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Патент USA US2406217

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‘' 2,406,217, '
Patented Aug. 20, 1946
Mortimer '1‘. Harvey, South Orange, N. 1., and
Solomon Caplan, New York, N. Y., assignors to
Harvel Research Corporation, a corporation 0
New Jersey
No Drawing. Application October 23, 1942.
Serial No. 463,132
2 Claims‘.
(Cl. 260-69)
2 ,
‘Tertiary butyl urea _____________ "grams" 11d
Formaldehyde solution (371/2%‘)_____do____ 10o
It is an object of the present invention to pro
duce stable aqueous solutions of the urea-form
aldehyde type of condensation product.
The present application is a continuation in
part of our copending application Ser. No. 294,
Ammonia solution (26°) ____________ __cc_.. 2.7
This mixture was re?uxed at boiling temperature
480, ?led September 12, 1939.
for one hour and allowed to cool. .
' When employing thermosetting resins for such
purposes as impregnation of porous compositions,
as coatings for laminating purposes, for plywood
Example 2
Tertiary butyl urea ,_ ________ -_‘..___'grams_- 116
adhesives, and the like,‘ it is usually necessary 10 Formaldehyde solution (SW/2%) -_-_do____ 160
Ammonia solution (26") ____________ .._cc_.. 2.7
Organic solvents have almost ‘universally been
‘This mixture was re?uxed at boiling tempera‘
employed for the purpose of obtaining such solu
to utilize solutions of such‘ thermosettingoresins.
tions and in the subsequent operations of con
ture for one hour and allowed to cool. .
verting the thermosetting resin to the infusible 15
Example 3
state, the organic solvents have been ‘driven off _
and lost. It/ would therefore be desirable to use
water as the solvent for the thermosetting resin.
Tertiary butyl urea ____; ________ "grams" 116
Formaldehyde solution (371/2%) ____do____ 240
Ammonia solution (26°) _________ _1__.._cc__ 2.7
Such water soluble thermosetting resins have‘
been developed in the nature of urea-formalde 20 This mixture was refluxed at boiling tempera
hyde condensatiomproducts. The great disad
ture for one hour and allowed to cool.
vantage of such aqueous solutions of urea-form
aldehyde resins has been their short storage life.
Examples 4, 5 and 6
The above series of experiments was repeated
This objection has long been recognized and vari
ous means of overcoming it have been proposed. 25 but instead or 116 grams of tertiary butyl urea,
Thus, for example, in an article published in In
130 grams of tertiary amyl urea was used.
dustrial and Engineering Chemistry, vol. 31, page
v673 (1939), the authors have drawn attention
to this failing of vaqueous Solutions of urea-form
aldehyde resins and have proposed the addition
of glycols for the purpose of stabilizing the solu
tions. Owing to the water solubility of the gly
cols, the ?nished products, even after conversion
to the infusible state, have rather poor water
30' the
use of 144 grams of tertiary hexyl urea in
stead of the 116 grams of tertiary butyl urea.
In all of the above examples the resulting aque
ous solutions showed substantially no increase in
viscosity after months of storage at room tem
densation products of the monotertiary-alkyl
40 resulting combined solutions were stabilized to a
The present invention is based upon the ?nd- ‘ 1
ing that aqueous solutions of formaldehyde con
Aqueous solutions of the formaldehyde conden
sation products where then mixed with aqueous
solutions of freshly prepared urea-formaldehyde
condensation products and it was found that the
It is further an object of the present invention
to produce stable aqueous solutions of the urea.
formaldehyde type of resin in which'the stabiliz
ing agent is itself-capable of reacting with the
formaldehyde with the production of thermos'et
ting resins having high moisture resistance.
Examples 7, 8 and 9
Examples 1, 2 and 3 were repeated but with
degree varying with the proportion of the ter
tiary‘ alkyl urea-formaldehyde condensation
product added.
, Instead of performing two separate formalde- ,
ureas are extremely stable and that mixtures of 45 hyde reactions, one with urea and the other with
the tertiary alkyl urea and then mixing the prod
urea with monotertiary-alkyl ureas, upon reac
ucts, the more economical procedure would con
tion with formaldehyde, produce stable aqueous
sistin mixing urea with the tertiary alkyl ureas
solutions of thermosetting resins. For the meth-'
and reacting upon that mixture with formalde
od of preparing such tertiary-alkyl ureas, refer 50 hyde. This was tried and found to produce sta
ence is made to our Patent 2,247,495, issued July
bilized solutions, the degree of stability again
1, 1941.
As illustrative examples of the formaldehyde
being dependent upon the amount of tertiary
condensation products of the mono-tertiary-alkyl
alkyl urea added to the urea.
' The following examples are presented for illus
ureas, the following are given: -
tratlve purposes.
Example 10
- This solution was re?uxed at boiling temperature
for one hour and allowed to cool. The solution
gelled to a non-?owing state within two weeks at
‘Formaldehyde solution (37%%) ---_do_-..--200
' Ammoniasolution (26°) _____________ --cc__
room temperature.
was re?uxed at boiling tempera
ture for ‘one hour and then permitted to cool.
The solution became a non-?owing gel within
10 Ammonia solution (26°).__'__‘_____.#___-_cc__ 1.4
This mixture was re?uxed for one hour at boil
Example 11
grams" ‘80
Tertiary butyl urea ______________ .._..do_-.._ 12
Formaldehyde solution (37%%) ____ _..do_..__ 120
\ two weeks of storage at room temperature. '
Example 18
ing temperature and allowed to cool. There was
only a slight increase in'viscosity after two months "
Tertiary butyl urea ______ _.'______ _-do_-__
Formaldehyde solution (37%%) ,-..__do-___ 200
'- Ammonia solution‘ (26°) _____________ ..-cc-.. 2.3 15 standing at room temperature.
