CA1264055A - Transition metal complex catalyzed reactions - Google Patents

Abstract

ABSTRACT

Transition metal-diorganophosphite complex catalyzed carbonylation processes, especially hydro-formylation, as well as transition metal-diorganophosphite ligand complex compositions and transition metal-diorganophosphite catalysts are disclosed.

Description

~1 2 G~ L9,~ S 5i TRANSITION METAL COMPLEX
CATALYZED REACTIONS

Brief Summary of the Invention Technical Field This invention relates to transition metal complex metalcatalyzed reactions using diorganophosphite ligands. More particularly this invention relates to transition metal-diorganophosphite complex catalyzed carbonylation processes, especially hydroformylation, as well as to transition metal-diorganophosphite ligand complexes.
This application is a division of copending Canadian Patent Application Serial No. 472,950 filed January 25, 1988. The parent application claims a certain novel diorganophosphite ligands. The present invention is diverted to a novel carbonylation process and catalyst useful therein using diorganophosphite ligands.

Background Art It is well known in the art the carbonylation reactions are enhanced by the use of a modified Group VIII metal catalysts e.g., catalysts comprising a Group VIII transition metal-phosphorus ligand complex.
Carbonylation processes directed to production of oxygenated products in the presence of a catalyst in general involve the reaction of an organic compound with carbon monoxide and preferably another reactant, especially hydrogen, and are well known in the art, 1~54-1 ,: .
:, ..

., :
: ~ : ,:
: :: .:, :. .: .
'. `'''"'.. ~ ~ `
, . , L~
. -2-e.g., see J. Falbe, "New Synthesis With Carbon Monoxide"
.Springer Verlag, New York 1980. Suoh processes may in clude the carbonylation of organic compounts ~uoh as olefins, acetylenes, a$cohols and activated chlorides with carbon monoxide alone or with carbon monox~de and either hYdrogen, alcohol, amine or water, as well as ring closure reactions of functional unsaturated compounds e.g. unsatura~ed amides with CO. One of the ~ajor types of known carbonylativn reactions is the hydroformylation of an olefinic compound with carbon monoxide and hydrogen to produce oxygenated products such as aldehydes using a Group VIII transition metal-phosphorus ligand complex wherein the phosphorus ligand is a triorganophosphine or triorganophosphite, followed by a subsequent aldolizat$on reactlon if desired.
It is further well known that the phosphorus ligand employed ln such catalyzed carbonylation processes may have a direet effect on the success of such a given process. Moreover~ while it is evident 20 that the selection of the particular phosphorus ligand ~ to ~e used in any 6uch ~ran~ition metal catalyzed carbonylation process depends in the main on the end resul~ desised, ~he best overall processing efficiency ~ay require a comprom;se selection among numerous factors involved, for it is known tha~ not all pho~phorus ligands will provide identical resul~cs with 1~54-1 , ~ , .

': ' ; :

2 ~ ~5 regard eo all factors under all conditions~ For example, in hydroformyla~ion ~uch factors as produet selecti~ cy~ catalyst reactivity and stability, and ligand stabil~ty are often of major concern i~ the selection of the d~sired phosphorus ligand ~o be em-ployed. Moreover, such a selec~ion may also depent on the olefini~ ~tarting material involved in the hy-droformylation process, since all olefins do not have the same degree of reactivity under all conditions.
For instance, internal olefins and sterically hindered alpha olefin~ e.g. isobutylene, are in genesal ~uch less reactive than ~terically unhindered alpha olefins.
Thu5, e.g. by tailoring.of the metal-phosphorus ligand complex catalyst, specific desired results for ~he product, the process and/or catalyst performance may be obtained. For example, U.S.P. 3,527,809 teaches how alpha olefin~ can be selec~ively hydroformylated with rhodium-triorganophos~hine or triorganophosphite ligand complexe~ to produce oxygenated products rich in normal aldehydes, while U.S. Patents 4,148,830 and 4,247,486 disclose both liquid and gas recycle operations directed to the same result using a rhodium-triphenylphosphlne ligand complex catalyst. U.S.P.
~,2B3,562 tisclose~ that ~ranched-chain alkylphenylphos-phine or branched-chain cycloalkylphenylpho~phine ligants can be employed in a rhodium catalyzed hydroformylatisn process of olefin to produce ~ldehydes in order to provide a more 6table eatalyst a~ainst ,. . . .

, ~L~ 55 intrinsic deactivation w~ile retarding the rate of ~he ;
hydroformylation reaction far less than n-alkyldiphenyl-phosphine ligands, relative ~o that obtained using ~riphenylphosphine. U.S~P. 4,400,5~8 disclo~es that bisphosph~ne monooxide ligands ean be employed to pro-vide rhod~um complex catalys~ of improved thermal stability useful for the hydroformylation production o~ aldehydes.
However, despite the obvious benefits attendent with the prior art references mentioned above, the search for a more effective phosphorus ligand which will provide a more active, more stable and/or ~ore all purpose type metal-phosphorus li~and complex catalyst is ~ constant one in the ar~ and heretofore, unlike the presen~ in-vention, has been centered for the most part on the useof triorganophosphine and triorganophosphite ligands.
Disclosure of Invention It has now been discovered that diorganophos-phite ligands may be employed as the phosphorus ligand ~n Group VIII.erans~tion metal complex catalyzed casbonylat~o~ proce~ses to provide numerous atvantages re~ati~e to heretofore co~monly proposed Group V$II
tran~ition metal-phosphorus ligand complex caealysts.
For instarlce, the dior~anophosphite ligand~
employable herein are u~eful in providing both improved cataly~i~ act~vity and at the same time impro~ed catalyst and ligand stabil~ty in carbonylation processes and par-..~....

.

ticularly hydroformylation, even wi~h less reactive ole-fins such as i~obu~ylene and i~ernal olef~ns. For ex ample, the hi~h eataly~ic ac~ivity provited by the di~ i organophosphi~e lignads allows one to carry out the hy-droformylation of olefins at l~wer temperatures than generally prefersed when conventional ligands such as ~riorganophosphines are cmploy~d. Likewise, in the hy-droformylation of olefins enhanced ligand and catalyst stability agalnst inherent side reactions, such as stability against reacting wit~ the aldehyte product, hydrolytic stability and stability against hydrogenolysis of the ligand may be achieved by the use of the dior~ano-phosphite ligands relative to the use of triorganophosphite ligands. Further, the use of the diorganophosphite ligands employable herein provide an excellent means for controlling product selectivity in hydroformylation reactions. For example, the diorganophosphites have been found to be very effective ligands when oxygenated products, e.~. aldehydes, having very low normal eo iso (branched) product ratios are desired. Moreover, the diorganophosphite ligands em-ployable herein have not only been found to provide ex-cellent cataly~t activity and both catalyst and ligand ~tability in the hydroformyla~ion of stericallv unhindered alpha olefi~s, as well as less reactive type olefins, uch as ste~lcally hindered alpha olefins e.g~ ~so-butylene, and internal olefins, but have also been found ., . _ .. .. . . _0, ~ _ .. _ __ _ _ _ . , ,, . . _ ,,_ .. . ~,, ,., _ .. . __ . . ... ~ .. ... . .. .

, .
.. ~ .
~. .

æ~ s to be especially useful in providing such catalyst activity and both catalyst and ligand stability when hydroformylating mixed alpha olefin and internal olefin starting materials.
The present invention is directed towards tha provisions of an improved carbonylation process and especially a hydroformylation process, wherein said process is carried out in the presence of a Group VIII
transition metal-diorganophosphite ligand complex catalyst, and an improved catalyst for utilization therein.
Accordingly, a generic aspect of this invention can be dascribed as a process for carbonylation comprising reacting an organic compound capable of being carbonylated with carbon monoxide in the presence of a Group VIII transition metal-phosphorus ligand complex catalyst wherein the phosphorus ligand of said complex catalyst is a diorganophosphite ligand having the general formula . -' ' :. .::
:.
. , ' ~ .

(Ar) o ( IH2)y (Q)n P - O - W
(IH2)y (Ar) O

wherein W represen~s an unsubstituted or substituted monovalent hydrocarbon radical; wherein each Ar group represents an identical or different substituted or un-substituted aryl radical, wherein each ~ individually has a value o 0 to l, wherein ~ is a divalent bridging group selected from the class consisting of -CRlR2-, -0-, -S-, -NR3-, -SiR4R5- and -CO-, wherein each Rl and R2 radical individually represents a radical selected from the group consisting of hydrogen, alkyl of 1 to 12 carbon atoms ~e.g.
methyl, propyl, isopropyl, butyl, isodecyl, dodecyl, etc.) phenyl, tolyl and anisyl, wherein each R3, R4, and R5 radical individually represents -H or -CH3, and wherein n has a value of 0 or 1. Preferably each Rl and R2 radical individually represents H or -CH3.
Another preferred generic aspect of this inven-tion comprises the Group VIII transition metal-diorganophos-phite ligand complexes and catalyQt precursor solutions thereof RS described more fully herein belo~.

Detailed Description As seen by the above formwla ~he diorganophosphitP
ligands employable herein represent an entireIy different 14054-l .. . .

`' .' ~ ~ ' L~ 5 class of compounds than triorganophosphitP ligands. The diorganophosphites employable herein contain only two organic radicals bonded to the phosphorus atom through oxygen 9 one of said organic radicals being bonded through two phenolic oxygen atoms (wherein each oxygen atom is bonded to a separ-ate aryl radical) and the other organic radical through a single phenolic or alcoholic oxygen atom. Triorganophos-phites contain three organic radicals each radical being bonded to the phosphorus atom through its own individual oxygen atom. Thus if hydrolyzed, the diorganophosphite ligands employable herein would yield both a diphenolic compound in which each phenolic oxygen atom is bonded to a separate aryl radical, and a mono-ol compound, while tri-organophosphite ligands would yield the equivalen~ of three mono-ol compounds.
Accordingly, he subject invention encompasses the carrying out of any known carbonylation process in which the catalyst thereof is replaced by a Group VIII transition metal diorganophosphite ligand catalyst as disclosed herein.
` 20 As noted above such carbonylation reactions may involve the reaction of organic compounds with carbon monoxide, or carbon monoxide and a third reactant e.g. hydrogen in the presence of a catalytic amount of a Group VIII transition metal-diorganophosphite ligand complex catalyst, said ligand having the general formula 14054-1 ~

. .

~Z~ 3~
_9_ (Ar) --O
\
~C~12)y (Q)n P - O
( tH2)y (Ar~ - O

wherein ~, Ar, Q~ ~ and n ~re the ~ame as defined above.
More preferably the sub~ect ~nvention in-volves the u e of ~uch a Group VIII transition metal-diorganophGsphite ligand complex catalyst snd free diorganophosphite ligand in ~he production of altehydes wherein an olefinic compound is reacted with carbon monoxide and hydrogen. The aldehydes produced corres-pond to ~he compounds ob~cained by the addition of a carbonyl group to an olefinically unsa~urated carbon atom ~n the startlng ma~erial with s~ultaneous saturation of the olefinic bond. Such preferred proces~es are known in industry under varying names ~uch as ehe oxo process or reaction, oxonat~on, the Roelen reaction and ~ose commonly hydroformylation. Accordingly, the processing techniques of this in~ent~on ~ay correspont to ~ny of the known processing techniques heretofore employed in conventional carbonylation and especially hydroformylatio reacions .
2S For ~nstance, the preferred hydroformyla-~' .
' ;:~

L~r~r~

tion process can be conducted in continuous~ semi- ;
continuous, or batch fashion and ~nvolve a liquid recycle and/or gas recycle operation as desired.
Likewise, the manner or order of addition of the reaction ingredient~, catalyst and ~olvent are also not critical ~nd may be accomplished in any conveD
tional fashion.
In general, the preferred hydroformylation reaction is preferably carried out ln a liquid re-aetion medium tha~ contains a $olvent for the catalyst,preferably one in which both the olefinically un-saturated oompound and ca~alyst are substantially soluble. In addition, as is ~he case with priDr ar~
hydroformylation processes that employ a rhodium-phosphorus complex catalyst and free phosphorus ligand,it is highly preferred that the hydroformylation pro-~ess of this invention be efected in the presence of free diorganophosphite ligand as well as in the presence of the complex catalyst. By "free ligand"
i~ meant diorganophosphite ligand tha~ is not com-plexed with he Group VIII transition metal atom in the active complex catslyst.
The ~ore preferred hydroformylation process of this invention is an improved ~elective hydrof~rmv-lation over tho~e known Group VIII transition metal-phosphorus ligand complex catalyzed hydroformyla~ion reacti~ns due ~o the ;~proved catalyst reactivity as well ~s simNl~aneous improved ca~alyst and ligand ~tability; and bthPr benefits, afforded by the use of the diorganDphosphite ligands employable herein, as 5 opposed to the trïorganophosphine and trio~ganophosp71ite ligands heretofore employed in the prior art.
The Group VIII transition metals which make up the ~etal-diorganophosphite complexes of this in- .
vention include those selected from the group consis~ing of ~hodium (~h), cobalt (Co), iridium ~Ir), ruthenium (Ru), i~on (Fe), nickel ~Ni), palladium (Pd), platinum ~Pt) ~nd osmium (Os), and ~ixtures there~f, with the preferred ~etals being ~h, Co, 1l and Ru, mo~e pre-ferably Rh ~nd Co, especially Rh. It is ~o be n~ted 15 that the successful practice of this invention does no~ depend and is not predicated on the exact structure of the ca~alytically active metal complex species ~
which may be present in their mvnDnucleas, dinuclear and or higher nuclearity forms. Indeed the exact active 20 struceure i5 not known. Although it is nDt intended herein to be bound t~ any theory or ~echanistic dis-course, it appears tha~ the active c~talytic species may in i~s simplest form consist essentially of the Group Vlll tr~nsition metal in complex combination 1~054-1 .. . . .. . --:

j Ll ~ rJ 1~

wich the carbos~ monoxide Emd a diorganophosphite ligand.
The term "complex" as used herein and in the claims rneans a coordina~cion compound f~rmed by ~I:he union of one or ~ore electronically rich molecules or atoms capable of independent existence with one or more electronically poor molecules or atoms, each of which ls also capable of independent existence. The diorganophosphïte ligands employable herein which possess the element phosphorus have one available or unshared pair of electrons and ~hus are capable of f~rming a coordina~e bond ~ith the Gr~up VIII ~ransition metal. As can be surmised from the above discussion, carbon monoxide (which is also propPrly classified as a ligand) i.c also present and complexed with the Group 15 VIII transition metalThe ultimate c~mposition of the active complex catalyst may also coneain an additional organic liga~d or anion satisfying the coordination sites or nuclear charge of the Group VIII transition metal as in the case of here~ofore conventional Group VIII transition metal-triorganophosphine or phosphite catalysts. Illustrarive additional organic ligands and anions include e.g. hydrogen (H ), halogen (Cl ~ Br , I ), alkyl , aryl , substituted aryl , CF3, C2F~, CN , R2PO and ~P(O)(OH) 0 (wherein e~ch R is alkyl or aryl), acetate , acetylace~o~ate , S042 , PF4, PF6, N02, N03 ~H30 , CH2-CHCH2; C6H5CN, CH3CN~ M0, NH3, pyridine, ~ns4-l .. .

-~3--(C2H5)3N, mono-olefins, diolefins and triolefi~s, tetrahydrofuran, and ~he like. It is of cour~e to be understood that the active complex species i~ preferably free o$ any additional organic l~and or anion that ~ight poison the catalyst and hAve an undue adverse effect on catalyst performance. For instance i~ is known that ln conventional rhodium catalyzed hydroformylation reactions that halogen anions and sulfur compounds c3n poison the .
cata~y~t. Accvrdingly it is preferred that in the rhodium catalyzed hydroformylation reactions of this invention ~hat ~he acti~e catalysts also be free of halo~en and ~ulfur directly bonded ~o the rhodium.
The number of avallable coordination sates on such Group VIII transition metals is well known in the art and may ra~ge in number from 4 to 6. By way of illustration i~ appears that ~he preferred active rhodium catalys~ species of this in~ention contains, in its simplest form, a~ amount of diorganophosphi~e l~gand and carbon monoxide equal to a total of four ~oles in complex combinatio~ with one mole of shodium. Thus the ~ctive species may comprise a complex catalyst mix-ture, in their monomeric, dimer~c or higher nuclearity forms~ which ~re characterized by one, two, and/or three di~rganophosphi~2 wolecules complexed per one molecule of rhodium. As noted ~bove carbon monoxide is also present 140~4 -1 .. -- , . ... .. . .. . . . .. _ .. .. . . . . . . .

~6~ 5 and complexed with the rhodium in the ac~cive ~pecies.
MoreovPr ~ as in ~che case of conventional rhodiuun-tsi organophosphine or phosphite ligand complexed catalyzed hydroformyla~lon reactions, the active catalyst ~pecies of which is generally considered to also cont~in hydrogen directly bonded eo ~he rhodium, ~t is likewise considered that the acti~e 8peCi2S of the preferred rhodium catalyst employed in this invention during hydroformylation may al~o be complexed with hydrogen in addition to the di-organophosphite and carbon monoxide ligands. Indeedit is believed that the active species of any Group VIII
transition metal catalyst of this invention may also contain hydrogen in addition to the diorganophosphite and carbon monoxide ligands during a hydroformylation process par~icularly in view of the hydrogen gas em-ployed in the process.
Moreover, regard~ess of whether one preforms the active complex catalyst prior to introductio~ i~to the carbonylation reaction zone or whether the active ~pecies i prepared in situ during the carbonylation reaction, it is pseferred that the carbonylationl and especially the hydroformylation reaction be effected in the presence of free diorganophosphite ligand. Thus by way of illustra~ion the ultimate composition of the preferred active rhodium complex species catalyst c~n ~e likened or attribu~a~le to t~e outcome of competing .
1405l, -1 .. ~ . . ....... , .. ~ . .. ..

' ;

seactions between carbon ~onoxide and ~he diorga~o-phosphite ligands for complexing or coord~rlation aites with the ~hodium element. These competing reactions can be di~turbed or influenced, within significant 5 limit~ 9 by increasing or decre sing the concentration of the diorganophosphite ligandO As a generalized statement, the component (carbon monoxide or diorgano-phosphite ligand) whlch can shift the equilibrium of the competing reaction ln its favor should enjoy the greater opportunities of occupying the coordination or complexing ~ites. For example, one may ~iew the function of free diorganophos~hite ligand as either maintaining the status quo of the various forms of active complex catalyst during the hydsofor~ylation~
or a~ a means for shifting the equilibrium of the competing reactions in it~ favor and therefore caus-ing addition 1 diorganophosphite ligands to enter into complex combination with rhodium with the probable evic-~ion of ~ ~imilar n~mber of carbon monoxide ligands from ~0 the complex cataly~t.
The diorganophosphite ligands employable in ~his i~vent~on as noted above are those having the general formula .

~4054-1 .

- .
;- ~,' ',, (Ar) ~ O
( I H2)y ~Q)n P - O - W
~CH~)y (Ar) ~ o wherein W represents an unsubstituted or substituted mono-valent hydrocarbon radical; wherein each Ar group represents an identical or different substituted or unsubstituted aryl radical, wherein each y individually has a value of 0 or 1, preferably 0, wherein ~ is a divalent bridging group selected from the class consisting of -CR~R2-, -0-, -S-, -NR3-, -Si4R5-and -C0-, wherein each Rl and R2 radical individually repre-sents a radical selected from the group consisting of hydro-gen, alkyl of 1 to 12 carbon atoms (e.g. methyl, propyl~ iso-propyl, butyl, isodecyl, dodecyl, etc.), phenyl, tolyl andanisyl ~ wherein each R3, R4, and R5 radical individually represent -H or -CH3, and wherein n has a value of 0 ~o 1.
Moreover, when n is 1, Q is preferably a -CRlR2- bridging group as defined above and more preferably methylene (-CH~-) or alkylitene (-CHR2-, wherein R2 is an alkyl radical of 1 to 12 carbon atoms as defined above, especially methyl).
Illustrative monovalent hydrocarbon radicals represented by W in the above diorganophosphite formula include ubstituted or unsubstituted monovalent hydro-carbon radicals contaaning from 1 to 30 carbon atomsselected from the gsoup consistang of substituted or un-substituted alkyl, aryl, alkaryl, aralkyl and alicyclic radicals. Preferably W represents a substîtuted or un-~' ' ', .

.

, ; . :,, , .. . ~; "
. -, -.17-substituted radical selected from the group consisting of alkyl and aryl radicals.
More specific illustrative monovalent hydro-carbon radicals represented by W include primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, t-butyl, t-butylethyl, t-butyl-propyl, n-hexyl, amyl, sec-amyl, t-amyl, iso-octyl, 2 ethyl-hexyl, decyl, octadecyl and the 1ike; aryl radicals, such as phenyl, naph~hyl~ anthracyl, and the like; aralkyl radicals, such as benzyl, phenylethyl, and the like; alkaryl radicals, such as tolyl, xylyl, and the like; and alicyclic radicals, such as cyclopentyl, cyclohexyl, cyclooctyl, cyclohexylethyl, and the like. Preferably the unsubstitu~ed alkyl radicals may contain from 1 to 18 carbon atoms, more preferably from 1 to 10 carbon atoms, while the unsubs~ituted aryl, aralkyl, alkaryl and alicyclic radicals preferably contian ~rom 6 to 18 carbon atoms.
Illustrative aryl radicals represented by the Ar groups in the above diorganophosphite formula include both substi~uted and unsubstituted aryl radicals. Such aryl radi~als may eontain from 6 ~o 18 carbon atoms such as phenylene (C6H4), naphthylene (CloH6~, anthracylene ~Cl4H8), and the like.
Illustrative substituent groups ~hat may be pre~ent on the monovalent hydrocarbon radicals represented 14~5~

'.: '..~. ..

', ' .;

L~ 3 ~r j ~ -by W as well 8~; the ~ryl group5 represented by Ar in th¢
3bo~e diorg~nophssphite formul~ include m~n~valent hydroc~-'bon r~icals such ~s ~e same ~cype ~f ~ubs~cituted o~ unsu~- .
stitu~ed alkyl, aryl p ~lkaryl, ~ralkyl ~nd alicyclic 5 r~dicals ~ent;orled ~bove for ~, 8~ well as ~ilyl radicals such as -Si(R6)3 and -Si(ûR6)3, ~mino radicals such as -N(R6);~, acyl r~dic~ uch as -C(O)R, carb~nyloxy radicals such as -C(O)OR6, oxycarbonyl ~adicals such as -OC(O)R6, amido sadicals ~l~ch as -C(O)N(R6);~ and -N(R6)C(O)R6, 10 sulfonyl radicals such as -S(0)2R6, sulfinyl radicals such as -S(O)R6, ether ti.e. oxy) radicals such as -oR6, thionyl ether radical~ such as -SR6, phosphsnyl sadicals such 85 -P(O) (R6~2, and halogen, nitso, cyan~, triflu~rc~-~ethyl and hydroxy radicals, and the like, wheTein each 15 R6 individually represents the ~ame or different, sub-stituted or unsu'bstituted monovalent hydrocarbon radical having the ~ame meaning as defined herein with the prc.viso that in amino ~ubstituents such as -N(R6)2, each R6 takesl together can ~lso represent a divalent b~idgin~ ~,roup ~hat 20 forms a heterocyclic radical wich the nitsogen atom and in amino ~nd amido l;ubseituents 6uch as -N(R6)2, -C~O)NtR6~, and -N(R6tC5O)R6each _R6 bonded to N can also be hydrogen, while in phosphc7nyl substituents ~uch as -P~o)~R6~ 2, one R~ radic~l can ~lso ~De hydrogen. Pseferably ehe monovalent 25 hydrocarbc)n ~bstieuen~ r~dicals, incl~ding~ tl ose repre-~ented by R6,, are unsubstituted alkyl os aryl r~dicals, 405~ -1 , _ , .. .. .. . . .

although if desired they in ~urn may be ~ubstituted with any substi~uen~ which doe~ not unduly adversely effect the proce~s of thi invention, such a~ e.g.
those hydrocarbon and non-hydrocarbon substituent radicals already herein outlined above.
Among the more speclfic unsubstituted mono-valent hydrocarbon ~ubstitu~e radicals, including those represented by R6, that ~ay be bonded to the monovalent hydrocarbon radicals represented by W and/or the Ar groups of the above diorganophosphite formula that may be mentioned are alkyl radicals including primary, secondary and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-bu~yl, t-butyl, t-butylethyl, t-butylpropyl, n-hexyl, amyl, sec-amyl, t-amyl7 i~o-octyl, decyl, and the like; aryl radicals ~uch as phenyl, naphthyl and the like; aralXyl radicals such as benzyl, phenylethyl, triphenylmethy7ethane, and the like; alkaryl radicals such a~ tolyl, xylyl, and the like; and alicyclic radicals such as cyclopentyl, cyclo-hexyl, l-methylcyclohexyl, cyclooctyl, cyclohexylethyl, and the like. More ~pecific $11ustrative non-hydrocarbQn sub tituent~ that may be present on ~he monovalent hydro-carbon r~dicals represented by W and/or the Ar group~ of the above d~organophosphite formula include e.g. halogen, preferably chlorine or flu~rine, -NO2, -CN, -CF3, -OH, -Si(CH3)3, ^Si(OCH3)3, -Si(C3H7~3, -C(O~CH3, -C(O)C2H

.. . . .. . . . . .

:' . ~ ,."' : .

~,. .

~ -20-OC(O~C H , -C(O)OC~ ,-N(CH3)2, -NH2, 3 2~5 2 ~ 3)2~ S(~)2C2HS~ -~CH3, -~C6H5, -C(O~6h5 -O~t-C4H9)~ ~SC2H5~ -~CH2c~2oc~3~ -~O~H2~ 2~2 3 CH CH ~ DCH -SCH3. _S(Q~H3~ 5C6 5' ~ 5 (O)(C~3)2- ~~(~)(C2~s)2J -P(O)~C3~7~ -P(~)~C4~ ) -P(O~(C6Hl3)2. -~(O)CH3(C6H5~. -P(~ )(C6~5)- -~HC(O)c~3 CH2Ch2 ,~CH2 CH2 ~Ch2C~2~ ~-CR2 -N O, -N ¦ , -N ~ CH2, CH2CH2 ~C -~H2 ~H2~ 2 ~-CH2 lû and the like. In æeneral, the substituen~c radicals present on the mono~alen~c hydrocarbon radieals represented by W and the Ar groups of the above diorganophosphite foImula may also contain from 1 to 15 carbon atoms and may be bonded to the monovalent hydsocarbon radicals 1~ represented by 1~ and/or such Ar groups in any suitable p~sition as may the brid~,ing group - (CH2)y~ (Q)n(CH2)y~
conneeting, the two A~ groups of the above fo~nula.
~oseover, each Ar radical and/o~ radical represented by. t~
may contain one or more such substituent ~,roups which 20 substituent groups may also be the same or different in any ~i~en diorganophosphite.
AmDn~, the more preferreà diDrganophosphite ligands ase those wherein the twt) A~ groups linked b~ the bridging ~,roup represented b~ - (CH2)y~ ~Q)n tC112)y 2~ abo~e dior~anophosphite fol~Nla cre bonded t~ro~gh tneir j L~- 0 .1; j 5 ortho positions in relation to the oxygen atoms that connect the Ar groups to the phosphorus atom. It is also preferred that any substituent radical, when present on such Ar groups, including any aryl radical represented by W be bonded in the para and/or ortho position of the aryl group in relation to the oxygen atom that bonds the given substituted aryl group to the phosphorus atom.
Accordingly, a preferred class of diorganophos-phite ligands employable ~erein are those wherein W is a substituted or unsubstituted alkyl radical. Preferred alkyl radicals include those unsubstituted alkyl radicals con-taining from 1 to 18 carbon atoms, more preferably rom 1 to 10 carbon atoms, such as those defined above, and such alkyl radicals when substituted with a non-hydrocarbon sub-stituent as discussed above e.g. silyl radicals such as-Si(R6~3, and -Si(OR6)2; acyl radicals such as -C(O)R6;
carbonyloxy radicals such as -C(O)OR6; oxycarbonyl radicals such as -OC(O)R6; amido radicals such as -C(O)N(R6)2 and -N(R6)C(O)R~; sulfonyl radicals such as -S(0)2RS; sulfinyl radicals 8UCh as -S(O)R6; ether (i.e. oxy) radicals such as -oR6, thionyl ether radicals such as -SRS and phosphonyl radicals such as -P(O)(R6)2, wherPin R6 is the same as d~-fined above, QS well as halogen, nitro, cyano, trifluoro-methyl and hydroxy radicals, and the like. An electro-negatively subs~ituted alkyl radical has the potential offorming a weak coordinate bond with the Group VIII transi-tion metal comple~, and such substituents may render ~he Group .. .. . ~ . ..

