selectively hydrogenated,
.. c) unsaturated olefine oligomers7
: d) unsaturated olefine polymers~ homopolymers and copolymers
:~ from conjugated olefines.
Such catalyst systems are active irrespective of possible
variations in the order of addition of the substrate and/or the
- 2 -
. .
3~7
components of the catalyst system. They maintain their efficiency unal-
tered relative to the hydrogenation reaction, r,o further additions of
catalyst being required, as a substrate is fed ba-tchwise, and different sub-
trates, either in admixture or in subsequent times can equally be fed in.
It is possible, moreover, to control and to improve the selectivity of the
reaction by the addition of appropriate agents which tone dcwn the catalyst
activity, such as amines, alcohols and others.
G~lerally speaking, the activity of binary hydrogenation cata-
lyst systems varies as the molar ratio of the tw~ components of the catalyst
]0 is varied, such as, for exemple, in the case of systems based on aluminium
trialkyls, when the ratio R*/Me (Me = transition metal - R* = alkyl group
bounl to the aluminium) is varied. Also the catalyst systems according to
the present invention display variations of their activity when the ratio
H*/Me is varied ( H* = hydride hydrogen bound to al~Nnium - Me = transition
metal); but the special advantage is afforded of attaining the top activity
for a ratio H*/Me lesser than the ratio H*/Me described for the m~ximNm
activity o~ the systems based Oll aluminium alkyls. For example, by adopting
Co com~ounds in the hydrogenation of monoolefines and diolefines, the systems
according to the present invention attain their maximum activity
for H*/Co ~ 7 while for similar tests made with the use of alumin-
ium alkyls the maximum activity has been reported for R*/Co = 18.
(W. R. Kroll - J. Catalysis, 15, 281, (1969)). It has been re-
ported, moreover, (J. C. Falk, J. Polymer Sci., P.. 19, 2617, 1971
that the systems AlR3/Co derivatives are active in the hydro-
genation of unsaturated polymeric substrates with R*/Co 9.75,
and in such a case the systems according to this invention, based
on hydrides~ have proven to be active for H*/Co ~ 4. This is
indicative of a greater economical advantage as obtainable with
the catalyst systems of this invention inasmuch as the hydride
hydrogens are completely exploited for the formation of the
active catalyst, whereas, for systems based on aluminium alkyls,
only a part of the Al-C bonds is exploited to this purpose,
", ~ ~,3~7
and the remainin~ bonds are left unused.
Another advan-tage of the c~alyst sy~tems of this invention
over the systems based on aluminium is that, while the latter
display the maximum of their activity for a sin~le value of t1~e
R*/Me ratio, the activity being rapidly decreased both above and
below such value (see the above ci-ted reference), for a few cata-
lyst systems of this invention~ the activity rcmains at very hi~h
levels~ which are near the ma~imum or a-t the very max:imum, within
a very wide ran~ of values of the 11*/~1c ratio, This has been
ascertainecl, for example, within the ran~e 6 to 30 for -the
(HAlN-iso C3H7)6 - Co(2-ethylhexanoate)2 system.
The catalyst systems accordin~ to this invention afford
still further advantages. It is known, for example that~ as a
rule, as`the de6ree of substitu-tion of the double bond of the
substrate is increased, a decrease of the hydro~enation velocity
is experienced. This fact hS such, for example, as to cause the
; ydrogenation of isoprene with systems based on aluminiun1 alkyls
requiring higher temperature and, above all, higher hydrogen
ressures, than those which are required for 1-ydrogenating simpler
substrates~ such as, for example~ alpha-olefines (Yoshio Tajima, E.
Kunicka, J. Catalysis, ll, 83, (1968 ) ).
Conversely, the catalyst systems of this invention ensure
he ~irtually quantitatiYe hydrogenation of isoprene to iso- ¦
entane under the same bland conditions of temperature and pressure1
which are required for the hydrogenation of simpler subs-trates and
no place is left for olig~omerization side reactions.
As the ~nolecular structure of t~e derivative of aluminium
hydride ancl or the rcaction conditior1~ are varied, it is possible
to have seloctive hy(1ro~enation.s in tho casc of substra-tes having
3 nsaturat.ions of different natures.