This solution was re?uxed at boiling tempera
- Example 19
ture for one hour and permitted to cool. Upon
Tertiary amyl urea ...... ..-_ ....... --do-.._-
standing at room temperature, it became a non
?owing gel after three weeks.
Example 12
20 Formaldehyde solution (37%%) .... .._do__-- 120
Ammonia solution (26°)_..__' ..... __'____cc..- 1.4
grams" 60
Tertiary amyl urea _______________ "do-.."
This mixture was re?uxed for one hour‘ at boil‘
ing temperature and allowed tov cool. There was
Formaldehyde solution (37%%) _---do--_- 200
Ammonia solution (26") _____________ --cc-..- 2.3 25
This mixture was re?uxed at‘boiling temperature
iorone hour and allowed to cool at room temper
ature. The solution gelled to a non-?owing state
30 Formaldehyde solution (37%%) .... 120
Ammonia solution- (26") ..--.' ........ _-cc_- 1.4
Example 13
This mixture was re?uxed for one hour at boll
ing temperature and allowed to cool. There was
Formaldehyde solution (37%%)--___do_--- 275
Ammonia solution (26°) _____________
35 only a slight increase in viscosity after two months
This solution was re?uxed for one hour at boll
ing temperature and allowed to cool. The solu
standing at room temperature.
In each ofthe above examples, where mixtures
tion gelled to a non-?owing state after two weeks '
on standing at, room temperature.
Erample 14
only a slight increase in viscosity after two months ‘
standing at room temperature.
Example 20
grams.._ 80
Tertiary hexyl urea............... ..-do_-..-' 12,
I I after four weeks at room temperature.
of urea and tertiary‘urea were employed, the so
lution of the reaction products, upon acidi?ca- '
40 tion and heating at 110° 0., produced intusible
?lms which had good water resistance.
In addition to the urea and substituted ureas
. Formaldehyde solution (37 $6 %) ----_'_do-;.-_ 275
disclosed in the preceding examples, other sub- .
stances may be present for the purpose‘ of modi
45 iying the properties or the resins obtained and in
This solution was re?uxed for one hour at.boil
particular those addition substances which pos
sess the property of reacting with formaldehyde
ing temperature and allowed to cool. There was
no change in viscosity after two months standing
with the production or water soluble condensa- .
at room temperature.
tion products. Such a substance, for example,
Tertiary butyl urea .... -_>__- ________ --do-.._Ammonia solution (26°) _____________
Example.- 15
60. would be melamine.
Tertiaryamyl urea ................
18 _
Formaldehyde solution (37 Vz%) .... 27;
Ammonia solution (26‘) ____________ ....‘-cc-
This solution was re?uxed for one hour at boil
proportions of from ten to thirty per cent of the
55 alkyl urea, based on theweight or the urea. are
suitable for 1 the production or water-resistant -
coatings, laminated products. plywood veneers and
‘ I ing temperature‘ and allowed to cool. There was
the like.
no change in viscosity after two' months standing
at room temperature.
As previously stated, the aqueous solution oi
the reaction products or formaldehyde with the
mixtures of urea\and tertiary alkyl ureas in the
Although‘ the present invention is particularly
suited for the production or aqueous solutions of
resins, there are occasions when the solutions or.
these resins in organic solvents are desirable, par
3 'Urea
ticularly when it is desired to incorporate such
Tertiary hexyl urea_____ __' ________ __do..--_ 18
resins into oleoresinous varnishes. For such pur
. "Formaldehyde solution (37%%) 275
pose, the aqueous solutions obtained in accord
‘ Ammonia solution (26°) _____________ -_cc__
365 ance
with the preceding examples are acidi?ed
This mixture was re?uxed for one hour at boiling
and then shaken with such solvent as butyl al- .
Example 16
temperature and allowed to cool. There was no
3 change in viscosity after two months standing
‘at room temperature.
Example 17
' grams"
cohol, a'mylalcohol. octyl alcohol or combinations
‘ Formaldehyde solution (37%%) .... -_do._-_- 120
or these. It has been found that the solutions
in organic solvents or the joint resins disclosed
in this invention are capable of dilution with
appreciably greater proportions of mineral sol-V
vents,~such as the various paint thinners obtained '
from petroleum, than is possible with similar so
‘ Ammonia solution (26°)-_- ___________ -..cc__ 1.4 75 ,iution or urea-formaldehyde condensation prodw
- 2,400,917
1. The method of produoinl
not which comprises heat
It is aiso possible to prepare moidins' powders
from the aqueous solutions or the joint, resins
disclosed inthisinventionbytheadditionoi ab
‘ sorhent nllers, suoh as wood
solutions or the resins and
hour. to the aqueous
ot-the wa-v.
solution of urea-iormaidehriie condensation prod
containing one moie of urea
5. a mono-tertiary-
i-urea havina from tour to
six carbon-atoms in the'aikyi group equal to from
ter either by “Dilution so! suction and heat or
2. A composition oi matter comprisins a heat
bymeans oihotmixinsroiis. Acidicaaentsmay reaction product of iron; one to three moles of
be incorporated either with the aqueous solution 10 aqueous iormaidehyde with a mixture containins
iinai molding powder.
\ottheresinsorwiththe suchmoidins
one moleioi urea and an amount of a mono-ter
powders '
It has been found that
tiary-aikyi-urea havinl'i’roin four to six carbon
have a ionser storase iii'e thanisthecasewith
atoms in the aikyi sroup‘equol totromtento'
similar moidins compositions prepand from the
thirtypercent oi theurea.
straisht urea-formaldehyde condensation prod
Having thus described our invention, what we
claimanddesinetoproteot hyletterlratent is:
uonkrnm '1'; mm.
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