6~ ~ S

VIII transition metal-diorganophosphi~e complex catalyst, and .
in particular ~he rh~dium c~talys~s, in hydroformylation, more catalytically ~able. The ~ost preferred electro-ne~a~ively subs~ituted ~lkyl r~dical~ ~re those of ehe formula ~C(R7)2jpp(o)(R6)2 wherein each R6 is the ~ame ~s defined abo~e, wherein each R7 is individually a radical which may be the ~ame or differen~ and which is selected from th group cons~sting of hydrogen and an slkyl ratical containing from 1 ~o 4 carbon atoms, and ~ has a value of 1 to 10, e~pecially -(CH2)-pP(O)(R6)2 radicals wherein p is 1 to 3 snd each R6 is individually the ~ame or different and is a radical ~elected from the group consisting of alkyl radicals csntaining from 1 to 4 carbon atoms, phenyl~
and cyclohexyl radicals, with the proviso that one R6 radical can al~o be hydrog~n.
Such types of diorganophosphite ligands em-ployable ~n this inYenticn and/or ~ethods for their preparatisn ~re well kn~wn. For instance a conventional ~ethst for prepari~g ~uch li~ands comprises re~cting a - corresponting urganic diphenolic compound (e.g.
2,2'-dihydroxybiphenyl) w~th phosphorus trichloride ~o form an organic phosphorochloridi~ce interulediate (e.g. 1,1'-~iphenyl-2,2'diyl~phssphorochloridi~e) ~hich in turn ~s reaceed ~th a co~respondin~ ~ono-hydroxy compound (e.g. 2,6-di-t-butgl~4-methylphenol) ~n ehe presence of i2 6'10~.

an HCl acceptor, e.g. an amine, to produce the desired di-organophosphite ligand ~e.g. l,lg-biphenyl 2,2'-diyl-(296-di t-butyl-4-methylphenyl)phosphite]. Optionally, these ligands may also be prepared in the reverse order, for instance, from a preformed organic phosphorodichloridite ~e.~. 2,6-dl-t-butyl-4-methylphenyl phosphorodichloridi~e) and a corres-ponding diphenolic compound (e.g. 2,2'-di-hydroxybiphenyl) in the presence of an HCl acceptor, e.g. an amine, to pro-duce the deslred diorganophosphite ligand, ~e.g. 1,1'-biphenyl-2,2'-diyl-(2,6-di-t-butyl-4-methylphenyl)phosphite~.
Accordingly, a pr~ferred class of diorganophos-phit~ ligands employable in ~his invention is that of ~he formula ~ \
(Q~ B ~ W
z3_~ D
.~2 wherein Q is -CRlR2 wherein each Rl and R2 radical intivid-ually represents a radical selected from the group consisting of hydrogen, alkyl of 1 to l~ carbon atGms ~e.g. methyl, propyl, isopropyl, butyl, isodecyl, dodecyl, etc.) phenyl, tolyland anisyl, and _ has a value of 0 to 1; w~esein each ~4054~1 j -L~ j 5 - . . _ yl~ y2~ z2, and Z 3 group individually represen~s a radicalselected from the group consisting of hydrogen, an alkyl radical having from 1 to 8 carbon atoms, substituted or un-substituted aryl, alkaryl 9 aralkyl and alicyclic radicals as defined and exemplified herein above ~e.g. phenyl, benzyl, cyclohexyl, l-methylcyclohe~yl, and the like), cyano, halogen, nitro. trifluoromethyl, hydroxy, as well as the car~onyloxy, amino, acyl, phosphonyl, oxycarbonyl, amido, sulfinyl, sul-fonyl, silyl, ether, and thionyl radicals as defined and ex-emplified herein above, with the proviso that both yl and y2are radicals ha~ing a steric hindrance of isopropyl, or more preferably t-butyl, or greater, and wherein W represents an alkyl radical having from 1 to 18 carbon atoms, preferably from 1 to 10 carbon atoms. Preferably Q represents a methy-lene (-CH2-) bridging group or an alkylidene (-CHR2-) bridging group wherein R2 is an alkyl radical of 1 to 12 carbon atoms as defined above, especially methyl (-CHCH3-). The preferred ligands are those of Formula (II) above, wherein both yl and Y are branched chain alkyl radicals having three to five carbon atoms, especially t butyl, z2 and 23 are hydrogen or an alkyl radical, especially ~-butyl.
Another preferred class of diorganophosphite ligands employable herein are those wherein W is a ~ubstituted or unsubstitu~ed aryl radical such as de-~4054-1 ' : . .`

fined above, especially ~ubstituted or unsubstituted phenyl radical~O
Further, lt has been ob~erved that in rhodium catalyzed hydroformylation reactio~s, when 5 the diorganvphosphite ligand employed is one in w~ich W represent~ an aryl radical, ehat ~ubstitution (ex-cluding any substitution causet by the bridg-in~ group -(CH2)y~(Q)n~(CH2)y-) of the ortho positi~n of the aryl group (W) and the two Ar groups of Formula(l), ~.e.
10 those posltions relatiYe ~co the oxygen ~tom that bonds each aryl group to the phosphorus atom of she dior~ano-pho~phite ligands may influence the catalytic activity and/or 6tability of the ligand. Apparently steric hindrance around the phosphorus atom of the diorgano-pho~hite l~gand caused by 6ubstitution in such orthopositions of all the aryl groups has an influence on ligsnd s~abili~y ~nd/or catalytic activity, particularly wlth regart to hydroformylations carr~ed out in ~he presence of exce~s free diorganopho~phite ligand. For ~ lnfitance, diorganophosphite ligands $n which all the ~ryl group~ are un~u'bst~cuted aryl rsd~cal~ ('coo little 6'ceric h~nd~ance) ~nd t~orgas10phosphite ligands ~n w~l~ch fous ~3f ~he ~ot~l ~ccu~Nlative number of ~uch ortho positions .054-1 . .. . . . . . .. . . . . . .. . . ....... . .

~- :

-2~-;

~n ~che aryl group~ are ~ubstitu~ed with a radical having a ~teric hindrarlce of i50propyl or greater, (too aDu~h ~teric hindrance)~ are ~ot considered desirable because of the poor ligand ~eabillty and/~r ca~calytic activity S tllat may be obtained ~ ch their use pasticularly in the presence of excess free ligand. 0~ the other hand improved ligand stability gmd/or catalycic acti~Jity in rhsdium catalyzed hydsoformylation even in the presence of excess free liga~d ~ay be obtainet when at least two of the total lû accumulative number of sueh ortho positions on all ~che aryl g~oups of the diorganophosp~i~ce ligand are substituted with a substi~c~aent radical having a steric hindrance of .
isopropyl, os ~ore preferably t-bueyl, or greater, providPd that no more than three and preferably no~ ~ore than two 15 of the total ~ccumulatlve number o ~uch ortho positions on all the ~ryl groups are subs~ituted with a radical having a ~teric hindrance of isopropyl or greater at the same tlme. In addi~ion, diorganophosphite ligands in which two 6ueh available ortho positions of the tw~ Ar ~roups of generic F~rmNla ~I) above sre substituted with a radical ha~ing ~ steric hindrance of isopropyl, ~r more preferably t-butyl, os greater, appeas to possess better ligand 6tab~ y ~s a general rule than if the diorganop~sphice ligands were ~ ~ubstitu~ed in ~che ~dO
25 such ~vail~ble ~rtho po~lt~on~ of the aryl group represented by W. P50revver9 in the pseferret tiorganophosphite ligands~.
..
14~5~-1 . -, : ' :
': ~
.

-~x~ f~s ~27-the ca~alytic act~vity and/or ~tability may be further enhanoed if one of sa~d ortho po~i~ions of the aryl ratical represented by W is subs~ituted with an electro-negative substituent, e.g. cyano, having the capability of orming a weak coordinate bond with the Group VIII
transition me~al.
Thus another preferred class of diorganophosphite ligands employable in this invention are those of the formulas z2 ~ _ 0 \ . X

~ zl (III~

z3_ ~ ~ x2 Y

and ; ~ 1 (IV) _ 0 2 140~4-1 .. .. . . . . . . .

wherein Q is -CRlR2 wherein each Rl and R2 radical indi-vidually represents a radica~ selected from the group con-sisting of hydrogen, alkyl of 1 to 12 carbon atoms (e.g.
methyl, propyl, isopropyl, butyl, isodecyl, dodecyl, etc.), phenyl, tolyl and anisyl, and n has a value of 0 to 1;
wherein each Xl, x2, yl~ y2~ zl, z2, and Z3 group in-dividually represents a radical selec~ed from the group consisting of hydrogen, an alkyl radical having from 1 to 8 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl and alicyclic radicals as defined and exemplified above (e.g. phenyl, benzyl, cyclohexyl, l-methylcyclohexyl, and the like), cyano, halogen, nitro, trifluoromethyl, hydroxy, as well as, amino, acyl, carbonyloxy, oxycarbonyl, amido, sulfonyl, sulfinyl, silyl, ether, phosphonyl, and thionyl radicals, as defined and exemplified hereinabove, with the proviso that at least both of the Xl and x2 groups or at least both of the yl and y2 groups on a given diorgano-phosphite of Formulas (III) and (IV) above are radicals having a steric hindrance of isopropyl, or more preferably t-butyl, or greater, and with the proviso that in FormNla ~III) above no more than three and preferably no more than two of the Xl, x2, yl~ or y2 groups is a radical having a steric hindrance of isopropyl or greater at the same time.
Preerably Q represents a methylene (-CH2-) bridging group or an alkylidene (-CHR2-) bridging group wherein R2 is an alkyl radical of 1 to 12 carbon atoms as defined above, especially methyl (-CHCH3-). Preferably ~he Xl, x2, yl~ and : , .

., . ~ .

s~

y2 groups are branch~d chain alkyl radicals having 3 to 5 carbon atoms, ~specially t-butyl. The more preferred ligands in Formula III are those wherein either both yl and y2 groups are t-butyl or both X1 and x2 groups ar t-buytl.
Yet another preferred class of d.iorganophosphite ligands, which are considered to ~e novel compositions of matter per se and are claimed as such in the patent application Serial No. 472,950, employable in this invention are those o~ the formula z2 ~ O

(CH2)y 20 (~)n p - O - W (V) (ICH2)~

z3 ~ ~ O /

wherein z2 and Z3 each individually represent a radical selected from the group consisting of hydroxy (-OH) and an ether (i.e. oxy) radical surh as _oR6 wherei~ R6 is the same as defined above and wherein W, yl~ y2~ ~, n and are the same as defined above. Preferably R6 ~s an alkyl radlcal of l to 18 carbon atoms, re preferably from 1 to lO carbon a~oms, e.g. primary, 14054-~

' '~

secondary, and ter~iary alkyl radicals, such as methyl, ethyl, n-prcpyl, isopropyl, butyl, sec-butyl, t-butyl, t butylethyl, t-butylpropyl, n-hexyl, amyl, sec-amyl, t-amyl, iso~octyl, 2-e~hylhexyl, decyl, dodeeyl, octadecyl, and the like. Further each y group preferably has a value of zero, and when n is 1, Q is preferably a -CRlR2 bridging group as defined above, and e~pecially -CH2-and -CHCH3-. Most preferably n has a value of zero.
Preferred unsubstituted and substituted monovalent hydro-carbon radicals represented by W include those as defined and exemplified above, for exemple alkyl radicals having from l to 18 carbon atoms, preferably from 1 to 10 carbon atoms, such as primary, secondary and tertiary alkyl radicals e.g. methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, t-butyl, t-butylethyl, t-butylpropyl, n-hexyl, amyl, sec-amyl, t-amyl, iso-octyl, 2-ethylhexyl, deeyl, octadecyl, and the like, as well as, aryl radicals, such as alpha-naphthyl, beta-naphthyl, and aryl radicals of the formula xl ~ 2 wherein Xl and x2 are the same as defined above, and Z4 represents a radical selected from the group consisting of hydrogen, an alkyl radical having from 1 to 18,pref~rably from 1 to 12 carbon atoms, e.g. primary, secondary and 14054-l . .

" - ' .
~

tertiary alkyl radical6 such as methyl, ethyl, n-psopyl, iso-propyl, butyl, sec-butyl, ~-butyl, t-butyle~yl, t-butyl-propyl, n-hexyl, ~myl D sec-amyl, t-amyl, iso-oc~yl, 2-ethylhexyl, nonyl r decyl, dodecyl, octadecyl, and the like, as well as, substituted and unsubstituted aryl, alkaryl, aralkyl and alicyclic radicals (e.gO phenyl, benzyl, cyclo-hexyl, l-methylcyclohexyl, and the like), and cyano, halogen, nitro,trifluoromethyl, hydroxy, amino, acyl, carbonyloxy, oxycarbonyl, amido, sulfonyl, sulfinyl, silyl, ether, phosphonyl, and thionyl radicals as defined and exemplified above, with the proviso that at least both of the Xl an~ x2 groups or at least both of the yl and y2 groups on a given diorganophosphite ligand of Formula (V) above are radicals having a steric hinderance of isopropyl, or more preferably t-butyl, or greater, and with the proviso that in Formula (V) above, no more than ehree and preferably no more than ~wo of the Xl, x2, yl or y2 groups is a radical having a steric hinderance of isopropyl or greater st the same time.
Among the even ~ore preferred diorganophosphite ligands of Formula (V) above are those of the fGrmula I

z2 ~ )_ O
I ~ D (~I) z3 ~2 . .. ... . , . . . . ~

. 1 ~

: ' .. ~

~3~- .

wherein z2 and Z3 each individually represent a radical ~elected from the group eonsi~ting of hydroxy and & _oR6 radical wherein R~ is an alkyl radical having fro~ 1 to 18 csrbon a~oms0 more prefer~bly from 1 to 10 carbon atom~, 5 ss defined above; wherein S~. represent~ a -CRlR2- bridging group as de:Eined above and n has a value of O to 17 preferably O; wherein yl and 2 each individually repre-~ent a radical selec~ed from the group consis~ing of branched chain alkyl radicals having from 3 to 12 carbon atoms, phenyl, benzyl, cyclohexyl and l-methylcyclohexyl, preferably a branchet chajn alkyl radical of 3 to 5 carbon atoms; and wherein W repsesents a radical selected from the group eon-~isting of an alkyl radical of 1 to 18 carbon atoms~ pre-ferably from 1 to 10 carbon atoms, alpha-naphthyl, beta-naphthyl, and an aryl radical of the formula ~ Z4 wherein Z4 is ~he 6ame as defined above.
- The most preferred tiorganophosphite li~ands represen~et by Formula (VI) above are those wherein z2 and ~ Z3 are hydroxy or methoxy radicals, especially methoxy, wherein yl and y2 bo~h represen~ a branched chain alkyl radical of 3 to 5 carbon atoms; especially t-butyl;

..

.. . . . . .. . . .. . . .

, ... .

.~f~6'3 -'33-wherein W is selected from t~he group consisting of an alkyl radical of 1 to 10 carbon atoms and an aryl radical having the formula ~24 wherein ~4 is ~elected from the group consisting of hydrogen and a methoxy radical~especially hydrogen; and wherein Q is a -CRlR~- bridging group as defined abo~e;
n having a value of ~ to 1. More preferably W is a methyl radical .
Illustrative examples of such diorganophosphite 10 ligands include e . g .

u HO ~ O.

HO ~ ID

t-8u - .

', ~2~ 5

-3 t ~Bu ,~
H0 <~ ~

~P - O--ClH3 H0~ 0/

~ -~u t-~BU

3 --~O~-- \
~ / 3 ,~

~-~u t-Bu ~H30 --~O>~ E~
~ ~ _0~ (CH2)17CH3 CB30 ~_ D

1t,~Bu û5 ~

:............... .
;

~ ~ .
, r-j c-u ~ ' .
3 --~,O~
~ \

CH3 --(O--) y t-BIl t-Bu \
CH3CH P-- o o_ CH3 t-Bu ~1 . .
et~3 ~ O\ t-Bu ~ ~OCH3 CH3 ~0~--145~5~1-1 ~. .. . . .. . . . .
. , ~.
.
.

', ,.:
i s~u g~3~

t-Bu C1~30 ~ O
\p- o ~0~3 CH30 --~ 0 g _g~

t -~u C~3 ~O~--\~-- I) ~C9H19 ~3 -<O~--~-~u ~eos4-l .
:

: ~ .

~64io55 . ~37-t - amyl CH30--~ ID
J9 _ t~ H3 3(~<0~--~ .
t - amyl t-Bu C~j,~O~
~ p - o--CH3 C2H5~
.~ .
t-Bu t-E~u CH30_~ 0 .' ~ / ~ .
~H30~0 t-Bu a40~

., ... , .. ~ .. . . _ .. . .... . . . . .

-. :' :. '.: . -L~ ~D5 ~3 ~H2-Ph {~ ~ t-Bu 0}oCH3 CH30 ~

CH2-Ph Ph CH3~ \ c-~u ~H3 o Ph ~ 0~ t-Bu ~_ o ~CHCH2CH3 6~/ t-Bu ~1405~

' ~

~` ` ,. , , "

6L~5 \~_o_~-t~l3 u lt-Bu I

t-~lu ~0 ~-3u ~ 0/

~-~u t-Bu p ~ 0 ~ \33 ~ / t~

` 1l.~54-1 .. . . . ..
.
..
, :~

L~ 3~5 _ ~- ;

lE ~Bu \ p_o_~_C~3 ~_ o ~ Bu Bu t-Bu t ~u ~ o\ --~ CH3 t ^BU _ f ~ ~.-Bu t -P,u O

~\P - ~
~_ 0/ t..~U

î40s4 -1 .. . . . . . . . .. . . . .

~4~3~iiS

~h ~ ~ 0~ , ~h t-Bu ~ o_~
~ o~ It_~u ~H3 t-~Bu CH3 ~ O--~ c~3 CH3 ~ ~-Bu ~3 r,-Bu I

\ ~ !~CH3 ~-~U ~0~o t~u 14 û5~

. .

_ 42 ~-~Bu --~0~ ~
~ ~) ~-Bu--~ ~ e-~u u ~ , t~Bu t -BU--~0~ -t-P,u ~0 t-~u ~-~u \F-- O --~r CN

~u 1~54 -1 .. .. .. .. ... . . --~z~ s~ i t ~ Y~u ~-U~ O ~

~ -~u t~Bu t-Bu ~--O\
~ P~ ~ ~
t-Bu --~ O

t -~u t-Bu CH3 --~O~--O.
~ \ ~
C~2 P ~

3 --<~0 ~--t~Bu .
';
.

~,2 6LIl~ O~i 5 t~ie~

~:H ~--O
T2 ~ ~ ~ ~

t~Bu t-Bu ~ \ o ~CH

C~3--~ c~3 t~u t -~u ~U
- CH ~--O <~ CH3 ~H3 ~ t-~u ~1 .
~g~
~DS4 -1 ' ... . . . .. ~ ... . . . . . . . . .
" ~ , ~, '~' " " :

-4~-U

~ t-Bu eH3 ~ 0 ,~2 t-Bu \P-- O ~ C~33 ~ t-Bu 1405~ -1 , `

~4S-t~3u r~~

~ \

t -Bu t~
~ .
\
CH2 P-- o-CH2C(cH3)2cH3 ~3 ~ O~

t-~u - t -~u .. I

tH3 ~ p_ O _~C~>

~3~

e~u 1~05~ -1 .
- .. ' ~ `

. . .
.; .

~_~ f,,jL~" fJJ~5 ,, ~,7_ t -Bu -B~ --<0~
p - O--CH2cH2ot CH3 t-~U ~}/

t -~u t -Bu ~c-Bu ~)_ ~ w ~ C~2~ t)CH3 ~ /
~-~u ~0~

t-Bu t -~u ~-~U--~ ~
--CH;~cH~N (CH3) 2 t-Bu ~C

~-~u l4as~ -1 ... . .. .. . . . . . . .

. ., ;` :: :
- . .~

~L26'~55;
-4.8-,~
~-~u ~
~ - D-- t ~2cH2se}~3 t-Bu ~

~ -~u t~Bu 'C BU --~O>-- \ "
~ p _ o - CH:2CH2SCH3 ~-~Bu ~ 0/

'6 ~U

~ ~u . ~
~-Bu --<O)-- ~ 3 ~ p ~ H2C~25C~3 t-Bu ~ID

t-Bu 1~0~

: '`' ' '': ~ ' ~49-~-~U--~0~- ~
~ ~ O--CH2CH2P (C~3) 2 t -Bu ~ ~

~ -~u e-8u t-Bu ~ ID~ o p ~ O-- C~12CH;2P(CH3) (Ph) /~ /
~U ~0~

t-Bu t-Bu .
t-gu~
~ ~ --~:H2CH2P(H) lPh) t-~U--<O>--Ct t-Bu 1~10~

.... . . .. . ..

~ - ~
- -

5~ .

~ ~U

~H3 ` ~--~ Q

CH,~ CH2~ H2~3HC~3 ~0 t-Bu 1:~myl t-~ylrO~\
OC~3 t-~myl~ o/

.

t~
$~ r - o ~ CH3 g.- Amyl .
l~D54 1 - ~ -~. ~
.`
: ' ~ : . ' : ' " ~` .
:,; . `:
-.~ ,. :
.

o5~_ ~L2~ 55 S~

U ~

3F' - --CH2CH2CH2~H2CH3 t-~u U

t -Bu ~' ~\' ~--I P - O-- C112--Ph t-BU --~O~
'`-1 , t-Bu u t-~u~
~ 11 O-- CH2cH2p ~Ph~ 2 /
. t-~3u--<O~

t ~Bu 1405~1 1 .
.. . . . .. . .. ~ _ .. _ _ . . _ . _ . . .. . . . . . . . . . . . .. . . . . .

'~ ' "

~ .
`:

3s~

~-~U

t-~u~
~ _ O-- CH2C~25~ 3~ 3 U--~--0/

t-Bu t Bu I

t-BU J~--O~--\

~ P - ~--CH2CH25i (OCH3) 3 t-Elu--(O--)--O

t -~Su -t-Bal '' ~

~-8~
S ~32~2CH3 1; -BU ---CO~

t -~SU

1~054 o l ..

:: :

.~ . . . :, ~.2 ;
I~ the above diorganopho~phite formulas t-Bu represent a terti~ry bu~cyl radical, Ph represents ~
phenyl (-C6~53 radl~al ~nd (-C~3Hlgj represes~t~ branched mixed nonyl ~ad~ O The most preferred diorganopho~-ph~ te ligands employable in this invention are tho~e of the f ormula6 t~u ~ ~

~lD ~B~

1 ,1 '-bi~eny~2~,2'-diyl-(2,6-d~-t-~utyl-4-saethylph~nyl) ~ ph~

t~lu .

t_30_~0\ ~ .

t-~u ~ 1~

~0 phenyl ~3~3' ~5,5'-~cet~a-~ utyl~171'-b~p~ngl~
2 ~ 2 ' -d~yl ~ ph~phite l~D5~ -1 .:

~L2~ ~5 -_ ~5 4 -t-Bu g~3 b~naph~hylene-2, 2'-d~yl-t2,6 di-t-butyl-4 -me~hylp~enyl )phD~ph$ee u i ' ' eH3--<O)--C~
~_ ~ ~ o--~H3 CH30~ >_ 0/

~-~u methyl 13, 3 ' - dl- t -butyl - 5, 5 ' ~ t imethoxy- 1 ,1 i -bipherlyl-2, 2 ' - diyl 1 phosphite 14û51~
.

~6 -5~-~ n~t@d ~ove ehe ~ivr~,~noph~sphi~e l~gand~;defined ~bove ~re employe~ ~n th~ ~nvent~n a~ lboth ~the ~phvsph~rus l~ga~d ~f the Grou~ VIII tr~n~ie~on ~et~l complex ca~caly~t p as ~ell ~116, ~le ~Free pho~ph~rus ~ n~
5 eh~t ~ pr~ferD'bly prc~eslt ~n the react~on ~n2d~ f the proces~ o~ thi~ ~nvent~ n ~dd~t~ , lt ~8 tC~ ~e ~ er-~to~ ~hat whil~ the ph~6phoru~ l~gand ~f the Group YIII
~run~ n me~ d~rg~nopho6ph~te cDmpl~x ca~ealy~ ~nd exce~s free phD~phosu~ l~Lgand preferably pre~ent ~
10 ~,~ven prcces~ of ~shi~ $nven~on are normally ~ch~ ~aTne type of ~iorg,anopho~phite l~g~nd, difgerent types of di~
org~n~pho~ph~te l~gands, a~ well ~11;9 ~xeusg~ of t~o or mose differen~ diorgan~phoaph~te l~ean~s D~ay be emplo~re~
f~r ~ch purpo~e ~ ~ny ~,lven proce~ f ~e~lrea.
A~ e~se of pr~or ~rt Cr~up YIII tr~n~i-t~on me~al-phc~6phs~ ; cc~mples~ cst~yst~, ~che Gr~up VIII
tran6it~0n ~etall-d~osganPph~phi~e complex cataly~t~ of ~h~
~nvent~Gn ~nay be formed 'by ~et~ct~ knawn ~n ehe ~rt. For ~n~eanc~, p~fom~et ~roup VIII eran~ n ~eé~l hydr~o-20 e~shonyl (d~organopho~ph~ee) ca~caly~gs ~y po6s~bly ge~reparea ~nd ~ntrt~dused ~tc~ ~h~ r~tlc~n ~ediu~ of ~a ~ydro-fonnyla~c~g>n proce~ 02~e prefer~ly, the Group VIII tran~1-14~

:. ' _5 6-~c~n me~ d~o~g,ar~t~phosphl~e eo~plex c~t~lyst~i ~f ~i~ ~a~
veno~ csn ~e der~7ea fro~ a me~l cat~ly~t pre~r~r wh~ch ~ay be fntr~duced ~nl:o the geaction ~edium for in ~i~cu fo~at~on of the ~ct~v~ c~talys~. F4r exacnpl~" rhod~
5 c~taly~e precur~or~ ~uch ~s rht~diu~ dicas~nyl ~cetylsce~conate"
Rh203'Rh4(C~ h6~)16~ ~hSN3)3 and the l~ke ~ay be lntroduced ineo the react~Qn ~ed~ium ~long wi~h the d~-organoph~ph~ee ligand for the ~n 81tu formatiorl of the active cst~lyst. ~n ~ preferred embod~ent rhodium dic~s-10 ~onyl ~cetylacetor1a~e ~B employed as ~ r~odium psecur~orand resc~cea ~n ~he pre~enc~ of ~ ~olv~n~ with the diorgano-pho~ph~te ~o onn ~ c~ lytic rhodium c~sbonyl diorg~ans-~ho6phlte ~cetyl~ceton~te precus~or which $s ~ntroduced ~to the reactDr ~lon~ with exc2ss free diorganopho~ph~te 15 ligand for ehe ~n eitu form~t~on o~ the ~ct~e ca~c~ly~
In ~y ~vent~ ~t ~ ~uffic~ent ~or the puspo~e of ~hi~
vent~ ~o landers~cand thf~ c~r'bon monoxide, hydrogen ~TId aiorganopho~ph~ce ~are ~ gand~ that ~re capable of being co~apl~xe~ ~th ~he Group VI~I ~r~nslt~osl ~et~l~ e.g. ~hodiu~
20 snd tha~c ~n act~e t~roup VII~ tran6it~cr~ ~et~l-diorgano-pho~ph~ee catalyl~t ~13 pseces~ the sc~ction ~ediu~ under ~hc c~rd~ion~ of the c~r'Donyl~ltl~n hnd ~Dore pref~r~bly hydrofo~ tlon ~roce~.

14~5~-1 ... ... , ... .. . .. ., . _. .... _ . _ _ ., .. .. _ . _ . ._ . . ..... . . .. . .. . . . . . . . . . . . ...

~2t ~L~

Aceordirlgly~ the t:soup YII~ ~ran6~0n ~et~
dior~anopho~ph~Le ec>mple~c c~tA~yse~ of thi~ $nven~io~a laay be def~Lned a~ cost~ c~ng ee~en~ciall~ e~f a t;roup YIII es~n~
t~on ~et81 complcxed ~h carbon monox~de ~snd a diorgano~
5 phosph~te ligand. Of l~ Uf$~ t ~6 ts: be under~ood t~at the catalyRt ~ermi~ology "e~ns~t~ng e~6en~ally of" ~ not Deant ~ exclude, but ra~h~r ~nclude hydrogen complexed v~th the ~etal p~r~icularly ~n the ease of rh~d~u~
catalyzed hydroforDyl~t~on~ ~n ~dit~on to carbon moslox~te 10 ~nd the diorganophs~ph~te l~gand. Moreover, ~ noted a~ov~
~uch t~smlr~Glsgy ~le all~s not ~eant to exclude the pos~ ty of other organ~c ligand~ ~nd/or anion~ ~chat ~igh~ o ~e complexed ~'ch the IDe~cal. Ho~ever, ~uch c~taly~t ~enn-~nology preferably 18 lDea~ t~ ex~lude o~cher ~terisl~ ~
15 ~mount~ ~ch ~mduly a~rer~ely po~son or unduly dea~t~vate ~he cat~l~6t ~sld thu~ rhod~um stoc~c de~irably 1~ fre~ o~
cont~inan~s ~ueh ~ rh~dilam'b~und h~l~gen ~.g. chl~r~
~nd the l~ke. ~ n~ted, ~ hy~so~,en ~nd/~r c~rbonyl llg~n~ of ~ llct~e ~o~ d~organ~pho;~ph~te cos~lex 20 c~e~ly~t ~r ~e pre~en~ esult of b~ng l~ n~
bouna ~ ~ pr~cur~r c~t~ly~t ~ d/~r 8~ ~ re~uPc of ln_ u f4~t~ O ~ue ~ tl~e ~y~s~ge~ ~n~ c~s~n lDonox~de ~z e~ploy~ hy~rs~f~ylat~ roce~.

, -: ' .. `'~ ~:~ ` ..

