Note: Descriptions are shown in the official language in which they were submitted.
~ ~5~693
BACKGROUND OF THE INVENTION
.
Polyepihalohydrin polymers, particularly polyepi- -
chlorohydrin polymers, are known to react with tertiary ;~
alkylamines to ~orm quaternary ammonium salt adducts (see
U.S. Patents 3,320,317 and 3,428,680). These quaternized
polymers are employed as flocculating agents, antibacterial
agents, antistatic agents, emulsifying agents, dispersants,
and the like. The quaternized polymers may also be used as
thickening agents, but they are inferior to known agents
such as sodium alginate, carboxymethyl cellulose, and
particularly the polyacrylic acid salts. Because of their
low thickening efficiency these quaternized polymers are not
preferred as thickening agents.
It is also known to quaternize low molecular weight
polyepihalohydrins with alkanolamines. For example,
Austrian Patent 213,383 and U.S. Patent 3,674~725 teach
quaternization of polyepihalohydrins having upper molecular ;
welghts of 25,000 and 100~000, respectivel~, with various
- amines such as N,N-dimethylethanolamine and N,N-dimethyl-
amino-2,3-propanediol. U.S. Patent 3,640,766 teaches
quaternization o~ polyepichlorohydrin having a molecular
weight from about 750 to 300,000, preferabl~ from 2,000 to
150,000, with various amines. The reactants are simply
mixed, coated on paper, and "dried" or "conditioned",
e.g. with radiant energy ~rom heat l~mps, to form an
electroconductive product. ~ow molecular weight epihalo- ;
hydrin polymers are required in the three patents ~ust
described9 and only quaternization, not crosslinking, is
suggested. These quaternized, water-soluble, low molecular
weight polyepihalohydrin-alkanolamine compositions disclosed
by the prior art are poor water thickening agents. A new,
effective water thickening agent is desired.
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~596~3 ~ :
SUMMARY OF THE INVENTION
Polyepihalohydrin polymers having high molecular
weights from about 350,000 to about 2,000,000 are both
quaternized and lightly crosslinked with N,N-dimethylethanol-
amine. The quaternized, lightly crosslinked polymers areexcellent thickening agents for water and water-based compo-
sitions.
DETAILED DESCRIPTION
hpihalohydrin pol~mers suitable for use in this
invention have high molecular weights from about 350,000
to about 2,0009000, more preferably ~rom about ~00,000 to
about 13500,000. Excellent results were obtained at a
molecular weight of about 500,000. The epihalohydrin
polymers may be homopolymers or copolymers, more pre~erably
homopolymers. The epihalohydrin polymers contain polymerized
therein at least about 80% by weight o~ at least one epihalo-
hydrin selected ~rom the group consisting of epichloroh~drin
and epibromohydrin. Excellent results were obtained with ~-
epichlorohydrin. Suitable epihalohydrin polymers ~or use
in this invention include the amorphous polymers described
in U.S. Patent 3,158,580.
The epihalohydrin polymers described hereto~ore may
contain copolymerized therein up to about 20% by welght, more
preferably up to about 10% by weight, of at least one other
oxirane monomer Suitable oxirane comonomers include
(a) epifluoroh~drin and epiiodohydrin, (b) glycidyl ethers
and haloalkyl glycidyl ethers such as methyl glycidyl ether,
ethyl glycidyl ether, methylethyl glycidyl ether, bu~yl
glycidyl ether, n-hexyl glycidyl ether, phenyl glycidyl ether,
3 allyl glycidyl ether, 232-bis(chloromethyl)ethyl glycidyl
ether, 2-chloroethyl glycidyl ether, 2-bromoethyl glycidyl
ether, 2-chloro-1-methylethyl glycidyl ether, 2,2,2-tris
.
....
