Note: Descriptions are shown in the official language in which they were submitted.
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BACKGROUND OF THE INVENTION
1. Field of the Invention-
The present invention pertains to polyalkylene-
polyamine polyethers. More particularly, the present invention
pertains to processes for the preparation of such polyethers.
Even more particularly, the present invention concern
processes for the preparation of such polyethers by the
reaction of an alkylenepolyamine and an epihalohydrin.
2. Prior Art-
The preparation of condensation products by the
reaction of an amine and an epihalohydrin is well documented
in the prior art. Within this broad class of compounds
numerous sub-classes have been denoted. Thus, the reaction
of alkylamines and epihalohydrins has been documented
numerous times.
Generally, this latter sub-class of compounds have
been developed to enhance the properties of paper, to provide
improved drainage aids and so forth.
As the art has developed, there has been an
increasing amount of activity toward the development of
polyalkylenepolyamine polyethers as wet and dry strength
paper additives; drainage aids; flocculants and the like.
Furthermore, such compounds often define intermediate for
the preparation of other compounds, such as surfactants,
ion exchange resins and the like. In preparing such
polyethers, normally, an alkylamine is reacted with a
polyhalohydrin under controlled conditions. The controlled
conditions are necessary in order to preclude and prevent
cross-linking of the reactants. Cross-linking provides a
water-in-soluble, gelled mass which is of substantially no
utulity. On the other hand, control of the reaction con-
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ditions provides water-soluble highly useful compounds.
Within the context of controlling the reaction
conditions, the art has taught maintaining a strict molar
ratio minimum. Falling below the minimum results in highly
cross-linked products. The art, also, teaches control of
temperatures and reaction times.
In United States Patent No. 3,746,678, there is
taught the reaction of ethylene diamine and polyepichlorohydrin.
The reference specifically discloses that at least about
three moles of polyamine be reacted per chlorine atom in the
chlorinated alkylene oxide polymer. The reference further
teaches that using a ratio of less than 3:1 is an inoperable
procedure.
As will subsequently be detailed, the present
invention provides a process whereby ratios of less than
3:1 can be utilized to prepare non-gelled polyalkylene
polyamine polyethers by the reaction of an alkylamine and
a polyhalohydrin.
STATEMENT OF RELEVANT ART
To the best of applicant's knowledge, the following
- is the most relevant prior art:
U.S. Patent No. 3,746,678
3,497,556
3,031,505
1,977,253
SU~ARY OF THE INVENTION
In general, in accordancewith the present invention,
water-soluble amine-derived polyethers are prepared by
xeacting an amine with a halogen-containing polymer of an
epihalohydrin in the presence of an organic solvent which
defines a diluent for the amine reactant. Specifically,
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the present invention enables the production of water-soluble
amine~derived polyethers with reduced molar quantities of
amine reactant.
In particular, the present invention provides a
method for preparing a water-soluble amine-derived polyether,
comprlsing:
reacting an amine with a halogen-containing polymer
of an epihalohydrin in the presence of a suitable solvent, and
wherein the ratio of moles of amine per available
halogen atom is less than 3:1.
Any amine can be used herein, such as, alkylamines,
polyalkylene polyamines, alkylenepolyamines, polyoxyalkylene
amines, cyclic amines, such as piperazine, and the like.
The halogenated epoxides used to carry out the
reaction are, preferably, the epihalohydrins, as noted.
Any solvent can be utilized herein which is non-
reactive with either of the reactants. Ordinarily, the
condensation reaction proceeds at high ~emperatures to
minimize cross-linking. Therefore, optimally, high boiling
point solvents, such as glycals and derivatives therof,
toluene, xylene and the like can be used herein.
In a preferred embodiment of the present invention,
ethylenediamine and polyepichlorohydrin and reacted in the
presence of an organic solvent in a ratio of less than
three moles of amine per chlorine atom in the alkylene
oxide polymer.
