TRIAZONE FERTILIZER AND METHOD OF MAKING

ENGRAIS A BASE DE TRIAZONE, ET SA PREPARATION

English Abstract

TRIAZONE FERTILIZER AND METHOD OF MAKING
Inventor: Edwin F. Hawkins
ABSTRACT OF THE DISCLOSURE
In a preferred embodiment, a triazone mixture
contains triazone present in an amount of at least about
30% calculated on a dry weight basis of 100% solids,
methylene diurea in an amount less than about 2.5%,
monomethylolurea in an amount less than about 3%, and
total methylene diurea and monomethylolurea taken together
being less than about 5%, and hexamethylenetetramine in an
amount less than about 1%, in water solution, of which on
a dry weight basis the ratio of triazone to methylene
diurea is at least about 6 and the ratio of triazone to
urea is greater than about 1, of which typically about 80%
of the triazone present is of the empirical formula
C3H7N3O in cyclic form, and a majority of remaining
triazone present is of the empirical formula
C5H10N4O3 in cyclic substituted-amine form, the
triazone mixture being produced by a two-stage method in
which urea and/or substituted urea is reacted with
aldehyde(s) and ammonia and/or primary amine(s) with the
urea to formaldehyde ratio ranging from preferably about
0.5 to 1.4, and with ammonia on a weight percentage of the
batch being at preferably about 4% to about 6%, such that
total nitrogen in solution ranges between about 16 and 31%
by weight, the first stage including heating reactants
within a preferred range of about at least 87 degrees
Centigrade up to about 92 degrees Centigrade while
maintaining the pH at about pH 8.5 to about pH 9 by the
continual addition of strong caustic such as sodium
hydroxide over a heating period ranging preferably from
about 20 to about 30 minutes, and the second stage
proceeding at about the same temperature devoid of further
addition of a caustic permitting the pH to drop during a

- 2 -
continued heating over a period o-f preferably from about
10 minutes to about 30 minutes, the optimum mole ratio
during the process of reactants urea, formaldehyde and
ammonia, for example, being about 1.2/1.0/0.25.

Claims

CLAIMS:
1. A liquid fertilizer composition comprising, as
calculated on a dry weight basis of 100% solids:
one or more substantially water soluble triazone
compounds in an amount of at least 30%;
one or more urea compounds in an amount of from
10% to 60; and
water,
the composition containing not more than the indicated
amounts (dry weight basis) of the following urea compounds
and of hexamethylenetetramine compounds:
methylene diurea compounds 7.9
monomethylol urea compounds 7.2%
hexamethylenetetramine compounds 2%,
all the above compounds being dissolved in the water and
the triazone compound methylene diurea compound weight
ratio being 6:1 or more.
2. A liquid fertilizer composition as claimed in
claim 1, in which the triazone compound content is between
35% and 50%, the urea compound content is not more than
35%, the methylene diurea compound content is not more
than 2.5%, the monomethylol urea compound content is not
more than 3%, with the total dry weight of methylene
diurea compounds and monomethylol urea compounds being not
more than 5%, and the hexamethylenetetramine compound
content is not more than 1%.
3. A liquid fertilizer composition as claimed in
claim 1 in which a major portion on a dry weight basis of
the triazone compounds are of the formula:
<IMG>
(I)
32

4. A liquid fertilizer composition as claimed in
claim 3, in which a minor portion of the of the triazone
compounds are of the formula:
<IMG>
5. A liquid fertilizer composition as claimed in
claim 3 or claim 4 in which the triazone compound of
formula (I) constitutes at least 80% of all triazones
present, on a dry weight basis.
6. A liquid fertilizer composition as claimed in
claim 1 or claim 2 which includes triazone compounds
having empirical formulae C3H7N3O and
C5H10N4O3.
7. A method for producing a water-solution
fertilizer composition of substantially stable
water-soluble components as a reaction product containing
one or more substantially water-soluble triazone-type
compounds, comprising:
(a) reacting in aqueous solution a urea compound, an
aldehyde and ammonia or a primary amine;
(b) thereafter further reacting in a first heating
stage at a temperature between 80°C and 95°C for an
additional reacting period of from 15 minutes to 1 hour
while adding as necessary during the additional reacting
period a strong base to maintain the pH within the range
of 8 to 9.5 and while adding as necessary during the
additional reacting period the urea compound and the
aldehyde to maintain a mole ratio of the urea compound to
33

the aldehyde within the range of from 0.5 to 2, and while
adding as necessary during the additional reacting period
ammonia or the amine to maintain a mole ratio of ammonia
or amine to the aldehyde within a range of from 0.15 to
0.65, the ammonia or amine being reacted in an amount
ranging from 2% up to 6% on a total water-mixture weight
basis of 100% of reactants of the urea compound, the
aldehyde and the ammonia or amine; and
(c) thereafter as a second heating stage maintaining
the reaction temperature between 80°C and 95°C for a
further period up to 1 hour, such that the final reaction
product has a triazone compound unreacted urea compound
weight ratio of at least 0.5:1.
8. A method as claimed in claim 7 wherein the
temperature in stages (b) and (c) is between 85°C and 93°C.
9. A method as claimed in claim 7 in which during
step (b) the temperature is between 87°C and 92°C for from
20 minutes to 30 minutes, the urea compound: aldehyde
molar ratio is from 0.9:1 to 1.2:1, the ammonia or amine:
aldehyde mole ratio is from 0.25 to 0.65, and the ammonia
or amine is in an amount from 4% to 6% such that total
nitrogen on a basis of total weight of solution is between
16% and 31%; and in which step (c) lasts from 10 minutes
to 30 minutes.
10. A method as claimed in any one of claim 7 to 9 in
which as the aldehyde there is used formaldehyde or a
mixture of aldehydes a major portion of which is
formaldehyde.
11. A method as claimed in any one of claims 7 to 9
in which as the aldehyde there is used acetaldehyde or a
mixture of aldehydes a major portion of which is
acetaldehyde.
12. A method as claimed in any one of claims 7 to 9,
in which as the urea compound there is used urea or a
mixture of urea compounds of which a major portion is urea.
34

13. A method as claimed in any one of claims 7 to 9
in which as the urea compound there is used thiourea or a
mixture of urea compounds a major portion of which is
thiourea.
14. A method as claimed in any one of claims 7 to 9
in which as the urea compound there is used methyl urea or
a mixture of urea compounds a major portion of which is
methyl urea.
15. A method as claimed in any one of claims 7 to 9
in which as the ammonia or amine there is used ammonia or
a mixture of ammonia and one or more amines of which a
major portion is ammonia.
16. A method as claimed in any one of claims 7 to 9
in which as the ammonia or amine there is used methylamine
or a mixture of amines or of one or more amines and
ammonia, a major portion of which is methylamine.
17. A method as claimed in any one of claims 7 to 9
in which as the ammonia or amine there is used
monoethanolamine or a mixture of amines or of one or more
amines and ammonia, a major portion of which is
monoethanolamine.
18. A method as claimed in any one of claims 7 to 9
in which as the ammonia or amine there is used
ethylenediamine or a mixture of amines or of one or more
amines and ammonia, a major portion of which is
ethylenediamine.
19. A method as claimed in claim 9 in which the
aldehyde comprises formaldehyde, the urea compound
comprises urea, and the ammonia or amine reactant
comprises ammonia.
20. A method as claimed in claim 19 in which the
aldehyde is formaldehyde, the urea compound is urea, and
the ammonia or amine reactant is ammonia.
21. A method as claimed in claim 7 in which the
temperature is maintained below