~Cl 59693
(chloromethyl)ethyl glycidyl ether, and the like; (c) alkylene
oxides and haloalkylene oxides such as ethylene oxide,
propylene oxide, cis- and trans- but pre~erably cis-butene-2
oxide~ butene-l epoxide, cis- and trans-pentene-2-oxide3
cis- and trans-hexene-2-oxide, cis- and trans-hexene-3-oxide,
cyclohexene oxide, 1,2-dichloro-3,4-epoxybutane, l-chloro-
3,4-epoxybutane, 1-chloro-4,5-epoxypentane, 1,1-dichloro-2,3-
epoxypropane, l,l,1-trichloro-2,3-epoxypropane, l~ tri-
chloro-3,4-epoxybutane, 1,1,1-trifluoro-2~3-epoxypropane,
l,l-bis(chloromethyl)ethylene oxide~ 3-chloro-2-methyl-1,2-
epoxypropane, cis- and trans-1,4-dichloro-2,3-epoxybutane,
and the like; (d) glycidyl acrylate and glycidyl methacrylate;
and (e) phenyl alkylene oxides such as styrene oxide, and
the like.
More preferred oxirane comonomers are alkylene i~
oxides containing from 2 to 8 carbon atoms, such as ethylene
oxide, propylene oxide, cis- and trans- but pre~erably cis-
butene-2-oxide, butene-l epoxide, cis- and trans-pentene-2
oxide, cis- and trans-hexe~e-2 oxide, cls- and trans-hexene-
3 oxide, c~clohexene oxide, and the like. Ethylene oxide
and propylene oxide are even more preferred comonomers.
Excellent results may be obtained with propylene oxide. `;
The epihalohydrin polymers described heretofore
are both quaternized and lightly crosslinked with N,N-di-
methylethanolamine. N~N-dlmethylethanolamine is (1) sterically
suitable for quaternization and crosslinking, (2) tertiary
and ~3) monohydroxylated. Other alkànolamines are unsuitable
for use in this invention~ since they are (1) more sterically
hindered, (2) nontertlary in nature, and/or (3) polyhydroxyl-
ated. Such unsuitable alkanolamines include N,N-diethyl-
ethanolamine (too sterically hindered and therefore unreactive),
N-methyldiethanolamine (dihydroxylated - produces too highly
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l~)S96~3
.
a crossllnked product when reacted with an eplhalohydrin
polymer), 2 ~ethylamino)~thanol (nontertiary and unreactive),
and the like. The N,N-dimethylethanolamine is used at a
level of at least about 0.5 mole up to about 25 moles and ~;
more per mole equivalent of halogen initially present in
the epihalohydrin polymer. Excellent results may be obtained
- at a level of at least about 1 mole up to about 15 moles of
N,N-dimethylethanolamine per mole equivalent of halogen. A
level of about 2 moles per mole equivalent of halogen provides
good results. Use of over about 2 moles N,N-dimethylethanol-
amine per mole equivalent of halogen is not necessary to
achieve satisfactory quaternization and crosslinking.
The quaternization and crosslinking may be effected
at a temperature from about 50C. to about 120C., more
preferably from about 80C. to about 110~C. Below about
50C. the reaction 1s so slow as to be impractical. At
temperatures above about 120C. the polymer may degrade.
The reactlon is generally performed at atmospheric pressure
or in a pressure reactor under autogenous pressure. Reaction
time may be from about 1 to about 48 hours, more often from
about 2 to about 10 hours. The reaction is preferabl~
conducted in an inert atmosphere such as nitrogen or the like.
The reaction may be conducted in bulk using an
excess of N,N-dimethylethanolamine, i.e. up to about 25 mo'es
and more of N,N-dimethylethanolamine per mole equivalent of -
halogen initially present in the epihalohydrin polymer.
Alternatively, the reaction may be performed in a diluent.
Shorter reaction times are obtained if the reaction is
performed as a bulk process rather than in a diluent, and
bulk reaction is therefore preferred.
Suitable diluents are those which are inert in the
reaction mixture. Suitable diluents include (a) water and
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5~693
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lower alkanols containing 1 to 10 carbon atoms, more prefer-
ably 1 to 6 carbon atoms such as methanol, ethanol, n-
propanol~ isopropanol, sec-butanol, and the like; (b) lower
ketones containing 2 to 10 carbon atoms, more preferably 2
to 6 carbon atoms such as acetone, methylethylketone, methyl-
isobutylketone, and the like, (c) ethers containing 4 to 8
carbon atoms, such as tetrahydrofuran, dioxane, and the
like; (d) alkanes and cycloalkanes containing 5 to 10 carbon ;
atoms, such as pentane, hexane, heptane, cyclohexane, and
the like; (e) benzene and benzene derivatives containing 6 -
to 10 carbon atoms, such as toluene, xylene, mesitylene, ;
and the like; and (f) other diluents such as dimethylformamide,
dimethylsulfoxide, and the like. More preferred diluents
: : .
include dimethylformamide and dimethylsulfoxide.
