Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
I
Background of the Invention
The present invention relates to the preparation of
amino substituted polymeric hydrocarbons and more
particularly/ to a process for forming polymeric products
having a hydrocarbon backbone and a large amount of
pendant secondary and/or tertiary alkyleneamine groups by
the reaction of polymeric hydrocarbons having olefinic
groups therein with hydrogen, carbon monoxide, and a
primary and/or secondary amine in the presence of a
catalytic amount of a Group VIII metal compound.
Catalytic aminomethylation of monoolefins with
monomeric secondary monoamine, carbon monoxide and
hydrogen is well known and was initially taught by Dr.
Walter Wrap in Experimentia, Vol. 5, p. 93 (1949); German
Pat. No. 839,800 (195~) and Liebigs Ann. Chum., vol. 582,
p. 148 (1953). The process was, however, of limited value
due to the required use of large quantities of toxic iron
or nickel carbonless as the catalyst, the rapid rate of
consumption of the catalyst, the slow rate of reaction,
poor selectivity and the poor yields of product.
Moreover, the reaction was taught to be restricted to
monoolefins and to low molecular weight monoamine.
Aminomethylation of other monoolefins has been carried
out in the presence of other metal carbonless, but the
reactions have been found to be non-selective and produce,
at best, only moderate yields of amine. For example,
U.S. Pat. Nosy 2,422,631 and 3,234,283 disclose that lower
olefins, carbon monoxide, hydrogen, and a secondary
monoamine will form, in low yields, tertiary amine in the
presence of cobalt hydrocarbonyl or dicobalt octocarbonyl
as well as certain other cobalt compounds.
More recently, U.S. Pat. Nos. 3,513,200 and 4,096,150
have disclosed the utilization of Group VOW metal
I
compounds as suitable compounds to catalyze the reaction
between monoamine and monoolefins with hydrogen and
carbon monoxide to form low molecular weight monomeric
tertiary amine. These reactions, however, generally only
provide the desired product in low yields while forming
significant amounts of by-products.
In addition, U.S. Patent 4,312,965 may be referred to
as teaching the formation of a polymeric product having a
mixture of amine and aside pendant groups by contacting a
10 polymer with an amine, carbon monoxide and water in the
presence of a rhodium metal compound. The required use of
water as the hydrogen source and rhodium as the catalytic
metal is taught to provide a means of aminomethylation of
the polymeric polyolefin. The process, however, yields a
15 product having low degrees of amine incorporation and,
therefore, does not provide for a highly active polymer
normally desired for commercial utilization. The above
and other references teach that aminomethylation generally
leads to the formation of significant quantities of
20 undesired by-products. This is confirmed in general
treatises such as: "Carbon monoxide in Organic Synthesis"
of alibi.
In general, the yields of desired amine incorporation
in previously formed polymeric material and of monomeric
25 amine products by aminomethylation has been viewed by
those skilled in this art as being poor at best.
Summary of the Invention
The present invention it directed to a one-step, cost
efficient method of forming polymeric products having a
30 hydrocarbon backbone and a high degree of alkaline
alkylamine pendant groups by contacting, in a liquid
media, a polymer having unsaturated groups therein, a
I
primary or secondary amine, carbon monoxide and hydrogen
gas in presence of a Group VIII organometallic compound. The
formed product is useful for a variety of applications, e.g.
as a surfactant, a flocculating agent, softener, and as a
component in coating compositions.
The present invention provides a process of forming
polymeric products having a hydrocarbon backbone and
secondary or tertiary or mixed alkyleneamine pendant groups
comprising contacting in a reaction zone, a mixture of an
inert substantially an hydrous, organic liquid media, a
polymeric hydrocarbon having olefinic groups present in its
hydrocarbon backbone, a primary or secondary amine, carbon
monoxide and hydrogen heating the mixture at a temperature
of from about 100 C. to about 250 C. at a pressure of from
about 30 to 300 atmospheres in the presence of a catalytic
amount of at least one Group VIII metal containing compound for
a sufficient period of time to cause -the formation of the
polymeric polyamide product, and recovering the polymeric
polyamide product.
