Useful solutions of the tetramethylol derivative of 4,4'iso-propylidenediphenol

The tetramethylol derivative of 4,4'iso-propylidenediphenol is dissolved in a solution of water and ethylene or propylene carbonate to yield concentrated solutions of the derivative in a form which may readily be used in the manufacture of foams or used as a liquid binder for molded ceiling products. Based on 100 parts by weight of the tetramethylol derivative, these solutions contain from about 15 to about 35 parts by weight of water and from about 5 to about 30 parts by weight of ethylene carbonate or propylene carbonate, with the total parts by weight of the water and carbonate varying from about 40 to about 45.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The invention is directed to useful stable solutions of the tetramethylol 
derivative of 4,4'iso-propylidenediphenol. 
2. Description of the Prior Art 
A procedure for forming the tetramethylol derivative of 
4,4'iso-propylidenediphenol is disclosed in U.S. Pat. No. 2,912,395. When 
separated from the water as described in Example 1 of this reference, a 
wet, oily liquid is recovered. This material, although soluble in water at 
an elevated temperature, separates out at about 70.degree. C. which limits 
its utility. 
SUMMARY OF THE INVENTION 
I have discovered that when ethylene carbonate or propylene carbonate is 
combined with water and the tetramethylol derivative of 
4,4'iso-propylidenediphenol, useful solutions may be formed in which the 
tetramethylol derivative remains in solution at lower and more 
conventional processing temperatures. Preferably, based on 100 parts by 
weight of the tetramethylol derivative, the solutions contain from about 
15 to about 35 parts by weight of water and about 5 to about 30 parts by 
weight of ethylene carbonate or propylene carbonate, or mixtures thereof, 
with the total parts by weight of the water and the carbonate ranging from 
about 40 to about 45. These solutions find utility in the manufacture of 
foams, and the solutions may be also used as binders in forming molded 
acoustical products. 
DETAILED DESCRIPTION 
The tetramethylol derivative of 4,4'iso-propylidenediphenol employed herein 
is prepared by the following procedure (except where otherwise noted): 
228.29 parts by weight of 4,4'iso-propylidenediphenol are dissolved in 
991.92 parts by weight of an 8.07% aqueous sodium hydroxide solution. 
171.22 parts by weight of paraformaldehyde are next added and the mixture 
maintained at 38.degree. C. for nine hours. The free formaldehyde content 
is determined at this point and the mixture is then neutralized to a pH of 
7.0 by the gradual addition of a 20% aqueous sulfuric acid solution. 3.04 
parts by weight of polyoxyethylated nonyl phenol are next added followed 
by the calculated amount of sodium bisulfite to react with the free 
formaldehyde. The temperature rises to 60.degree. C. during this stage and 
crystallization begins. The solid is collected, thoroughly washed, and 
dried. The product (75% yield) is a light tan solid analyzing 3.75-4.00 
mols of formaldehyde reacted per mol of 4,4'iso-propylidenediphenol. It is 
soluble in water at an elevated temperature (Table I) but separates upon 
cooling to 70.degree. C. which limits its utility. 
When 10% of the water is replaced by ethylene carbonate, the temperature at 
separation is lowered to 45.degree. C. A 20% replacement lowers the 
separation temperature of 25.degree. C. Complete replacement of the water 
by ethylene carbonate no longer yields a useful solution. As shown in 
Table I, useful resin solutions are formed when about 20 to about 60% of 
the water in the formulation specified above is replaced by ethylene 
carbonate. 
Based on 100 parts by weight of the tetramethylol derivative, the typical 
solution will contain from about 15 to about 35 parts by weight water and 
from about 5 to about 30 parts by weight ethylene carbonate, with the 
total parts by weight of the water and the carbonate ranging from about 40 
to about 45. When all of the water is replaced by ethylene carbonate, the 
temperature at separation is greater than 80.degree. C. 
TABLE I 
______________________________________ 
Ingredient 
Parts by Weight 
______________________________________ 
Tetramethylol 
4,4'Isopropyl- 
idenediphenol 
100 100 100 100 100 100 100 
Water 42.9 38.6 34.3 23.0 17.1 14.3 -- 
Ethylene 
Carbonate -- 4.3 8.6 19.9 25.7 28.6 42.9 
Cloud 
Point (.degree.C.) 
70 45 25 -- -- -- &gt;80.degree. C. 
Viscosity 
(cps at 40.degree. C.) 200 400 600 810 
______________________________________ 
Surprisingly, propylene carbonate can be used in place of the ethylene 
carbonate even though it is reported as immiscible in water when present 
in the range of 17.5 to 93% by weight (Physical Chemistry of Organic 
Solvent Systems, Covington and Dickinson, 1973, page 11). This is shown in 
Table II. Since propylene carbonate is reported as being moderately 
irritating to the mucous membranes of the eyes and respiratory tract, the 
use of ethylene carbonate is preferred. 
TABLE II 
______________________________________ 
Ingredient Parts by Weight 
______________________________________ 
Tetramethylol 4,4'Iso- 
propylidenediphenol 
100 100 
Water 23 23 
Ethylene Carbonate 24.6 -- 
Propylene Carbonate 
-- 24.6 
Viscosity (cps at 40.degree. C.) 
510 315 
______________________________________ 
Phenolic resins based upon 4,4'iso-propylidenediphenol are more resistant 
to oxidation, i.e., possess better heat stability, than those based upon 
phenol. Degradation occurs primarily through the methylene linkages and 
this is interrupted when these linkages are partially replaced by the 
isopropylidene type linkages. Such improvement has been heretofore limited 
to nonaqueous systems. The present invention not only permits processing 
by procedures normally limited to aqueous systems, but also allows 
modification by water insoluble materials such as epoxy novolacs or 
unsaturated polyesters.

Examples 1 and 2 illustrate foam formation with this new system, and 
Examples 3 and 4 illustrate modified systems. 
EXAMPLE 1 
100.00 parts by weight of tetramethylol 4,4'iso-propylidenediphenol were 
dissolved in 23.00 parts by weight water and 24.60 parts by weight 
ethylene carbonate by heating to 80.degree. C. with intermittent stirring. 
The solution formed was cooled to 41.degree. C. and 4.92 parts by weight 
of a non-hydrolyzable silicone surfactant (Union Carbide L5340), and 9.84 
parts by weight of a blowing agent (E. I. duPont Freon 113, CCl.sub.2 F. 
CClF.sub.2, B.P. 47.6.degree. C.) were stirred in. High speed agitation 
was next used to quickly introduce 23.62 parts by weight boric anhydride 
followed by 24.60 parts by weight of an acid solution consisting of 9.84 
parts by weight toluene sulfonic acid, 4.92 parts by weight sulfuric acid, 
and 9.84 parts by weight water. The blend was immediately placed in a 
65.degree. C. oven for fifteen minutes. A white, fine-pored, open-celled 
foam formed. This foam, after removal and conditioning measured 6.0 
lbs./cu. ft. in density. 
EXAMPLE 2 
100.00 parts by weight of tetramethylol 4,4'iso-propylidenediphenol were 
dissolved in 23.00 parts by weight water and 24.60 parts by weight 
ethylene carbonate by heating to 80.degree. C. with intermittent stirring. 
The solution formed was cooled to 75.degree. C. At this point 1.23 parts 
by weight of a nonionic fluorosurfactant (duPont Zonyl FSN) and 12.30 
parts by weight of trichloroethylene (B.P. 113.8.degree. C.) were stirred 
in. High speed agitation was then used to quickly introduce 7.38 parts by 
weight boric anhydride followed by 12.30 parts by weight of stannous 
chloride dihydrate. The blend was placed immediately in a 150.degree. C. 
oven for five minutes. A white, fine-pored, open-celled foam of 5.9 
lbs./cu. ft. density was obtained. This foam, exposed to 350.degree. C., 
gradually yellows in contrast to that of Example 1 which blackens. 
EXAMPLE 3 
100.00 parts by weight tetramethylol 4,4'iso-propylidenediphenol and 12.3 
parts by weight epoxy novolac (epoxy equivalent 175-182, which is employed 
to provide a more uniform foam) were dissolved in 23.0 parts by weight 
water and 20.5 parts ethylene carbonate by heating to 80.degree. C. with 
intermittent stirring. The solution formed was cooled to 40.degree. C. and 
3.28 parts by weight of a non-hydrolyzable silicone surfactant (Union 
Carbide L5340) and 14.35 parts by weight of a blowing agent (duPont Freon 
113,CCl.sub.2 F.CClF.sub.2, B.P.47.6.degree. C.) were stirred in. High 
speed agitation was next used to quickly incorporate 14.76 parts by weight 
boric anhydride followed by 36.90 parts by weight of acid solution of the 
composition shown in Example 1. The blend was immediately poured into a 
suitable container and the whole placed in a 65.degree. C. oven for 
one-half hour. The foam upon removal possessed a density of 3.8 lbs./cu. 
ft. A 6 in..times.6 in. cube showed no exotherm in seven hours at 
350.degree. F. A phenolic control foam exothermed in less than two hours. 
EXAMPLE 4 
An unsaturated elastomeric polyester was prepared from the following 
starting materials. 
______________________________________ 
Ingredient Mols 
______________________________________ 
Phthalic Anhydride 10 
Tetrahydrophthalic Anhydride 
40 
Trimethylol Propane Mono Allyl Ether 
2 
Polyoxyethylene Glycol (M.W. 400) 
35 
Ethylene Glycol 27.5 
______________________________________ 
by the method described in U.S. Pat. No. 3,703,498. The resultant polyester 
possessed a hydroxy number of 24.4 and an acid number of 0.5 
100.0 parts by weight of tetramethylol 4,4'iso-propylidenediphenol and 12.3 
parts by weight of the above polyester were dissolved in 23.0 parts by 
weight water and 24.6 parts by weight ethylene carbonate by heating to 
80.degree. C. with intermittent stirring. The solution formed was cooled 
to 70.degree. C. and 1.2 parts by weight of a nonionic fluorosurfactant 
(duPont Zonyl FSN) and 12.3 parts by weight of a blowing agent (duPont 
Freon 112A, CCl.sub.2 F-CCl.sub.2 F, B.P. 92.8.degree. C.) were stirred 
in. High speed agitation was then used to quickly introduce 14.8 parts by 
weight of boric anhydride followed by 12.3 parts by weight stannous 
chloride dihydrate. The blend was immediately placed in a 150.degree. C. 
oven for fifteen minutes. A tough foam of 3.8 lbs./cu. ft. density 
emerged. 
The following examples illustrate tile manufacture. 
EXAMPLE 5 
100.00 parts by weight of tetramethylol 4,4'iso-propylidenediphenol were 
dissolved in 25.17 parts by weight water and 22.10 parts by weight 
ethylene carbonate by heating to 80.degree. C. with intermittent stirring. 
The solution formed was cooled to 40.degree. C. and blended with 147.27 
parts by weight expanded perlite (0.12 gm./c.c.) for ten minutes in a 
Baker Perkin mixer at room temperature. The above was transferred to a 
6-inch.times.6-inch frame and compressed to a thickness of one-half inch. 
The compacted material was subjected to microwave heating for four minutes 
in a 700 watt unit. 51.42 parts by weight were lost. The ceiling tile thus 
formed displayed an indentation (MEP #170) of 39 mils, a modulus of 
rupture of 34.2 lbs./sq. in., and a density of 28.8 lbs./cu. ft. It 
displayed only 1.6% by weight moisture pickup after twelve days exposure 
to 75.5% relative humidity at room temperature, and, 2.0% by weight 
moisture pickup after twelve days exposure to 96.5% relative humidity at 
room temperature. 
EXAMPLE 6 
A phenolic foam (0.033 gm/c.c.) was crushed and passed through a #5 screen 
(4.00 mm opening). 16.25 parts by weight of this foam and 16.25 parts by 
weight expanded perlite (0.12 gm/cc) were tumbled together for one minute 
at room temperature in a Baker Perkins mixer. 32.5 parts by weight of a 
solution consisting of: 
______________________________________ 
tetramethylol 4,4'iso-propylidenediphenol.sup.(1) 
100.0 parts 
by weight 
water 31.6 
ethylene carbonate 24.8 
______________________________________ 
.sup.(1) Prepared in accordance with Example 1 of U.S. Pat. No. 2,912,395 
 
were then added and mixing continued for an additional five minutes. The 
mix was transferred to a 6-inch.times.6-inch frame and compressed to 
one-half inch. The compressed material was subjected to a microwave 
heating for four minutes in a 700 watt unit. A weight loss of 11.8 parts 
by weight was observed. The emerging tile displayed a density of 10.0 
lbs./cu. ft. 
EXAMPLE 7 
35.0 parts by weight of perlite (0.12 gm/cc) was mixed with 35.0 parts by 
weight of a solution consisting of: 
______________________________________ 
tetramethylol 4,4'iso-propylidenediphenol.sup.(1) 
100.00 parts 
by weight, 
water 31.7 
ethylene carbonate 24.6 
______________________________________ 
.sup.(1) Prepared in accordance with Example 1 of U.S. Pat. No. 2,912,395 
at room temperature in a Baker Perkins mixer. 35.0 parts by weight of the 
above was uniformly spread at the bottom of a 6-inch.times.6-inch frame. A 
piece of a 6-inch.times.6-inch.times.3/4-inch phenolic foam (0.033 gm/cc) 
was inserted and the remaining 35.0 parts by weight of mix uniformly 
spread over its surface. The composite was compressed to one-half inch and 
subjected to microwave heating for four minutes in a unit capable of 
delivering 700 watts. The emerging material possessed a density of 12.6 
lbs./cu. ft.