Self-compatibilizing polyester polyol blends based on dimethyl terephthalate residues

Fluorocarbon blowing agent compatible polyol blends are provided comprising reaction products of a combination of (a) a residue from the manufacture of dimethyl terephthalate, (b) a low molecular weight diol compound, (c) a nonionic surfactant compound, (d) optionally a hydrophobic compound, and (e) optionally a polybasic carboxylic acid compound. These polyol blends are produced by a simple heating process and are thereafter optionally blendable with various conventional polyols and other additives (including fluorocarbons and catalysts) to make resin prepolymer blends. Such resin blends can be catalytically reacted with organic isocyanates to produce cellular polyurethanes and polyurethane/polyisocyanurates.

BACKGROUND OF THE INVENTION 
1. Field Of The Invention 
This invention lies in the field of polyols useful in formulating resin 
prepolymer blends for reaction with organic isocyanates to produce 
polyurethane and/or polyurethanepolyisocyanurate cellular polymers, and, 
more particularly, in the field of polyester polyols based on dimethyl 
terephthalate residues which polyols are compatible with high levels of 
fluorocarbon blowing agents. 
2. Prior Art 
Aromatic polyester polyols are coming into widespread usage in the 
manufacture of polyurethane and polyurethanepolyisocyanurate foams. Such 
polyester polyols are attractive because they tend to be low in cost, yet 
can produce rigid cellular polymers of excellent properties adapted for 
many end use applications. 
One class of aromatic polyester polyols which has recently become 
commercially available comprises esters produced by esterifying phthalic 
acid or phthalic acid anhydride with an aliphatic polyhydric alcohol. For 
example, a diethylene glycol phthalate is available commercially from 
Stepan Company, Northfield, Ill. Such liquid product has a desirably low 
viscosity, a desirably high aromatic ring content, and a desirably low 
acid number. Even though such product typically has a reactive hydrogen 
functionality of less than about 3, it catalytically reacts well with 
organic isocyanates to produce, for example, rigid cellular 
polyurethane-polyisocyanurate polymers that can have commercially 
acceptable characteristics. 
Another class of aromatic polyester polyols which has recently become 
commercially available comprises esters produced by reacting polyethylene 
terephthalate (PET) with alkylene polyols. For example, scrap or waste PET 
can be digested (glycolized) with a diol or triol as taught by Svoboda et 
al U.S. Pat. No. 4,048,104, or transesterified with a residue from dibasic 
acid manufacture as taught by Brennan in U.S. Pat. No. 4,439,550, or the 
like, to produce a polyester polyol product which catalytically reacts 
well with organic isocyanates to produce, for example, rigid cellular 
polyurethane-polyisocyanurate polymers that can have commercially 
acceptable characteristics. 
A further class of aromatic polyester polyols which has recently become 
commercially available comprises esters produced by reacting dimethyl 
terephthalate (DMT) residues with alkylene polyols. For example, in 
DeGuiseppi et al U.S. Pat. No. 4,237,238 a DMT residue obtained from the 
manufacture of dimethyl terephthalate is transesterified with a glycol of 
molecular weight ranging from about 60 to 400 and the resulting polyol is 
reacted with isocyanates to produce polyisocyanurate foams alleged to have 
a high degree of fire resistance with low smoke evaluation. See also, for 
examples, Walker U.S. Pat. No. 3,647,759, Grube et al U.S. Pat. No. 
4,444,917, Grube et al U.S. Pat. No. 4,444,916, Grube et al U.S. Pat. No. 
4,444,915, Anderson U.S. Pat. No. 4,469,821, and Zimmerman U.S. Pat. No. 
4,442,238. 
One problem with most such commercially viable aromatic polyester polyols 
is that they characteristically are poorly compatible with fluorocarbon 
compounds of the type conventionally used as blowing agents to make such 
cellular polymers. 
The usual solution to this problem has been to admix with such a polyol a 
separately formed compatibilizing agent in an amount sufficient to produce 
a resulting mixture with a desired amount of compatibility (solubility) 
for fluorocarbons. For examples, Koehler et al U.S. Pat. No. 4,246,364 use 
a class of amide diols, while Wood U.S. Pat. No. 4,529,744 issued July 16, 
1985 uses a combination of relatively high molecular weight propoxylate 
ethoxylate compounds with amine and/or amide diol compounds. The amide 
diols employed by Wood are similar to those taught by Koehler et al. The 
propoxylate ethoxylate compounds employed by Wood are, in fact, similar to 
those employed in practicing the present invention, as hereinbelow 
described. 
The necessity to compound a fluorocarbon compatibilizing agent with 
aromatic polyester polyol means an extra cost in the formulation of a 
so-called resin prepolymer blend. Such resin prepolymer blends are 
conventionally employed in the trade for reaction with organic isocyanates 
to produce polyurethane and/or polyurethane-polyisocyanurate cellular 
polymers. Resin prepolymer blends are uniform, homogeneous liquid 
compositions comprised of polyol, urethane-forming and/or 
isocyanurate-forming catalyst, fluorocarbon blowing agent, other optional 
additives, and, in the case of aromatic polyester polyols, a fluorocarbon 
compatibilizing agent, as is well known to those skilled in the art. A 
desired quantity of a compatibilizing agent is blended with an aromatic 
polyester polyol before such fluorocarbon is added, and such a blending 
step itself adds to the cost of resin prepolymer blend manufacture. 
However, the cost of a compatibilizing agent is even more significant. 
Moreover, the costs of such an agent are escalating. For example, the cost 
of the cochin oil, which is used as a starting material to make an amide 
diol as above identified, increased by approximately 60 percent in price 
in 1984. Unless the cost of producing resin prepolymer blends of aromatic 
polyester polyols can be controlled and maintained at economically 
competitive levels, aromatic polyester polyols will not have a commercial 
place in this field. 
There is a need for fluorocarbon compatibilized aromatic polyester polyols 
which not only are economical to produce, but also are convertible into 
cellular foams having excellent properties. 
Aromatic polyester polyols, especially polyols based on residues from the 
manufacture of dimethyl terephthalate are producible by 
transesterification of dimethyl terephthalate residues as referenced 
above. The idea of somehow modifying the reaction components without 
substantially increasing costs so as to result in a polyol product that is 
directly compatible (self-compatibilized) with fluorocarbons is certainly 
attractive. Not only would this avoid the need for a separate 
compatibilizing agent admixing step, but also this could avoid the cost of 
an added compatibilizing agent. 
So far as is known, no one has heretofore produced a class of polyester 
polyol blends based on dimethyl terephthalate residues which is both 
fluorocarbon self-compatibilizing, and produces polyurethane and 
polyurethane-polyisocyanurate foam with improved properties. Such a 
polyester polyol can be formulated into a resin prepolymer blend and then 
reacted with organic isocyanate to produce cellular 
polyurethane-polyisocyanurate type polymers of generally commercially 
acceptable quality. 
BRIEF SUMMARY OF THE INVENTION 
This invention relates to a new and surprisingly useful class of polyester 
polyol blends comprised of reaction products of a starting mixture of (a) 
dimethyl terephthalate residue, (b) at least one low molecular weight 
aliphatic diol compound, and (c) at least one nonionic surfactant 
compound. Preferably at least one hydrophobic compound is also present in 
the starting mixture. These product blends are characterized by low acid 
numbers, low viscosity, and low reactive hydroxyl functionality (less than 
about 3). 
The invention also relates to methods for making and using such polyester 
polyol blends, and further relates to cellular polyurethane and 
polyurethane/polyisocyanurate foams made therewith. 
Optionally, but preferably, a polyester polyol blend of this invention is a 
reaction product of a starting mixture as above described which mixture 
additionally contains a dibasic carboxylic acid compound so that such 
dibasic acid compound becomes reacted into such product polyol blend. 
The product polyester polyol blends of this invention are 
self-compatibilized, and, in addition, have a desirable combination of 
other characteristics which make them useful precursors for producing 
cellular polyurethane and/or polyurethane-polyisocyanurates. So far as is 
known, no prior art polyester polyol blend reaction product based on 
dimethyl terephthalate residues has had such a surprising combination of 
self-compatibility with other desirable properties. 
The polyester polyol blends of this invention can be regarded as being 
synergistically enhanced in properties, especially fluorocarbon solubility 
characteristics, by reason of the presence therein of the above indicated 
reacted mixture containing both at least one such nonionic surfactant 
compound particularly and at least one such hydrophobic compound is 
present. 
The polyol blends of this invention display a characteristic improvement in 
fluorocarbon compatibility (solubility) which is surprisingly better than 
the fluorocarbon solubility achievable with corresponding blends which 
contain neither reacted nonionic surfactant (compound(s) or only reacted 
hydrophobic compound(s). 
Also, the polyol blends of this invention provide characteristic 
improvements in the properties of cellular polyurethane and 
polyurethane/polyisocyanurate polymers made therefrom by catalytic 
reaction thereof with polymeric isocyanates in the presence of blowing 
agent. These cellular polymer properties are surprisingly better than the 
corresponding properties which are achievable in similar cellular polymers 
made from corresponding polyol blends which do not contain such reacted 
nonionic surfactant compounds. Such improved product properties include, 
for example, tumble friability, compressive strength, burn char, and the 
like. 
The polyester polyol blends of the present invention are readily 
compoundable generally with prior art polyols, if desired, and also with 
the various additives conventionally used in the formulation of resin 
prepolymer blends. 
The polyol blends of this invention are prepared by a single step 
transesterification process which is simple, reliable, and well adapted 
for practice with conventional chemical processing equipment. 
Other and further aims, purposes, features, objects, advantages, utilities, 
embodiments, and the like will be apparent to those skilled in the art 
from the teachings of the present specification taken with the appended 
claims. 
DETAILED DESCRIPTION 
Polyol Blend Characteristics 
The polyester polyol blends of this invention, as indicated, are made by 
using as one class of starting material low molecular weight aliphatic 
diols. The present polyol blends differ from the above prior art dimethyl 
terephthalate residue derived polyester polyols made with aliphatic diols 
in that, in effect, a portion of the low molecular weight aliphatic diol 
needed to achieve a desired (theoretical) stoichiometry between such diol 
and the dimethyl terephthalate residue is replaced by at least one 
nonionic surfactant compound, and, more preferably, by a mixture of such 
nonionic surfactant compound with at least one hydrophobic compound during 
formation of such present blends. Thus, the quantity of aromatic rings 
present in a nonionic surfactant compound modified polyol blend of this 
invention is maintainable at a level closely related to that in the 
corresponding prior art unmodified dimethyl terephthalate residue based 
ester polyols, but the quantity and nature of the aliphatic radicals 
present in a product polyester polyol blend of this invention are altered 
to an extent considered desirable or necessary (the exact amount depending 
upon user wishes) to achieve a level fluorocarbon compatibilization along 
with other favorable product polyol properties and favorable cellular foam 
properties. Thus, in general, product polyester polyol blends of this 
invention are characterized by a surprising combination of properties, as 
now explained: 
Most importantly, the product polyester polyol blends are surprisingly 
fluorocarbon compatibilized as produced so that they can be formulated 
into fluorocarbon compatible resin prepolymer blends with for example 
little, or preferably no, added (after polyol blend formation) unreacted 
nonionic surfactant compound in order to produce a desired level of 
fluorocarbon solubility therein. Such a self-compatibilization is achieved 
easily and simply by incorporating the characteristically relatively 
inexpensive nonionic surfactant compound into a starting mixture of 
dimethyl terephthalate residue, low molecular weight aliphatic diol, and 
(optionally but preferably) hydrophobic compound, as herein explained. 
For another thing, these product polyester polyol blends have relatively 
low viscosities. Viscosities typically fall in the range from about 200 to 
50,000 centipoises measured, for example, at 25.degree. C. with a 
Brookfield viscometer, such as a Model LVT, as is desirable for many end 
use applications for polyols being used in the manufacture of polyurethane 
and/or polyurethane/polyisocyanurate cellular products. If desired, the 
viscosity of a product polyol blend of the present invention can be 
increased to some desired extent through incorporation into the starting 
mixture used for transesterification of a quantity of a polyfunctional 
(that is, having a functionality higher than 2) carboxylic acid or 
aliphatic alcohol, as taught herein. 
For another thing, these product polyester polyol blends, when converted 
into polyurethane and/or polyurethanepolyisocyanurate rigid cellular 
polymers, characteristically produce favorable product properties, 
including, for examples, compressive strength, tumble friability, and the 
like. 
For another thing, these product polyester polyol blends are surprisingly 
capable of dissolving thereinto significant quantities of added 
compatibilizer compounds, especially polyalkoxylated nonionic compounds of 
relatively high molecular weight, if desired, for example, to heighten 
fluorocarbon compatibility of a resin blend formed therefrom in 
combination with various ingredients. No gelation upon subsequent addition 
of fluorocarbon is observed when the total amount of compatibilizer 
compound (both reacted and admixed) ranges from 0 to about 30 weight of a 
total product blend basis. Thus, when, for example, such relatively high 
molecular weight propoxylate ethoxylate compounds are admixed with 
preformed prior art dimethyl terephthalate residue based polyester polyols 
which contain no such reacted nonionic surfactant compound(s) therein, 
gelation is prone to occur, particularly when fluorocarbon is subsequently 
added to the mixture. 
In a further development of the present invention, there is provided a 
preferred class of nonionic surfactant compound modified polyester polyol 
blends which are prepared by incorporating into a starting 
transesterification reaction mixture, in accordance with this invention, a 
relatively high molecular weight nonionic surfactant which is a 
propoxylate ethoxylate compound. Such a propoxylate ethoxylate compound 
becomes at least partially chemically reacted into the dimethyl 
terephthalate residue polyester polyol blend being produced during the 
transesterification. The resulting product polyester polyol blend displays 
excellent and improved fluorocarbon compatibility characteristics, and 
cellular polymers produced therefrom display excellent tumble friability 
characteristics. Also, such a product polyester polyol blend appears to 
have a lower freezing temperature than corresponding blends produced by 
merely admixing thereinto after a transesterification (which contains in 
the starting mixture no such propoxylate ethoxylate compound) an 
equivalent amount of the same propoxylate ethoxylate compound. Thus, such 
a product blend of this invention is believed to avoid certain processing 
problems and storage problems in winter. Further, if desired, additional 
quantities of such a propoxylate ethoxylate compound can be admixed with 
such a product polyol blend of this invention after the formative 
transesterification without adding some additional anti-gelation agent and 
without causing system gelation upon subsequent addition of fluorocarbon. 
The polyester polyol blends of the present invention which contain such 
reacted and/or unreacted high molecular weight propoxylate ethoxylate 
compounds characteristically have an unusual and surprising ability to 
form, when catalytically reacted with organic isocyanates, cellular 
polyurethane and/or polyurethane-polyisocyanurate foams of not only 
superior tumble friability, but also superior uniform small sized closed 
cell structure. 