Detailed Description of the Invention
The subject invention is directed to a new one-step,
cost efficient catalytic method of forming polymeric polyamides
having a structure of a hydrocarbon backbone and pendant amino
groups which are connected to the polymer backbone by an
alkaline bridge. The method is achieved by contacting, in an
inert solvent, a polymer having a multiplicity of olefinic
unsaturation therein, hydrogen, carbon monoxide and a primary
or secondary amine in the presence of a Group VIII metal
compound as more completely described hereinbelow.
The aminomethylation of the olefinic containing polymer
has been unexpectedly found to produce a polymer product
having a high degree of incorporation of alkaline alkylamine
pendant groups when formed according to the presently
described method requiring the utilization of hydrogen and
the presence of at least one Group VIII organometallic
a:
9 ~3~9
compound as described hereinbelow. Thea aminomethylation
of polymeric materials has been previously described, in
U.S. Patent 4,312,965, as being capable of providing products
having amine/amide pendant groups if one uses the required
water and a rhodium metal compound as the catalyst, the
process has several defects. The primary defect is one which
is common to aminomethylation reactions (even when simple,
small olefinic compounds and/or other catalyst materials are
used), and that is the low degree of formation of amino
- pa -
I
containing compounds or low degree of incorporation of
amino groups onto the polymer product by the process
described in U.S. 4,312,965. In contrast, it has been
presently unexpectedly found that by performing the
aminomethylation using the conditions described herein,
specifically, using a single organic liquid phase,
hydrogen as the hydrogen source and Group VIII
organometallic compounds as the catalyst, one unexpectedly
achieves a polymeric product having a combination of
desired properties. The polymeric product presently
attained has (a) a higher degree of alkaline alkylamine
pendant groups therein than possible by prior known
methods, (b) substantially no residual amount of olefinic
groups in the backbone of the polymer (c) substantially
no amino groups (a generally undesired group due to its
inactivity or substantially low activity with respect to
polyamide utilities), (d) absence of Showoffs base,
alluded and examine groups normally found in small
amounts in prior art aminomethylation products and (e)
increased stability of the polymeric polyamide product and
reduced tendency to gel in comparison to products formed
by prior art methods.
The present process has also been unexpectedly found
very effective in forming polymeric polyamides with high
concentration of alkaline amine groups from high molecular
weight olefinic containing polymers. Such ability
provides a method to produce unique amine polymers of high
molecular weight. Finally, the instant process, due to
its high efficiency in incorporating amine into the
polymeric reactant, has been found useful in forming
unique amine containing polymers having substantial amine
groups therein even when the olefinic concentration is low
in the polymer reactant (e.g. EPDM polymers).
The olefinic containing polymers useful herein can be
formed from monomers having multiple olefinic groups
I
therein alone (homopolymexs), or in combination with other
monomers, by conventional cat ionic, anionic, free radical,
coordination or supported metal catalytic processes, as
are well known by the artisan. The term "olefinic
containing polymer" or ~'olefinic prepolymer", as used
herein, is meant to define homopolymers and copolymers
which contain a multiplicity of olefinic bonds distributed
throughout the polymer chain either as a part of the
polymer backbone or as a part of the pendant group. The
average molecular weight of the olefinic containing
polymer should be at least about 500 and preferably from
about 500 to 200,000 and above. The subject process has
been found to be an especially effective method when
processing high molecular weight olefinic containing
polymers having an average molecular weight of from about
10,000 to 200,000 to readily provide a high molecular
weight polymeric polyamide. incorporation of amino groups
in high molecular weight polymer starting materials is
difficult, at best, by previously known techniques.