For a more complete understanding of the presen-t
invention reference is made to the following detailed
description and accompanying exemples.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Generally, and in accordance jwith the present inven-
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tion, there is provided a process for the production of
amine-based or derived polyethers, by reacting an amine and
a halogenated epoxide in the presence of an organic solvent.
More particularly, the present invention provides
a process for the preparation of a polyalkylene polyamine
polyether by the reaction of: (a) an alkylenepolyamine and
(b) a polyepihalohydrin in the presence of an organic
solvent.
The reaction is carried out at elevated temperatures.
Ordinarily, reactions of amines with halogen-containing
polyethers proceed at temperatures ranging from about 25C
to about 200C, at ambient pressures. The preferred tem-
perature range is 120C to ahout 180C since these elevated
temperatures result in rapid reactions of halogen and amine
groups. This minimizes and discourages cross-linking reactions.
Thus, the present invention, preferably, employs solvents
having boiling points of 120C and above. However, lower
boiling solvents can be used if the reaction is carried out
under superatmospheric pressures. Thus, in practicing the
present invention the one criticality which attaches to the
solvent is tha-t it be capable of withstanding the reaction
temperature.
The process of the present invention is particularly
adapted for preparing non-gelled polyamines from the reaction
of an alkylenediamine and a polyepihalohydrin at a less than
3:1 ratio, and as low as 2:1 or less, of amine to available
halogen atom in the epoxide. Although the present invention
is applicable to any epoxide-amine reaction, the process is,
as noted, eminently efficacious for the diamine polyepi-
chlorohydrin reaction.
Hence, in accordance herewith any amine, such asmonoalkylamines, alkylene polyamines, polyalkylenepolyamines,
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cyclic amines, and the like can be used herein. Representative
monalkylamines include methylamine, ethyl amine, propylamine,
i-propylamine, n-propylamine n-butylamine, i-butylamine,
t-butylamine and so forth. Representative alkylene polyamines
include ethylenediamine, propylenediamine, 1,2,3-triamino
propane, butylenediamine, triaminobutane and so forth.
~uitable polyalkylenepolyamines include diethylene triamine,
dipropylenetriamine, triethylenetetramine, and so forth.
Suitable cyclic amines are represented by piperazine and
the like. In addition to primary amines, secondary or
tertiary amines can be used if quaternary end products are
desired. Furthermore, the amine may be substituted or
unsubstituted. Where substituted, it is preferred, that
the substituent be non-reactive with either the solvent or
the halogenated epoxide.
As heretofore noted, and in accordance with the
preferred embodiment hereof, the amine most efficaciously
employed herein is an alkylenepolyamine, such as ethylene-
diamine. The other reactant used herein is a halogenated
polyether prepared from a halogenated epoxide. Representative
halogenated epoxides used as intermediates for the poly
haloethers include epichlorohydrin, epibromohydrin,
3-chloro-1,2-epoxy butane, 3-brome-1,2-epoxy butane,
l-chloro-2,3 epoxy butane and the like. Thus, halogen
substituents include chlorine, bromine, and iodine and
preferably chlorine, are useful herein.
In practicing the present invention, again, the
halogenated epoxide may be further substituted. However,
the substituent must be non-reactive with either the
amine or the solvent. Preferably, the epoxide is not
otherwise substituted. In carrying the present invention,
the preferred epoxide is an oligomer of epichlorohydrin, to
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wit, polyepichlorohydrin.
Polyepichlorohydrin is, of course, produced by
polymerizing epichlorohydrin by any well known method, such
as by reacting epichlorohydrin with water in the presence
of a Lewis acid catalyst.
The solvents utilized herein comprise any non-
reactive solvents which can withstand the elevated reaction
temperatures, i.e. > 100C. Thus, glycols, glycol ethers,
aromatic hydrocarbons and the like can be use~ herein.
