This invention relates to polymeric polyols based on bis(hydroxymethyl)octadecanol with polybasic acids to make polyester polyols which have acid numbers less than about ten, and which polyester polyols are useful for a variety of known polyol applications as well as for making new urethane polymers which are advantageously useful in coatings, elastomers, adhesives, and caulking and sealing compositions or formulations.

FIELD OF INVENTION AND PRIOR ART 
This invention relates to polymeric polyols. More particularly, this 
invention relates to polymeric polyols based on 
bis(hydroxymethyl)octadecanol with polybasic acids to make polyester 
polyols which have low acid numbers, e.g., less than one, and which 
polyester polyols are useful for a variety of known polyol applications as 
well as for making new urethane polymers which are advantageously useful 
in coatings, elastomers, adhesives, and caulking and sealing compositions 
or formulations. 
In U.S. application Ser. No. 81,953, filed Oct. 4, 1979, there are 
described and claimed some gem-bis(hydroxymethyl) alcohol compounds having 
the general formula 
EQU CH.sub.3 (CH.sub.2).sub.m [C(CH.sub.2 OH).sub.2 ].sub.n (CH.sub.2).sub.p 
[C(CH.sub.2 OH).sub.2 ].sub.q (CH.sub.2).sub.r [C(CH.sub.2 OH).sub.2 
].sub.s (CH.sub.2).sub.t CH.sub.2 OH, 
wherein n, plus q, and s are separate numbers totaling 1 to 3; each of n, 
q, and s is 0 or 1; the sum of m through t totals 12 to 20; and, t is 3 or 
greater. The preferred specific alcohols of that formula are 
gem-bis(hydroxymethyl) octadecanols. Also described therein are a short 
history of hydroformylation technology for making alcohols, a list of 
prior patents relating to hydroformylation products, and methods for 
preparing the specific new polybis(hydroxymethyl) alkanols claimed 
therein. 
Hydroformylation is basically defined as the addition of a formyl group 
through the reaction of an unsaturated compound with carbon monoxide and 
hydrogen. The basic technology for the manufacture of hydroformylated 
products and, consequently, their derivatives is amply set out 
hereinafter. Among the difficulties which must be met in the manufacture 
of hydroformylated products is the consideration that hydrogen gas, an 
explosive, and carbon monoxide, a hazardous material, are utilized in the 
process. Hydroformylation processes are also dependent on expensive 
metallic catalysts, such as carbonyls, which have high toxicity and high 
cost. The conditions for running a hydroformylation reaction also involve 
the use of substantial temperature and pressure, thus necessitating costly 
equipment which must be maintained. 
Thus, due to the various factors and considerations which go into the 
manufacture of hydroformylated products and their derivatives, it is 
essential that the reactions, individually and cumulatively, give high 
purity of the desired end product and high yield, thereby avoiding 
excessive handling of hazardous materials while minimizing the high 
capital cost and maintenance of such production facilities. 
In the past, several attempts have been made to prepare hydroformylated 
products or similar materials, such as is described in U.S. Pat. No. 
2,437,600 to Gresham et al., issued Mar. 9, 1948. The Gresham patent 
relates to the synthesis of organic oxygen containing compounds, in 
particular, aldehydes. U.S. Pat. No. 2,533,276 to McKeever et al., issued 
Dec. 12, 1950, describes ester-acetals obtained with cobalt catalysts. 
U.S. Pat. No. 2,599,468 to McKeever, issued June 3, 1952, describes the 
process of preparing nonadecyl glycols. 
U.S. Pat. No. 3,040,090, issued June 19, 1962, to Alderson et al., 
discusses the reaction of hydrocarbons with aldehydes and higher alcohols 
in methanol to prepare organic oxy compounds. The Alderson et al. patent 
sets forth a number of metallic catalysts which may be employed in 
effecting the reactions described therein. 
In U.S. Pat. No. 3,043,871, issued July 10, 1962, to Buchner et al., the 
production of heptadecane-dicarboxylic acid is described. Foreman et al., 
in U.S. Pat. No. 3,227,640, issued Jan. 4, 1966, describes the production 
of olefinically-unsaturated alcohols which are of use in manufacturing 
some of the end products of the present invention. U.S. Pat. No. 
3,420,898, issued to Van Winkle et al., on Jan. 7, 1969, discusses the use 
of cobalt complexes with certain phosphine compounds in the production of 
primary alcohols with carbon monoxide and hydrogen. 
U.S. Pat. No. 3,530,190, issued Sept. 22, 1970, to Olivier, discusses 
hydrocarbonylation of olefins using certain metal salts. The foregoing 
reference also discusses the recovery of the complexed metal catalyst. In 
a patent to Ramsden, issued Jan 16, 1973 as U.S. Pat. No. 3,711,560, the 
production of polyolefins and other oxygenated organic compounds which are 
polyunsaturated is discussed. 
In U.S. Pat. No. 3,787,459, issued Jan. 22, 1974, to Frankel, a process is 
described for converting unsaturated vegetable oil into formyl products 
which are subsequently reduced to the corresponding hydroxymethyl 
derivative or oxidized to the corresponding carboxy products. U.S. Pat. 
No. 3,899,442, issued Aug. 12, 1975, to Friedrich, discusses a 
complementary system to that of the Frankel patent, whereby rhodium 
catalysts are recovered from the spent hydroformylation reactants. 
Frankel, again in the U.S. Pat. No. 3,928,231, issued Dec. 23, 1975, 
discusses a process of preparing carboxy acid products in high yields 
while minimizing isomerization of the starting unsaturated vegetable oil. 
Miller et al., in U.S. Pat. No. 4,093,637, issued June 6, 1978, discusses 
the use of formyl stearic acid to prepare bis acyloxymethylstearic acid 
which is stated to be useful as a plasticizer. 
U.S. Pat. No. 3,931,332, issued Jan. 6, 1976, to Wilkes, discusses 
hydroformylation reactions in which the destructive disassociation of the 
catalyst is inhibited by the presence of organic nitrogen compounds. 
Reichspatentamt Patentschrift No. 745,265, to Mannes et al., published 
Mar. 1, 1944, discusses the preparation of dicarboxylic acids and their 
salts. In Bundesrepublik Deutschland Pat. No. 965,697, issued June 13, 
1957, to Blaser and Stein, the reaction of unsaturated alcohols and their 
derivatives with metal carbonyls and carbon monoxide is discussed. A 
by-product which is obtained through the technology of Blaser et al. 
includes substantial amounts of monoformylated product. Similarly a 
formylation technique, which results in a monoformylated product when 
using unsaturated alcohols, is discussed in an article by Ucciani et al. 
in the Bull. Soc. Chim. (France) 1969, pp. 2826-2830. Similarly, 
Bundesrepublik Pat. No. 1,054,444, published Apr. 9, 1959, to Waldmann and 
Stein, discusses the treatment of unsaturated fatty substances with 
formaldehyde in the presence of a carboxylic anhydride and an acidic 
catalyst to provide formyl products. 
Substantial work has been done on the production of various hydroformylated 
products by the U.S. Department of Agriculture at both the Eastern and 
Western Regional Research Laboratories. For example, in an article by Roe 
entitled "Branched Carboxylic Acids from Long-Chain Unsaturated Compounds 
and Carbon Monoxide at Atmospheric Pressure," published at J. Am. Oil 
Chemists' Soc. 37, pp. 661-668 (1960), the production by direct 
carboxylation at atmospheric pressure of unsaturated acids with carbon 
monoxide or formic acid is discussed. The hydroformylation of unsaturated 
fatty esters is discussed by Frankel et al. at J. Am. Oil Chemists' Soc. 
46, pp. 133-138 (1968). Frankel has also reported a selective catalyst 
system for the hydroformylation of methyl oleate utilizing rhodium 
catalyst in the presence of triphenylphosphine in an article entitled 
"Methyl 9(10)-Formylstearate by Selective Hydroformylation of Oleic Oils" 
at J. Am. Oil Chemists' Soc. 48, pp. 248-253 (1971). 
In a paper presented at the American Oil Chemists' Society meeting in 
Atlantic City, N.J. in 1971, Dufek et al., discusses the esterification 
and transesterification of dicarboxylic acids under the title 
"Esterification and Transesterification of 9(10)-Carboxystearic Acid and 
Its Methyl Esters." The foregoing article was published at J. Am. Oil 
Chemists' Soc. 49 (5), pp. 302-306 (1972). Frankel, again, discusses the 
use of specific catalysts to obtain hydroformylated products in an article 
titled "Selective Hydroformylation of Polyunsaturated Fats With a 
Rhodium-Triphenylphosphine Catalyst," J. Am. Oil Chemists' Soc. 49, pp. 
10-14 (1972). Friedrich at Vol. 17, No. 3 of Ind. Eng. Chem. Prod. Res. 
Dev. (1978) presents an article entitled "Low-Pressure Hydroformylation of 
Methyl-Oleate With an Activated Rhodium Catalyst." 
Pryde, working with Frankel and Cowan discuss hydroformylation via the oxo 
reaction, Koch carboxylation and Reppe carbonylation in an article 
entitled "Reactions of Carbon Monoxide with Unsaturated Fatty Acids and 
Derivatives: a Review," reported at J. Am. Oil Chemists' Soc. 49, pp. 
451-456 (1972). 
Friedrich discusses the hydroformylation of unsaturated esters combined 
with catalyst recovery in an article entitled "Hydroformylation of Methyl 
Oleate with a Recycled Rhodium Catalyst and Estimated Costs for a Batch 
Process" at J. Am. Oil Chemists' Soc. 50, pp. 455-458 (1973). A similar 
area of technology is also reported by Frankel et al., in an article 
entitled "Hydroformylation of Methyl Linoleate and Linolenate with 
Rhodium-Triphenylphoshine Catalyst" from I&EC Product Research & 
Development, Vol. 12, pp. 47-53 (1973). 
Certain condensation polymers prepared from pentaerythritol acetal 
derivatives are reported in an article "Poly(Amide-Acetals) and 
Poly(Ester-Acetals) from Polyol Acetals of Methyl 9(10)- Formylstearate: 
Preparation and Physical Characterization" reported at J. Am. Oil 
Chemists' Soc. 53, pp. 20-26 (1976). Compounds obtained through 
hydroformylation technology useful as plasticizers are discussed in a 
Frankel et al. article entitled "Acyl Esters from Oxo-Derived 
Hydroxymethylstearates as Plasticizers for Polyvinyl Chloride" printed in 
the J. Am. Oil Chemists' Soc. 52, pp. 498-504 (1975). 
Friedrich, in an article entitled "Oxidation of Methyl Formylstearate with 
Molecular Oxygen" at J. Am. Oil Chemists' Soc. 53, pp. 125-129 (1976) 
reports the use of air or oxygen to form methyl carboxystearate from 
methyl formylstearate in an emulsion with a soluble rhodium complex. The 
reuse of catalyst in hydroformylation reactions is described by Awl in an 
article entitled "Hydroformylation with Recycled Rhodium Catalyst and 
One-Step Esterification-Acetalation: A Process for Methyl 
9(10)-Methoxymethylenestearate from Oleic Acid," which is printed in J. 
Am. Oil Chemists' Soc. 53, pp. 190-195 (1976). 
Useful diols for resin purposes are described in U.S. Pat. No. 2,933,477, 
issued Apr. 19, 1960 to Hostettler. Nonadecanediols are described as being 
utilized in urethane formulations in U.S. Pat. No. 3,243,414 to DeWitt et 
al., issued Mar. 29, 1966. The production of triols which are not 
particularly useful in resins due to the close positioning of the hydroxyl 
groups is reported in "Improved Synthesis of 1,1,1-trimethylolalkanes from 
Hexanal and Nonanal," J. Am. Oil Chemists' Soc. 45, p. 517 (July 1968) by 
Moore and Pryde. 
Frankel et al., in a paper entitled "Catalytic Hydroformylation and 
Hydrocarboxylation of Unsaturated Fatty Compounds" at J. Am. Oil Chemists' 
Soc. 54, p. 873A (1977) also describes formylation technology. Frankel 
also describes the use of carbonyl metallic compounds in hydroformylations 
in an article entitled "Catalytic Hydroformylation of Unsaturated Fatty 
Derivatives with Cobalt Carbonyl" at J. Am. Oil Chemists' Soc. 53, pp. 