The olefinic containing polymers useful herein can be
homopolymers formed from C4 to C10 monomers having
multiple olefinic groups therein, such as, for example,
from butadiene; isoprene, cyclopentadiene; divers of
cyclopentadiene; 1,3-pentadiene; 1,4-pentadiene;
25 1,3-hexadiene; 1,4-hexadiene; 1,5-hexadiene;
2,4-hexadiene; 1,3,5-hexatriene and the like, as well as
such monomers containing substituents thereon which are
inert with respect to aminomethylation, such as Cluck
alkyd, halo and carbonyl radicals. The olefinic
containing polymer used in the subject invention may be in
any of their isometric stereo configurations. In the case
of polybutadiene, or example, it can be in its Swiss-;
trueness-; or trueness configuration or a mixture
thereof. Further, the polymers useful herein may be
copolymers formed from two or more monomer compounds which
I
are each capable of forming a polymeric segment containing
olefin bonds therein, such as copolymers having
polybutadiene segments as, or example, copolymers of
poly(butadiene-isoprene), poly(butadiene-1,4-pentadiene)
and the like.
The olefinic containing polymers useful herein can
also be copolymers formed from at least one monomer as
described above capable of producing olefin containing
polymer segments and at least one copolymerizable vinyl
monomer which does not form olefin containing polymer
segments, such as acrylamides, acrylonitrile, styrenes
actylates, alkyd vinyl ethers, alkyd vinyl kitten and the
like, and mixtures thereof, and Cluck hydrocarbyl
derivates of such monomers, such as alpha-methyl styrenes
methyl methacrylate and the like. Such materials are
formed in conventional manners by free radical, cat ionic
or anionic polymerization techniques, as are well known.
A large variety of these polymers can be readily obtained
commercially, such as poly(butadiene-acrylonitrile),
poly(butadiene-styrene), acrylonitrile-butadiene-styrene
(ABS) resins, ethylene-propylene-diene (EPDM) polymers or
the like. The olefinic containing polymers can be formed
with non-olefin containing monomer groups in any degree
desired as long as the resultant polymer contains
sufficient amounts of olefinic bonds therein to act as an
active precursor of the desired amine containing polymer
product It is desirable that the copolymers contain at
least about 3 percent by weight of olefinic containing
polymer segments therein and, preferably, that the
copolymer contain at least about 30 percent by weight of
the olefinic containing polymer segments.
The polymers found useful as reactants in accordance
with the present process can also be formed from olefinic
monomers such as propylene, battalion, cyclopentene
decylene and the like which produce, through branching,
-- 7
isomerization and the like polymeric material having
residual olefinic bones therein. In addition, asphalts
and asphaltene compositions can also be used herein. The
particular olefinic containing polymer to be used will, of
course, depend on the nature of the resultant polyamide
polymers desired.
The primary or secondary amine group containing
reactant can be selected from compounds having the formula:
R
\
Al
wherein R is selected from hydrogen or a Cluck
hydrocarbon radical, such as alkyd, aureole, alkaryl,
aralkyl, and cycloalkyl groups, preferably a Cluck
alkyd, aureole or cycloalkyl groups and is selected from
a Cluck, preferably a Cluck hydrocarbon radical
as described with respect to R above. Illustrative
examples of amine found suitable as a reactant in the
present process are methyl amine, ethyl amine, propylamine,
bellmen, n-pentylamine, hexylamine, decylamine,
dodecylamine, dimethylamine, diethylamine, dipropylamine,
diisopropyl amine, di-n-butylamine, diisobutylamine,
dipentylamine, di-2,2,4-trimethylpentylamine, dihexylamine
ethylhexylamine diheptylamine, dinonylamine,
butylpentadecylamine, diphenylamine, ditolylamine,
methylcumenylamine, dibenzylamine, aniline
methyl-2-phenylethylamine, methylnapthylamine,
diidenylamine, di-m-xylylamine, dioctenylamine,
dipen~enylamine, methylbutenylamine, dicyclopentylamine,
di(methylcyclopentyl)amine, and butylcylococtylamine and
the like. In addition, R and R can be joined to form a
single alkaline radical having from 2 to 6 carbon atoms,
as illustrated by pyrrolidine and the like. Each R and R'
or the joined OR alkaline radical can contain hotter
atoms or groups which are substantially non-reactive with
- 8 -
I
respect to the aminomethylation reaction as presently described. Such heteroatoms can be oxygen, sulfur or
tertiary or hindered secondary nitrogen and the like and
such groups can be ethers alcohols, ~hioalcohols,
thioethers, amino, cyan, tertiary amino and starkly
hindered secondary amino groups. Illustrative examples of
amine reactants containing such heteroatom or group are
morpholine, amino ethanol, 4-amino-2,2,6,6-tetraalkyl
10 piperidine and the like.
