Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
10'.3Z738
Aldrich Case 25-31
This invention relates to novel aqueous suspensions or
dispersions which contain finely divided particles of a blend of
wax and a fatty acid or a blend of wax and an alkyl ketene dimer.
The novel aqueous suspensions are useful in the sizing of paper.
Aqueous dispersions of wax and their use in sizing paper
are known in the art. Such aqueous suspensions consist essenti-
ally of water, finely divided wax particles, and a dispersing
agent for the finely divided wax particles.
According to the invention there is provided an aqueous
dispersion of finely divided solid particles consisting essenti-
ally of, by weight,
i (A) from about 5% to about 50% of finely divided solid
., : particles, said solid particles being selected from the group
consisting of (1) a blend consisting essentially of, by weight,
from about 99% to about 93% of a wax selected from the group con- ~ -
sisting of petroleum waxes, synthetic hydrocarbon waxes, and mix-
tures thereof and from about 1% to about 7% of a C18 to C24 sat-
urated fatty acid, (2) a blend consisting essentially of, by
weight, from about 99.5% to about 75% of a wax selected from the
group consisting of petroleum waxes, synthetic hydrocarbon waxes,
and mixtures thereof and from about 0.5% to about 25% of at least
one alkyl ketene dimer having the formula ~RCH=C=O]2 where R is
an alkyl radical having 10 to about 20 carbon atoms, and (3) mix-
tures of (1) and (2),
(B) from about 0.5% to about 20% of water-soluble cation-
ic resin dispersing agent selected from the group consisting of
(i) a water-soluble polyaminopolyamide--epichlorohydrin
resin, - ?
(ii) a water-soluble alkylenepolyamine--epichlorohydrin
resin,
(iii) a water-soluble poly(diallylamine)--epichlorohydrin
resin, and
- (iv) mixtures of any two or more of (i), (ii), and (iii),
and
- 2 -
... . ,
.;, . , . ' - ! ,
10~3~73~
(C) water to 100%.
A preferred blend (1) is a blend consisting essentially
of, by weight, from about 99% to about 95% of a wax selected from
the group consisting of petroleum waxes, synthetic hydrocarbon
waxes, and mixtures thereof and from about 1% to about 5% of a
C18 to C24 saturated fatty acid. A preferred blend (2) is a blend
consisting essentially of, by weight, from about 99% to about 90%
of a wax selected from the group consisting of petroleum waxes,
synthetic hydrocarbon waxes, and mixtures thereof, and from about
1% to about 10% of at least one alkyl ketene dimer.
A suitable polyethylene wax for use in the dispersion ac-
cording to the invention will have a molecular weight of from
about 1500 to about 10,000 and a density of from about 0.91 to
about 0.94.
i The C18-C24 saturated fatty acid component of the disper-
; sion according to the invention may be, for example, stearic acid,
nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic
acid, tricosanoic acid, and tetracosanoic acid. The fatty acid
~ component can consist of mixtures of two or more of the saturated
,; 20 acids. Up to about 50% of the C18-C24 saturated acid can be sub-
`d~ stituted with saturated C14-C16 fatty acids such as myristic
acid, pentadecanoic acid and palmitic acid.
The alkyl ketene dimers which are used as components of
the blend are dimers having the formula [RCH=C=O]2 where R is an
alkyl radical (saturated or unsaturated) having 10 to about 20
~j carbon atoms. In naming ketene dimers, the radical "R" is named
j followed by "ketene dimer". The decyl ketene dimer is
[CloH21~CH=C=O]2. Examples of ketene dimers include decyl,
dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, and
tetracosyl, as well as the ketene dimers prepared from palmit-
-~ oleic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic
acid, myristoleic acid, and eleostearic acid. Mixtures of any of
the above-named fatty acids with each other may also be used. A
fatty acid fractiGn obtained from the fractional distillation of
-- 3 --
.
10~738
call oil, whlch is predominantly oleic acid and linoleic acid, is
-~ an example of a fatty acid mixture.
The dispersing agents used to prepare the substantially
stable aqueous dispersions or suspensions of this invention are
cationic polymeric resinous materials that are water-soluble.
Particularly suitable dispersing agents are the cationic
thermosettable water-soluble aminopolyamide--epichlorohydrin res-
ins disclosed and described in U.S. patents 2,926,116 and
2,926,154. These resins are water-soluble polymeric reaction
..,~
products of epichlorohydrin and an aminopolyamide. The amino-
polyamide is derived by reaction of a dicarboxylic acid and a
polyalkylenepolyamine in a mole ratio of polyalkylenepolyamine to
dicarboxylic acid of from about 0.8:1 to about 1.4:1.