138-141 (1976). The use of esters of various carboxystearic acids is 
discussed by Dufek et al. in an article entitled "Some Esters of Mono-, 
Di-, and Tricarboxystearic Acid as Plasticizers: Preparation and 
Evaluation" at J. Am. Oil Chemists' Soc. 53, pp. 198-203 (1976). Dufek et 
al. also report catalyst recovery in an article entitled "Recovery of 
Solubilized Rhodium from Hydroformylated Vegetable Oils and Their Methyl 
Esters" in J. Am. Oil Chemists' Soc. 54, pp. 276-278 (1977). 
Frankel discusses hydroformylation generally in an article entitled 
"Selective Hydroformylation of Unsaturated Fatty Acid Esters" at Annals 
N.Y. Academy of Sciences 214:79 (1973). Catalyst technology is reviewed at 
"Recent Developments in Hydroformylation Catalysis" in Catal. Rev. 6 (1) 
page 49 et seq. (1972). 
Dufek alone, at J. Am. Oil Chemists' Soc. 55, pp. 337-339 (1978) reports on 
the conversion of methyl 9(10) formylstearate in an article entitled 
"Conversion of Methyl 9(10)-Formylstearate to Carboxymethylstearate." 
Acetal esters obtainable through hydroformylation technology are reported 
by Adlof et al. in an article entitled "Preparation and Selective 
Hydrolysis of Acetal Esters" at J. Am. Oil Chemists' Soc. 54, pp. 414-416 
(1977). Selective catalyst systems are again reported by Frankel in the J. 
Am. Oil Chemists' Soc. 54, pp. 873a-881a (1977) in an article entitled 
"Catalytic Hydroformylation and Hydrocarboxylation of Unsaturated Fatty 
Compounds." 
The plasticization of polyvinylchloride resins is also reported in patent 
applications and coded P.C. 6333 and 6375 bearing respectively the titles 
"Acetoxymethyl Derivatives of Polyunsaturated Fatty Triglycerides as 
Primary Plasticizers for Polyvinylchloride," and "Alkyl 
9,9(10,10)-Bis(acyloxymethyl) octadecanoates as Primary Plasticizers for 
Polyvinylchloride." 
Each of the foregoing, to the extent that it is applicable to the present 
invention, is herein incorporated by reference. 
In U.S. application Ser. No. 26,854, filed Apr. 4, 1979, there are 
described and claimed some polyol derivatives based upon the 
above-described gem-bis(hydroxymethyl) alcohol compounds and 
poly(oxy)alkylene or caprolactone adducts and sulfates of such 
derivatives. Ethylene oxide adduct derivatives, propylene oxide adduct 
derivatives, propylene oxide capped with ethylene oxide adducts, sulfate 
adducts, urethane adduct derivatives and caprolactone adduct derivatives 
are specifically described and claimed therein. 
The whole of the disclosure of those prior applications is incorporated 
herein by reference thereto. 
OBJECTS OF THE INVENTION 
An object of this invention is to provide certain new polyester polyols 
based upon the gem-bis(hydroxymethyl) alcohols referred to above. 
Another object of this invention is to provide certain new polymeric 
polyols based on bis(hydroxymethyl)octadecanol with polybasic acids to 
make polyester polyols which have low acid numbers and which polyester 
polyols are useful for a variety of known polyol applications as well as 
for making new urethane polymers which are advantageously useful in 
coatings, elastomers, adhesives, and caulking and sealing compositions or 
formulations. 
Another object of the invention is to provide a new polyester polyol based 
upon bis(hydroxymethyl)octadecanol, a polybasic acid and a dicarboxylic 
acid ester. 
Another object of this invention is to provide new polyurethane polymers 
which are reaction products of a polyisocyanate and a new polyester polyol 
described herein, in either foamed or non-foamed condition, whether or not 
such polyurethane product contains other known ingredients, such as 
foaming agents, flame retardant agents, and the like. 
Other objects, advantages, and purposes of this invention will become 
apparent from reading the specification and claims which follow. 
SUMMARY OF THE INVENTION 
Briefly, this invention provides certain new polymeric polyols which are 
the reaction products of my above-referred to 
gem-bis(hydroxymethyl)alkanols and polybasic acids, preferably dibasic 
acids, e.g., adipic acid or maleic acid, fumaric acid, or other economical 
di- or poly- basic acid. The reaction product can also be the result of 
the reaction of the new gem-bis(hydroxymethyl) alkanols, referred to 
hereinabove, with a dibasic or polybasic acid and a dibasic acid mono- or 
diester, to effect transesterification in situ to form new polyester 
polyol products of this invention. These new polyester polyols provide the 
basis for the formation of new and advantageous polyurethane products 
which are known to have a variety of uses, e.g., in coating compositions, 
polyurethane foam insulating and packaging applications, adhesives, in 
caulking and sealing compositions, and in applications where non-foamed 
hard rubber-like uses are required, giving improved wear and tear 
resistance. 
DETAILED DESCRIPTION OF THE INVENTION 
The polyester polyol products of this invention can be prepared by mixing 
and reacting an above-referred to gem-bis(hydroxymethyl)alkanol, 
preferably bis(hydroxymethyl)octadecanol, with a polybasic acid, 
preferably a dibasic acid such as adipic acid, or other alkane or 
alkene-dicarboxylic acid, in an economical, non-toxic, organic solvent 
which will dissolve the reactants and form an azeotrope with water 
by-product of the poly-esterification reaction, and heating the mixture at 
a temperature sufficient to drive the esterification to completion in a 
reasonable period of time, in the presence of an economical acid to 
catalyze the esterification. Sulfuric acid is a preferred catalyst. 
Heating of the reaction mixture to from about 100.degree. C. to about 
200.degree. C. for from about 10 hours to about 24 hours while removing 
water, and returning the azeotroping liquid to the reaction mixture, is 
generally sufficient. Examples of azeotroping liquids include benzene, 
xylene, mesitylene, hexane, heptane, halogenated hydrocarbons such as 
dichloroethane, and the like. It is preferred to use xylene for reasons of 
cost and safety to employees operating the process. The molar ratio of 
triol to dibasic acid should not be less than about 1:1, otherwise the 
product will gell due to excess crosslinking if the aci number is reduced 
to a low value. The ratio of triol to dibasic acid should not be higher 
than that required to give a hydroxy equivalent weight of about 200 when 
the acid number is about 1. 
The gem-bis(hydroxymethyl)alkanol starting materials and how to make them 
are described and exemplified in my above-identified prior applications. 