The reaction is performed under a liquid phase formed
by an organic liquid which is a solvent or the polymer
reactant and the amine. It is preferred that an an hydrous
liquid phase be used. The presence of small (less than 5
15 percent of total liquid) amount of water may be tolerated
but is not preferred as its presence tends to inhibit
achieving the desired high degree of amine incorporation.
Any suitable organic hydrocarbon liquid can be employed
which is inert to the reaction conditions, the reactants,
20 the catalyst and the products. Examples of suitable
hydrocarbons include aromatic hydrocarbons such as
Bunsen, Tulane, zillion, ethyl Bunsen, tetraline, etc.,
aliphatic hydrocarbons such as butane, pontoon,
isopentane, Hun, isohexane, Hutton, octane, isooctane,
25 nephtha, gasoline, kerosene, mineral oil, etc., alicyclic
hydrocarbons, such as cyclopentane, cyclohexane,
methylcyclopentane, decline, insane, etc.
Ethers can also be employed as the reaction solvent,
such as diisopropyl ether, di-n-butyl ether, ethylene
30 glycol diisobutyl ether, methyl o-tolyl ether, ethylene
glycol dibutyl ether, dismal ether, methyl p-tolyl
ether, methyl m-tolyl ether, ethylene glycol dismal
ether, diethylene glycol deathly ether, ethylbenzyl ether,
diethylene glycol deathly ether, diethylene glycol
35 dim ethyl ether, ethylene glyco] deathly ether, ethylene
glycol diphenyl ether, triethylene glycol deathly ether,
_ 9 _
diethylene glycol di-n-hexyl ether, tetraethylene glycol
dim ethyl ether, tetraethylene glycol dibutyl ether,
Dixon, tetrahydrofuran etc.
Alcohols can also be employed as a reaction solvent.
The alcohols can be any primary, secondary or tertiary
alcohol which are liquid at both ambient and reaction
conditions. It is preferred that the alcohol be a
Cluck alcohol such as, for example methanol, ethanol,
isopropanol, n-butanol, iso-butanol, t~butanol, timely
alcohol, 2-pentanol, 3-ethyl~2-pentanol and the like.
Tertiary amine can also be employed as the reaction
solvent the nitrogen atom, by definition, being
substituted with three hydrocarbyl groups which are inert
with respect to the reaction, such as, for example, alkyd,
aureole, alkaryl, aralkyl groups and the like Examples of
- suitable tertiary amine include triethylaminel
tripropylamine, triisobutylamine, trihexylamine,
trihepty]amine, triamylamine, dibenzyl ethyl amine, dibutyl
ethyl amine, dim ethyl pentylamine, diphenyl ethyl amine,
diphenyl methyl amine, dim ethyl aniline, pardon, dim ethyl
pardon, Matthew pardon, methyl pyrrolidine, ethyl
pyrrolidine and the like.
The particular solvent to be used will depend on its
ability to remain in the liquid state at both ambient and
at reaction conditions to facilitate the mixing of the
components, its salivating ability with respect to the
polymer and amine reactants, and its ease of handling, as
can be readily determined by the artisan.
The reaction is performed under relatively mild
30 conditions including temperatures from about 100 to about
250C; preferably from about 125 to about 200C.