Lastly, differently from the aluminium alkyls which are
yroforic, a few of the hydride deriva-tives of this invention, and
more particularly the poly(N-alkyliminoalanes or PIA)~ are not
yroforic and, when in contact with air and moisture, they are
decomposed by moderate reactions. In addition, the YIA are stabl~
- 4 -
at high temperatures ( for example (HAIN-isoC3H7)6 decomposes
at about 250C) and have a virtually unlimi-ted storage life.
The reaction is preferably carried out in inert
solvents such as aromatic or aliphatic hydrocarbonaceous
solvents or ethereal solvents, at temperatures of from -50C
to 200C, more preferably from 20C to 70C, and under a
pressure of Erom 0.1 to 100 atmospheres absolute, preferably
from 1 to 3 atmospheres absolute, with an atomic ratio of
the hydride hydrogen to the transition metal higher than two.
The present invention will be further understood
by referring to the enclosed drawings and to the following non
restrictive examples.
The plots of Figures 1 and 3 show the trends of
the percentage yield of isopentane and of the percentage of
unreacted isoprene in the reaction of hydrogenation of iso-
prene, as a function of the hydride hydrogen to cobalt ratio;
and
The plot of Figures 2 and ~ shows the trend of the
percentage yield of nor. hexane in -the reac-tion of hydrogenation
of hexene 1 as a function of the value of the ratio of the
hydride hydrogen to cobalt.
EXAMPLES 1~
By adop-ting the ~uan-tities and the reaction conditions
of TABLR 1, to a stirred solution of the olefins in toluene
there are added, in -the order given Co (acetylacetonate~2
(toluene solution 0.06 M~ and the derivative of aluminium
hydride (generally in solution in toluene 0.2 M to 0.5 M of Al).
The solution is then introduced in a stainless steel autoclave
of the volume of 200 mls which has been evacuated of air. Then
the autoclave is thermostatically heated to the desired temper-
ature ans pressurized with hydrogen. Stirring is carried out
magnetically under the conditions which are prescribed and for
~ ~3~
the indicated period of time. As a rule, the complete conversion
is achieved within a -time which is definitely shorter than
that which is adopted: especially in the case of the olefines,
the hydrogenation step is completed within 10-15 minutes. At
the end of the hydrogenation, the autoclave pressure is released
and the products which have been obtained in solution are
analyzed by gas chromatography. -
- 5a -
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EX.~MPLIS 12 --29
By using the quantities and the- reaction conditions set forth
in TABLE 2, a solution of the olefine is supplemented~ in the.
order given~ by Co(2-ethy-~exanoalJe)2 d.issolve-d in to].uene (o.o6M)
and tl1e cleri.vative of alumini1m1 hydride (gencrally in solution in
toluene at 0.2~1 - 0.5~1 of ~l).
The solut.ion is introduce~ in a st;ainless-steel 200-ml
auttoclave whi.ch has been evacuated Oe air. Then the autoclave
is thermostatically heatecl to the desired tcmperaturc and preesu-
rized wit;h hydrogen. Magnetic s-tirrin~ is maintained for a
definite time interval and the comple-te conversion is generally
obtained within a time which is definitely shorter than the one .
which has been aclopted: especially in the case of the alpha -
~lefines the hydrogenat;ion step is completed within 5-15 minutes~
On complction of the hydrogenation step~ the autoclave
pressurc is relea.sed ancd -the products which have been obtaired
in solution ~e analyzed by gas chrt~atography.
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- 12 -
~ 3
:.
rXAMI~LES 30 - 32
Tllese ~xamplcs show that VariatiOns of the order o~ a~di-
tion of thc substrate and/or of the catalyst components do not
impair the performance of the cata]ys-t system.
EXA~IPLE 30
To a stirrcd solution of Co(2-et~yl hexanoate)~ 0.1 milli-
mol in 17 ml o toluenc aIe addcd :;n the ordcr glven (~lAlN-iso
C3117 )6 (o.6 m~ gramatomS of Al~ corresponding -to 3 mls of a
tol~ene solution 0.2~1 oE Al) anc1 isoplene (10 mil]imols). The
niixture is intlo(lu~ed in a stainless steel 200-ml autoclave evacua
ted of air. Th~n the autoclave is thermosta-tically hea-ted to the
temperature of 30C and pressurizecl~itl- 2 a-tm of hydrogen.
~Sagnetic stirring is maintained uncler such conditions during one
hour. On comple-tion o the hydrogenation step pressure in the
autoclave is released and the gaschromatographic analysis of
the solution 5110~s that isoprene has beell hydrogenate(l to iso-
pentane to 100%.
EXAMPL~ 3l
To a stirred solution o-E (~lN-isoC3117)6 (oA6 milligram~
atoms of Al) in toluene (18 mls) are added, in the order given,
Co(2-ethylhexanoate) (0.1 millimol~ corresponding to 2 mls of a
0.05M solution in toluerle) and isoprene (10 millimols). The
mixture is in-troduced in a 200-ml ~c:tainless steel autoclave
evacuated of air Then the autoclave is thermosta-tically brougrht
to a temperature of 30C and pressuri~ed ~ith hydrogen at ~ a~m.
Magnetic stirring is maintained w1der these conditions for one
hour. Last]y~ the autoc]ave pressule is released and the gas
chromatographic analysis o~ the solution shows that the isoprene
has been hydrogenated to 100% (isopentane : 86%~ 2-methyl-butenc-2
14%).
EXAMPLE 32
rO a Stil'l'illg svlutiun o~ ~sopreIle (10 millilIlols) in ~oluen~
(17 mls) are added~ in the or~er given~(llAlN-iso C3117)6 (o.6
milligramatoms o~ Al eorrespondin6 to 3 mls of a toluene solution
0.2M of Al) and Co(2-ethylhexanoate) (0~1 millimols~ corresponding¦
~ ~ 3 ~J~
to 2 mls of a 0.05M solu-tion in toluene). The solution is
introduced in a 200-ml stainless steel autoclave which has
been evacuated of air. Then the temperature is thermostati-
cally brought to 30C and the autoclave is pressurized with
hydrogen to 2 atm. Magnetic stirring is maintained under
these conditions during one hour. Lastly, the autoclave
pressure is released and the gas chromatographic analysis of
the solution indicates that isoprene has been hydrogenated to
100% (isopentane 70~ and 2-methyl-butene-2 30%).
EXAMPLE 33
This example shows that it is possible to feed the
substrate in batches and without any supplemental addition of
the catalyst. It is possible to feed in different substrates,
both simultaneously and sequentially. The results show that,
in fact, the catalyst retains its activity unaltered in time
~` and, moreover, they confirm that satisfactory results can be
achieved with low amounts of catalyst. To a stirred solution
of octene-l (20 millimols) in toluene (15 mls) are added, in
the order given, Co(2-ethylhexanoate)2 (0.1 millimol corres-
ponding to 2 mls of a 0.05M solution in toluene) and (HAlN-
isoC3H7)6 (0.6 milligramatoms of Al, corresponding to 3 mls of
a 0.2M solution in toluene of Al). The solution is introduced
in a 200-ml stainless steel autoclave which has been evacuated
of air. Then the temperature is thermostatically brought to
~, 30C and the autoclave is pressurized to 2 atm with hydrogen.
Magnetic stirring is maintained for 15 mins. and the pressure
drop indicates that the hydrogenation reactionhav~ been com-
pleted. Portions of octene-l (20 millimols each) have been
added and lastly, portions of cyclohexene (20 millimols) dis-
solved in toluene l12 mls) have been added at the time inter-
vals indicated below, the pressure being brought again to 2
atm of hydrogen each time.
- 14 - `
,: '
~ 7~3~
TIME INTERVAL ADDITION N SUBSTRATE
- initial octene-l
15 mins 2nd octene-l
20 mins 3rd octene-l
30 mins 4th octene-l
60 mins 5th cyclohexene
Upon the addition of cyclo~exene the reaction mix-
ture has been maintained 2 hours under the conditions indica-
ted above. Then the pressure has been finally released and
the reaction products have been analyzed by gas chromatogra-
phy. The conversion of octene-l and of cyclohexene into oc-
tane and cyclohexane, respectively, was quantitative.
