Note: Descriptions are shown in the official language in which they were submitted.
1119199
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BACKGROUND OF THE INVEN~IO~
1. Field of the Invention
The present invention pertains to amine compounds.
More particularly, the present invention concerns polymeric
polyamines derived from epihalohydrins and primary amines.
Even more particularly, the present invention concerns
polyamines derived from epihalohydrins and primary amines and
derivatives thereof, such as highly functional polyamine
derivatives thereof.
2. Prior Art
There has been developed a wealth of art relative
to the formation of polyamines. Within the art, there has
been documented the reaction of amines with epihalohydrin
polymers and, especially, those from epichlorohydrin. Such
products are traditionally divulged as being used in the
manufacture of paper.
As will be appreciated from a review of the prior
art, the reaction normally comprises the deployment of a
polyamine and monomeric epihalohydrin or an epihalohydrin
polymer.
Because of the plurality of uses of polyamines, the
art has consistently attempted to produce new, economical
compounds which enhance the end products produced from the
polyamines by virtue of the distant structure associated
with the polya~ines, per se.
As will subsequently be detailed, the present
invention provides new polyamines.
STATEMENT OE RELEVANT ART
To the best of applicant's knowledge, the most
relevant art is found in the following patents:
U. S. Patent Nos. 2,753,372 3,031,505
3,864,288 3,655,506
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U. S. Patent Nos. 3,313,742 3,607,792
3,310,504 3,951,888
2,174,762
SUMMARY OF THE INVENTION
-
In accordance with the present invention there is
provided new polyaminesprepared by reacting (a) an epihalohydrin
oligomer or a mixture of an epihalohydrin oligomer and a
chlorohydrin ether-terminated polyol and (b) a primary amine.
These resulting linear amines may then be further reacted with
primary, secondary or tertiary amines which replace the
haloalkyl groups in the polyamine to provide further new
polyamines.
In practicing the present invention, the halohydrin
oligomer, preferably, comprises a polymeric epihalohydrin and,
specifically, a polymer of epichlorohydrin.
The polyol which may be used herein is, generally,
an alkoxylated polyhydroxyl compound.
Any primary amine can be used with efficacy herein.
The resulting polyamines can be characterized by
the formula:
~ OH CIH2X fH R
HN ~ CH2CHCH2- ( OCHCH2)n OCH2CHcH2N ~a
OH Z OH R
~ CH2CHCH2 ~ OlHCH2 ~ OCH2CHCH2~ ~ ~ H
wherein:
R is either Cl to C4 alkyl group, 2-hydroxyethyl,
or 2-hydroxypropyl,
X is a halogen atom
Z is either hydrogen, methyl or ethyl,
n is a whole number ranging from 2 to 30
m i 5 an integer from 2 to about 100
a is a value from about 0 to about 20
b is a value fr0m 0 to about 20 and ordinarily is
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no greater than A.
In those instances where b equals 0, the polyamine
is a derivative of the formula:
OH CH2X OH
XCH2CHcH2 ( 0CHCH2~0CH2CHCH2X
where X is the same as defined above.
I~here b is greater than 0, the polyamine is a
derivative of polyepichlorohydrin and a chlorhydrin terminated
polyether of the formula:
O~ H
XCH2CHCH2~0CHCH2~ OCH2CHCH2X
wherein Z and M have the same meaning as given above.
The reaction between the epihalohydrin terminated
polyether and amine proceeds at a temperature ranging from
about 25~C to about 150C for a period ranging from about 0.5
to about ten hours.
The polyamines hereof may be further reacted with
primary, secondary or tertiary amines to replace the haloalkyl
groupsof the polyamines to provide, yet, further polyamines.
These further polyamines may then be used to prepare paper
additives and the like.
For a more complete understanding of the present
invention reference is made to the following detailed descrip-
tion and accompanying examples.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In accordance with the present invention, substantially
linear polyamines are provided which correspond to the formula:
7 OH TH2X OIH IR
HN ~ CH2CHCH2 ( OCHCH2 ~ 0CH2CHCH2N ~
~H Z OH R
~ (CH2CHCH2-)b ( OCHCH2--t----OCH2CHCH2N ~ H
whe rein:
~ _ ~.
~.~
11191~g
R is a Cl to C4 alkyl radical, 2-hydroxyethyl or
2-hydroxypropyl,
X is halogen;
Z is hydrogen, methyl or ethyl;
n is a whole number ranging from 2 to 30;
m is an integer ranging from 2 to about 100;
a is a value ranging from about 0 to about 20;
b is a value ranging from 0 to about 20 and,
preferably, is less than or equal to a.
The products thereof are prepared by reacting (a) an
epihalohydrin oligomer or a mixture of an epihalohydrin oligomer
and a chlorohydrin-terminated of a polyoxyalkylene glycol with
(b) a primary amine.
In the above formula, when b is 0, thc polyaminc is
a derivative of the epihalohydrin oligomer, alone, havi.ng the
postulated formula:
OIH fH2X OH
XCH2CHCH2 ( 0cHcH2~0CH2CHCH2X
When b is greater than O then the polyamine is a derivative
of the epihalohydrin oligomer and halohydrin-terminated
polyether having the formula:
I IH
XCH2CHCH2~0CHCH2~ OCH2CHCH2X
The polyamines hereof can be further reacted with
primary, secondary, or tertiary mono- or polyamines. Such
further reaction replaces the halogen of the haloalkyl groups
of the original polyamines with Eurther amino-groups.
The present invention is based upon the fact that
halohydrin oligomers or active hydrogen derivatives thereof
contain two kinds of halogen substituents. First, there are
highly reactive terminal halohydrin halogen atoms. Secondly,
thcre arc pendant haloalkyl halogen atoms which are of lower
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reactivity with nucleophilic reagents, such as amines, than the
terminal halogen atoms. By proper control of the reaction
conditions, the above-defined linear polyamines can be
obtained.
In reacting the ingredients, the control is achieved
through amounts of reactants, reaction times and temperatures.
Generally, the reaction proceeds at a temperature ranging from
about 25C to about 130C for a period of time ranging from
abou-t 0.5 to ten hours. Generally, the reactants are employed
in a molar ratio of amine to halohydrin or halohydrin and
polyether ranging from about 1:1 to about 5:1. Preferably,
the reaction p~oceeds at a temperature of from about 30C to
about 130C for a period of from about 0.5 to 5 hours.
Preferably, a molar ratio of amine to halohydrin or halohydrin
and polyether mixture, of from about 1:1 to about 4:1 is
employed.
The halohydrin oligomers used herein are, preferably,
epihalohydrin polymers derived from monomers of the formula:
CH -~H-CH2-X
where X is Cl, Br, or I and preferably Cl. Other useful halo-
hydrin oligomers can be based upon 4-halo-1,2-epoxy butane,
1-(1,3-dihaloisopropoxy)-2,3-epoxypropane; 4,4,4-trihalo-1,2-
epoxy butane, l-haloethyl glycidyl ether; l,l,l-thihaloethyl
glycidyl ether; 1,2-epoxy-2-methyl-4,6,6,6-tetrahalohexane;
and the like. As noted, the preferred oligomers and derived
from the epihalohydrin monomer and, in particular, epichloro-
hydrin.
The polyepichlorohydrins contemplated for use herein,
generally, have from about two to about thirty chlorohydrin
units in the polymer.
The halohydrin-terminated polyethers used herein
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are, gene~ally, polyoxyalkylene polyether polyols that have
been reacted with epihalohydrins to provide halohydrin-
terminated polyethers. They are, preferably, of the formula:
OH Z OH
XCH21HCH2- ~OCHCH2 )m OcH2~HcH2x
- where X is halogen, m is an integer from about 2 to about 100
and Z is, preferably, hydrogen, methyl or ethyl.
Conventionally, these products are prepared by
reacting a halohydrin with a polye!ther polyol. Generally,
the polyether polyols, as contemplated for use herein, comprise
an alkylene oxide adduct of a polyhydric alcohol. Examples
of such compounds include the ethylene oxide and/or propylene
- oxide adducts of polyhydroxy compounds, such as glycols, triols,
tetrols and the like.
Representive polyhydroxy compounds include ethylene
glycol, propylene glycol, glycerol, trimethylopropane,
erythritol, penetraerythritol, and the like as well as mixtures
thereof. The compounds being well documented in the art.
Other useful oxides include 1,2-butylene oxide;
2,3-butylene oxide as well as other oxirane compounds. Such
compounds are well known to the skilled artisan.
In practicing the present invention the preferred
alkylene oxides are ethylene oxide and propylene oxide.
Where used, any desired proportional mixture of
oligomer and polyether can be used. However, it is contemplated
that no greater than a 1:1 molar ratio of oligomer to poly-
ether be used. Yet, 100% of polyethers can be the reactant,
if desired.
As heretofore noted, the present polyamines are
prepared by reaction the oligomer or oligomer and polyether
mixture with a primary amine. Any primary amine can be
utilized to prepare the polyamines hereof. Thus, linear or
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branched alkyl amines having one reactive hYd~Qgen site
attached to the nitrogen group can be used. ~lthough any
length alkyl chain can be used, preferably, the alkyl amlne
is a Cl to C4 alkyl amine, such as, methyl amine, ethyl
amine, n-propyl amine, n-butyl amine, i-propyl amine and the
like can be used herein.
Substituted amines can be used herein as long as
the substituents are not reactive with the chlorine atoms
of the oligomer and/or polyether.
In practicing the present invention, the preferred ~-
amine is isopropylamine.
The polyamines hereof, which are coupled polymers,
can be used directly such as a flame retardant, curing agent,
cross-linking agent or the like. However, the primary utility
of the present polyamines is derived from the subsequent or
further reaction thereof with either primary, secondary or
tertiary amines. Such further reaction replaces the halo-
alkyl group halogen atom with an amine group to provide a
highly functional intermediate useful for preparing paper
additives such as drainage aids; wet and dry strength additives, ~ ~-
and the like. Other uses are those conventionally denoted for
polyamlnes. Useful primary, secondary and tertiary rPactants
include mono- and polyamines well-known to the skilled artisan.
