Copolyester polyol resins comprising the reaction product of an aromatic component, an aliphatic component selected from certain dibasic compounds, at least one primary hydroxyl glycol, and at least one secondary hydroxyl glycol, the mole ratios of the components being: PA1 (i) glycols to aromatic plus aliphatic component of about 1.3 to 2:1, PA1 (ii) aliphatic component to aromatic component of about 0.3 to 1.7:1, and PA1 (iii) primary glycol to secondary glycol of about 0.6 to 2.5:1. The invention also comprises foamable blends utilizing such resins and resultant polyisocyanurate foams.

BACKGROUND OF THE INVENTION 
The present invention relates to certain polyester polyols suitable for 
preparing polyisocyanurate foams having excellent dimensional strength and 
achieving ASTM E 84 Class 1 (25 Flame Spread) flame retardancy without the 
use of flame retardant additives. The use of Flame Spread rating data is 
not intended to represent large scale fire hazard resistance properties, 
but is used only as a reference to historical data. 
The use of polyester polyols to prepare urethane foams is an old and well 
known procedure. Over the years many inventions have been made to improve 
the resultant products in terms of lower cost, low viscosity to permit 
ready handling in conventional urethane mixing and pumping systems, better 
dimensional strength of the foam, increased fire retardancy of the foam, 
and many other properties. While some success has been encountered in one 
or more of the desired properties it has not been possible to have 
polyester polyol resins with the requisite low viscosity and resultant 
foams having the desired dimensional strength, necessary fire retardancy, 
and low cost. 
Thus, for example, it has been necessary to add fire retardants such as 
tri(.beta.-chloroisopropyl) phosphate to polyester polyols to obtain the 
necessary fire retardancy. In some instances such fire retardants also act 
to make the polyester polyol blend miscible with the CFC-11 
(chlorofluorocarbon #11) conventionally used to make the foam or to lower 
their viscosity sufficiently to make them useful. Efforts to avoid the 
negative plasticizer effect of fire retardants by use of certain 
surfactants to lower viscosity and/or provide miscibility with the CFC-11 
have not been successful since the resultant foams burn too readily and 
lack the adequate fire retardancy. 
With some low molecular weight polyester polyols which have an adequate low 
viscosity, it has been found that they oftentimes have a high hydrogen 
content which produces poor fire retardancy or a hydroxyl number so high 
as to require a large proportion of isocyanate to form a suitable foam, 
thereby greatly adding to cost. Because of a low proportion of polyol, the 
CFC-11 must be blended into the isocyanate into an "A" blend portion as it 
is conventionally called. This imbalance precludes the use of normal 
urethane mixing equipment and creates mixing problems. 
Further efforts to solve the problems of making suitable polyisocyanurate 
foams involve the use of a low molecular weight polyether diol or a 
polyether polyol resin mix with a functionality slightly above 2 as the 
urethane modifier to reduce the friability of the foam. These approaches 
have the same limitations as previously explained with respect to the use 
of low molecular weight polyester polyols. 
It has not been possible to use existing polyols in a conventional (normal) 
"B" blend with a suitable amount of CFC-11 to make a low density foam (2 
lbs./cu. ft. or less) without the need to dilute or blend the polyol with 
a suitable fire retardant to make a Class 1 (25 Flame Spread) foam. 
SUMMARY OF THE INVENTION 
The present invention overcomes the problems of the prior art and provides 
a polyol which eliminates the need for a fire retardant to achieve the 
ability to make a conventional "B" blend with CFC-11 (or other 
conventional chlorofluorocarbons used to make polyisocyanurate foams) and 
without any need to add coupling agents to insolubilize the CFC-11 in the 
resin blend; which "B" blend can be used to make Class 1 (25 Flame Spread) 
foams. Moreover, the polyol has a viscosity low enough to be commercially 
suitable and requires no other material blended with it to achieve 
sufficient chlorofluorocarbon miscibility. Other advantages of the polyol 
of the present invention are that it has a sufficiently low percent 
hydrogen content that it can be used in high weight ratios with 
isocyanates; i.e., about 65 parts by weight polyol per 100 parts by weight 
isocyanate, and still achieve a Class 1 (25 Flame Spread) flame 
retardancy; and the polyols will give highly dimensionally stable 
polyisocyanurate foams with an Index of 4. The term "Index" is used herein 
to mean its conventional usage of the ratio of active isocyanate groups 
(--NCO) to the active hydroxyl (--OH) groups. 
Briefly, the present invention comprises a hydroxyl terminated copolyester 
polyol resin having a functionality between about 2 and about 3 comprising 
the reaction product of: 
(i) an aromatic component selected from phthalic anhydride; phthalic acid 
isomers; di-lower alkanol esters of phthalic acids; di-, and 
tri-carbomethoxy substituted diphenyls, benzyl esters, toluenes, benzenes, 
benzophenones; or mixtures thereof, and 
(ii) at least one aliphatic component selected from dibasic aliphatic 
acids, esters, anhydrides, or mixtures thereof, 
(iii) at least one primary hydroxyl glycol, and 
(iv) at least one secondary hydroxyl glycol; the mole ratios of the 
components being: 
(i) glycols to aromatic plus aliphatic component of from about 1.3 to 2:1, 
(ii) aliphatic component to aromatic component of from about 0.3 to 1.6:1, 
and 
(iii) primary glycol to secondary glycol being from about 0.6 to 2.5:1, 
where the charged mole ratios are the same as the final mole ratios since 
no removal of glycols is made during the reaction. 
The invention also comprises a foamable copolyester polyol blend 
comprising: 
(a) A hydroxyl terminated copolyester polyol resin having a functionality 
between about 2 and about 3 comprising the reaction product of: 
(i) at least one aromatic component selected from phthalic anhydride; 
phthalic acid isomers; di-lower alkanol esters of phthalic acids; di-, and 
tri- carbomethoxy substituted diphenyls, benzyl esters, toluenes, 
benzenes, benzophenones; or mixtures thereof, and 
(ii) at least one aliphatic component selected from dibasic aliphatic 
acids, esters, anhydrides, or mixtures thereof, 
(iii) at least one primary hydroxyl glycol, and 
(iv) at least one secondary hydroxyl glycol; the mole ratios of the 
components being: 
(i) glycols to aromatic plus aliphatic component of from about 1.3 to 2:1, 
(ii) aliphatic component to aromatic component of from about 0.3 to 1.6:1, 
and 
(iii) primary glycol to secondary glycol being from about 0.6 to 2.5:1; 
where the charged mole ratios are the same as the final mole ratios since 
no removal of glycols is made during the reaction. 
(b) A catalyst suitable for preparing a polyisocyanurate foam; 
(c) A foaming agent suitable for preparing a polyisocyanurate foam; and, 
optionally, 
(d) A surfactant suitable for controlling foam cell size and shape. 
Further, the invention comprises a polyisocyanurate foam comprising the 
reaction product of: 
(a) A polymethylene polyphenylisocyanate, 
(b) A hydroxyl terminated copolyester polyol resin having a functionality 
between about 2 and about 3 comprising the reaction product of: 
(i) an aromatic component selected from phthalic anhydride; phthalic acid 
isomers; di-lower alkanol esters of phthalic acids; di-, and tri- 
carbomethoxy substituted diphenyls, benzyl esters, toluenes, benzenes, 
benzophenones, or mixtures thereof, 
(ii) at least one aliphatic component selected from dibasic aliphatic 
acids, esters, anhydrides, or mixtures thereof, 
(iii) at least one primary hydroxyl glycol, and 
(iv) at least one secondary hydroxyl glycol; the mole ratios of the 
components being: 
(i) glycols to aromatic plus aliphatic component of from about 1.3 to 2:1, 
(ii) aliphatic component to aromatic component of from about 0.3 to 1.6:1, 
and 
(iii) primary glycol to secondary glycol being from about 0.6 to 2.5:1; 
where the charged mole ratios are the same as the final mole ratios since 
no removal of glycols is made during the reaction. 
(c) A catalyst suitable for preparing a polyisocyanurate foam, 
(d) A foaming agent suitable for preparing a polyisocyanurate foam, and, 
optionally, 
(e) A surfactant suitable for controlling foam cell size and shape. 
DETAILED DESCRIPTION 
The exclusive use of aromatic ester groups in making a polyester polyol 
results in a polyol which must be further blended because it is too 
viscous to use by itself and has poor CFC-11 compatibility. Some aliphatic 
ester polyester polyols have been made with a low viscosity and excellent 
CFC-11 miscibility, but have contained a large amount of hydrogen, and 
have had to either use a fire retardant to achieve a Class 1 (25 Flame 
Spread) foam or else use a large weight ratio of isocyanate to polyol, and 
thus require CFC-11 be mixed with the isocyanate in order to introduce 
enough CFC-11. In attempting to reduce the hydrogen content of a polyol to 
a level low enough where about 65 parts by weight (Pbw) per 100 parts by 
weight (Pbw) polymethylene polyphenylisocyanate (PMDI) would produce a 
Class 1 (25 Flame Spread) foam, it became apparent that the level of 
CFC-11 miscibility was proportional to the level of hydrogen. Miscibility 
in chlorofluorocarbons appears to be related to hydrogen content, getting 
better as the percentage hydrogen goes up, especially when the hydrogen 
appears as --CH.sub.3, such as in secondary polyols and glycols. 
It was found, surprisingly, that at a certain low calculated percent 
hydrogen, neither aliphatic nor aromatic carboxylic group sources alone 
could provide a polyol with sufficient CFC-11 miscibility, but that within 
a certain range of aliphatic to aromatic mixture which was reacted 
together, the same percentage hydrogen content polyol would have 
sufficient CFC-11 miscibility. It is predictable that the viscosity of a 
polyol made from an aromatic/aliphatic blend would be higher than the same 
molecular weight polyol made with the same glycol mixture with pure 
aliphatic carboxylics, and that it would be lower than with the same 
molecular weight polyol made with the same glycol mixture with pure 
aromatic carboxylics. These predictions proved true, but it was not 
predictable that when making polyols with equal percentage hydrogen 
content, a copolyester using both aliphatic and aromatic sources of 
carboxylic groups, mixed and reacted, would have better CFC-11 miscibility 
than a simple polyester polyol using either aliphatic or aromatic 
carboxylic groups. Advantageously, the ratio of aliphatic to aromatic 
mixture where CFC-11 miscibility is good also provides a favorable 
viscosity with the needed low percentage hydrogen content. 
It is an object of the instant invention to maintain an equivalent weight 
in the range of about 320 to about 350 so that a normal "A" to a "B" blend 
ratio of about 50:50 would provide a foam with an Index of about 4.0. 
Since the trimerized isocyanate linkage is a more desirable linkage than 
urethane linkages in accomplishing fire resistance and dimensional 
stability, the polyol equivalent weight must stay high enough to provide a 
4 to 1 ratio of --NCO groups to --OH groups (4.0 Index) while preparing a 
"B" blend with about 65 Pbw polyol which will then mix with 100 Pbm of 
PMDI. It was decided to keep the functionality near 2, since the higher 
the functionality, the lower the Index of the foam at any given weight 
ratio. 
It is likewise necessary with the present invention to provide a polyol 
with sufficient primary hydroxyl tips to make a fast enough reaction with 
isocyanate groups to be commercially useful, and at the same time retain 
enough secondary hydroxyl units to provide CFC-11 compatibility. 
Predominant use of secondary hydroxyl tips provides a slow reacting polyol 
which, in turn, makes unacceptably large and open cell structure foam. 
While the longer chain polyethylene primary glycols such as PEG 200, and 
PEG 300 provide both CFC-11 solubility and reaction speed, they contain 
too much hydrogen to provide a product which obtains a Class 1 foam when 
used as the only glycols in the present manner. Predominant use of the 
lower molecular weight primary mono- and di- ethylene glycols keeps the 
hydrogen content down, but they make polyols with poor CFC-11 
compatibility. 
An additional advantage of the polyols of the present invention is that due 
to their high equivalent weight, low hydrogen content, and good CFC-11 
miscibility, they can be used in enough mass weight to hold enough CFC-11 
in solution that no CFC-11 needs to be added to the PMDI, and no diluents 
nor coupling agents such as non-ionic surfactants or fire retardants need 
to be added to the polyols to hold CFC-11 in a quantity sufficient to 
provide a nominal 2.0 lbs./cu. ft. foam. Even using a high mass of pure, 
undiluted polyol, the high equivalent weight of the present invention 
makes it possible to produce a foam with a 4.0 Index. It has been found 
that when plotting foam Index versus strength, dimensional stability, and 
fire resistance properties, that all the physical properties of foam 
improve sharply up to an Index of about 4.0, and then gradually increase, 
or level out, before dropping again at a high enough Index where excess 
friability causes poor compressive strength and flexural strength. Thus, 
the ability to provide a 4.0 Index foam at a normal "A" to "B" blend ratio 
of about 50:50 Pbw is a significant advantage of the present invention. 
A narrow range of certain blends of secondary glycols with low-medium mole 
weight primary glycols could be used advantageously with a narrow range of 
certain blends of aromatic esters and aliphatic esters to accomplish all 
the objects of this invention. It is required to use at least one aromatic 
component selected from phthalic anhydride; phthalic acid isomers; 
di-lower alkanol esters of phthalic acids; di- and tri- carbomethoxy 
substituted diphenyls, benzyl esters, toluenes, benzenes, benzophenones; 
or mixtures thereof and at least one aliphatic component selected from 
succinic, glutaric, or adipic acids, esters, anhydrides, or mixtures 
thereof. Also one must use at least one primary hydroxyl glycol and at 
least one secondary hydroxyl glycol. Primarily, for reasons of lower cost, 
it is preferred to use commercially available mixtures of the aromatics, 
aliphatics, and/or glycols. As aromatics, mixtures of ortho, meta, and 
para dimethyl phthalates and monomethyl toluate esters (MPME by 
Hercofina), and mixtures of DMT with mono-, di- and trimethyl (or benzyl) 
biphenyl esters (DMT/HBR by DuPont and TERATE 101 by Hercules) are 
available. Also, these products contain amounts of mono-functional ester, 
which aids in reducing the friability of the finished foam due to 
plasticizing effect. As to the aliphatics, a mixture of dimethyl esters of 
succinic, glutaric, and adipic acids is preferred. The primary glycols 
that can be used are ethylene glycol, diethylene glycol, tetraethylene 
glycol, polyethylene glycol 200, 1,4 butylene glycol, triethylene glycol, 
or mixtures thereof, with the ethylene glycol being suitable only when 
used with other primary glycols. The secondary glycols that can be used 
include propylene glycol, dipropylene glycol, and 1,3 butylene glycol, or 
mixtures thereof. 
Specific embodiments of the present invention include a specific reaction 
product comprising ethylene glycol, propylene glycol, diethylene glycol, 
triethylene glycol, and tetraethylene glycol mixed to react with 
dimethylterephthalate, di- and tri-methyl biphenyl carboxylate, and the 
dimethyl esters of the mixed succinate, glutarate and adipate family. A 
major oligimer of the reaction product can be represented by: 
##STR1## 
where: R.sub.1 can be --CH.sub.2 --CH.sub.2 --(ethylene glycol core), or 
--CH.sub.2 --CH.sub.2 --O--CH.sub.2 --CH.sub.2 --(diethylene glycol core), 
or 
##STR2## 
or the oxyethylene core of tri- or tetra- ethylene glycol, and R.sub.2 
can be --CH.sub.2 --CH.sub.2 --, or --CH.sub.2 --CH.sub.2 --CH.sub.2 --, 
or --CH.sub.2 --CH.sub.2 --CH.sub.2 --CH.sub.2 --(Succinate, glutarate, 
and adipate aliphatic dicarboxylic cores), and 
R.sub.3 can be the same glycol core, or one of the other glycol cores shown 
in R.sub.1, but probably not the same glycol core as 
R.sub.1, and 
R.sub.4 can be: 
##STR3## 
As to proportions, the mole ratios of the various components should be as 
follows: 
(a) glycols to aromatic plus aliphatic component in the range of from about 
1.3 to 2:1; preferably 1.4 to 1.5:1; 
(b) aliphatic component to aromatic component in the range of from about 
0.3 to 1.7:1 and preferably 1.0 to 1.5:1; and 
(c) primary glycol to secondary glycol in the range of from about 0.6 to 
2.5:1; preferably 1.0 to 1.5:1. 
With the instant invention the charged mole ratios are the same as the 
final mole ratios since no removal of glycols is made during the reaction. 
Also, as a general rule the higher the single benzene ring content, as 
opposed to bi-ring content, of the aromatic component, the lower the 
amount of aliphatic component necessary for optimum results. 
The transesterification reaction of the mixed esters with the mixed glycols 
takes place between 130.degree. C. and 250.degree. C., preferably between 
160.degree. C. and 220.degree. C., with the use of a suitable catalyst 
such as tetrabutyltitanate, dibutyl tin oxide, potassium methoxide, lead 
oxide, or zinc oxide used in the amount of 0.1% to 0.5% of the weight of 
the whole mixture. The reaction of laboratory amounts takes from 4 to 6 
hours with methanol being removed constantly to drive the otherwise 
equilibrium reaction to completion. At least 95%, and preferably 100%, of 
the available methyl alcohol is removed by packed column separation 
distillation, aided in the late stages by mild vacuum application, taking 
care not to remove glycols. 
After the instant copolyester polyol resin is made, a "B" blend is formed 
by admixing the polyol with a conventional catalyst, blowing agent, and 
surfactant. 
As to the catalysts, one can use any conventionally used in producing 
polyisocyanurate foams such as a combination of a metallic carboxylate 
with a tertiary amine or a quaternary amine salt catalyst. 
Any alkali metal carboxylate can be employed such as sodium or lithium 
octoate, lithium stearate, or sodium caprioate; with the preferred metal 
being potassium used with acetate, adipate, butyrate, decanoate, 
isobutyrate, nonate, and stearate; with the most preferred form being 
potassium 2-ethylhexoate, also known as potassium octoate. The preferred 
version of potassium octoate is one which has at least 14% potassium. One 
such product is "Potassium HexCem, Code 977," as sold by Mooney Chemical 
Company. Other suppliers include M&T Chemicals, Inc. and Jim Walter 
Resource Company. 
In conjunction with an alkali metal carboxylate catalyst, some form of an 
amine catalyst must be used. Common tertiary amine catalysts used in 
conjunction with alkali metal carboxylate catalysts include 
N,N-dimethylcyclohexylamine, N,N-dimethylbenzyl amine, tetramethylethylene 
diamine, tetramethyl propane diamine, triethylene diamine, 
N,N-dimethylethanolamine, and 2,4,6 tris (dimethylaminomethyl) phenol, 
which is the preferred tertiary amine. This tertiary amino phenol is sold 
by Rohm and Haas Co. under the name "DMP-30", and by Thiokol Corporation 
as "EH330". 
Other trimerization catalysts can be used in place of, or in conjunction 
with, the preferred catalysts shown in the Examples. For example, certain 
amine salts, preferably quaternary ammonium compounds, such as the 
N-hydroxypropyl trimethyl ammonium salt of formic acid can be used 
advantageously as a replacement for all, or part, of the catalysts of the 
preferred compositions. Such quarternary ammonium salts can be obtained 
under the trade name "DABCO TMR" or "DABCO TMR-2" from Air Products & 
Chemicals Company. It has been found that the total weight percent of 
potassium 2-ethylhexoate plus the tertiary amino phenol can be used as a 
good starting point for the weight percent addition rate of the quaternary 
amine salt catalysts. The total catalyst level usually comprises from 0.1 
to 4.0, and preferably comprises from 0.7 to 3.0, weight percent of the 
composition. 
With respect to surfactants, any commercial grade of 
polydimethylsiloxane-polyoxyalkylene block copolymer, such as "L-5420" and 
"L-5340" from Union Carbide Corporation and "DC-193" from Dow Corning 
Corporation can be used. The surfactant generally comprises from 0.05 to 
4, and preferably comprises from 0.1 to 2, weight percent of the 
composition. 
The blowing agent can be any commonly employed in similar prior art foam 
products. These include water (for CO.sub.2 blowing), methylene chloride, 
and chlorofluorocarbons such as C--Cl.sub.2 F--C--ClF.sub.2, C--Cl.sub.2 
F--CF.sub.3, C--Cl.sub.2 F.sub.2, and fluorotrichloromethane, C--Cl.sub.3 
F, (CFC--11), which is the preferred blowing agent. The blowing agents are 
employed in an amount sufficient to produce the desired foam density which 
is generally between 0.5 and 10, and preferably between 1 and 5 pounds per 
cubic foot. The CFC type blowing agents generally comprise from 1 to 30, 
and preferably comprise from 5 to 20, weight percent of the composition. 
Any commercially available isocyanates can be employed within the broadest 
aspect of the present invention. The preferred versions are polymethylene 
polyphenylisocyanates, and are those with a functionality between 2.1 and 
3.2, and most preferable are those between 2.5 and 3.2 functionality. The 
preferred molecular weight PMDI's are those with the above preferred 
functionalities and with an equivalent weight between 130 and 145. These 
products tend to produce viscosities in the range of 250 to 2500 cps (at 
25.degree. C.), and are practical for commercial use within the scope of 
this invention. As indicated, the level of PMDI used should provide a 
ratio of --NCO to --OH of about 4.0 to 1.0. 
The invention will be further described in connection with the following 
examples which are set forth for purposes of illustration only.

In all of the following examples of acceptable foams, the foam produced 
exhibited excellent dimensional stability in that the expansion rate at 
225.degree. F. dry heat and at 158.degree. F. at 95+% RH was less than 
4.5% volume change in 14 days. One or more of the example foams tested 
produced excellent fire resistance properties in that the Oxygen Index 
(ASTM D 2863-77) was about 24, the Butler Chimney (ASTM D-3014), and the 
48-inch tunnel both indicated a 25 Flame Spread had been achieved. 
EXAMPLE I 
A reactor which was equipped with a center mixer, a separate chemical 
inlet, a temperature monitoring probe (thermocouple or thermometer), and a 
packed column with stillhead was used. The packed column was topped with a 
stillhead fitted with condensate thermometer. The downleg of the stillhead 
was connected to an 18 inch water cooled condenser followed by a 
vertically bent downleg vacuum/collection adapter fitted to a graduated 
Erlenmyer flask in the vertical position. All glassware had ground glass 
joints. The 2 liter reaction kettle was jacketed with a form-fitted 
heating mantle. 
The kettle was charged with: 
(1) 2.0 moles (540 grams) of the mixed DMT/mono-, di-, and tri-methyl (or 
benzyl) biphenyl esters; DMT/HBR by DuPont (hereinafter referred to as 
"Aromatic Esters"), 
(2) 2.5 moles (400 grams) of the mixed dimethyl esters of succinic, 
glutaric, and adipic acid series (hereinafter referred to as "Aliphatic 
Esters"), 
(3) 2.9 moles of propylene glycol; (220.4 grams) (hereinafter referred to 
as "PG"), 
(4) 3.1 moles of diethylene glycol; (328.6 grams) (hereinafter referred to 
as "DEG"), and 
(5) 0.5 moles of tetraethylene glycol; (97 grams). 
This mixture was melted and brought to a temperature of 180.degree. C. with 
rapid stirring without catalyst being present. At this temperature, a 
mixture of methanol and glycol vapors filled the packed column and 
methanol started to condensate over the stillhead slowly. At this time, 
2.0 grams (0.126 weight %) of tetra n-butyl ortho titanate was added 
through the chemical addition opening to the hot mixture with the agitator 
stopped. The reaction proceeded rapidly and mixing was resumed, taking 
care not to allow the stillhead temperature to elevate to 70.degree. C. In 
order to keep glycols from co-distilling over with methanol it is 
important to maintain this temperature at 65.degree. C., closer to the 
boiling point of methanol. The methanol condensate was collected rapidly 
for almost one hour, but the reaction speed, as measured by condensate 
production rate, slowed markedly at about 11/2 hours. At this point, 
another 2.0 grams of tetrabutyl titanate was added in the same manner as 
before. As the reaction proceeded to completion, the reaction kettle 
temperature increased without adding more power. At 220.degree. C. kettle 
temperature, the heat input was reduced 30% and a very slight vacuum 
(minus 2-4 inches of Hg) was added to the system through an ice chilled 
vacuum trap in line with the vacuum adapter connection at the condenser 
discharge. The kettle temperature stopped rising. The vacuum was increased 
as the methanol condensate rate slowed, taking care not to exceed minus 
ten inches Hg vacuum. As the vacuum was slowly increased, the stillhead 
temperature slowly dropped from the normal 64.degree.-65.degree. C. at 
atmospheric pressure to approximately 40.degree. C., and the kettle 
temperature slowly dropped to 210.degree. C. At 205.degree. C. kettle 
temperature, the methanol had essentially stopped condensing. About 41/2 
hours had elapsed since the initiation of kettle heat. 
This resin exhibited the following properties: 
______________________________________ 
1. Viscosity: 11,000 cps at 25.degree. C. 
2. Hydroxyl Number 
164 
3. CFC-11 Solubility 
100% CFC-11 retained without 
separation in a blend of 30 
Pbw CFC-11 and 70 Pbw Resin 
______________________________________ 
The foam for this example was made with the formula 
______________________________________ 
Component Pbw 
______________________________________ 
"A" Blend or PMDI 100.0 
Polyol, Polyester Resin 66.0 
Surfactant DC-193 2.0 
Catalyst, Potassium HexCem, Code 977 
2.6 
Catalyst, DMP 30 1.7 
Blowing Agent, CFC-11 26.7 
"B" Blend Total 99.0 
______________________________________ 
Some properties of this foam and the reaction rates include: 
______________________________________ 
Cream Time: 6 seconds 
Gel Time: 25 seconds 
Firm Time: 28 seconds 
Full Rise Time: 56 seconds 
Density: 1.7 lbs./cu. ft (Free Rise) 
Friability: Acceptable 
Foam Appearance: Good, fine cell structure 
______________________________________ 
EXAMPLE II 
In another example, the same equipment was used to prepare the following 
resin: 
______________________________________ 
(1) 2.0 moles (540.0 grams) of Aromatic Esters, 
(2) 2.5 moles (400.0 grams) of Aliphatic Esters, 
(3) 2.6 moles (197.6 grams) of PG, 
(4) 2.9 moles (307.4 grams) of DEG, 
(5) 0.8 moles (Approx. 160 grams) of 
polyethylene glycol 200 (PEG 200). 
______________________________________ 
This mixture was melted and mixed rapidly following the same procedure 
outlined in Example I. As was the case in Example I, the catalyst used was 
tetrabutyltitanate and it was added in 2 stages, 2.0 grams at each time. 
Similarly, when the kettle temperature reached 220.degree. C. the vacuum 
was added slowly, increasing vacuum as the kettle and head temperatures 
decreased. This reaction covered 4.3 hours. 
______________________________________ 
POLYOL PROPERTIES: 
______________________________________ 
Viscosity: 14,000 cps at 25.degree. C. 
Hydroxyl Number: 155 
CFC-11 Solubility: 100% retained without 
separation in a blend 
of 30 Pbw CFC-11 and 
70 Pbw Resin. 
______________________________________ 
FOAM FORMULATION: 
COMPONENT Pbw 
______________________________________ 
Polyol Resin 65.0 
Surfactant DC 193 2.5 
Potassium HexCem 1.9 
DMP-30 1.0 
CFC-11 28.6 
"B" Blend Total: 99.0 
PMDI ("A" Blend): 104.0 
______________________________________ 
FOAM PROPERTIES: 
______________________________________ 
Cream Time: 8 seconds 
Gel (2nd Rise): 43 seconds 
Firm Time: 48 seconds 
Full Rise: 80 seconds 
Density: 1.63 lbs./cu. ft. 
Friability: Acceptable 
Foam Appearance: Good, fine cell size. 
______________________________________ 
EXAMPLE III 
The same equipment was used to transesterify: 
______________________________________ 
(1) 2.0 moles (540.0 grams) of Aromatic Esters, 
(2) 2.3 moles (368.0 grams) of Aliphatic Esters, 
(3) 4.5 moles (342.0 grams) of PG, 
(4) 1.5 moles (159.0 grams) of DEG, 
(5) 0.4 moles (Approx. 80.0 grams) of PEG 200. 
______________________________________ 
In this example the catalyst used was a laboratory prepared potassium 
methoxide, KOCH.sub.3. A total of 7.0 grams, 2 additions of 3.5 grams, was 
used. The same procedure as outlined in Example I was followed. This 
catalyst appeared to be less active as the elapsed time of this 
preparation was 5.5 hours. 
______________________________________ 
POLYOL PROPERTIES: 
______________________________________ 
Viscosity: 5100 cps at 27.degree. C. 
Hydroxyl Number: 182 
CFC-11 Solubility: 
100% of the 30 Pbw CFC-11 
added to 70 Pbw Resin 
______________________________________ 
FOAM FORMULATION 
COMPONENT Pbw 
______________________________________ 
Polyol Resin 68.0 
Surfactant DC 193 2.1 
Potassium HexCem 3.1 
DMP-30 2.0 
CFC-11 24.8 
"B" Blend Total: 100.0 
PMDI ("A" Blend): 102.0 
______________________________________ 
FOAM PROPERTIES: 
______________________________________ 
Cream Time: 18 seconds 
Gel (2nd Rise): 55 seconds 
Firm Time: 75 seconds 
Full Rise: 105 seconds 
Density: 1.85 lbs./cu. ft. 
Friability: Unacceptable 
Foam Appearance: Large, coarse cell structure; 
not acceptable. 
______________________________________ 
EXAMPLE IV 
The same equipment was used to transesterify: 
______________________________________ 
(1) 2.0 moles (540.0 grams) of Aromatic Esters, 
(2) 3.0 moles (480.0 grams) of Aliphatic Esters, 
(3) 3.8 moles (402.8 grams) of DEG, 
(4) 3.1 moles (235.6 grams) of PG. 
______________________________________ 
The catalyst was tetrabutyltitanate used as in Example I, 1.8 grams added 
twice. The total elapsed time to completion was 4.7 hours. 
______________________________________ 
POLYOL PROPERTIES: 
______________________________________ 
Viscosity: 14,100 cps at 24.degree. C. 
Hydroxyl Number: 151 
Solubility: Only 86.8% of the CFC-11 of a 
30 Pbw CFC-11 with a 70 Pbw 
resin mixture was retained; 
not acceptable. 
______________________________________ 
FOAM FORMULATION: 
COMPONENT Pbw 
______________________________________ 
Polyol Resin 70.0 
DC 193 2.1 
Potassium HexCem 2.0 
DMP-30 1.5 
CFC-11 24.4 
"B" Blend Total: 100.0 
PMDI 104.1 
______________________________________ 
FOAM PROPERTIES: 
______________________________________ 
Cream Time: 8 seconds 
Gel (2nd Rise): 35 seconds 
Firm Time: 40 seconds 
Full Rise: 55 seconds 
Density: 1.80 lbs./cu. ft. 
Friability: Acceptable 
Appearance: Excellent, fine cells 
______________________________________ 
EXAMPLE V 
______________________________________ 
(1) 2.0 moles (540.0 grams) of Aromatic Esters, 
(2) 2.5 moles (400.0 grams) of Aliphatic Esters, 
(3) 5.6 moles (425.6 grams) of PG, 
(4) 1.3 moles (137.8 grams) of DEG. 
______________________________________ 
In this example, the catalyst used was dibutyltinoxide at a total rate of 
3.4 grams for the preparation, with 1.7 grams being added twice as in the 
procedure of Example I. The reaction elapsed time was 5.0 hours. 
______________________________________ 
POLYOL PROPERTIES 
______________________________________ 
Viscosity: 5555 cps at 25.0.degree. C. 