Useful glycols include
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dietlly:!ene ~ co,, ~;)ropylene glyco~ and the ike. Suitable
glycol el;he-~s include monoethers, such as ethy]ene glycol
monobutyl etl.el-, d~elhylene g]ycol monoethyl ether and the lil~e,
polyethers such as diet~lylene glycol diethyl ether and the like.
Representative aromatic solvents are toluene, xy~ene and the
like. Any of the above-denoted solvents as well as mixtures
thereof are applicable to the present process.
In a preferred embodiment of the present invention,
propylene glycol is the preferred solvent.
The solvent is employed in any amount sufficient to
maintain the amine in solution therewithin.
In practicirlg the present invention, the amine is
admixed with the solvent and is heated to a temperature in
excess of 120C. Thereafter, the selected halogenated polyether
is added thereto and the reaction is carried out at a temperature
of about 150C for about one to twenty-four hours, depending on
the reactants.
In a preferred embodiment of the present invention,
the process hereof, as above noted, is used to prepare poly-
ethers from the reaction of polyepichlorohydrin and ethylene
diamine, in an organic solvent, at a ratio of less than 3 moles
of diamine per gram atom of chlorine. The reaction is carried
out within the parameters set forth above. The products are
non-gelled polyamines which are useful as intermediates for the
preparation of drainage aids~ as well as other products.
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~ polylmines prepared ln accordance herewith are
substan.iaLly llnear ~-tructures of the formula:
Y~C~æC ~ z~ S~C~2~oc~zC~c~2,y
wherein Y represents a polyamine function or an amine function,
H
and, prefe:~ably, ~12CH2CH2N and n ranges from about one to
thirty. I~ addition, there is some cross-linking due to the
intermolecular action of the diamine and the pendant chloro-
methyl groups. The present invention, as noted, minimizes the
cross-linking to provide the non-gelled products hereof.
For a more complete understanding of the present in-
vention reference is made to the following examples. In the
examples, which are to be construed as illustrative, rather
than limitative of the present invention, all parts are by weight,
absent indications to the contrary.
1~ EXAMPLE I
Into a reaction flask equipped with a stirrer,
thermometer, addition funnel and reflux condenser was charged
one hundred and eighty parts of ethylenediamine and one hundred
and eighty-four parts of propylene glycol. The solution was
r.eated to 118C and, then, one hundred and forty-three parts
of hexaepichlorohydrin was added thereto over about a one hour
per~od. ~uring this time the temperature in the flask was
allowed tG increase to 149C. The reaction was highly exothermic,
maintaining a rapid reflux of ethylenediamine.
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l~fter the additlon was completed the mixture in
the flask was stirred for about one hour at about 150C to
about l~O;'C, and, ~hen, left to stand for aoout fifteen hours.
Thereafter, excess diamine and solvent were stripped
from the flask at 1~2C and 10 torr. The product in the flask
(two hundred forty-three parts) was, then, diluted with one
hundred and sixty-two parts of water to provide four hundred
and five parts of a solution calculated as having 60~ polyamine
polyhydrochloride.
EXAMPLE II
Using apparatus of the type described in Example I,
one hundred and eighty parts of ehtylene diamine and five hun-
dred and forty parts propylene glycol were charged into the
~lask. The solution was stirred at 142C. Then, one hundred
thirty-eight and one-half parts of a thirty unit polyepi-
chlorohydrin oligomer was added thereto, with stirring. The
addition occurred over a ninety minute period during which time
the temperature in the flask rose to 157C.
After letting the product stand for a few hours,
excess diamine and solvent were stripped by distilling at a
- temperature of up to 150C and 5 torr. A yield of two hundred
fifty-eight and seven-të`nths of produ~t was obtained which was
diluted with one hundred and seventy-two parts of water to
give a ~0~ solution of polyamine polyhydrochloride.
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.'~nal~s s ~or amino nltrogen was 7.22~ corresponding
to 1.57 moles of et`riylenediamine reacting per available
chlorine atom. Theoretical calculations showed 1.5 moles of
diamine to react per atom of available chlorine.