EXAMPLE 34
This example shows that the addition of amines
lowers the catalyst activity without, however, suppressing it.
Due to the variations of the reaction velocity, it is thus
possible, in the case of polyolefines, to adjust the selecti-
vity of the hydrogenation.
To a stirred solution of Co(2-ethylhexanoate)2 (0.1
millimol in toluene (17 mls) are added, in the order given
IHAlN-isoC3H7)6 (0.6 milligramatom of Al corresponding to 3
mls of a toluene solution of 0.2M of Al), iso C3H7NH2 (0.7
millimol) and vinylcyclohexene (10 millimols). The solution
is introduced into a 200-ml stainless steel autoclave which
has been evacuated of the air. Then the autoclave is thermos-
tatically heated to 30C and pressurized with hydrogen at 2
atm. Magnetic stirring is provided under pressure for one
hour. Lastly, the autoclave pressure is released and the so-
lution analyzed by gas chromatography. The result is that vi-
nylcy~lohexene has been hydrogenated to 100% lethylcyclohexene:
77~ - ethylcyclohexane: 23~).
EXAMPLE 35
15 -
,
:
~ t~
This example shows that the addition of alcohols
lowers the catalyst activity but does not suppress same and,
in the case of polyolefines, it can adjust the selectivity of
the hydrogenation. To a stirred solution of Co(2-ethylhexa-
noate)2 in toluene (17 mls) are added, in the order given,
(HAlN-isoC3H7)6 (0.6 milligramatoms of Al corresponding to 3
mls o~ a solu~ion in toluene, 0.2M o~ Al), C2H5OH (0.7 milli-
mol) and vinylcyc~ohex~ne (10 milli~ols). The solution is
introduced in a 200-ml stainless steel autoclave which has
been evacuated of air. Then the autoclave is thermos~atically
heated to 30C and pressurized with hydrogen to 2 atm.
Magnetic stirring is provided under pressure for one hour. On
completion of this step the autoclave pressure is released and
the solution is analyzed by gas chromatoyraphy. The result is
that the vinylcyclohexene has been hydrogenated to 100~ (ethyl-
cyclohexene 98.5% - ethylcyclohexane 1.5%).
EXAMPLE 36
To a stirred solution of 2-methylbutene-2 (3~ milli-
mols) in toluene (17 mls) are added in the order given Co
(laurate)2(0.1 millimols~ and (HAlN-isoC3E17)6 (0.6 milligrama-
toms of Al corresponding to 3 mls of a toluene solution 0.2M
o~ Al). The solution thus obtained is introduced in a 200-ml
stainless steel autoclave evacuated of airO The autoclave is
pressurized to 2 atm of hydrogen and thermostatically heated
to 30C. Magnetic stirring is provided during one hour. At
last, the autoclave pressure is released and the solution is
analyzed by gas ch:romatography. The result is that 2-methyl-
butene-2 has been hydrogenated to 82% to isopentane.
EXPMPLES 37 - 48 (FIGURE 1~
---- .
The data plotted in FIGURE 1 shows that the AlH3.N
(CH3)3 - Co(2-ethylhexanoate)2 system shows a maximum activity
in correspondence with H*tCo = 7 (E~* is the hydride hydro~en)
~1~
- 16
.
3~
in the hydrogenation of isoprene. The tests have been con-
ducted according to the following procedure.
To a solution of Co(2-ethylhexanoate)2 are added, in
the order given, AlE13.N(CH3)3 ~solution in toluene O.lM) in
variable quantities, and isoprene (1~ millimols). The initial
quantity of toluene is such that, at the end, the volume of
the solution is 20 mls. The solution is introduced in an eva-
cuated 200-ml stainless steel autoclave. The autoclave is
then thermostatically heated to 30C and pressurized to 2 atm
of hydrogen. Magnetic stirring is provided under these con-
ditions for 30 mins. Finally, the autoclave pressure is re-
leased and the solution of the obtained products is gaschro-
matographically analyzed, the results being those plotted in
FIGURE l. The plots of FIGURE 1 show the trends of the per-
centage yield of isopentane and of the percentage ~
~ . ._ .. , .. . . .. _ .. .. , ~ .. ., ,. __ ,_ , ~ _ ___ __
~ - 16a -
o~ unreacted isoprene in the reaction of hydrogenation of
isoprene, as a function.of the hydride hydrogen to cobalt
ratio. The abscissae are the values of the atomic ratio of
hydri.de hydrogen to cobalt, and the ordinates are the
percentage values. The plot N 1 relates to the percentage
yield of isopentane as produced, and the plot N 2 is the
percentage of unreacted isoprene.