65°C during step (a) of claim 7.
22. A method as claimed in claim 21, in which the
temperature is maintained below 60°C during step (a) of
claim 7.
23. A method as claimed in any one of claims 7 to 9
in which a strong base is added as necessary to the aqueous
solution to adjust the pH thereof to within a range of from
7.5 to 9 prior to the step (a) reaction.
24. A method as claimed in any one of claims 7
to 9 including, immediately subsequent to completion of step
(c), cooling the reation product thereof to a temperature
of from 33 to 37°C.
25. A method of fertilizing vegetation and/or soil
which comprises applying to vegetation foliage and/or soil
a liquid fertilizer composition as claimed in claim 1.
26. A method as claimed in claim 25, in which the
triazone compound is hydrogen-triazone (S-tetrahydrotriazone).
27. A method as claimed in claim 25, in which the
triazone compound is methyl-triazone.
28. A method as claimed in claim 25, in which the
triazone compound is beta-ethanol-triazone.
29. A method of fertilizing vegetation comprising
applying to vegetation foliage, a water solution of fertilizer
consisting essentially of, as calculated on a dry weight
basis of 100% solids:
one or more triazone compounds that are
substantially soluble in water in an amount
36

of at least 30%;
one or more urea compounds in an amount of
from 20% to 60%;
the composition containing not more than the
indicated amounts (dry weight basis) of the following
compounds:
methylene diurea compounds 7.9%
monomethylol urea compounds 7.2%
(methylene diurea compounds +
monomethylol urea compounds) 10.2%
hexamethylenetetramine compounds 2%
and the composition containing water in an amount
at least sufficient for solution of all the above
compounds, and the triazone compound methylene diurea
compound ratio being at least 6:1 on a dry weight basis.
30. A method of fertilizing vegetation as claimed
in claim 29, in which the triazone compound content is
from 35% to 40%, the urea compound content is up to 35%,
the triazone compound urea compound ratio being at least 1:1,
the methylene diurea compound content being not more than
2.5%, the monomethylol urea compound content being not more
than 3%, with the total (methylene diurea compound plus
monomethylol urea compound) content being not more than 5%,
and the hexamethylenetetramine compound content being not
more than 1%, the trizaone compound methylene diurea compound
ratio being at least 11:1.
31. A method of fertilizing vegetation as claimed in
claim 29 wherein a major portion, on a dry weight basis, of
the triazone compounds is S-tetrahydrotriazone.
37

32. A method of fertilizing vegetation as claimed
in claim 31 wherein the triazone compounds further include
N-hydroxymethylformanide triazone.
33. A liquid fertilizer composition in accordance
with claim 1 in which said triazone composition comprises a
major amount, relative to the total triazone composition, of
the triazone having the empirical formula C5H11N3O2 and the
cyclic formula:
<IMG>
34. A method of fertilizing vegetation in accordance
with claim 29 wherein said triazone composition of said
fertilizer comprises a major amount, relative to the total
triazone composition, of the triazone having the empirical
formula C5H11N3O2, and the cyclic formula
<IMG>
38

Description

12~
. .
TH~ SPECIFIC~TION
This invention relates to a novel liquid
fertilizer ancl the novel method of ma]cing it.
BACI~GROUN~
Prior to the present inVentiOII there has been no
method which w~len repeated continually will produce either
triazones and/or a high concentration thereof reliabl~
and/or consistently. Also, by prior methods of making
fertilizers by somewhat similar or related method(s), the
resulting product or mixture of products exhibit low or
poor stability, decomposing and/or converting to
crystalline compounds or products that precipitate out
thereby destroying their utility for use as liquid
fertiiizer, solid fertilizer of the triazone or related
types of insoluble (in water) nature not bein~ capable of
releasing nitrogen to the roots suf-ficiently rapidLy as to
be economically or commercially feasible or practica
Moreover, it has been found that by current
technology, it is impossible to separate individual
triazone compounds from mixtures thereof in
water-containing reaction product mixtures thereof, and
until procedures utilized by the present inventor it has
heretofore not been readily possible to ascertain exact
structure(s) and formula(s) of aqueous reaction products
of process(es) related to or somewhat similar to the
present method. Likewise until research by the present
inventor, it hereto-Eore had not been recoynized nor known
what factors and/or yield of the final product(s) thereof
such as in the present inventive process resultin~ in iligh
concentration of hiyh solubility and stable products of
principally triazone compound(s) of the ~resent invention
presellt as a water-soluble mixture.
While there is no certainty that somewhat similar
or related processes have resulted in the production of
any triazone product~ as a part of the product-mixture in
water solution, or that -- if any were present or so

12~8i8~
~f
produced -- that amount of triazone therein was present in
any appreciable nor significant amount, or for how long
such would be present prior to decomposition thereof or
prior to the overall-mixture (reaction product) beco~ing
worthless insofar as utility for liquid fertilizer because
of crystallization and precipitation of constituents
thereof, the closest superficially related method or
process to that of the present invention appears to be
that of the Justice et al. United States Patent 3,462,256
issued on August 19, 1969, which is directed to and claimc
a process utilizing different process parameters and
different mole ratio-parameters for reactants, failing to
recognize the presence (if any~ oE the triazone(s) of the
present invention and the importance thereof as a liquid
fertilizer and the importance of such parameters and
resulting reaction product from the standpoint of each and
both effectiveness as a fertilizer of liquid nature, lack
of sensitivity thereto of human skin and long-term
stability thereof of the present invention. The broad
limits of the Justice patent include employing urea and
formaldehyde reactants in urea/formaldehyde ratio of l/2,
preferably 1.3/1.8, utilizing ammonia at a weight
percentage of 0.3 to 6 broadly, preferably 0.7 to 3, at
reaction temperatures ranging from 75 degrees Centigrade
to boiling broadly, preferably from 85 to 95 degrees
Centigrade, at a pE3 ranging broadly from 8.5 to lO,
preferably 9 to 9.8, during a heating time of reaction
broadly for 30 to 180 minutes, preferably froM 75 to 115
minutes. While some of the parameters overlap, there has
been no recognition by Justice nor other prior art of the
critical parameters of Applicant/inventor and of tihe
combination thereof critically necessary for the obtaining
of the present invention, as shall be evidenced by some of
Applicant's experiments contained herein as Examples of
methods that do not work.