The polyol of that type for use herein can be referred to as a 
bis(hydroxymethyl)akanol which has the structural formula 
##STR1## 
wherein the sum of x plus y ranges from 13 to 17, and preferably x plus y 
averages about 15 in a particular bis(hydroxymethyl)alkanol. A C.sub.20 
triol of this type is the general aim for production and use, but it is 
understood that in normal plant scale operation and use, the composition 
of the triol can be a mixture of such bis(hydroxymethyl)alkanol molecules 
where the sum of x plus y will vary from batch to batch and, in fact, be 
an average of the x and y moieties in the various molecules in the 
mixture. Preferably, the sum of x and y is about 14.5 to 15.5 in any given 
batch of triol starting material, and such sum is referred to herein as 
being "about 15." 
The preferred C.sub.20 triol alcohols used to make the polyester polyols of 
the invention can be prepared by known hydroformylation and reduction 
procedures referred to in my prior above-identified patent applications by 
converting commercially available methyl oleate to oleyl alcohol and 
converting oleyl alcohol to formyl octadecanol 
##STR2## 
by the above-referenced hydroformylation procedure and converting the 
formyl octadecanol to the C.sub.20 triol as described in application Ser. 
No. 081,953, filed Oct. 4, 1979 (case 4176). 
Such gem-bis(hydroxymethyl) alcohols have the formula 
EQU CH.sub.3 (CH.sub.2).sub.m [C(CH.sub.2 OH).sub.2 ].sub.n (CH.sub.2).sub.p 
[C(CH.sub.2 OH).sub.2 ].sub.q (CH.sub.2).sub.r [C(CH.sub.2 OH).sub.2 
].sub.s (CH.sub.2).sub.t CH.sub.2 OH, 
wherein n plus q plus s are integers the sum of which is from 1 to 3; n, q, 
and s are 0 or 1; and m through t are integers, the sum of which is from 
12 to 20 and t is 3 or greater. 
Such gem-bis(hydroxymethyl) alcohols are formed through hydroformylation 
which is the process for the production of aldehydes from 
olefinically-unsaturated compounds by reaction with carbon monoxide and 
hydrogen in the presence of a catalyst. The aldehydes produced generally 
correspond to the compounds obtained by the addition of a hydrogen and a 
formyl group to an olefinically-unsaturated group in the starting 
material, thus saturating the olefinic bond, as referred to above. 
More particularly, these gem-alcohols are prepared by hydroformylating an 
unsaturated alcohol of the formula 
EQU H(CH.sub.2).sub.a (CH.dbd.CH).sub.b (CH.sub.2).sub.c (CH.dbd.CH).sub.d 
(CH.sub.2).sub.e (CH.dbd.CH).sub.f (CH.sub.2).sub.g CH.sub.2 OH 
where, hereinafer, (1) a and g are not equal to 0; (2), the integers b plus 
d plus f are equal to y, which has a value of from 1 to 3; (3) the sum of 
the integers a plus c plus e plus g is equal to x; and (4) x plus 2y is 
equal to from 13 to 21; (5) m through t are integers, the sum of which is 
from 12 through 20; (6) n plus q plus s are 1 through 3, and; (7) n, q, 
and s are 0 or 1, preferably such that the sum of m through t is from 14 
to 18 and x plus 2y is 15 to 19. A second preferred embodiment is where n, 
p, r and s are 0 and m plus t is 11 through 19. It is also preferred that 
n and s are 0 and q is 1. 
Preferably, herein, m and t are each 4, 5 or 6, and greater. Most 
preferably, the starting raw material is oleyl alcohol, although linoleyl 
or linolenyl alcohol may be employed. It is, of course, noted that any 
number of synthetic unsaturated alcohols and alcohol mixtures may also be 
employed in the present invention. However, for the most purposes, the 
naturally-occurring alcohols derived from plant sources are presently most 
convenient and inexpensive. 
The unsaturated alcohol is reacted with hydrogen gas and carbon monoxide in 
the presence of a rhodium catalyst, as later described, to form the 
corresponding formyl alcohol having the formula 
EQU CH.sub.3 (CH.sub.2).sub.m [CH(CHO)].sub.n (CH.sub.2).sub.p [CH(CHO)].sub.q 
(CH.sub.2).sub.r [CH(CHO)].sub.s (CH.sub.2).sub.t CH.sub.2 OH, 
wherein the various subscript numbers are as previously described. 
The addition of hydrogen and carbon monoxide is accomplished in practice by 
conveniently adding stoichiometric amounts of the hydrogen and carbon 
monoxide to give the formyl alcohol. To assure completeness of the 
reaction, the amounts of hydrogen and carbon monoxide may be each 
maintained at from about 1.5:0.5 to about 0.5:1.5 molar ratio to one 
another. It is noted that the ratio is not critical as long as the 
pressure is maintained in the reaction vessel by the component gases and 
that the amount of hydrogen is not so great as to substantially reduce the 
unsaturated starting material. 
The rhodium catalyst, as later described, is necessary in the 
hydroformylation reaction in that it has been found that the use of the 
more conventional cobalt catalyst results in a substantial amount of 
cross-linking and gelation. It is believed that the gelation is due to the 
coproduction of polyhemiacetals and polyacetals in competition with the 
production of the hydroformylated alcohol. It was first believed that it 
would be necessary, even with a rhodium catalyst, to employ the ester of 
the unsaturated alcohol, e.g., oleyl acetate, to avoid the unwanted 
by-products. Of course, the ester is more expensive and eventually is 
converted to the alcohol in any event. 
Higher yields of product are obtained through the use of the rhodium 
catalysts than if a cobalt catalyst is employed. It has also been observed 
that a much higher degree of isomerization of the double bond occurs with 
a cobalt catalyst than with a rhodium catalyst. 
The conditions for pressure and temperature during the batch 
hydroformylation are conveniently conducted at from about 90 degrees C. to 
about 170 degrees C., preferably from about 100 degrees C. to about 130 
degrees C. Above the higher temperatures listed above, increased amounts 
of unwanted by-products are formed in the reaction mixture. The pressure 
conditions are such that the pressure in the scaled system is maintained 
at from about 20 to about 500 atmospheres, preferably from about 30 to 
about 100 atmospheres absolute, during the hydroformylation. Higher 
temperatures and pressures are employed when using a continuous process. 
The preferred end product obtained from conducting the foregoing process is 
9(10) formyl octadecanol when the starting material is oleyl alcohol. The 
positioning of the 9(10) indicates that the product obtained is a mixture 
of the 9 and 10 isomer with respect to the formyl group. One additional 
reason for using a rhodium catalyst is that, if a cobalt catalyst were 
employed, a considerable amount of terminal aldehyde would be formed due 
to bond migration prior to the addition of the formyl group. When the 
terminal aldehyde group is formed, the resultant alcohol, obtained by 
carrying out the remainder of the herein-described process, is unsuitable 
for many of the purposes that the geminal alcohols may be utilized for. 
It should also be appreciated that, if 9,12-linoleyl alcohol is the 
starting material, then the formyl alcohol so formed will be a 9(10), 
12(13) diformyloctadecanol. That is, the end product obtained here will 
actually be a mixture of the 9-12, 9-13, 10-12, 10-13 diformyl alcohols. 
Similarily, without discussing all the particular isomers present when 
9,12,15-linolenyl alcohol is employed, the product so obtained will be a 
mixture of the 9(10), 12(13), 15(16) triformyloctadecanol isomers. 
It is particularly important that the expensive rhodium catalyst is 
recovered. This may be conveniently done by distillation of the formyl 
alcohol leaving the rhodium in the residue. What is particularly 
surprising is that the rhodium can be recovered from the distillate, in 
that the art would predict that, when hydroformylating an unsaturated 
alcohol, the products obtained would include considerable quantities of 
polyhemiacetals and polyacetals as a portion or all of the reaction 
product, and that these products would not be recoverable by distillation. 
Thus, not only is the desired end product achieved in a high degree of 
purity and yield through the use of the rhodium catalyst, but the rhodium 
catalyst is recoverable in extremely high quantities from the reaction 
mixture. 
It may be stated that the polyacetal and polyhemiacetal formation might be 
prevented by the utilization of the corresponding unsaturated acid or its 
ester in place of the unsaturated alcohol. However, this substitution, 
which eventually involves the acid ester, is undesirble in that an aqueous 
neutralization step is required, which forms a soap as a by-product. The 
soap so formed then emulsifies the reaction products and the water present 
to make separation extremely difficult, thus diminishing recovery of both 
the alcohol and the expensive catalyst. Thus, the present invention is 
highly selective to both the unsaturated alcohol and the particular 
rhodium catalyst so employed. 
Any convenient source of rhodium may be employed, as in the present 
reaction mixture; the rhodium catalyst is actually converted through the 
presence of the hydrogen and carbon monoxide into its active form, which 
is a rhodium carbonyl hydride. Conveniently, the source of rhodium for use 
in the rhodium catalyst may be rhodium chloride, rhodium dicarbonyl 
chloride dimer, rhodium nitrate, rhodium trichlorite and other similar 
materials. 
The rhodium catalyst in the present hydroformylation reaction is preferably 
present with a ligand, such as trisubstituted phosphine or trisubstituted 
phosphite. The term trisubstituted includes both alkyl and aryl compounds 
and the substituted compounds of the alkyl and aryl compounds. A 
particularly valuable ligand for the rhodium carbonyl hydride is 
triphenylphosphite or triphenylphosphine in that both compounds are 
particularly useful in minimizing migration of the double bond, thereby 
avoiding a large number of isomers with respect to the formyl group, 
including the undesired terminal formyl compound, as previously discussed. 
In general, triarylphosphines or triarylphosphites may be used for this 
purpose in the formation of the rhodium carbonyl hydride ligand. In 
addition, the foregoing materials are extremely valuable in minimizing the 
undesired reaction of saturation of the double bond or the reduction of 
the formyl group,. This frequently occurs in the absence of such ligands 
because the rhodium catalyst functions excellently as a hydrogenation 
catalyst. That is, the ligand tends to eliminate such side reactions. 
In general, any one of several other additional ligands may be used with 
the rhodium catalyst. Such additional ligands are discussed in the 
"Selective Hydroformylation of Unsaturated Fatty Acid Esters" by Frankel 
in the Annals N.Y. Academy of Sciences 214:79 (1973). 
The various ligands are conveniently employed in mole ratio to the rhodium 
metal content of the catalyst of from about 2 to 50, preferably from about 
3 to 20. The rhodium catalyst, based upon its metal content, is 
conveniently employed in catalytic amounts, preferably from about 20 ppm 
to about 10,000 ppm, most preferably from about 50 ppm to about 500 ppm by 
weight of the unsaturated alcohol. 
The various formyl alcohols are useful, as previously stated, in preparing 
the highly desired gem-bis(hydroxymethyl) alcohols. The alcohols may be 
formed from the foregoing formyl alcohols via a Tollens' reaction (aldol) 
condensation followed by a crossed-Cannizzaro reaction). 
Schematically, the Tollens' reaction is as described below: 
##STR3## 
wherein in the above formula R indicates an organic moiety, compound (I) 
is a hydroxymethyl aldehyde and MOH is a strong base. 
The Tollens' reaction is thus carried out by reacting one mole of a 
monoformylated alcohol with two moles of formaldehyde in an inert 
atmosphere such as nitrogen. Where the formyl alcohol contains more than 
one formyl group, two moles of formaldehyde are required for each formyl 
group present. Thus, if the reactant is formyloctadecanol, then two moles 
of formaldehyde are required for conversion to the gem-bis (hydroxymethyl) 
alcohol whereas, if linoleyl alcohol is utilized in the first instance to 
give a diformyloctadecanol, then four moles of formaldehyde are required 
to obtain the di-gem-bis(hydroxymethyl)octadecanol. Conveniently, an 
excess of up to 1.5, preferably up to 1.2, times the amount of 
formaldehyde actually required to form the corresponding 
gem-bis(hydroxymethyl) alcohol is employed. A convenient manner of adding 
the formaldehyde in the Tollens' reaction is by using a methanol solution 
of formaldehyde. 
The Tollens' reaction utilizes a strong base as both a reactant and a 
catalyst. Such strong bases include sodium, potassium or calcium 
hydroxide. Other strong bases, such as carbonates or other hydroxides, may 
be used as well. The strong base is conveniently employed on an equivalent 
basis per formyl group to convert the formyl group to the hydroxy methyl 
group. The amount of base required in the Tollens' reaction is at least an 
equivalent of that required, preferably up to 1.5, most preferably up to 
1.2 equivalents. The Tollens' reaction is conducted at a temperature of 
from about 0 degrees C. to about 100 degrees C., preferably from about 20 
degrees C. to about 70 degrees C. 
The crude gem-bis (hydroxymethyl) alcohol so formed is washed with water to 
remove any excess caustic and salts formed and then obtained in a 
relatively pure state by vacuum drying. 
In obtaining the gem-bis (hydroxymethyl) alcohol, the crossed-Cannizzaro 
reaction predominates over the rate of reaction for the simple Cannizzaro 
reaction. The Cannizzaro reaction, which is promoted by base, water, and 
heat, is the process by which an aldehyde reacts with itself to form the 
corresponding alcohol and formate salt. That is, the formyl group on the 
formyl alcohol reacts faster with formaldehyde to give the alcohol than 
does the formaldehyde react with itself. 
It is also surprising that the formation of hemiacetal, which may be acid 
or base, catalyzed, does not occur upon the addition of base to the formyl 
alcohol while forming the intermediate hydroxymethyl formyl alcohol. Thus, 
two potential side reactions, the Cannizzaro and the hemiacetal formation 
(and thereafter the acetal) which might be expected, given the reactants 
and the processing conditions involved, do not in fact occur, and the 
useful alcohol is obtained in substantial quantities. 
It has been found, however, that the more complicated crossed-Cannizzaro 
surprisingly predominates in rate and amount of product 
[gem-bis(hydroxymethyl) alcohol] produced despite the steric hindrance of 
the larger formyl alcohol molecule even under conditions which are known 
to promote the simple Cannizzaro reaction. 
An alternative method of accomplishing the formation of the 
gem-bis(hydroxymethyl) alcohol is to use only about one-half the 
equivalent amount of the formaldehyde required in the Tollens' reaction, 
thereby forming the corresponding hydroxymethyl formyl alcohol via the 
aldol condensation. That is, the hydroxymethyl group is attached to the 
carbon in the alpha position to the formyl group. Where a polyformyl 
alcohol is the intermediate product, the formaldehyde is halved from that 
utilized in the Tollens' reaction to give the corresponding 
polyhydroxymethyl polyformyl alcohol. 
This variation of forming the gem-bis (hydroxymethyl) alcohol eliminates 
the need for the strong base required in the Tollens' reaction and 
utilizes instead only catalytic amounts of base which may be either a weak 
or strong base. A preferred weak base is triethylamine. Even here, some 
care must be taken, as it is possible even when using a weak base to 
obtain compound (I), as the Cannizzaro reaction may compete with the aldol 
condensation. 
The hydroxymethyl formyl alcohol so formed by this alternative route is 
then reduced to the alcohol conveniently, by using hydrogen gas and a 
suitable hydrogenation catalyst, such as copper, or nickel, via 
conventional hydrogenation practice, or by lithium aluminum hydride 
reduction. A significant advantage to the alternative route is the absence 
of large amounts of salt and solvents needed in the Tollens' reaction 
route. 
A distinct advantage in the gem-bis(hydroxymethyl) alcohol is that it is a 
ligant at room temperature and, further, has no tertiary hydrogens which 
are a weak point for chemical attack on the molecule. 
The polybasic acid reactant has from 4to about 36 carbon atoms per molecule 
and is preferably a C.sub.4 to C.sub.10 -dicarboxylic acid, examples of 
which are well known in the chemical literature. Examples include maleic 
acid, fumaric acid, 1,5-pentanedicarboxylic acid, adipic acid, 
1,7-heptanedicarboxylic acid, sebacic acid, 1,10-decanedicarboxylic acid, 
heptadecanedicarboxylic acids (such as described in U.S. Pat. Nos. 
3,864,314 and 2,891,084) and C.sub.21 or C.sub.22 dicarboxylic acids (such 
as described in U.S. Pat. Nos. 3,821,075 and 3,899,476), and dicarboxylic 
acids having single or double carbon-to-carbon unsaturation or additional 
hydroxy groups therein, such as itaconic acid, itamalic acid, and malic 
acid. Other useful dicarboxylic acids are the well-known dimeric 
dicarboxylic acids resulting from the polymerization of unsaturated fatty 
acids. The dicarboxylic products resulting from the dimerization of the 
C.sub.18 unsaturated fatty acids such as oleic, linoleic, or linolenic 
will contain 36 carbon atoms. These acids and their corresponding alcohols 
or glycols are generally discussed in U.S. Pat. No. 3,511,792, including 
references to other patents relating thereto. 
Aromatic dicarboxylic acid esters which may optionally be incorporated into 
the reaction mixture include the o-, m-, and p-phthallic acid C.sub.1 to 
C.sub.2 esters, e.g., the dimethyl and diethyl esters of phthallic, 
isophthallic and terephthallic acids, and the exters of trimellitic acid 
and similar tri-carboxylic acids, when some degree of three-dimensional 
polymerization my be desired later in use applications of the polyol. 
As indicated above, one aspect of this invention involves the use of these 
new polyester polyols as the polyol component in making new polyurethane 
products by reaction of the new polyol with a polyisocyanate by known 
procedures and in known formulations for making foamed or non-foamed 
polyurethane products. Suitable polyisocyanates and other components of 
the polymeric reaction mixture are exemplified in prior application Ser. 
No. 26,854, filed Apr. 4, 1979. For example, suitable polyisocyanates 
include ethylene diisocyanate, trimethylene diisocynate, hexamethylene 
diisocyanate, propylene-1,2-diisocyanate, ethylidene diisocyanate, 
cyclopentylene-1,3-diisocyanate, the 1,2-, 1,3-, and 1,4-cyclohexylene 
diisocyanates, the 1,3- and 1,4-phenylene diisocyanates, polymethylene 
polyphenylene-isocyanates, the 2,4- and 2,6-toluene diisocyanates, the 
1,3- and 1,4-xylylene diisocyanates, bis (4-isocyanatophenyl)methane, 
4,4'-diphenyl-propane diisocyanates, bis(2-isocyanatoethyl) carbonate, 
1,8-diisocyanato-p-methane, 1-methyl-2,4-diisocyanato-cyclohexane, the 
chlorophenylene diisocynates, naphthalene-1,5-diisocyanate, 
triphenylmethane-4,4',4"-triisocyanate, 
isopropylbenzene-alpha-4-diisocyanate,5,6-bicyclo[2.2.1]hept-2-ene 
diisocyanate, 5,6-diisocyanatobutylbicyclo[2.2.1]hept-2-ene, and similar 
polyisocyanates. 