Sufficient pressure should be used to maintain the
reaction medium in a liquid phase The reaction should be
carried out at a pressure of from about 30 to about 300
- 10 -
~3~9
atmospheres and, preferably, from about 30 to 150
atmospheres. The pressure can be maintained by the
pressure of the carbon monoxide and hydrogen supplied to
the reaction zone. It desired, a suitable inert gas, such
as nitrogen, can also be charged to the reaction zone to
increase the pressure within the reaction zone.
The ratio of the reactants can be widely varied. The
mole ratio of hydrogen to olefinic double bonds should be
at least about 2:1 with from about 2:1 to 20:1 being
10 preferred. The molar ratio of carbon monoxide to olefinic
double bond should be at least 1:1. The carbon monoxide
can be used in excess to form sufficient pressure required
in the reaction zone, as described above. Finally, the
mole ratio of amine reactant to olefinic double bond
contained in the polymer should be at least about 1:1 or
greater and preferably from at least about 1.2:1 or
greater with from about 1.2:1 to 20:1 being most preferred.
The catalyst required to be used in the present method
to achieve the high degree of amine incorporated polymer
20 product comprises at least one compound having a
Group VIII metal of the Periodic Chart therein (the term
"Group VIII metal compound" or "catalyst" as use herein
is meant to describe such compounds). Such Group VIII
metal compounds can be inorganic compounds, such as, for
25 example, Group VIII metal salts, oxides, carbonless and the
like. The Group VIII metal compound can be an
organometallic such as, for example, (although rhodium
metal or~anometallic compounds are given here for
illustrative purposes it is understood that other similar
30 Group VIII metal compounds can be used) tetrarhodium
dodecacarbonyl, hexarhodium hexadecacarbonyl,
tris(dimethylphenylphosphine) norbornadiene rhodium
hexafluorophosphate, Boyce diphenylphosphino) ethanes
norbornadiene rhodium per chlorate, chlorobis(ethylene)
I
rhodium diver, chloro(l,5-cyclooctadiene) rhodium diver,
chlorodicarbonylrhodium diver, chloropentaaminerhodium
chloride, hydridocar~onyl tris(triphenylphosphine)
rhodium, rhodium acetate diver, rhodium acetylacetonate,
sodium hexachlororhoda~e hydrate,
dicarbonylacetylacetonato rhodium,
chlorocarbonylbis(triphenylphosphine) rhodium,
chlorochiorbonyl Teledyne rhodium and trichloro rhodium
pardon. The preferred catalyst to be used by the
10 present process are formed from Group VIII metal compounds
of the metals, rhodium, ruthenium and iridium and most
preferably those formed from a mixture of at least two
compounds of Group VIII metals selected from rhodium,
ruthenium or iridium. When mixtures of compounds are used
15 it is preferred that a rhodium containing compound be
present and be the minor component of the mixture. The
most preferred catalyst used in the present process are
mixtures of a rhodium compound and a ruthenium compound.
of such mixtures the best catalytic activity is attained
20 when the ratio of rhodium metal atom to ruthenium metal
atom is less than about 0.5.
The exact chemical and physical composition of the
entity which acts as the catalyst for the subject reaction
is not known with certainty because of the possible
25 restructuring and/or interaction of the metal compound and `
the reactants contained in the reaction zone. Whether the
Group VIII compounds described herein acts directly as the
catalyst or as the precursor for the catalyst entity which
causes the presently desired aminomethylation is
30 immaterial. The subject Group VIII metal compounds will
be referred herein as the "catalyst" as they have
unexpectedly been found, when used with hydrogen, to
directly and/or indirectly provide the desired polymers
having high amine incorporation by the present one-step
35 process and to give the desired product in good yields.
- 12 -
....
I
The catalyst found useful in the subject process can
be a Group VIII metal salt of an inorganic acid such as,
for example, a chloride, nitrate, sulfate, per chlorate or
the like inorganic salt or of an organic acid salt such as
an acetate or the like. The salts are well known
commercial products formed conventionally by the reaction
of the metal oxide with an acid. The salt can be used in
its an hydrous state or as a hydrated salt.
The catalyst of the subject process can be an
organometallic compound. Such compounds can be formed in
coordination with the metal in any one of its valence
states. The organometallic compounds are normally formed
from chemical moieties which contain unshared electrons
such as atoms selected from nitrogen, oxygen, phosphorous
or sulfur or which contains unsaturation. the compounds
can be in the form of a carbonyl; an olefin such as
ethylene, butane and the like; dolphins, such as
norbornodiene, cyclooctadien-1,5 and the like; aliphatic,
aromatic, aureole aliphatic phosphates, such as triethyl
phosphitel tributyl phosphate, trim ethyl phosphate,
triphenyl phosphate, dimethylphenyl phosphate, tritolyl
phosphate, tribenzyl phosphate, ditolyl phenol phosphate,
and the like; aliphatic, aromatic, aureole aliphatic
phosphines such as triphenyl phosphine and the like
wherein the phosphine to metal is equal or less than 3;
aliphatic and cyclic ethers such as dim ethyl and deathly
oxide, Dixon, dialkyl ether glycols, acutely acetone and
the like; primary, secondary and tertiary amine which
contain alkyd, aureole, alkaryl, arallayl cycloalkyl groups
or mixtures thereof such as trim ethyl amine, deathly
amine, Teledyne and the like; heterocyclic bases such as
pardon, and the like; ammonia, sulfides such as dialkyl,
diary, alicyclic heterocyclic sulfides and the like and
mixtures thereof. When the compound is formed from
- 13 -
uncharged ligand components with a charged Group VIII
metal, the compound is formed into a stable neutral state
with an anion such as a chloride, per chlorate, nitrate,
hexaflourophosphate and the like.
The catalyst can be added directly to the reaction
liquid phase either prior to, with or subsequent to the
introduction of other required reactants. The Group VIII
metal compound which are useful as a catalyst in the
present process must have some degree of volubility in the
liquid media in which the subject aminomethylation takes
place. The choice of liquid media and/or catalyst to be
used in a particular reaction so that the catalyst has
some degree of volubility can be readily determined by the
artisan using conventional methods.
The catalyst has been wound to be effective to cause
the formation of the desired polymeric polyamides as
described above when used in a molar ratio of Group VIII
metal atom to olefin bond of from about 1 x 10 5 to
2.5 x 10 and preferably from about 1 x 10 5 to
1 x 10 3. The most preferred range from both
effectiveness and economy is from 5 x 10 5 to
5 x 10 . Although greater amounts of catalyst can be
used, such has not been found required.
The process is carried out by contacting the above
described reactants and the catalyst in a vessel which is
preferably adapted for gas injection, agitation and
heating. The polyolefin, the amine, and the catalyst are
added to the solvent and the reaction mixture is
pressurized and heated. The reactor and its contents are
maintained at the desired elevated temperature and
pressure for a sufficient period to cause the formation of
the desired polymeric secondary amine. The vessel it then
cooled and when appropriate, degassed and the polymeric
product is recovered by standard technique such as by
- 14 -
I
precipitation in a non-solvent or extraction and drying in
a vacuum. For additional purification the product may be
further subjected to fractional precipitation and the
quantity of desired product may be determined by standard
analytical techniques.
he following examples are given for illustrative
purposes only and are not meant to be a limitation on the
subject invention as defined in the appended claims. All
parts and percentages are by weight unless otherwise
indicated-
The preparations of polymeric polyamides we reconducted using, unless otherwise indicated hereinbelow,
0.75 part (14 mole C = C) polybutadiene with 22.4 moles
amine reactant in the presence of a Group VIII metal
catalyst as specifically indicated below. The reactants
were diluted with tetrahydrofuran to form a 10 ml
mixture. The mix was charged into a 150 ml Hove cylinder
reactor which was then pressurized with CO and Ho in a
1:1 molar ratio to 1000 psi. The reactor was heated to
I 150C and maintained there for a period of 4 hours. The
polymer product was recovered from the reaction mixture by
organic solvent/water extraction.