~81t~
-- 5
OBJEC`T~ ok-llrH~ INVENTION
An object of the present invention is to obtain a
novel liquid fertilizer composition 4uitable for foliar
application and sod application devoid of potential
burning o~ foliage and/or sod.
Another object is to obtain a novel liquid
fertilizer composition suitable for situations requiring
slow-release nitrogen sources.
Another object is to obtain a novel composition
havinc~ an elevated or high percentage of triazone
composition suitable for use as a fertilizer for foliar
and/or sod applications.
Another object is to obtain the above-noted
compositions characterized by good stability and long-terl,l
lS stability against crystallization(s) of components thereof
and/or precipitation therefrom of components thereof
immediately or during storage.
Another object is to obtain a novel triazone
composition having a high triazone composition in aqueous
form, that has a higll level of stability against
decomposition of the triazone or against degradation
thereof.
Another object is to obtain a novel triazone
composition in aqueous solution having high concentration
of particular triazone(s).
Another object is to obtain a novel
method/process for producing said novel liquid fertilizer
composition(s) and improved high stabilities and
composition(s) having said slow-release and having the
characteristics of non-burning of foliàge and/or sod when
applied there~o.
Another object is to obtain a novel method of
fertilizinc~ vegetation of varying types and includinc~ sod,
utilizing novel compositions of this invention.
Other objects become apparent from the preceding
and following disclosure.

12S8~39
6 ~
One or more objects of the invention are obtained
by the invention as set forth herein, and as claimed in
the appended claims.
SUMMARY OF THE INVENTION
Broadly the invention may be characterized as
three inter-related inventions, namely a li~uid
fertilizer of novel compositions(s), a novel method of
producing those compositions, and a novel method of foliar
fertilizer application.
More particularly, broadly stated the invention
includes a liquid fertilizer composition having colnponents
thereof present in particular amounts within stated
ranges, including a triazone-type composition that is
substantially solubl~ in water sufficiently to obtain
stability to a practical commercial degree, a urea-type,
compound, water sufficient in amount to obtain and retain
a solution of the triazone(s), limited minor percentages
of a monomethylol urea-type compound and a methylene
diurea, and potentially minor amounts of a dimethylol
urea-type compound and a hexamethylene tetramine-type
compound. The triazone-type composition is present in an
amount of at least about 30~, preferably about 35~ to
about 50% and in an amount in ratio to urea by weight of
at least 0.48, preferably at least about 1. The urea-type
com!~ound on a dry-weigl~t basis i~ about 10% u~ to a~out
50%, preferably less than 35%, and the monomethylolurea-
type compound is u~ to about 7~. On the dry-weight basis,
the methylene diurea-type compound may be present up to
about 3~, preferably less than about 2%, and the
monomethylolurea Inay be present up to about 7%, ~referably
less than about 3~, and provided the total weight of
methylene diurea an~ monometllylolurea does not exceed
about 10%, preferably less than about 6~ (u~ to 6%). The
ratio of triazone(s) on a dry weight basis, to ~ethylene
diurea is at least about 6, preferably at least about 11.
Dimethylol urea and hexamethylenetetramine may or May not

lZ58189
-- 7
be present, with dimethylolurea ranging up to a~out 2.75%
on a weight basis of total weight of the aqueous solution,
and with hexamethylenetetramine u~ to about 2 percent,
preferably up to about 1~ on a weight basis (dry weight),
or less, normally th~re being no hexamethylene tetramine
present. The above-stated amounts of triazone composition
and its ratio to urea are critical to the utility of the
total composition of fertilizer and water solution thereof
as the liquid fertilizer for the above-stated objects.
The improved lower urea-content in the product achieves
both lower phytotoxicity and higher triazone content, by
this improved invention. When treating the aqueous
solution of urea-type compound and aldehyde-type compound,
with the ammonia, preferred results are obtained by
maintaining the temperature below 65C, preferably below
60 de~rees Centigrade. Also, in order to have the high
level of stability of the composition of this invention,
the method must be limited critically to not more than the
above-stated maximum amounts of compounds such as the
monomethylol urea, dimethylol urea and methylene diurea
because of their low and limited water-solubility and
instability insofar as tending to crystallize and/or
precipitate out. Substantially the same thiny is true for
hexamethylenetetramine that is likewise limited in its
maximum permissible amount of the inventive composition.
The present invention, then, in one aspect,
resides in a liquid fertilizer composition comprisin~, as
calculated on a dry weight basis of 100~ solids:
one or more substantially water soluble triazone
compounds in an amount of at least 30~;
one or more urea compounds in an amount of from
10~ to 60%, and water,
the composition containing not more than the indicated
amounts (dry weight basis) of the following urea compounds
35 and of hexamethylenetetramine compounds:
methylene diurea compounds 7.9

125E31~39
8 --
monomethylol urea compounds 7.2
hexamethylenetetramine compounds 2%,
all the above compounds beiny dissolved in the water and
the triazone compound:methylene diurea compound weight ratio being 6:1 or more.
According to another embodiment of the invention
there is provided a method for producin~ a water-solution
fertilizer composition of substantially stable
water-soluble components as a reaction product containiny
one more more substantially water-soluble triazone-type
compounds, comprising:
(a) reacting in aqueous solution a urea compound, an
aldehyde and ammonia or a primary amine;
(b) thereafter further reacting in a first heating
stage at a temperature between 80C and 95C for an
additional reactiny period of from 15 minutes to 1 hour
while adding as necessary during the additional reacting
period a strony base to maintain the pl~ within the range
of h to 9.5 and while addin~ as necessary during the
additional reacting period the urea compound and the
aldehyde to maintain a mole ratio of the urea compound to
the aldehyde within the range of from 0.5 to 2, and while
adding as necessary during the additional reactiny period
ammonia or the amine to maintain a mole ratio of ammonia
or amine to the aldehyde within a range of from 0.15 to
0.65, the ammonia or amine being reacted in an amount
ranging from 2~ up to 6% on a total water-mixture weight
basis of 100~ of reactants of the urea compound, the
aldehyde and the ammonia or amine, and
(c) thereafter as a second heatiny stage maintaining
the reaction temperature between 80C and 95~` for a
further period up to 1 hour, such that the final reaction
product has a triazone compound:unreacted urea compound
weight ratio of at least 0.5:1.
The present invention further provides a method
of fertilizing vegetation and/or soil which comprises

~2sal~
applying to vegetation foliage and/or soil a li~uid
fertilizer composition as described above.
In a preferred embodiment of the invention, on a
weight percentage basis, a maJor amount of the triazone
composition and/or mixture are triazones having the
empirical formulas C3H7N30 (5-S-tetrahydrotriazone)
and C5HloN403 ~N-hydroxymethylformamidetriazone),
with cyclic formulas
H~ H ~H~ H
H2 -~-CH2 and 2 ~ CH2 respectively,
C=~NH-CH2-OH
of the total triazone the C3H7N30 on a weiyht basis
amounts to preferably and normally at least about 80~
which is critical to obtaining preferred results as to the
above-stated objects.
The method of the invention has a combination of :
critical temperature ranges, pH ranges, reactant ratios,
essential reactants, and periods of reaction, as well as
being a two-phase method insofar as periods of time of
heating at different pH levels. In the absence of these
critical limitations, it has been discovered by the
present inventor to be impossible to obtain the high level
of production of the triazone composition(s) of this
invention, or to obtain a liquid fertilizer containing
5uch Witil a high level of stability, particularly in
conjunction with the high level or weiyht percentage
produced. Likewise, to obtain the non-burning triazones
of this invention suitable for fertilizer Eoliar
application as well as soil application, the critical
limitations are necessary to obtain such product(s).
Naturally there are broad ranges for many of these
limitations within which some degree of success may be