Of particular interest in the present invention are trimethylene hexamethyl 
diisocyanate available from VEBA, and heptadecyl (C17) diisocyanate, 
DDI.RTM. 1410, an aliphatic C-36 diisocyanate available from the Henkel 
Corporation of Minneapolis, Minn. (Generally, diisocyanates having from 12 
to 40 carbons in the aliphatic radical may be used in the present 
invention, e.g., toluene diisocyanate, available from Allied Chemical; 
isophorone diisocyanate, available from VEBA; and Desmodur N, an aliphatic 
triisocyanate, available from Mobay). Desmodur N is more particularly 
defined as the tri-isocyanate adduct of 3 moles of hexamethylene 
diisocyanate and water having an isocyanate equivalent weight, as later 
defined, of 191 grams. Other adducts or prepolymers of polyisocyanates 
include Desmodur L and Mondur CB, which are the adduct of toluene 
diisocyanate. The foregoing materials have an isocyanate equivalent weight 
of approximately 250 grams. 
The amount of the polyisocyanate utilized in forming the urethane 
compositions of this invention is expressed on a percentage equivalent 
weight basis with respect to the hydroxyl functionality of the alcohol. 
Desirably, each hydroxyl functional group on the alcohol will react on a 
1:1 stoichiometric basis with the isocyanate functionality on the 
polyisocyanate compound. It is quite feasible, however, to form the 
urethane linkage using from about 80 percent to 120 percent, preferably 
from about 95 percent to 105 percent, on a hydroxyl-isocyanate equivalent 
basis, of the polyisocyanate to form the urethane product. 
To determine the amount of the polyisocyanate required for a given 
saturated polyol, the hydroxyl or isocyanate equivalent weight of the 
respective polyol or polyisocyanate is determined as that weight in grams 
of the material which contains one gram equivalent weight of the 
respective functional group. More particularly, to determine the number of 
equivalents in a given saturated polyol, the hydroxyl value is first 
determined by known methods and reported in milligrams of potassium 
hydroxide. The calculation to determine the hydroxyl equivalents is then 
given by the following equation: 
##EQU1## 
where 56,100 is the milligram equivalent weight of potassium hydroxide. 
Alternatively, if the weight percentage of the hydroxyl groups in the 
saturated polyol is known, the hydroxyl equivalent is determined as 
follows: 
##EQU2## 
where 17 is the equivalent weight of the hydroxyl radical and the weight 
percent OH is the percentage of the saturated polyol which is hydroxyl 
groups. 
In similar fashion, the isocyanate equivalent may be determined if the 
weight percent of the isocyanate functional groups in the polyisocyanate 
is known. This equation is given below, where 42 is the molecular weight 
of an isocyanate functional group and the weight percent NCO is that 
portion of polyisocyanate made up of isocyanate functional groups: 
##EQU3## 
To form the urethane reaction product, the polyester polyol of the present 
invention and the organic polyisocyanate are merely mixed together in the 
proper proportions. When utilized as a coating, the compounds are then 
quickly spread with a knife blade, brushed, or sprayed over the surface of 
the article to be coated. Where molded articles are desired, various 
techniques, such as injection molding, are employed. Specific technique 
for forming urethane reaction products is hereinafter described in the 
examples. 
If desired, various urethane catalysts may be employed to promote the 
reaction. Examples of such urethane catalysts include triethylene diamine, 
morpholine, N-ethyl-morpholine, dimethyl piperazine, triethylamine, 
N,N,N',N'-tetramethylbutane-1,3-diamine, dibutyltin dilaurate, stannous 
octoate, stannous laurate, dioctyltin diacetate, lead octoate, stannous 
oleate, stannous tallate, dibutyltin oxide, and hexabutylditin, as well as 
other art-recognized urethane catalysts. Typical levels of the urethane 
catalyst are from about 0.001 percent to about 5 percent by weight of the 
urethane linking components. 
An additional polyol may be included with the alcohols of the present 
invention. Such polyols may be an alkyl or cycloalkyl polyol, an 
ether-linked polyol, an ether and ester-linked polyol, or hydroxy 
functional acrylic copolymers. 
Specific examples of alkyl and cycloalkyl polyols include 2,5-hexanediol 
available from Aldrich Chemical; 1,6-hexanediol, available from Celanese 
Chemical; ethylene glycol available from Baker; Dimerol or dimer glycol, a 
36 carbon diol prepared from the dimerized fatty acids discussed earlier 
herein; which dimer glycols are discussed in U.S. Pat. Nos. 2,347,562, 
2,413,612, and 3,091,600, among other references; glycerol, 
1,2,6-hexanetriol available from Union Carbide; pentaerythritol, and 
1,4-cyclohexane diol. Additional examples of such polyols include Poly BD 
R-45HT.TM., a butadiene diol having an approximate molecular weight of 
2800, available from Arco; and, trimethylol propane available from 
Celanese Chemical. 
The ester-linked saturated diols of the present invention are more 
particularly described as polyols where the predominate linkage 
(functional group other than the hydroxyl) are ester radicals. The 
ester-linked saturated polyols are structurally represented as 
##STR4## 
where R and R' are organic residues which contain at least two hydroxyl 
radicals and at least one ester link. 
Examples of ester-linked saturated polyols include Niax PC00200.TM. and 
PCP0240.TM., both available from Union Carbide and having respective 
molecular weights of approximately 530 and 2000. Both of the foregoing 
compounds are diols. Niax PCP0300, also available from Union Carbide, is a 
caprolactone-ester triol having approximate molecular weight of 540. Niax 
PCP0310.TM., also available from Union Carbide, is a caprolactone-ester 
triol having a molecular weight of approximately 900. 
The ether-linked saturated polyols of the present invention include 
compounds such as diethylene glycol and triethylene glycol, both available 
from Fisher. Further ether-linked saturated polyols useful in the present 
invention include the Polymeg Q0650.TM., Q0100.TM., and Q0200.TM., all of 
which are ether diols available from Quaker, having a respective molecular 
weight of approximately 650, 1000, and 2000. Pluracol P1010.TM., having an 
approximate molecular weight of 1050, available from Wyandotte, is an 
example of a polypropylene oxide ether-linked diol useful in the present 
invention. Similar Wyandotte products useful as saturated polyols in the 
present invention include Pluracol TP440.TM., and 150, which are propylene 
oxide ether-linked triols having respective molecular weights of 
approximately 425 and 1560. In similar fashion, Pluracol GP3030.TM. is 
another saturated polyol suitable for the present invention, available 
from Wyandotte. The foregoing material is a glycerine polypropylene 
ether-linked triol having an approximate molecular weight of 2900. 