A quaternized, lightly crosslinked polymer of this
invention may have at least about 20%, more preferably at
least about 50%, of the halogen groups present reacted with
N,N-dimethylethanolamine to form quaternar~ salt structural
units in the polymer. Each unit may have the following `
formula: ;
_ _ ,, . '
~CH2-CH-O~ ~: '
, CE2
H3C-N+-CH3 C1-
CH2
CH2
_ OH _ -
At least about 0.5%, more preferably at least about 1%, of
the above quaternary salt structural units may be reacted
further through free hydroxyl groups with available polymerlc
halogen groups to form quaternary crosslinks. The latter
reaction is both surprising and unexpected, and each
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. ~Sg6~3
quaternary crosslink may have the ~ollowing formula:
_ _
CH2-~H-
CH2
3 , 3 Cl-
CH2
CH2
,0 .,
CH2
_~_O-CH-cH2-~-
The quaternized~ cro~slinked epihalohydrin polymer
is often insoluble in the reaction diluents and separates
from them upon ~ormation. If it remains in solution, the
polymer may be isolated by direct drying, e.g. in a vacuum
oven at 50 - 80F. and 0.1 torr pressure. Alternatively,
the polymer may be isolated by coagulation using an alcohol,
ether, ketone, or the like. The coagulated polymer may be
washed using an alcohol, ether, ketone,or the like, to puri~y
it and then vacuum dried, e.g. at 50 - 80C. and 0.1 torr
pressure. The mQterial is hygroscopic and should be stored
~ree from moisture.
The ~uaternized~ crosslinked epihalohydrin polymer
is an excellent cationic thickening agent. The polymer may be
used as a thickening agent at a level from about 0.05 part
to about 5 parts by weight per 100 parts by weight of water
or solvent. A more preferred level is from about 0.1 part
to about 3 parts by weight thickening agent per 100 parts
by weight of water or solvent. The resulting thickened
composltions have good stability and show no evidence of
supporting growth of fungi or bacteria. Typicall~, the t
thickened compositions are smooth and transparent in a pH
range from about 4 to about 12.
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~596~3
Viscosity of the thickened compositions varies
according to concentration o~ the quaternized, crosslinked
epihalohydrin polymer in water or solvent3 the amount o~
N,N-dimethylethanolamlne reacted, composition o~ the epihalo-
hydrin polymer backbone, and other ~actors such as temperature,
presence o~ ions in the water~ and the like. However
thickened compositions having viscosities (at a 1~ b~ weight
concentration of thickening agent) o~ over 500 centipoise,
and up to and over 15,000 centipoise are prepared readily~
viscosity being measured at 27C. using a Brookfield Model
RVT Viscometer, with ~pindle numbers and velocities varying
according to the viscosity measured.
Many types o~ additive ingredients may be used if
desired together with a novel thickening agent o~ this
invention. Such additives include pigments and colorants;
fillers such as silicas~ carbonates, and the like; polymeric
resins and plasticizers; perfumes and fragrances; bactericidal
and fungicldal agents, and the like.
The thickened compositions o~ this invention have
excellent yield values, i.e. initial resistance to flow
until a minimum shear stress is applied. This property
makes the thickened compositions use~ul for suspendlng heavy
ob~ects or ~or holding down light ob~ects. At lower concen-
trations of the thickening agent o~ this invention, the
thickened or gelled state may be broken by additlon of a
salt such as sodium chloride, calclum chloride, or the like.
The thickened or gelled state may also be broken by additlon
o~ a strong acid or base such as hydrochlorlc acid, sodlum
hydroxide, or the like.
The ~ollowing examples illustrate the present
invent~on more ~ully.
~9693
EXAMPLE 1
Example 1 demonstrates preparation of a novel
thickening agent of this invention. An`epichlorohydrin
homopolymer was used having a raw polymer Mooney viscosity
of about 65 (ML ~ 4 at 212F.), a specific gravity of about
1.36, a molecular weight of about 500,000, and a chlorine
content of about 38~ by weight. N,N-dimethylethanolamine
was used having a purity of about 99~ by weight.
A l-liter, 3-neck, round-bottomed flask reactor~
a stirrer and flask adapter, a thermometer and flask adapter,
and a reflux condenser were well-cleaned prior to the experi-
ment with soap and water, followed by an acetone rinse and
flushed with nitrogen until dry. An electric heating man-tle
was used to heat the reaction vessel. A dry nitrogen
atmosphere was maintained in the reactor. 300 ml. (286
grams) N,N-dimethylethanolamine was charged to the reactor
which was equipped with stirrer and thermometer. 25 grams
of finely chopped homopolymer was charged to the reactor.
Thus, about 3.21 moles N,N-dimethylethanolamine was used
~or 0.26 mole equivalents o~ chlorine originally present in
the epichlorohydrin homopolymer, i.e. a molar ratio of about
12 moles N,N-dimeth~ethanolamine per mole equivalent o~
chlorine.
The heating mantle was turned on, and the reactants
were heated to about 110C. with stirring. After about 3.5
hours, 50 ml. of distilled water was added to prevent the
polymer from settling out of solution. About 5 hours after
reaction began, another 50 ml. portion o~ distilled water
was added for the same purpose. After a total reaction time
o~ about 6 hours, the reaction mixture was cooled to about
30C. 400 ml. of isopropanol was added to the reactants with
stirring in order to precipitate the polymer. The polymer
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1~596~3
precipitated as a single, white, slightly sticky lump.
The lump was washed four times, each time with a fresh 300 ml
portion of isopropanol. The washed polymer was dried for about
24 hours in a vacuum oven at 40 - 50C and 0.1 torr.
The final product was 37.0 grams of a white, flaky
solid. The produ~t was effectively 66~o quaternized and lightly
crosslinked. The polymer was found to be hygroscopic and was
stored free from moisture.
EXAMPLES 2 - 8
l~ The quaternized, crosslinked epichlorohydrin polymer
prepared in Example l was evaluated as a thickening agent for
water. The polymer~ in powder form, was added in small portions
to the water while agitating it using a spatula. Several levels
of polymer and water were evaluated. Ultra-high shear mixing
may cause polymer chain ~racture and permanent viscosity loss.
This explanation may account, at least in part, Por the viscos-
ity difference between examples 4 and 5. Data is set forth in
Table I.
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The data in Table II shows that good thickening is ;
achieved at low levels of the novel thickening agent. All of the
thickened compositions were transparent, colorless and had a
buttery consistency.
For comparison, thickened compositions were prepared
using known thickening agents and techniques known to the art.
The viscosity measurements were made using a Brookfield Model
~VT Viscometer and spindle #5 at 20 rpm and 27C. In each of
Examples 6 - 8, a 1% by weight concentration of agent in water
was used. Data is set forth in Table II.
TABLE II
Thickening Agentiscosity(cps)
6 Gum Tragacanth 300
7 Sodium Alginate 2,000
8 Carboxymethyl Cellulose 3,000
The data in Tables I and II together shows that the
novel polymers of this invention yield thickened compositions
having viscosities far superior to viscosities obtained using
the known thickening agents.
EXAMPLE 9
Example 9 demonstrates that N,N diethylethanolamine
is unsuitable for preparing the novel polymeric thickening agents
of this invention. An epichlorohydrin homopolymer was used
having a raw polymer Mooney v~scosity of about 65 (ML + 4 ~ 212F),
a specific gravity of about 1.36 (ML + 4 ~ 212F), a molecular
weight of about 500,000, and a chlorine content of about 38% by
weight. N,N-diethylethanolamine was used having a purity greater
than 99% by weight.
A 500 ml, 3-neck, round-bottomed flask reactor, a
stirrer and flask adapter, a thermometer and flask adapter,
and a reflux condenser were well-cleaned prior to the experiment
with soap and water, ~ollowed by an acetone rinse and flushed
-12- ;
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:105~1693
with nitrogen until dry. An electric heating mantle was used
to heat the reaction vessel.~ A dry nitrogen atmosphere was
maintained in the reactor. 300 ml (265 grams) of N,N-diethyl-
ethi~nolamine was charged to the reactor, which was equipped
with stirrer and thermometer. 25 grams of finely chopped
homopolymer was charged to the reactor. Thus about 2.26 mole
N,N-diethylethanolamine was used for 0.26 mole equivalents
of chlorine originally present in the epichlorohydrin homo- `
polymer, i.e. a molar ratio of about 8.7 moles N,N-diethyleth~ -
olamine per mole equivalent of chlorine.
The mixture was stirred for 3 hours and then allowed
to stand for 16 hours. The homopolymer did not dissolve.
The heating mantle therea~ter was turned on, and the reactants
were heated to 115C with stirring. About 8 hours after heating
began the reaction mixture was cooled to 30C and allowed to ji;
stand for 16 hours. The mixture was then stirred and heated at --
115C for another 8 hours and therea~ter cooled to about 30C.
The reaction product was precipitated with 500 ml heptane.
The precipitate was washed twice with 500 ml portions of heptane.
The washed polymer was dried for about 23 hours in a vacuum oven
at about 60C and 0.1 torr. The dried product weighed 24.8
grams and showed virtually no tendency to swell in water, making
it a poor thicke~ing agent.
EXAMPLE 10
Example 10 demonstrates that N-methyldiethanolamine
is unsuitable for preparing the novel polymeric thickening
agents of this invention. An epichlorohydrin homopolymer was
used having a raw polymer Mooney viscosity of about 65
(ML + 4 ~ 212F), a specific gravity of about 1.36 (ML + 4 ~ 212F),
a molecular weight of about 500,000, and a chlorine content of
about 38% by weight. N-methyldiethanolamine was used having a
purity of about 97% by weight.
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lC~S9~93
A 500 ml, 3-neck, round-bottomed flask reac-tor, a
stirrer and flask adapter~ a thermometer and flask adapter,
and a reflux condenser were well-cleaned prior to the experiment
with soap and water, followed by an acetone rinse and flushed
with nitrogen until dry. An electric heating mantle was used
to heat the reaction vessel. A dry nitrogen atmosphere was
maintained in the reactor. 300 ml (311 grams) N-methyldiethanol-
amine was charged to the reactor which was equipped with 2
stirrer and thermometer. 25 grams of finely chopped homopolymer
was charged to the reactor. Thus about 2.61 moles N-methyl-
diethanolamine was used for 0.26 mole equivalents of chlorine
originally present in the epichlorohydrin homopolymer, i.e.,
a molar ratio of about 10 moles N-methyldiethanolamine per mole
equivalent of chlorine.
The mixture was stirred ~or 8 hours and thereafter -;
allowed to stand ~or 16 hours. The heating mantle thereafter
was turned on, and the reactants were heated to 115C with
stirring. About 8 hours after heating began the reaction ;
mixture was cooled to about 30C. The reaction product was
precipitated with a mixture of 1000 ml acetone and 1000 ml
heptane. The precipitate was washed three times, first with a
mixture of 500 ml acetone and 1000 ml heptane, and thereafter
with two 1000 ml heptane portions. The washed polym~r w~s
dried for about 92 hours in a vacuum oven at about 60C and
0.1 torr. 46 grams of dried product was soaked in 1800 ml
of distilled water for 72 hours, the yellowish wash water de-
canted and discarded, and the product soaked in another
1800 ml portion o~ distilled water for 4 hours. The wash
water was decanted and discarded and the product was vacuum
dried for about 65 hours at about 75C and 0.1 torr.
The final product was 26.2 grams of a transparent,
light amber-colored solid. The polymer appeared to be highly
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1~5g6~3
crosslinked and showed poor ability to swell in water. Thus
N-methyldiethanolamine appears to be unsuitable for preparing
the novel polymeric thickening agents of this invention.
The quaternized, lightly crosslinked epihalohydrin
polymers of this invention may be used to thicken latices and
paints including printing pastes and printing inks; to prepare
solvent gels such as cleansing gels, paint and varnish strippers
and the like, to prepare shampoos, hair gels and other hair
grooming aids; and to prepare a multitude of other products
which are convenient and/or aesthetically desirable in thickened, -
gelled,paste or semi-solid form.
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