Particularly suitable dicarboxylic acids are diglycolic
~1 acid and saturated aliphatic dicarboxylic acids, containing from
3 through 10 carbon atoms such as malonic acid, succinic acid,
glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic
acid, and sebacic acid.
Other suitable dicarboxylic acids include terephthalic
acid, isophthalic acid, phthalic acid, maleic acid, fumaric acid,
itaconic acid, glutaconic acid, citraconic acid, and mesaconic
acid. ~-
The available anhydrides of the above acids can be used ~ s
in preparing the water-soluble aminopolyamide as well as the
esters of the acids. Mixtures of two or more dicarboxylic acids,
their anhydrides, and their esters can be used to prepare the
water-soluble aminopolyamides, if desired.
A number of polyalkylene polyamines, including poly-
ethylene polyamines, polypropylene polyamines, polybutylene poly- ~ ~-
amines and the like can be employed. Polyalkylene polyamines are
polyamines in which the nitrogen atoms are linked together by
groups of the formula ~CnH2n- where n is a small integer greater
than unity and the number of such groups in the molecule ranges
from two up to about eight. The nitrogen atoms can be attached
.,
~ - 4 -
~ .
lOg,4~738
co adjacent carbon atoms in the group -Cn~2 - or to carbon atom~
farther apart, but not to the same carbon atom. Polyamines such
as diethyle~etriamine, triethylenetetramine, tetraethylene-
pentamine, arld dipropylenetriamine, which can be obtained in
reasonably pure form are suitable for preparing water-soluble
aminopolyamides. Other polyalkylene polyamines that can be used
include methyl bis-(3-aminopropyl)amine; methyl bis-(2-aminoethyl)-
amine; and 4,7-dimethyltriethylenetetramine. Mixtures of poly-
alkylene polyamines can be used, if desired.
The spacing of an amino group on the aminopolyamide can
be increased if desired. This can be accomplished by substitut-
ing a diamine such as ethylenediamine, propylenediamine, hexa-
methylenediamine and the like for a portion of the polyalkylene
polyamine. For this purpose, up to about 80% of the polyalkylene
polyamine can be replaced by a molecularly equivalent amount of
:;~
diamine. Usually, a replacement of about 50% or less will be
adequate.
Temperatures employed for carrying out reaction between
the dicarboxylic acid and the polyalkylene polyamine can vary
from about 110C. to about 250C. or higher at atmospheric pres-
sure. For most purposes temperatures between about 160C. and
210C. are preferred. The time of reaction will usually vary
from about 1/2 hour to 2 hours. Reaction time varies inversely
with reaction temperatures employed.
In carrying out the reaction, it is preferred to use an
amount of dicarboxylic acid sufficient to react substantially
completely with the primary amine groups of the polyalkylene poly-
amine but insufficient to react with the secondary amine groups
and/or tertiary amine groups to any substantial extent. This will
usually require a mole ratio of polyalkylene polyamine to dicar-
boxylic acid of from about 0.9:1 to about 1.2:1. However, mole
ratios of from about 0.8:1 to about 1.4:1 can be used. The
aminopolyamide, derived as above described, is reacted with epi-
chlorohydrin at a temperature of from about 45C. to about 100C.,
5 --
.
`
- 10.'~:73~
and preferably between about 45C. and 70C., until the viscosity
of a 20% solids solution in water at 25C. has reached about C or
higher on the Gardner-Holdt scale. This reaction is preferably
carried out in aqueous solution to moderate the reaction. pH ad-
justment is usually not necessary. However, since the pH de-
creases during the polymerization phase of the reaction, it may
be desirable, in some cases, to add alkali to combine with at
least some of the acid formed. When the desired viscosity is
reached, water can be added to adjust the solids content of the
resin solution to a desired amount, usually from about 2~ to
about 50%.
In the aminopolyamide--epichlorohydrin reaction, satis-
factory results can be obtained utilizing from about 0.1 mole to
about 2 moles of epichlorohydrin for each secondary or tertiary
amine group of the aminopolyamide, and preferably from about 1
mole to about 1.5 moles of epichlorohydrin.
A monofunctional alkylating agent can be employed as an
additional reactant in carrying out the above reaction, if desired.
A monofunctional alkylating agent can be first reacted with the
aminopolyamide followed by reaction of the aminopolyamide--
alkylating agent reaction product with epichlorohydrin, or the
alkylating agent can be reacted with the aminopolyamide--epi-
chlorohydrin reaction product. Thus, for example, epichlorohydrin
can be added to an aqueous solution of the aminopolyamide at a
temperature from about 45C. to 55C. The reaction mixture is
then heated at a temperature from about 50C. to 100C., and
preferably from about 60C. to 80C., depending upon the rate of
reaction desired. After a suitable time at this temperature,
i.e., from about 10-100 minutes, and preferably until the viscos-
ity of an approximately 25% solids solution of the reaction mix-
ture at 25C. is from A to B on the Gardner-Holdt scale, at which
time most of the epoxy groups of the epichlorohydrin have reacted
with the amine groups of the aminopolyamide, a monofunctional
alkylating agent is added and the reaction mixture heated,
6 -
1C~'3Z73~
preferably at a t~mperature from about 60C. to about 80C.,
until the viscosity of an approximately 25% solids solution at
25C. is at least A and preferably at least B to C on the Gardner-
Holdt scale. The solids-viscosity relationship can be obtained
by direct reaction at the 25~ level followed by dilution to 25%
solids, or reaction at a lower level followed by concentration at
less than 40C. and under reduced pressure to 25% solids. Lower
alkyl esters of mineral acids such as the halides, sulfates and
phosphates, substituted alkyl halides, and the like are suitable
monofunctional alkylating agents. Illustrative of the compounds
` which can be used are dimethyl, diethyl and dipropyl sulfate;
` methyl chloride; methyl iodide; ethyl iodide; methyl bromide;
~ propyl bromide; and the mono-, di- or tri-methyl, ethyl and propyl
`~'t phosphates. Certain aromatic compounds such as benzyl chloride
and methyl p-toluene sulfonate can be used. From about 0.1 mole
to about 0.9 mole of monofunctional alkylating agent for each
, . .
amine group can be used.
In the examples that follow, all parts and percentages
are by weight unless otherwise specified. Sizing results are set
forth in some of the examples. Sizing results are determined on
the Hercules Sizing Tester. The sizing test determines the re-
sistance of a sized sheet of paper to penetration by No. 2 Test
Solution, (an aqueous solution of, by weight, 1.0% formic acid and
.~
~; 1.25% naphthol Green B). The time necessary for ink penetration
to reduce light reflectance to 80% of the sheet's initial value is
used to represent the degree of sizing.
The following example is illustrative of the preparation
of an aminopolyamide-~epichlorohydrin resin that is particularly
useful as a cationic resin dispersing agent for use in this
invention.
Example 1
An aminopolyamide is formed by adding 219.3 parts of
adipic acid slowly, with stirring, to 151.3 parts of diethylene-
triamine in a flask fitted with a stirrer and a condenser for
,~ - . . . . .
1()9Z738
collecting water distillate. The reaction mixture is stirred and
heated at 170-180C. under a nitrogen blanket until amide forma-
tion is complete. After air cooling to approximately 140C., hot
water is added with stirring to provide a 50% solids solution of
polyamide resin with an intrinsic viscosity of 0.140 measured by
using a 2% solution in 1 N NH4Cl. An epichlorohydrin derivative
of the aminopolyamide is prepared by adding about 110.25 parts of
water to about 50 parts of the 50% solids solution and then adding
14.4 parts (0.157 mole) of epichlorohydrin. The reaction mixture
is heated at 70C. with stirring under a reflux condenser until
the Gardner-Holdt viscosity attains a value of E to F. The reac-
;/` tion mixture is diluted with water to a solids content of about
12.5~.
Other suitable dispersing agents that can be used in thisinvention are the water-soluble alkylene polyamine--epichlorohydrin
resins which are water-soluble polymeric reaction products of epi-
chlorohydrin and an alkylene polyamine.
Alkylene polyamines which can be reacted with epichloro-
hydrin have the formula H2N(CnH2nNH)XH wherein n is an integer 2 ;
through 8 and x is an integer 1 or more, preferably 1 through 6.
~' Examples of such alkylene polyamines are the alkylene diamines - -
. ~ - . .
such as ethylenediamine; propylene diamine-1,2; propylene diamine- -
1,3; tetramethylenediamine; and hexamethylenediamine. The poly-
, alkylene polyamines such as the polyethylene polyamines, polypro-
pylene polyamines, polybutylene polyamines and the like are ex-
amples of alkylene polyamines that can be used. Specific examples
of these polyalkylene polyamines include diethylenetriamine, tri-
ethylenetetramine, tetraethylenepentamine, and dipropylenetriamine.
Other polyalkylene polyamines that can be used include methyl bis-
(3-aminopropyl)amine; methyl bis(2-aminoethyl)amine; and 4,7-
dimethyltriethylenetetramine. Mixtures of alkylene polyamines
j can be used if desired.
The relative proportions of alkylene polyamine and epi-
~ chlorohydrin employed can be varied depending upon the particular
-- 8 --
.
.;~.. . .
~.... . . .
10'~73~
alkylene polyamin~ used. In general, it is preferred that the
molar ratlo of epiclhlorohydrin to alkylene polyamine be in excess
of 1:1 and less thdn 2:1. In the preparation of a water-soluble
resin from epichk~rohydrirl and tetraethylenepentamine, good re-
sults are obtained at molar ratios of from about 1.4:1 to 1.94:1.
Reaction temperature is preferably in the range of from about
40C. to about 60C.
The followln~ example illustrates the preparation of a
; dispersing agent of the above type.
Example A
To a mixture of 29.2 parts triethylenetetramine and 70
parts water is added 44.4 parts epichlorohydrin over a period of
i3 about 12 minutes with periodic cooling. After the epichlorohydrin
addition is complete, the reaction mixture is heated to 75C. and
maintained at a temperature of from about 70C. to about 77C.
for about 33 minutes, at which point the Gardner-Holdt viscosity
reached about I. The resulting reaction mass is diluted with
t 592 parts water to provide an aqueous solution that has a solids
content of about 11.7% and a pH of about 6.3.
Another suitable dispersing agent for use in this inven-
tion is a poly(diallylamine)--epihalohydrin resin. Resins of
this type can be prepared in accordance with the teachings of U.S.
patent 3,700,623, reference to which is hereby made.
A poly(diallylamine)--epihalohydrin resin is the resin-
ous reaction product of (A) a linear polymer having units of the
formula
(I) R\CH~ R
-s . H2C / CH2
s \N
R'
where R is hydrogen or lower alkyl and R' is hydrogen, alkyl or
a substituted alkyl group and (B) an epihalohydrin.
s 30 In the above formula, each R can be the same or different
and, as stated, can be hydrogen or lower alkyl. The alkyl groups
g _
,., . :
~10'~'~73~
contain frorn 1 to 6 carbons an~ are preferably methyl, ethyl,
isopropyl or n-butyl. R' of the formula represents hydrogen,
alkyl or substituted alkyl groups. The R' alkyl groups will con-
tain from 1 to 18 carbon ato~s (preferably from 1 to 6 carbon
i atoms) such as methyl, ethyl, propyl, isopropyl, butyl, tert-
butyl, hexyl, octyl, decyl, dodecyl, tetradecyl and octadecyl.
R' can also be a substituted alkyl group. Suitable substituents
include, in general, any group which will not interfere with
polymerization through a vinyl double bond. Typically, the sub-
stituents can be carboxylate, cyano, ether, amino (primary, sec-
ondary or tertiary), amide, hydrazide and hydroxyl.
Polymers having units of the above formula can be pro-
duced by polymerizing the hydrohalide salt of a diallylamine
~ ~ ( II ) jIH2 CH2
R-C -R
I H2 1H2 ~ -
N /
R'
where R and R' are as indicated above, either alone or as a mix-
ture with other copolymerizable ingredients, in the presence of
~ .
a free radical catalyst and then neutralizing the salt to give
, ,
the polymer free base.
Specific hydrohalide salts of the diallylamines which
can be polymerized to provide the polymer units of the invention
.~
include diallylamine hydrcchloride; N-methyldiallylamine hydro-
chloride; N-methyldiallylamine hydrobromide; 2,2'-dimethyl-N-
methyldiallylamine hydrochloride; N-ethyldiallylamine hydrobromide;
N-isopropyldiallylamine hydrochloride; N-n-butyldiallylamine hydro-
bromide; N-tert-butyldiallylamine hydrochloride; N-n-hexyldiallyl-
amine hydrochloride; N-octadecyldiallylamine hydrochloride; N-
acetamidodiallylamine hydrochloride; N-cyanomethyldiallylamine
:
hydrochloride; N-~-propiGnamidodiallylamine hydrobromide; N-
carboethoxymethyldiallylamine hydrochloride; N-~-methoxyethyl-
diallylamine hydrobromide; N-~-aminoethyldiallylamine
-- 10 --
:`
:.................................... .. . . .
-: -
. .- -. - ., . , . :. . , ::
IO~Z73~
nydrochloride; N-hydroxyethyldiallylamine hydrobromide; and N-
acetohydrazide substituted diallylamine hydrochloride.
Diallylamines and N-alkyldiallylamines, used to prepare
the polymers employed in this invention, can be prepared by the
; reaction of ammonia or a primary amine with an allyl halide em-
ploying as a catalyst for the reaction a catalyst that promotes
the ionization of the halide such~ for example, as sodium iodide,
zinc iodide, ammonium iodide, cupric bromide, ferric chloride,
ferric bromide, zinc chloride, mercuric iodide, mercuric nitrate,
mercuric bromide, mercuric chloride, and mixtures of two or more.
Thus, for example, N-methyldiallylamine can be prepared by reac-
tion of two moles of an allyl halide, such as allyl chloride,
with one mole of methylamine in the presence of an ionization
catalyst such as one of those enumerated above.
In preparing the homopolymers and copolymers, reaction
can be initiated by redox catalytic system. In a redox system,
the catalyst is activated by means of a reducing agent which pro-
duces free radicals without the use of heat. Reducing agents
commonly used are sodium metabisulfite and potassium metabisul-
fite. Other reducing agents include water-soluble thiosulfates
and bisulfites, hydrosulfites and reducing salts such as the sul-
fate of a metal which is capable of existing in more than one
valence state such as cobalt, iron, manganese and copper. A
specific example of such a sulfate is ferrous sulfate. The use
of a redox initiator system has several advantages, the most im-
portant of which is efficient polymerization at lower temperature.
Conventional peroxide catalysts such as tertiary-butyl hydroper-
oxide, potassium persulfate, hydrogen peroxide and ammonium per-
sulfate used in conjunction with the above reducing agents or
metal activators, can be employed.
As stated above, the linear polymers of diallylamines
~ which are reacted with an epihalohydrin can contain different
i units of formula (I) and/or contain units of one or more other co-
~ polymerizable monomers. Typically, the comonomer is a different
-
-- 1 1 --
r
109Z'~3t~
diallylamine, a monoethylenically unsaturated compound containing
a single vinyl or vinylidene group or sulfur dioxide, and is pres-
ent in an amount ranging from 0 to 95 mole % of the polymer. Thus
the polymers of diallylamine are linear polymers wherein from 5~
to 100~ of the recurring units have the formula (I) and from 0 to
95% of the recurring units are monomer units derived from (1) a
vinylidene monomer and/or (2) sulfur dioxide. Preferred comono-
p mers include acrylic acid, methacrylic acid, methyl and other
alkyl acrylates and methacrylates, acrylamide, methacrylamide,
10 acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ethers such
i as the alkyl vinyl ethers, vinyl ketones such as methyl vinyl ke-
; tone and ethyl vinyl ketone, vinyl sulfonamide, sulfur dioxide or ;
a different diallylamine embraced by the above formula ~II).
! Specific copolymers which can be reacted with an epihalo-
hydrin include copolymers of N-methyldiallylamine and sulfur di-
oxide; copolymers of N-methyldiallylamine and diallylamine; co-
polymers of diallylamine and acrylamide; copolymers of diallylamine
and acrylic acid; copolymers of N-methyldiallylamine and methyl
acrylate, copolymers of diallylamine and acrylonitrile; copolymers
20 of N-methyldiallylamine and vinyl acetate; copolymers of diallyl-
amine and methyl vinyl ether; copolymers of N-methyldiallylamine
and vinylsulfonamide; copolymers of N-methyldiallylamine and methyl
vinyl ketone; terpolymers of diallylamine, sulfur dioxide and
acrylamide; and terpolymers of N-methyldiallylamine, acrylic acid
and acrylamide.
The epihalohydrin which is reacted with the polymer of a
diallylamine can be any epihalohydrin, i.e., epichlorohydrin, epi-
bromohydrin, epifluorohydrin or epiiodohydrin and is preferably
~ epichlorohydrin. In general, the epihalohydrin is used in an amount
.
30 ranging from about 0.5 mole to about 1.5 moles and preferably about
1 mole to about 1.5 moles per mole of secondary plus tertiary amine
;~ present in the polymer.
The poly(diallylamine)--epihalohydrin resin can be prepared
by reacting a homopolymer or copolymer of a diallylamine as set
- 12 -
,
.
'': , ~ : :: ,
- lO~Z73~
forth above with an epihalohydrin at a temperature of from about
! 30C. to about 80C. and preferably from about 40C. to about 60C.,~
until the viscosity measured on a solution containing 20% to 30~
solids at 25C. has reached a range of A to E and preferably about
, C to D on the Gardner-Holdt scale. The reaction is preferably
carried out in aqueous solution to moderate the reaction, and at a
pH of from about 7 to about 9.5.
When the desired viscosity is reached, sufficient water is
added to adjust the solids content of the resin solution to about
,.~
10 15% or less and the product cooled to room temperature (about 25C.)
The poly(diallylamine)--epihalohydrin resin can be stabi-
.
lized against gelation by adding to the aqueous solution thereof
sufficient water-soluble acid (such as hydrochloric acid and sul-
furic acid) to obtain and maintain the pH at about 2.
The following example illustrates the preparation of a poly-
~ .
(diallylamine)--epichlorohydrin resin.
Example B .
A solution of 69.1 parts of methyldiallylamine and 197 parts
of 20 Be hydrochloric acid in 111.7 parts of demineralized w~ter
.
20 i9 sparged with nitrogen to remove air, then treated with 0.55 part
of tertiary butyl hydroperoxide and a solution of 0.0036 part of
ferrous sulfate in 0.5 part of water. The resulting solution is
allowed to polymerize at 60-69C. for 24 hours to give a polymer
solution containing about 52,1% solids with an RSV of 0.22. 122
;~ parts of the above solution is adjusted to pH 8.5 by the addition
of 95 parts of 3.8% sodium hydroxide and then diluted with 211
~i, parts of water and combined with 60 parts of epichlorohydrin. The
; ~
- , mixture is heated at 45-55C. for 1.35 hours until the Gardner-
;~ Holdt viscosity of a sample cooled to 25C. reaches B+. The rer
~`~ 30 sulting solution is acidified with 25 parts of 20 Be hydrochloric
acid and heated at 60C. until the pH becomes constant at 2Ø The
~` resulting resin solution has a solids content of 20.8% and a Brook-
field viscosity = 77 cp. ~measured using a Brookfield Model LVF
Viscometer, No. 1 spindle at 60 r,p.m, with guard).
- 13 -
10~738
Examples 2, 3 and 4 below are illustrative of suspensions
of unblended wax particles.
Example 2
,
Three hundred twenty parts of a 12.5% solids solution of an
aminopolyamide--epichlorohydrin resin prepared in accordance with
Example 1 and 440 parts water are mixed and heated quickly to 90C.
and added to the supply tank of a Manton-Gaulin laboratory (15 gal.
per hour) homogenizer. Two hundred forty parts of fused refined
paraffin wax ~m.p. 140-145F.) is added to the hot solution in the - ~
' 10 supply tank with mixing by means of a propeller type stirrer. Be- ~ -
fore addition of the aqueous resin solution to the supply tank, the
homogenizer is preheated by circulating water at about 85C. through
the body of the homogenizer and back to the supply tank where the
water is heated by flowing steam through a stainless steel coil
brazed onto the outside of the tank. The mixture is homogenized
~! with two passes through the homogenizer at 3000 psi. The homoge-
nized product is collected in a glass bottle and cooled to room
temperature by placing the bottle in a cold water bath with stir-
ring of the product during cooling. The product is a blue-white
20 aqueous dispersion with 28% total solids (24% wax and 4% amino-
polyamide--epichlorohydrin resin). After standing 24 hours, a
small amount of undispersed wax present in the dispersion is sepa-
rated by filtration through a 100 mesh screen. This is collected,
dried and weighed to measure the percentage of the added wax which
separates under these conditions. Longer term stability is meas-
ured by allowing about 235 parts of the filtered dispersion to
stand about four weeks when it is filtered a second time through a
100 mesh screen. The separated wax is dried and weighed. Wax
separation results are set forth in Table I below.
Example 3
Example 2 is repeated. Wax separation results are set forth
in Table I below.
i Example 4
) ~ Example 2 is repeated. Wax separation results are set forth
- 14 -
.
.... . .
~: '
1092738
n Table I below.
Table I
Parts Wax From 235 Parts of
wax Separated Filtered Dispersion After 4
. Example (24 Hours) Weeks Standing
'` 2 3.9 .13
~ 3 2.8 .05
f, 4 1.0 .01
Examples 5-7 below are illustrative of the suspensions of
10 this invention.
s Examples 5-7
Examples 2, 3 and 4 are repeated using the same starting
materials with the exception that, instead of the 240 parts of
fused wax, there is added to the hot solution in the supply tank,
in the fused state, a blend of 9.6 parts hydrogenated tallow fatty -
~; acids and 230.4 parts refined paraffin wax prepared by melting the
two components together. Solids (blend of the wax and fatty acid)
separation results are set forth in Table II below.
Table II
Parts Solids From 235 Parts of
Solids Separated Filtered Dispersion After 4
Example ~24 Hours) _ Weeks Standing
0.2 None
6 0.1 None
7 0.1 None
Example 8 shows sizing properties of the dispersions of Ex-
amples 2-7-
Example 8
The dispersions of Examples 2-7 are applied to 40 lb./3000
`~ 30 ft.2 bleached kraft waterleaf paper in a size press in an amount
sufficient to provide 0.38% ~dispersion solids) based on the
:~
weight of the paper and the thus treated paper drum dried. Sizing
- test results are as follows;
` Hercules Sizing Test,
Example Seconds
2 234
270
4 259
251
40 6 253
7 230
- 15 -
., :
: .,
- ~09Z73H
Example 9
Example 2 is repe~ted. Solids (wax) separation results are
set forth in Table III below.
Examples 10-15
Example 2 is repeated using varying amounts of commercial
docosanoic acid (a mixture of saturated fatt~ acids containing
about 27% stearic acid, 12% eicosanoic acid, 56% docosanoic acid
and small amounts of other fatty acids) in place of part of the
~,~ wax. Prior to addition to the hot solution in the supply tank the
10 wax and acid are blended together by melting the two together. The
blend is added in the fused state. In these examples, the second
filtrations are made five weeks after the first. Solids (wax--
fatty acids blend) separation results are set forth in Table III
below.
..
Table III
Parts Solids From
235 Parts of
Parts% Solids Filtered Dispersion
Docosanoic Parts Separated After 5 Weeks
20 Example_ Acid Wax(24 Hours) Standing
9(Control) 0 240 .33 .63
1.2 238.8.05 .00
11 2.4 237.6.08 .00
12 4.8 235,2.04 .00
13 9.6 230.4.00 .00
~ 14 16.9 223.1.06 .01
`~ 15 24.0 216.0100
Example 16 shows sizing properties of the dispersions of
Examples 9-14.
Example 16
3 ~` 30 The dispersions of Examples 9 through 14 are applied to 40
lb./3000 ft.2 bleached kraft waterleaf in a size press in an amount
: .
su~ficient to provide 0.38% (dispersion solids) based on the weight
~ of paper and the thus treated paper drum dried. Sizing tests re-
`~ sults are as follows:
Hercules Sizing Test,
~ Example Second
l ~ 174
200
11 204
- 12 2I8
13 247
14 305
: - 16 -
.~ ~
'.~
.~............. . . . .
1092738
Example 17
Example 9 is repeated. Solids (wax) separation results
are set forth in Table IV below.
Examples 18-23
Examples 10-15 are repeated using an alkyl ketene dimer
;1 made from tall oil fatty acids in place of commercial docosanoic
acid. In these examples, the second filtrations are made two
weeks after the first. Solids (wax--ketene dimer blends) separa-
tion results are set forth in Table IV below:
TABLE IV
Parts % Solids Parts Solids From 235 Parts
Ketene Parts Separated of Filtered Dispersion
Example Dimer Wax 24 Hours After 2 Weeks Standing
17(Control) 0 240 .98 .05
18 1.2 238.8 .14 .02
19 2.4 237.6 .14 .06
4.8 235.2 .08 .00
21 9.6 230.4 .03 .00
22 16.9 223.1 .02 .00
23 24.0 216.0 .02 .00
Example 24 shows slzing properties of the dispersions of
Examples 17-23.
~ 20 Example 24
-~ . The dispersions of Examples 17-23 are applied to 40 lb./
3 3000 ft.2 bleached kraft waterleaf in a size press in an amount
sufficient to provide 0.38% (dispersion solids) based on the
weight of paper and the thu~-treated paper drum dried. Sizing
re-ult- are as fol low~
Hercule~ 81~1ng Te~t
xalr~le ~0ao~d~
17 ~ lC2
1~ 15
~ 19 139
i51
21 245
22 ~8
~ 23 473
¦ Example 2$ i~ a ~ont~ol to be compared with Example 26
which 18 an example o~ applicant'~ invention~
- 17 -
'5_ . ; . . ;. ' . 1
,"'' '' ~ "'
1092738
; Example 25
Three hundred parts polyethyl~ne wax having a mol. wt.
2200, a ring and ball softening point 108C., and a density 0.921
(Epolene 11) is dissolved in 300 parts xylene by heating to about
95C. To this solution is added a hot (about 90C.) mixture of
400 parts of aminopolyamide--epichlorohydrin resin prepared as in
~ Example 1 with 1060 parts water. The hot premix i8 homogenized
$ twice at 3000 psi in a homogenizer preheated to about 95C. The
resulting product is a stable oil-in-water emulsion from which
10 sub~tantially all of the xylene is removed by distillation at at-
mospheric pressure during which the product temperature increa~es
from about 94C. to about 100C. The solids content of the
resulting stable aqueous suspension is about 25%. After cooling
to room temperature, the mixture is filtered through a 100 mesh
screen to separate the undispersed wax. The dried undispe~sed ~ax
represents about 2.6~ of the wax in the dispersion.
Example 26 -
Example 25 is repeated using 3 parts stearic acid to re-
.
place 3 parts of the polyethylene wax in the xylene solution. In
20 this case, less than 0.1% of the dispersed wax is collected when
the final product is filtered through a 100 mesh screen.
~ ~,
Example 27 illustrates the preparation of a dispersing
agent for u8e in this invention, the dispersing agent being a
water-soluble poly(diallylamine)--epichlorohydrin resin.