EXAMPLES 49 - 59 (FIGURE 2)
The plo-ts of FIGURE 2 con~irm that the AlH3. N(CH3)3-
Co(2-ethylhexanoate)2 system attains its maximum activity
for H*/Co = 7 also in the hydrogenation of monoolefines : -
(hexene-l). Apart from the different nature of the substrate
and its quantities t20 millimols of hexene-l) and the reaction
time (15 mins.), the quantity and the nature of the solvent
and tha components of the catalyst, as well as the other
reaction conditions, are the same as for FIGURE 1.
On the plot of FIGURE 2 the curve N 1 shows the
trend of the percentage yield of nor.hexane in the reaction
of hydrogenation of hexene-l as a function of the value of
the ratio of the hydride hydrogen to cobaltO The abscissae
report the values of the hydride hydrogen to cobalt, and
the ordinates are the percentage yield values.
.. _ . ...
- 17 -
.: ~ ,'.,,'.' ,'
EXAMPLES 60 - ~9 IEIGURE 3)
The results of FIGURE 3 show that, in the hydrogena-
tion of isoprene the (HAlN-isoC3H7)6~Co(2-ethylhexanOate)2
system attains its maximum activity for H*/Co = 6 (H* being
the hydride hydrogen). For ra-tios of H*/Co smaller than 6,
the activity, though being decreased somewhat, still remains
at very high levels.
~ part from the different derivative of aluminium
hydride, the quantities and the nature of the solvent, of the
Co compound, of the substrate, as well as the reaction condi-
tions, are those of FIGURE 1. In the plots of FIGURE 3 are
shown the trends of the percentage yield of isopentane and the
percentage of unreacted isoprene in the hydrogenation reaction
of isoprene as a function of the atomic ratio of hydride hy-
drogen to cobalt. The abscissae report the values of the ato-
mic ratio of the hydride hydrogen to cobalt, and the ordinates
the percentage values of the yield of isopentane (curve N 1)
and of unreacted isoprene (curve N 2).
EXAMPLES 70 - 78 (FIGURE 4)
The results oE FIGURE ~ confirm that also in the
hydrogenatlon of hexene-l, the (HAlN-isoC3H7)6-Co(2-ethylhexa-
noate)2 exhibits its top activity for E-l*/Co o~ about 6 (H* is
the hydride hydrogen) and that for ratios H*/Co higher than 6
the activity is still at a maximum. Apart from the different
derivative of aluminium hydride, the quantities and the nature
of the solvent, of the compound of Co, of the substrate and
the reaction conditions as well, are those of FIGURE 2. In
the plots of FIGURE 4, the curve N 1 shows the trend of the
percentage yield on nor.hexane in the reaction of hydrogenation
of hexene-l as a function of the value of the atomic ratio of
the hydride hydrogen to cobalt. The abscissae report the va-
lues of the ratio of the hydride hydrogen to cobalt, and the
- 18 -
~ ~3~
ordinates the percentage yield values.
EXAMPLES 79 - 83 (TABLE 3)
By adopting the quantities and reaction conditions
as tabulated, to a stirred toluene solution of the olefine
concerned are added in the order given, Ni(acetylacetonate)2
(0.06M toluene solution) and the hydride derivative of alumi-
nium (generally in 0.lM 0.5M toluene solution). The solu-
tion is introduced in a 200-ml stainless steel autoclave
which has been evacuated of air. The autoclave is thermosta-
tically heated to the indicated temperature and pressurized
with hydrogen. Magnetic stirring is applied under the tabu-
lated conditions and for the tabulated time interval. On
completion of this step, the autoclave pressure is released
and the solution of the products which have been obtained is
analyzed by gas chromatography.