1258~8~3
-- 10 --
obtained, but with the rnaximum and high quality production
being limited to the method's preferred ranses.
More particularly, for the broader aspects of the
invention, the process may be described as a method for
producing a water-solution fertilizer composition of
substantially stable water-soluble components, of ~hich
the major novel component(s) thereof as reaction
product(s) are substantially water-soluble triazone
compounds, reaction components and steps being as follows.
rrhe urea-like component must be selected from
urea and/or substituted urea. A second necessary reactant
is an aldehyde. A third and ammonia-source reactant may
be ammonia and/or a primary amine. Finally, there must ~e
utilized a strong caustic during the initial first step or
phase of period of heating an admixture of the above-noted
reactants, which strong caustic is added gradually over
the period of time of the first period of heating and
reaction to the extent required in order to maintain the
p~I within the critical broad or preferred ranges. During
an initial first pnase of reaction, reaction of the
above-noted reactants is achieved by heating the admixture
thereof at a temperature within a range of from about 85
degrees Centigrade to about 93 degrees Centigra~e for a
period of time ranging from about 15 minutes to about 60
minutes while maintaining pEI within a critical range of
about 8 up to about 9.5 by adding the strong caustic as
the pH tends to droy during that reaction ~eriod, during
the initial first phase of reaction, the above-noted
urea-like component relative to the aldehyde reactant must
be maintained at least during the earlier and a dominant
portion of the first phase at a reactant mole ratio of
from about 0.5 to about 2.0, and likewise for ammonia on
the basis of weight of ammonia, from the ammonia source
above-noted, relative to the aldehyde within a ratio range
of from about 0.20 to about 0.85. On a weight-basis of

i2S~89
ammonia, relative to weight basis of 100% of reactants,
the ammonia, relative to a weight basis of 100% of
reactants, m~st be reacted in an amount within a ranye of
from about 2.2% to about 6~, relative to the above-noted
reactants on a weight basis of total water-solution
weight. Following the first stage of heatiny and
reacting, heating is continued within the same temperature
range, for an additional period of about 0-60 minutes,
preferably 10-30 minutes, while permitting the pll to
decrease by reducing or terminating any further addition
of the strong caustic, sufficiently to result in reaction
product(s) of which triazone composition(s) thereby
produced relative to unreacted amounts of the urea-like
component on a weig~lt basis has a ratio of at least
about l.
For the above-stated method, optimal results and
production critically representing the heart of the
present method are as follows. During the first phase
above-noted, the reaction temperature is maintained at
between about 91 deyrees Centigrade and about 93 degrees
Centigrade, and the period of first-phase heating ranges
between about 28 minutes to about 35 minutes, and the
ratio of the urea-like component to aldehyde is maintained
between about 0.5 and 1.2, and the ammonia to aldehyde
above-noted ratio is about 0.55 to about 0.8, and the
above-noted ammonia weight is maintained at from about 3%
to about 3.5%; and during the second, final phase of
heating, the temperature of reaction is maintained at from
about 90 degrees Centigrade to about 93 degrees
Centigrade. In the method, for preferred reactants for
optimal results critically representin~ the heart of the
present invention, the aldehyde at least in a major
proyortion thereof is formaldehyde, and the urea-like
component at least in a major proportion thereof is urea,
and the ammonia source in a Ina jor proportion thereof is

~L2S~89
- 12 -
ammonia. Good results are also obtained by use of methyl
urea, in part or in w~lole as the urea-like component, and
by use of methylamine as a substitute for ammonia, and
likewise for ethylene diamine, and likewise for
methylolamine and/or monoethanolamine. As the above-noted
urea-like component, also good results are obtained by use
of thiourea, in part or in whole as the urea-like
component, and by use of acetaldehyde, in part or in whole
as the aldehyde source, for example.
As a third aspect of the present invention,
namely the method of fertilizing vegetation, the method
may be broadly described as applying to vegetation
foliage, a water solution of the fertilizer composition
described above for each respectively of broad and narrow
(preferred) statements of limitations, and including the
method of applying each respectively or both of the
triazones above-identified by the empirical formulas
3 7 3 nd/o C5HloN4O3 and having the
cyclic formulas above stated respectively.
Urea-aldehyde mixture, as commercially available,
is normally of pH range of about 7.5 to about 9; an old
solution that might have a lower plI should be adjusted to
pH 7.5-9 for preferred results.
DETAILED DESCRIPTION
For the method of this invention, and the
product(s) thereof so produced, it has been determined
that stable products cannot be made witn less than about
2~ (by weight of ammonia relative to about total weight of
reactants) of ammonia up to about 6% ammonia, and that
stable product(s) cannot be made at temperature(s) ~ligher
than about 93 degrees Centigrade, and that it is difficult
to make products at pEi values above about pE~ 9.5. During
the developiny of the critical limitations of this
invention, it was determined that the ~II of the reactant
mix as above~described, the reaction temperature(s), and

~25~3189
- 13 -
the mole % of ammonia above-stated, each and all were much
more critical to the reaction than had been initially
believed. It is noted that the development of the procesC
of the present invention, and the eventual production of
the novel composition(s) thereof, resu:Lted from finding
and recognition that the currently heretofore available
liquid fertilizer concentrates, such as obtained from the
practice of the process of U.S. patent 3,462,256 to
Justice et al., had unreliable shelf life as to period of
time of stability prior to crystallization and/or
precipitation rendering the products commercially useless
and commercially impractical for foliar application, the
shelf life having been observed to be variable from batch
to batch produced. As a result, the process/method of the
present invention was undertaken by the present inventor
to produce the novel composition(s) thereof and the novel
method of fertilizer application. Also, the present
inventor discovered that monomethylolurea and
dimethylolurea convert to methylenediurea on standing at
ambient temperature and over a period of several weeks
typically, causing solids to deposit. Moreover, it nas
been found that methylol compounds when reacted with urea
at low temperatures merely sufficiently high to dissolve
the urea over a period of about 15 minutes results in an
unstable mixture, due to slow reactions at ambient
temperatures to form methylolureas, such product being
typically produced by the Moore patent U.S. 4,304,588
issued 12/8/81 and U~S. patent 4,244,727 issued 1/13/81,
in which patents the product(s) are identified as
monomethylol urea. Moreover, it was discovered by the
inventor, that concentration of methylene diurea is a
major limiting factor to the storage stability of the
product(s) of the present invention, and that the amoul~t
of methylenediurea converted from urea, should not exceed
about 3~ on a weight~basis as previousl~ set forth above,

- 14 -
in order to insure adequate storaye life from a commercial
practical viewpoint of utility of a liquid fertilizer
product. Also, because each of monomethylol urea and
dimethylolurea ilave been found to be unstable in solution
and tend to convert to urea and methylene ureas, each and
both should be kept to a minimum, as previously stated
herein .
While the inventor is not to be bound by
hypothesis of the exact reactions that occur, studies and
research conducted by t~e present inventor indicates that
the triazone(s) of the present invention are formed as a
result of serially consecutive reactions as follows. Urea
reacts with formaldehyde, for example, to produce
monomethylol urea; the monomethylol urea reacts with
formaldehyde, for example, to product dimethylol urea; and
typically methyl amine reacts with the dimethylol urea to
produce a methyltriazone, or an unsubstituted amine reacts
with dimethylol urea to produce a hydrogen-triazone
(S-tetrahydrotriazone), for example.
In experiment(s) using hexamethylenetetramine as
the source of ammonia, it was found that the reaction
proceeds very slowly and that an unsatisfactory product is
formed which rapidly crystallized on standing. A large
percentage of the ~lexamethylenetetramine remained
unreacted. Also, in the method, too little ammonia and/or
too much formaldehyde (or other aldehyde) results in too
high a percentage of unreacted urea, for the
above-described method of this invention. ~nen on a ~ry
weiyht basis the ratio of triazone to methylene diurea of
the final reaction product is less than 6%, yield of the
triazone composition of this invention is unsatisfactorily
low and poor; accordinyly, the method of the invention
maintains the methylene diurea in the final product at a
satisfactory minimum.
The product of this invention is prepared by
mixiny together the required amount of urea, formaldehyde

l'~S8~89
- 15 -
and ammonia in an aqueous solution, as a typical example.
The admixture and/or solution is heated thereafter to a
carefully controlled temperature, maintained at about that
temperature for a specific length of time while also
carefully controlling the pEL during the initial first
phase of heating and reacting by a slow addi-tion of strong
alkali. Thereafter, the approximate same temperature is
maintained for a second phase time period to bring about a
completion of reaction. The batcil is then cooled and
packaged.
The order of addition of the source(s) of urea,
formaldehyde, ammonia and water are not considered to ~e
very important provided there does not occur any prolonged
periods of time of addin~ a final ingredient and/or
provided imbalance of reactants in the required necessary
amounts is not permitted for any significant period during
reaction, and provided the one or more reactants are in
admixture not permitted to sit in an unreacted state for
any unreasonable or ~,rolonged period of time. The
ammonia-type reactant sllould be slowly added to the above
mix with controlled temperature of reaction.
The urea may be added either as pelleted or
crystal urea, as urea solution or at least partially as an
already partially condensed urea-formaldehyde reaction
product. The formaldehyde may be added as commercially
available formaldehyde solution or as ~araformaldehyde, or
partially in the form of hexamethylene-tetramine or as an
already partially condensed urea/formaldehyde reactant.
The ammonia may be added as anhydrous, aqua ammonia or
partiall~ in the form of hexamethylenetetramine. The
total nitroyen in the solution should be between at least
16% and 31~ or more on a weight basis of the total
reaction product solution which may be later diluted.
Because, as noted-above, it had proven impossible
to obtain stable liquid urea-formaldehyde fertilizer

lZS818~
- 16 -
solutions when followiny the procedures and/or metnods of
prior art patents and literature, due to the limited
solubility of monomethylol urea, dimethylol urea and
methylene diurea and also due to the inherent instability
of these materials, it therefore became necessary for t~le
present inventor to separate dnd to identify the
components of the reaction product(s) of the present
invention of liquid fertilizer solution.
High pressure liquid chromatography was used to
separate the separate reaction products prepared by the
method of this invention, and prepared by related
methods. Most of its components were identified by the
preparation of pure compounds and running them as
standards on the liquid chromatography (HPLC).
One major component could not be identified by
this procedure.
Paper chromatographic separation was used to
concentrate this unknown component which was subsequently
purified by recrystallization and identified as the
~ unknown by further HPLC analysis.
This invention-sample was then analyzed by mdss
spectrophotometric, NMR, infrared and by an elemental
analyzer, and determined to be an 80/20 mixture of
S-tetrahydrotriazone above-identified herein as haviny the
empirical formula C3H7N30 having the cyclic formula
set forth above herein, and N-hydroxymethyl formamide
triazone havin~ the empirical formula C5~10~4o3
having the cyclic formula set forth above.
A suitable caustic includes any one or Inore of
sodium hydroxide, potassium hydroxide, lithiunn hydroxide,
sodiurn carbonate or other strong caustic.
The triazones within the contemplation of this
invention as liquid fertilizer suitable for application to
foliage and/or sod, include the relatively few triazones
that are cllaracterized by beiny substantially readily
soluble in water, most triazones bein~ insoluble in water.

~Z581t~
- 17 -
The liquid fertilizer product(s) of this
invention were compared to certain other chemical and
commercial products with regard to phytotoxicity, as
follows. ~en averaged over all ~our species of turf,
grasses, for St. ~ugustine, Hybri~ Bermuda, Fescue and
Perennial Ryegrass, for a series of tests eml~loying
different numbers of pounds per square ft. as the i~ rate,
the urea-triazone mixture of this invention was less
phytotoxic than "Formolene"(~) or urea by 37.5% and 44.4
percent, respectively, at the most commonly used rate of N
on turf (1 lb./1,000 sq. ft.). When averaged over all
species and rates, the urea-triazone mixture of this
invention was 6.6~ and 30~ less phytotoxic than
"Formolene"(~) and urea, respectively.
The urea-triazone of this invention is
substantially safer than Formolene(~) when applied at
2.65 lbs. N/1000 sq. ft. (an undiluted application).
Accordingly, the triazone(s) (urea-triazones)
above-identified for this invention, are a safer turf
nitrogen than the other items above-tested for comparable
uses.
Likewise, for the DOT skin corrosion tests, the
triazone products were found to be not corrosive.
Following are typical runs, some by the method of
this invention, and others outside of the limitations of
the inventive method, serving in part to illustrate some
of the critical limitations of the method of this
invention.
EXA~PLE I
(samples 1-2, 2-2, 3-2, ~-~, tested at one point in time)
(Based on water soln. wt.)

lZ5818~
- 1~3 -
ComporIellts of / Percentage pre~sent
reaction product / by weiqht
1-2 2-2 3-~ 4-2
-
Urea 28.7 27.3 30.0 3~.9
MonometIIylol urea1.8 1.8 6.1 0.9
Methylene diurea 0.8 1.3 1.1 1.1
Dimethylol urea 0-7 1.1 0.7 1.2
Triazone 18.8 19.6 12.9 8.2
IIexamethylene tetramine ~ 2.5
The Sample 3-2 having am monomethylol urea (MM~)
percentage of 6.1~ had poor stability, the methylene
diurea crystallizing-out as the monomethylol decomposed
when stored for a short period on the shelf. Likewise,
the sample, 4-2 was unsatisfactory in its yield of
triazone, at 8.2%, as a result of the final product having
a high concentration of unreacted urea at 36.9% and as
well there being present an unsatisfactorily large
percentage of hexamethylene tetramine at ~.~%, causing
also instability resulting in crystallization and
precipitation of components, rendering the products
totally unsatisfactory for use as a liquid foliant. From
the above table of which the balance of percentage for
each sample is water, the percentages present on a basis
of total solids are:
1_2 2-2 3-2 4-2
Urea 56.50 53.33 5g.04 72~00
Monomethylol urea (M~IU) 3.54 3.52 12.01 1.76
Methylene diurea (MDU) 1.57 2.54 2.17 2.15
Dimethylol urea (DMU) 1.37 2.15 1.41 2.34
30 Triazone 37.01 3~.28 25.89 16.0
Hexamethylenetetramine -- -- -~ 6-36
Wt. ratio of
Triazone/urea 0.65 0.72 0.43 0.22
Wt. ratio of
Triazone/MDu 23.5 15.1 11.7 2.6

i~S8~89
-- 19 ~
Four days later, again the components percentages after
that ad~itional shelf-life, were tested, giving the
following results for the above-noted samples.
(% Oll basis of total water solution~
Com~onents of reaction pdt. 1-2 2-2 3-2 4-2 5-2
__ _
(prior
run)
Urea 29.4 27.9 30.0 35.5 28.7
MMU (less than) 0.1 0.8 5.3 0.4 2.3
YDU 0-9 1.2 1.2 1.2 1.2
DMU 0.5 0.5 0.8 1.0 0.6
Triazone 20.0 20.4 13.7 9.5 18.3
Hexamethylene tetramine -- -- -- 6.36 --
The solids percentages by weight for this preceding table
15 are:
1_2 2-2 3-2 4-2 5-
Urea 57.7 54.9 59.5 69.9 56.2
MMU 0.2 1.6 10.5 0.~3 4~5
MDU 1.~ 2.4 2.4 2.4 2.4
DMU 0.98 0.98 0.4 1.2 1.. 2
Triazone 39.3 40.2 26.9 1~.7 35.8
Hexamethylene tetramine -- -- ~~ 5-7 ~~
As can be seen, the amount of hexamethylenetetramine is
high and the triazone is low for experiment 4-2.
Some of the preferred triazones of this invention
include S-tetrahydrotriazone, and methyl-triazone, and
beta-ethanol-triazone.
~'or the several above-noted reaction products of
the preceding Example I above discussed and disclosed, the
formulations utilized and the common (same) method applied
to each were as fo.llows:

i2S8~8~
-- 20 --
Formulation (wt.%) 1-2 2-2 3-2 4-2
Urea: 52.3 52.353.2 48.5
25% urea-60g6 formal-
dehyde: 31.3 31.331.3 29.0
KOH Soln. (25%): 3.0 3.0 0.3 0.
Aqua Ammonia (28%~I!)3 10.710.7 10.7 19.7
Water 2.7 2.7 5.4 2.5
Mole ratio (1.6/1/.28 1.6/1/.28
(urea/HCHO/NH3): ( 1.6/1/.28 1.6/1/.56
10 The procedures followed for the above-noted
formulations, were as follows:
1-2: ~ater, urea-formaldehyde and the urea were mixed
together in a reaction kettle and slowly the aqua ammonia
was added while mixing. That mixture was heated to &3
15 degrees Centigrade and maintained at a temperature below
90 degrees Centiyrade and at a pH between about pH 8.7 and
pH 9 for 45 minutes, the pEI being maintained by the
addition of the KOH. Thereafter, further heating and
reaction were accomplished by maintaining tha temperature
20 of reactants at between 83 degrees Centigrade and about 9
degrees Centiyrade for an additional 15 minute~.
Thereafter, the reaction product was permitted to cool and
was packaged.
2-2: The water, urea-formaldehyde and the urea were
25 mixed together in a reaction kettle and the pH was
adjusted to p~l 9.0 by addition of ~OH. That mixture was
then heated to 81 degrees Centigrade and the pH durin;~ th~
heating was maintained at between 8.7 to 9.0 by continual
additions of KOH~ 13 mixture while heatirlg to 90 degrees
30 Centigrade. The temuerature was thereafter maintained at
between 8~ to 90 degrees Centigrade at a pEI ranging from
8.7 to 9.0 until all of the KOH-NE13 mixture had been
added. Thereafter heating and reactants' temperature was
maintained at between ~38 and 90 degrees Centigrade for an
35 additional 15 minutes, followed by ~ermittin~ the reaction
~roduct to cool, after which it was packaged.

;~s~9
- 21 -
3-2: The water, urea-formaldehyde and urea were
admixed in the reaction kettle and the pH was adjusted to
9.5 with addition of the KOH solution. The
admixture/solution of reactants was then heated to about
73 degrees Centigrade at which point the urea was
completely dissolved, and thereafter the reactant
mixture/solution was maintained at a p~ of 8.5 to 9.~ witn
a slow addition of aqua ammonia for approximately 10
minutes while heatiny to 90 degrees Centigrade.
Thereafter heating and maintaining reactants at 88 to 90
degrees Centigrade were continued for an additional 30
minut s, followed by permitting the reaction ~roduct to
cool and then by packaging the reaction product.
_ : The same steps were followed as for 3-2 above,
except as follows. The addition of aqua ammonia was
started at about 75 degrees Centigrade and pH was
maintained between 8.5 and 9.0 by a slow addition of the
KOH while heating the reactants to 90 degrees Centigrade
for approximately 1~ minutes. Thereafter the reactants'
temperature was maintained by heating, at between 88 and
90 degrees Centigrade for an additional 3 minutes.
From the above procedures, ~hich resulted in the
reaction products already discussed, it will be seen tilat
the limitations of the method of this invention are in
fact critical. It is also noted that in the above 3-2
procedure, the first-phase above-noted addition of aqua
ammonia for the ten minutes, was not the equivalent of use
of a strong caustic such as KOH and proved to be
unsatisfactory and unacceptable for the method of the
present invention. It is also noted that the pH 9.5 of
procedure 3-2, was slightly above the broad range of the
method of this invention, and that tlle yield of it was
relatively poor, as compared (for example) to the much
higher yields of 1-2 and 2-2. The reaction product of 4-2
crystallized when permitted to stand (shelf-life) for 72
hour s .

lZ~81~9
- 22 -
EXAMPLE II
Another series of experiments were designed in
order to determine and illustrate the effects of v~rious
reaction conditions on the quality of the ~roduct. The
first of the conditions investigated was the percentaye of
ammonia in the cook. This was varied from 0~ to 3.C% (on
the basis of weight of the water solution) with the
followin~ results.
Run #: 1 2 3_ 4 5 6
10 ~eactant or product
96 NH3 0 1.0 1.5 2.0 2.5 3.0
Unreacted urea 31. 8 30 . 6 34 . 8 37 . 7 34. 7 35. 8
MMU* 20.2 4.3 7.1 1.~ 1.7 Tr. (trace)
MDU* 27.7 14.2 15.8 7.9 5.9 7.7
DMU* 18.2 7.1 Tr. Tr. Tr. Tr.
Triazones
(the water soln) 1. 3 43. 8 42.3 52.7 57.7 56.5
Tr.=Trace
The runs nos. 4, 5 and 6 represent limitations within the
method of the present invention.
For the above-noted runs, ratios of triazone(s)
to MDU and of NH3 to formaldehyde, and of triazones to
unreacted formaldehyde, were as follows:
1 2 3 4 5 C
2 5 Reactant - Pdt
triazone(s)/MDU 0.08 5.9 5.0 12.5 18.2 13.7
NH3/HC~lo 0- 05 0.14 0.18 0.23 0.28
triazones/unreacted
urea 0.013 0.46 0.39 0.45 0.54 0.51
30 It is noted particularly that triazone(s)/MD~l ratios of
runs 1, 2 and 3 were all below 6, and that the resultant
yields were poor for the triazone(s), the ~ NH3 reactant
for those runs being far below the required limitations of
the method of this invention.
35 (NOTE*: MMU=monomethylol urea; MDU=methylene diurea
DMU=dimethylol urea)
J:

iZ5~189
- 23 -
It is noted that the #4 run has insufficient
ammonia reactant which results in excessive unreacted urea
and also in a ~roduct of poor stability, i.e.,
crystallization and ~uick precipitation, i.e., poor shelf
life resulted and can be expected, even thouyh yield of
the triazone(s) was reasonably acceptable. Also these
tests (runs) show that ammonia is necessary for production
of a storaye stable composition that includes t~le triazone
products in a acceptable yields, within the range of the
method of this invention, and the importance of the ratio
limitation.
It is within the scope and contemplation of this
invention to make such variations and modifications and
substitution of equivalents as would be apparent to a
person having ordinary skill in this particular art.
In a preferred method of the invention, improved
content is obtained by cooling the reaction product
immediately (i.e., promptly) after the final second-stage
final heating period, down to a lower temperature within a
ran~e of about 33 degrees Centigrade to about 37 degrees
Centigrade.
Urea type compounds include substituted ureas
typically such as thiourea, and monourea and diethylurea
and the like, there being many well known conventional
such substituted ureas.
Typical aldehydes utilizable, are HCHO
(formaldehyde), para-formaldehyde, acetaldehyde,
propionaldehyde, HI~T (commercial designation), and the
like.
Typical ammonia sources include ammonia, aqua and
anhydrous ammonia, ~T, and primary amines sucn as
monoethanolamine, methyl amine, ethylene diamine, and the
like.
With regard to use of substituted and/or
alternative compounds utilized as reactants in the

lZ5~1~39
~ 24 -
above-disclose~ process(es), and to the therefore
substituted and/or alternative intermediate and final
products and/or compounds, the suffix "-type compound" is
utilized herein, and in the accompanying claims to
generically encompass such substituted and/or alternative
compound~s) of the same root or common structure(s), such
as for example terms urea-type compound, triazone-type
compound, methylene diurea-type compound, monomethylol
urea-type compound, hexamethylene-tetramine-type compound,
for example. Likewise, "ammonia source" is intended to
generically encompass alternative ammonia-type compounds
that either produce or provide ammonia as a reactant
and/or that react similarly such as above-noted ammonia
sources discussed above.
For the followiny two examples of products
produced within the preceding preferred parameters (ranges
of temperature, l~ercentages, etc.), the content based on
analysis, on a wet (solution) basis, was as follows, where
the processes employed a urea/formaldehyde ratio of 1.2,
as contrasted to prior examples herein having had a ratio
of 1.6.
Batch #: #l _#2 _~
% urea 19.5 20.2
% MMV (monomethylolurea) 3.8 4.3
25 ~ MDU (methylene diurea) 1.8 1.8
% Triazone 30.8 28.8
Triazone/urea ratio1.58 1.43
(by weight/dry)
Triazone/MDU
(by dry weight) 17.1 16.0
For the above data, expressed on à dry basis, the analysis
i s :
% urea 32.5 33.7
~ MMU 6.3 7.2
35 % MDU 3.0 3.0
% Triazone 51.3 4&

izs~s
SUPPLEMENTARY DISCLOSURE
The present in~ention, in one aspect, as described
hereinbefore in the Principal Disclosure, resides in a liquid
fertilizer composition consisting essentially of: as calculated
on a dry weight basis of 1~0% sol;ds, a triazone composition
that is substantïally soluble in water, present at at least
about 30% tdry weight~, a urea-type compound present in an
amount of from at least about 10~ up to about 50% (dry weight)
such that the ratio of amount of trïazone-type compound present
~elati~e to the amount of said urea-type compound present is
at least about 0.48, a methylene diurea-type compound up to
about 3% (.dry weight), a monomethylol urea type compound up
to about 7~ (.dry weight) with total weight ~dry weight) of
methylene diurea-type compound and monomethylolurea-type
compound up to about 10%, a hexamethylenetetramine type compound
up to 2% (.dry weight2, and water in an amount at least
sufficient for solution of said triazone composition, said
urea-type compound, said methylene diurea-type compound, said
monomethylolurea-type compound and said hexamethylenetetramine-
type compound being dissolved therein, and said triazonecomposition on a dry weight basis, relative to said methylene
diurea type compound being in a ratio of at least about 6.
The present invention, in another aspect, as described
hereinabove in the Principal Disclosure, resides in a method
for producing a water-solution fertilizer composition of
substantially stable water-soluble components as a reaction
product containing substantially water-soluble triazine type
compounds, comprising: reacting an aqueous solution of a urea-
type compound and an aldehyde-type compound, with an ammonia
-SD~-

lZ58~89
source selected from the group consisting of ammonia and primary
amines; ~nd therea~ter further reacting at a temperature heated
to and maintained between about 85 degrees Centigrade and 93
degrees Centigrade for an additional reacting period of from
about 15 minutes to about 60 minutes while adding as necessary
during said additional reacting period a strong caustic
sufficient in amount(.s) to maintain the pH within a range of about
8 to about 9.5 and while adding as necessary during said
additional reacting period sufficient amounts of any of said
urea-type compound and said aldehyde-type compound to maintain
a mole ratio of said urea-type compound relative to said
aldehyde-type co~pound within a range of from about 0.5 to
about 2, and while adding as necessary during said addit~onal
reacting period a sufficient amount of said ammonia source to
maintain a mole ratio of ammonia-type compound f~om said
ammonia source relative to said aldehyde-type compound within
a range of fr~m about 0.2 to about 0.85, said ammonia-type
compound from said ammonia source being reacted in an amount
ranging from about 2% up to about 6~ of ammonia-type compound
on a total water-mixture/solution weight basis of lO0~ of
reactants of said urea-type compound, said aldehyde-type
compound, and said ammonia source; and thereafter as a second
stage of reaction, maintaining reaction temperature at said
temperature for a further period up to about sixty minutes,
such that for a final reaction product including the triazone-
type compound, said triazone type compound relative to
unreacted amounts of said urea-type compound on a weight
basis has a ratio of at l~ast about 0.48.
In an embodiment deemed most preferred and optimal,
the composition of the invention has about 20% by weight, of
unreacted urea, and has about 50% by weight, of the triazone
, . ,
-SD~2-