Additional Pluracols.TM. useful in the present invention include Pluracol 
PEP450, which is a pentaerythritol polypropylene oxide ether-linked 
tetrol, having a molecular weight of 405, and Pluracol 493, an 
ether-linked tetrol having a molecular weight of approximately 3630. 
Ester and ether-linked saturated polyols suitable in the present invention 
are described structurally as 
##STR5## 
where R, R', and R" are organic residues containing at least two hydroxyl 
radicals and at least one ester and one ether linkage.

Detailed examples of how to prepare the polyester polyols of this invention 
are set forth hereinbelow without any intent that these examples be 
limiting as to the scope of the invention. Throughout the specification 
and claims hereof, the percentages and ratios are by weight and the 
temperatures are in degrees Celsius, unless otherwise indicated. 
EXAMPLE I 
A polyester polyol is prepared by reacting 131.2 grams (1.8 equivalents) of 
adipic acid with 414 grams (3.6 equivalents) of 
bis(hydroxymethyl)octadecanol in 100 grams of xylene which serves as the 
azeotrope to remove water of condensation. The reaction is maintained at 
175.degree. C. for a period of twenty hours, 0.13 grams of concentrated 
sulfuric acid being added at the beginning and 0.05 grams later on in the 
reaction. The water removed is collected in a Dean and Stark tube. At the 
end of the heating period, the xylene is removed under vacuum leaving a 
viscous liquid which at 22.5.degree. C. has a viscosity of 175 PA/S, 
Pascal-seconds (sometimes also designated as Pa.multidot.s or merely Pas), 
an acid value of 0.9, and a hydroxy equivalent weight of 356. In U.S. Pat. 
No. 4,045,389, the reference to "Pas" is made with 1 Pas equal to 10 
poises. In a subsequent patent to the same inventors, U.S. Pat. No. 
4,150,002, the term is "Pa.multidot. s." 
This polyester polyol (50.6 grams, 0.142 equivalents) and 125.3 grams 
(0.833 equivalents) of hydroxymethyl octadecanol are blended at room 
temperature. To this is added 88.6 grams (1.0 equivalent) of toluene 
diisocyanate with stirring under vacuum. After three minutes the 
temperature rises spontaneously to 55.degree. C. and the reaction product 
thereafter is poured into metal molds. The elastomer is cured 22.5 hours 
at 100.degree. C. The polymer sets to a solid before one hour of the final 
cure time has passed. 
This elastomer is evaluated for hardness, strength, water absorption, 
hydrolytic stability, and resistance to torsional stress at low 
temperatures. The findings follow: 
______________________________________ 
Hardness, Shore Durometer, D Scale (ASTM-D-2240-75) 
66 
Tensile strength at break, PSI (ASTM-D-412-75) 
3630 
Tensile strength at yield, PSI (ASTM-D-412-75) 
1380 
Elongation at break, % (ASTM-D-412-75) 
160 
Compression Set, % (ASTM-D-395-69) 
22.5 
Water absorption, 24 hrs, 70.degree. C., grams/1000 cc 
8.6 
Hydrolytic stability, retention of tensile 
strength after 18 hrs, wet steam 125.degree. C. (14 PSI), 
71 
T.sub.f, temperature to achieve 45,000 modulus, .degree.C. 
(ASTM-D-1043-72) -7 
______________________________________ 
EXAMPLE II 
A second polyester polyol is produced by reacting 414 grams (3.6 
equivalents) of bis(hydroxymethyl)octadecanol with 43.74 grams (0.6 
equivalents) of adipic acid and 58.26 grams (0.6 equivalents) of dimethyl 
isophthalate in 150 grams of xylene as azeotrope using as catalyst 1.81 
grams of dibutyl tin oxide. Over a period of about four hours the 
temperature is raised to 180.degree. C. by gradual removal of xylene by 
distillation. The temperature is then maintained at 180.degree. C. for 
about 61/2 hours, after which no further water evolves and the xylene is 
removed by distillation under vacuum. The polyester polyol has a viscosity 
of 43.8 PA/S, an acid number of 0.1, and a hydroxy equivalent weight of 
202. 
EXAMPLE III 
To 170 grams of toluene containing 3.49 grams of dibutyl tin oxide catalyst 
were added 673.4 grams (1.952 moles) of bis(hydroxymethyl)octadecanol and 
325 grams (0.975 moles) of heptadecane dicarboxylic acid, (a C.sub.19 
diacid). The reactants were heated and stirred with a nitrogen atmosphere, 
gradually distilling off toluene and water through a Dean and Stark 
take-off unit. Over a period of 71/2 hours the temperature was raised from 
an initial 153.degree. C. to 190.degree. C. while taking off water. The 
next day the heating was continued for 6 hours at 190.degree. C. until the 
acid value of 0.7 based on solids was obtained. 
The product was stripped of the remaining toluene on a rotary evaporator. 
The product analyzed as follows: 
Acid No.=0.7 
Hydroxyl equivalent weight=278 
Visc. at 23.degree. C.=132.4 poises 
EXAMPLE IV 
To 150 grams of toluene containing 1.76 grams of dibutyl tin oxide catalyst 
were added 276 grams (0.8 mole) of bis(hydroxymethyl) octadecanol and 228 
grams (0.4 mole) of VERSADYME.RTM.52, a polymerized tall oil fatty acid 
having the following analysis: 
Saponification value--196.8 
Saponification Equivalent weight--285.1 
Acid Value--195.4 
% Monomer (M)--2.3 
% Intermediate (I)--3.5 
% Dimer (D)--91.0 
% Trimer (T)--3.2 
The temperature was raised from an initial 128.degree. C. to 185.degree. C. 
in 21/2 hours and maintained there for 11 hours using the same procedure 
and apparatus as in Example III above. The product was stripped and 
analyzed as follows: 
Acid No.=0.3 
Hydroxyl equivalent weight=328.5 
Visc. at 23.degree. C.=415 poises 
It is to be understood that the invention is not to be limited to the exact 
details of operation or structure shown and described, as obvious 
modifications and equivalents will be apparent to one skilled in the art.