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I~MPLI1 IIl
This example shows the results of carrying out the
reaction at too low of a temperature.
Using a flask equipped as described in Example I,
four hundred and eighty parts of ethylenediamine and nine
hundred and sixty parts of propylene glycol were charged to the
flask. The mixture was heated at 115C. Then, three hundred
and seventy-eight parts of decaepichlorohydrin was addea
thereto over a sixty-seven minute period at a temperature
fluctuating between li5C and 136C. After a fifteen minute post
reaction period, excess diamine and glycol solvent were stripped
off by distillation at a temperature of about 120C at 30-50
torr. The product gelled, due to the low reaction temperature.
_A~`IPIE IV
Example III was repeated, except that the amine-glycol
solution was heated to 155C and one hundred and eighty-nine
parts of the chlorohydrin was added thereto over a thirty minute
period. During this period, the temperature in the flask rose
to 170C. After the addition was completed the product was
allowed to stand for about twenty hours. Then, the excess glycol
and amine were stripped at 118 to 122C during which time the
pressure reduced from ~0 torr to 5 torr. A yield of three hundred
twenty and seven-tenths of product was obtained. The product
was then diluted with two hundred thir-teen and seven tenths of
water to provide a 60~ polyamine polyhydrochloride.
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[X~MPI.I V
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This example shows the preparation of a paper pulp
dra,nage aid from an lntermedlate prepared by the process of the
present invention.
Using the product of Example IV, one hundred parts
of the 60~ hydrochloride solution was diluted with ninety parts
of wa~er. Thirty parts of sodium hydroxide (50~) was added
thereto to neutralize the hydrochloride. This solution was,
- then, heated to 99C and one hundred and twenty-three and two-
tenths parts of a 20~ solution of a bio chlorohydrin ether
polyol was added thereto. The polyol comprised the reaction
product of epichlorohydrin and a ~00 molecular weight poly-
oxypropylene glycol prepared by the reaction of propylene oxide
and propylene glycol.
The resulting solution had a viscosity of 21.1 seconds
as determined by the Ford cup. Thus, an additional twelve and
eight-tenths parts of the polyol was added to the solution to
increase the Ford cup viscosity to 115 seconds. The, thus,
obtained three hundred and fifty-three parts of product was
evaluated as a drainage aid using the Canadian freeness procedure.
The product performed extremely well.
EXAMPLE VI
Using equipment similar to that described in Example
I, one hundred and eighty parts of ethylene diamine and three
I hundred and sixty parts of propylene glycol were added to the
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flasl; and heated -to 14~C. Thereaiter, one hundred and thirty-
nine parts of a twenty unit polyepichlorohydrin was added over
a ninety minute period at a temperature of 148C to 15~C.
After the addition was completed, excess diamine
and solvent were stripped off up to a temperature of 138C at
4 torr. ~. yield of two hundred and fifty-six and two-tenths of
product was obtained which was diluted to a 60~ polyamine poly-
hydrochloride solution with one hundred and seventy parts of
water.
This product was then reacted with the same polyol
and by the same procedure described in Example V. The product
was then tested as a drainage aid using the Canadian freeness
procedure. The product performed extremely well.
In each of the examples, a mole of amine to available
chlorine atoms ~atio of 2:1 was used.
In addition to their use as intermediates the products
produced hereb~ which are polyamine polyethers, are useful as
intermediates for preparing retention aids; dry and wet strength
paper additives; flocculants for metal aids and both industrial
and domestic sewage wastes, intermediates for preparing cationic
and amphoteric surfactants; intermediates for quaternary
amr.1onium salts for ion exchange resins, as well as other uses
evident to the skilled artisan.
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The use of the solvent process hereof enables the
reduction of the amount of expensive amine used resulting in
reduced costs and lower recovery costs.
~ Iaving, thus~ described the invention~ what is
claimed is:
