Scrap rim polyurethane modified extender polyols

Mixtures of aromatic polyols containing ester functionalities suitable for use as polyol extenders in polyurethane foams prepared by reacting dibasic acid residues with an alkylene glycol residue, the reaction product of which is reacted with recycled polyethylene terephthalate into which scrap RIM is dissolved, are described. Scrap RIM is recycled reaction injection molded polyurethane material which has been chopped or pulverized. From about 10 to 50 wt. % of the resulting modified extender polyol mixture may be scrap RIM. Surprisingly, the process is non-catalytic. These novel polyols may be blended with conventional polyols to yield excellent rigid foams, thus serving as useful polyol extenders.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The invention relates to polyols for rigid polyurethane foams and more 
particularly relates to such aromatic polyester polyols which are made 
from the waste streams of dibasic acids, alkylene glycols, recycled or 
scrap polyethylene terephthalate and scrap reaction injection molded 
polyurethane. 
2. Description of Other Relevant Compounds in the Field 
It is known to prepare polyurethane foam by the reaction of polyisocyanate, 
a polyol and a blowing agent such as a halogenated hydrocarbon, water or 
both, in the presence of a catalyst. One particular area of polyurethane 
technology is based upon rigid polyurethane foams. 
Rigid foams generally have good insulative properties and are thus 
desirable for use in building insulation. As with all building materials, 
it is desirable to provide rigid foams that are as fire resistant as 
possible. One approach to this goal is to modify the polyol. 
Polyisocyanurate foams are a type which are considered to be fire resistant 
and show low smoke evolution on burning. However, polyisocyanurate foams 
tend to be brittle or friable. Various types of polyols have been devised 
to lower the foam friability, but what frequently happens is that the fire 
and smoke properties of the polyisocyanurate foam deteriorate. Thus, a 
fine balance exists between the amount and type of polyol one adds to a 
polyisocyanurate foam formulation in order to maintain maximum flame and 
smoke resistance while at the same time reach an improvement in foam 
friability. U.S. Pat. Nos. 4,039,487 and 4,092,276 describe attempts at 
this fine balance, although each has its disadvantages. 
The recovery of polyalkylene terephthalate scrap or residues has long been 
practiced. U.S. Pat. No. 3,344,091 describes a process for converting 
scrap polyester, such as polyethylene terephthalate (PET) into active 
prepolymer particles by mixing the scrap PET with the glycol originally 
used in preparing PET, with or without the additional presence of a lower 
dialkyl ester of the aromatic dicarboxylic acid whose dehydroxylated 
residues are present in the scrap PET. Chemical Abstracts (CA), vol. 84, 
paragraph 5638h, relates that British Pat. No. 1,458,486 teaches dialkyl 
terephthalates, such as dimethyl terephthalate (DMT), recovery by heating 
scrap PET with monohydric alcohols with a catalyst and a sequestering 
agent. 
PET scrap may be recovered by depolymerization with glycols as seen in CA 
78:160452n, abstract to East German Patent No. 92,801. U.S. Pat. No. 
4,166,896 teaches that a mixture of glycols and oligomers (such as low 
molecular weight polyesters of terephthalic acid and a glycol) may be 
depolymerized (transesterified) by heating. Subsequently, ethylenically 
unsaturated dicarboxylic acids or their anhydrides are added and the 
mixture is heated again. An unsaturated polyester resin is produced. A 
suitable dicarboxylic acid is phthalic acid, the anhydride of which is 
also useful in this process. 
Scrap polyalkylene terephthalate, such as polyethylene terephthalate is 
known to be incorporated into polyurethanes. For example, U.S. Pat. No. 
4,048,104 relates that polyisocyanate prepolymers for use in polyurethane 
products may be prepared by combining an organic polyisocyanate with 
polyols which are the hydroxyl-terminated digestion products of waste 
polyalkylene terephthalate polymers and organic polyols. A polyol 
ingredient which is the digestion product of polyalkylene terephthalate 
residues or scraps digested with organic polyols is also described in U.S. 
Pat. No. 4,223,068. Another case where terephthalic acid residues are 
employed is outlined in U.S. Pat. No. 4,246,365 where polyurethanes are 
made from polyesters containing at least two hydroxyl groups and 
terephthalic acid residues. 
More relevant to the compounds of this invention is the solution proposed 
in U.S. Pat. No. 4,237,238. In this patent, a polyol mixture is prepared 
by the transesterification of a residue from the manufacture of dimethyl 
terephthalate with a glycol, which is then used to produce 
polyisocyanurate foams having a combination of a high degree of fire 
resistance with low smoke evolution, low foam friability and high 
compressive strength. The preparation of such a polyol mixture (from 
ethylene glycol and dimethyl terephthalate esterified oxidate residue) is 
described in U.S. Pat. No. 3,647,759. J. M. Hughes and John Clinton, in 
the Proceedings of the S.P.I. 25th Annual Urethane Division Technical 
Conference, Scottsdale, Arizona (October 1979), describe other foams 
prepared from the polyols of U.S. Pat. No. 3,647,759. 
U.S. Pat. No. 3,755,212 teaches air blown polyurethane foams prepared from 
ester-modified polyether polyols, a polyisocyanate and a polyurethane 
catalyst. The modifying agents for reaction with the polyols apparently 
are internal anhydrides of polycarboxylic acids, such as phthalic 
anhydride. Rigid polyurethane foams may be made from a fluid polyol made 
by hydrogenating a DMT process residue, then reacting the hydrogenation 
product with an alcoholic material, according to U.S. Pat. No. 3,892,796. 
Further, U.S. Pat. No. 4,186,257 reveals that high molecular weight 
polyurethanes from polyols linked with ester groups may be made by 
reacting diols with phthalic acid or DMT. Polybutylene terephthalate diols 
and polyhexamethylene terephthalate diols are also used. 
Brominated ester-containing polyether polyols may be prepared by the 
sequential reaction of a polyether polyol with 
4,5-dibromohexahydrophthalic anhydride and an alkylene oxide according to 
U.S. Pat. No. 4,069,207. Flame-retardant polyurethane foams are prepared 
using these modified polyols. Also relevant is East German Pat. No. 
122,986 cited in CA 86:190834 which teaches that polyurethanes may be 
manufactured from polyester polyols made by condensation and 
transesterification of PET synthesis distillation residues with polyols, 
polyamino alcohols and fatty acid ester diols. 
SUMMARY OF THE INVENTION 
The invention concerns a mixture of scrap reaction injection molded 
polyurethane modified extender polyols being produced by the process 
comprising reacting a dibasic acid with an alkylene glycol and recycled 
polyethylene terephthalate in the presence of scrap reaction injection 
molded polyurethane.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
In general, it has been discovered that polyurethane foams, particularly 
rigid foams, may be made using the mixture of aromatic polyester polyols 
of this invention either alone or as polyol extenders together with other 
polyols. In addition, such a polyol mixture is compatible with the 
trichlorofluoromethane blowing agent, a problem with prior art polyol 
extenders. The novel aromatic polyester polyol mixtures are made by using 
recycled polyethylene terephthalate (PET). This may be any scrap residue 
from old polyethylene terephthalate which contains compounds which have 
the moiety 
##STR1## 
Generally, the scrap or recycled polyethylene terephthalate may be in any 
particulate form. A frequently seen form is fragmentized soft drink 
bottles which appear as clear or colored chips. Polyethylene terephthalate 
film can also be recycled. Any chopping or pulverizing process which 
produces small bits of solid PET from the larger, waste recycled article 
would be appropriate to produce scrap PET useful herein. Sometimes the 
scrap PET is mixed with a solvent to make a kind of slurry. While scrap 
PET slurry could be used in the method of this invention, the recycled PET 
chips without the solvent is also useful. 
The polyester polyol with which the polyethylene terephthalate scrap is 
reacted is produced by the esterification of a residue of dibasic acid 
manufacture, as noted before. Dibasic acids are those acids which have two 
displaceable hydrogen atoms. Examples of such acids are succinic, glutaric 
and adipic acid. Especially preferred are the residues from adipic acid 
manufacture which contain portions of each of the three acids listed 
above. It is necessary that the acids be dibasic so that polymer chains 
can be formed upon reaction with the glycol. These materials may also 
include waste dicarboxylic acids. 
Preferably, the alkylene glycol has the formula 
##STR2## 
where R is hydrogen or lower alkyl of one to four carbon atoms and n is 
from 1 to 3. Glycols which meet this definition are ethylene glycol, 
propylene glycol (1,2-propylene glycol), diethylene glycol (DEG), 
dipropylene glycol, and triethylene glycol (TEG), among others. The glycol 
may be a residue or flash-separated glycol. 
The polyester polyol which results from the reaction of the dibasic acid 
residue and an alkylene glycol, such as DEG, may be a diester diol. Such a 
diol may be defined by the formula 
##STR3## 
where x is 2 to 4. 
The proportions of the reactants should be such as to give a resulting 
mixture of aromatic polyester polyols which have an average OH (hydroxyl) 
number within the desired range of about 100 to 400. The saponification 
number of the scrap polyethylene terephthalate (a measure of 
transesterification sites) should be considered in selecting proportions, 
if obtainable. One PET unit has a molecular weight of 192.2. Preferably 
the approximate mole ratio of scrap polyethylene terephthalate to dibasic 
acid to alkylene glycol may be about 1:1:2. These proportions could vary 
5% in either direction. What actually forms the "polyol" of this invention 
is a mixture of polyols having ester functions, even though the mixture is 
sometimes referred to as a singular "polyol". 
A preferred embodiment of these aromatic polyester polyols has the 
following approximate structure, known herein as formula (II): 
##STR4## 
where x is an integer of from 2 to 4. The mixture that results from the 
process described has an average value of x of around 3. 
Generally, both reactions need heat between ambient and about 300.degree. 
C. to proceed. Preferably, the temperature for both steps should be 
between 140.degree. and 220.degree. C. Unlike some prior art processes, 
both steps are non-catalytic. The pressure can be atmospheric, 
subatmospheric or autogenous. The polyol should have a hydroxyl number in 
the range of 100 to 400, with an especially preferred hydroxyl number 
range of 125 to 300. 
The improvement of the instant invention involves adding scrap reaction 
injection molding (RIM) polyurethane to the aromatic polyester polyol 
extender described above, which is the subject of U.S. Pat. application 
Ser. No. 443,778 filed on Nov. 22, 1982. The scrap RIM may be added to the 
finished aromatic polyester polyol extender such as the one portrayed in 
formula (II). However, scrap RIM is even more soluble in the precursor to 
the finished product, the bis-ester diol suggested by the structure of 
formula (I). The recycled PET component would then be reacted with the 
intermediate diol containing the RIM and the mixture processed normally as 
described above. 
RIM polyurethane is the reaction product of a high molecular weight 
polyhydric polyether, a low molecular weight active hydrogen containing 
compound of at least two functionality and a polyisocyanate. A RIM machine 
is used to inject the reactants into a mold where they react to make an 
article of RIM polyurethane elastomer. Reaction injection molded 
elastomers are useful as molded articles of commerce. One of the most 
important uses is as automotive body parts. For more information on RIM 
polyurethanes, see the numerous patents and articles in the field, 
particularly U.S. Pat. Nos. 4,243,760; 4,254,069; 4,272,618 and 4,297,444, 
incorporated by reference herein. 
The scrap RIM should be pelletized in the same manner as the recycled PET 
described above. The proportion of scrap RIM in total aromatic polyester 
polyol should be from 10 to 50 wt.% with the aromatic polyester polyol 
being the balance, 90 to 50 wt.%. The scrap RIM is added preferably at a 
temperature between 170.degree. and 250.degree. C., or at an especially 
preferred temperature in the range of 180.degree. to 220.degree. C. As 
noted above, the scrap RIM may be added during various stages in the 
processing of the aromatic polyester polyol at appropriate temperatures. 
This invention thus provides an economical extender polyol that utilizes 
two kinds of recycled polymer. More accurately, the products of this 
invention are mixtures of scrap RIM modified aromatic polyester polyols. 
These mixtures can serve as polyol extenders when they are blended with 
conventional polyols for use in polyurethane foams. The polyols of this 
invention can also be used alone to prepare isocyanurate foams. 
There is good compatibility of the polyols of this invention with 
trichlorofluoromethane. Trichlorofluoromethane, sold under the tradename 
FREON.RTM. R11B, a conventional blowing agent, is the gas entrapped in 
closed-cell rigid foams which accounts for the excellent insulating 
properties of these foams. 
The second constituent of the overall polyol combination found particularly 
useful in preparing rigid polyurethane foams is a polyether polyol having 
a hydroxyl number of 200-800. Usually the polyether polyol comprises 0-95 
percent by weight of the total polyol combination weight. Preferred 
polyether polyols of this type are the reaction products of a 
polyfunctional active hydrogen initiator and propylene oxide, ethylene 
oxide or mixed propylene oxide and ethylene oxide. The polyfunctional 
active hydrogen initiator most preferably has a functionality of 2-8. 
A wide variety of initiators may be alkoxylated to form useful polyether 
polyols. Thus, for example, polyfunctional amines and alcohols of the 
following type may be alkoxylated: monoethanolamine, diethanolamine, 
triethanolamine, ethylene glycol, polyethylene glycol, propylene glycol, 
polypropylene glycol, glycerine, sorbitol, trimethylolpropane, sucrose and 
alphamethyl glucoside. 
Such above amines or alcohols may be reacted with an alkylene oxide such as 
ethylene oxide, propylene oxide, or mixed ethylene oxide and propylene 
oxide using techniques known to those skilled in the art. Thus, for 
example, the reaction of alkylene oxide with initiators of this type is 
set forth in U.S. Pat. Nos. 2,948,757 and 3,000,963. Essentially such 
alkoxylations are carried out in the presence of a basic catalyst at a 
temperature sufficient to sustain the reaction. The hydroxyl number which 
is desired for the finished polyol would determine the amount of alkylene 
oxide used to react with the initiator. As noted above, the polyether 
polyols useful here have a hydroxyl number ranging from about 200 to about 
800. The reaction mixture is then neutralized and water and excess 
reactants are stripped from the polyol. The polyether polyol may be 
prepared by reacting the initiator with propylene oxide or ethylene oxide, 
or by reacting the initiator first with propylene oxide followed by 
ethylene oxide or vice versa in one or more sequences to give a so-called 
block polymer chain or by reacting the initiator at once with propylene 
oxide and ethylene oxide mixture to achieve a random distribution of such 
alkylene oxides. 
Especially preferred as the second polyol constituent are the 
nitrogen-containing polyether polyols described in U.S. Pat. Nos. 
3,297,597 and 4,137,265, incorporated by reference herein. These 
particularly preferred polyols are marketed by Texaco Chemical Company as 
THANOL.RTM. R-350-X and THANOL R-650-X polyols. These polyols are prepared 
by reacting from 2 to 3 moles of propylene oxide with one mole of the 
Mannich reaction product of a mole of phenol or nonylphenol with one or 
two moles of diethanolamine and formaldehyde. 
The final polyol combination more preferably comprises 0-95 percent by 
weight of said polyether polyol and 100-5 percent by weight of scrap RIM 
modified aromatic polyester polyol. Although the aromatic polyols of this 
invention may be used alone, it is preferred that they be present in an 
amount of from 30 to 70 wt.% of the polyol blend. The polyol combination 
in many instances has a total hydroxyl number ranging from about 100 to 
about 500. 
Any aromatic polyisocyanate may be used in the practice of the instant 
invention. Typical aromatic polyisocyanates include m-phenylene 
diisocyanate, p-phenylene diisocyanate, polymethylene 
polyphenylisocyanate, 2,4-toluene diisocyanate, 2,6-tolylene diisocyanate, 
dianisidine diisocyanate, bitolylene diisocyanate, 
naphthalene-1,4-diisocyanate, diphenylene-4,4'-diisocyanate, 
aliphatic-aromatic diisocyanates, such as xylylene-1,4-diisocyanate, 
xylylene-1,2-diisocyanate, xylylene-1,3-diisocyanate, 
bis(4-isocyanatophenyl)methane, bis(3-methyl-4-isocyanatophenyl)methane, 
and 4,4'-diphenylpropane diisocyanate. 
Greatly preferred aromatic polyisocyanates used in the practice of the 
invention are methylene-bridged polyphenyl polyisocyanate mixtures which 
have a functionality of from about 2 to about 4. These latter isocyanate 
compounds are generally produced by the phosgenation of corresponding 
methylene bridged polyphenyl polyamines, which are conventionally produced 
by the reaction of formaldehyde and primary aromatic amines, such as 
aniline, in the presence of hydrochloric acid and/or other acidic 
catalysts. Known processes for preparing the methylene-bridged polyphenyl 
polyamines and corresponding methylene-bridged polyphenyl polyisocyanates 
therefrom are described in the literature and in many patents; for 
example, U.S. Pat. Nos. 2,683,730; 2,950,263; 3,012,008; 3,344,162; and 
3,362,979. 
Most preferred methylene-bridged polyphenyl polyisocyanate mixtures used 
here contain from about 20 to about 100 wt.% methylene diphenyl 
diisocyanate isomers with the remainder being polymethylene polyphenyl 
diisocyanates having higher functionalities and higher molecular weights. 
Typical of these are polyphenyl polyisocyanate mixtures containing about 
20 to 100 wt.% methylene diphenyl diisocyanate isomers, of which 20 to 
about 95 wt.% thereof is the 4,4'-isomer with the remainder being 
polymethylene polyphenyl polyisocyanates of higher molecular weight and 
functionality that have an average functionality of from about 2.1 to 
about 3.5. The isocyanate mixtures are known commercially available 
materials and can be prepared by the process described in U.S. Pat. No. 
3,362,979, issued Jan. 9, 1968 to Floyd E. Bentley. 
In the production of rigid polyurethane foams in the practice of the 
invention, other known additives are necessary. One such constituent is 
the blowing agent. Some examples of such material are 
trichloromonofluoromethane, dichlorodifluoromethane, 
dichloromonofluoromethane, 1,1-dichloro-1-fluoroethane, 
1,1-difluoro-1,2,2-trichloroethane, chloropentafluoroethane, and the like. 
Other useful blowing agents include low-boiling hydrocarbons such as 
butane, pentane, hexane, cyclohexane, and the like. See U.S. Pat. No. 
3,072,582, for example. The polyols of this invention are quite compatible 
with fluorocarbon blowing agents unlike some of the prior art polyols 
which are made from DMT residues. 
Surfactant agents, better known as silicone oils, are added to serve as a 
cell stabilizer. Some representative materials are sold under the names of 
SF-1109, L-520, L-521 and DC-193 which are, generally, polysiloxane 
polyoxyalkylene blocked co-polymers, such as those disclosed in U.S. Pat. 
Nos. 2,834,748; 2,917,480; and 2,846,458, for example. 
Should fire retardancy be required for the polyurethane foam, two types of 
fire retardants are available; those that are incorporated by mere 
mechanical mixing and those that become chemically bound in the polymer 
chain. Representative of the first type are tris(chloroethyl)phosphate, 
tris(2,3-dibromopropyl)phosphate, diammonium phosphate, various 
halogenated compounds and antimony oxide. Representative of the chemically 
bound type are chlorendic acid derivatives, and various 
phosphorous-containing polyols. 
The catalysts which may be used to make the foams of this invention are 
well known. There are two general types of catalyst, tertiary amines and 
organometallic compounds. Examples of suitable tertiary amines, used 
either individually or in mixture, are the N-alkylmorpholines, 
N-alkylalkanolamines, N,N-dialkylcyclohexylamines and alkylamines where 
the alkyl groups are methyl, ethyl, propyl, butyl, etc. Examples of 
specific tertiary amine catalysts useful in this invention are 
triethylenediamine, tetramethylethylenediamine, triethylamine, 
tripropylamine, tributylamine, triamylamine, pyridine, quinoline, 
dimethylpiperazine, dimethylhexahydroaniline, piperazine, 
N-ethylmorpholine, 2-methylpiperazine, dimethylaniline, nicotine, 
dimethylaminoethanol, tetramethylpropanediamine and 
methyltriethylenediamine. Useful organometallic compounds as catalysts 
include those of bismuth, lead, tin, titanium, iron, antimony, uranium, 
cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, 
molybdenum, vanadium, copper, manganese, zirconium, etc. Some examples of 
these metal catalysts include bismuth nitrate, lead 2-ethylhexoate, lead 
benzoate, lead oleate, dibutyltin dilaurate, tributyltin, butyltin 
trichloride, stannic chloride, stannous octoate, stannous oleate, 
dibutyltin di(2-ethylhexoate), ferric chloride, antimony trichloride, 
antimony glycolate, tin glycolates, etc. Selection of the individual 
catalysts and proportions to use in the polyurethane reaction are well 
within the knowledge of those skilled in the art, and an amine and 
organometallic compound are often used together in the polyurethane 
reaction. 
The rigid polyurethane foams prepared here can be made in one step by 
reacting all the ingredients together at once (one-shot process) or the 
rigid foams can be made by the so-called "quasi-prepolymer method." In 
accordance with this method, a portion of the polyol component is reacted 
in the absence of a catalyst with the polyisocyanate component in 
proportion so as to provide from about 20 percent to about 40 percent of 
free isocyanato groups in the reaction product, based on the polyol. To 
prepare foam, the remaining portion of the polyol is added and the two 
components are allowed to react in the presence of a catalyst and other 
appropriate additives such as blowing agents, foam stabilizing agents, 
fire retardants, etc. The blowing agent, the foam stabilizing agent, the 
fire retardant, etc., may be added to either the prepolymer or remaining 
polyol, or both, prior to the mixing of the component, whereby at the end 
of the reaction a rigid polyurethane foam is provided. 
In a preferred embodiment the amount of polyol combination is used such 
that the isocyanato groups are present in the foam in at least an 
equivalent amount, and preferably in excess, compared with the free 
hydroxyl groups. Preferably, the ingredients will be proportional so as to 
provide for about 1.05 to about 8.0 mole equivalents of isocyanato groups 
per mole equivalent of hydroxyl groups. 
The invention will be illustrated further with respect to the following 
specific examples, which are given by way of illustration and not given as 
limitations on the scope of this invention. The synthesis of the polyols 
of this invention will be presented along with examples of how these 
polyol mixtures are used as polyol extenders to prepare foams. 
It may be readily seen from the examples that the polyol mixtures of this 
invention work as well in the role of polyol extenders as do commercially 
available materials. Many modifications may be made in the polyol mixtures 
of this invention and their method of production without departing from 
the spirit and scope of the invention which is defined only in the 
appended claims. For example, one skilled in the art could adjust the 
temperature, pressure, proportions and modes of additions to provide 
polyol mixtures that give foams with optimal properties. 
The first two examples will illustrate the preparation of mixtures of 
aromatic polyester polyols before any modification with scrap RIM. 
ESTERIFICATIONS OF WASTE DIBASIC ACID STREAMS 
Example 1 
Diethylene Glycol (DEG) 
A 2-liter three-neck round bottom flask, equipped with a thermometer 
(Therm-O-Watch), magnetic stirring bar, nitrogen inlet, distillation head 
with water cooled condenser and a tared receiver, was charged with 521.8g 
(4.04 moles) of DuPont solid dibasic acid (DBA; 56% glutaric acid, 23% 
succinic acid, 20% adipic acid, .about.1% organic nitrogen compounds, 
.about.0.2% nitric acid; 868.22 acid no., 0.41% N, 0.82% water, 221 ppm 
copper and 162 ppm vanadium) and 857.2g (8.08 moles) DEG. The whole was 
then stirred and heated under nitrogen. The reaction solution became 
homogeneous at 100.degree. C. Distillate (132.0g; 98.1% water) was 
collected overhead at 85.degree.-99.degree. C./144.degree.-215.degree. C. 
(pot)/1 atmosphere over 32/3 hours. The bottoms product (1244.0g), a dark 
mobile liquid, was recovered after cooling under nitrogen to room 
temperature. Total recovery was 99.78%. Proton nuclear magnetic resonance 
spectra confirmed the product structure to be a diester diol of formula 
(I). The product analyzed as follows: 
______________________________________ 
Hydroxyl number 368 
Acid number 26.12 
Saponification number 
342.06 
Water, % 0.83 
Nitrogen, % 0.07 
Viscosity, cs, 25.degree. C. 
165 
Copper, ppm 47.2 
Vanadium, ppm 27.3 
______________________________________ 
Prior art references report hydroxyl numbers of 327 (viscosity, 210 cp at 
25.degree. C.) and 365.+-.5 for a product prepared by tetraoctyl titanate 
catalyzed transesterification of dimethyl glutarate with DEG 
(150.degree.-225.degree. C., 16 hours), see U.S. Pat. No. 4,048,104. 
CLEAVAGE/ESTERIFICATIONS OF RECYCLED PET 
Example 2 
PET/DBA-DEG Diester Diol (Mole ratio = 1/1) 
A 1-liter three-neck round bottom flask, equipped with a mechanical 
stirrer, thermometer (Therm-O-Watch), water cooled distillation head, 
nitrogen inlet and a tared receiver was charged with 232.0g (1.2 equiv.) 
PET chips (green and clear from recycled soft drink bottles) and 368.0g 
(1.2 moles) of DBA-DEG diester diol from Example 1. The whole was then 
stirred and heated under a nitrogen atmosphere at 1 atmosphere pressure to 
210.degree. C. over 1.0 hour and then held at 210.degree.-220.degree.C. 
for 6.0 hours. A small amount of distillate (3.9g; expected 3.0g water 
from Example 1) was collected during the total reaction time at 
71.degree.-44.degree. C./200.degree.-220.degree. C. (pot). The product 
(592.0g), a dark, mobile liquid, was recovered after cooling to near room 
temperature under nitrogen. Total recovery was 99.3%. Analyses of product 
and the prior art product (dimethyl glutarate derived) follow: 
______________________________________ 
CHEMPOL 
Example III 
30-2150 
______________________________________ 
Hydroxyl number 231 210 
Acid number 4.45 1.76 
Saponification number 
438.09 431.33 
Water, % 0.23 0.05 
Viscosity, cs, 25.degree. C. 
3,564 3,529 
Copper, ppm 18.1 -- 
Vanadium, ppm 25.3 -- 
Titanium, ppm -- 439 
______________________________________ 
The scrap RIM material used in the following examples was made from a 
formulation of THANOL.RTM. SF-6503 (a 6500 molecular weight polyether 
triol containing oxyethylene groups and approximately 90% primary hydroxyl 
groups, made by Texaco Chemical Company), ethylene glycol, L-5430 Silicone 
Oil (a silicone glycol co-polymer surfactant containing reactive hydroxyl 
groups, made by Union Carbide), dibutyltin dilaurate, 
trichlorofluoromethane blowing agent and ISONATE.RTM. 143L [pure methylene 
bis(4-phenylisocyanate), MDI, modified so that it is a liquid at 
temperatures where MDI normally crystallizes, made by the Upjohn Company]. 
The bis-ester diol used in Example 4 was made in situ much as in the manner 
of Example 1, and had a hydroxyl number of 368 and a viscosity of 165 to 
195 centistokes (cs) at 25.degree. C. Serving as the finished aromatic 
polyester polyol product in Example 3 is THANOL R-510, made by Texaco 
Chemical Company, which has a structure like formula (II), a hydroxyl 
number of 226 and a viscosity of 4400 cs at 25.degree. C. It was prepared 
by a procedure similar to that of Example 2. 
Example 3 
THANOL R-510/RIM, 90:10 wt.% 
A 1-liter three-neck round bottom flask, equipped with a mechanical 
stirrer, thermometer (Therm-O-Watch), nitrogen inlet, water cooled 
distillation head and a tared receiver, was charged with 450.0g of THANOL 
R-510 and 50.0 g RIM material. This heterogeneous mixture was stirred well 
and heated under N.sub.2 to 220.degree. C. maximum over 12/3 hours and 
held 1.0 hour. The RIM material appeared to dissolve at 
190.degree.-200.degree. C. over about a 15 minute period. A small amount 
(1-2 drops) of distillate was discarded. The reaction solution was cooled 
to near room temperature and 498.0 g of a dark, viscous liquid product was 
isolated. Analyses follow. 
______________________________________ 
Hydroxyl number 201 
Acid number 2.03 
Saponification number 
409.19 
Water, % 0.02 
Viscosity (25.degree. C.), cs 
9,764 
______________________________________ 
Example 4 
Bis-Esterdiol/RIM, 80:20 wt. 
Using the apparatus of Example 3 and the procedure of Example 1, the 
bis-ester diol with a structure of formula (I) was prepared from 172.0g 
(1.34 moles) of AGS flakes (Monsanto) and 283.8g (2.68 moles) of 
diethylene glycol (DEG). AGS typically contains 13-18% adipic acid, 55-59% 
glutaric acid, 22-24% succinic acid, 0.2-1.4% other dibasic acids, 
0.1-1.0% monobasic acids, 0.1-0.3% picric acid, 2-3% other organics and 
0.01-0.2% nitric acid. Water (48 ml) of esterification was collected as 
overhead distillate 
To this dark, mobile liquid product there was added 102.0g of RIM material 
and the resulting heterogeneous mixture was stirred well and heated under 
nitrogen to 220.degree. C. maximum over 1 1/6 hours and held for 1.0 hour. 
The RIM material appeared to dissolve at 180.degree.-200.degree. C. over 
about 5-10 minute period. The product (507.5 g), a dark, mobile liquid, 
was isolated as before. Analyses follow. 
______________________________________ 
Hydroxyl number 330 
Acid number 3.96 
Saponification number 
258.48 
Water, % 0.20 
Viscosity (25.degree. C.), cs 
873 
______________________________________ 
Example 5 
Polyurethane and Polyisocyanurate Foams 
Each experimental polyol was used as an extender in THANOL R-350-X and 
THANOL R-650-X in polyurethane formulations and as the sole polyol in 
polyisocyanurate formulations. Components were mixed at 2700 rpm and 
poured (600 g pour) into an 8".times.8".times.12" open mold and allowed to 
rise. The foams were allowed to stand for at least three days before 
determination of physical properties. 
Formulations and physical properties are listed below. 
__________________________________________________________________________ 
A B C D E F 
__________________________________________________________________________ 
Formulation, pbw 
THANOL R-350-X (OH = 534) 
25.7 
24.5 
-- -- -- -- 
THANOL R-650-X (OH = 442) 
-- -- 28.0 
26.5 
-- -- 
Polyol, Ex. 3 (OH = 201) 
11.0 
-- 12.0 
-- 25.3 
-- 
Polyol, Ex. 4 (OH = 330) 
-- 10.5 
-- 11.4 
-- 17.4 
Antiblaze 80.sup.1 
5.0 5.0 5.0 5.0 -- -- 
Water 0.2 0.2 0.2 0.2 -- -- 
FREON R-11.sup.2 
12.0 
12.0 
12.0 
12.0 
12.0 
12.0 
L-5420.sup.3 0.5 0.5 0.5 0.5 -- -- 
DC-193.sup.4 -- -- -- -- 0.5 0.5 
FOMREZ UL-32.sup.5 
0.01 
0.01 
0.01 
0.01 
-- -- 
T-45.sup.6 -- -- -- -- 1.5 1.5 
MONDUR MR.sup.7 (index = 
45.6 
47.3 
42.3 
44.4 
60.7 
68.6 
1.2; 5.0) 
Times (seconds), mixing 
8 8 6 6 4 4 
cream 16 15 15 13 6 9 
gel 54 49 53 42 22 26 
tack free 74 69 67 58 31 33 
rise 131 133 126 122 51 65 
Initial surface None 
None 
None 
None 
Yes Yes 
friability 
Foam appearance Good 
Good 
Good 
Good 
Good 
Good 
Physical Properties 
Density (lbs/ft.sup.3) 
1.91 
1.93 
1.99 
1.98 
2.09 
1.98 
K-factor 0.122 
0.120 
0.120 
0.118 
0.121 
0.123 
Compressive strength, 
psi, 
with rise 43.81 
41.59 
43.11 
42.10 
42.30 
29.08 
against rise 14.77 
15.12 
16.16 
15.21 
19.41 
15.90 
Heat distortion, .degree.C. 
110 113 119 100 &gt;225 
&gt;225 
Closed cells, % 92.91 
92.89 
93.21 
93.04 
92.47 
92.91 
Friability, % wt. 
2.24 
0.76 
1.58 
1.64 
28.65 
41.68 
loss, 10 min 
ASTM 1692 Burn, 1.57 
1.78 
1.57 
1.76 
1.45 
1.38 
in/min (BHA) 
Butler Chimney Test 
Flame height, in. 
&gt;11 &gt;11 &gt;11 &gt;11 6.17 
6.00 
Sec. to extinguish 
35 30 13 27 10 10 
% wt. retained 33.7.sup.8 
21.6.sup.8 
66.4 
31.0.sup.8 
93.7 
93.9 
__________________________________________________________________________ 
.sup.1 Tris(2-chloropropyl phosphate) fire retardant made Mobil Chemical. 
.sup.2 Trichlorofluoromethane made by E. I. duPont de Nemours & Co. 
.sup.3 A silicone surfactant sold by Union Carbide Corp. 
.sup.4 Silicone surfactant sold by DowCorning. 
.sup.5 An organic tin catalyst sold by Witco Chemical Corp. 
.sup.6 Potassium octoate in glycol made by M & T Chemical Co. 
.sup.7 A polymeric isocyanate sold by Mobay Chemical Corp. 
.sup.8 These results are somewhat questionable.