Patented Dec.

14, 1948 watts

UNH'E'ED STATES PATENT GFFHQE

' 2,456,161

PARAFORMALDEHYDE COMPOSITIONS
Joseph Frederic Walker, Staten Island, N. Y., as
signor to E. I. du Pont de Nemours & Company,
Wilmington, Del., a corporation of Delaware
No Drawing. Application August 29, 1945,
a Serial No. 613,453 ' ,

6. Claims. (Cl. 260-6115)

1 2
This invention relates to paraformaldehyde ter from the solution. The removal of waterv
compositions and method for producing the same. from the aqueous formaldehyde may be accom
More particularly, it relates to paraformaldehyde plished by vacuum distillation, evaporation at re
having a high degree of reactivity and having an duced pressure, or in any other desired manner
improved stability against loss of reactivity on readily apparent to one skilled in the art. The
storage. water may, for example, be removed by the addi
Paraformaldehyde is a mixture of polyoxy tion of a nonmiscible liquid such as benzene or
methylene glycols, HO-(CI-IzOhl-H, containing ethyl acetate to the aqueous formaldehyde solu
from 93% to 99% formaldehyde, CHzO, and in tion, followed by distillation of a low-boiling aze
which the polyoxymethylene glycol molecules 10 otrope formed by the non-miscibleliquid and the
may contain from 8 to 100 formaldehyde units. water. Preferably, the water is removed by vac
When ?rst prepared, a polymer of this type has uum distillation or evaporation at a pressure not
a low average molecular weight, but on standing to exceed 150 mm. Hg.
polymerization takes place and the molecular The product of this invention is a modi?ed par
weight increases. This change is indicated by a 15 aformaldehyde containing 0.1% to 10% of penta
decrease in solubility and chemical activity as erythritol, preferably 0.5% to 2.5 pentaerythritol.
vwell as an increase in melting point. In 1932, The preparation is carried out by dissolving pen
Staudinger (“Die Hochmolekularen Organischem taerythritol in an aqueous formaldehyde solution
Verbindungen,” pages 251-254, Berlin, Julius containing preferably 30% to 50% dissolved form
Springer) reported that a crude mixture of poly 20 aldehyde in such proportion that there is not less
oxymethylene glycols obtained by cooling hot than one-half pound nor more than eighty
80% formaldehyde contained a considerable pounds of pentaerythritol per one thousand
quantity of low molecular weight polymer which pounds of formaldehyde. The resultant solution
was soluble in hot acetone. On standing in a -is then converted to modi?ed paraformaldehyde
desiccator, a polymer prepared in this manner 25 by distillation or evaporation of water, prefera
decreased in solubility until it became completely bly by vacuum evaporation.
insoluble in hot acetone. According to Btau-' The following examples illustrate preferred de
dinger’s solubility measurements, this would in tailed processes for practicing the invention, it
dicate the disappearance of polymer molecules 30 being understood that the scope of the inven
containing 12 or less formaldehyde units. tion is not limited to the speci?c details set forth
Commercial paraformaldehyde, as well as par therein.
aformaldehyde prepared in the laboratory by Example I
' commonly employed methods, decreases in reac
Five parts of pentaerythritol were dissolved in
tivity and solubility in water’ and other solvents, 35 one
and increases in melting point, on storage. Many thousand parts of 37% formaldehyde solu
attempts have been made, heretofore, to slow up tion. This, solution was then placed in a distilling
or prevent such loss of reactivity and solubility; flask and subjected to vacuum distillation at a
pressure of approximately 135 mm. This distil
however, such attempts failed to produce a satis
factory and practical method for slowing up or 40 lation was continued until approximately three
hundred parts of solid paraformaldehyde was
preventing the above-said decrease in reactivity
left in the distillation ?ask. This material was
of paraformaldehyde. then removed from the ?ask and ground to a ?ne
It is an object of this invention to provide a
method for the production of paraformaldehyde powder. Analyses indicated that this polymer
having a high reactivity and an improved stabil 45
contained 93.3% combined formaldehyde and
ity against loss of reactivity on storage. melted in the temperature range 128-136“ C.
It is another object of this invention to pro After sixty days’ storage at room temperature the
vide a new and improved paraformaldehyde com melting range of this material was 128-138° C.
A similar product prepared from formaldehyde
position. solution to which no pentaerythritol had been
Other objects of the invention will appear here
added was found to contain 93.9% by weight com
inafter. bined formaldehyde and melted in the range 148
The objects of this invention may be accom
plished, in general, by dissolving a small quan 153° C. After sixty days the latter sample melted
tity of pentaerythritol in an aqueous solution of at 166-176” C. These ?ndings indicate that the
formaldehyde,‘ and converting the aqueous form paraformaldehyde modi?ed with the pentaeryth
aldehyde to paraformaldehyde by removal of wa ritol'p'o‘ssesses a lower average molecular weight
 2,400,101
3 4
than the unmodified’ product and. at the same 10% to 15% or more of polypentaerythritols or
time, shows little tendency to undergo further chemically pure nitration grade pentaerythritol.
polymerization on storage. _ In the preparation of adhesives and other res
Reactivity measurements were made on the inous products, paraformaldehyde is often used
above polymer by determining its glue coagulation as a hardening agent. In such uses, the reactivity
values. This value was determined by adding 5 of the polymer is important. In some cases, a
grams of the formaldehyde polymer suspended ‘ highly‘ reactive paraformaldehyde is desired,
in 7 cc. of‘water to a glue solution containing 50 whereas in other cases a product of low reactivity
grams of a high grade, commercial, flake glue and is more suitable. A particular casein which para
2.75 grams of oxalic acid in 105 cc. of distilled 10 formaldehyde of high reactivity is desired is
' .-_water- maintained at to“ c. . The .glue solution found in its use as a setting agent for cold press
containing the formaldehyde polymer was agi ‘ adhesives. In these uses, it is highly desirable to
tated occasionally until the glue was coagulated. have a polymer showing a low degree of reac
The coagulation time at 60’ C. expressed in min- ' 1 tivity-loss on aging.
utes is taken as the "glue coagulation value." 15 Throughout the speci?cation and claims, any
This method of determining the reactivity of reference to parts, proportions and percentages
formaldehyde polymers is described by Browne refers to parts, proportions and percentages by
,and Hrubesky in the Journal of Industrial and weight unless. otherwise speci?ed.
Engineering Chemistry, vol. 19, page 218 (1927). Since it is obvious that many changes and mod
‘The following table indicates the difference 20 i?cations can be made in the above-described
between the modi?ed sample of paraformalde details without departing from the nature and
hyde and the control containing no pentaerythri spirit of the invention, it is to be understood that '
tol: the invention is not to be limited to these details
except as set forth in the appended claims.
I claim:
Glue Coagulation Value 1. Paraformaldehyde containing, as an agent
Aiter—
for controlling and stabilizing polymer reactivity,
0 Days 30 Days 60 Days 0.1% to 10% pentaerythritol.
2. Paraformaldehyde containing, as an agent
Modi?ed Product ................ . . 1s’ 25 2s for controlling and stabilizing polymer reactivity,
Unmodi?ed Product ......... .. .-._- 28 87 44 0.5% to 2.5% pentaerythritol.
3. The process of producing a modi?ed para
formaldehyde having a high stability against in
The properties of the above-described modi?ed crease in molecular weight which comprises add
paraformaldehyde were also studied by measur 35 ing pentaerythritol in an amount equivalent to
ing its rate of solution in water adjusted to a 0.05% to 8.0% of the dissolved formaldehyde to
pH of 4. In this procedure, 5 grams of the poly an equeous solution of formaldehyde, and heating
mer were agitatedv with 25 cc. of a buffer solution said solution under vacuum to remove Water
consisting of a mixture of ,N/10 solutions of therefrom until said paraformaldehyde is formed.
sodium formate and formic ,acid adjusted to a_ 4. The process of producing a modi?ed para
pH of 4. Agitation was continued for two hours formaldehyde having a high stability against in
at 35° C. by rotating samples in sealed one-inch crease in molecular weight which comprises add
by six-inch test tubes at four revolutions per ing pentaerythritol in an amount equivalent to
minute in a constant temperature'bath. The 0.05% to 8.0% of the dissolved formaldehyde to
mixture in the test tube was then ?ltered and a 30% to 50% aqueous solution of formaldehyde,
the ?ltrate analyzed for formaldehyde by the and heating said solution under vacuum to re
standard sodium sul?te procedure. The modi?ed move water therefrom until said paraformalde
paraformaldehyde was found to dissolve to the hyde is formed.
extent of 14.4% when freshly prepared and still 5. The process of producing a modi?ed para
dissolved to the extent of 6.1% after sixty days. 60 formaldehyde having a high stability against in
An unmodi?ed control sample of polymer dis crease in molecular weight which comprises add
solved. to the extent of 6.2% when freshly pre ing pentaerythritol in an amount equivalent to
pared and was only 2.3% soluble after sixty days’ 0.05% to 8.0% of the dissolved formaldehyde to
storage. an aqueous solution of formaldehyde, and con
Examrc II _ verting said solution to paraformaldehyde by re
A charge of 3660 pounds of 45.4% formaldehyde moval of water therefrom.
‘ to which was added 8.2 pounds of pentaerythritol
6. The process of producing a modi?ed para
formaldehyde having a high stability against in
was vacuum distilled at a pressure of 100 mm. to
140 min. of mercury. In this way, approximately crease in molecular weight which comprises add
ing pentaerythritol in an amount equivalent to
1077 pounds of modi?ed paraformaldehyde con
taining 96.6% formaldehyde was obtained. This 0.05% to 8.0% of the dissolved formaldehyde to a
material contained approximately 0.8% pentae 30% to 50% aqueous solution of formaldehyde,
rythritol and melted at a temperature of 122° C. . and heating said solution under a. pressure not to
to 128° C. The melting range ‘of unmodi?ed para exceed 150 mm. Hg. to remove water therefrom
formaldehyde prepared in this way normally falls until said paraformaldehyde is formed.
between 127° C. and 140° C. The solubility of JOSEPH FREDERIC WALKER.
the modi?ed material in water, buffered to a REFERENCES CITED
pH of 4, as described in Example I, was 10.7%?
After six days’ storage, the solubility was still ‘The following references are of record in the
10.7%. An unmodi?ed batch of paraformalde 70 file of this patent:
hyde was found to have a solubility of_3.4% .as UNITED STATES _ PATENTS I
freshly prepared, and this value fell to 1.2% after
seven days’ storage. \ Number Name Date
The pentaerythritol used in this invention may 1,948,069 Fuchs et al. ______ __ Feb. 20, 1934
be either the commercial product which contains 75 (Other references on following page)
 2,456,161
5, - 6
_ UNITED STATES PATENTS OTHER REFERENCES
Number ' Name Date Walker: "Formaldehyde,” page 44 (1940).
2,042,657 Hinegardner ______ __ June 2, 1936 }
2,373,777 Peterson _________ __ Apr. 17, 1945 5
v FOREIGN PATENTS
Number Country Date
54,789 Sweden __________ -_ Dec. 6, 1921