In general, a self-compatibilized polyester polyol blend of this invention 
comprises the reaction product of a starting mixture which comprises on a 
100 weight percent total such mixture basis: 
(A) from about 15 to 80 weight percent of dimethyl terephthalate residue, 
(B) from about 8 to 80 weight percent of at least one low molecular weight 
aliphatic diol characterized by the generic formula 
EQU HO--R.sup.1 --OH (1) 
where: R.sup.1 is a divalent radical selected from the group consisting of 
(a) alkylene radicals each containing from 2 through 6 carbon atoms, and 
(b) radicals of the formula: 
EQU --(R.sup.3 O).sub.n --R.sup.3 -- (2) 
where: R.sup.3 is an alkylene radical containing from 2 through 3 carbon 
atoms, and n is an integer of from 1 through 3, and 
(c) mixtures thereof, 
(C) from about 2 to 30 weight percent of at least one nonionic surfactant 
compound, and 
(D) from and including 0 to about 20 weight percent of at least one 
hydrophobic compound provided that the sum total of both said nonionic 
surfactant compound and said hydrophobic compound is not greater than 
about 30 weight percent. 
By the term "nonionic surfactant" reference herein is generally made to a 
compound which contains both a hydrophobic moiety and a hydrophilic moiety 
and which has no moieties which dissociate in aqueous solution or 
dispersion into cations or anions. 
In the practice of the present invention, such a nonionic surfactant 
compound is characterized by: 
(1) containing from about 10 to 600 carbon 
atoms per molecule, 
(2) containing at least one and not more than four hydroxyl radicals per 
molecule, and 
(3) containing from 4 to about 270 radicals per molecule of the formula 
EQU --(R.sup.3 O)-- 
where: R.sup.3 is as above defined. 
By the term "hydrophobic compound" reference herein is generally made to a 
compound which contains a substantially nonpolar organic moiety that 
results in such compound being substantially water insoluble and which 
contains an active hydrogen group, such as an hydroxyl group or a carboxyl 
group. 
In the practice of the present invention, such a hydrophobic compound is 
characterized by: 
(1) having an equivalent weight of from about 130 to 900, 
(2) containing from 8 to about 60 carbon atoms per molecule, and 
(3) containing one group per molecule selected from the group consisting of 
carboxyl and hydroxyl. 
In addition, such a starting mixture optionally but preferably contains at 
least one dibasic carboxylic acid compound in an amount ranging from 
greater than 0 up to about 60 weight percent (100 weight percent total 
mixture basis). Such a dibasic carboxylic acid compound is characterized 
by: 
(1) containing from and including 2 to about 35 carbon atoms per molecule, 
(2) containing two carboxyl 
##STR1## 
groups per molecule, (3) containing at least one and no more than two 
functional groups selected from the class consisting of carboxylic acids, 
carboxylic acid anhydrides, carboxylic esters, hydroxyl radicals, and 
mixtures thereof. 
When a mixture of hydrophobic compound with nonionic surfactant compound is 
employed, preferably such mixture is characterized by having a weight 
ratio of said hydrophobic compound to said nonionic surfactant compound in 
the range from about 0.1 to 10. 
Preparation Conditions 
In general, a self-compatibilized polyester polyol blend of this invention 
is prepared by heating at a temperature ranging from about 180.degree. to 
240.degree. C. a starting mixture as above characterized. 
Such heating of a starting mixture is continued until a liquid reaction 
product is produced which is characterized by having: 
(A) an hydroxyl number ranging from about 200 to 500, 
(B) an acid number ranging from about 0.1 to 7, 
(C) a saponification value ranging from about 130 to 400, and 
(D) a viscosity ranging from about 200 to 50,000 centipoises measured at 
25.degree. C. using a Brookfield viscometer. 
The term "hydroxyl number" is defined as the number of milligrams of 
potassium hydroxide required for the complete neutralization of the 
hydrolysis product of a fully acetylated derivative prepared from one gram 
of a polyol or a mixture of polyols. 
The term "hydroxyl number" is also defined by the equation: 
##EQU1## 
wherein: OHV is the hydroxyl number (of the polyol or polyol blend), 
F is the average functionality (i.e., the average number of active hydroxyl 
groups per molecule of the polyol or polyol blend), and 
M.W. is the average molecular weight of the polyol or polyol blend. 
Similarly, "acid number" is defined by the number of milligrams of 
potassium hydroxide required to neutralize the acid material present in 
one gram of sample. The "saponification value" is defined by the number of 
milligrams of potassium hydroxide required to react with the ester groups 
present in one gram of sample. To determine saponification value, the 
American Chemist Society official Method no. C-d-3-25 is preferably 
employed. 
Reaction (heating) time can vary, but typically ranges from about 8 to 16 
hours, but longer and shorter reaction times can be used depending upon 
temperature, starting mixture composition, and like factors, without 
departing from the spirit and scope of the invention. 
Process conditions are summarized in Table I below: 
TABLE I 
______________________________________ 
Process Conditions* 
Presently 
Process Variable 
Broad Preferred 
______________________________________ 
1. Temperature 
180-240.degree. C. 
210-230.degree. C. 
2. Pressure 10 to 760 mm of Hg 
autogeneous 
______________________________________ 
*The reactants are agitated during processing and preferably sparged with 
an inert gas (e.g. nitrogen) to aid in the removal of water vapor. 
Starting Mixture 
The composition comprising a starting mixture employed in the practice of 
this invention (as indicated above) is summarized in Table II below: 
TABLE II 
______________________________________ 
Starting Mixture* 
Range 
(100 wt % total basis) 
Item Pre- More 
No. Reactive Component Broad ferred 
Preferred 
______________________________________ 
1 Dimethyl terephthalate residue 
15-80 30-40 25-35 
2 Aliphatic Diol (formula(1)) 
8-80 30-65 50-60 
3 Nonionic Surfactant Compound 
2-30 5-25 10-20 
3a 
high mol. wt. 
0-30 0-10 0-0.5 
propoxyethoxy compound 
4 Hydrophobic compound 
0-20 2-12 5-10 
5 Dibasic carboxylic acid 
0-60 2-30 5-15 
6 Aliphatic polyol (other) 
0-10 0-4 0-3 
7 Aromatic polycarboxylated 
0-10 0-8 0-5 
acid compound (other than 
dibasic) 
8 Aliphatic polycarboxylated 
0-10 0-8 0-5 
acid compound (other than 
dibasic) 
______________________________________ 
Table II footnotes: 
*Values herein identified for any given mixture must conform with the 
composition limits disclosed herein above for a starting mixture of this 
invention. 
A starting mixture always contains the reactive components identified in 
Table II as items (1) through (3) with components 3a and 4 being 
optionally but preferably being present. Generally, the sum totoal of all 
nonionic surfactant compounds plus any optional hydrophobic compounds 
present in a starting mixture ranges from about 2 to 30 weight percent 
(based on 100 wt % of total starting mixture). The individual respective 
quantities of each of the compatibilizer compounds identified as 3a, and 4 
in Table II can range as shown within such broad range. A starting mixture 
can optionally but preferably contain a mixture of 3, 3a and 4 compounds 
as above indicated. 
In general, any dimethyl terephthalate residue can be used as a starting 
material in the practice of this invention. The term "dimethyl 
terephthalate residue" as used herein has reference to the purged residue 
which is obtained during the manufacture of dimethyl terephthalate in 
which p-xylene is oxidized and the crude oxidation product is then 
esterified with methanol to yield the desired product in a reaction 
mixture along with a complex mixture of by-products. Typically, the 
desired product (i.e., dimethyl terephthalate) is removed from the 
reaction mixture with the volatile methyl p-toluate by-product by 
distillation leaving a residue. The dimethyl terephthalate and methyl 
p-toluate are separated. Some of the residue is purged from the process 
while the remainder of the residue and the methyl p-toluate are recycled 
for oxidation. Thus, it is this purged residue which is employed as a 
starting material in the present invention for transesterification with 
glycols of formula (1) and nonionic surfactant. U.S. Pat. No. 3,647,759, 
for example, describes such residue and characterizes its properties; the 
disclosure and teachings of this publication are incorporated by reference 
herein in their entirety. 
A class of suitable aliphatic diols is shown in formula (1) (above). 
Examples of suitable aliphatic diols of formula (1) include ethylene 
glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 
butylene glycols, 1,2-cyclohexanediol, poly(oxyalkylene) polyols derived 
by the condensation of ethylene oxide, propylene oxide, or any combination 
thereof, and the like. As those skilled in the art will appreciate, in the 
preparation of mixed poly(oxyethylene-oxypropylene) polyols, the ethylene 
and propylene oxides may be added to a starting hydroxyl-containing 
reaction either in admixture or sequentially. Mixtures of such diols can 
be employed, if desired. A presently most preferred aliphatic diol of 
formula (1) is diethylene glycol. 
Any hydrophobic compound as above characterized can be employed so far as 
now known, such as monocarboxylic acids (especially fatty acids), lower 
alkanol esters of monocarboxylic acids (especially fatty acid esters), 
triglycerides (especially fats and oils), alkyl monohydroxy alcohols (for 
example, those containing from 8 to 18 carbon atoms per molecule), 
substituted phenols (for example, alkyl phenols), and the like. Mixtures 
of different hydrophobic compounds can be employed if desired. 
Examples of fatty acids include caproic, caprylic, capric, lauric, 
myristic, palmitic, stearic, oleic, linoleic, linolenic, ricinoleic, 
mixtures thereof, and the like. 
Examples of fatty acid methyl esters include methyl caproate, methyl 
caprylate, methyl caprate, methyl laurate, methyl myristate, methyl 
palmitate, methyl oleate, methyl stearate, methyl linoleate, methyl 
linolenate, mixtures thereof, and the like. 
Examples of alkyl alcohols include decyl, oleyl, cetyl, isodecyl, tridecyl, 
lauryl, mixtures thereof, and the like. 
Examples of fats and oils include castor, coconut (including cochin), corn, 
cottonseed, linseed, olive, palm, palm kernel, peanut, safflower, soybean, 
sunflower, tall oil, tallow, mixtures thereof, and the like. 
Other suitable acids include 2-ethyl hexanoic acid and the like. 
Presently preferred types of hydrophobic compounds include alkyl alcohols, 
fats and oils, and the like. Examples of particular presently preferred 
such hydrophobic compounds include decyl alcohol, soybean oil, and the 
like. 
Any nonionic surfactant compound as above characterized can be employed so 
far as is now known. In general, in the practice of the present invention, 
it is preferred that a nonionic surfactant contain from 4 to about 270 
individual oxyalkylene groups per molecule with the oxyalkylene groups 
typically being selected from the group consisting of oxyethylene and 
oxypropylene. 
The hydrophobic portion of a nonionic surfactant is preferably derived from 
at least one starting compound which is selected from the group consisting 
of: 
(a) Fatty alcohols containing from about 6 to 18 carbon atoms each, 
(b) Fatty amides containing from about 6 to 18 carbon atoms each, 
(c) Fatty amines containing from about 6 to 18 carbon atoms each, 
(d) Fatty acids containing from 6 to 18 carbon atoms each, 
(e) Phenols and/or alkyl phenols wherein the alkyl group contains from 
about 4 to 16 carbon atoms each, 
(f) Fats and oils containing from 6 to about 60 carbon atoms each, 
(g) Polyoxypropylene glycols containing from 10 to 70 moles of propylene 
oxide, and 
(h) mixtures thereof. 
In making a nonionic surfactant, as is known, such a starting compound is 
sufficiently alkoxylated to provide a desired hydrophilic portion. 
Typically, alkoxylation results in chains totaling from at least about 3 
to about 125 moles of alkylene oxide per molecule with the alkylene oxide 
preferably being selected from the group consisting of ethylene oxide, 
propylene oxide, and mixtures thereof. 
One class of nonionic surfactants employable in the practice of this 
invention is characterized by the formula: 
EQU RO(CH.sub.2 CH.sub.2 O).sub.n H (3) 
where: 
R is a radical selected from the group consisting of alkyl phenyl radicals 
wherein the alkyl group in each such phenyl radical contains about five to 
eighteen carbon atoms, and alkyl radicals each containing from two through 
eighteen carbon atoms, and 
n is a positive whole number which is sufficient to keep the molecular 
weight of the product surfactant below about 1500. 
It is presently preferred that all nonionic surfactants employed in the 
practice of the present invention contain both units of ethylene oxide and 
units of propylene oxide. Thus, for example, the hydrophobic part of a 
molecule can contain mainly recurring propylene oxide units, or, in some 
cases, block units of largely propylene oxide, with some ethylene oxide 
units being present. 
One preferred class of nonionic surfactants comprises at least one 
relatively high molecular weight propoxylate ethoxylate compound having a 
molecular weight ranging from about 1500 to 12,000. Preferably, such a 
compound contains at least one block polyoxypropylene group containing at 
least about 10 propoxy units and also at least one block polyoxyethylene 
group containing at least about 20 ethoxy units. 
One presently particularly preferred class of nonionic surfactant is 
characterized by having: 
(1) a molecular weight of at least from about 3000 to 8000, 
(2) a solubility in diethylene glycol phthalate to such an extent that at 
least 5 parts by weight are soluble in each 100 parts by weight of a 
diethylene glycol phthalate (which is a stoichiometric reaction product of 
one mole of phthalic acid anhydride with two moles of diethylene glycol 
(or equivalent), 
(3) at least one block polyoxypropylene group which contains from about 10 
to 70 repeating propoxy units, 
(4) at least one block polyoxyethylene group which contains from about 15 
to 200 repeating ethoxy units, and 
(5) both a hydrophobic moiety and a hydrophilic moiety. 
In such a particularly preferred such nonionic surfactant as above 
characterized, the total alkoxyl content includes at least about 40 weight 
percent of ethylene oxide, and preferably the ethylene oxide content 
ranges from about 55 to 75 weight percent, and most preferably the 
ethylene oxide content ranges from about 60 to 70 weight percent. 
Preferably such a nonionic surfactant is end capped with at least one 
ethylene oxide group. 
In general, a "low molecular weight nonionic surfactant compound" 
references herein such a compound which has a molecular weight below about 
2000. Thus, a "high molecular weight nonionic surfactant" references such 
a compound which has a molecular weight greater than about 2000. 
If desired, mixtures of high and low molecular weight nonionic surfactants 
can be employed. 
Optionally, after its formation by a heating step as described herein, a 
liquid product polyester polyol blend of this invention can be admixed 
with, and/or have dissolved or dispersed therein, for each 100 parts by 
weight of such liquid polyol blend, from 0 to about 30 parts by weight of 
at least one such high molecular weight propoxylate ethoxylate compound. 
Such an admixture and dissolution is preferably carried out while 
maintaining a temperature ranging from about 50.degree. to 100.degree. C. 
However, the total quantity of such high molecular weight propoxylate 
ethoxylate compound present in such a product polyol blend, whether such 
compound is present during such heating, or is subsequently admixed with 
such a polyol blend, as indicated, ranges from greater than 0 to about 30 
weight percent on a 100 weight percent total liquid polyol blend product 
basis. 
When such a starting mixture containing dibasic carboxylic acid compound(s) 
are employed, it is preferred that such mixture contain about 2 to 30 
weight percent (on a 100% by weight total such mixture basis) of dibasic 
carboxylic acid compound(s) which can include dimer acids. 
In addition to such dimethyl terephthalate residue, such aliphatic diol, 
such nonionic surfactant compound, such optional hydrophobic compound, and 
such optional dibasic acid compound, a starting mixture can also, if 
desired, contain minor amounts (generally less than about 10% by weight 
based upon total starting mixture weight) of other reactive components 
such as shown in Table II. For example, polyhydroxylated and/or 
polycarboxylated compounds, that is, compounds having at least two or more 
functional hydroxyl and/or carboxyl groups per molecule can be present. 
Such compounds can be used, if desired, to increase and to regulate 
viscosity of a product polyol blend. Thus, polyols (especially aliphatic 
polyols), polycarboxylated aromatic acid compounds, polyaromatic ester 
compounds, and corresponding esters, and polycarboxylated aliphatic acid 
compounds and corresponding esters can be employed, as shown in Table II 
above. 
For example, such a starting mixture can optionally incorporate low 
molecular weight polyols (that is, compounds which preferably contain 6 or 
less carbon atoms per molecule, but which contain at least three or more 
hydroxyl groups per molecule). Examples of such polyols comprise glycerol, 
1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, pentaerythritol, 
sorbitol, mixtures thereof, and the like. 
For another example, such a starting mixture can optionally incorporate 
aromatic polycarboxylic acid or acid anhydride compounds, or aromatic 
polycarboxylic esters, or mixtures thereof; that is, acids and/or esters 
which contain aromatic carboxylated compounds containing at least three 
carboxyl groups per molecule (including anhydrides) and which preferably 
contain less than 13 carbon atoms per molecule. Examples of such aromatic 
polycarboxylated acid compounds and esters comprise phthalic anhydride 
residues, trimellitic anhydride, trimellitic acid, mixtures thereof, and 
the like. Of interest in this regard are the acidic residues resulting 
from the manufacture of phthalic anhydride and of terephthalic acid. 
For another example, such a starting mixture can optionally incorporate an 
aliphatic polycarboxylic acid, an acid anhydride compound, or an alkyl 
ester compound, or a residue from the manufacture of aliphatic 
polycarboxylated acids or esters, that is, aliphatic carboxylated 
compounds which contain at least two carboxyl groups per molecule 
(including anhydrides) and which preferably contain less than 9 carbon 
atoms per molecule. Examples of such aliphatic polycarboxylated acid 
compounds comprise adipic acid, glutaric acid, succinic acid, their 
respective alkyl esters, mixtures thereof, and the like. 
Dimethyl Terephthalate Residue Based Polyester Polyol Product Blends 
A liquid product blend of this invention is a reaction product of a 
starting mixture as above described. Preferred preparation conditions are 
as above described. Such a reaction product has characteristics as above 
indicated and as further summarized in Table III below: 
TABLE III 
______________________________________ 
Dimethyl Terephthalate Residue Based Polyester Polyol Blends 
Range 
Characteristic More 
Item or Property Broad Preferred 
Preferred 
______________________________________ 
1. Hydroxyl 200-500 225-400 250-350 
number 
2. Acid number 0.10-7.0 0.2-5.0 1.0-3.0 
3. Saponification 
130-400 150-350 250-310 
value 
4. Viscosity 200-50,000 
500-20,000 
1000-5000 
(centipoises)* 
______________________________________ 
*measured with a Brookfield viscometer at 25.degree. C. 
Such a polyol blend is also a reaction product of any other minor reactive 
additional components present in a starting mixture, as described above. 
In effect, during the heating (transesterification), the dimethyl 
terephthalate residue becomes esterified by the hydroxyl groups of the 
polyhydric alcohol compounds present, thereby producing polyester polyol 
blends. A polyol blend reaction product is thus inherently a complex 
mixture of various esterified alcohols and certain other compounds. The 
quantity of dimethyl terephthalate residue based polyester polyol present 
in any given product is generally proportional to the quantity and 
composition of dimethyl terephthalate residue present in a starting 
mixture. 
The fact that a polyol product of this invention is an interreacted system 
derived from the starting components present in a starting mixture can be 
demonstrated by any convenient means. When, for example, a starting 
mixture and a corresponding product mixture are examined by HPLC (high 
pressure liquid chromatography), it is found that the reaction product has 
a most substantially altered composition compared to that of the starting 
mixture. 
Also, HPLC analysis shows that a polyol blend reaction product of this 
invention has a substantially different composition from a mixed 
composition which has been prepared by transesterifying a dimethyl 
terephthalate residue with only an aliphatic diol of formula (1). 
Further, HPLC analysis of a product polyol blend appears to 
characteristically show peaks in the 15 to 17 minute range when using a 
Regis octadecylsilane column with 5 micron packing and having a length of 
about 25 centimeters. Such peaks appear to be absent when mere physical 
mixtures of nonionic surfactant compound and/or hydrophobic compound are 
present in a dimethyl terephthalate residue based polyester polyol blend 
made only with low molecular weight diol (e.g. formula (1) diol) are 
involved. 
A post formation admixed hydrophobic compound or nonionic surfactant 
compound is characteristically soluble in a dimethyl terephthalate residue 
based polyester polyol blend of this invention. In contrast, if, for 
example, a hydrophobic compound is admixed with a prior art dimethyl 
terephthalate residue based polyester polyol then a two-phased mixture 
results. 
It is a feature of the present invention that one can admix with, and 
dissolve in, a product polyol blend as characterized in Table III above 
additional quantities of compatibilizer compound. Thus, for example, for 
each 70 parts by weight of such product blend, from 0 to about 30 parts by 
weight of at least one nonionic surfactant compound is admixable with and 
dissolved therein provided that the total quantity of nonionic surfactant 
compound (both reacted and admixed) ranges from greater than 0 to about 30 
parts by weight from each 100 parts by weight of such product blend. 
Preferably, the admixed nonionic surfactant compound is a nonionic 
propoxylate ethoxylate compound. Such a resulting mixture generally 
retains the characteristics shown in Table III. 
Furthermore, in the case of the class of preferred liquid reaction products 
of this invention which have been prepared from a starting mixture that 
has had incorporated thereinto a high molecular weight nonionic 
propoxylate ethoxylate compound, it is found by HPLC analysis that such 
products display a characteristically different composition from that 
shown by, for example, a diethylene glycol transesterified dimethyl 
terephthalate residue polyol to which has been added after formation such 
a low or high molecular weight nonionic surfactant compound. 
Product polyols produced by incorporating into a starting mixture a residue 
from the manufacture of phthalic anhydride or a residue from the 
manufacture of dimethyl terephthalate tend to have a black color which can 
characteristically be very dense. It is presently difficult if not 
impossible to measure accurately by known direct techniques the 
fluorocarbon solubility capability or characteristics of such a black 
liquid product polyol. For present purposes generally, fluorocarbon 
solubility is conveniently directly measured or defined as the maximum 
amount of trichlorofluoromethane (known commercially as Freon 11, 
available from the duPont Company) which can be dissolved in a polyol 
blend. However, the dark or black colored product polyols do produce 
improved cellular polymers when catalytically reacted with isocyanates, as 
taught herein, and such polymers apparently have excellent physical 
characteristics, such as tumble friability, burn char, and the like. 
Resin Prepolymer Blends 
Resin prepolymer blends of this invention can be easily and conveniently 
prepared from product polyol blends of this invention by admixing 
therewith a urethane-forming, an isocyanurate-forming, and/or mixed 
polyurethane/polyisocyanurate forming catalyst or catalyst system. In 
addition, a fluorocarbon blowing agent is mixed therewith (dissolved 
therein). 
Many different types of resin prepolymer blends using polyols of this 
invention can be prepared using the additives, polyols, and know-how 
familiar to those skilled in the art. The polyols of this invention appear 
to be readily blendable with such materials. 
One presently preferred and illustrative class of prepolymer resin blend 
formulations which incorporate polyol blends of this invention and which 
class is now believed to be particularly suitable for making 
polyisocyanurate rigid foams is characterizable as shown in the following 
Table IV: 
TABLE IV 
______________________________________ 
Preferred Resin Precursor Blends For Polyurethane- 
Polyisocyanurate Foams 
(100 weight percent basis) 
Item wt. % wt. % More 
No. Component Preferred range 
Preferred Range 
______________________________________ 
(A) polyol blend 20-65 40-60 
(B) trimerization 1.0-7.0 1.5-5.0 
catalyst 
(C) cell stabilizing 
0-5.0 1.0-2.0 
surfactant 
(D) fluorocarbon 20-60 25-40 
blowing agent 
(E) low molecular wt. 
0-20 0-10 
nonionic surfactant 
compounds* 
(F) high molecular wt. 
0-20 0-10 
nonionic surfactants* 
(G) other additives 
0-15 0-10 
______________________________________ 
*admixed after polyol blend formation 
One presently preferred and illustrative class of prepolymer resin blend 
formulations which incorporate polyol blends of this invention and which 
class is now believed to be particularly suitable for making polyurethane 
rigid foams is characterizable as shown in the following Table V. 
TABLE V 
______________________________________ 
Preferred Resin Precursor Blends For Polyurethane Foams 
(100 weight percent basis) 
Item wt. % wt. % More 
No. Component Preferred range 
Preferred Range 
______________________________________ 
(A) polyol blend 20-65 40-60 
(B) urethane forming 
0.5-10.0 1.0-4.0 
catalyst 
(C) cell stabilizing 
0.5-3.0 1.0-2.0 
surfactant 
(D) fluorocarbon 0-30 5-20 
blowing agent 
(E) water 0-20.0 0-2 
(F) low molecular wt. 
0-10 0-5 
nonionic surfactants* 
(G) high molecular wt. 
0-10 0-5 
nonionic surfactants* 
______________________________________ 
*admixed after polyol blend formation 
Preferably, the viscosity of such a B-side resin prepolymer blend 
formulation of Table IV or V ranges from about 100 to 2000 centipoises at 
25.degree. C. (measured, for example, with a Brookfield viscometer) and 
the hydroxyl number thereof falls in the range from about 40-300.

EMBODIMENTS 
The present invention is further illustrated by reference to the following 
examples. Those skilled in the art will appreciate that other and further 
embodiments are obvious and within the spirit and scope of this invention 
from the teachings of these present examples taken with the accompanying 
specification. Unless otherwise indicated all product polyol blends of 
this invention hereinbelow described have a saponification number of from 
about 130 to 400. 
STARTING MATERIALS 
EXAMPLE A 
A dimethyl terephthalate residue based polyester polyol for testing and 
comparison purposes is prepared as follows: 
To a 3 liter, four-neck, round-bottom flask equipped with a stirrer, 
thermometer, nitrogen inlet tube, and a distilling head consisting of a 
straight adapter with a sealed-on Liebig condenser there is added 789.6 
grams (7.45 moles) of diethylene glycol and 1396.6 grams of dimethyl 
terephthalate residue (obtained from Hercules Incorporated). The mixture 
is heated to 220.degree. C. with stirring and kept at this temperature 
until the rate of methanol being removed slowed down. 
Stannous octoate (200 ppm) is then added to the mixture and the heating 
continued until the acid number reaches about 2.8. The reaction mixture is 
then cooled to room temperature and analyzed. The hydroxyl number is found 
to be about 257 and the acid number about 2.8. 
This product is a dark colored liquid which has a hydroxyl number of about 
257 and has a viscosity of greater than about 2,000,000 centipoises at 
25.degree. C. measured with a Brookfield viscometer. 
EXAMPLE B 
A specimen of a phthalic anhydride bottoms-composition is obtained from 
Stepan Company having: 
(a) a phthalic anhydride content of about 60 weight percent (total 
composition basis), 
(b) a hydroxyl number estimated to be about 0, and 
(c) an acid number estimated to be about 700. 
The phthalic anhydride bottoms used as a starting material in the practice 
of the present invention results from the process of converting o-xylene 
to phthalic anhydride. 
Distillation of the reaction product known as "crude" or "PA crude" results 
in a first distillate known as "light ends" or "phthalic anhydride light 
ends", a second distillate comprising substantially pure phthalic 
anhydride and a residue known as bottoms or phthalic anhydride bottoms. 
The crude, the light ends and the bottoms can each be regarded as having a 
somewhat variable composition, such compositional variations being the 
result of variations in the starting o-xylene feed, and also of variations 
in the exact conditions employed for the respective process steps. 
In actual commercial practice, it is believed that, in a bottoms 
composition, the quantity of phthalic anhydride present can range from a 
low of about 10 weight percent to a high of about 99 weight percent on a 
100 weight percent total bottoms basis, with the balance up to 100 weight 
percent thereof in any given bottoms compositions being mainly trimellitic 
acid and/or trimellitic acid anhydride plus insolubles. 
EXAMPLE C 
("Terate 131"), brand of dimethyl terephthalate residue comprising a 
mixture of methyl and benzyl esters of benzene and biphenyl di- and 
tricarboxylic acids obtained commercially from Hercules Incorporated. See 
Table A. 
EXAMPLE D 
An esterified dibasic acid is obtained from Dupont under the trade 
description "DBE-2". This material is manufactured from a mixed acid 
co-product stream typically composed of 20-35% dimethyl adipate, 65-80% 
dimethyl glutarate, and 0-3% dimethyl succinate. This material has the 
following characteristics: 
______________________________________ 
Molecular weight: about 163 
Acid number: 1 max 
Ester Content; wt % 99.5 min. 
______________________________________ 
EXAMPLE E 
A 17006 pound batch of presently preferred nonionic block propoxylate 
ethoxylate of nonyl phenol is produced by first charging 3,900 lbs. of 
appropriate nonyl phenol feed stock to an appropriate alkoxylation reactor 
of the proper size. This material is then heated to 110.degree. C. and an 
appropriate amount of potassium hydroxide catalyst is added. After the 
addition of the catalyst, 4106 pounds of propylene oxide (about 35 moles 
of addition) is added slowly. Care should be taken to maintain a reaction 
temperature of between 110.degree. C. to 160.degree. C. during the 
addition of the propylene oxide. After this addition, the reactor is 
brought to approximately 110.degree. C. and about 9000 pounds of ethylene 
oxide (about 65 moles of addition) are added to the reactor very slowly. 
This is a very exothermic reaction and care should be taken to maintain a 
reaction temperature of between about 110.degree. to 160.degree. C. The 
ethoxylation is terminated when the appropriate degree of ethoxylation is 
achieved; this should occur after approximately all of the 9000 pounds of 
ethylene oxide are added to the reactor. Proper agitation in the 
alkoxylation should be maintained during both ethylene oxide and propylene 
oxide additions. The product contains about 65 moles of condensed ethylene 
oxide in block form and about 35 moles of condensed propylene oxide in 
block form. 
The product has the following characteristics: 
______________________________________ 
Molecular weight about 4800 
Hydroxyl number about 12 
Functionality: about 1 
Physical state: solid at 25.degree. C. 
______________________________________ 
EXAMPLE F 
An organic polyisocyanate trimerization catalyst is obtained under the 
trade designation "Hex-Chem 977" from the Mooney Chemical Company. This 
catalyst is believed to comprise potassium octoate in glycol solution. 
EXAMPLE G 
A silicone cell stabilizing surfactant is obtained under the trade 
designation "DC-193" from Dow Corning Company. This surfactant is believed 
to be comprised of a polyalkylene oxide silicone. 
EXAMPLE H 
A trimerization catalyst is obtained under the tradename "TMR-30" from Air 
Products Company. The catalyst is believed to be an ammonium compound of 
an organic base. 
EXAMPLE I 
(PAPI-27) An organic polyisocyanate believed to comprise polymethylene 
polyphenyl polyisocyanate obtained commercially from Dow Chemical Company. 
EXAMPLE J 
(Freon 11) Trichlorofluoromethane obtained commercially from E. I. duPont 
de Nemours and Co., Wilmington, Delaware. 
EXAMPLE K 
("Makon 6"), Ethoxylated nonyphenol available commercially from Stepan 
Company. See Table B. 
EXAMPLE L 
("Sylfat 96"), Tall oil fatty acids, available commercially from Union Camp 
Corporation. 
TABLE A 
______________________________________ 
Typical Values for "Terate 131" 
Terate 131 
______________________________________ 
Property 
Softening point, .degree.C. 
80-100 
Acid number 70-90 
Viscosity at 100.degree. C., cps 
7,000 
Saponification number (drastic) 
430 
Ash, % 0.3 
Flashpoint (Cleveland open cup), .degree.C. 
200.degree. C. 
Specific gravity at 120.degree. C. 
1.22 
Methoxyl content, % 9 
Color dark brown 
Average Composition 
DMT, % 1 
Substituted benzenes, % 
1 
Polycarbomethoxy diphenyls, % 
10 
Benzyl esters of toluate family, % 
4 
Dicarbomethoxy fluorenone, % 
1 
Carbomethoxy benzocoumarins, % 
0.1 
Carbomethoxy polyphenyls, % 
45 
Molecular weight average 
600 
Average Functionality 2.5 
______________________________________ 
TABLE B 
______________________________________ 
Typical Properties of "Makon 6" 
______________________________________ 
Physical Appearance 
Lt. Straw Liquid 
Solidification Point, .degree.C. 
-34 
Pour Point, .degree.C. 
-29 
Color, APHA 100 
Hydroxyl Number 115-118 
Approximate HLB 11 
Moles of EO, Average 
6 
pH (5% in 50:50 IPA-Water) 
7.0-8.5 
Density, lbs/gal @ 25.degree. C. 
8.7 
______________________________________ 
EXAMPLES 
Example 1 
Preparation Of A Polyol Blend From Decyl Alcohol, Diethylene Glycol, and 
Dimethyl Terephthalate Residue 
To a three liter, four-neck, round-bottom flask equipped with stirrer, 
thermometer, Barrett distilling receiver, condenser, and nitrogen inlet 
tube there is charged 609.1 grams of diethylene glycol, 400.0 grams of 
decyl alcohol and 1143.4 grams of dimethyl terephthalate residue. 
This mixture is heated to 225.degree. C. with constant agitation and with a 
constant nitrogen sparge. Theoretically, about 152.5 grams of methanol 
forms and substantially all of such formed material is taken off at the 
distilling receiver. After this distillate material is collected, 200 ppm 
of stannous octoate is added to the flask as a transesterification 
catalyst. Additional material removed from the distilling receiver is 
replaced by an equal weight of diethylene glycol. The heating is continued 
until the acid value of the product liquid is less than about 4.0. This 
reaction (heating) is stopped at an acid value of about 3.6. The product 
polyol has a hydroxyl number of about 253.6, a viscosity of about 27,450 
cps at 25.degree. C., and contains about 0.14 water. 
Example 2 
Preparation Of A Polyol Blend From Decyl Alcohol, Example K Material, 
Diethylene Glycol and Dimethyl Terephthalate Residue 
To a three liter, four-neck, round-bottom flask equipped with stirrer, 
thermometer, Barrett distilling receiver, condenser, and nitrogen inlet 
tube there is charged 378.0 grams of decyl alcohol, 590.7 grams of 
diethylene glycol, 210.0 grams of Example K material (Makon 6) and 1063.0 
grams of dimethyl terephthalate residue. This mixture is heated to 
225.degree. C. with constant agitation and with a constant nitrogen 
sparge. After approximately 95% of the theoretical methanol has been 
removed, 200 ppm of stannous octoate is added to the flask. Any additional 
material taken from the distilling receiver is replaced by an equal weight 
of diethylene glycol. The reaction is carried out until the acid value is 
about 2.1 and the hydroxyl number is about 255.6. The viscosity is found 
to be about 15,430 cps at 25.degree. C. measured using a Brookfield 
viscometer (model LVT). 
Example 3 
Preparation Of A Polyol Blend From Decyl Aclohol, Example E Material, 
Diethylene Glycol, and Dimethyl Terephthalate Residue 
To a three liter, four-neck, round-bottom flask equipped with stirrer, 
thermometer, Barrett distilling receiver, condenser, and nitrogen inlet 
tube there is charged 200.0 grams of Example E material, 548.2 grams of 
diethylene glycol, 360.0 grams of decyl alcohol and 1029.1 grams of 
dimethyl terephthalate residue. 
This mixture is heated to 225.degree. C. with constant agitation and with a 
constant nitrogen sparge. Theoretically, 137.2 grams of methanol forms and 
substantially all of such formed material is taken off at the distilling 
receiver. After this distillate material is collected, 200 ppm of stannous 
octoate is added to the flask as a transesterification catalyst. 
Additional material removed from the distilling receiver is replaced by an 
equal weight of diethylene glycol. The heating is continued until the acid 
value of the product liquid is less than about 4.0. This reaction 
(heating) is stopped at an acid value of about 3.2. The product polyol has 
a hydroxyl number of about 229.7, a viscosity of about 17,220 cps at 
25.degree. C., and contains about 0.13% water. 
Example 4 
Preparation Of A Polyol Blend Of Decyl Alcohol, Example E Material, Example 
D Material, Diethylene Glycol and Dimethyl Terephthalate Residue 
To a three liter, four-neck, round-bottom flask equipped with stirrer, 
thermometer, Barrett distilling receiver, condenser, and nitrogen inlet 
tube, there is charged 500.0 grams of Example D material (DBE-2) 827.9 
grams of diethylene glycol, 391.2 grams of decyl alcohol, 217.3 grams of 
Example E material and 500 grams of dimethyl terephthalate residue. This 
mixture is heated to 225.degree. C. with constant agitation and with a 
constant nitrogen sparge. Theoretically, 263 grams of methanol forms and 
substantially all of such formed material is taken off at the distilling 
receiver. After this material is collected, 200 ppm of stannous octoate is 
added to the flask as a transesterification catalyst. Additional material 
removed from the distilling receiver is replaced by an equal weight of 
diethylene glycol. The heating is carried out until the acid value of the 
product liquid polyol reaches about 3.0. The product polyol has a hydroxyl 
number of about 256.6, a viscosity of about 8320 cps at 25.degree. C. and 
contains about 0.16% water. 
Example 5 
Preparation Of A Decyl Alcohol, Example E Material, Phthalic Anhydride, 
Diethylene Glycol, and Dimethyl Terephthalate Residue 
To a three liter, four-neck, round-bottom flask equipped with stirrer, 
thermometer, Barrett distilling receiver, condenser, and nitrogen inlet 
tube, there is charged 450.0 grams of phthalic anhydride, 825.6 grams of 
diethylene glycol, 402.7 grams of decyl alcohol, 223.7 grams of Example E 
material and 450 grams of dimethyl terephthalate residue. This mixture is 
heated to 225.degree. C. with constant agitation and with a constant 
nitrogen sparge. Theoretically, 54.7 grams of water and 60 grams of 
methanol (total 114.7 grams of material) forms and substantially all of 
such formed material is taken off at the distilling receiver. After this 
material is collected, 200 ppm of stannous octoate is added to the flask 
as a transesterification/esterification catalyst. Additional material 
removed from the distilling receiver is replaced by an equal weight of 
diethylene glycol. The heating is carried out until the acid value of the 
product liquid polyol reaches about 2.9. The product polyol has a hydroxyl 
number of about 252.9, a viscosity of about 10,120 cps at 25.degree. C., 
and contains about 0.13% water. 
Example 6 
Preparation Of A Polyol Blend From Example L Material, Diethylene Glycol 
and Dimethyl Terephthalate Residue 
To a three liter, four-neck, round-bottom flask equipped with stirrer, 
thermometer, Barrett distilling receiver, condenser, and nitrogen inlet 
tube there is charged 850.9 grams of diethylene glycol, 439.9 grams of 
Example L material (Tall Oil) and 1081.2 grams of dimethyl terephthalate 
residue. This mixture is heated to 225.degree. C. with constant agitation 
and with a constant nitrogen sparge. After approximately 95% of the 
theoretical methanol has been removed, 200 ppm of stannous octoate is 
added to the flask. Any additional material taken from the distilling 
receiver is replaced by an equal weight of diethylene glycol. The reaction 
is carried out until the acid value is about 4.0 and the hydroxyl number 
is about 257.2. The viscosity is found to be about 15,500 cps at 
25.degree. C. measured using a Brookfield viscometer (model LVT). 
Example 7 
Preparation Of A Polyol Blend Of Tall Oil Example E Material, Diethylene 
Glycol and Dimethyl Terephthalate Residue 
To a three liter, four-neck, round-bottom flask equipped with stirrer, 
thermometer, Barrett distilling receiver, condenser, and nitrogen inlet 
tube, there is charged 765.8 grams of diethylene glycol, 395.9 grams of 
Example L (Tall Oil), 220.0 grams of Example E material and 973.1 grams of 
dimethyl terephthalate residue. This mixture is heated to 225.degree. C. 
with constant agitation and with a constant nitrogen sparge. 
Theoretically, 129.8 grams of methanol and 25.1 grams of water (Total 
154.9 grams of material) forms and substantially all of such formed 
material is taken off at the distilling receiver. After this material is 
collected, 200 ppm of stannous octoate is added to the flask as a 
transesterification catalyst. Additional material removed from the 
distilling receiver is replaced by an equal weight of diethylene glycol. 
The heating is carried out until the acid value of the product liquid 
polyol reaches about 3.6. The product polyol has a hydroxyl number of 
about 232.6, a viscosity of about 10,800 cps at 25.degree. C. and contains 
about 0.24 water. 
Example 8 
Preparation Of A Decyl Alcohol, Example E Material, Example B Material, 
Diethylene Glycol and Dimethyl Terephthalate Residue 
To a three liter, four-neck, round-bottom flask equipped with stirrer, 
thermometer, Barrett distilling receiver, condenser, and nitrogen inlet 
tube, there is charged 450.0 grams of Example B material, 825.6 grams of 
diethylene glycol, 402.7 grams of decyl alcohol, 223.7 grams of Example E 
material and 450.0 grams of dimethyl terephthalate residue. This mixture 
is heated to 225.degree. C. with constant agitation and with a constant 
nitrogen sparge. Theoretically, 54.7 grams of water and 60 grams of 
methanol (Total 114.7 grams of material) forms and substantially all of 
such formed material is taken off at the distilling receiver. After this 
material is collected, 200 ppm of stannous octoate is added to the flask 
as a transesterification/esterification catalyst. Additional material 
removed from the distilling receiver is replaced by an equal weight of 
diethylene glycol. The heating is carried out until the acid value of the 
product liquid polyol reaches about 3.0. The product polyol has a hydroxyl 
number of about 256.3, a viscosity of about 19,500 cps at 25.degree. C. 
and contains about 0.09% water. 
Example 9 
Resin Prepolymer 
Each of the polyols of Example 1-8 is mixed (blended with) a 
urethane/isocyanurate forming catalyst and with a cell stabilizing 
surfactant to form a resin prepolymer blend suitable for reacting with 
organic isocyanate to form a cellular polymer. Each such resin prepolymer 
blend has the following composition: 
TABLE VI 
______________________________________ 
Resin Prepolymer Composition 
(100 wt. % total weight basis) 
Component weight percent 
______________________________________ 
polyol 94 
potassium octoate.sup.(1) 
4 
silicone surfactant.sup.(2) 
2 
______________________________________ 
Table VII footnotes 
.sup.(1) Example "F 
.sup.(2) Example "G 
Examples 1-8 Tumble Friability 
To illustrate tumble friability for polyurethane-polyisocyanurate foam 
prepared from self-compatibilized polyols of this invention, polyol blends 
were prepared as shown in Table VII below and these blends were then 
converted to cellular foams using a procedure similar to that of Example 
9. The foams are then evaluated for tumble friability according to ASTM 
procedure C421-77. The date obtained are given in Table VII below and such 
data show that the tumble friabilities of the foam prepared using polyols 
of the prior art have tumble friabilities that are about 20% higher 
(Examples 1 and 6) than those found for foam prepared from polyols of this 
invention (Examples 2, 3, 4, 5, 7, and 8). 
TABLE VII 
__________________________________________________________________________ 
Tumble Friabilities Of Polyurethane-Polyisocyanurate Foams Prepared From 
Self-Compatibilized Dimethyl Terephthalate Residue Based Polyester 
Polyols 
Example 
1 2 3 4 5 6 7 8 
__________________________________________________________________________ 
Components, weight in grams 
Dimethyl terephthalate residue 
1143.4 
1063.0 
1029.1 
500 450.0 1081.2 
973.1 450.0 
(Example C material) 
phthalic anhydride 
-- -- -- -- 450.0 -- -- -- 
phthalic anhydride bottoms, 
-- -- -- -- -- -- -- -- 
(Example B material) 
-- -- -- -- -- -- -- 450.0 
(Example K material) 
-- 210.0 -- -- -- -- -- -- 
Diethylene glycol 
609.1 590.7 548.2 827.9 
825.6 850.9 765.8 825.6 
Decyl alcohol 400 378.0 360.0 391.2 
402.7 -- -- 402.7 
PO--EO blocked polymer, 
(Example E material) 
-- -- 200.0 217.3 
223.7 -- 220.0 223.7 
(Example D material) 
-- -- -- 500.0 
-- -- -- -- 
(Example L material) 
-- -- -- -- -- 439.9 395.9 -- 
Characteristics 
Acid number 3.6 2.1 3.2 3.0 2.9 4.0 3.6 3.0 
Hydroxyl number 253.6 255.6 229.7 256.5 
252.9 257.2 232.6 256.3 
Viscosity, centipoises at 25.degree. C. 
27450 15430 17220 8320 10120 15500 10800 19500 
Foam Formulation 
polyol, grams 100.0 100.0 100.0 100.0 
100.0 100.0 100.0 100.0 
DC-193, grams 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 
Hex-cem 977, grams 
5.1 3.6 3.5 2.5 3.0 5.1 3.5 3.6 
TMR-30, grams 1.0 0.7 0.7 0.5 0.6 1.0 0.7 0.7 
Freon 11, grams 58.0 51.0 50.5 54.0 52.0 56.5 50.5 52.0 
PAPI-27, grams 197.1 195.1 174.9 192.8 
191.8 202.5 179.8 196.2 
Foam Properties 
Density, PCF 1.72 1.72 1.73 1.74 1.72 1.76 1.75 1.74 
Tumble friability, % 
41.90 33.98 33.03 31.21 
31.84 51.12 42.54 31.76 
(ASTM C421-77) 
__________________________________________________________________________ 
As is apparent from the foregoing specification, the invention is 
susceptible of being embodied with various alterations and modifications 
which may differ particularly from those that have been described in the 
preceeding specification and description. It should be understood that we 
wish to embody within the scope of the patent warranted hereon all such 
modifications as reasonably and properly come within the scope of our 
contribution to the art.