The product was analyzed by standard Nuclear Magnetic
Resonance (NOR) using a Variant EM 390. In addition,
selective determination of amine incorporation was done by
the standard techniques of (a) determining the total amine
incorporation by direct titration with hydrochloric acid
in isopropanol; (b) determining secondary and tertiary
amine content by first reacting any residual primary amine
present with salicyladehyde and then titration with
hydrochloric acid in isopropanol for secondary and
tertiary amine content; and (c) treating a sample with
phenylisothiocyanate to react primary and secondary amine
and then titrate with hydrochloric acid in isopropanol to
- 15 -
determine concentration of tertiary amino groups in the
polymer product. The results from a, b, and c allows one
to calculate primary, secondary and tertiary amino groups,
as appropriate r for the reactant and product.
Example 1
A series of products were formed from polybutadiene
with a variety of amine, of liquid reaction media, of
concentration of catalyst, of temperature and of polymer
molecular weight. The amine to olefinic double bond molar
ratio was 1.6. The reactants were dissolved in
tetrahydrofuran or N-methyl pyrrolidine. The reactants
were added to a 150 ml Hove cylinder reactor, pressurized
with KIWI in a 1:1 molar ratio or with equal amount of
CO with inert gas (No) where water was used in lieu of
Ho for comparative purposes. The reactor was heated to
the indicated temperature for a period of 5 hours, cooled
and the product recovered and analyzed by titration and
NOR. For each of the reactions, a duplicate back-to-back
comparative reaction was conducted to show the benefit of
using the combination of a Group VIII metal catalyst with
hydrogen instead of the combination of the metal and water.
Further, samples of series 1, 2 and 3 further show
that the resultant product has a significant reduction in
residual unsaturation in the polymers and thereby forms a
more stable material.
The results are listed in Table I below.
- 16 -
_ us o I
I ED
do
o
Pi H
I o o o I o Inlay It) or
do I or r
to I 11~ I Lo If 11~ Irk O 010 Us O O
En
okay
O O O O O O O 0 00 I O
I) O O O O O 00 ox O O O pa
V U
I Lo O
Jo ,_ .,~ Lo
or
g _ c my D D Lo
a .5 I: S 5
' C) Lo ; K H
I Us to
Us I
a c I
En Ho _ , c c
o m : m en m o c
EN Al En ; Z En
o .,~ ~,~ 0
o 0
P
o cc "0
us a) a) I O
c c 0 0 0 0 o -
Pi C 1 I I Jo Jo C I Z 0 0
En ,1 O O O O O O 0 I a
O it S S S ; C
a
X a a a a ox æ O .
o
1,1 Q O Us
En O I o I o o o o o o ox o c:, Jo o 1~1
I O O O O O O O O 00 0 0
I OOOOOOOOO~DW~D O
O I I I I U O I
Pi P
. 0- '
V U ` U --
o o o o o o o so e
o
r I) m m m m m I m m cam m m
S O H I,
a) I, _ Jo _ _
V ) O
Q
0 0 8 0 _
Example 2
0.75 part polybutadiene having a molecular weight of
1000, 1.30 parts isopropyl amine, OKAY part RhS(CO)l6
was dissolved in tetrahydrofuran (15%) and the reaction
mixture placed in a 150 ml Hove cylinder which was
pressurized to 1,000 psi with carbon monoxide and hydrogen
(KIWI = I The temperature was raised to 150C over
90 minutes and maintained there for 4.5 hours. The
product mixture was analyzed by conventional titration
methods, with standardized hydrochloric acid in
isopropanol to determine the total amount of amino groups
incorporated in the polymer and by selective titration to
determine the ratio of secondary and tertiary amino
groups. 51~ of the double bonds were found to be
aminomethylated. The ratio of secondary to tertiary amine
was 4:1.