~ZS818~
(.soluble trïazonel, and a triazone~urea weïght ratio of about
2.5, and has methylenediureas up to a maximum of 3~, and has
monomethylolurea up to a maximum of 4%, and has hexamethylene-
tetramine up to a maximum of 0.5%, all percentageslbeing by weight
on a dry basis.
Specific triazones which.may consti.tute a major amount
of the trïazone composition, as prevïously described in the
Principal Disclosure, are triazones having the empirical formula
C3H7N30 (5-S-tetrahydrotriazone) and th.e empirical formula
C5HlON~03~N-hydroxymethyl-formamide triazone), which are
designated by the respectïve cyclic ~ormulas:
o
HN-~-NH HN-C-NH
~ I andl l
t H2C-N_ CH2
H O=CNH-CH2-OH
(5-S tetrahydrotriazonel (N-hydroxymethylformamide
triazone~
- Another triazone which. may constitute a major amount
of the triazone composition is the triazone having the
empirical formula C5HllN302 (5-B-hydroxyethyltriazone) and
ha~ing the cyclic formula
O
H~N-C-NH
2 ~C 2
H2 -CH2-OH
(5-~-hydroxyethyltri.aæone~
The 5-B-hydroxyethyltriazone may be present in the
triazone composition, by weight, in an amount ~preferably and
normallyl of at least about 80%; this is critical to obtaining
preferred re~ults ïn accordance ~ith this invention. All
of the above-mentïoned three triazones are characterized
by high solutility in water.
~ 7
-SD~-

lZS8~39
The above-noted compound o~ empirical formula
C5HllN3O2(5-~-hydroxyethyltriazone) is the more preferred
product typi.cally obtained by the most preferred optimal
process of this invention in greatest purity and highest
weight percent. It i.s particularly preferred because of
its high solubility, its good stabilïty and virtual absence
of phytotoxicity. Th.is particular trïazone has a multiple
utility, namely being the better foliar fertili~er of this
invention, as well as having good fungïcidal properties. The
5-~-hydroxyethyltriazone is produced by using ethanolamine
as a substitute for ammonia, as the ammoni.a source, the
method being other~ise the same as described for the generic
and preferred methods of producing the triazones of this
invention.
The most preferred and optimal method of making the
composition of this invention, is as previously described
for the broad and preferred processes, e~cept that during the
previously identifi.ed ini.ti.al first phase of reaction,
reaction of the noted reactants is achieved by heating the
admixture thereof at a temperature withi.n a range of from about
88 to about 90 degrees Centi.grade, and while maintaining the
pH at between 8.5-9, the first phase reaction period being
heated for a period of from about 20 to 30 minutes, and the
second phase of heating being from about 10 minutes to about
30 minutes; the urea/aldehyde ratio during the initial first
phase is maintained at between.a~out 0.~ to about 1.2, and the
ammonia/aldehyde ratio as previously described, is maintained
at between about 1.5 to about 3, and th.e trïazone/urea wt.ratio
is about 2.5 and the nitrogen content is from a~out 24 to
about 31 on a ~eight basis of the total reaction product
solution, which may be later diluted.
-SD`2~-

~258~89
For the abo~e-stated method, the broad range of reactants
is as follows.
~ he mole ratio of the urea-like component to aldehyde is
maintained between about 0.5 and 1.6, and the ammonia to aldeh~de
mole ratio is between about 0.2 to about 0.65 and the abo~e-
noted ammonia ~eight is maintained at from about 2% to about
11%. ~he reaction condit;ons are as follows: During the first
phase above-noted, the reaction temperature is maintained
between about 80 degrees C. and about 93 degrees C, and the
period of first phase heating ranges between about lS minutes
to about 60 minutes, and while maintaining the p~ at between
8.0 to 9.5 and during the second phase of heating, the
temperature of reaction is maintained at from about 80 degrees
C, to abollt 83 degrees C.
For the abo~e-stated method, optimal results and
production critically representing the heart of the present
method are as follows. During the first phase above-noted, the
reaction temperature is maintained at between about 90 degrees C.
and about 92 degrees C., and the period of first phase heating
ranges between about 20 minutes to about 30 minutes while
maintaining the pH between about 8.5 and about 9, and the
mole ratio of the urea-like component to aldehyde is maintained
between about 0.25 and 0.40 and above-noted ammonia weight is
maintained between about 3% and about 6~; and during the
second, final phase of heating, reaction temperature is maintained
betweenabout 90 degrees C. and about 92 degrees C. In the method,
for preferred reactants for optimal results critically rep-
resenting the heart of the present invention, the aldehyde at
least in a predominant proportion thereof is formaldehyde, and
the urea-like component at least in a predominant proportion
thereof is urea, and the ammonia source in a predominant
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proportion thereof is a~nonia. Good results are also obtained
by use of methylurea, in part or in whole as the urea-like
component, and by use of methylamine as a substitute for
ammonia, and likewise for sthylene dïamine, and likewise for
monoethanolamine. As the above-noted urea-like component, also
good results are obtained ~y use oE thiourea, in part or in
whole as the urea-like component, and E~y use of acetaldehyde,
in part or in whole as the aldehyde source, for example.
The following is a further example of the present
10 invention:
Example III
Example of Triazone Production on a Co~nercial Basis
Twenty-three batches of triazone product were prepa^ed
in a 2800 gallon capacity vessel equipped with good agitation
and cooling coils and containing a sparger tube for the
introduction of the anhydrous ammonia. The first three batches
were approximately eleven tons while all subsequent batches were
twelve ton batches.
Formulation (Wt.g6) Tons/12 Tons
UF-85 (25% Urea, 6096HCHOJ 25.07 4.208
Urea (100%~ 41.70 5.004
Anhydrous Ammonia 3.00 0.360
50% Sodium HydroxideSolution 1.40 0.168
Water 18.83 2.260
Mole Ratio Urea/Formaldehyde/Ammonia-1.2/1/0.25
P_edure Followed:
A) Add the water, UF-85 and urea to reactor.
B) Slowly add the anhydrous ammonia to the reactor at a
rate to prevent localized overheating and such that the
temperature does not go above 65 degrees Centigrade
(approximately 18 lbs. per minutel.
C) Initial Reaction -- Heat the ~atch to 89 degrees Centi-
grade + 1 degree Centigrade and maintain this temperature
~ ~,
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for forty-five minutes while simultaneously maintaining
the p~ between 8.5 and 8.8 by the slow addition of 50%
sodium hydro~ide solution.
D) Secondary Reaction - Continue to maintain temperature
at 89 degrees Centigxade ~ 1 degree Centigrade for an
additional twenty minutes but end pH control. (pH will
slowly drop.~
E) Turn off steam and cool the batch as rapïdly as possible
to no more than 40 degrees Centigrade (preferably 30
degrees Centigrade~ and pump to storage.
Composition of Commercial Production
Of the twenty-three batches, the retained samples of
twenty of them have remained clear on storage. Composition of
these batches is as follows:
% Unreacted % Methalol- %Methylene %
Urea Ureas Ureas Triazones
Min. 21 1.9 2.7 29.1
Ma~. 23.3 5.3 3.5 38.1
Avg. 22 3.0 3.0 36.9
The composition of the three batches which became cloudy
on storage is as ~ollows:
Avg. 21.1 4.2 4.3 30.3
The three bad ~atches were due to failure of the pH or
temperature c~ntrollers resulting in pH above 9.0 or temperature
above 92 degrees Centigrade.
The variation in the triazone content of the products is
due primarily to variations in the ammonia addition.
The composition of these triazone products has been
determined by the use of a Hewlett/Packard Model 1084B high
pressure liquid chromatograph (HPLCi after first preparing pure
s~ples of the constituents and determining their retention times
and sensitivity factors under our test conditions.
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