~L~6'~0~ .
-S~

M~re~ver, like pri~r art Group Vlll transition ~et~l p~ph~ ligand complex c~talys~6 ~t ~6 clear thdt the amount ~f complex e~talyst pre~ent ~n the react~on medium l~f ~ given proce~ ~f th~ ~nven~ion need ~nly lt~e ~t minimum a~un~ nece~sary ~ ps~vide the ~,iven Group Vlll transition metal c~ncen~ratiorl de~ired t~ ~e em-ployed and wl~ich will fu~nish the bas~s f~r at~îeast tha~
c~t~lytic ~mount of Group Vlll transition metal neces~Ary ~o cataly~e ehe partic~ r carbonylati~n process desired.
More~ver, one.of the lben~fits of thi~ inventic~n i~ the generally improved catalytic ~ct~vity ob~inable ~y the use ~f the disrganoph~sphite ligands empl~yable hereiFI.
5~ch ~mpsoved cat~lytic ~c~c~vity can translate jnto ~
considerable processing ~sset, pareicul~sly w~en rare and expensivg Grc~up VIII ~ransitiosl ~e~cal~ ~uch as rhodiu~
are ~o be employed, ~nce lower react~on ternperatures and/
or l~wer amoun~c~ of catalytic~lly ~ctive ~etal may ~e e1n-ployed tc~ ~ehieve ~ desired rat~ of prc~ductivity th~n may ~e pcssi~le w~en le~s ~acti~e c~ealys~Ls are employed. Isl 2~ ~,eneral, Group VIII tran~tio~ metal concentr~tiDsls in ~e sange s3f from ~bc~ut 10 ppm tc~ ~bcut lOûO pp~n, c~lcul~eed ~
free mee~ hould ~e liuff~cient for ~st carbonyl~tion pro-ee~se~. Mo~euver n the rhodium c~t~lyzed hydr~formylation proces~e~ ~f th~ ~nYentic~ll, iit ~ s ~,ener311y preferr~d to e~-ploy rom ,~ US 10 ~o 500 ppm of rht~diu~n ~nd ms~re pre~er~bl~
r~sn 25 to 350 ppm o~ shc-diun~ ~alcu~ted ~s fsee met~l~
lb~54-1 ~59-~ he olefinic st~r~ing maeer~al reactants en-compassed by the processes of this inYent~on can be terminally or ~nternally unsa~urated and be sf straight-chain, branched~chain or cyclic ~tructure. Such olefins can contain fr~m 2 to 20 carb~n atoms and may c~nta~n one o~ more ethylenic un~atur~ted ~rGups. Moreover, ~uch ole-fins may contain groups cr ~ubstituents which d~not essentially adver~ely interfere with the hydroformylation process ~uch as carbonyl~ carbonyloxy, ~xy, hydroxy, oxy-carbonyl, halo~en, alkoxy, aryl, haloalkyl, and the like.
Illustrative olefinic unsaturated compounds include alpha olefins, lnternal olefins, alkyl alkenoates, alkenyl alkanoates, alkenyl ~lkyl ethers, alke~ols, and ~he like, e.g. ethylene, propylene, l-butene, l-pentene, l-hexene, l-octene, l-decene, l-todecene, l-octadecene, 2~butene, 2-methyl propene (i6~butylene), i~amylene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, cycloh2xene, propylene dimers, propylene trimer~, psopylene tetramer~, 2-ethyl l-hexene, styrene, 3-phenyl-1-propene, 1,4-hexadiene, 1,7 oct3d~ene, 3-cyclohexyl-l~butene, allyl alcohol, hex-- l-en-4-ol, oct-1-en-4-ol~ ~nyl acetate, allyl ~ceta~e, 3-bu~enyl ~ce~a~e, vinyl psopionate, allyl pr~pionate, allyl bu~yr~te, methyl ~ethacrylate, 3-butenyl ~ceta~e, vinyl ethyl e~her, ~nyl methyl e~her, ~llyl ethyl ether, n-propyl-7-~eteno~te, 3-bute~enitr~le, 5-hexenamide, ~nd the lik~. Of cour~, lt is under~tood ~hat ~ixtures of ~4054~

,;
~ ,' ' .

o~ 2, ~ L~,, OJ 5 5

6~
different oleflnic 6~arting ~ter~als can be e~ployed9 if deslred, by ehe hydrofor~ylation process of thc ~ub~ect inve~t~on. Mose preferably the 6ub~ect ~nven-~ion ~B especially u~eful for the produc~on of aldehydes, by hydroformylating alpha oleins eontaining from 2 eo 20 carbon ~toms ~nd internal olefi~s containing from 4 to 20 ,carbon atoms as well ~s star~ing ~aterial ~ixtures of such alpha olefins snd internal ole$ins. The most preferred olefin ~tart~ng materials are butene-l, butene-2 (c$s andtor trsns), ~sobutene and various mixture thereof.
The carbonylation and preferably hydroformyla-tion process of this invention ls also preferably con-ducted ~n the presence of an oTganic solvent for the Group VIII transi~cion metal-diorganophosphite complex 15 cat~lyst. Any ~uitable ~olvent which does not u~duly adversely ~nterfere with ~che ~ntented carbonylation pro-cess can ~se employed 2nd ~uch solvents may include those heretofore commonly employed in knows~ (;roup VIII transi-tion T~e~al ca~calyzed processes. By ~ay of illustration ~uitable 6Dlvent~ for rhodium cat~lyzed hydroformylat~on processes include ~hose ti3closed e.g. in U.S. Pat..NosO
3,527,~09 ~nd 4,148,830. Of cour~e, ~ixtures of one ~ore different ~lvent~ ~y be e~pl~yed if desired. In gen-er~ n rh~d~um cat~lyzed hydroformylation ~g $s prefesred ~5 to employ ~ldehyde comp~unds corresponding to the ~ldehyde pr~duct6 de~$red to be produced ~ndlor higher ~oil~
21dehydQ liqu~d conden~tion by-ps~duct~ as ~he primary ~olvent ~uch ~ the higher bo$~ing aldehyde l~quid con-~405~1 26~ S~ ;

densation by-produet~ that are produced in ~itu during the hydroformylatioll proce~s. Indeed, while Dne m~y employ, if de~ired, ~ny ~uitable ~olveTIt ~c the ~car~c up of a coneirluou~ process (aldehyde compo~mds corres-S ponding to the desired aldehyde products being preferred),the primary s~lvent will normally eventually comprise both aldehyde product~ and higher boillng aldehyde liquid eon-densation by-product~ due to ~che nature of ~uch continuous processes. Such ~ldehyde eondensation by-product~ car also be preformed i desired and u~ed ~ccordingly. More-over, ~uch higher ~oiling aldehyde condensation by-products and meth~d~ for their prepar~cion are more fully described in U.S. Pat. Nos. b~l48~83o and 4,247,486. Of cour~e, ~t âs obviou~ th~t the ~mount of solvent employed is no~
critical eo the 6ub~ece invention and need only be that Amount sufficient to provite the reac~ion medium with the particular ~r~up VIII transition metal concentration de- .
~red for ~ given proces~. In general, the smount of ~olvent w~lPn employed may range from ~bout 5 percent by 20 weight up to 8bou~ 95 percent 'by weight t~r more based on the total welght of ~che reac~ion med$um.
It 1~ further gener~lly preferred to carry out lthe carbonylatlon and esp2cially the hydrofor~ylation process of thi~ iM~7ention in ~ contlnuous m~nn~r. Such 25 types of cont~nuou~; processes ~re well known ig~ the ~rt snd ~ay $~av~1ve e.~. ~sydr~formyla~c~g the t~lefin~c stareing 14~54 -1 .

,.
:-:, .

L2~ 5 62_ material with carbon m~noxlde and hydrogen in a llquid homogene~u~ reaction medium compri~ing a ~olvent, the Group VIII transition metal-diorgsnopho~phite cdt~lysc.
and free dior~anophosphite lig~nd; ~upplying ~ake-up 5 quan~ities of ~che olef~nic starting mater~al, car'borl monox~de and hydrogen to the rescelon ~edium; ;z~a~ntain-~ng reaction temperature and pressure conditions fa~orable to the hydroformylation of the olef~nic ~tarting material;
and recovering the desired aldehyde hydroformyl~tlon prod-10 uct ~n any con~entional manner desired. While the con-tinuous process can be carried out in a single pass ~ode, i.e. wherein ~ vaporous mixture compri ing unreacted ole-fin~c 6tarting Faterial and vaporized aldehyde product is removed from the liquid re~ction medium from whence the aldehyde produc~ is recovered and make-up ~lefinic starting ~aterial, c~rbon monoxide ~nd hydrogPn are ~upplied to the liquld reaction medium for the next ~ingle pass through without recycling ~he unreacted olefi~c starting m~terial, ~t ~s gener~lly desirable to ~plDy a continuous pracess 29 that lnvolves either 8 liquid and/or gas recycle procedure Sueh ~ypes of ~cycle procedures ~re well known ~n the ar~
~nd may involYe the liqu~d recycling of the Group VIII
~rans~tion metal-dlorganophosphite complex catalyst solu~ion ~eparated fro~ ~che deslred aldehyte re~ction product, ~uch ~ disclosed ~.~. ~ U.S.P. 4~14B,830 or a ~as recycle procedure ~;uch ~ disclosed ~.g. in U.S.P. 4,247,4~6, a~

.... . .. . .. ,. .. . _ ... .. . . . ... ,, . _ .. . ... . . . .... . . . . . . .. . .... . .

~6~5S

well as a combination of both a li~uid and gas recycleprocedure if desired. The most preferred hydroformylation process of this invention comprises a Gontinuous liquid catalyst recycle process.
The desired aldehyde product may be recovered in any conventional manner such as described, e.g. in U.S. Patents 4,148,830 and 4,247,486. For instance, in a continuous liquid catalyst racycle process the portion of the liquid reaction solution (containing aldehyde product, catalyst, etc.) removed from the reactor can be passed to a vaporizer/separator ~herein the desired aldehyde product can be separated via distillation, in one or more stages, under normal, reduced or elevated pressure, from the liquid reaction solution, condensed and collected in a product receiver, and further purified if desired. The remaining non-volatilized catalyst containing liquid reaction solution may then be recycled back to the reactor as may if desired any othe volatile materials, e.g. unreacted olefin, together with any hydrogen and carbon monoxide dissolved in the liquid reaction solution after separation thereof from the condensed aldehyde product, e.g. by distillation in any conventional manner~ In general, it is preferred to separate the desired aldehyde product from the rhodium 14054-l : . .. ....
.- :
.; ~: . , , . . : ..

j L~ 5 . ~6~

eatalyst cont~ining product 601ution under reduced pressure ~nd at low tempera~ures such as below 150C. ~nd more preferably below 130C.
As no~ed sbo~e, the carbonylation proce~s ~nd especially the hydroformylation process of this invent~on is preferably carried ou~ ~n the pre6ence of free diorgano-phosphite ligand, i.e. ligand that is not complexed with the Gro~p VIII transit~on ~etal of the ~etal complex catalyst employed. Thus ~he free diorganDphosph~te ligand may correspond to any of the ~bove def~ned diorganophosphite ligands discu~sed above. Howe~er, while lt i~ preferred to ~mploy a free diorganophosphite ligand that ~s the same as the diorganophosphite ligand of the Group VIII transition metal-diorganopho~phite complex catalyst such ligands need not be the ~me ~n a ~i~en process, but can be diferent if desired. While the carbonylation and preferably hydro-formylstion process of this ~n~ention may be carried out in any excess ~mount of free dior anophosphite ligand de-siret, e.g. a~ least ~ne mole of free diorganopho~phite l~gand per ~ole of Group VIII transltlon ~et81 present ~n the reaceio~ met~u~, le has ~een found tha~ in rhodium catalyzed hydroformylat~on large amounts of free diorgano-pho~phite ligand sre not necessary for catalytic sctiv~ty . ~nd/or ca~aly~t ~t~biliz~tion, ~nd gener~lly re~ard the ~ceivity of the rhodium ca~aly~t. Accordingly, ~n ~eneral amoun~ of diorganoph~fiphite lig~nd ~f from about 4 to about .
~4Q54-1 . - , , .

2~ 35 50, ~nd preferably from about 6 ~o about 25, ~ole per ~ole of ~roup VIII ~ransition ~eeal (e.~. rhodium) presen~
~n the react~on medium ~hould be ~uitable for most purposes, particularly w~th regard to rhodium çatalyzed hy~roformyl~-tlon; ~aid amounts of diorganophosphite ligand employed beingthe ~um of ~oth the ~mount o$ diorganophosphite that is bound (complexed) to the Group VIII transition me~al present and the amoun~ of free (non-complexed) diorganophosp~ite ligand preserlt. Of course, lf desised, make-up diorganophosphite ligand can be ~upplied to the reaction medium of ~he hydro-formylation process~ at any ~ime and ~n any suitable m~nner, to m~intAin a predetermined level of free ligand in the re-~ction medium.
. The abil~ty to carry out the process of this inven-tion ln the presence of free diorganophosph$~e ligand i~ an important beneficial aspect of thi~ invention in that it re-moves the criticality of employ~ng very low precise concen-trations of ligand that nay be required of certaln co~plex catalysts who~e ~ctivi~cy ~y ~e retarded when even any amount 20 of free ligand i~ ~lso present during the proces, par~icularly when large licale co~Derc~al operations are involved, thus help-- ~ng o pro-Jide the oper~tor with ~reater processing laeieude.
~ e r~a~t$on condieilons for effecting a carbonyla~
e~on ~nd more preferably ~ hydr~foa~nylat~on p~oces~ of this 25 ~vent~on m~y be those heretofore convention~lly u6ed 2nd ~ay co~pr~e a reAction temper~ture of from a~bout 45C.
to a~ut 200C. Iand pres~ures rangin fa~om ~bout 1 eo 10,000 psia. Wh~le ~he preferred casb~nylation process ~ the l~ydrofomlylation of ol~f~nic~lly unsatur~ced com-14û54-1 -:
- . ..

i i ~i6-pounds and more preferably olefinil: hydrocarbons ~ with carbon ~onoxide and hydroKen lto produce aldehydes, lt iL~
to be under~tood thae the Group VIII transition metal-diorgarlopho~ph~e complexes of this ~nvention may be ~m-5 ployed as cataly~t~ in tmy o~her type of prior art ear-bonylation proce~s to obtain good resul~cs. Moreover whil. ~uch other prior carbonylation art processes may be performed under eheir usual conditiorls, in general it is believed that they ~ay be perfonmed at lower t2mpera-1~ ture~ than normal and/or a~ a higher rate of reactiondue to the Group VIII ~ran~ition metal-dicrganophosp~l~e complex cataly~ts of thi~ invention.
As noted ehe more preferred process of thi~ in-ventlon int olves the prcduc~cion of ~ldehydes via hydro-formylation of ~n olefinic unsat~rated compound with car-bon ~onoxide and hydro~en ~n the presence of a Group VIII
tr~nsition metal-diorganophosphite complex cataly6t and free diorganophosphiee ligand. While it may be po~lble ~o produce aldehyde productfi having a high normal (straight 20 chair~) to 'branched chain aldehyde product ratio, e.8. on ~he order of ~bou~ S ~co 1 or g rea~cer, by ehe hydroformyla-tion proces6 of th~ in~ention, in E~eneral the preferred hydroformylat~n will be th~t pr~cess ~ich i~ mose effi-cient in produeing alde21yde pr~duc~ rich in branched chain 25 ~ldehyde, $.~. ~ldehyde product havin~ a low nor~al ~tr~igl~ ha~n) ~ldehyde to ~r~nched chain ~ldehyde prod-' `
.

~64~)S ~r3 uct rat~o, e.g. on ehe orde~ of 5 moles or less of ~-~ldehyde produrt to 1 ~ole of branched aldehyde produc~O
Moreover, a un$que feature ~f the pre~ent invention 1~ the overall process~ng l~itude ~fforded $n con~rolling the S aldehyde product ~elect~vity that i~ provlded by the u~e of the diorganophosphite l~gands employable hereih. For ins~cance, due to ~omerization of the olef in 6tarting material during hydroformylation ~hat occurs with the use of the diorKanophosphite l~gands employable herein, lG one may control or preselect the particular richness of branched aldehyde $n ~he product desired li.e. preselect the par~icular des~red ratio of normal to branched aldehyde protuct), which i~ ~n marked contrast to hydroformylations ~hat employ ph~sphorus ligands which 6how l$ttle or no abili~y to 15 permit isomerization of the olefin 6tarting material during ~uch reactions leaving one with little or no ability to eontrol the rat~o of normal to ~ranc~et chain aldehyde protuc~ thae m~y be desired.
For exampled alpha-oleflns such as butene~ y 20 ~e readily hydr~formylated by the process of this invent~on t~ produce aldehyde products h~vln~ ~tra~ght chair~ eo branched chain ~ldehyde.product rat~o~ of less than 5 eo 1, preferably less than 3 to 1 ~nd ~nore preferably about 2 to 1. On the ~her hand i~ternal olefins ~y be surpris~ngly hydroformy-lated by t~e process of ehi5 ~n~ention eo ~bt~ln ~ldehydeproduct~ that ~re even r~cher ~n their branched ch~in $so~ers.
For inst~nce pure ~utene-2 c~n be hytroformylated to obealn more 2~ethyl-butyr~ldehyd~ ~.e~ ~ldehyde product~ wherein ehe ~405~ -1 ' , .

: .

~2~

ratio of ~-valer~ldehyde eo 2-methylbutyraldehyde is about 2 to 1 or less, preferably less ~chan 1 eo 1 and more prefer-~bly less than 0.5 to 1. Such processlng latitude of the present invention, provided $n part by isomerizat~on of ~he olefin ~tarting m~terial during hydroformylation ~nd the choice of the diorganophosphite ligand employed, ~s especlally useful in those ins~ances when a particular optimization of the branched chain aldehyde product is desirable. For in-stance, slnce 2-methylbutyraldehyde is the precur~or of isoprene which i~ used to produce synthetic rubber, the ability to produce e6sentially only 2-methylbutyraldehyde directly by the hydroformylation process ~f ~his inven~ion is extremely beneficial to the art ln that it grea~ly facilitate~ ~he refining operation (separation fr~m n-~aleraldehyde) and allows for the product~on of higheramounts of deslred ~-methylbutyraldehyde product per given ~mount of butene-2 starting ~ateri~l. On the other hand, there ~re clearly instances when it ~sy be tesirable that the aldehyde product need not be qui~e ~ rich in branched chain ~ldehyde, but may comprise a slightly higher normal to branched chain Aldehyde product ratio ~uch as when the ~ aldehydes ~re employed as preeursors for alcohols and ~cids which in turn may find util$ty in such di~erse fields a~
synthetic lubricants a ~olvent~, paint~, festilizers, ~nd *he like.
Llkewi~e mixture~ of ~lpha-olefins snd ~nternal olef$ns can als~ ~e re~dily hydrofor~yl~ted by the process of .~
14054~

........... ..... .. .__ __., _. _ _ ,._ ., .. _ . _ . .. .. . .. ... , .. . ,. ~. . . . . . .

:~L2 ~ L~ 15 5 - ~9-this in~ention ~co obtain aldehyde products ~chat are rich ~n their ~branched chain iso~ers~ For instance 6tarting materlal mixtures of butene-l and butene-2 c~n readily be hydroformylated to obtain ~lde~yde products wherein the 5 r~tio of ~trai~ ht chain ~ldehyde to branched chain alde-hyde is about 3 ~o 1 or less lmd more preferably about 2 to 1 or less. The abil~ty to hydrofo~nylate both types of olefins concurrently with comparable fscility from the ~ame ~tarting ~terial mixture is highly beneficial to the art 10 ~ince ~uch mixed alpha olefin and internal olef~n startin~
materials are readily ~vAilable snd ~re ~he most econo~ical olefin feedstocks. Moreover, the versatility af ~he di-organophosphite ligants employable herein lend ~hemselves readily ~o the cont~nuous hydroformylatio~ of both alpha-olefins snd ~nternal olefins wherein different reactors infieries ~ay be employed. Such aiblity not only provides one wi~h the pr~ce~ing lat~tude of further hydrofor~Dylating in the ~econd reactor any unreacted olef~n passed to lt from the first reactor ~ut ~lso allows one, if desiret, to opti~ize 20 the reaction cDnditions for hytrofor~ylation of e.g. the alpha-olef~n $n t~e fir~t react~r, while al~o optimizing the resctlon condit~ons for the hydrofonnylation of e.g.
1:he intesnal olef~n ln ehe second reactor.
Of cour~e, ~t ~ to be under~tood that wh~le 25 the op~cimiza~cion of ehe react~ cn conditions ~4~54 -1 .. . ____._. _ ., ___, _ .. ,_ _ .. _ .... _ ... .. ..

;~ :

.

necessary eo achieve the best results ~nd eff~eieney desired ~re depende~t upon one's experience i~ he utili-zatlon of ~he ~ub~ect hydroformylation invention, only a certain measure of experimentation ~hould be necessary to ascertain those conditions which ~re opti~um for ~ gi~en ~ituation and ~uch 6hould be well with~n the knowledge of one ~killed in the art and easily obtainable by~ following the more preferred aspects of this invention as explainet herein and/or by simple roueine experimentation~
1~ For instance, the total gas pressure of hydrogen, carbo~ monoxide and olefinic unsaturated starting compound of the hydroformylation proce~s of t~is ~nven~ion m2y range from about 1 to about 10,000 p~ia. More preferably, how-ever, ~n the hydroformylation of olefins ~o produce alde-hydes ~t i~ preferred that the process be operated a~ a total gas pressure ~f hydrogen, carbon monoxide and ole-finic unsaturated ~tarting compound of less than ab~ut 1500 p~ia. And more preferably les ~han about 500 psia. The minimum total pre~sure ~f ~he reactants i8 not particularly crieical and ~6 l~mited predom~na~ely only by the am~unt of react~nt~ neces~ry to ob~ain a des~red rate of reac~ion.
More ~pecificslly the carbon monoxide par~ial pressure of ~he hydrofor~ylat~on process of ~his ~nvention ~s pr2fer~bly from ~bout 1 ~o ~boutl20 psia. and ~ore preferably fro~
~out 3 tD ~bout 90 pS~, while the hydrogen p~r~i~l pressure preferably ~bout 15 to about 160 psia and ~ore prefersbly fro~ ~bou~ 30 to ~bout 100 ps~ general H2:CO molar r~tio of g~eou~ hydrogen t~ c~rbon ~onoxide m~y ran~e fro~

~L ~ ~i L~ ~t3 5 ~ j ~71-about 1:19 ~o 100:1 or higher, the more preferred hYtro-gen to carbon ~onoxide molar rAtio being from about 1:1 ~o about 10~
Further as noted above the hydroformyl~ation pro-cess of this invention may be conducted at a reaction temp-erature from about 45~C. to about 200C. The preferred re-~ction tempera~ure employed in ~ given process ~ill of cour6e be dependent upon the psrticular olefinic starting material and metal catalyst employet as well as the effi-ciency desired. While conventional carbonylation and/orhydroformylation reaction temperatures may also ~e employed ~erein, the operation of ~he hydroformylat~on process of this invention can be optimized in a 6urprisingly lowes temperature range tha~ heretofore prefer~bly ~d~ance by the prior nr~.
For example, compared ~o pr~or art rhodiu~ c~talyzed hydroformylation systems9 the ~mproved catalytic act~vity and/ or ~ca~ility affordet by ~he rhodium-diorganophosphite complex cataly~ts of this in~ention i~ pasticularly unique 20 for achieving high rates of selec~iive hydroformylation at - comparatively low react~on ~emperatures. In general, hydro-f~rmylaticns at ~eactioa temperaeures of about 50~C. to about 120C. ~re preferred for all ~ype6 ~$ ~lefi~ic ~tarti~g ~aterials. More preferably, ~-olefins can ~e effectively hydroformyla~ed at a temperature of rom a~oue 60C ~o about llO~C ~hile even le~s reactive olef$~ ehan ~onventional ~ ~
olef~n~ ~uch ~5 i~obutylene ~nd intern~l ~lefins as well a~
14054~1 . _ .. . . .. ...... , .,__ _ ._.. .. _ . _ .. ~_ . , .. ~ _ .. ..... .. . .

3Ll ~ r}~ . _ ~12 -mixtures o D~olefins ~nd inter~al olefins are effectiYely an~ preferably hydroformylated at a temper~ture of fro~
~b~ut 70~C. eo abou~ 120C. Indeed in the rhodium-catalyzed hydroformyla~ion process o~ this ~nvention no substantial benefit is seen in operating at react~on temperatures mweh ~bove 120C. and ~uch is considered to be less desirable, due to possible catalyst activity decline ~d/o~ rhodium . losses that may be causet by the hi~her temperatures.
As outlined herein the carbonylation and more preferably hytroformylation proces~ of this ~nvention can be carried out in either the liquid ~r ~aseous state and involve a continuous liqu~d or gas recycle sy~tem or çom-bination of such gystems. Preferably the rhodium catalyzed hydroformylation of this invention $nvolves a continuous homogeneous catalysis process wherein the hydroformylation is carried out in the precence of both free tiorganophosphite ligand and any suitable ~onven~ional ~ol~ent as further ou~-lined herein. Such ~ypes of cont~nuou~ hydroformylation ~ystems and methcds for carrying them out sre well known in the art ~nd thu~ need not ~e partieularly tetailed here~n~
- ~hile the hydroformylatlon process of ~his i~ven t~on ~ay be carr~ed out employing any olefinic unss~urated ~tarting mater~al ~uch ~s already noted herein, ~he pre-- fersed rhodium catalyzed hydrofor~ylat~on proces~ of ~his lnvention has ~een found to ~e psrticular1y effective in convert~n~ ~lef~ns ~uch ~s ~r-olefins h~ving from 2 to 20 s , _ , . .. .. .. .. . . . . . .

^18,~ r~

carbon atoms and ~n~ernal olefins hav~n~ from 4 ~o 20 carbon atoms9 as well ~s m~xtures of such olef~ns, to the~r corresponding aldehyde products. Moreover, the hydroformyl~on of olefins ~hat ~re normally less re-active ~han ~heir correspsnding s~erically unhindered 5~ ~olefins, guch PS i~obutylene and internal olefinsis an even more preferred aspect of this i~vention, as is the hydroformyl~tion of mixtuses of ~ -olefins and internal ~lefin~.
In gen~ral the use of the diorganophosphite ligands provide a far more catalytically active and ~table rhodium catalyst for the hydroformylation of olefins, es-pecially internal and other ~uch less reactive 6ter~cally hindered olefins e.g. ~sobutylene than obtainable with con-ventional tri~rganophosphine ligands, thus allowing for greater rates and/or increased amounts of sldehyde production at much lower reaction temperatures. The rhodium catalyzed hydroformylat~on process of this invention Df mixtures of ~-olefins ~nt internal olefins is further unique in that 20 the ~u~ect proce6~ of this ~nventiion re5ult6 ~n a high de-gsee of ~ldehyde product produceion from both eypes of olefins ~n the ætar~ing ~zterial, ~n contra.~t t~ those prior ar~ proce6~es ~chat promote hydroformylation of primarily only the ~se reacti~e ~terically unhindered ~;~
25 olef$n~. Of c~ur~e, lt $~ ~ be under~t~od .hat ~che pro-~ortional make up of the mixet olef~n tart~ng ~aterial~

14~5l~ -1 .... . _ ...... _ .. .. .. .. _ . ... ... ... . ... ..... .. . . .. . .... .. .. . .

Fi4~5 ~7 emplDy~ble in this ~nveneic~n i~ not cr~ical and any de~
~ired p~op~rtic~nal am~unt~ ~f such ~lefins may be employe~
~n ~e ~tarting olef~D m~xture. In general " ~e ~ especially preferred t~ hydroformylate mixture~ of t:~utene-l ~nd ~uten~-2 5 (c~ and/or tras-~, ~ich mixtures may als~ optiol-ally con-~c~in i~butene, ~n ~der ~o o~ta~n propoTtionate prc~duc~c mixt~re~ o$ ~raler~lde~yde, 2-methylbutyraldehyde and c)ption-~lly 3-methyl~utyraldehyde.
Further, unde~isable ~de Teacti~ns that may occur 10 ~n ~dium ch~alyzed hydroformyl~tion may be cur~a~led ~y the use of the diorganc~phcsphite ligands of thi~ invent~e~n ~uch ~s, undue aldehyde by-!prcduct heavie~ formatio~, ~s well a~ ligand eta~ility tc>wards the aldehyde product. For exa~ple, ~hile the u~e c~f the diorganc)phc~sph~te ligands em-15 ploy~ble herein may curtail undue l igher bc~iling ~ldehyde con-dens~tic~rl by-prsduct fDrmat~osl, ~t i~ axiomatic th~t ~n coTmnesc~l continuot~s hydrofor~ylat~on Df eu~h olefins the cc~ncentr~tios~ of ~uoh h~,her bo~ling ~ldehyde condens~tisn ~y-p~oduct~ dimer~c $nd trimesic ~ldel~ydes) 7,~ill e~en~
20 ~ u~lly c~ntinue t~ bui~d o~er ~ per~od of time until ~t finally de~irable c~r neeessary tt) remo~e a~ least ~ portios of ~u~ h~g~er b~lin~, ~ldellyde condensa~i~n b~-produc~s, ~s describe~ e.g. in l~.S. Patentli 4,148,430 ~nd 4,247,486.
In ~ n c~ccurranc~ it ~c desir~b~e ths-~ phosp~rus li~,and ~4~4 -1 . .

5i5 which is also present (preferably in an excess amount) have a lower vapor pressure (higher boiling point) than that of the aldehyde condensation by-products so that the ligand will not be lost or depleted when such aldehyde condensation by-products are removed. For example, volatility is related to molecular weight and is inversely proportional to molecu-lar wight within a homologous series. Accordingly, it is desirable to employ a diorganophosphite ligand whose molecu-lar weight exceeds that of the aldehyde by-product trimer corresponding to the aldehyde being produced. For instance, since the molcular weight of valeraldehyde trimer is about 258 (C15H3003) and all the preferred diorganophosphites of this invention exceed 330 in molecular weight, it is clear that the diorganophosphites of this inven-tion are especially suitable for use in hydroformylating butene-l and/or butene-2. is as much as there should not be any considerable loss of the diorganophosphite ligand during product aldehyde and higher boiling aldehyde by-product removal, as might pre-dictably be the case wgen a different phosphorus ligand 2~ having a lower molecular weight (e.g. higher vapor pressure or lower boiling point) than the higher boiling aldehyde by-product is employed (and which would re~uire additional processing steps if recovery and reuse o~ the phosphorus ligand is desired).
D~14,05~-1-C

: . ,.. ,.. ;~ ~' .

: ....~ , ~2 ~76~

Further~ while triorganophosphite ligands ~n general will provide a metal-complex catalys~ with ~ufficient activi~y to hydroformylate ~nte~nal olefins, experience has shown that ~heir use, particularly with regard to continuous hydroformy-lation, has been less tha~ ~ati~factory. This drawback inemploying triorganophosphites is believed due to their very high affinity for reacting with aldehydes, ~he produet of which has been found to readily hydrolyze ~o a oorresponding hydroxy alkyl phosphonic acid~ as ~hown by the following ~keletal reactlon mode:
\

14~54 -1 i Ll 0 5 5 (C6H50!31~ ~ n^e4~9C~ ~ e45î9~ o~6H5~3 -t ~I CH ~3(oC H ) ~e~rr~ngement C t~ CH~~c6H5 ? i C4HgCH-p~oH
OH - C6H50H OH ~C6H5-~cSH OH OH OH
o~ -hydroxy-pentylphl~sphonic ~cid Moreover, the formation of such acid is an auto-catalytic process, thus rendering triorganophosphite ligands even more susceptible to the production of such undesirable acid by-products, particularly in continuous rhodium catalyzec liquid recycle hydroformylation wherein contact between the phosphite ligand and aldehyde product is prolonged. Sur-prisingly, the diorganophosphite ligands employable in this invention have been found in general to be far less moisture sensitive and far less reactive toward forming such phos-phonic acid than conventional triorganophosphites, thusproviding a more prolonged stable and active continuous rhodium catalyzed li~uid recycle hydroformylation than may be possible with triorganophosphite ligands. Such is not to say however, that hydroxy alkyl phosphonic acid by-product will not be eventually formed over the course ofthe continuous rhodium catalyst liquid recycle hydroormy-lation process of this invention. However, ~he accumula-tion of such indesirable hydroxy alkyl phosphonic acid, D-14,054-1-C

:, j L~

during a continuous recycle hydroformylation process of this invention/ takes place at a much slower rate than when triorganophosphite ligands are employed, which allows for a longer and more efficient continuous operation. For in-stance, rapid decomposition of the phosphite ligand may notonly adversely effect catalyst activity and/or stability, but obviously leads to a quick loss of the phosphite ligand that must be replaced with make-up phosphite ligand, as well as helping to further promote the autocatalytic forma-tion of the undesirable hydroxy alkyl phosphonic acid whichis often insoluble in the genral liquid hydroformylation reaction medium. Consequently rapid and high build-up of such hydroxy alkyl phosphonic acid can lead to precipi-tation of the acid to an obviously undesirable gellatinous by-product, which may plug and/or foul the recycle lines of a continuous liquid reaction system, thus necessitating periodic processing shut-downs or stoppages for removal of such acid and or precipitate from the system by any appro-priate method e.g. by extraction of the acid with a weak base, e.g. sodium bicarbonate.
Moreover, it has been surprisingly found that the above mentioned disadvantages attendent with such hydroxy alkyl phosphonic acid by-product may be effectively and pre-erably controlled by passing the liquid reaction effluent D-14,054-1-C

:

` ., ';; .

L~5S

stream of continuous liquid recycle process either prior to or more preferably after separation of the aldehyde product therefrom through any suitable weakly basic anion exchange resin, such as a bed of amine-Amberlyst ~ resin, e.g. Amberlyst ~ A-21, and the like, to remove some or all of the undesirable hydroxy alkyl phosphonic acid by-product that might be present in the liquid catalyst containing stream prior to its reincorporation into the hydroformy-lation reactor. Of course if desired, more than one such basic anion exchange resin bed, e.g. a series of such beds, may be employed and any such bed may be easily removed and/
or replaced as required or desired. Alternatively if de-sired, any part or all of the hydroxy alkyl phosphonic acid contaminated catalyst recycle stream may be periodically removed from the continuous recycle operation and the con-taminated liquid so removed treated in the same fashion as outlined above, to eliminate or reduce the amount if hy-droxy alkyl phosphonic acid contained therein prior to reusing the catalyst containing liquid in the hydroformy-lation process. Likewise, any other suitable method forremoving such hydroxy alkyl phosphonic acid by-product from the hydroformylation process of this invention may be em-ployed herein if desired.

D~14,054-1-C

, .: .
.
- :

. . .

L~ rj -8~

Aecord~ngly another preferred and novel aspect of the sub~ect lnvention i~ directed ~o an improved con-tinuous hydroformylat~on process for producin~ aldehydes which comprises reacting an olefin with carbon monoxide and hydrogen in the presenre of a liquid-medium contalning a solubilized rhodium-organophosphite complex catalyst, a solvent, free orKanophosphite ligand, and aldehyde product, the improvement comprising minimizing decomposition of the free organopho~phite ligand by ta) removing a s~ream of ~aid liquid medlum fr~m the hydroformylation reactlon zoneJ
(b~ treat~ng the liquid medium ~o removed with a weakly basic aniPn exchange resin and (c) returning the treated reaction medium to the hydroformylation reac~ion zone.
Such treatment of the liquid medium with a weakly basic anion exchange re~in comprises passing the liquid medium, i.e., liquid reaction effluent stream, after re-moval of ~aid s~ream from the hydroformylat~on reac~on zone, either prlor to ~nd/or ~fter separation of aldehyde `- product therefrom, through a weakly basic anion exchange resin bed.
Any suitable wea~ly basic anion exchange resin bed ~ay be employed herein. Illustrative weakly basic ~nion exchange se~in ~ets employable herein ~ay include, e.g., cro~slin~ed ter~i~ry amine polystyrene ~nion ex-change resin~ of the gel or macrcreticular type, such ~s 1~054-1 -_ .. .. . . ~ . . .. . . . .

- ' ~'''' ~;
, .. . ..

L~ ~L~5~

-Bl-a bed of amine-Amberlys ~ -resin and more preferably, ~m-berlys ~ A-21, which compri~e~ a crosslinked polystyrene backbone wlth pendan~ benzyl dimethyiamino l-C6H~-CH2-N
~CH392~ func~ional groups. Such type~ sf weakly basic S ~nion exchange resin beds and/or methods for their manu-facture are well known in th~ art.
As noted above decomposition of the organophos-ph$~e l~gand may be effectively controlled and minimized by the preferred treatment of thi~ invention which as postulated removes ~ome or all of the undes~rable hydroxy alkyl phosphonic acid by-product that might be present in the liquid ~edium as a result of ~n ~tu build-up over the course of the hydroformylation react~on and which i an autocatalytic material for decomposition of the organophos-IS phite, e.g., v~a the side reaction Gf phosphite ligand andaldehyde product~ While ~all amount~ of such hydroxyalkyl phos-phonic ac~ds ln hydroformylation reaction mediums are difficult t~ ~nalyze for by seandardanalytical me~h~ds 20 ~uch a~ Bas ~hromatography or llquid chromstography due ~n .
par~ ~o the high bo~ling and pol~r nature o 6UC~ acids, 31~ ~MR ~NucleQr ~agnetic Resonance~ CflTI ~e ~ucces~fully em-ployed to detect ~uch acid~ in amou~ts as low as about 100 ppm by weight. For example, one need only determine the detect-~ble re~on nce peak (chemical shift in ppm relative to external 14~54-1 -~ .

, ~ ,.-.~..,... .-' ` ' - -`` ' ' -~

~82-P04~ vla 31p NMR for a compara~cive ~ he~ic ~olution containing lOû ppm of ^che hydroxyalkyl pho~phonic acld, then monitor ~che hydroformyla~ion reaction ~edium of ~che proces~ in question for evidence of the corresponding acid 5 resonance peak via ~he same 31p NMR technique. Thus while the sub~ect improvement ~enerically encompas,qes ~ process for removal o~E hydroxyalkyl phosphonic acit from a liquid hydroformyl~t~on reae~lon medium tha~c a~ready eontains more than ~erely a trace amount of ~u~ acid to thereby minimize 10 further ~ecomposition of the organophosphite~ and, ex-perience has shown that decomposition of the organoph~s-phite lig~nd can be very rapid when the Amount of hydroxy ~lkyl phosphonic ~cid is allowed ~co build up to more than a trace ~mount. ~hus the preferret process of this in~en-15 tion iE one in which the liquid l~nedium So be treated doesnot even contain s readily deteetable amount of ~uch hydroxy alkyl phospllonic-acid ~nd 6uch 1~ accomplished by beginning ~aid ~cre~tment of ~che liquid medium prior to ehe build~up of ~ readily detect~ble amount (e.g. 100 ppm) by weight of such 20 hydroxy alkyl pho~phonic acid vi~ 31p N~ BO ~; to remove ~aid hydroxy alkyl phosphonlc ~cid as lt ~ being formed.
Accordingly~ while thi~ lnYent:lon ~ncompa~es ~oth inte~nit-tent ~nd c~n~cinuous treat~ene OI~ ~he liquid ~ed~um to ~ini-~ze ~rganopho~phite ligand decomposltion, ~ont$m~ou~ ~creat-25 ~ent of the l~qu~d mediu~ dur~ g the hydroformylation processprefer2eed.

14û5b-1 : ~ ' , .. .

~: , ,.. ~-i2 ~4 05~.

~83-Moreover the minimixation of the degree vf decomposition of ~he organophosphite ligand obtain~ble by the process of this invention can be readily observed and quantit~t~vely calculated if deslred, by determining ~n a glven process, the amount of organophosphite ligand remaining and/or 105t in the hydroformylation reaction medium from that amoun~ initially employed, after ~ gi~en period of time of the continuous hydroformylation process, ~n oontrast to the amount of organophosphi~e l~gand remainin~
and/or lost in a corresponding continuous hydroformylation process carried ou~ under the ssme cond~t~ons, but without employing t~e weakly basic anion exchange re~in treatment outlined herein.
~ccordingl~ nim~zing ehe degree of decompo-15 6ition oiE` the organophosphite ligsnd by pre~en~ing and/or slow~ng dawn the rate of ~eact~on between 8uch l~and6 ~nd ~ldehyde product, ~ or ~ lo~ger ~ndl re e$f~cient con~inuou~ ~per~tion ~ha~ a comp~ra~ve hydroformylaeion p~sce~s carrled ~ut in the ~b~ence of ~ weakl~ ~a~ic ~nl~n æxchan~e re~in treatmen~. M~reover in addition ~o preven~ing and/or ~inlmizing ligand and sldehyde pr~duct loxs, ~he ~ub~ect treatment msy al o h~lp ~uat~i~ ehe r~ of hydrofvrmyl2~ion ~nd ~ltehyde pr~duct r~tio ~e6ired oves ~ lDnger per~d of t~e~ ~8 ~ell ~ help ~aint~in cataly~t ~ctivity ~nd/or ~t~ gg, _ _ . _ .. . .. . . _ ._ . .. . . .. ~_ _ . . .. .. . . ..... , . .. __ .. . .. . . . . .
.
.
` , ,~ .
~,:
, ~

~L~ 5 -~
-~4~ .

w~lch allay ~e ~dver~e~ ~2ffected ~y rap~a decompo~t~sn of ~he ~rganopho~ph~te l~gand. Further ehe drawback of r~p~d ~nd h~gh lt~uild-up of I~U*l hydroxy ~lkyl pho~phon~c ~Cid ~1~ e~n le~d ~o prec~p~tat~on of ~e 5 ~cid t~ ~2n c>bv~u61y unde~rable gell~t~n~u~ ~y~produet ~nd whish alay pltag ana/or fou~ ~e recycl~ l~ne~ of csntinuou~ taydroforDylae~on ~y~tem can ~e overc~me .. .
~y ~he prOf:eB6 6~f ehl~ invent~
The Qmployment o ~ weakly ~asic ~nion exchasl~e 10 resin as descr~bed ~n th~ nvention is ~ndeed un~que and surpri~ing, Eince l;uch res~ns, e.g., Amberlyst~A-21 ~:re lcnown to ~e h~ghly reactlve with carboxylic ~c~ds, which ~re al~ minor oxo reaction by-product~. Thi6 property alone would 8U gest that the ~lse of 6uch res~l~s 15 ~ould not be a prac~cal s~eans fDr the removal of phos-phon~c acid fro~ a hydrof~rmylat$on proces~ ~tream, s~nce ~e ~uggest~ ~hat the a~d neutraliz~on ~ili~y of the resin would b~ consumed too rapidly ~y the carboxylic acid gener~ted by the hydr4fsrmylatic~n. H~wever~ it ha~ been 20 ~urprl6ingly found ochat ehe carboxylic ac~d neutra~ized form of Amberlyst~A-21 resin l~ ~t~ll ba~c enough, ~o TemoVe ehe ~ero~eer hydroxy~lkyl pho~phonic ac~d from hydroformylat~on etrea~s a~ven ln the presence of c~rgoxylic ~d~. ~oreover, experien~e 1~8 ShlDWn that ~che ~dd~on of 2~ eerti~ry ~mines (~uch ~ia6 di~nethylanil~ne~ triethanolamine~

~I~û54~1 .

pro~on sponge 9 etc.) to phosphite li~and promoted shodium complex hydrof~rmylation catalysts can cause rapid rhodium precipitation ~n ~he fonm of black sollds. ~ikewi~e9 Amberlys ~ A~21 resin ~tself when added to a hydroformyla^
5 tion reaction medium under hydroformylation conditions has been found to cause rhodium precipitation on th~ resin sur-face snd pores. It is therefore clearly unexpeeted and fortunate that the u~e of a wea~ly basic anion exchange resin as described herein, e.g., Amberlys ~ A-21 on a llquid medium stream that has been removed fsom the hydro-formylation reaction zone does not adversely precipi~ate rhodium or unduly adversely affect the rhodium catalyst and process in any s~nificant adverse manner, such as by ~n-creasing the r~te of aldehyde heavies formation.
It is to be noted, however, ~hat commercial grade wea~ly basic anion exchange resin beds, such as Amberlys -21, may contain halide impurities, e.g. chlorlde eontaminates, w~ich are known to poison (adversely affect) rhodiu~ complex hydroformylation cstalysts. Thus it is preferred that the weakly baslc ~nion exchange resin beds employable herein be at leas~ substanti811y free of halogen contam~nstes and more preferably essentially or entirely free from such halogen contaminates. Removal of ~uch halogen contam~na~es, ~s well as any other undes~rable 1~054~1 ....... ... , , , ~__ , _._ . .. _ ., _ _, _ . .... . .. . .. . _ .... ... .. . . _ . . .. .

.
:
` -: -~2~ 3~5 contamin~te~, from ~uch weakly ba~ic anion exchange re~in beds prior ~o their use may be readily accomplished by conventional washing ~echniques that are well known in the art.
As further noted herein the treatment of the l~quid medium containing a solubilized r~odium-organophosphite complex cataly~t, a ~olv~nt, free organophosphi~e ligand and sldehyde product ~ust take place out~ide of the hydro-formyla~ion reac~ion zone of the continu~u~ hydroformyla-ti4n process and the medium ~o trea~ed returned to the hydro~formylation reactor. Accordingly, this treatmen~ is adapt-able to both well ~nown continuou~ type gas and/or liquid recycle hydrof~rmyla~ion processes.
~or exa~ple, $n a contlnuous as recycle hydro-~5 formylat~on process, the treatment of thi~ ~nvention m~y be carried out ~y intermittently or continuously ~ithdraw-~ng a portion e~g. 81ip stream of ~he l~quld reac~on - mixture from the re~ctor, pa6sing ~t through ~ wea~ly ~ic anion ~xchange re~in ~ed and returning the ~o ~reated ~llp 6trea~ of the l$quid resotion mix~ure t~ ~he reactar.
~n ~ liquid recycle hydroformyl~t~on process, ehe l~qu$d weti~m r~moYed from the re~e~or c~n ~ passed th~ou~h the 14~54-~

.26 ~7~

weakly bas~c anlon excharlge re~in ~ed at any point thraugh-out the recycle proce~. For instaslce, ~n 8 l~quid recycle hydrofonnyla~ n procedure; it i8 co~on pla~e to con-tinuously remo~le a portion of the liquid react~on product 5 ~edium gro~ the reactor and the desired aldehyde product recoveret in one ~r more dis~cillaeion ~taEse`s eOE~. by pass~ng said l~quid medium ~o ~ vspor~zor/separator where$n che des~red produet ~ di6tllled and separated from said medium and eventually c:onden~ed ~nd recovered. The re 10 uJaining l$qu~d re~idue obtainea upon 6uch sepasation o~
aldehyde product, which residue contain~ the rhodi~n-orgaTIophGsphite catalyst, ~olvent D free organopho~ph~ee ligand and ~o~e undistilled aldehyte product is therl re-cyeled ~aclc to the reactor along with w~atever by-produet~
15 e.g. hydroxy alkyl phoEphon~c ~c~d that mlght 1;11BO ~e present ~n ~a~d recycled res~due. While the treatment of ~uch liquid snedium~, of ~uch continuou~ liquid recycle hydro~ormyla~n proce6ses~ ~ccord$ng ~co th~s inven~c~on c~n be carr~ed ~ut p~lor ~co ~nd/or ~ub~equent to ~:he 2û 6ep~rati~n of ~ltehyde pr~duet ~cherefrom, it i6 preferred to c~rry out ~ch~ kreatment of ~h~ ~nven~clon ~fte~ ~he rg-moval or ~epara~cior~ of ~ldehyde produE~c. For exampl~, ~t ~ preferred ~o po~i~ic~n ~e ~e~ly ~a~ic ~r~io~ ~xc~ange re61n 7~ed ~fter ithc ~ldehyd produc~ v~por~zor/~epar~cor 14054~1 . _ _ .. .. ..... ... ~_. _ ._ _ __ .. _ . _ ._ . .. , . .. ~_ .. .. .... . . . .

. . .

~ .

~,2 ~ 6.)5 ~3 -~8-~o tha~ what i8 pa~6ed throuE~h the ~ealsly ~as~o ~nion exchan~e resin bed ~.B ~he c8taly8t containing liqu~d rg-cycle residue a~ expl~ined abuve. In addition eo being ~ ~nore convenient and ecc>nomical po61tion ~n ehe react~on 5 sy~tem for ut~lizinE~ Ruch a weakly basic anion exch~nge res~n ~ed, ~t ~ bel~eved that ~uch po~itlonYng minimlzes the amount of the ~ydriti~ form 4f the rhodium cataly~t ~ch i~ to come ~n c~nt~ct with the weakly basic ~nion çx-hange rerin,and lt i~ the hydr~tic fo~m o~E ~che rhodiu~
10 cat~ly6t that i8 believed ~co be the reactive forla whi~h the presence of e.g. ~mine~ ~ay form ~nsolu~le anio~ic rhodium clu~ter~ i5 believed that the hydritie ~
of the rhodium cat~ly~t ~s changed ~o a less react~Lve non-hydridic form a~ ~t passes through the aldehyde product recove~y d~illa~ion ~tage, e.g. vaporizor/~epar~tor, of the hydroformylation process and that th~ le ~ react~ve rhod~um c~taly~t form ~8 l~s~ l~kely to cause proce~s complications when contaceed wlth the weakly ~asic ænion exchange re~n.
In v~ew of the fact that the ~eakly basie ~nio~
exchange re~in treatmen~ ~ne~mpa~6ed here~n ~ de~l~n~d t~
o~t~in ~ de~s~d ~mpr~vement ~n Ae le~s~ m~ni~izing ~he ~e~ree of dec~po~it~on of the os~anophosphite ligand a~-ploy~d ~n the hydroformyl~t~on proce~ ~ver th~t experienced ... ... _ .. _ ., ." . _ ._, . _ . ,_ . _, _ , . . ... _ .. .. . _ . . . ..... ... . . . . . .

' ' . " - ' $~ ~ 5i 5 ~n ehe ~bsence of 8UCh 11 resin ~creatmen't, ~t 1~ ~ppares~c that 6pee~fic ~lue~ csnnot 'be asbitrarily given to 6uch condit~ ons a~ ~e deslgn, number ~nd po~ition~rlg of t~e res~n bed ~n the react~on ~y~tem, temperature and contact 5 time for the treatmer;l~ . Such condi t~on6 sa~e not narrowly crltical and obviou~ly need only be at least suff~ien~
to ob~calr1 ~che ~provement de~ret. For ~stance, ~he ~ub-~ ect $nventio~ con~emplates ehe employmen~ of any conven-t~onal an~on æx~hange resin l~ed des:Lgn through ~hl~ the 10 liquid ~ned~um to ~e trested may ~e pa~ed, ~nd ~ny ~uch ~ed may ~e e~sily removed and/or repl~ced ~15 de~ir~d. 3~ore-over, the num~er of beds employed, ~ well as their posi-eiOning in the reaction system $n~rolved ~ al~ not con-~dered ~bsolutely critical ~nd need ~nly be such that 15 $s s~itable ~co obta~n the result deslred. L~kewl~e, treat-ment conti~ions ~uch as tempera~cure, pre~sure and contact tillnR l!lay al~o vary greatly depending on the wi~he~ oiE ~che opera~cor and ~ny ~uieable co~nb~natlon ~f such c~ndition~
may be employed herein ~o long a the des~red effec~c~veness 20 of t~e treatment i~ achleved . Likewi6e ~ the treatment is preferably carr~ed ou~ under nor~n 1 operating pres~ures within the ~y6te~ employed although higher or lower pres~ures ~ay be employed if desired~ while ehe contac~c ti~2 of the l~quid ~Dedium passing througll the resin bed ~i8 n~r~ally 1405~

:
:

.

LF~ ~) 5i 5 _91~_ only a matter o 8 E!COnd8 .
Of c~ur~e, i~ is to be understood that whlle the Relection of the optimum levels and csndi~ions of ~uch variables ~s diseussed above are dependent upon one'~
experience in the utilization of the ~ub~ect resin treat-ment, only a certa~n ~easure of experimentation should be . ..
neces~ary in order to ascertain those conditions wh~ch are optimum for ~ given situation, For exsmple ~ ~ince the preferred sub~ect in~ention is directed to a c~ntinuous hydroformylation process in which decomposit~on of the organo-pho~phite ligand employed will be prevented and/or minim$zed for as long as possible, and since ~uch decomposition is considered to be accelerated by the build-up of undesirable hydroxy alkyl pho~phonic acld by-product, it is obviously preferred and beneficial eo ha~e the weakly basic anion ex-change resin bed ln place, at the start-up of the hydro-formylation pr~ces~ involved, or in place 800nly thereafter, ~o that the liquid medium to be treated can ~e continuous~y passed through the resin bet, thus prevent~ng any undue build-up of undesisable acld by-product BS di~ussed above.
Of cour~e, if desired, the re6~n bed can be used later on ~n the process to re~ove readily detectable amounts of ~uch hydroxy ~lkyl pho phonic ~cid ~y-product bu~ld-up, although ~u~h ~s a less des~rable way o minimizing decomposition of the or~anDpho~phite l~gand.

-~ .
`~
--.
: ~ .
~, ' '' , .. . .

-91~ ~ 5 Moreover, the diorganophosphite ligands employ-able herein have the added benefit of improved storage stability or shelf-life over that of conventional ~riorgano-phosphi~es, such as trialkylphosphites, e.g. trimethyl phosphi~e, triethylphosphite, and the like, and triarylphos-phi~es e.g. triphenylphosphite, tris (2-biphenyl) phosphite and the like, particularly with regard to moisture sensi-tivi~y and hydrolytic stability.
Thus it should be clear that one of the featured beneficial factors involved in the employment of the di-organo phosphite ligands in this invention, in contrast to that heretofore employed in the prior art, ~s the wide pro-cessing latitude as taught herein tha~ one has in selecting the proper combination of conditions that will be most useful in obtaining or at least beRt approaching a particular de-sired result or need.
- ThUB while it is clear that the rhodium hydro-formylation process of this inven~ion represents a clear technical advanceme~t in the art, it should be noted that some rhodium loss, i.e. precipitation of the rhodium from ~olution, has been found to occur in the continuous liquid recycle hydrofor~ylation proce s of this invention. It i8 believed that such rhodium loss has been caused by high temperatures employed in separating the desired alde-, , _ ~ ~ 3 ~ r~ Cj hyde produc~ from the rhodium c~talyst containing produc~
~olution and ~ha~ such rhodium 10.~5 may be ~educed, if not eliminated, by sepasating ehe tesired aldehyde produce fr~m the rhodiu~. catalyst con~aining produo~ ~olution under re-duced pressure and at low temperatures such as below 130C.~nd more preferably below 110C~
- In addition ~o providing the basic benPfi~s of ca~alyst reactivity and s~ability ln t~e hydroformylation of olefins to aldehyde3 as outlined hereinabove, ~he di-organophosphite ligands of Formula~ ~V) and (VI~ above,as well as the rhodium complex catalyst6 containing such diorganophosphite ligands of Formul~s ~Y) and (VI) above, are considered to be novel compo~itions of mat~er and uniquely ~enefidal in that they may allow for ~he use of higher aldehyde vaporization (separation) temperatures ~n the conti~uous l~qu~d recycle hydroformylati3n process of th~6 invention then heretofore oon~idered preferred.
For in tance~ ~s noted above, ~o~e rhodium 108s has p~e-viously been experienced in some continuous l~qu~d recyele hydroformylaticn proce~s experiments and such loss has been ~t~ributed in part eo ~he ~aporizatlon temperature employed in ~eparat~ng the desired aldehyde produc~ from ~he rhotium caealyst containing prQduct solution. Accordingly, hereto-fore it has ~2en recommendet ehat ~uch ~eparation of the des~red ~lde~yde product be pre~erably conducted at ~elow llO~C. to ~void ~uch rhodium 10~8. It has n~w been ~ur-14054~1 `
",~

, .

~L2 ~4.-C) ~ ~rD

prisingly ound tha~ such separation of the desired aldehyde product ~ay preferably be oonducted at even h-lgher temperatures , e .E~ . up co 120C., and poss~bly even higher, w~en a diorganophosphite ligand of Formulas ~V) 5 or (VI) is employed as witnes~ed by an experiment wherein no rhodium loss was observed over ~ prolonged period of oontinuous hydroformyla~ion and at ~uch a higher preferred aldehyde vaporization (separation) temperature, when methyl [3,3'-di-t-butyl-5,5'odimethoxy-l,l'-biphenyl-2,2'diyl~
phosphite was employed. Of course, the benefits ~ttributable to a continuous process wherein the loss of rhodium ~s pre-vented or at least mini~zed o~er a long period of ti~e and those attri~utable to being able ~o employing a hlgh~r temperature for Qeparating the desired aldehyde product from 15 the catalyst contalning reaction ~olution without the attend-ent drawback of rhodium loss are self-eviden~. The higher the aldehyde eeparation temper~ure emplsyed the more ~ldehyde produc~ one may reeover per given unit of time.
In turn, the ~bility to be able to separa e more aldehyde product more quickly, allows for gr.eater processing control with regard to the build-up of hlgher boiling aldehyde con-den~ation by-produc~ that take pl~ce during ehe hydro-formylation pro~e~s, thus providing ~n effec~i~e means for eli~inatin~ and/or ~inimizing any adver~e build~up of ~uch hlgher boil~ng ~ldehyde conden5ation by-produet6.
ddit$on, the diorganophosphite ligands of ~4~54~

~. ~L2 ~j L~

Fo~nulas (V) and (VI) ~bove and the rhodium comple~
oatalysts con~aining ~uch li~ands are believed to be more ~oluble in the hydroformylation reaction medium than the diorganophosphite compound coualterparts of the ~ame type 5 wherein ~che z2 and Z3 radicals of ~che above for~ula~ are hydrocarbon rsdical~ (e.g. t-butyl~ ~ns~ead of the ether ~i . e . oxy) radicsls , ~uch ~s hydroxy and/or _oR6 ~s de~
fined in ~aid Formulas (V) and (VI) above. ~hile not wishing to be held ~o any theory or mechani t~c discourse, ~uch ligand solubility may be the reason no r~odium loss was observed over a prolonged period of time at an altehyde separation temperature higher shan heretofore recommended as preferred when methyl [3,3'~di-t~bueyl-5,5'-di~etho~y-1,1'-biphenyl-2,2'-diylJ phosphite was employed. Alterna-tively, rhodium complex c~talysts containing a ligand asdefinet in sa~d Formulas (V) and ~VI~ above may undergo ~ome structural change u~der hydrofonmylatlon and/or vaporizer/separat~on condition~ to ~ ~ore 6table or ~oluble rhodium complex due to the ether (i.e. oxy~ radlcals represented ~y z2 and Z3 ~n Formulas (V) and (VI) abvve.
~ oreover, while ~he diorganophosphite ligands of Formulas (V) and (VI) ~bove and the rhodium oomplex catalysts containing ~uch a diorgaTlophosphite ligand ~re considered 'co be no~7el cc~Dpo~itlons s~f ma$tes, lt iB of cour~e ~co lbe 25 under~9tood that ~uch li~ands and c~taly~ts can be readily ~ade 'by the ~ame general procedures 9 disclosed el~ewher2 here~ , or o~Dta~ning diorganophosphlte 1~ gands ~n~ rhodium complex c~ly~t8 ~r~ general. Likewi~e diorganol)hosphite~
1405l~-1 ... . .. _ .. _ . _ . . _ .. _ . _ _ . _ _ _ ~ _ .. _, _ _ . _ .. . _ . .. . .. -- . . . . . . . .
.

~.26~055 -ss-wherein z2 and Z3 of Formulas (V3 and (VI) are hydroxy radicals can be readily prepared by first obtaining the corresponding l~gand wherein z2 and Z3 are an alkoxy (e.g. benzyloxy) radical followed by any co~ventional de-alkylation procedure (eOg. hydrogenolysis3.
A further aspect of this invention can be de-scribed as a catalyst precursor composition consisting essentially of a solubilized Group VIII transition metal diorganophosphite complex precursor catalyst, an organic solvent and free diorganophosphite ligand. Such pre-cursor compositions may be prepared by forming a solution of a Group VIII transition metal starting material, such as a metal oxide, hydride, carbonyl or salt e.g. a nitrate, which may or may not be in complex combination with a di-organophosphite ligand, an organic solvent and a free diorganophosphite ligand as defined here~n. Any suitable Group VIII transitio~ metal starting material may be em-ployed e.g. rhodium dicarbonyl acetylacetonate, Rh203, Rh4 (CO)12, Rh6(CO)16, Rh~N03)3, diorganophosphite rhodium car-bonyl hydrldes, iridium carbo~yl, diorganophosphite iridiumcarbonyl hydrides, osmium halite, chloroosmic acid5 osmium carbonyls, palladium hydride, palladou~ halides, platinic acid, platinous halides, ruthenium carbonyls, as well as other salts of other Group VIII transition metals and car-. .

5~ -_ boxylate~ sf C2-C~ cid~ ~uch ag cob~lt chlorlde~ cobalt nitrate, cobalt ~cetate~ cobalt oc~oatc~ fers~ic ~ce'cate, ferric nitra~e, niclcel fluoride, s~ el ~ulfa~e, palladium ~cetate, o~mium octo~'ce, lridium ~ulf~te, ruthenium nltrate, 5 ant ~che ~lke. Of courl!ie any ~uies~ble ~olven~c may be em-ployed ~uoh ~ e.E!~. those employable ~a *3he carbonyl2~cion process de~ired to ~e carried out. The de~ired c~rbonyla-tion process may of ~ourse al~o dictate the various amoualt~
of metal, ~clvent and ligand present ~n the precur~or 601u-10 t~ on. Carbonyl ~nd diorganopho6phi~e l~E~and~ ~f not ~lreadycomplexed with the inieial Group JIII transitiorl metal may be complexed to the ~etal either prior tD or in ~itu dur~n the carbonyl~tion proeess. By way of illustra~ion, ~inee the preferred t:roup VIII ~ransit~on ~etal ~ ~hodium and 15 ~ince ~he p~eferred carbonylat~on proce~s i~ hydrofo~ylat~on, ehe preferred cataly~ precursor composi~on of ~hi~ inven-tion consi~es cs~ent~slly of ~ ~olubilized shodium carbonyl diorganopho~phi~e acetylacetonate complex precursor catalyst, an osgan$c ~01Ye~t ~nd ~ree diorgarlophosphite l~gant. Such 20 precur~or eomposi~ciorl6 are prepared ~y ~l~2~ing a ~olu~cion of rhodium d~c~r~onyl ~cetylacet~nate. ~n osganic ~olven~c ~md ~ d~organoph~phioce l~gand as define~ here~. The d~-organopho~phi~e read~ly replaces one of g:he dicarl~onyl l$gand~ of ~he rhod~u~-acetyl~c~tonate co~nplex precur~or ~5 t roo~n te~per~tur ~!116 witne~ed ~y the evolut~oal ~f c~rbor .~, : .

~Z~ i5 monoxide gas. This substitution reaction may be facilitated by heating the solution if desired. Any suitable organic solvent in which both the rhodium dicarbonyl acetylacetonate complex precursor and rhodium carbonyl diorganophosphite acetylacetonate complex precursor are soluble can be em-ployed. Accordingly, the amounts of rhodium complex cata].yst precursor, organic solvent and diorganophosphite, as well as their preferred embodiments present in such catalyst pre-cursor compositions may obviously correspond to those amounts employable in the hydroformylation process of this invention and which have already been discussed herein. Ex-perience has shown that the acetylacetonate ligand of the precursor catalyst is replaced after the hydroformylation process has begun with a different ligand, e.g. hydrogen, carbon monoxide or diorganophosphite ligand, to form the active rhodium complex catalyst as explained above. The acetylacetone which is freed from the precursor catalyst under hydroformylation conditions is removed from the re-action medium with the product aldehyde and thus is in no way detrimental to the hydroformylation process. The use of such preferred rhodium complex catalytic precursor com--positions thus provides a simple economical and efficient method for handling the rhodium precursor metal and hydro-formylation start-up.
Finally, the aldehyde products of the hydroformy-D-14,05~-1-C

-~: ;

: :

- :; -ri~ ) l~ti~n proces~ of thi~ ~nventie3n have a wide range of ut~ y th~t 15 well ~nown and docu~ented ~n the pr~os ~rt e.3~. they ~re espec~slly u~eful as start~ng matesial~
for the product~oTI of alcshols and ae$d~.
The fc~llow~n3~ example~ ~re ill~ rat~re of ~che present lnvention and ~re not to be regarded as l~ita-tive. I~c ~s to be uTlder~tood that all of She,parts, per-centages and propc~rtions referred to herein and ~ the appended claims ~re l~y we~ght unless othen~ise ~ndicated.

-~4~541 4q~55 A series of various rhodium complex catalystprecursor solutions consisting essentially of solubilized rhodium carbonyl diorganophosphite acetylacetonate complex precursor catalyst, organic solvent and free diorganophosphite ligand were prepared and employed to hydroformylate trans butene-2 into C5 aldehydes in the following manner.
- Rhodium dicarbonyl acetylacetonate was mixed with sufficient 1,1'-biphenyl-2,2'-diyl(2,6-di-tertiary-butyl-4-methylphenyl) phosphite ligand having the formula u lS ~ / P - o - ~ C~3 ~ t-~u the amount of ligand being varied in each instance as shown in TABLE 1 below) and diluted with sufficient solvent Texanol ~
(2,2,4-trimethyl-1,3~pentadediol monoisobutyrate) to produce the various rhodium catalytic precursor solutions containing the amounts of rhodium and ligand shown in TABLE 1 below.
Each rhodium catalytic precursor solution so prepared was then employed to hydroformylate D-14,054-1-C

.

.;

, ~ 2 ~ 3 trans-butene-2 in a magnetically stirred, 100 ml capacity, stainless steel autoclave which was attached to a gas manifold for introducing gases to the desired partial pressures. The autoclave was also equipped with a pressure calibrator for determining reaction pressure to + 0.01 psia and a platinum resistance thermometer for determining reactor solution temperatures to + O.l~C.. The reactor was heated externally by two 300 Watt heating bands. The reactor solution temperature was controlled by a platinum resistance sensor connected to an external proportional temperature controller for controlling the temperature of the external band heaters.
In each hydroformylation reaction, about 20 milliliters of the rhodium catalytic precursor solution so prepared containing the rhodium complex, the diorganophosphite ligand and the solvent was charged to the autoclave reactor under nitrogen and heated to the reaction temperature employed (as given in TABLE 1 below). The reactor was then vented down to 5 psig. and 5 ml (2.9 grams) of trans-butene-2 introduced into the reactor. Then carbon monoxide and hydrogen (partial pressures given in Table 1) were introduced into the reactor via the gas manifold and the trans-butene-2 so hydroformylated.
D-14,054-1-C

:,., . :

' ~ ' ' s~
- ' 101~ .

The hydro~or~Dylatio~a . eaction rate ~ gr~m ~ole~; pe~ eP p~r Ihour o~ e5 al~lehyde~ pro~uceCI
va6 ~e~errnined ro~a &~quenc~l 5 p6ia. p~e~ure dlrop~
~rl tl~e rea~t~r ll;pa~ning the nor~Lnal operat~ ng pres~ure in ~e reac~or, w~ mole ratio of linear (n-~leralde~yae) to branc~a~ ~2-~ethylbutyrslaehyae~
product wa~ measured 'Dy ga6 ~hro~at~graphy ~nd the re6ullc~ a~re ~iven in ~BLE 1 below, said re~ult being deter~ned ~er albout al 5 to 20 percent ~onver6io~ o~ th~ t~ans-butene-2 6tar~inq ~at~r~

1405~-1 . :, .

r~ r~
-1~2-,. , , ~ , ~ ~ ~ ,, ~ y ~ , I o~
'~ " ~ ~ ~ '' g g~ o ~ g ,, g ~ In ~ ~ ~ o ~ o ~ g ~ o o ~ o ~ ~ ~

l--o C7 s~ ~ o o ~ o o ~ ~ ~ ~ 1~ ~ o ~ ~
.. . p '_ w O ~o g r~ O L~ w O O ~ O ~

~-g ~p C~ o o o ~ o o ~ ~ o o o C~ o ~ ~3 C ~

~ n o ~
'`~
~D

D ID
~ o o ~ ~ ~ o ~ ~ ~ c:~

1~54-1 "' ~ ' ' - ' :
. ., :., .

' ` ':

~.264~`~5 -103 ~

F~MPL~

T~e ~a~e ~roceaure and con~ition~ ~mploy~d in Exar~ple 1 o~ prepar~ng a rt~o~iu~ ~a~lyt~
precur60~ ~olu~ion u~ng rho~iu~ di~arbonyl acetyla~etonate, Texanol ~) ~n~ biphenyl-2 . 2 ' - d iyl - ( 2, 6~ d i - 'c ert -butyl - 4 -methylpherlyl ~
pho~p~ ligana and ~y~rofor~ylating t~an6-~utene 2 v~re repeated liave ~or t~e ~x~ption~ of hydroormyl~tiDg but~ne-l ~n~t~ad of erans-bu~ne-2 an~ u~iny ~bout 15 Irillili~ers of ~he rho!l~um precur~or $olut~on $nst~a~ of 20 mdlliliters ~rld varying t~e r2~0aiu~ ~omple~ cat~ly~t p~ecurcor ~olu~ion6 ~tnd hyarofor~ylation r~a~t~osl ~on~ition~
~own in TABLlE 2 b~lo~. The hydro~or~yla~on ~ea~tion ~te ~n ter~ o ~ran~ ~ole6 lper l~ter p~r ~our o~ C5 al~hy~es ~roauc~ ~s well a6 tlle aole ra~o o linear (D.-~raler~la~rae) to ~ran~he~
(2-1aetllyl~utyr~laehyae) ~I?ro~uct vere ~ete~min~a ~
ttle ~a~e ~nner ~ Exampl~ 1 ~nd the re~ult~ ~re 20 . ~ven i~ TA~L~ 2 ~low.

1405~1 - .:

o ~ ~ w ~
~ q ~ Y ~ in~ .

o o C~
W
~0 3: ~, r tD ~ D~
O U~ D O P 3--O

~ ~ O ~ ~ p~, ~
n g g ~ ~g e P~

a -o C~ o ~ ~ o o ~
U~ ,_ C~ :~tD
n~ 1~
n ~- ~ ~ ~ o ~
. _o~

~: n r c-- ~ pa ~ ~ ~ ~
~n . .
P.
~054-1 , . .
~: f ~,',. -. ' : ' .

~MPLl~3 ~ he ~alae proce~ure an~ ~onaitions e~ployed ~n Exa~nple 1 of preparing ~ rho~ula catalyei~
preour60r ~olution u6iDg ~llodium ~icarbonyl ~cetylace~onate, Te%~nol~ an~ l,l'-biphenyl-2,2~ diyl- (2,6-di-tert-but:yl-4-methylphenyl~
pho~ptlite lig~nd ~nd ~ydroforllnylatinq ~ran6-butene-2 vere ~epeate~, ~ave o~ the exoeption6 of u~ing the ~arious organopho6ph~te liganas ~n~ ~a~ying ~he lQ ~hodau~ ~omplex cat~lys~ pre~uræor solution~ ~n~
hyaroor~ylation rea~tioa condi~ions a~ ~ho~n in ~L~ 3 below. She hyd~ofo~yl~tion reaction r~t~ in term6 o~ gra~ ~ole6 per lite~ per hour of C5 alaehy~e~ (pentanal~) plOau~ea a~ well as ~he ~ole rat~o of l~ne~r (n-YaleraldeSlyde~ to br~nched l2-~et~YlbutYr~l~e~Y~) pr~u~t were det~r~ned ~n t~e 6a~e ~anner ~6 ~ Ex~pl2 1 ~nd the results ~re ~v~n i~ TABLE 3 ~elow.

1~054-1 ..... . . . .. , ~, . _.. . ..... .... .. . ...... . .... . . .

~ ' ..

-106~ ~LZ~L~.~5 Pr~curst~r l.ine~r/
5clut~on ~nd ~eactiDn R~te ~araneh~
~un ~ etion i'-s~m ~olee/ ~ldehyde l~c. ~ ~9~ Conditi~n~ _ L~t~s/H~ur Ml~le R-~o (~
1 ~P - O - ~NT ~b~ 4.7 0.7 ~J , (~Q~ .
2 P-D- B~IS (~) 3.S~ (h"3 O.~g ~D

3 $P-D_ I~N~ (b) 17,E12(i) 0.86 t-BY
e ~u~-O~,~
4 -1 p-o- ~N~ (~) 0.46 O.S6 t-~u ~
t-DU

.. . . .. . ... . ... . ... .. . .. . .. . . ... .

.
... , - . ,: -.
. ~ . - .
.

~2~ 5 /~LE 3 tCOt;TlN~lED) Yre~ur~sDr ~.in~t 501~t~i~n and ReDeti~ c~ Br3nch~d llun Re~c~ion Crl~r~ Mc~es/ Aldehy~e Po. Li~n~ i9) l~ di~$l~ns_ LiterlHour ~blr R~l~iD

5 ~ c3 1.1 (j) ~.o ~, ~ >,~ e~ 2.9 (j) l.o e-Bu

7 ~ >.0~ (~c~ 2.6 (j) 1.0 t-au 3 ~ ~-c-~ ~c~ a.l 0.~3 ~ t-Bu (Cc~ntinued next p~ge) ..... ... . .. . . . ~ . .. . . .

.; . . .

,,: . , ~, . . .. . .

., ,.. , .. : - .:

~.,2~ 5 ABLE 3 ( CON~ UED ) Precussor ~.inear/
5~1ution and Reaction Rate Branched Run Reaction Gra~ Moles/ ~ldehyde Nc. Li~and (9) Conditions Liter/Hour _ Mole Ra-io 9 ~ --P-O-BHT (a~ 4 5 1.12 ~0/

t-llu t ~ U _~o~ D ~
0 ~ P - c-CH3 ~ e~f) 5.4 0.68 ~-D- --~0>--t-3u t-~U--~O~--\
o- CH2CH2CN (e, f~ 0 . 65 0 . 68 t-~lu ~ o/
-~u ~llu t-~u -~O~

12~ /~ - -C~2CH2~ (e ~ o.Sl 0.
~u ~0~ o ~-.,.

(Contirlued next page) 140s4 -l-C-l ~' , ; ~ .: . . . . . . .

- 10~ -TA~ 3 (CONTINUED) PreeuTsor Line2rt Solution and Reaction R~te Branc`,ed Run Reac~ion Gra~ Moles/ Alde~.vde No Li~and (~) Conditions Liter/Hour Molt Ra:io l -au t-Bu ~ \ o 13 ~ / P-0-~H2PPh2 ~e,~9 0.92 0.67 t - B u ~ O

~ -~u ~ / ~ (d) 8.7 0.82 t'-Bu ~ O
-t-9u ~-tu I

t-BU ~ O ~ ~
15 r - ~ /~ - o~ ( d~ 4.0 0.88 ~-au ~ ~ o t ~u 9u t.iU ~ol~_o 16 ~ ~P - ~ ( d ) 7.6 1 1 t.~u ~o c~
t-~u ( C~;1n tinued next page ) 14û54 - 1 - C - 1 '; ~ "` .

.
.; ~ " ~

,, ~, ~, .

~L2 ~
TABL~ 3 ~CONTINUEDl .
(~) Pre~ur60r ~olu~ion and ea~ion ~onaition~:
200 ppm r~od~u~: 6 mole~ aiorganopho6ph~e~
ligand p~r ~ole o~ rhodiu~; reaction t~mperature 100C.: partial pre~sure6; ~2 ~ 20 p6ia., CO 8 20 psia, trans-butene-2 ~ 50 ~ ~ol~
(b3 Preoursos ~oluSion and re~etion condition6:
200 pp~ rhodiu~; 10 ~ole6 dlorganopho6p~ite ligand per ~ole of rhodium; r~action temperature 105CC.: partial pre66ure6,-~2 ~ 30 p6ia, CO
30 p6ia, tran~-butene-2 ~ 50 ~ ~oles.
(c~ PLe~ur60r ~olution ~nd rea~on con~itio~:
230 ppm r~od~u~ 3 mole6 diorganopho6phite ligand per ~ole of zhodium: r~ac~ion te~perature 100~C.: part~al pre~ur~ 2 ~ 20 p~ia, CO G
~0 p6ia, ~rans-butene-2 50 2 ~01~8. Usea 15 millili~er ~Oaiu~ caealytic pr~cur60r ~olution ~n6teaa o 20 ~illilit~r6.
(d) Precur60r ~olutio~ an~ reaction condition~:
200 pp~ rhodiu~: 10 ~01~8 ~iorgano-pho~phite ligand per ~ol~ o~ rhodium: ~action te~perature 105C.: partial pre66ure~, H2 ~ 30 p~i~., eo -30 ~6~a, tran~-~utene-Z ~ SO m ~ole6. U6ed lS
~illilit~r6 rhodiu~ catalyti~ precur~o~ 601u~0n ~nstead of 20 ~ ter~.
~e~ precurBo~ 501utio~ ana reaction condlt~o~z:
~00 pp~ ~hodiu~ ole~ ~iorganophosp~ite li~and per ~ole of rbod~u~; ~e~ction tempe~ature 100C; parti21 pre6~ure6, H2 ~ 20 psi~, CO ~
20 p6ia, ~ran~-~ut~ne-2 ~ SO ~ ~ole~. U~ed lS
llter~ r~od~um ca~alytic precur60r 601ut~0n 4n6tead o~ ZO ~ r~.
~) Used Rh~(CO) 2 ~ rhodium ~recursor ln~te~d of rhodlu~ d~carbo~yl acetylacetonat~.
(g~ ~H~ ~ ~,6-ai-ter~-bu~yl ~-~e~hylp~2nyl t-Bu ~ ter~ry-butyl r~fl~c~l ~h ~ nyl (Co~tinued next page3 1~0~4-1 .... . ,. ._ _ .. . . _., . . .. .... ,... _ . . . .. . .. . .

~BIE 3 ~a~D) (h) A~tiv~ty o~ thi~ comparativ~ triorganopho6pb~t~
promote~ c~taly~ rapidly de~l~ned uDder cont~nuou6 hydro~ormylatio~ ~See Exa~ple 5).
~ Aetivlty of t~iB ~iorqanopho~p~ite promotea ca~aly~ de~linea very rapidly in a ~o~nuou~
glass reac~or e~peri~en~ si~ r ~o tb~
de6crlbe~ in Exa~pl~ 5.
~3) ~he actiYity of the~e ~iorganopho6phite pro~o~ed catalyst~ was ~harply ~nhibited when t~e hydrofor~yl~ion ~a6 carr~ea oue u ing ~ore ~an 3 ~ole equiYalent6 of ligan~ per ~ole of rhvdiu~.

14~54-1 ... . . . .. . . . ... . ... ... .. .. .... .. . .. .

-`

(~
~12_ ~he ~ame procedur~ a~d eonaition~ ~ploy~a ~n Exampl~ 1 of ~Lepar~n~ 3 rho~ium c~talytic ~reour~cr ~olu~on u~ ho~iu~ ~ioarbo~yl ~cetylacetonate, Texanol ~ an~ l,l'-biphe~yl-2,2'~diyl-(2,6-di-tert-butyl-4-methylphenyl)phosph-ite li~and ana ~ydrofor~yl~ting ~ran~-butene-2 were ~epeatea, ~DVe ~or t~e exceptions of e~ploying variou6 ~ifferent olefin6 ~ the 6tarting 10 ~y~rofor~ylation ~ater~l and ~arying the rhodium comple~ c~talyst ~reeuL~or ~olution6 ~nfl hydrofor~ylDtion reac~ion conditions as ~hovn ~n TA~LE 4 below. T~e ~ydrofor~ylation r~action rat~ in ~er~ of ~r~m oole6 per l~ter per ~our of aldehyde 15 pro~ueed ~ well a6 ~he ~ol~ ratio of linear alaehyd~
~o ~ran~ed alae~y~e proDuct ~ere ~eter~inea a6 i~
~xample 1 ~nd the re~ults ~r~ gi~on ~n T~L~ ~ ~elow.

~405~-1 .. .. .... . . ., . . . . .. _ . _ . . .. . . . . . .. .. ... . . . . . .
~ . . .
:. .; ' ~. ~ , 5 r~

qc ~ 9 ~ ~ D n ~
~ o ~ 1- IJ "
r ~ z- O

~r o O O D C7 o 1~ l ~ ~ _ 1~ r O O ~ O O O O O O O ~

o o o o s~ o o ~ o o @, O
o o o C~ ~ g ~ ~

~ 3 ~ ~ ~ .

g o o ~, o o o ~ o o ,;

r o ; 13 n o I ~ ~ ~ a ~ ~ ~
--O O
o ~ J ~ ~ s b ~r . _ O ~ ~_ _ I~

1~54-1 . , , .. .. , . . . . _ .. . .. .. . . .

-114 ~ i; L~ ~ S

r ~ v ~
O ~ ~1 0 ~ 9 Q ~ C~ O ~: n o ~D 11~ .C ~ ID ~ r _ n ~ ~ b ~ b P- r~ 111 p~U :~
,, ~ " 1, ~ ' ~ '' & ~ ~ ~
C o C~ ~ o ~ C C ~
n n ~ r r n n ~ O
1 o ~ ~ n r~ ~ w "C D
~W U O ~- O n ~ D ~ _ S~ O O D~ _ ~
b ~ e ~ C o O E~

n o o D r b~ ~ C ~ O O ~ J _ ~ ' D &. ~ O O O ~ ~ C
~ _ ~ o C ~ o :J ~
_ o ._ ~, r~
n O ::1 O ~ ~_ W ~ ~1 O V~ ~ O ~
O C; ~ ~ ~ ~ ~1 ~I c~ O V' ~ ~ A
O ~ n ! ~ ~ ~ _ ~
n o ~ O N g ~ ~ O 1~ O ka r O

e e~ U~
O o ~ ~ o O l;

z:r ~ r n ~
O ~ b ~n O ~ d ~ O C
S~

n _ n ~

~4054-~

... .. . .
:
:

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6~

E~AMPL~_~

~he lon~ term eat~ly6t ~t~billt~ o l,1'-bi- ¦
pheny~ 2~-diy~ ert-buty~ ~eth~lphenyl) ~bosphite gthe a~ ocganopho6ph~te ligan~ of ~xa~ple 1 ~romoted r~o~iu~ r~t~y~t a~ ~o~pa~e~ to ~iphenyl(2,6-di-t2rt-butyl-~ thylp~enyl)phcsphite (the triorganophosphite ligand of Run ~o. 2 in Table 3 ~bove~ ~ro~ot~d rhoaiu~ c~aly~t was ~et~r~inet $~
~he ~ollowing ~n~r.

The~e lonq ~e~ taly~t ~tab~ y experiment6 ver~ ~ondu~ted by hyarofor~glat~ng ~rans-buten@-2 ~ ~ ql~S6 ~oac~or ~D a ~ontinuoug s~n~le pa6~ ~o~e. T~e ~etor ~on6i~ted o~ a t~ee ounc~.pr~66ure ~o~le 6u~mersed ~n an oil bae~
91a66 ron~ ~or YieYi~g. In ~aeh experi~ent ~bou~ 20 ~L ~ ~ fre6hly p~par~a rhcdiu~ ca~Jlyti~ ~rccur~or ~olut~on w~ c~arge~ to t~e t~actor Wit~ ~ ~y~iu~
~gt~r purg~ng t~ ~y6te~ Y~t~ ~it~o~en. ~DCh ~sg~ur~r ~olutio~ eont~ne~ ~bout 200 ~p~ rh~um intro~ue~ a~ rhoaiu~ ~earbo~yl c~tylace~on~te, ~bout 5 ~ole ~quivsl~nts of ~bo~p~Qrous ligan~ per ~ole o~ r~o~u~ ae~ a~ ~-val~r~ hyae ~ri~er ol~at. ~ter elo~iag the ~eactor, ~e ~y6t~
g~ u~a vi~ t~og~ ~n~ t~e oil ~tb a~os~l .

:: :

{ ~L2~4 fO~j heate~ to furni6~ t21e de~ired hyd~oormylat~on 2eacti on ~empecatur~ . ~he hyd~oor~ylat~on reac'~ion .
~n eac~ exper;ment ~a~ conducte~ ~t ~ ~o~al ga6 ~re6~u~e of about i65 p6ig. u~ing aboul: 30 p6ia.
hydrogen, ~bout 24 p6i~1. tran6-but~ne-2 and agout 30 t psia. car~orl monoxide, ~he reloainaer being n~trogen.
The flows of ~he feed ga6e~ ~carbon ~onoxide, ~yd~ogen ~nd propylene) ~2re ~on~olled individually with ~aass flo~ meter~ and the feed ~a~e~ disper~ed into the precur~or solutio~ tainless steel sparqer6. The unr~acted portion of ~he feed sla~es ~tr~pped out the p~oduct C5 aldehyae~ and the outlet ga6 was a~alyzed ~o~ C5 aldehyde product~
peciodically ov~r fouc ~ay6 of ~ontinuous ope~2ltion at the r~ac~ion tempe~atuEes given in ~ABL~ 5 ~elow. The ~ve~age ~eaction rate6 ~or ~c~
experiment ~ term6 of g~am ~ole~ per lite~ p~r ~ou~
of product C5 ~ldehydes a~ ~ell as th~
n-Yaleraldehyd~ to 2-~ethylbuty~aldehyae proauc~
~atio ~o~ each aay o operat~on a~e given in T~BL~ 5 l~elow.

14~54 -1 ~ . ~ 5" ~ _ 11 D ~ ~ ~ r ~I j O C ~ ~ ~ o .. ~
~ o r ~ D

::1 b e ^
O ' o ~ ~o ~ ~ ~

~ o o e~ o o o o o o o ~ r ,~

C ~ O O o ~ C ~ ~ g S ~

~ ~ ~ r r ~ y ~ 5 D ~,~ r a ~ .. u ~ J ~ ~ ~

n ~c g c r~ a~
n . D 111 1~
o ~ D ~ O O
~ b ~r . 3_ _ O O O ~ O ~ 1 e ~
~ v ~ ~D

14~54- l . .
' - :' .

', .

s The above da-ta show that the diorganophosphite ligand [l,l'-biphenyl-2,2'-diyl-(2, 6-di-tert-butyl-4-methylphenyl)phosphite] of this invention maintained catalytic activity after over four days of continuous hydroformylation whereas the comparative triorganophosphite ligand [diphenyl(2, 6-di-tert-butyl-4-methylphenyl)phosphite] promoted catalyst, which is not of this invention, lost about 75% of its catalytic activity over the same period of time. Analysis of the outlet gas composition indicated that total (equilibrium) isomerization of the pure butene-2 feed was achieved when the diorganophosphite (Ligand A) was employed. The outlet butene-l concentration (of the total butenes in the outlet) approximates the calculated thermod~namic equilibrium value of 5.77 mole percent of butene-l a~ 105C and a total pressure of 175 psia. The triorganophosphite (Ligand B) showed an ability to iso-merize butene-2, but this rapidly diminished over the period of the test.

D-14,054-1-C

- : :

, ~6~0~$
-11~

~LE 6 ~ ~er~ es of variou~ ~hodiu~ ~omplex ~ae~ly~t preCUr60r 601utions con~i~ti~g essentially of ~o1ubilized rhodiula ~arbonyl ~ior~anophospbit~
acetylaceeonate corllpl~x precur60r cataly~t~ orga~i~
solvene anfl ~Eree disrqanopbospl~ite liga~d wero prepared a~a employea to byd~o~o~yla~e i~obutyl~ne into ~lde~yae ia the followiT~g manner.

~hodiu~ dic~rbonyl acetylacetonate was ~ixed with ~ ~uf~ici~t amount of dliorganopho6~lite liqand ana ~ilut~d w~th ~u~ficient solYent, ~exanol~ o produce ~ e~odiu~ catalyt~ precur~or golu~ion eontaiElinq abou~ 150 pp~ of rhodium calculated a~
f~ etal an~ a~out 10 ~ole equivalents o diorqanopho6phie~ ligand per aole of rbodium. The ligand bei~g ~raried a~ ~iven i~ T~LE 6 belo~.

a~h hydrof o~layl~tion reaotion. ~bout 20 nilliliter~; o~ th~ rhodiu~ c~tDly~ci~ pr~ur60r ~0 ~olutio~ ~o prep~r~ wa6 ~har~d ~1~ the ~uto~la~e reaotor l~escr~bea io E~ar~ple 1 under nit~ogen and heate~ to ~h~ r~a~tio~ temp~r~cure 2~nployed ~ ve 1~ TABLE 6 ~lo~). Tbe ~acto~ ~a~ then pr~6~u~ized eo 10 ~ . v~th ~i'cro~e~l ~n~ 5 3aI. ~out 3 . ~ graal6 1~05~1 .. .. ... .. . .. ... ... . . . ,. ~ . .. , . . -: - :
,, .~ .
....
: . - ~- .. , . ~ . .
:.. : .. .
:. : - . .
.i ..

~2~ 3S

of isobutylene) in~roduced into the reac~or. ~hen about 3~ p~ia hy~roge~ ana about 30 p~iD. 0~
syn ga6 ~ix~ure (15 p~ia. 9f carbon ~onoxide ~n~ 15 p6ia of ~ydrogen) wele ~ntroduced into the reactor Yia the ga6 ~an~~1d and t~e ~60butylene ~o ~ydrofor~ylate~.

~Q hydro or~ylation reaot~on rate in gram ~ole6 per l~ter per ~our o~ alaehyae produccd . (3-~e~hylbutyraldehyde being ~he only aldehyde product) wa6 aeter~inea ro~ ~equent~al 5 ~sia.
pre6~ure ~rop~ iD t~e rea~tor. 6panning the nomi~al operating pres6ure ~ the reaotor and the re6ults are given ~n TABLE 6 below. 6aid re6ult6 ~ei~g ~eter~ised up to abou~ A 30 per~ent co~Yer6ion of the ~obutylene ~tarting ~at@ri~l.

~os~-l . ... . . . . . _ . .. ... . . .. . ~ . .. .. . . . . .

~ 6~ 5S

~BLE 6 Reac~tion Rate ~un gram moles/
No. Li2a~d Temp. C Liter/~r.

~ u C~ ~0~
~ ~ CH3 1~ 5 O . 0 7 a~ ~ o ~--u ~.~u CH~ ~ O CH~
~ 3 . 4 2 CH~ --~ CH~
~U

.~u CH3 ~0 115 1. 80 CH~ ~-- O

4 do . loo 1 . 50 X

- , .
, .
,;. .- , . ..
. . .

.
., . .: :
.
, L",9C O Sj S

TABLE 6 (contlnued) ReactiDn Rate gr~un moles/
Rlm No. Ligand Temp, C Liter/Hr.
~ . ~= . ~

S do. B5 1.15 t.~u CH~ ~ O
6 C~H~ \r - ~ Cl 100 1.3B
CH~ ~ O
.

CV~
CH~
O ~ CH ~ l o o 2 . 15 ~ O CH~

r.lc

8 C H ~ $ p o ~ ¦ 1 o o 1 4 9 c~ _~ o ~C

1~054 - 1 - C - 1 `-. , :

- -.

'' ~
~': . :
- : , . , 5~

6 (contin~ed) i?eaction Rate gr~m mol es Run ?~o. MC Liqand TemD. C Liter/Hr.

9 ~"~ \p_ O ~c~ 100 1.92 CN~ ~ C
NC

~r c~) 100 O.Oj t-~u CN~ ~ O loo 1 . 56 tjN~ r - O-- CN~
CU~o/
u C~
12 1 . 100 0 . 3~

~ O )--\ CU
CN~ ~ O ~

j~g 1405~- 1 - C - 1 . : , - - ::: ,`
`, ,~: . . : ~, -: -: - , , . -: , ::: ~. , .:
~ '- ' .
,, ~ :: `
: ~:
:, .

- 124 _ TABL 6 (continued) Re~c~t on Rate Rur~ No. .~ emP. ~C Liter/~r.

13 / ~> O.B6 CH~ ~ O

14 (~ \ ~u 100 3.2 a~ ~ o\

lB ~_ r-- o _~ 100 0. 40 C ~ t--O ~ C H ~
t r~, 100 0. 22 CH3~ OH

1405~ C - 1 :', ' `

:, .

4~3 TABLE 6 (continued~
Reaction Rate cyram mc)les/
Run No. Liclan~ Temp. C. Liter/~r.

Cl ~-0 ~,~q 7 C H 2 ~ 1 0 0 0 . 0 5 C~ I / ~-...
C~ cl , 18 ~ \ t-~ 100 1.29 j~2 ; ~ CH~
-tt~
Cl~

1 9 CH~ ~ o~ CH~ 1 00 1 . 2 5 ~n~ t-- O--CH$~CH~
a~ a~

do. 115 0. 87 T~BLE 6 (continued) gr~m ~oles/
~un Nc. Liqand Temp. C. Liter~Hr.
~u t.~u ~o\ ~ 100 2.99 t-Du ~ O
~.~u 22 ~-~U 100 3.30 ~-~u ~o ~u _ . _ t-Bu = Tertiary-butyl radical MC ~ l-Methylcyclohexyl radical 1~054 - 1 - C - 1 , ;

`: ~ ` ` ' :' s E~ .e 7 ~ ~eri~ o~ ~ariou6 rhoaiu~ co~plex ~ataly~
precutsor ~olu~ions con~i~ti~g essentially o ~olubili2~d r~oa~u~ carbonyl ~ior~anopho~phite ~ceeylacetonat~ ~o~plex ~recur~or catalyst, organic solv~n~ and ~ree ~$ac~anopho6phite ligand were prepare~ ana employed to hydLoor~yl~te tran6-butene-2 i~to ~5 ~ldehydes i~ t~e followi~g ~anne~.

Rho~iu~ dicarbonyl ae~tylaceton2te wa6 ~ixed ~ith ~ ~u~fici~t ~oun~ o~ rganopho6phite ligand ~nd ailut~d with ~uffic~ent ~olv~t~
Texanol ~ , to ~roduce ~ rhod$u~ ca~alyt~
precur60E ~ol~tio~ eont~ining ~bou~ 250 ~p~ o ~odiuD ~alculate~ r~e ~etal ~na about 10 ~ol~
equ~val~t6 of ~or~anopho6ph~te ligand pe~ ~ole of ~hod~u~. T~ ligan~ Yari~ B~ ~Yen ~ TABLE 7 below.

~ c~ ~yaroo~yl~t~o~ rea~o~ out 15 ~ t~e r~o~lu~ ~at~lytic ~recur~or ~olutio~ ~o ~r~Ar~ ~aR cbarged ~o ~h~ ~utoclave r~actor u~r ~trogon ~nd ~atod to ~he ~yaroorayl~tio~ ~aet~oD t~pe ~tur~ o~ lOO'C. T~e 1~0~1 _ _, . .. ...
". ~

; `, ~:

`` ~2~5S

-12~

reactor wa6 ~en ~en~ed ~own to 5 p~ig. ana 5 ~o ~2.9 ~ra~6~ o~ ~he olefin e~ploye~ (~6 g~n ~n S~ 7 ~elo~) introdueed lnto t~e reactor. Then about 90 p~ia. o~ yn ga~ ~ixture ~45 p~a. of carbon ~onoxiae ~nd ~5 p~ia of hydrogen) were in~ro~uc~d ~to ~he react~r Yi~ t~e ga6 ~anifold and ~he ole~in so hydroformylate~.

~he hydro~ormyla~io~ reac~lo~ rate in ~ram ~oles per lit~r per ~our o C5 aldehydes produc~a 0 wa6 aetermine~ fEO~ B~quentlal 5 p61a. ~re6sure drops in ~he reac~or ~anning the no~inal oper~
~r~sure in the r~actor, ~hile ~ole ratio o l~ne~r (n-valeraldehy~e) to branche~ ~2-~ethylbutyraldehy~e) product ~as ~ea~ure~ by ga~ chromatGgraphy ~n~ the 1~ results are ~ n ~n TA~L~ 7 b~low, said resulSs being ~et~r~ t~r ~bout ~ 5 to 20 pereent ~o~*ræion o~ t~ trans-butene-2 ~tarting material.

~4~4-1 . . . . . .. _ _, _ _ _ . _ _ . _ . _ _ _ . .. _. .. ... . . .. . . .. .. . .... . . . .

." ~ ' .

s ~A3LE 7 Peaetion Linear/
~te Branehed Run Gram/Moles Aldehyde No. Liqand /Liter/~our Mole Ratio ~-~u Ch~ ~ O~

~-~u t-~u ~h 3 ~ o ~ 2 . 6 o . 7 2 CH --~ 0/ ~

7.0 ~.62 Ch~ ~ O
3 'H2 ' . --~
Ch~ ~ O

8.1 0.6, ~u. F - O--~Cl CH3 ~r o t G~

~4054 - 1 - C -:

4(~

TABLE 7 (continued) Run Reaction Linear/
~ate Branched _- _ Llgand /Liter~Hos Alaehyde c~

'~ o\ ~f3 C~ o/ ~C~3 ~ C~
c~ 12.0 0.78 ~ ~P--r3 - ~ CH 12 0.93 CR~

7 ~, \,~

1. 9 1. ' 1~054 - 1 - C - l .. ,: ' -: .

. .

~6~ ~55 T~3L~ 7 ~continued) Reaction Linear/
Rate ~ranched Run GraTr. Moles Aldehyde No. Liqand _ /Liter~lour Mol~ Ratlo ~-~u cu~O\
8 'ql ~ - c~-- Ch~
~ s . s o . ~ 7 -t ~u 9 ~ .69 t-Bu, ter~ciary-but;~l radicaI

, ~, E~ PL~_ ~

~ h~ reac~ ty o~ ~ariou6 aiorganophosp~te ~Ind trlo~ganopho~p~ e îigana~ to~ara6 aldellyde w~
determined ~6 ~Eolle~6.

A.~erie~ of pho~phi~ce-~ldehyde 601UtiO~16 were prepared, each iT~ ~he sa~e ~anner, by ~ucce~ively char~in~, ~o an oven aried ~150~C. or one ~our) 2.0-oz. n~o~neck bo~:tle vhicIl had cool~a to ambient temp~rature i~ ~ ary box ana w2~h ~ontainea ~ aqn~t~c ~ir2ing ~ar, about ~.5 ~ ~oles of ~ho6p~te l~ana, a~out 3.0 al mole~ of t~ipllenyl pho6phine oxide, a6 a pho~phoru~ eontaining internal 6tandara, 2n~ ficient amou~t of a mixtur~ o~
~-valeralaellya~ and ~-me~hylbutyralae21yde ~co o~tai~
co~b~ned weigllt o~ 30 ~ra~6 ~or eac~ ~olution. The bottle wa~ the~ ~ealea ~it~ ~ ~eru~ opper,, re~o-ved ~o~ e ary bo~ ~In~ ~la~e~ o~ ~ ~agrlet~G stirrer ~mbient te~peratu~e une~ olu~o}l was obt~e~.
- T~ bottle wa~ ~be~ returnea to ~he ~y box ~o remain . 20 unaer ~itroge~ at~o~plle~e ~t a~bi~nt te~perature.
Perio~icaaly 3 m~ iter ~ople6 o ~ach ~olution - were ~r~w~ e ~llo~ph~ onc~ntratio~ an~lyz by ~hoæ~horua;-31 N2~ ~pa~c~rog~opy. Tbe ~xterl~ o~

1~1a05~ -. .. .... . . ... . . . .

.. . .
, ~3~

p~osp~ e ~e~ompo6itlo~ (~a6 a~ resull: of ~eacti~g Wi~t ~ldehyde) wa6 qualitatively determin2~ from t~e ~el~t~Ye inten~iei~s of the 31p NMR resonances ~orre6pondi~ ~o those of t~e pure ~hospll; te lig~n~
elDployed a~d ~che internal ~t~ndara. The pho~pl~t~
ligand6 ~mployed ~nd ~e test re~ult~ are gi~Je~-in T~L~ 8 below.

.

_134 ~
~Z6L~C3~S
~ABLE 8 ___ PJo. ~i~= Exten~ of PhDsphite Decompc~sition Day Day Day Day 4 7 llD
1- (~ o ~3p Some All _ _ 2. ( _ tH - CH~O )3P Some MDSt - -3~ O ~P hone SomeMDst . Al l Ph P -- 0~> All ~ p--O ~H3 S~m~ MDst - _ 6. ~ ~ P-- ~1 hDne None hDne None t-Bu ~ tert~ary bu~yl radical Ph ~ Phenyl ratical ~.2~ )5 EXAMPL~

The re~t~ity of Yarisus pho6p~ite ligand~
toward6 al~e~yae a~ high tem~er~tur~ were determa~ed ~ ~ollo~0 A ser~es o pho&phit~-aldehyde ~olution~
were prepared, ~ach i~ e~ sa~e ~anner by ~ucce6sively char~i~g ~ 12~oz. Fi~cher-Porter bo~tle containing a ~agneti~ ~tirring bar, ~ith about 0.00 ~01~6 of pho~phite liganfl, about 0.~075 ~ole~ o bar~u~ carbonate, about 0.002~ ~ole~ of bariu~
vale~ate (the bar~um s~lt6 being ~mployed ~o ma;ntain neutr~ y o~ ~e solutio~) a~d ~ ~uffici~nt a~ount of a ~i~ture of ~-~aleraldehyde and Z-~etbyl~utyral~e~y~e eo obt~in ~ combi~@d weigh~ 9 100 gr~m6 or ~a~h ~olut~o~. T~e ~ot~le wa~ ~aled wit~ a pre~6ure ~p Qodified eo Gontai~ a ~e~hanical ~tirre~ ~na g~ purging and ~a~pli~y valYe~ ana ins~rt~ o ~ 6t~nl~6 ~te~l ~ire ~es~ protece~e ~o~er~g. The bottle ~ontain~n~ the phofiph~te-31~e~y~ ~olutao~ wa6 t~en purged wi~
n~troge~ ~n~ ~bou~ 50 p6~g nitrsgen ~llove~ to teaa~ aeb ~olue~o~ va6 the~ ~tirr~ ~or one bour a~b~en~ t~p~r~SUE~. ~ach pho6phit~ n~
~olution w~ e~ h~tea ~y placiny ~he botSlo lnto ~r~ea~ 0C) ~ con~ h. Period~c~lly 1~054-1 - .

.. .. .,: .. .

~IL26 6ample~ of ~ac~l ~olution wete vithdravn anfl th~
pho6phite eoncentratlon de~eemined quantitat~vely ~y high pr~6ure ~i~uid ~hromatography. ~he pho~phit~
ligand6 employe~ and extent of pho~p)lite deco:apo6it~0n ~ a ~e6ult of rea~ting w~th tlle aldehyde) ~r~ ~ven ~n 'rABLE!: ~ b*low.

1~05~-l .
~

1 3 7 r - -~ABLE g Reaction Percen~
~ime Ligand Run ~i~and ~ (hrs~ com~osed )3P ~60 23.5 44 Ph 2 ~ ~ P--0~SH3 160 21 13 ~p 0 ~CH3 160 ~

- t-~u t-~u~ ~ p--0--Pn 160 21 4 t-~lJ~0 t-B~I

t-Bu CB3~ ~ p E~ ~h 160 21 4 ~:H3~O~
~u ~ ., : . . . .

. ' . ,: , , :

~2~355 W~38 l~BLE g (CûN~

!Reat~i~n Percent Run Ligand 7emp lrime Ligand Mo ~ thr53 Dec~mp~s~d k __ ~ u 6 ~H2 Q\~o --~CH16û 25 0.5 ~ t~u 3 t-Bu ~ tertiary butyl radical Ph - Phenyl radical 1~5~-1 .

, .. . ..

:: :
.
. ,, ...

.: . . ~ .... -.. .

--,.39 -~7~MPLE lQ

In ~ cDntiEIuou~ cataly~ uid re~ycle ~anner. ~ ~ix~ ol~in ~arting ~at~rial of bu~erle-l ~n~ bu~enç-~ ~el6 ~na tr~n~) Ya~ ~ydrofor~ylat~d for six day~ followea by tbe continuou6 ~ataly6t l~qu~a recycle hydroforlDylation oî butene-l a~ ~E011011~6~

T~e li~ui~ recy~le reactor 6y6~ empl~yed conta~ned ~o 2 . 8 liter ~;~alrl1~66 ~teel 6tirred ~ank reactoE6, conne~e~ in ~erie6, ~a~ contain~n~ zl

10 ~ertically ~oun~efl ~gitator Dna ~ eircular ~ubular ~parg~r ne~r ~he bottom of ~e Pea~tor for ~ee~ing ~che olefin ~nd/or ~yn gas. ~e ~parqer ~osnta~nea a plural~y o holes Df 6uffi~ient ~ize to provide the de~irel~ ~a~ ~low ~to tbe liqu~l~ body. R~ctor 1 15 oontaine~ ~ sllioo~e oil ~hQll ~s ~an6 of bringing the oontent6 o ~h@ rea~tor~ up to r~action ~e~nperatur~ vhile the r~ot~o~ ~olution ~a ~eactor 2 W;96 ~eate~ by ~ lectric~l he2ter. 80t~ ~aceor~
eonta~e~ ~t~r~al ~oli~ ~oil~ ~or ~ontroll~n~ t~e reac'cio~ te~per~tur~. aea~tor6 1 Dl~l!l 2 s~ere conneotea ~ .n@ to tr~nsfer ~ny unrea~t~ 0D~e~
~ro~ a~tor 1 ~o r~actor 2 ~na vere fsr~er ~o~n~c~ a l~e ~o ~at ~a portio~ o ~e l~qui~
~s~ct~on ~;olut~o~ eont~in~nq alde~y~e pro~uct an~
e~ly~t ~ro~ CtOF 1 I:oula b~ pu~pea ~n~o ~a~tsr Z
~ihere~n the unre~ct~d ~lefin of react~r 1 i~ furcher hydrofoa~mylaeed in r~sctor 2.
~ll0~4 ^1 ~ . . . . .. .. . _ ....... ... .... . , . . . ..... . . . . .. _ . . .. . . . . .
,.

:, ~ .. .
.
::, . ..
.. ~ ':' :
.
. .

-~o -lEach rea~tor al~o ~:on~airlea ~ pneuma~c~c li~ui~
level controller ~or ~utomati~ oon~rol o ~e liquid level~ ~n t~le reac~or6. ~eac~os 1 furt~er containedl ~ line for in~rodu~ia~ t~e ole~in an~ ~y~ ga~ ~hroug~
5 the sparger, while 3llake up ~yn gas wac addea ~co ~:eactor 2 ~ia t~e 6am~ tran6fer line ca~rying t~e unreaoted gase6 rom reactor 1. P~eaotor 2 al~o containea a blow-of ~ent o~ removal o ~he unreactea ga~es. A line from the botto~ o~ reaetoÆ 2 10 was ~onrlecee~ to e~e top o ~ Yaporizer 60 that ~ortion of t21e liqui~ zea~tio~: ~olutioll coul~ be pumpea rom rea~tor 2 to 2he ~raporizeE. Vaporizea alaehyde ~a~ ~i6engaged fro~ t~e aon-volat~li2~d compone~t6 of the 1 iguia rea~tion ~olution in ~Ae 15 Slas-:liquid ~eparator lpart of the vaporiz~r. T~e remainiDg ~on-volatil~zea ~ataly~ containing liquid reactiorl 601utio~ wa~ pu~nped t~roug~ ~ recycle line back into r~actor 1. The ~ecycle l~ne al~o Gontained a pneur~ati~ 11quia l~vel controll~r. Tlle ~aporized Dldehyde 20 p~oduct va~ ~a~ea into ~ vater~cooled conden~er, liQui~i2a and eollecte~ i~ a product rece~er.

14 OS~ -1 . , . . ...... .. . . _ ... .. . ... . . . . . .

..

.
' ~

126~H~5 -l 41-The ~yd~ofor~ylation r~act~on ~a~ ~onducted by ~arg~nq about 0.7~9 ll~er~ of a ~ealy~
precur60r ~olutio~ of rbo~iu~ di~arbo~yl acetylace~onat~ ~bout 200 ~p~ rhodium)~ ~bout 1.0 wt. ~ 1,l'~biphenyl-2,2'-d~yl-(2,6-di tert-but,vl-4 -~ethylphenyV phosp~it~ an~ ~about 10 ~ole eguiYalent6 o~ l~gand per ~ole of zh~diu~3, a~ou~ 0.5 vt. ~ 2~6-~ ert-butyl~ ethylphenol ~ ~n ~nt~sxiaant, and ~bouS ~B.5 ~t. ~ of C5 aldehyde (abou~ 68.5 ~t ~ ~sler~laehy~ an~ about 30 vt ~
Yal~ralaeby~e ~ri~er) ~6 ~olv~t to r~c~or 1. about 0.96 l~ters o the ~me c~taly~t precur~or solution va6 cha~ge~ ~o r@~ctor 2. ~e reactor ~y6tem va~
t~en purge~ ~ith nitrog~n to ~e~ove any oxy~en pre6ent. Then ~b~ut 100 p8i9. n~troqen pres~uxe wa~ -put on b~th reac~o~6 ana ~e re~t~rc be~e~d to ebe~r reaction te~per~ture6 ~i~ea i~ TABLE 10 belov.
Coll~rOllea ~10~6 o ~uri~iee hydrogen, ~arbon Donox~de a~a ~ ~ixea ole~ tarting ~a~erinl of b~ten~-l an~ ~utcne-2 t~i6 ~nd tr~n~3 ~ere fed ~hr~ug~ the ~p~rge ~ato t~e botto~ o~ roa~tor 1 and t~ se~eeo~ pr~66ur~ tnGrea6e~ tD ~he operat~ng 6ur~ ~iYe~ ~n TAB~ 10 belov. ~ t~e liquid ~vel ~a r~a~tor 1 ~ar~a to ~ncrc~6~ ~6 ~ re~ult of l~u~ hy~e ~ro~uct ~or~a~io~ ~ pDrt~on ~ t~e 14~5~_~
.

.

. ' - ~
' ' -1~2--l~quid react~on solutioa o~ reac~or 1 wa6 ~u~ped ~nto ~ea~tor 2 through a line into the top of r~actor ~ at ~ ~a~e 6uf f i~ien~ ~o ~ain~in a ~on~an~
liQui~ level ~n reactot 1. The ~r~6ur~ ~f reaetor 2 ~ncrea6e~ ~o ~ts opera~ing pr~ure ~iven ~n TABLE 10 below. Blow-o~f ga~ fro~ reactor 2 wa~ ænalyz~d and ~ea~urea. A o~tnolled ~low of ~ake-up ~yn gas (CO ~nd ~2) vas ad~ed ~o reactor 2 in ord~r to ~aintain their desired partial pressures in reactor 2. The operatin~
es~ure6 Bn~ rea~tion temperatures vere ~intain~d ehrcugh~u~ ~he ~ydroormylation. a~ t~e l~qu~d lev~l ~n ~e~ctor 2 ~tarted to ~n~rea6e a~ a r~ult o~
liquid aldehyde pro~ue~ or~ation, ~ portion of e~e liqui~ reaotion ~olut~on ~3E pu~pea to ~e lS vaporizer/~ep~a~r st a rDte ~uffi~ient to ~ai~ta~n a ~on~tant l~qui~ l~vel in ~ea~or 2. The cru~e aldehyae ~roauct va6 ~epar~ted as 115-~. hna 20 ~ia.
fro~ t~e liquia ~eact~o~ ~olusion, conden6e~ an~
collect~a ~ a ~roauet r~eeiver. ~e remain~ng non-vol~t~l~ze~ catalyct co~t~inln~ llquid re~otion ~olutio~ v~s ~cyclea baEk e~ ~eaotor 1.

Th~ ~ydrofor~yl2tio~ of ~a~d ~lxea ol~in fe~ o~ ~ut~ne-l ~na buten~-2 V~6 c~rried oue con~i~uou~ly ~Dr ~ y5 ~f~er ~hi~h ti~ olefin ~d ~a6 e~a~g~ o~er to ~ ~r~ao~in~ely bu~ene-~
~eo~-an~ eo~ u~d for ~ ait~n~ y.
a~os4-l .. . . ..

The ~ydroformylatio~ reac~ion ~ondition~ a~
well as tbe r~tÆ o~ C5 aldehy~e~ produced ~ eer~
o~ gram ~ol~ p~r li~er p~r hour and the linear ~o branch~ aldehyae p~oduct Ea~io o~ ~-valeraldehyd~ ~o 2-~ethylbutyraldehyde are gi~e~ in TABLE 10 below.

Day6 of Oper~tion 2 6 7 ~ute~e Feed, DOl ~
Butene-l 5.22 41.27 99.97 Trans-Butene-2 57.00 34-06 -Ci6-Buten~-2 37.7~ 24-67 -~

Reac~or Wo. 1 Tempe~a~ure, ~C ~5.2 85.4 66.1 Pres~ure~ p~i~ 205 205 205 ~2. P~3 ~6.3 64.2 7~.3 CO, p~ia 43.7 63.1 ~5.9 ~uten~ s~ 0.7 1.5 25.3 Tran6-Butene 2. ~ia 23.0 la.S 1.1 Ci~-Butene-2, ~ 7.3 7.1 1.7 ~eactor_No._2 Temperatu~ C ~5.1 85.S 66.5 Pre~ure, p~ia 195 1~5 ~5~2~ p6ia ~3.a 55.1 54.4 CO. ~a 37.~ ~4.~ 52.0 ~ut~ne-l, p8i~ . 0.5 0.3 ~.0 ~an~-Butene-2, ~ia 16.2 11.0 2.1 Cie-~u~ene-~, p~ 3.~ 2.9 2.8 ~e6ult~
C5 ~ldehy~6, g~ol~L~r3.03 3.19 3.19 ~inear/B~an~e~ ~ld~y~e ~tlo 0.47 0.7~ 2.~4 1~0~

..... _ . . .. . . ; , _ , _ . . _ . _ . . . .. _ . . _ . .. , . . _ _ ., ., ., . _ . . . .

. .; .

5ubsequent ~naly~i~ o th~ rhod~u~n cornplex sataly~ 601ut~oD after completion of ~he a~oYe ~ontinuou~ 6e~en day hydrofor~Qylation experiment ~how~d ~a~ u6ed ca~aly6t ~olution to contai~ about 173 pp~ rhodiur~.

A comparable experiment 7~as ~onducted employing a 6imilar proce~ure a6 de6cribed in Example 10 æboYe, but wherein the crude al~ehyde pro~uce was ~eparated ~ vapo~izer ~on~itlcn~ o~ about 87 to 85~C. and ~bout 5 pl;ia. ~ro~ ~be liquid reac~or fiolution an~ wterein ~cbe recycled catalyfi~ containing ~olution vas ~as6ed tbrough ~n ~mberlys~(~) A-21 bed to remove llcia~e by-pcodu~t6. After ~n equilibration period o~ one a~y wherein ~ome rhodium wa6 bel~e~ed to b~ 3d60rbed onto ~he Amberlyst ~res~n be~ t~lere vere no ~etectable 1066e8 0~ rbodium inventory ~rl tbe ~e~ctor ovor the next 10 d~y~ of ~oneinuous ~yaroforr~yl~tiDn.

EJ~AMPL~

A ~o~lar continuou~ hydrofo~myla~ioncomparative e~perioen~ a6 ~et orth ~ ~x~ple 10 ~a~-c~rrie~ out u6i~ eri$-ortho-b~ph~ylylpho~phibe~ (~un No. 3 o~
~ABLE 8, ~ phosphite nct of this invention~ as the 1~5~

~ 5-ligand promoter. The ~art-up and operatlng procedure ~et forth in Example 10 were employed with ~he exception that in this test only a single seactor (in place of two reactors ln ~eries) was used with butene-l as the olefin feed. The reactor was charged with 0.88 lites~ of a catalyst compo~tion consist~ng of 100 ppm rhodium ~s rhod;um dicar~onyl acetylacetonate, 10 wt% tris-ortho-biphenylylphosphite (about 192 mole equivalents of phos-phi~e ligand per mole equivalent of rhodium) dissoived in a 1~1 weight:weight mixture of valeraldehyde and Texano ~. At the ent of 0.8 days of operation massive percipitat on of alpha-hydroxypeneyl phosphonic acid occurred which caused plugging of the reactor transfer lines and subsequent ~hut-down of the continuous hydro formylation. Analysis of the catalyst solution by Phos-phorous-31 Nuclear Ma~netic Resonance Spectroscopy, ~howet that all tsis-ortho-biphenylylphosphite had decomposed. The hydroformylation ~est was eerminatet. The data set for~h in Table II below describes the operating conditions and performance prior to the forced shut-down of the process.

.. . . . .. ..... . . .. . . .. . . . .... ..... . . . .

()55 TABLE~

Days o~ opera~lon 0. 8 3u~ene Feed. ~o~le ~

~utene- 1 99 Z
Tran6-Butene-2 3 . 2 Ci ~ -But~ne- 2 0 . 05 13utane 0. 55 Reaction Conditions Temper~ture, C 0o . 3 Pre6~ure, PGia 150.0 , Psi~ 32.3 C0, p~ia ~113 7 ~uteA~-l p~ia 60.1;
Results ___ C Aldehyd~s; 1. Q2 5Reaotiorl Rate ole6~1~t~r~0ur~
Linear~Branched 3 ~4 Aldehyde Mole Ratio 1~135~-1 . .
..... . ... . .. . . . .. . . . ... .
- . ~ - , .
. .. ~ .
, . .

''., ' `;~
.
. . .

L~

~LAMPLE _l2 The long ter~ ~ataly~t ~tability of 1,1 '-~i phenyl-2, 2 ' odivl~Q, 6~ tert-blltyl-4-~ethylph~nyl~
pho6p~ite pror~oted rho~iur& cataly~t wa~ ~e~eronine~ ~n ttle ~ollowing mann~r.

Tl~e hydrofor~yl~tion wa~ ~on~ucted ~ ~
511a~i6 reactor op~ra~inq ill a ~on~inuou6 æ~ngle pasæ
Propylene hydrofor~Dyl~t~o~ ~o~e. ~he reactor eon6i6t~d of a three~ounce pr~6~ure ~ot~l~ fiubroer~ed 10 ln an oil ~atl~ vit~ a ~ s ~ront ~or ~iewin~. Abou2 20-lDL of ~ f~e6hly pt~pared rbodiulD ca~alytic pr~cur60r ~olut~on va~ cll~rged ~o the r~actor wi~h ~
l~yringe,after purging t~le ~yctem vith ni~ro~en. The precursor ~olu~on eonts~ned abou~ Z00 ppm rhod~um 15 ~ntrodu~a ~ rho~iu~ ar~onyl ~cetylaceton~e, abou~ 10 ~ole equ~ lonte of l.l'-biphenyl-2,2'-diyl-(296 -ai-tert-bu~yl-4-~etbylp~nyl)~ho~phite li~nd pe~
Dol~ of rhod~ etal and Scx~ the ~ol~nt. Af~r elo~g t~ re~torO t~ 8y6tem vas 20 aga~ purg~d v~t~ ~tro~n nd t~e oil ~tb was h~e~ to ~ur~h t~e ~ yaro~or~ylat~on ~aet~on t~pe~ure. ~he ~y~r~or~yl~tisn ~ction ~a~ con~uct-~ ~t a t~t~ rog~ure of ~bout lS0 ., the parti~l pse~ure~ ~f h~dro~e~, ~05~-1 .. .. , .. .. .. ~ . .. .

:`',: ~ , .

~ 5 S
-~8-carbon monoxide, and propylene being given in Tabie 12 below, ~he remainder being nitrogen and alde~yde product. The flows of ~he feed gases (carbon ~onoxide, hydrogen, propylene ant nitrogen) were controlled indi~idually with mass flow ~eters and the feed gases dispersed into the precursor ~olution via fritted glass spargers. The unreacted portion of the feed gases ~trippet out ~he protuct C4 aldehydes and the outlet gas analyzed over 22 days of continuous operation at the reac~ion temperaeures given in TABLE
12 below. The a~erage reaction rates for each experiment in terms of gram moles per liter per hour of product C4 aldehydes as well as the n-butyraldehyde to iso-butyraldehyde product ratio are given in TAB~E 12 below.

1~0~4 -1 .. ., .. ......... ~ .__ .... ....

... : ~ .

," ~

. .
"~

-149 - ~L2~)55 6~ o C~ , ~D '~ ~ ~ V Vt ~' 6 f~ 51 C ~ ~ ~ ~ ~ ~ ~ W ~ ~

O O O O O O O O O r 9 o o c~
~l .U ~ ~ O ~ ID O ~ ~
@~ n ~D
O ~ O ~ I o o W ~ o o, _~ ~ ~
'~1 D
o ~

v a ~ ~ " 3 r~
O ~ . r~
d~ I ~ ~ ~ ~ ~ ~` i~ ~r O O
O ~ ~ ~ ~ O ~ ~ ~

jF~Or ~ o . .e~ I o -' O ~. O C~ O C ~ O i~
o, ~ ~ ~ o ~ ~ ~ . ~ ~ ~ o~ - o 1~5~
. ~

. , - : .~ `; ~ ~;
.
-, , , ~

, . .

~L2~ 55 ~ ~ ~ Ul :~r ~ n ~9.
C ~ 4 11 .J U IU P~ Y il~
8 ~ d~ 5 ~ ~o n 3 r~
O ~ ~ I ~ .
::~ ~ ~ ~
t C~
O ~ g "aC l;;' ID
E g g g o g o g o :~ .
~: ~ al ~ c g ~

b :1 ~-r'n jg n D ~D
n o o o o ~ r :g n 9 01.
. .

140~4 -1 ~

... .. .. . .

` . : .` . ~

, .~: : ;
:.: , :

s ..~51 -EX~MPLE 13 A similar continuous hydroformylation ~x-periment 88 ~et forth in Example 10 was oarried out uslng isobutylene as the olefin and phenyl 12,2'-methylene-bi~(6-t-butyl-4-methylphenyl~] phosphite (the ligand ln Run No. 3 of Table 6) as the ligand promoter~ The 6tart-up and operating procedure set forth in Example 10 were employed with the exception ~hat only a s~ngle reactor (ln pla e of ~he two re-actors in series) was used with isobutylene as the olefin feed and the above mentioned phosphite as the ligand. The reactor was charged with 1127 mL. of a catalyst compDsition consisting of 200 ppm rhodium as rhodium dicarbonyl acetylaoetonate, 0.9 wt. % of phenyl 12.2' methylene-bis(6-t-butyl-4-methylphenyl)3 phosphite (ab~ut 10 ~ole equivalents of phosphite ligand per ~ole equivalent of rhodium) dissolved in a mixture of abou~ 475 gr. of valeraldehyde and about 466 gr. of Texanol ~ The data ~et forth in Table 13 below deseribes the operating conditions and perform-ance ~n gram moles per l~ter per hour of 3-methyl-butyraldehyde product over three days of continuous hydroformylat~on.

. .. .... .. . ..

~ ~ ~L~ ~5 -~2 Days of Operation 1 2 3 .
Olefin Feed Mole ~
Isobutylene 9g.96 99.94 100 Isobutane 0.04 0.06 Temperature; C. 84.8 8~.8 84.8 Pres~ure, Psia 201 204 206 H~, Psia 73.92 75.65 65.76 CO, Psia 3.34 7.g8 41.64 Isobutylene, Psia 106.0 98.24 85.59 Resul ts . _ 3-Methylbutyraldehyde 1.55 1.60 0.64 Reaction Rate (g ~oles/liter/hour) ' ' ' ' - -.- r - _ .. .. _. ... _ ._, _ , _ _ ,, . ~ , ~, " ,' ';, ,~ ;, '` ' ' '''~'` ' ' ' , ' ~

' . ', ' ,~, .

~ 5 Butene-2 was hydroformylated in the same manner as Example 12 u~ng 1,1'-binaph~hylene-2,2'- 1 diyl-(2,6-di-t-butyl-4-methylphenyl) phosphi~e as ~he ligand, (the ligand of Run No. 9 sf Table 3).
S The hydroformylation was conducted in a glass reactor operat~ng in a roneinuous 6ingle pas~
butene~2 hydroformylation mode. The reactor consisted of a three ounce pressure bo~tle submer~ed in ~n oil bath with a glass front for vle~ing. A~out 20 mL of a freshly prepared rhodium catalytic precursor solution was charged to the reactor with a syringe sfter purging the syst~m with nitrogen. The precursor solution con-tained about 200 ppm rhodium introduced as rhodium di-carbonyl acetylacetonate, about 9.6 mole equivalents of 1,1'-binaphthyle~e-~,2'-diyl-(2,6-di-tert-butyl-4-methylphenyl~ phosphlte ligand per mole of rhodium metal and Texanol ~) as the solvent. After closing the reactor, the ~ystem was again purged with nitro~en and the oil bath was heated to furn~sh the desired hydroformylation reaction ~en~perature. The hydrof~rmyla~cion reaction was conducted ~t ~ total gas pressure of about 160 psig., the partial pressures of hydrogen, carbon monox~de, and ~u~ene-2 being given in Table 14 below, the remainder belng nitrogen and aldehyde product. ~he flows of the 140~4-1 ' .

-154~ 05 ~

feed gases (carbon monoxide, hydrogen and butene~2) were controlled individually wi~h mass 10w meter~
and ~he feed gases di~persed into the preeursor 801u-tion via fri~ted glass ~pargers. The unreacted portion of the feed gases strlpped out the product C5 aldehydes and the outlet gas analyzed over about 14 ~ays of eon-tinuous operation at the reaction temperatures given in TABLE 14 below. The average reaction rates for each experiment in terms of gram moles per liter per hour of product C5 aldehydes as well as the linear n-valer-aldehyde to 2-methylbutyraldehyde branched product ratio are g$ven in TABLE 14 below.

14~54-1 ' : ~ :

;. :, : .

:~l26'~

Q~, ` . ~ `~ `' ` '^ ~ ~ ~ ~ 13 o o n c~ o c~ o ~ ~, o ~ ~ c~ o o o ~ o ;~ ~ ~ 1. ~
rl o o~ o ~o ~c t r oo o ~ ~9, .~ v~
W ~ 8 ~
s ~ u r e ~ _ ~ w ~ ~ ~ ,,Jr ~ ~, ~ ., r r, ~
b~WW~ C C ~
o ~ U
c rw ~u It n ~ ID
- -- ~ . r ~ ~
o ~ i~ or ~i _ . ~
:S 9 r, G
r~ _ ~ ~ ~ ~ ~ O V~ r ~ OSL~ 1 ,, ~ . . . :

.
.
.

: ' ' 4~35 5 EXAMRLE 15 _ Isobutylene W8S hydroformylated ~n the ~ame manner ~s Example 12 us~g 1,1'-biphenyl-2,2'-diyl-(2,6-di-tert-butyl-4 methylphenyl) ph~sphite as the ligand (the ligand of Example 1).
The hydroformylat~on was conducted in a glass reactor operating in ~ continuous single pass isobutylene hydroformylatlon ~ode. The reactor consisted of a three ounce pres~ure bot~le ~ubmersed in an oil b~th with a glass front for viewing. About ~0 ~L of a freshly pre-pared rhodium c~talytic precursor olution was charged to the reactor with a syringe 2fter purging the system wieh nitrogen. ~he precursor solution c~ntained about 250 ppm rhodium introduced a~ rhod~um dicarbonyl acetylacetonate, about 10 mole equivalents of 1,1'~
biphenyl-2,2'-diyl-(2,6-di-~ert-butyl-4-methylphenyl) phosphite ligand per mole of rhodium met~l and Texanol ~s ~he solvent. After cl~sing the reactor, the 5ys~m was again purged with nitrogen ~nt ehe oil bath was heated to furhi~h the desired hydroformylation reaotion temperature. The hydroformylatlon reaction was conducted ~t ~ otaI gae pres~ure of about 160 psig., the par~
pressures of hydr~genOcarbon monoxide, and ~sobutylene be~ng glven $n Table 15 below, the remainder being 1405~-1 .

., . ~

~ . . . . - , -. ~
. ~. . . .
- . .~, :

~ 2 ~ 5 5 ~1 5~

nitrogen and aldehyde product. The flows of the feed gases (carbon monoxide, hydrogen and isobutylene) were controlled individually with mass flow meters ~nd the feed gases dispersed into the prPcursor solution via fritted glass spsrgers. The unreacted por~ion of the feed gases stripped out the 3-methylbutyra~dehyde product and the outlet gas nalyzed over 7 days of continuous opesation at the reaction temperatures given in TABLE
15 below. The ~verage reaction rates for each experiment in terms of gram moles per liter per hour of 3-methyl~
butyraldehyde product is given in Table lS below.

1~054-1 . ' , ' ' -.

; ~

~1 ~8-* ~
: n ~ c~

OQ
.- ~ ~ O
t~ D ~ 8 ~rD ' 1~ 9 '0 PS
~'D
~ F~
~ 8 ID
o ~

,, V~
I OD 1~ W W
~o ~ F~lW~

: :1 ~ ` ~ q- e~ ~ ~ C r~
l_ r~o f~
~ ~;D ~ ~ ~ O~ D ~ ~
~ W ~
~ . `~~a ` : .
' , ., , ;

,.;

~6'q ~s Methyl [3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl] phosphite having the formula Q13~iD~
~ 0-C}i3 CH3~>--O

~-~u was prepared in the following manner.
A solution of about 90 grams (about 0.5 moles) of 2-t-butyl-4~methoxyphenol and 170 ml. of H~O containing about 56 grams (about 1.0 mole) of potassium hydroxide was heatçd with stirring to about 80~C. Air was then passed through the solution until precipitation of a diphenolic 10 compound (i.e. 2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethoxy-l,l'-biphenyl) was complete (total reaction time of about 135 minutes). The white, ~olid ~ipheno~ic pre-cipitate was then flltered hot and washed twice with about _ 200 ml. of w~ter. About 78 grams (87.6 Z of theory) of 15 the i~olated 2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethoxy-l,l'~biphenyl product was recovered which had a melting point of about 222 to 224C. and whose structure was con-~irmed by ~nfrared and mass spectroscopy.

.

-16~-About 75.2 grams of ~he 2,2'-dihydroxy-3,3'-di-t-butyl-5,5'~dimethoxy-l,l' biphenyl diol 8 o prepared was then added ~o about 1 liter of toluene. Sufficient toluene was then removed azeotropically to remove residual traces of moisture from the solut~on. The diol-toluene solution was then cooled to 0C. and about 70 grams of trie.thylamine added followed by the dropwise addi~ion of about 29 grams of phosphorus trichloride at O~C. over about 20 minutes. The resction solution became thick with triethylamine hydrochloride salt and was heated for about 30 minutes at about 100C. The suspension was then cooled to about 55C. and about 13.44 grams of methanol added over about 15 minutes and the reaction medium heated at about 90 to 95C. for about one hour. The reaction medium was then filtered hot to remove the solid triethylamine hydro-chloride precipitate and the filtrate evaporated to dryness under vacuum. The recovered residue was then dissolved in about 100 ml. of refluxing acetonitrile and cooled ts pre-cipitate the desired methyl [3,3l-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl~ phosphite ligand, about 75 grams (85.4% yield of theory) of which was recovered. The de-sired crystalline~ ~olid phosphi~e ligand product was found to have a melt~ng poin~ of about 64 to 69C. and a character-.~stic 31p p~ phosphite reso~ance at 131.9 ppm (relative to ucternal H3P~) 14051~-1 ~L~ 6LC~f a~

EXAMPLE l7 r The follDwing diorganophosphite ligands wexe prepared in the same manner as described in Example 16 above, save of course for e~ploying the hydroxy compound reactants that correspond to and account for their di-organophosphité structures.

t-~U
~' c~o ~ ~

~J~ t-e.~u phenyl l3,3'-di-t-butyl-5,5'-dimethoxy-191'-biphenyl-2,2'-diyll phosphite.
(Crystalline product having a ~elting point of 131 ~o 132C. and having a characteri6tic 31p ~MR phosphite res~n~nce at 140.1 ppm~ relat~ve to external H3PO4) 1~054-1 ' '' ' ~ :

:' ~ .. ': .

' ': , , 4~)5 -162~

Li~;as~d B

t--U
CB~pO ~ ~
\~, o ~C9~19 01~0 ~0 t~

4-nonylphenyl ~3,3'-di-t butyl-5,5'-dimethoxy-l ,1 ' ~b~ phenyl- 2, 2 ' -diyl l phosphite (~on-crys~alllne gum product hav~ing a charac~
teristic 31p ~ phosphite sesonance!s at 140.1 ppm and 139.9 ppm, relative to external H3P04;
"nonyl" represents branched mixed nonyl radicals~.

C
t -~u cli3~--9/ ~) t-su 140~4-1 ,.

, .

.
, -163~ 4 ~5 ~

.beta-naphthyl ~3,3-~di-t-butyl- _ 5,5'-dimetho~y-l,lY-b~phenyl-2,2'-diyl] phosphi~t~ ~Non-crystalline gum product ha~ing a charac~istic 31p NMR phosphite resonance at 139.2 pp~, relative to external H3PO4).
EXAMP~E 18 Butene-2 wa~ ~yd~v~ormylated in the ~ame mann~r as Example 12 using m~thyl l3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl] p~osphite as the li~and, (the ligand of Example 16)o The hydrofo~mylation was conducted in a glass reactor operating in a ~ontinuous single pass butene-2 hydroformyla~i~n mode. ~he reactor consisted of a three ounce pressure bottle ~ubmersed in an oil bath with a glass front for viewing. About 20 mL of a freshly pre-pared rhodium cataly~i~ ~recursor solution was eharged to the reaetor with a ~ysi~ge after purging the ~y5t~m with nitroge~. The pr~c~ssor ~olution conta ned about 250 ppm rhodium introduced ~ rhodium dicarbonyl acetyl~
scetonate, about 2.~ weigh~ percent ligand ~about 19.7 mole equivalents of mæ~hyl [3,3~-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl] p~osphite ligand per mole of shodi~
metal) and valeraldehyde ~rimer ac the ~olvent. After ~4054-1 .... . "., . . . . . .. , . . . . .. ... . ., .. . _ .. ... . . .

- .. ..

.
.

:~ `

-16~--closing the reactor, the system was again purged with nitrogen and the oil ba~h was heated to fu~nish the desired hydsoformylation reaction temperatur~. The hydroformylation reaction was conducted at a total gas L
5 pressure of about 160 psig., the partial pressures of hydrogen, carbo~ moncxide, and butene-~ being given in Table 16 below, ~he remainder being ni~rogen snd aldehyde product. The flo~s of the feed gases (carbon monoxide, hydrogen and butene-2) were controlled individually with 10 mass flow me~ers and the feed gases dispersed ~nto the precursor solution via fritted glass spargers. The un-reacted portion of the feed gases stripped out the product C5 aldehydes and the outlet gas analyzed over about 11 days of continuous operation at the reaction temperature of 15 about 90C. given in TABLE 16 below. The average reaction rates for this experiment in terms of gram moles per liter per hour of product C5 aldehydes ~s well as the linear n-valeraldehyde to 2-methylbutyraldehyde bra~ched product ratio are given in TABLE 16 below.

ll~O54-~

. . .
: , , ,:
, -1Ij50 3L;~

1~ O ~P
~ .

~ ~ ~ ~ 0 ..I ~ o o o o o o o In,~

Q ~ O
P) ~ ~
~ ~ C~ ~3 O
~D ~ ~-0~ ~
~D
0 00 ~ O ~ O p~ ~~
U~

~: O p ~D
r 3~

o o ~ O ~ ct O C~
oiD~
~ .
~41~54-1 .. , ~ . . .. . . . .
.
-.~, . , ~ : ., ` ~ ~
, ` : ;- :: `

s _ Butene-2 w~s hydroformylated in the same manner as Example 12 using phenyl 1313'-di-t-butyl-5 9 5'-dimethoxy-1,1'-biphenyl~2,2'-diyl] phosphite as the ligand, ~Ligand A of Example 17).
The hydroformylation was conducted in a glass reactor operating in a continuous single pass butene-2 hydroformylation mode. The reactor consisted of a three ounce pressure bottle submersed in an oil bath with a glass fron~ for viewing. Abou~ 20 ~L o a freshly prepared rhodium catalytic.precursor solution wa~ charged to the reActor with a ~yringe after purging the system with nitrogen. The pre-cursor solution contained about 250 ppm rhodium introduced as rhodium dicarbonyl aoetylacetonate, sbout 2.0 weigh~
percent ligand (abou~ 17.2 mole equivalents of phenyl E3~3l-di-t-butyl-5~5~-dimethoxy~ -biphenyl-2~2l-diyl]
pho~phite ligand per mole of rhodium metal) a~d valeraldehyde tri~er as the 601vent. A$ter closing the reactor, the ~ystem was again purged with nitrogen and the oil bath w s heated to furnish the desired hydrofosmylation re-action tempera~ure. The hydroformylation reaction was con-ducted a~ a total gas pressure of about 160 psig., the partial pressures of hydroge~, carbon m~noxide, and butene 2 being given in Ta~le 17 below, ~he remainder being nitrogen . . . . . ... . . . . .... .
, ~:
.. .. . .

and aldehyde product. The flows of the feed gases _ (carbon monoxide, hydrogen and butene-2~ were controlled individually with mass flow meters and the feed gases dispersed into ~he precursor solution via fritted glass h 5 spargers. The unreacted portion of the feed gases fitrîpped out the product C5 aldehydes and the outlet gas analyzed ov~r about 13 days of continuous operation at the reaction temperature of about 90C. given in TABLE 17 below. The average reaction rates for this experiment in terms of grEm 10 moles per liter per hour of product C5 aldehydes as well as the linear n-valeraldehyde to 2-methylbutyraldehyde branched product ratio are given in TABLE 17 below. Analysi~ after 2.5 days of operation indica~ed poor butene-2 feed due to plugging of the sparger. The problem was corrected and 15 the reaction continued.

1~054-~ `

.

)5S
-16~-O

c~oooooooooIn,~

. 8 ~ ~ .

O g O O O ~ o ~n ~ ~

t~ O ~ ~ W ~ ~ ~D ~k D U~ ~i ~ U~
ro~ :d ~ ID
rt P~ P
O l-- l-- I:~: o 0 0~ 0 C~ ~ e ~
~D .

~ .,0, O ~ ~ o O ~ C> O
o .

., : , ;

i L~- ~) 5 ,r3 -1~9-Butene-2 was hydroformylated in the same manner as Example 12 using 4-nonyl [3,3'-di-t-butyl,~5,5'- 1 dimethoxy-l,l'-biphenyl-2,2'-diyl~ phosphite as the ligand, (Ligand B of Example 17).
The hydroformylation was conducted in a glass reactor operating in a continuous single pass butene-2 hydroformylation modeO The reactor consisted of a three ounce pressure bottle submersed in an oil b th with a glass front for viewing. About 20 mL of a freshly pre-pared rhodlum catalytic precursor ~olution was charged to the reactor with a ~yringe after purging the system with nitrogen. The precursor solution contained about .
250 ppm rhodium introduced as rhodium dicsrbonyl aoe~yl-a~etonate, about 2.0 ~eight percent ligand (about 13.6 mole equivalents of 4-nonyl ~3,3'-di-t-butyl-5,5'-dimetho~y-l,l'-biphenyl 2~2~-diyl] phosphite liE~and per mole of rhodium - ~etal) and valeraldehyde trimer as the solvent. After clo~ing the reactor, the ~ystem was again purged with nitrogen and the oil bath was heated to furnish the tesired hydroformyla-tiorl reaction temperature. The hydroformylation reaotion was conducted ~t a ~otal gas pressure of about 160 psig., the partial pre~sure~ of hydroge~, c~rbon monoxide, and butene-2 being given in Table 18 below, the remainder being nitrogen and aldehyde product. The flows o~ the feed ~ases ~4054-1 .
,, ;: .

.
.-, ~ . ..

` :` :

(3S5 (carbon monoxide, hydrogPn and butene-2) were controlled _ individually with mass flow meters and the feed gases dispersed into the precursor solution via ritted glass spargers. The unreacted portion of ~he feed gases stripped out the product C5 aldehydes and the outlet gas analyzed over about 13 days of continuous operation at the reac~ion temperature of about 90C. given in TABLE 18 bel~. The average reaction rates for this experiment in terms of gram moles per liter per hour of product C5 aldehydes as well as the linear n-valeraldehyde to 2-methylbutyraldehyde branched product ratio are given in TABLE ~8 below.

1~054-1 ,;
~; . . '' " ; :
. ' : ~', ... " ` :

o~ ' ~ o ~e ~ n Vl ~ , _ In,~
o C:~ O O O ~ C: o ~ O I

~., ~
.2 ~ :~ 0 V~ ~
~00~ ~00~ ~ D ~ 1~

kB ¦ ~

r~
.9 ~ Z:g g u~ OD `.1 CO ~ ~ ~ O
.

r~
X~9D ' '' I Ul IJI Ul O t~ g~D ~
~ '. &

14~54-1 . .
., ~, . .

` ,, ,~ ` - ,, : ' ': : ' :~
.

-17~-A simllar con~inuous hydroformylation ex-periment as set forth in Example 10 W2S carried out using isobutylene as the olefln and methyl 13.3'-di t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2~2'-dlyl] phosphite (the ligand of Example 16) 85 the ligand promoter. The start-up and operating procedure set forth in Example 10 was employed.
The hydroformylation reaction was oonducted by charging abou~ 1.03 liters of a catalyst precursor solution of rhodium dicarbonyl acetylacetonate (about 450 ppm rhodiumt, about ~.8 wt. me~hyl 13.3'-di-t-butyl-5.5'-dimethoxy-1.1'-biphenyl-2,2'-diyl) phosphite ligand (about 15.3 mole equivalents of liga~d per mole of rhodium), about 2.0 triphenylphosphine oxide as an internal standard, and about 95.8 wt. Z of C5 aldehyde (about 82.8 wt % valeraldehyde and about 13.0 wt Z valeraldehyde trlmer) as solvent to reactor lo About 1.2 liters of the same catalyst precursor solution was charged to reactor 2. The reactor system was then purged with nitrogen to remove any oxygen pres~nt. Then 20 a~out 100 pslg. nitrogen pre~ure was put on both reactors a~d the reactors heat~d to their reaction temperatures given in TABLE 19 bel~w. Controlled flows of purified hydrogen, carbon monoxide and isobutylene (the composition of the ~sobutylene feed throughout this process consisted of at 25 least 99 . 9 mole % or Esreater of isobutylene, any reT~ainder be~ng sobutane) were fed through the sparger into the 140sl.-1 . .
'~ ' , ~
:
:.

;.

-173- ~ 2 ~ ~5 S

bottom of reactor 1 and ~he reactor pressure increased to the operating pressure giv~n ~n TABLE 19 below. When the liquid level in reactor 1 ~tarted to increase as a result of liquid aldehyde product formation a portion of the liquid reaction 801u~ion of seactor 1 was pumped ~nto reaceor 2 through a li~e into the ~op of reactor 2 at rate suficient to maintain a constant liquid level ln reaetor 1. The pressure of reactor 2 increased to its -operating pressure g~ven ~n TAB~E 19 below. Blow-off gas from reactor 2 was analyzed a~d ~easured. A controlled flow cf make-up 8yn gas (CO and H2~ was added to reactor 2 in order to maintain their desired partial pressures in reactor 2. The operating pressures and reaction tempera-tures were ~aintained throughout the hydroformylation. As the liquid level ~n reactor 2 started to increase as a result of liquid aldehyde product formation, a portion of the liquld reaction ~olution was pumped to ~he Yaporizer~
sep~rator at a rate ~ufficient to maintain a constant liquid level in reactor 2. The crude aldehyde product was sep~
arated ~at varying temperatures) from the iiquid resction ~olut~on, conden~ed and collected in a product receiver.
The remaining non-volatilized catalyst containing liquid reaction ~olution was recycled back to reactor 1.
The hydroformylation expe~iment ~as carried out continuously for about 33 days. During the firs 15 days of operation the aldehyde product was separated fro~ the . .
~4054-~

. -17~-liquid reaotion solution at abou~ 115~C. and ~2-26 psia.; from day 16 ~o day I9 this separa~ion was con- _ ducted at about 117~C. and 22-26 psia; from day 19 ~hrough day 22 this separation was eonducted at about 123C. and 22-26 psia. and from day 23 to day 32.5 th~s separation was conducted ~t 133C. and 22-26 psia.
The dats set forth in Table 19 below describes the operating conditions and performance in gram moles per liter per hour of 3~me~chylbutyraldehyde produc~ over about 33 days of cont$nuous hydroormylation.

Days of Operation 6.9 13.9 21.8 32.5 Reactor No. 1 Temperature,C 95.0 95.0 94.9 95.5 Pressure~ psia 185 185 185 185 H2~ psia 72.7 70.8 70.6 62.5 CO, p~i~ 57.9 55.2 53.1 55.9 Isobutyle~e~ psia34.3 37.5 39.7 46.9 . Reactor No. 2 Temperature, C 95.3 95.4 95.5 95.4 Pressure, psia 165 165 165 165 H2, psia 76.3 75.0 73.0 66.1 CO, psia 48.4 43.3 49.2 53.6 I60bu~ylene, psia13.7 15.4 16.4 24.3 Result~
3-Methylbutyraldehyde 1.77 1.81 1.74 1.49 (g ~ol/L/hr) 1405~-1 .:

- . ~L~ ~L~ , j 5 -1~5- .

The rhodium inven~ory in the reactor system was monitored daily during the course of the experiment and no detectable loss of rhodium in the reactor system was ob-served o~er the first 26 days of continùous hydroformylation.
However, continued analysis ~howed that about a 10 perce~t loss of rhodium inventory in the reactor system occurred over the continuo~s period from day 26 to day 32 . 5 (completion of the experiment) .
The above experiment demons~rates the high rhodium 10 complex catalyst activl~y and 6tability obtained ln employin~
methyl ~3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl] phosphite li~,and when hydrofos~ylating even a normally highly unreac~ive olefin, such as isobutylene. In addition, , said experiment demonstrates tha~ the use of a ligand such as methyl l3.3'-di-t butyl - 5,5'-timethoxy-l,l'-biphenyl-2,2'-diyl~ phosphit permitted the crude aldehyde product to be separated from ~he liquid reaction solution at vapor-i7,ation temperatures even as high as about 120C. without experiencing any loss in rhodium inventory over a prolonged 20 period of operation, wh~le the ~teady production of 3-~ methylbutyraldeh~de indicates the ligsndls high ~tabilityagainst in situ phosphite decomposition to undesirable hydroxy alkyl phosphonic acid by-product.

~40~4-1 .

' ~ ~ 6L~ 5 ~XAMPL~ 22 .
Buten~-l ~2~ hydroformylated ~n the ~me manner .
Example 12 u~l~g beta-naphthyl [3,3'-di-t-butyl-5?5'-dimethoxy-l,l'-biphenyl 2,2'-diyl] phosphi~e as the ligand, (Ligand C ~f Example 17.

The hydroormylation wa~ conducted ~n a gl~8 reactor operat~g ~ a con~nuou~ ~ingle pa~ butenel hydroformylation mode. The reactor eon6~sted of ~ ehree ounce pressure ~ottle ~ubmersed in an oil bath wi~h ~ gl~88 front for v~ew~ng. A~out ZO ~L of ~ freshly prepared rhodium cat~lytio precursor solut~on wa~ cha~ged to the reactor with syringe ~f~c~r purging th~ 8y8tem wit~ nitrogerl. The pre-cur~or ~olution contained abou~c 25 ppm rhod~ ntroduced 5~ rhodium dicarbonyl ~eetylacetonate, ~bout 2.0 weiglht percent liga$ad (about 155 ~ole equivalent~ of beta-naphthyl ~3~3'di~t-butyl-5r5'-d~methoxy-1,1'-bipheny~2,2'~di~1~
pho~phi~e ligand per ~ole of rho~iu~ ~etal) ~nd vsleraldeh~de ~r~er 88 t~e ~o~vent. ~fter closi~g the reactor, ~he 8~8~e~ wa~ ~ga~n ~ur~ed with nitroge~ ant ~he ~11 b~th was ~eated to f~rni~h t~e ~esired hydroformylatio~ r~
~ction ~emper~t~re. The ~ydro~or~yl~tion reaction was eon~
. ~uct~d at æ tot~l gas pres~ure ~f ~bout 160 p~ig., the ~art~l pre~suse~ o hydroge~, c~rbon ~ono~ide~ ~nd ~utene-l ~eing ~iven in Ts~le ~0 bel~w, the remainder be~ng nitrogen l bû5b-1 .

V~S

and aldehyde produc~. The flow~ of the feed gaSeB
(carbon monoxide, hydrogen and ~u~ene-1) were conerollet lndi~idu~lly with m~s flow ~eterR and the feed ga~e~
disper~ed into the precur~or ~olution Vifl fritted glas~
spar~er~. The unreacted portion of the feed gas s 6tripped out the produc~ C5 aldehydes and the outlet gas analyæed over abou~ 14 days of cont~nuous operation at the reac~ion temperature of ~bout 90C. g$ven ~n TAB~E 20bel~w. The ~verage reac~ion ~ates for each exper~ent in term~ of gra~
~oles per liter per hour of product C5 aldehydes as well a6 the linear n-valeraldehyde to 2-methylbutyraldehyde br~nched pro~uct ratio are given ln TAB~ 20 bel~. The decreasing reaction rate of C5 aldehydes produced over time is considered attri~utsble ~o the very low concentration of rhodium employedO

1~0~

, ' ., ,, ' -17~ )55 .
ooooooooooooooIn,~
i~ y ~, g w ~ ~ ~ ~ ~ ~ w ~ ~ ~~ ~ o ~ ~" ~ e~

~ u~
o c~ v t~ o c~ o l~i~ ~ o Ul l,n ~ ~J O ~ ~n ~I Vl 1~ ~
-~ - p~
ID
3 1~
~ ~--o o o ~ ~ o o s~ o o c> `~ o o rt o~
Sb 1405~

~-179-A similar continuous hydroformylation experi- ~
ment as set forth in Example 10 was conducted and the Lformation of hydroxyalkyl phosphonic acid monitored.
The hydroformylation reaction was conducted by charging about 770 mL of a catalyst precursor solut~on of rhodium dicarbonyl acetylacetonate (a~out 492 ppm rhodium~, about 3.5 wt. % 1,1'-biphenyl-2,2'-diyl-(2,6-di-teYt-butyl-4 -methylphenyl) phosphi~e ligand ~about 16.8 mole e~ivalen~s of ligand per mole of rhodium), and about 96.3 wt. Z of C5 aldehyde (about 69.3 wt Z ~aleraldehyde and about ~7 wt ~
valeraldehyde trimer~ as solvent to reactor 1. ~bout 900 mili-liters of the same catalyst precursor solution was charged to reactor 2. The start-up and operating procedures set 15 forth im Example 10 were employed.
~ he hydroformylation reaction conditions as well as the rate of C5 aldehydes produced in terms of gram moles per liter per hour and the linear to branched aldehyde product ratio of n-valeraldehyde to 2-methybutyraldehyde are given in T~BLE 21 below.

. . .
'' : ' . , ' -180~ 5 5 TABLE 21 r Days of Operation 7 ~1 12 U~ED~ 41.9 37.4 40.2 S Trans-Butene-2 22 9 24 ~ 23 4 Cis-Butene 2 Reactor ~o. 1 70 4 65.6 65.1 Temperature, C 205 205 205 Pressure, psia 88.7 86.4 82.4 1~ H2, psia 19.7 33.0 46.9 Butene-l, psia . 5.6 9.7 Trans-Butene 2 and 38 9 39,7 39.4 Cis-Butene-2, psia Reactor No. 2 Te~perature, C 185 185 185 Pressure, psia 89.1 77.9 69.7 H2, psia 8.6 23.2 39.7 CO, psia 1.4 2.3 2.2 Butene-l, psia Trans-Bu~ene-2 and 37 1 46.1 49.7 Cis-Butene-2, psia C5 Aldehydes, gmolJLlhr 2.892.76 2.31 ~inear/Branched Aldehyde Ratio 1. 87 1. 3~ 1. 39 ~405~-1 `: ~
: ,:

.. :

L9 ()~;

During ~hi~ hydroformylation experiment the hydsoformylation reac~on medium was mon~tored by routinely w~thdr~wing ~ampl~ of the continuous cataly~t~containing hydroformylstion reaction medium from reactor 1 and ex-amining same via 31p ~MR 3pectroscopy for a detectable 6ignal (resonance peak) of alpha-hydroxypentyl phosphonic scid. A comparatiYe synthetic solution containing 100 ppm (concentration by weight) of alpha-hytroxypentyl phosphonic acid whlch gave ~ detectable phosphonic ac~d signal (resonance peak) at about 25.8 ppm relative ~o external H3PO4 in the 31p NMR after 2000 pulses ~transients~ wa~ employed as the standard. Such ~et the low detection limit o the alpha-hydroxypen~yl phosphonic acit at a~out 100 ppm (concentra-tion by we~ght).
AfteY about 10 days of continuous hydrofor~yla-tion no detectable amount of alpha-hydroxyperltyl phosphon~c ~cid ~howed up on the 31p N~ spectrum. At day 11 of the continuou~ operation howe~er, a 8mall qualitative a~ount of alpha-hydroxypentyl phosp~on$c acid had for~ed as evidenced by a ~m&ll phosphonic acid resonance peak tha~
~ppeared on ~he pect~u~ of the 31p ~MR conducted that day.
At ~hi~ poine ~n day 11 ~n ~mberlyst~ A-21 ion exchange re~$n bed was employed ~n the cataly~t recy~le line of the liquid ~cycle proces and ~he catalyst containing l~O5b-1.

.... ...
'~

'' . ~ '` ' ' ' ( ~ 2 ~ ~ 5~

recycle solu~i~n, af~el remo~al ~ ~he ~esired aldehyde product, passed through s~id b~d ~n its re~urn to the reactor. Within hours the alp~a-hydlo~ypentyl phosphonic acid was scavenged from ~he reaction hydroformylation re-S action medium ~ evi~n~d by ~he ~isappearance of the de-tectable phosphonic acld peak i~ ~he 31~ NMR spectrum for ~he sample of the hyd~fo~myl ~i~ ~e~c~ion medium recorded on day 12. NotQ in thi exp~liment a c~mmercial grade Amberlyst~ A~21 ~esi~ ~vas employed. Apparently this resin contained chlorid~ im~uritie~ which ~on~aminated (poisoned) a port10n of ~he rhodium catalyst, as evidenced by new rhodium-ligand complex peaks on the 31p NMR spectra.

1~054-1 .... ..
.

``

~ 2 ~ ~ 05S

EXAMPL _ A similar con~inuous hydroformylation experi ment as set forth in Examp$e 10 was conducted and the formation o$ hydroxyalkyl phosphonic acld monitored.
The hydroformylation reaction was eonducted by charging about 770 mL of a catalyst precursor solution of rhodium dicarbonyl acetylacetonaee (about 300 ppm rhodium~, about 2.0 wt. Z 1,1'-biphenyl-2,2'-diyl-~2,6-di tert-butyl-4 -methylphenyl) phosphite ligand (about 15.8 mole equivalents of ligand per mole of rhodium)and about 98 wt. % of C~
aldehyde (about 70 wt Z valeraldehyde and about 28 wt %
valeraldehyde trimer) as solvent to resctor 1. About 900 mili-liters of the same catalyst precursor solution was charged to reactor 2. The start-up and operating procedures set forth in Example 1~ were employed. In this experiment a purified Amberlyst A 21 ion exchange resin bed was employed from the ~tart of ~he process. Said bed was situated in the catalyst recycle line ~o that the recycled rhodium catalyst containing liqu~d reaction ~edium after remo~al of the desired aldehyde product passed through said bed on its retu~n to the reactor, On day 1 of the process an addieional amount of the same phosphite ligand was ~dded to make up for the low concentration in the original oharge. On day 7 the Amberlyst resin bed was replaced with 14~54-1 ; ~ - .

. . .

-lB4-0~

a new purified Amberlyst~ A-21 ion exchange resin bed.
On day 8 the æystem was ~hut down for two hours due to a power failure. On day 14 the r~odium complex catalysts were removed from both reactors because reactor liquid L
level control indicat~ons appeared erroneous. ~n day 15 fresh rhodium dicarbonyl acetylacetona~e was added to raise the reaction rate and an additional amount of the same phosphite ligand employed was added to maintain target concentratlon.
The hydroformylation reaction conditions as well as the rate of C5 aldehydes produced in terms of gram moles per liter per hour and the linear to branched aldehyde product ratio of n-valeraldehyde to 2-methylbutyraldehyde are given in TABLE 22 below.

1~054-1 .. .... . . _ _ .. . _ _ . _ . ~ _ . _ . ~ _ _ _ . _ .. _ .. _ _ _ . . . . _ . _ . _ . ..... . .... . . .

' :

-185~ O5,5 Days of Operation 7 16 ~2 Butene Feed, mol ~ I
Butene-1 4Z.6 46.1 43.5 Tr~ns-8utene-2 3~.6 30.5 32.5 Cis-Butene-2 22.~ 23.3 24.0 Reactor ~o. 1 Temperature, C 85 85.5 85.4 Pressure, psia 205 205 205 H2, ps~a 86.4 93.1 87.~
~O, ps1~ 27.5 8.1 12.7 Butene-l, psia 6.8 6.4 7.3 Trans-Butene 2 a~d Cis-Butene-2, p6ia 52.6 56.8 61.2 ~
Temperaeure, C 95.2 95.3 96.7 Pres~ure, p~i~ 185 185 185 H2, ps1a 78.2 70.7 69.0 CO, 2s~ 15.1 15.0 16.0 Butene-l, p~ia 2.7 3.6 3.8 Trans-Butene-2 and Ci~-Buten2-2~ p~ia 53.0 66.6 70.1 Result~ .
C5 A1dehydes, gmol/~/hr 3.31 3.15 3.01 ~inear/Branched Aldehyde Ratio1.59 1.91 1.81 __ 14054-1 ' , , , , ,,, ,, ,,,, ~, . .. . .. . .. .. .. .. . . .

, : .
.~ . -:-,, ." . .: ~

`:
.. ~ ., ' .

2~4(~,S

~ During this hydroformylation Pxperiment the hydroformyla~ciorl reaction medium was'monitored for alph~-hydroxypentyl phosphon$c acid via the s~Lme 31p NMR proceduse of Ex~mple 23. 31p NMR spectra of samples of the hydro-formylation reaction medium taken from reactor I on days7, 16 and 22 of the continuous process showed no detectable amounts of alpha-hydroxypentyl phosphonic acid deco~position product. ~oreover, in this experiment the commercial grade Amberlys ~ A-21 ion exchange resin bed was purified before use via a ~eries of elution washings to remove contaminate chlorides and aluminum oxy polym~rs (oligomers~. The puri-fication of the resin was conducted as follows. A 250 gram (630 mL) portion of ~he resin was char~ed to a 50 cm x 36 mm glass column equipped with a stopcock and containing a glass wool plug. The resin was washed with the following solvents ~t the given rate of bed volumes per hour: (a) three bed volumes (1890 mL) of 10% aqueous HC1; (b) four bed volumes (2520 mL) of 5Z aqueous ~aOH9 (c~ five bed volumes (31$0 ~L) of deionized water; (d) four bed volumes (2520 mL) of methanol and ~e) three bed volumes (1890 mL) of toluene.
The resin was then discharged from the column to a one-llter flask and dried At about 40~C. and 10 mm Hg pressure using a rotary evapor~tor. It i8 noteworthy ~hat no ~hloride-r~odium complexes showed up on the 31p NMR spectra of this 2~ experiment which employed the purified Amberlys ~ A-21 resin.

.. . . . .. ... . . . . . . .

'' .....

:' Var~o~ o~iicatio~ a~d variatisn6 of t~s ~nYentio~ ~ill be olbviou6 eo a ~orlcer ~k~lled in ~be ~rt ~na ~ eo be un~e~6too~ t~at ~3uc~ .
fiea~ions an~ ~r~at~ora~ ~are to b~ lu~e~
h~ tbe ~ur~ v of this ~pl~ca~c~on ar~d ~ plrit and ~cope o~E the ~ppen~e~ glal3~.

1~05~

.. . . .. . . _ _ .. _ _ . _ . . . . . .. ., .. .. _ .. .
, _ . . . . ... . .
............. -. .; .. :
, ' . , , ,' ~" ' .
.

. .

Claims (45)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for carbonylation comprising reacting an organic compound capable of being carbonyl-ated with carbon monoxide in the presence of a Group VIII transition metal - diorganophosphite complex catalyst consisting essentially of a Group VIII transi-tion metal complexed with carbon monoxide and a diorgano-phosphite ligand having the formula:

wherein W represents an unsubstituted or substituted monovalent hydrocarbon radical; wherein each Ar group represents an identical or different substituted or un-substituted aryl radical, wherein each y individually has value of 0 to 1, wherein, Q is a divalent bridging group selected from the class consisting of -CR1R2-, -O-, - S-, -NR3-, -SiR4R5-, and -CO-, wherein each R1 and R2 radical individually represents a radical selected from the group consisting of hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl, wherein each R3, R4, and R5 radical individually represents -H or -CH3, and wherein n has a value of 0 or 1.

2. A hydroformylation process for producing aldehydes as defined in claim 1 which comprises reacting an olefinically unsaturated organic compound with carbon monoxide and hydrogen in the presence of a complex catalyst as defined in claim 1, and in the added presence of a free diorganophosphite ligand having the formula wherein W represents an unsubstituted or substituted monovalent hydrocarbon radical; wherein each Ar group represents an identical or different substituted or un-substituted aryl radical, wherein each y individually has a value of 0 to 1, wherein Q is a divalent bridging group selected from the class consisting of -CR1R2-, -O-, -S-, -NR3-, -SiR4R5- and -CO-, wherein each R1 and R2 radical individually represents a radical selected from the group consisting of hydrogen, alkyl of 1 to 12 carbon atoms phenyl, tolyl and anisyl, wherein each R3, R4, and R5 radical individually represents -H or -CH3, and wherein n has a value of 0 to 1, and wherein the Group VIII transition metal is rhodium.

3. A hydroformylation process as defined in claim 2, wherein the olefinically unsaturated compound is selected from the group consisting of alpha-olefins containing from 2 to 20 carbon atoms. internal olefins containing from 4 to 20 carbon atoms, and mixtures of such alpha and internal olefins.

4. A process as defined in claim 3, wherein the hydroformylation reaction conditions comprise, a reaction temperature in the range of from about 50°C
to 120°C, a total gas pressure of hydrogen, carbon monoxide and olefinically unsaturated organic compound of from about 1 to about 1500 psia., a hydrogen partial pressure of from about 15 to about 160 psia., a carbon monoxide partial pressure of from about 1 to about 120 psia., and wherein the reaction medium contains from about 4 to about 50 moles of said diorganophosphite ligand per mole of rhodium in said medium.

5. A process as defined in claim 4 wherein the diorganophosphite ligand complexed with the rhodium and the free diorganophosphite ligand also present are each individually ligands having the formula wherein Q is -CR1R2 wherein each R1 and R2 radical individ-ually represents a radical selected from the group consisting of hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl, and n has a value of 0 to 1; wherein each Y1, Y2, Z2, and Z3 group individually represents a radieal selected from the group consisting of hydrogen, an alkyl radical having from 1 to 18 osrbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl and alicyclic radicals, cyano, halogen, nitro, trifluoromethyl, hydroxy, carbonyloxy, amino, acyl, phosphonyl, oxycarbonyl, amido, sulfinyl, sul-fonyl, silyl, ether, and thionyl radicals with the proviso that both Y1 and Y2 are radicals having a steric hindrance of iospropyl or greater, and wherein W represents a sub-cuted or unsubstituted alkyl radical.

6. A. process as defined in claim 5, wherein the olefin starting material is selected from the group consisting of butene-1, butene-2, isobutylene, and an olefin mixture consisting essentially of butene-1 and butene-2, wherein Q is -CH2- or -CHCH3-. wherein Y1 and Y2 are branched alkyl radicals having from 3 to 5 carbon atoms and wherein W is an unsubstituted alkyl radical having from 1 to 10 carbon atoms.

7. A process as defined in claim 6, wherein Y1 and Y2 are t-butyl radicals, Q is -CH2- and wherein W
is an unsubstituted alkyl radical having from 1 to 8 carbon atoms.

8. A process as defined in claim 6, wherein Y1 and Y2 are t-butyl radicals, Q is -CH2- and wherein W
is a phosphonyl substituted alkyl radical of the formula -[C(R7)2]pP(O)(R6)2 wherein each R6 is the same or different and is individually selectcd from the group consisting of alkyl, phenyl and cyclohexyl radicals, wherein each R7 is the same or different and is individually selected from the group consisting of hydrogen and alkyl radicals having from 1 to 4 carbon atoms and wherein p has a value of 1 to 10, with the proviso that one R6 radical can also be hydrogen.

9. A process a defined in claim 8, wherein W is a -CH2CH2P(O)(C6H5)2 radical.

10. A process as defined in claim 4, wherein the diorganophosphite ligand complexed with the rhodium and the free diorganophosphite ligand also present are each individually ligands having a formula selected from the group consisting of (III), (IV).

wherein Q is CR1R2 wherein each R1 and R2 radical indi-vidually represents a radical selected from the group con-sisting of hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl; and n has a value of 0 to 1; wherein each X1, X2, Y1, Y2, Z1, Z2, and Z3 group individually represents a radical selected from the group consisting of hydrogen, an alkyl rsdical having from 1 to 18 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl and alicyclic radicals above (e.g. phenyl, benzyl, cyclo-hexyl, 1-methylcyclohexyl , and the like), cyano, halogen, nitro, trifluoromethyl, hydroxy, amino, acyl, carbonyloxy, oxycarbonyl, amido, sulfonyl, sulfinyl, silyl, ether, phosphonyl, and thionyl radicals, with the proviso that at least both of the X1 and X2 groups or at least both of the Y1 and Y2 groups on a given diorganophosphite of Formulas (III) and (IV) above are radicals having a steric hindrance of isopropyl, or greater, and with the proviso that in Formula (III) above no more than three of the X1, X2, Y1, or Y2 groups is a radical having a steric hindrance of iospropyl or greater at the same time.

11. A process as defined in claim 10 wherein Q is -CH2- or -CHCH3- and wherein Y1 and Y2 are branched chain alkyl radicals having from 3 to 5 carbon atoms.

12. A process as defined in claim 10 wherein the olefin starting material is selected from the group consisting of butene-1, butene-2, isobutylene and an olefin mixture consisting essentially of butene-1 and butene-2, wherein Q is -CH2- and wherein each X1, X2, Y1, Y2, Z1, Z2, and Z3 group individually represents radical selected from the group consisting of hydrogen, an alkyl radical having from 1 to 8 carbon atoms, cyano, halogen, nitro, trifluoromethyl, hydroxy, amino, acyl, carbonyloxy, oxycarbonyl, amido, sulfonyl, sulfinyl, silyl, ether; phosphonyl and thionyl radicals.

13. A process as defined in claim 12 wherein the diorganophosphite ligand is selected from the group consisting of and

14. A process as defined in claim 13 wherein the olefin starting material is an olefin mixture con-sisting essentially of butene-1 and butene-2.

15. A process as defined in claim 14, wherein the hydroformylation comprises a continuous catalyst containing liquid recycle procedure.

16. A process as defined in claim 3 wherein the diorganophosphite complexed with the rhodium and the free diorganophosphite ligand also present are each individually ligands having the formula wherein Z2 and Z3 each individually represent a radical selected from the group consisting of hydroxy and an oxy radical -OR6, wherein R6 represents a substituted or unsubstituted monovalent hydrocarbon radical; wherein Y1 and Y2 each individually represents a radical selected from the group consisting of hydrogen, an alkyl radical having from 1 to 8 carbon atoms, substituted or unsub-stituted aryl, alkaryl, aralkyl and alicyclic radicals;
wherein W represents a substituted or unsubstituted monovalent hydrocarbon radical; wherein each y individually has a value of 0 to 1, wherein Q is a divalent bridging group selected from the class consisting of -CR1R2, -O-, -S-, -NR3-, -SiR4R5- and -CO-, wherein each R1 and R2, radical individually represents a radical selected from the group consisting of hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl, wherein each R3, R4, and R5 radical individually represents -H or -CH3, and wherein n has a value of 0 to 1.

17. A process as defined in claim 16 wherein each y has a value of zero, wherein Q is -CH2- or -CHCH3-;
wherein R6 is an alkyl radical of 1 to 10 carbon atoms;
wherein Y1 and Y2 each individually represent a radical selected from the group consisting of hydrogen, branched chain alkyl radicals having from 3 to 12 carbon atoms, phenyl, benzyl, cyclohexyl and 1-methylcyclohexyl; and wherein W represents a radical selected from the group consisting of an alkyl radical of 1 to 18 carbon atoms, alpha-naphthyl, beta-naphthyl, and an aryl radical of the formula wherein X1, X2 and Z4 each individually represent a radical selected from the group consisting of hydrogen, an alkyl radical having from 1 to 18 carbon atoms, substituted and unsubstituted aryl, alkaryl, aralkyl and alicyclic radicals, cyano, halogen, nitro, trifluoromethyl, hydroxy, amino, acyl, carbonyloxy, oxycarbonyl, amido, sulfonyl, sulfinyl, silyl, there, phosphonyl, and thionyl radicals, with the proviso that at least both of the X1 and X2 groups of at least both of the Y1 and Y2 groups on a given diorganophosphite ligand are radicals having a steric hinderance of isopropyl, or greater, and with the proviso that no more than three of the X1, X2, Y1 or Y2 groups is a radical having a steric hinderance of isopropyl or greater at the same time.

18. A process as defined in claim 17, wherein Z2 and Z3 each represent a -OR6 radical wherein R6 is an alkyl of 1 to 10 carbon atoms, wherein Y1 and Y2 are both branched chain alkyl radicals of 3 to 5 carbon atoms and wherein W is an alkyl radical of 1 to 10 carbon atoms.

19. A process as defined in claim 18 wherein Z2 and Z3 each represent a methoxy radical, wherein Y1 and Y2 each represent a tertiary butyl radical, and wherein W
represents a methyl radical.

20. A process as defined in claim 18 wherein q is zero.

21. A process as defined in claim 3, wherein the hydroformylation comprises a continuous catalyst containing liquid recycle procedure.

22. A process as defined in claim 3, which comprises minimizing decomposition of the free diorgano-phosphite ligand by (a) removing a portion of the liquid hydroformylation reaction medium from the hydroformylation reaction zone, (b) treating the liquid medium so removed with a weakly basic anion exchange resin and (c) returning the treated reaction medium to the hydroformylation re-action zone.

23. A process as defined in claim 22, wherein the hydroformylation comprises a continuous catalyst containing liquid recycle procedure.

24. A process as defined in claim 23 which comprises removing a portion liquid hydroformylation reaction medium from the hydroformylation reaction zone and passing said medium, either prior to and/or after separation of aldehyde product therefrom, through a weakly basic anion exchange resin bed.

25. A process as defined in claim 24, wherein said weakly basic anion exchange resin comprises a cross-linked tertiary amine polystyrene anion exchange resin of the gel or macroreticular type.

26. A process as defined in claim 10 wherein the diorganophosphite ligand complexed with the rhodium and the free diorganophosphite ligand are each individually ligands as defined by Formula (III), wherein X1, Y1 and Y2 each represent a radical having a steric hindrance of isopropyl or greater and wherein X2 represents a hydrogen radical.

27. A process as defined in claim 26, wherein X1, Y1 and Y2 are branched chain alkyl radicals having from 3 to 5 carbon atoms, wherein Q
is -CH2- or -CHCH3-, and wherein Z2 and Z3 each individually represent a radical selected from the group consisting of hydroxy and an alkoxy radical -OR6, wherein R6 represents a substituted or unsubstituted monovalent hydrocarbon radical.

28. A process as defined in claim 27, wherein n is zero, wherein Z2 and Z3 are methoxy radicals and wherein X1, Y1 and Y2 are t-butyl radicals.

29. A process as defined in claim 28, wherein Z4 is a methoxy radical.

30. A process as defined in claim 17, wherein Y1 and Y2 are radicals having a steric hindrance of isopropyl or greater and wherein W
represents an aryl radical of the formula wherein X1 represents a radical having a steric hindrance of isopropyl or greater, and wherein X2 is hydrogen.

31. A process as defined in claim 30, wherein Z2 and Z3 each represent a methoxy radical, wherein X1, Y1 and Y2 each represent a tertiary butyl radical and wherein n is zero.

32. A process as defined in claim 31, wherein Z4 is a methoxy radical.

33. A process as defined in claim 28, wherein the olefin starting material is an olefin mixture consisting essentially of butene-1 and butene-2.

34. A process as defined in claim 33, wherein the hydroformylation comprises a continuous liquid catalyst recycle procedure.

35. A rhodium complex hydroformylation catalyst comprising rhodium complexed with a diorganophosphite ligand having the general formula wherein Z2 and Z3 each individually represent a radical selected from the group consisting of hydroxy and an oxy radical -OR6, wherein R6 represents a substituted or unsubstituted monovalent hydrocarbon radical wherein Y1 and Y2 each individually represents a radical selected from the group consisting of hydrogen, an alkyl radical having from 1 to 8 carbon atoms, substituted or unsub-stituted aryl, alkaryl, aralkyl and alicyclic radicals;
wherein W represents a substituted or unsubstituted monovalent hydrocarbon radical; wherein each y individually has a value of 0 to 1, wherein Q is a divalent bridging group selected from the class consisting of -CR1R2, -O-, -S-, -NR3-, -SiR4R5- and -CO-, wherein each R1 and R2, radical individually represents a radical selected from the group consisting of hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl, wherein each R3, R4, R5 radical individually represents -H or -CH3, and wherein n has a value of 0 or 1.

36. A hydroformylation catalyst as defined in claim 35, wherein each y has a value of zero, wherein Q is -CH2- or -CHCH3-; wherein R6 is an alkyl radical of 1 to 10 carbon atoms;
wherein Y1 and Y2 each individually represent a radical selected from the group consisting of hydrogen, branched chain alkyl radicals having from 3 to 12 carbon atoms, phenyl, benzyl, cyclohexyl and 1-methylcycloexyl; and wherein W represents a radical selected from the group consisting of an alkyl radical of 1 to 18 carbon atoms, alpha-naphthyl, beta-naphthyl, and an aryl radical of the formula wherein X1, X2 and Z4 each individually represent a radical selected from the group consisting of hydrogen, an alkyl radical having from 1 to 18 carbon atoms, substituted and unsubstituted aryl, alkaryl, aralkyl and alicyclic radicals, cyano, halogen, nitro, trifluoromethyl, hydroxy, amino, acyl, carbonyloxy, oxycarbonyl, amido, sulfonyl, sulfinyl, silyl, ether, phosphonyl, and thionyl radicals, with the proviso that at least both of the X1 and X2 groups or at least both of the Y1 and Y2 groups on a given diorganophosphite ligand are radicals having a steric hinderance of isopropyl, or greater, and with the proviso that no more than three of the X1, X2, Y1 or Y2 groups is a radical having a steric hinderance of isopropyl or greater at the same time.

37. A catalyst as defined in claim 36, wherein Z2 and Z3 each represent a -OR6 radical wherein R6 is an alkyl of 1 to 10 carbon atoms, wherein Y1 and Y2 are both branched chain alkyl radicals of 3 to 5 carbon atoms and wherein W is an alkyl radical of 1 to 10 carbon atoms.

38. A catalyst as defined in claim 37, wherein Z2 and Z3 each represent a methoxy radical, wherein Y1 and Y2 each represent a tertiary butyl radical, and wherein W
represents a methyl radical.

39. A catalyst as defined in claim 38, wherein q is zero.

40. A Group VIII transition metal complex hydroformylation catalytic precursor composition consisting essentially of a solubilized group VIII
transition metal-diorganophosphite complex, an organic solvent, and free diorganophosphite ligand, wherein the diorganophosphite ligand is a ligand having the general formula wherein W represents an unsubstituted or substituted monovalent hydrocarbon radical; wherein each Ar group represents an identical or different substituted or un-substituted aryl radical, wherein each y individually has a value of 0 to 1, wherein Q is a divalent bridging group selected from the class consisting of -CR1R2-, -O-, -S-, -NR3-, -SiR4R5-, and -CO-, wherein each R1 and R2 radical individually represents a radical selected from the group consisting of hydrogen, alkyl of 1 to 12 carbon atoms phenyl, tolyl and anisyl, wherein each R3, R4, and R5 radical individually represents -H or -CH3, and wherein n has a value of 0 to 1.

41. A composition as defined in claim 40 wherein the Group VIII transition metal is rhodium.

42. A composition as defined in claim 41 wherein the rhodium-diorganophosphite complex is a rhodium carbonyl diorganophosphite acetylacetonate complex.

43 . A catalyst as defined in claim 36, wherein Y1 and Y2 are radicals having a steric hindrance of isopropyl or greater and wherein W
represents an aryl radical of the formula wherein X1 represents a radical having a steric hindrance of isopropyl or greater and wherein X2 is hydrogen.

44, A catalyst as defined in claim 43, wherein Z2 and Z3 each represent a methoxy radical, wherein X1, Y1 and Y2 each represent a tertiary butyl radical and wherein Z4 is a methoxy radical.

45. A catalyst as defined in claim 44 wherein n is zero.