CATALYST COMPOSITION FOR HYDRO¬
FORMYLATION REACTION AND A HYDROFORMYLATION
PROCESS USING THE SAME
Technical Field
[1] The present invention relates to a catalyst composition for hydroformylation reaction
and a hydroformylation process using the same, and more particularly, to a catalyst
composition that include a transition metal catalyst and a mondentate phosphine ligand
for olefin-based compound, and a hydroformylation process using the same.
[2]
Background Art
[3] A hydroformylation reaction producing linear (normal) and branched (iso) aldehyde
which has one more carbon atoms than olefin by reacting carbon monooxide (CO) and
hydrogen (H2) that are commonly called as a synthesis gas in the presence of a h o
mogeneous organicmetalic catalyst and a ligand was originally discovered by Otto
Roelen in Germany in 1938.
[4] In generally, the hydroformylation reaction that is known as oxo reaction, is a very
important industrial reaction in view of a homogeneous system catalyst reaction.
Currently, about 9,600,000 tons of adhehydes (including alcohol derivatives) are
produced by the oxo process all over the world (SRIreport, September 2006, 682. 7000
page 7).
[5] Various types of aldehydes produced by the oxo reaction are oxidated to carboxylic
acids or hydrogenated to alcohols. In addition, aldehydes can also be converted to long
alkyl chain-containing acids or alcohols through aldol condensation and then oxidation
or reduction. In particular, hydrogenation alcohol of aldehyde, which is obtained by the
oxo reaction, as is called oxo alcohol. Oxo alcohol is industrially extensively used as a
solvent, additive, various types of raw materials of plasticizers, or synthetic lubricants.
[6] It is known that a metal carbonyl compound catalyst has a catalytic activity of the hy
droformylation reaction, and almost focused on cobalt (Co) rhodium (Rh). The N/I
(ratio of linear (normal) to branched (iso) isomers) selectivity, activity, and stability of
aldehydes vary according to the type of ligand used and operating conditions.
[7] To date, a rhodium-based low-pressure oxo process (LPO process) has been adopted
in at least 70% of oxo plants worldwide because of the high efficiency, high yield of
normal products, and mild reaction condition even though there are disadvantages of
the expensive catalyst and catalytic deactivation due to the poisoning.
[8]
[9] A central metal of oxo metal may be used a transition metal, such as iridium (Ir),
ruthenium (Ru), osmium (Os), platinum (Pt), palladium (Pd), iron (Fe), or nickel (Ir).
In respects to the transition metals, it is known that the order of the catalytic activity is
h » Co > Ir, Ru > Os > Pt > Pd > Fe > Ni.
[10] Pt and Rh as Group 8 transition metal have been mainly used in an oxo process, for
example, HCo(CO)4, HCo(CO)3PBu3 and HRh(CO)(PR 3)3. Pt and Ru are mainly
subjects of academic interest. Therefore, Co applied for academic research, and
currently most of oxo processes having industrial objects basically uses rhodium and
cobalt, and a representative example may include
[11] Examples of the ligand that is used during the oxo process include phosphine (PR3, R
is C H5, or n-C4H ), phosphine oxide (0=P(C H5)3) and phosphite. In case of using
rhodium as the central metal, it is known that the ligand having the catalytic activity
and the stability that are better than those of triphenylphosphine (TPP) is almost not
present. Thus, in most oxo process, erefore, rhodium (Rh) metal is used as a catalyst
and TPP is used as a ligand. In addition, to increase the stability of a catalytic system,
TPP ligand is used in an amount of at least 100 equivalent of the catalyst.
[12] Since the value of linear aldehyde derivative is generally high among aldehydes that
are products of the oxo reaction, many studies have been made to increase the ratio of
the linear aldehyde in respects to the catalyst. However, recently, products obtained by
using iso-aldehyde as the raw materials instead of the linear aldehyde, for example, an
isobutyric acid, neopentyl glycol (NPG), 2,2,4-trimethyl-l,3-pentanediol, isovaleric
acid and the like have been developed, thus the use of iso-aldehyde has been increased.
Accordingly, these is a demand to develop a technology of producing iso-aldehyde
required in a market by desirably controlling the N/I selectivity while the excellent
catalytic activity and stability, together with reducing the ligand amount.
[13]
Disclosure of Invention
Technical Problem
[14] The present invention has been made keeping in mind the above ploblems occurring
in the related art, and thus the inventors of the present invention have found that if a
mondentate phosphine ligand is applied to a hydroformylation reaction of olefin at the
same time, the catalyst activity and stability are excellent, a ligand is used as reduced
amount, and an iso-aldehyde selectivity can be controlled.
[15]
[16] Therefore, the object of the present invention is to provides catalyst compositions
containing a transition metal catalyst and a mondentate phosphine ligand, and a hydro
formylation process using the same, in which the catalyst compositions can increase a
catalytic stability, decrease the amount of ligand, show a high catalytic activity, and
also increase a selectivity of iso-aldehyde produced, at the same time.
[17]
Solution to Problem
[18] Accordingly, the present invention provides a catalyst composition for a hydroformylation
reaction that includes a mondentate phosphine ligand represented by the
following Formula 1; and a transition metal catalyst represented by the following
Formula 2:
[19]
[20]
[21] wherein R R2 and R3 are each independently alkyl group having 1 to 3 carbon
atoms; or alkoxyl group having 1 to 5 carbon atoms.
[22]
[23] M( )x( 2)y( )z
[24] wherein M is any one selected from cobalt (Co), rhodium (Rh) and iridium (Ir), L , L
2 and L3are each independently any one selected from the group consisting of
hydrogen, CO, cyclooctadiene, norbornene, chlorine, triphenylphosphine or acetylacetonato,
[25] x, y and z are each independently 0 to 5, x, y and z are not 0 at the same time.
[26]
[27] In addition, the present invention provides a hydroformylation process of an olefinbased
compound, which includes reacting the olefin-based compound, and a synthetsis
gas of carbon monooxide and hydrogen in the presence of the catalyst composition
according to the present invention to produce aldehyde.
[28]
[29] Hereinafter, the present invention will be described in more detail.
[30] The present invention relates to a catalyst composition for hydroformylation reaction
containing (a) a mondentate phosphine ligand represented by the following Formula 1;
and (b) a transition metal catalyst represented by the following Formula 2:
[31]
[33] wherein R R2 and R3 are each independently alkyl group having 1 to 3 carbon
atoms; or alkoxyl group having 1 to 5 carbon atoms.
[34]
[35] The present invention excludes that R R2, and R3 are each independently substituted
by any one selected from the group consisting of a nitro group (-N0 2), a fluorine group
(-F), a chlorine group (-C1), a bromine group (Br), and a silyl group (-SiR, wherein R is
selected from hydrogen, alkyl group or alkoxy group); or R i to R3are all hydrogen as
the mondentate phosphine ligand.
[36]
[37]
[38] M(U)x(L 2)y(L )z
[39] wherein M is any one selected from cobalt (Co), rhodium (Rh) and iridium (Ir), L , L
2 and L3are each independently any one selected from the group consisting of
hydrogen, CO, cyclooctadiene, norbornene, chlorine, triphenylphosphine or acetylacetonato,
[40] x, y and z are each independently 0 to 5, x, y and z are not 0 at the same time.
[41]
[42] The catalyst composition for a hydroformylation reaction containing the monodentate
phosphine compound represented by the above Formula 1 as ligand according
to the present invention has technical features such that increased catalytic stability and
high catalytic activity can be obtained, and the selectivity of iso-aldehyde produced
can be desirably controlled.
[43]
[44] Each constituents of the catalyst composition for a hydroformylation reaction will be
described in detail.
[45] (a) a mondentatephosphineligand
[46] It is preferable that the catalyst composition includes a mondentate phosphine ligand
represented by the above Formula 1. The mondentate phosphine ligand is continuously
consumed during an aldehyde recovering process of a continuous hydroformylation
process. Accordingly, a desirable ligand is selected in consideration of the desired isoaldehyde
selectivity and injected into the reactor. Thus, it is easy to apply the above
Jigans in practice.
[47] According to the catalyst composition of the present invention and the hydroformylation
process using the same, the monodentate phosphine ligand alone are
applied to the hydroforrnylation reaction of olefin to obtain increased catalytic
stability, high catalytic activity and reduced ligand amounts together with controlling
desirably the selectivity of iso-aldehyde produced.