'`g~7
-- 1 9
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rJ o\ ~1 ~n u) ~ N ~ I` Iri ~
1. u~ ~ ~t ~ ~ ~ ~ ~ r
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~ l S ~ '~
'Z; ___
O .~ . Ln
~ ~ o~ O O ~ I O
~ ~ ~1 rl ~f) ~ ~1
E~ ______ _ .____ .. _
_ ~ ~ ,..... _ ,_._.. __ ,. . __ .__. _ __.. _._._._.
l ~i ~o ~ ~'1 ~ /~ ~
H ~ ~ 1---- - -
_~ ______ ____ ~ N N ~
Z ~ -~ ~ ~ C ~ ~ ~ ~ ~ ô ~ ~
~ ... . _ ~ D H ~> ~ ~ ~ ~ ,C
~ 3 ~ ~ _ _
H __ _ _____. .___ ._ ¦____ _ w
O ~ .
~4 Z ~ o o o o o
O _ ___ _
H ~ ~ O ,i ~ ~ ~~-
~ ._ ____ Z ~-- ,.___ ~ :~
a) a) a
l ,~ô ~ ~ ,~0 ,~ô
~1 ~ ~3 ~ ~ , ~ ~ ~ ~-i
~ O ~ ~ ~ ~î
~ ~ Z r~ c~ co. ) ~ _ ~
-- 20 --
~3 '
l~ iC~.7
rXA~IPIr~ 84 ~ 8& (TA13Ir 4)
~ y adopting the cluallti-ties and tlle con(litions as tabulated~
to a toluene solution of the titaniu;n compound there are added~
in the orclel g:iven the deriva1;ive o~ al~llll.ini-mlllydridc (gereral-
ly solut:ions o~ O.l~l to 0.5M o~ Al) and the olef:ine concerned.
Tlle solut:iorl is introd~lced i.n a 200-ml stailllcss steel autoclavc
which ha(ll)eon previously evacuatecl of air, and is aged for one
hour at ~0C. Then the autoclave i.s thermostatically heated to
the desired tem~erature and pressurized with hydrogen~
~laglletic stirring is applied under -the tabulated condi-tions
nd for the tabulated ti.me interval. On completion of this
step~ the pressure in the autoclave is releasecl and the products
which have ~een obtai.ned in solution arcA analyzed by gas
-hromatography. .
~r ~
a ~ _ ~ _ _
a ~ sll ;'~b ~
~ ~ H ~ ~ H
æ
~ ~ , ..''.... ... ~ _ . _.
M ~ .__ __... .. .... ___.___.. ........ _
o I o~
:~ ~ ~ __ ~ __
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~ ,_. :~ ~ 0 ..... ... .. _.. _ ._. ......... _ _._.
11 ~ ~ 8
H ~ `J (`I t`l t`l
U~ ~ I~ r-l r-l -I rrl
æ _ _._ _ _ _ . __ . _
H ~ ~ ~ -- .~ ~ .~ _
O E ~1 ~1 0 ~ . t`l
O 'E~ ~' ~ ~ ~ ~ ~ _ l
æO -------------- ~ - -- -- ~---- ~
H Z ~ _ .~ ~
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X ~ ~ ~0~ ~0~ ~ ~
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a~ d' L(~ ~D
;~ ~ Z; CO 0~ CO ~
E~ ___. _ _
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- - :
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1~0 ~
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23-
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EXAMI'LES 89 and 90 (TA~
By adop-ting the tabulated quantities and conditions~ to a
toluene solution of the vanacLium compound are added~ in the order
given~ the derivative of aluminiu~ ydride (generally as a
toluene solution~ 0.1M to 0.5~1) and the ole~ine.
The solution is introduced in a 200-ml stainless steel
autoclavc which hcls been purged o~ air. Then the autoclave is
thermostatically heated to the tabulate~ t~!emperature and pres-
surized with hydrogen~
Magne-tic stirring is applied under the tabulated conditions
and for the tabulated tLme interval On completion of this
step, the pressure in the autoclavc is released and the product
as obtained in solution are analy~ed by gas chromatography
~d ..:~ 3~
, ,
Z ___ _
o .~ ~oP ~
r: i~ ~ ~
H .~ _
a ~ oP r~ ~
~ ~' a~ ~
H _._____ _ __ __ ___
Z ~ '~_ ~ ~
a
~ .... ___ .
E~ ~ O O
~ _____ .__ ._
u ;~m_ ~ ~
~ x~ ' ~
Z ~ ~ ~ o O m~
o ~ . _ ~
H ~i ~
~ _~ _ ~ _ ~
7~ ~U~ ,~0~ ,~0
In ~ ~ E~ - ~ -
1 1 -------------1-~ -- -~
a:l x O ~ o
Z 00
E~ .
- 25 -
ll ;
, " ~ ~.3 ,;~ ~9~
rX~II'~ 91 ~ r~3L~ 6 )
By adoptill~ the tabulate(l (luantitics and conditions~ to a
toluene solution o~ the iron compound are ad~cd~ in the order
givcn~ alu~ ydridc dcrivcl~ive (gencrllly in a O.l~l -
O.SM ~1 to:lu~rle ~ollltion) and -tl~c olcl~ial( concerllc~cl.
The solution is :introducecl into a 200-ml staillless stcel
autoclave ~hicll llas l~ec~n evacuatecl oE airO
Then the autoc:Lave is thermosta-tically heated to -the
-tabulatetl tc~perl-ture and pressurized wit]l hydrogen.
Ma~letic stirrin~ is applied under tlle conditions which
are tabulated and for the tabulated time interval.
On completion of this s-tep~ the autoclave pressure is
released and tlle products obtainecl in solution are analyzed
by s chromatogr~phy.
~ ~:
. .. .
_ . I
I ~ ~ t~
n I c~ ~ ___
~ ~o, ~ C
., I_
H l o ~ rl c~
~ r- a)a) .
~ I a ~ ~ ~_
~ c ~ o
.
~ .
tn
~,2. ~ o ~ ~
~ ~ rl ~ ~ ~ . .
E~ ~ ~ X ~ ~
~n ¦ ~ ,~~-- .
tn ~t~ ~1 c) o
~1 ~
5 ,~o ___
~: . O ~ ~ ~ o~
tn t~ ~ ~C
H ~1 ¢ .
~1 O t~ tQ ~ . ~
O ~ ~ O . ~
~ t_) I _"~ . ~ ' .
~ ¢ $ . ~rl
C~ 1~ ¢ ~1~ .C'
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l - ~ ~
~1 - tn ~ o~_ ,'~
¢1 x o~
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`~ il i
I,XA~i1'L~ 92
To a s-tirrecl solution of CoCl2 (O.l millimol) in toluene
(17 mls) is adclecl a solution of (11AlN-isoC31I7)6 (o.6 milli~ram-
atoms of Al) in toluer1e (3 m:Ls). A`reaction is noted WhiCIl
brings about a slo~Y conver,sion of (`o~ into a soluble eompounc1.
A~ter 15 mins. i,soprene (lO m:illimols) :;s ac1clec1 and the reaetion
nlxtur~ is introcl1lcetl i.rl a 200-n1l stainlo.ss steel autoelave
~hieh has previously been evaeuated o~ air. The autoelave is
thermostatically heatec1 to 30C an(l pressuri~e(l to 2 atm. of
hydro~en. Ma~1le~ic stirr:Ll1g is eol1ti$111ecl clurin~ one hour.
On completion of this step t,11e aut,oelave is vented and the solu-
tion is gas ehroma-to~raphieally analyzed. The result is that
isoprene has quartitatively hy(1ro~e~ate(1 to iso~ontane (yield
73%)~ 2-methy]-1~ ene-2 (yield 22.5~) anc] 3 methyl-butone (yie,ld
~-5%).