Hydroxyl Number: 201 
Solubility: Retained 100% of a 37 Pbw 
CFC-11 mix with 63 Pbw Resin. 
______________________________________ 
FOAM FORMULATION: 
COMPONENT Pbw 
______________________________________ 
Polyol Resin 68.0 
DC 193 2.1 
Potassium HexCem 2.5 
DMP-30 1.5 
CFC-11 25.9 
"B" Blend Total 100.0 
PMDI 105.0 
______________________________________ 
FOAM PROPERTIES: 
______________________________________ 
Cream Time: 7 seconds 
Gel (2nd Rise): 30 seconds 
Firm Rise: 35 seconds 
Full Rise: 45 seconds 
Density: 1.70 lbs./cu. ft. 
Friability: Acceptable 
Appearance: Good; fine cell structure. 
______________________________________ 
EXAMPLE VI 
The same equipment was used to transesterify: 
______________________________________ 
(1) 2.0 moles (540.0 grams) of Aromatic Esters, 
(2) 3.0 moles (480.0 grams) of Aliphatic Esters, 
(3) 3.4 moles (258.4 grams) of PG, 
(4) 3.3 moles (349.8 grams) of DEG, 
(5) 0.4 moles (80.0 grams) of PEG 200. 
______________________________________ 
The catalyst was tetrabutyltitanate used as in Example I. The reaction 
elapsed time was 4.9 hours. 
______________________________________ 
POLYOL PROPERTIES: 
______________________________________ 
Viscosity: 9100 cps at 25.0.degree. C. 
Hydroxyl Number: 159 
Solubility: 100% CFC-11 retained of 30 
Pbw CFC-11 mixed with 70 
Pbw Resin. 
______________________________________ 
FOAM FORMULATION: 
COMPONENT Pbw 
______________________________________ 
Polyol Resin: 64.0 
DC 193: 2.1 
Potassium HexCem: 2.6 
DMP-30: 1.6 
CFC-11: 28.7 
"B" Blend Total: 99.0 
PMDI 104.0 
______________________________________ 
FOAM PROPERTIES: 
______________________________________ 
Cream time: 10 seconds 
Gel (2nd Rise): 30 seconds 
Firm Time: 35 seconds 
Full Rise: 58 seconds 
Density: 1.7 lbs./cu. ft. 
Friability: Acceptable 
Appearance: Excellent fine cell structure. 
______________________________________ 
EXAMPLE VII 
The same equipment was used to transesterify: 
______________________________________ 
(1) 2.5 moles (485.0 grams) of Dimethyl Terephthalate, 
(2) 2.5 moles (400.0 grams) of Aliphatic Esters, 
(3) 3.4 moles (258.4 grams) of PG, 
(4) 3.6 moles (381.6 grams) of DEG, 
(5) 0.3 moles (62.2 grams) of PEG 200. 
______________________________________ 
In this example, the normally used mixture of DMT/mono-, di-, and 
tri-methyl (or benzyl) biphenyl esters was replaced by specification grade 
DMT. The catalyst used was tetrabutyltitanate as in Example I. The elapsed 
time was 4.0 hours. 
______________________________________ 
POLYOL PROPERTIES: 
______________________________________ 
Viscosity: 4175 cps at 25.degree. C. 
Hydroxyl Number: 217 
Solubility: 100% CFC-11 retained of 
33 Pbw CFC-11 in 67 Pbw Resin 
______________________________________ 
FOAM FORMULATION: 
COMPONENT Pbw 
______________________________________ 
Polyol Resin 66.0 
DC 193 1.0 
Potassium HexCem 3.0 
DMP-30 2.0 
CFC-11 28.0 
"B" Blend Total: 100.0 
PMDI 104.0 
______________________________________ 
FOAM PROPERTIES: 
______________________________________ 
Cream Time: 8 seconds 
Gel (2nd Rise): None 
Firm Time: 21 seconds 
Full Rise: 34 seconds 
Density: 1.66 lbs./cu. ft. 
Friability: Acceptable 
Appearance: Excellent, fine cell structure 
______________________________________ 
The present invention also contemplates a flexible foam and urethane-type 
elastomer in which the isocyanate used is primarily a difunctional 
isocyanate. The complete details of such are not presently understood, but 
it is presently theorized that they will utilize the instant copolyester 
polyols in possibly different ratios of components. The instant 
copolyester polyols also have the capability of performing as adhesives, 
again necessitating, possibly, different ratios of components. 
While the invention has been described in connection with a preferred 
embodiment, it is not intended to limit the scope of the invention to the 
particular form set forth, but, on the contrary, it is intended to cover 
such alternatives, modifications, and equivalents as may be included 
within the spirit and scope of the invention as defined by the appended 
claims.