[48]
[49] If is preferable that the mondentate phosphine ligand represented by the above
Formula 1 be one or more selected from the group consisting of tri-p-tolylphosphine
(TPTP), tri-p-ethylphenylphosphine (TPEtPP), tris-p-metoxyphcnyl phosphine
(TMPP) and tri-p-isopropoxyphenyl phosphine (TIPPP). Preferably, the mondentate
phoslhine ligand is one or more selected from the group consisting of trip-
tollylphosphine (TPTP) represented by the following Formula 4, and trisp-
methoxyphenyl phosphine (TMPP) represented by the following Formula 5:
[50]

The content of the mondentate phosphine ligand represented by the above Formula 1
is preferably in the range of 5 to 100 mole, and more preferably in the range of 10 to
50 mole, based on 1 mole of central metal of the transition metal catalyst represented
by the above Formula 2. In connection with this, if the content is less than 5 mole
based on 1 mole of central metal of the transition metal catalyst, there is a problem in
poor reactivity of catalyst. If the content is more than 100 mole, there is a problem in
reduced reaction velocity due to the excessive amount of the costly ligand.
Preferably, the content of the. mondentate phosphine ligand represented by the
Formula 1 is in the range of 1.5 to 4.0 wt based on total weight of the catalyst com
position. In connection with this, if the content is less than 1.5 wt based on total
weight of the catalyst composition, there is a problem in the catalytic stability. If the
content exceeds 4.0 wt , since an excessive amount of the costly ligand is used
without any additional benefit, there is a problem in that cost is increased.
[58] More preferably, the content is in the range of 1.5 to 3.0 wt based on total weight
of the catalyst composition as the catalytic activity may be maximized and also N/I se
lectivity can be improved.
[59]
[60] Particularly, in case of using tri-p-tollylphosphine (TPTP) represented by the above
Formula 4 as the ligand, the content is preferably in the range 2.0 to 3.0 wt based on
total weight of the catalyst composition, and selectivity for iso-aldehyde, and in case of
using tris-p-methoxyphenyl phosphine (TMPP) represented by the above Formula 5,
the content is preferably in the range of 1.5 to 2.1wt based on total weight of the
catalyst composition, for providing maximized catalytic stability, catalytic activity.
[61]
[62] More Preferably, the monodentate phosphine ligand is a mixture of trip-
tollylphosphine (TPTP) represented by the Formula 4 and tris-p-methoxyphenyl
phosphine (TMPP) represented by the Formula 5 .
[63]
[64] In case of when the monodentate is used as a mixture of tri-p-tollylphosphine (TPTP)
represented by the above Formula 4 and tris-p-methoxyphenyl phosphine (TMPP) rep
resented by the above Formula 5, may vary, preferably be in the range of 1 to 2 wt of
TPTP and 0.5 to 1.0 wt of TMPP based on total weight of the catalyst composition in
respects to the catalytic stability and N/I selectivity.
[65]
[66] ( ) TransitionMetalCatalvst
[67] In respects to the transition metal catalyst that is represented by the above Formula 2,
there are cases of when L is CO, L2is acetylacetonato, and x, and y are 2 and 1, r e
spectively (z is 0), when L is CO, L2is acetylacetonato, L3is triphenylphosphine, and x,
y and z are all 1, and when L is CO, L2is hydrogen, L3is triphenylphosphine, x, y and z
are each independently 1, 1 and 3.
[68] Preferably, the transition metal catalyst represented by the above Formula 2 be one or
more selected from the group consising of cobaltcarbonyl [Co2(CO) ], acetylacetonatodicarbonylrhodium
[Rh(AcAc)(CO) 2], acetylacetonatocarbonyltriphenylphosphinerhodium
[Rh(AcAc)(CO)(TPP), ROPAC], hydridocarbonyltri(
triphenylphosphine)rhodium [HRh(CO) (TPP)3], acetylacetonatodicarbonyliridium
[Ir(AcAc)(CO) 2], and hydridocarbonyltri(triphenylphosphine)iridium
[HIr(CO)(TPP) 3].
[69] More preferably, the transiaiton metal catalyst is selected from acetylacetonatodicarbonylrhodium
[Rh(AcAc)(CO) 2] and/or acetylacetonatocarbonyltriphenylphosphinerhodium
[Rh(AcAc)(CO)(TPP), ROPAC].
[70]
[71] In the case of when L in the transition metal catalyst represented by the above
Formula 2 is triphenyphosphine, it is substituted by Formula 4 or Formula 5 as ligand
having an excellent accessibility to metal electronically after addition to the reactor, so
that it have not any adverse effect for the reaction and the ligands are continuously
consumed during an aldehyde recovering process of a continuous hydroformylation
process.
[72] Preferably, in respects to the content of the above transition metal catalyst rep
resented by the above Formula 2, the content of the central metal is in the range of 10
to 1000 ppm based on a weight or a volume of the catalyst composition. More
preferably, the content is in the range of 50 to 500 ppm. In case of when the content of
the transition metal is less than 10 ppm, since the reaction rate of the hydroformylation
is slow, it is undesirable in practice. In case of when the content of the transition metal
is more than 1000 ppm, since the transition metal is costly, the cost is increased and the
excellent effect is not obtained in terms of the reaction rate.
[73]
[74] In addition, the present invention relates to a hydroformylation process of an olefinbased
compound, which includes reacting the olefin-based compound, and a synthetsis
gas of carbon monooxide and hydrogen in the presence of the catalyst composition
according to the present invention to produce aldehyde.
[75] The specific components and contents of the catalyst composition are as mentioned
above. The catalyst composition may be produced by dissolving the above components
in a solvent.
[76] In the above hydroformylation process, examples of the above solvent may include
one or more compounds selected from the group consisting of aldehydes including
propane aldehyde, butyl aldehyde, phentyl aldehyde, and valer aldehyde; ketones
including acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and cyclohexanone;
alcohols including ethanol, pentanol, octanol, and thesanol; aromatic
compounds including benzene, toluene, and xylene; halogenated aromatic compounds
including ortho-dichlorobenzene; ethers including tetrahydrofurane, dimethoxy ethane,
and dioxane; halogenated paraffins including methylene chloride; and paraffin hy
drocarbons including such as heptane. More preferably, aldehyde produced from the
hydroformylation reaction may be used.
[77] In the above hydroformylation process, it is preferable that the above olefin-based
compound be a compound that is represented by the following Formula 3:
[78]
[80] wherein R 4 and R5 are each independently any one selected from the group consisting
of hydrogen, an alkyl group having 1 to 20 carbon atoms, a fluorine group (-F), a
chlorine group (-C1), a bromine group (-Br), a trifluoromethyl group (-CF3) and an aryl
group having 0 to 5 substituent groups and 6 to 20 carbon atoms, and the substituent
group is nitro (-N0 2), fluorine (-F), chlorine (-C1), bromine (-Br), a methyl group, an
ethyl group, a propyl group or a buthyl group when the aryl group is substituted.
[81]
[82] Specifically, the olefin-based compound represented by the Formula 3 may be one or
more compounds selected from the group consisting of ethane, propene, 1-butene,
1-pentene, 1-hexene, 1-octene, and styrene.
[83]
[84] In the above hydroformylation process, the composition ratio of carbon monooxide
to hydrogen (CO:H2) that are the synthesis gas may vary, preferably be in the range of
about 5:95 to 70:30, more preferably about 40:60 to 60:40, and most preferably about
50:50 to 40:60. In case of when the mole ratio is less than 5:95 or more than 70:30,
since the unreacted gas in the reaction is too much in the reactor, there is a risk that the
reactivity of the catalyst may be decreased.
[85] In the hydroformylation process, other reaction conditions except the catalyst com
position may include those known in the art.
[86] For example, in the above hydroformylation process, the hydroformylation process is
performed at the reaction temperature in the range of preferably about 20 to 180°C,
more preferably about 50 to 150°C, and most preferably about 75 to 125°C. In case of
when the reaction temperature is less than 20°C, there is a problem that the hydro
formylation reaction is not proceeded. In case of when the reaction temperature is more
than 180°C, there is a problem in decreased catalytic activity due to greatly damaged
catalytic stability.
[87]
[88] In the above hydroformylation process, the hydroformylation process performed at
the reaction pressure in the range of preferably about 1 to 700 bar, more preferably
about 1 to 300 bar and most preferably about 5 to 30 bar. In case of when the reaction
pressure is less than 1 bar, since the hydroformylation reaction is not proceeded, it is
undesirable in practice. In case of when the reaction pressure is more than 700 bar,
since costly reactor should be used due to the explosion risk of the process without a
specific activity advantage, it is undesirable in industrial practice.
[89]
[90] The reaction caused by the above hydroformylation process may be shown in the
following Reaction Equation 1:
[91]
[92]
[93] As shown in the Reaction Equation , first, the transition metal catalyst and the
ligands are dissolved i a solvent such as benzene, toluene, ethanol, pentanol, octanol,
hexanol, butylaldehyde, and phentyladehyde to prepare a solution mixture of the
catalyst and the ligands.
[94] Then, the olefin-based compound 3, and the synthesis gas 4 of carbon monoxide and
hydrogen are injected in conjuction with the solution mixture of the catalyst and the
ligands into the reactor, agitated, heated and pressurized to perform the hydro
formylation reaction.
Advantageous Effects of Invention
[95] According to the catalyst composition of the present invention and the hydro
formylation process using the same, the monodentate phosphine ligand are applied to
the hydroformylation reaction of olefin to obtain increased catalytic stability, high
catalytic activity and reduced ligand amounts together with controlling desirably the
selectivity of iso-aldehyde produced.
[96] In addition, the mondentate phosphine ligand is continuously consumed during an
aldehyde recovering process of a continuous hydroformylation process. Accordingly, a
desirable ligand is selected in consideration of the desired iso-aldehyde selectivity and
injected into the reactor. Thus, it is easy to apply the above ligans in practice.
[97]
Best Mode for Carrying out the Invention
[98] Hereinafter, the present invention will be described in more detail in light of
Examples and Comparative Examples.
[99] The present invention may, however, be embodied in many different forms and
should not be construed as being limited to the Examples set forth herein. Rather, these
Examples are provided such that this disclosure will be thorough and complete and
will fully convey the concept of the present invention to those skilled in the art.
[100]
[101]
[102] Thehydroformylationreactionofpropeneusingthe acetylacetonatocarbonyltriphenylphosphinerhodium
(Rh(AcAc)(CO)(TPP), ROPAC) catalyst, andthe monodentatephosphinecompound
[103] 0.0957 g (0. 194 mmol) of ROPAC that was the catalyst, tri-para-tollylphosphine
(TPTP), tri-para-ethylphenylphosphine (TPEtPP), tris-para-methoxyphenyl phosphine
(TMPP) or tri-para-isoprophoxyphenyl phosphine (TIPPP) that were the monodentate
phosphine comound were dissolved in butylaldehyde solvent according to the contents
described in Table 1 so that the total weight of the solution was 100 g, and then added
in the autoclave reactor having the volumn of 600 ml volume. Propene (olefin): CO:H2
were injected into the above reaction solution, and the reaction was performed for 1
hour while the pressure in the reactor was maintained at 8 bar and agitation was
performed at 90 °C.
[104]
[105] The type of the catalyst and the ligand to the above reaction, a weight ratio of the
ligand in the catalyst composition, the N/I selectivity, and the catalytic activity are
described in Table 1 in the detail.
[106]
[107]
[108] Additionally, 0.0501 g (0. 198 mmol) of Rh(AcAc)(CO) 2 that was the catalyst, tripara-
tollylphosphine (TPTP), tri-para-ethylphenylphosphine (TPEtPP), trispara-
methoxyphenyl phosphine (TMPP) or tri-para-isoprophoxyphenyl phosphine
(TIPPP) that were the monodentate phosphine comound were dissolved in buty
laldehyde solvent according to the contents described in Table 1 so that the total
weight of the solution was lOOg, and then added in the autoclave reactor having the
volume of 600 ml.
[109] Propene (olefin):CO:H2 were injected into the above reaction solution, and the
reaction was performed for 1 hour while the pressure in the reactor was maintained at 8
bar and the agitation was performed at 90 °C.
[110] The types of the catalyst and the ligand to the above reaction, the weight ratio of the
ligand in the catalyst composition, the N/I selectivity, and the catalytic activity are
described in Table 1 in the detail.
[Ill]
[112]
[113] *N/I selectivity : it is the value divided the amount of normal-bytylaldehyde produced
from the reaction by the amount of iso-butylaldehyde. The amounts of each aldehyde
are obtained by gas-chromatography(GC) analysis.
[114] *catalvticactivitv : it is the value divided total amount of aldehyde produced during
the reaction by a molecular weight of butyl aldehyde, a concentration of the used
catalyst, and the reaction time. The unit of catalytic activity is mol(BAL)/mol(Rh)/h.
[115] *AgingTest : the synthesis gas (CO:H2) having mole ratio of 1:1 was injected into the
reaction solution, the reaction was maintained at 10 bar and the agitation was
performed at 120 °C. any change during the reaction was evaluated.
[116]
[117]
[118] Thehydroformylationreactionofpropenebyusing acetylacetonatocarbonyltriphenylphosphinerhodium
(Rh(AcAc)(CO)(TPP), ROPAC) catalyst, triphenylphosphinecompound,
tri-p-tollylphosphine (TPTP), tris -
p-methoxylphenylphosphine (TMPP), tri(p-chlorophenyl)phosphine (TCPP), tri -
o-toUylphosphine (TOTP)
[119] TPP, TPP and TPTP, TPP and TMPP, TCPP, TOTP that were the triphenylphosphine
compound were used as the ligand to perform the catalyst activity test by using the
same methods as Examples 1 to 11 according to the content described in the following
Table, and the result are also described in the following Table 1.
[120] Table 1
[Table 1]
[121]
[122] With reference to the above Examples 1 to 11 and Comparative Examples 1 to 8, the
catalytic activity is excellent as compared to the case of when only use triphenylphosphine
ligand is uased as the ligand under the same condition, and the case of
when triphenylphosphine ligand and monodentate phosphine ligand are used at the
same time.
[123] In addition, it can be seen that the N/I selectivity can be improved, and the com
position can be used during an oxo process in practice because the stability of the com
position is almost similar to that of triphenylphosphine of 120 equivalents based on Rh
(Comparative Example 1).
[124]
[125] Meanwhile, in the case of when the content of the mondentate phosphine ligand is in
the range of 1.5 to 4 wt based on total weight of the catalyst composition, and more
preferably 1.5 to 3 wt , it is preferable to provide maximized catalytic activity
together with improved N/I selectivity. Also it can be seen that in case of no substituents
and carbon atoms of 1 to 3 as a para site therein was shown desirable results.
PCT/KR2011/005173

Claims
A catalyst composition for hydroformylation reaction, comprising:
(a) a mondentate phosphine ligand represented by the following
Formula 1; and
(b) a transition metal catalyst:

R3
wherein R R2 and R3 are each independently alkyl group having 1 to 3
carbon atoms; or alkoxyl group having 1 to 5 carbon atoms.
The catalyst composition as set forth in claim 1, wherein the transition
metal catalyst (b) is represented by the following Formula 2:

M( )x( )y( )z
wherein M is any one selected from cobalt (Co), rhodium (Rh) and
iridium (Ir), L , L2 and L3are each independently any one selected from
the group consisting of hydrogen, CO, cyclooctadiene, norbornene,
chlorine, triphenylphosphine and acetylacetonato,
x, y and z are each independently 0 to 5, x, y and z are not 0 at the same
time.
The catalyst composition as set forth in claim 1, wherein the
mondentate phosphine ligand is one or more selected from the group
consisting of tri-p-tolylphosphine (TPTP), tri-p-ethylphenylphosphine
(TPEtPP), tris-p-metoxyphenyl phosphine (TMPP) and trip-
isopropoxyphenyl phosphine (TIPPP).
The catalyst composition as set forth in claim 1, wherein the
mondentate phosphine ligand is one or more selected from the group
consisting of tri-p-tollylphosphine (TPTP) represented by the following
Formula 4, and tris-p-methoxyphenyl phosphine (TMPP) represented
by the following Formula 5:

PCT/KR2011/005173

OMe
The catalyst composition as set forth in claim , wherein the content of
the mondentate phosphine gand is in the range of 5 to 100 mole based
on 1 mole of central metal of the transition metal catalyst.
The catalyst composition as set forth in claim 1, wherein the content of
the mondentate phosphine ligand is in the range of 1.5 to 4.0 wt%
based on total weight of the catalyst composition.
The catalyst composition as set forth in claim 4, wherein the monodentate
phosphine ligand is tri-p-tollylphosphine (TPTP) represented
by the Formula 4 in the range of 2.0 to 3.0 wt based on total weight
of the catalyst composition.
The catalyst composition as set forth in claim 4, wherein the monodentate
phosphine ligand is tris-p-methoxyphenyl phosphine (TMPP)
represented by the Formula 5 in the range of .5 to 2.1 wt based on
total weight of the catalyst composition.
The catalyst composition as set forth in claim 4, wherein the monodentate
phosphine ligand is a mixture of tri-p-tollylphosphine (TPTP)
represented by the Formula 4 and tris-p-methoxyphenyl phosphine
(TMPP) represented b the Formula 5 in the range of to 2 wt% of
TPTP and 0.5 to 1.0 wt% of TMPP based on total weight of the catalyst
composition.
The catalyst composition as set forth in claim 2, wherein the transition
metal catalyst is one or more selected from the group consisting of
cobaltcarbony 1[Co (CO) , acetylacetonatodicarbony lrhodium
[Rh(AcAc)(CO) ], acetylacetonatocarbonyltriphenylphosphinerhodium
[Rh(AcAc)(CO)(TPP)], hydridocarWO
2012/030065 PCT/KR2011/005173
bonyltri(triphenylphosphine)rhodium [HRh(CO) (TPP)3], acetylacetonatodicarbonyliridium
[Ir(AcAc)(CO) 2], and hydridocarbonyltri(
triphenylphosphine)iridium [HIr(CO)(TPP) 3].
[Claim 11] The catalyst composition as set forth in claim 2, wherein a content of
central metal of the transition metal catalyst is in the range of 10 to
1000 ppm based on a weight or a volumn of the catalyst composition.
[Claim 12] The catalyst composition as set forth in claim 1, wherein the
mondentate phosphine ligand excludes R R2, and R3 are each inde
pendently substituted by any one selected from the group consisting of
a nitro group (-N0 2), a fluorine group (-F), a chlorine group (-C1), a
bromine group (Br), and a silyl group (-SiR, wherein R is selected from
hydrogen, alkyl group or alkoxy group); or R i to R3are all hydrogen.
[Claim 13] A hydroformylation process of an olefin-based compound, the hydroformylation
process comprising reacting the olefin-based compound,
and a synthetsis gas of carbon monooxide and hydrogen in the presence
of the catalyst composition according to any one of claim 1 to claim 12
to produce aldehyde.
[Claim 14] The hydroformylation process as set forth in claim 13, wherein the
olefin-based compound is a compound represented by the following
Formula 3:

wherein R 4 and R5 are each independently any one selected from the
group consisting of hydrogen, an alkyl group having 1 to 20 carbon
atoms, a fluorine group (-F), a chlorine group (-C1), a bromine group
(-Br), a trifluoromethyl group (-CF3) and an aryl group having 0 to 5
substituent groups and 6 to 20 carbon atoms,
wherein the substituent group is nitro (-N0 2), fluorine (-F), chlorine
(-C1), bromine (-Br), a methyl group, an ethyl group, a propyl group or
a buthyl group.
[Claim 15] The hydroformylation process as set forth in claim 13, wherein the
olefin-based compound is one or more compounds selected from the
group consisting of ethane, propene, 1-butene, 1-pentene, 1-hexene,
1-octene and styrene.
[Claim 16] The hydroformylation process as set forth in claim 13, wherein the
PCT/KR2011/005173
molar ratio of carbon monooxide to hydrogen (CO:H2) of the synthesis
gas is in the range of 5:95 to 70:30.
The hydroformylation process as set forth in claim 13, wherein the hy
droformylation reaction is performed at a temperature in the range of
20 to 180°C.
The hydroformylation process as set forth in claim 13, wherein the hy
droformylation reaction is performed at a pressure in the range of 1 to
700 bar.
The hydroformylation process as set forth in claim 13, wherein the
catalyst composition is dissolved in one or more solvent selected from
the group consisting of propane aldehyde, butyl aldehyde, phentyl
aldehyde, valer aldehyde, acetone, methyl ethyl ketone, methyl isobutyl
ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol,
thesanol, benzene, toluene, xylene, ortho-dichlorobenzene, tetrahydrofurane,
dimethoxyethane, dioxane, methylene chloride, and heptane.