~,X~1rLr; 93
~ sall1ple (l,Ss ~ram) oE a block copolyn1er oE st~rene-bu1;adiend- -
-styrene eon-Sainir1g 8l.5~o of butadiene units (90% with l~4 link-
in~ and lO~o with l.2 linking) is solubilized in cyclohexan~
(lOO mls). T1le stirred solution is then su1~plemented~ in the
order given~ by Co(2-ethylhexanoate)~ (O.l mol correspondin~ to
0.78 ml of a 0.13~1 solution in cyclo11exane) ancl by Al113.N(C1t3)3
(0.2 mol corresponcling to o.66 ml o~ a 0.3~1 solution of Al in
toluene). The resultant solution is tlen eharged in a 200-ml
stainless steel autoclavo which had been evaeuated of air and
thermostatieally heated to 50C. The autoclave is yressuri7,ed
to S atn~. o~ hyc1~o~er1. Ma~netie stirring is applied uncler tl~ese
eonditions for one hour. 1inally, t11e p1ossuro is relc~ased anc1
t1~o 1)ro(1~et :is r-~covere~1 (lu;ll1t:it.1tively 1)y eva;)or,ltin~ oEf t]1C
solvent ~rom the roac,tion mixture which 1-acl previously been
rel)eteac1ly ~Yasl1et1 wil,1l water to reltlove -l;lle ca~,llys-l; :ini1)urities.
The IR spectruM (a very weak ~and at 10,35 micron whieh Call be
attributecl to traees Oe residual unsatul~ations ancl the ~IR show
that a bloe1c copolyn1er styrene-(ethylcrle~butene-l)-styre3le has
been obtained in agreement with the virtually quantitative hyc1ro- ¦
- 28 -
"`''' .,,
~1
;r
ge1lcl~ion ( al)out 100%) of t11e .stlrti1lg po:1yll1er.
~X~1P11 94_
The hydroge1latioll of a bloclc copolymer styrene-butadiene-
styrene has been carried ou-t hy using -tho sa1l1e coml)ounds ancl tlle
same conditiol~s of EXA~PLE 93 ~ith the only e~ception of the
aluminium hydri~te deriva~ive ~ ich Was now (11AlN-isoC3117)6 and
the ratio 11-~/Co which was ac1Op~ecl and was 4 (H~ is hydride .
hydrogerl ) .
At the elld o tlle reaction the IP~ s1)ectrum and the 11N~IK
show that a block polymer styrene-(ethylene-bute1le-l)-styre1le has
been obtained~ in agreement with the virtually quantitative hyd.ro-
genation (about 100%) of the butadiene units of the starting .
polymer.
EXAMPLE 95 .
_ .~..~.-, .
A sample (1.4 gram) of polybutacl.i.e1lc having a high contents
of 1~4-cis 1lns.lt~lrltions (about 99Yo) is sol1Ib.i.li.7ed in eyclo-
hexane (lnO mls). The stirred solution is tllen supplemente~,
in the order g:iven~ wikh Co(2-ethylllexanoate)2 (0.1 millimol
. correspont1ing to o.78 ml of a 0.13M solution in cyclohexane) and
with Al113.N(C1-13)3 (00167 mill.imol corresponc1ing to 0.5~ ml o~
a 0.31M so].uti.on in toluene). Tl-e resultan-t solution is then
. introduce(1 into a 200-ml. stainless s~eel autoclave which has
been evacuated o~ air and thermostatically heatec1 to 50C. The
autoclave is pressuri~ed wlth hydrogen to 3 atm. Magnetic stir-
ring is applied un~:er these conditions for one hour. Finally~
the pressure is released and the product is quantitatively re-
covered by evaporating off the solvent from the reaction mixture
which had previously been washed many times with water so as to
. remo~e the catalyst impurities. The 11NMR indicates that a co-
3 polymer of ethylene and butad.iene (1,4 trans) has been obtaine(1
wl-ich correspon(ls to tlle hydrogen1ti.on o the 88~o of the unsa-
turations of tlle starting poly1ner with an inversion of the
structure of the residual unsaturations.
LXA~11'LE 96
_ _
The hydrogenation of a sample of polybutadiene having a high
- 29 -
'
.,
contents of 1,4 cis unsaturations has been carried out by
adopting the same compounds and the same conditions as in
EXAMPLE 116, with the exception of the hydride derivative of
aluminium which was (HAlN-ISOC3H7)6. The ratio H*/Co which
has been used is 5. (H* is the hydride hydrogen).
On completion of the step, the lHNMR indicates that
a copolymer of ethylene and butadiene (1,4 trans) has been
obtained, which corresponds to the hydrogenation of the
86.7% of the unsaturations of the starting polymer, with an
inversion of the structure of the residual unsaturations.
- 30 -
~r--~
JI