For a more complete understanding of the present
invention reference is made to the following examples thereof.
In the examples, which are illustrative and not limitative
of the invention, all parts are by weight absent contrary
indications.
EXAMPLE I
This example represents the preparation of a polyamine
in accordance herewith from a epihalohydrin polyether.
Into a reaction vessel equipped with reflux condenser,
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heating means, agitation means, addition funnel and thermometer
was charged six hundred and seventy parts (1 mole) of a
halohydrin adduct of an alkoxylated polyhydroxy compound.
The adduct consisted essentially of an epichlorohydrin adduct
of a propoxylated propylene glycol having a molecular weight
of about 400. Under a nitrogen blanket, the polyether was
heated to 30C and maintained thereto while two hundred and
thirty-six parts (4 moles) of isopropylamine was added thereto
over a minute period. The mixture was heated, with stirring,
to 60C and maintained there at to effectuate reaction. Some
amine was removed to eliminate excess. After the reaction was
completed one hundred and sixty parts (2 moles) of 50% NaOH
was added to the vessel to neutralize the amine hydrochloride.
Excess amine was stripped off at 112C and 4 torr. The
product was taken up in methanol and sodium chloride was
filtered off, followed by stripping off of methanol. A yield
of 659.4 parts of a viscous product was obtained. The product
had a 3.5% amino nitrogen content corresponding to an 82.5%
conversion of chlorohydrin group.
EXAMPLE II
Using equipment similar to that described in Example
I, under a nitrogen blanket 1,435 parts (2.5 moles) of
hexaepichlorohydrin was charged to the vessel ànd heated to
60C. With stirring and maintenance of the blanket 295 parts
(5 moles) of isopropylamine was added thereto. During the
addition, which lasted fifty-five minutes, the temperature
was maintained at 60C.
After the addition was completed, the reaction
temperature was maintained thereat for thirty-five minutes.
Then, the temperature was raised to 116C at which an exotherm
occurred raising the temperature in the vessel to 128C. A
cooling both was applied to reduce the temperature. After
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an additional seventy-five minutes reactio~ time a-t a temperature
of between 107 to 125C reflux subsided. Volatiles were,
then, stripped up to 128C at 4 torr. Six parts of volatiles
were removed and 1,720 parts of a viscous, clear amber product
were recovered.
EXAMPLE III
Into a three-liter flask equipped with agitation
means, reflux condenser, addition funnels, heating means and
thermometer was charged 1,435 parts (2.5 moles) of hexaepichloro-
hydrin. The hexaepichlorohydrin was heated to 60C and 147.5
parts (2.5 moles) of isopropylamine was added thereto over
a seventy-six minute period.
After the addition was completed, the reactants were
further reacted at 60C for an additional forty-five minutes
while agitation was maintained.
After the reaction was completed, a pH meter was
placed in the flask and B00 parts of 25% NaOH (5 moles) was
added thereto over a two hundred and five minute period. The
initial pH was 6.74 and the final p~ was 9.55.
Twenty parts of water was then added to the vessel
to promote layer separation and after standing for fifteen
minutes the upper aqueous layer was decanted. The crude
product was washed with 2,210 parts of water. The crude wet
product, which yielded 2,502 parts thereof, was stripped
- up to a temperature of 11C at 4 ml. A yield of 1427 parts -
of a light amber viscous product was, thus, obtained.
EXAMPLE IV
This example illustrates the utility of the present
polyamines as well as the further reaction thereof with a
polyamine.
Into a one-liter flask equipped with heating means,
agitation means, thermometer and additional funnel was added
111~199
252 parts (4.2 moles) of ethylene diamine. The diamine was
heated to 118C and maintained thereat. At a reaction tempera-
ture ranging between 116C and 130C was added 170 parts of the
polyamine of Example II hereof. The addition took place over
a 175 minute period. The polyamine had previously been heated
to 80C to reduce its viscosity.
After the addition was completed, the reactants
were stirred for an additional hour at the reaction temperature.
After standing for about fourteen hours, the product was
stripped up to 133C at 5 torr. A yield of 180 parts of
distillate was recovered. Thus, a yeild of 242 parts of
stripped product was obtained. The stripped product was
diluted with 161 parts of water to provide 403 parts of
60% polyamine in the hydrochloride form.
Into a one-liter flask was combin3d 134 parts of
the hydrochloride solution, 94 parts of water and 40 parts
of 50% NaOH. These ingredients were then heated to 98 to 99C
in the flask. Then, 151 parts of a 30% solution of a 670
molecular weight epichlorohydrin adduct of a 400 molecular
weight propoxylated propylene glycol polyol was added to the
flask at 100C over a 160 minute period. The addition was
halted when a neargel state was reached.
The resulting product had a viscosity, as measured
by a No. 4 Ford cup at 250C, of 57 seconds. The product
evidenced superior properties when evaluated as a paper
pulp drainage aid using the Canadian Freeness drainage test.
Having, thus, described the invention what is
claimed is:
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