Exhume 3
This reaction was carried out in the same way as
described in Example 2, the difference being that 2.21
parts cyclohexylamine was used as starting material.
54.6% ox the double bonds were found to be aminomethylated.
example 4
This reaction was carried out in the same way as
described in Example 2, the difference being that 1.60
parts tert-butylamine was used as starting material.
48.9~ of the carbon double bond were found to be
aminomethylated.
Example 5
. In each of the following series of samples
polybutadiene and amine compound, as identified in the
- 18 -
I
table below, (amine/C = C = 1.6 molar ratio) were
dissolved in tetrahydrofuran. Rh6~CO)l6 was added in
amount to provide one Rho atom per 500 C = C bonds. The
reactants were added to a 150 ml Hove cylinder reactor or
a 2 liter Magnadrive autoclave, as indicated, and then
pressurized to 1000 psi with KIWI in a 1:1 molar
ratio. The reactor was heated to 150C for about 5 hours,
cooled and the product recovered and analyzed. The
results are given in Table II below.
TALE II
Scope of the Aminomethylation Reaction in Respect to
Different Pol~butadienes as starting Materiels
Amine
Malta. % is I % vinyl) Nitrogen Incorporation
Molly. trays units units Source %
4,500(C) 55 45 DAM 70
14,000(C) 20 80 DAM 53
30~000(C) 20 80 DAM 51
owe 100 - DAM 49
Lowe 10 90 DAM 82
3,00~(d) lug 90 pram 84
tax - Molecular weight of the polybutadiene~
(b) - DO = dimethylamine, pram - isopropyl amine
(c) - 150 ml Hove cylinder used as reactor
(d) - 2 liter Magnadrive (Autoclave Engineering)
autoclave used as reactor.
(e) double bond distribution of startling
butadiene polymer.
- 20
g
Example 6
A series of experiments were conducted according to
the procedure of Example 5 above. The polymer used in
each experiment was a phenol terminated polybutadiene of
MY of Lowe having 25% vinyl double bonds, 99~
unsaturation. The amine was varied as indicated in
Table III below. The amine incorporation was determined
by selective titration method. Hydrogen was used in each
experiment with Rh6(CO)16, as the Group VIII metal
10 catalyst
Table III
Catalyst Cone. Polymer
Amine = C per Group VIII metal Amine Incorp.
Pyrrolidine20~0 64
15 Dimethylamine 2000 49
Isopropyl amine 1000 51
Cyclohexylamine 1000 55
t-butylamine1000 49
Methyl amine 500 63
Example 7
A series of products were formed according to the
procedure of Example 5 above except that the catalyst used
was composed of a mixture of Group VIII metal compounds as
indicated in Table IV below. In each case hydrogen was
used as the hydrogen source to provide, in combination
with the catalyst, a high incorporation of amino groups
into the polymer. Sample 6c is included for comparative
purposes to show that much lower amine incorporation is
attained when water is used as the hydrogen source.
21 -
I
TABLE IV
Aminomethylation with Mixed My tat Systems
Polymer
Catalyst Hydrogen Amine
Sample Catalyst_ Amount ) Amine Source Inquiry
( )
1 Rucl2(DMso) 500 DAM Ho 61
5000
2 RUC12(CO)2(PO3)2 50 _ DAM I 80
Rho 5000
3 RUH(OCOCH2)(Po3)3 500 DAM Ho 74
Rho 5000
4 Focus 40 DAM Ho 74
Rh6(CO)16 2000
5H7_2)3 500 DO Ho 62
Rho 5000
6 Rucl2(po3~3 .500 DAM Ho 71
Rho 5000
I REEQUIP 500 DAM HO 26
ho 5000
(a) - determined by selective titration
(b) - [C=C]/[Metal]
Rho = [Rh(NBD)Ph((CH3)2)3]PE~6 ~NBD=norbornadiene)
DAM = dimethylamine
- I -