Example ~7 .-
To 250 parts of methyldiallylamine is added slowly 230
:
paxts 37% hydrochloria acid in about 240 parts demineralized
water. The mixtuxe is cooled as needed to prevent volatilization
of materlal~ due to the heat of reaction. The pH of the resulting
~ ~ 30 mixture is then adjusted to 3.1 by additional (19 part~) methyl-
'r, `~:'`. ` diallylamine. After the oxygen in the reaction ves~el i8 dis-
placed with nitrogen, 2.2 parts t-butyl hydroperoxide is added.
.
This is followed by .0014 part ferrous sulfate hepta hydrate in
, ~ .
1.1 parts demineralized water. When the reaction miXture is
t
-- 1 8
'}
. , ,, , , , . ~
,~: '- ; . -
~ . ' ` ... . .
iO92738
warmed to 60C., there is a mild exothermic reaction which
carries the reaction temperature briefly to about 66-70C. For
the remainder of the 24-hour reaction time, the temperature i8
- held at about 60C. After cooling to 25-30C., the total solids
of the product is about 48.4% and the RSV is .21 cp. To 220 parts
of the above polymer solution is added sufficient (about 160 parts)
sodium hydroxide solution (10 parts sodium hydroxide in 376 part~
water) to adjust the pH to about 8.5. The neutralized polymer
solution is diluted with 366 parts demineralized water and then
10 heated to about 40C. To the warm solution is added 106 parts
epichlorohydrin and the reaction warmed further to react the epi-
chlorohydrin at about 50-55C. Reaction is continued until the
reaction mixture reaches a Gardner viscosity of about B+ (about
1.7 hours)~ At this time the reaction is quenched by the rapid
addition of about 35 parts 37% hydrochloric acid to give a final
pH of about 2. There is obtained 859 parts of a product con-
taining about 20.7% total solids. A series of runs are made sub-
stantially as described above to give a total of about 7395 parts r:
of product with about 20.4% total solids.
, 20 Example 28 uses as a dispersing agent the resin of Example
;j 27 and is a control for comparison with Examples 29-33.
Example 28
Two hundred and seven (207) parts of a 20.4~ solids solu-
~ tion of an epichlorohydrin modified tertiary amino polymer prepared
¦ in accordance with Example 27 and 473 parts water are mixed and
heated quickly to 90C. and added to the supply tank of a Manton-
Gaulin laboratory (15 gal. per hour) homogenizer. Two hundred
forty part8 of fused refined paraffin wax (m.p. 140-145F.) is
added to the hot solution in the supply tank with mixing by means
~ 30 of a propeller type stirrer. Before addition of the aqueous resin
j solution to the supply tank, the homogenizer is preheated by cir-
' culating water at about 85C. through the body of the homogenizer
and back to the supply tank where the water is heated by blowing
steam through a stainless steel coil brazed onto the outside of
- 19 -
:; - . - - - . . .
~09Z~738
the tank. The mixture is homogenized with two pas~es th~ough the
homogenizer at 3000 psi. The homogenized product i8 collected in
a glass bottle and cooled to room temperature by placing the
bottle in a cold water bath with stirring of the product during
cooling. The product is a blue-white aqueous dispersion with 28%
total solids, 24% wax and 4~ poly(diallylamine)--epichlorohydrin
resin. After standing 24 hours, a small amount of undispersed
wax present in the dispersion is separated by filtration through
a 100 mesh screen. This is collected, dried, and weighed to
10 measure the percentage of the added wax which separates under
these conditions. Longer term stability is measured by allowing
about 235 parts of the filtered dispersion to stand for about 4
weeks when it is filtered a second time through a 100 mesh screen.
The separated wax is dried and weighed. Results are given in
Table V below.
Examples 29-33
!
Example 28 is duplicated with the exception that varying
amounts of wax are replaced by an alkyl ketene dimer made from
commercial stearic acid. The wax and the alkyl ketene dimer are
20 fir9t fused together to provide a homogeneous blend which is
added, in the fused form, to the hot solution in the supply tank.
ll
Solids (wax--ketene dimer blend) separation results are set forth
in Table V below.
TABLE V
Parts Solid From
235 Parts of
Parts ~ Solids Filtered Dispersion
Ketene Parts Separated After 4 Weeks
Example Dimer Wax (24 Hours) Standing
. 28 (Control) 0 240 16.4 .58
i 29 2.4 237.66.6 .15
`~ 30 4.8 235.26.7 .18
`' 31 9.6 230.43.5 .03
32 16.9 223.14.0 1.82
33 24.0 216.00.25 2.19
Example 34
The dispersions of Examples 28-33 are applied to 40 lb./
3000 ft.2 bleached kraft waterleaf in a size press in an amount
- 20 -
.
.
....
~092738
sufficient to provide 0.38% (dispersion solids) based on theweight of paper and the thus-treated paper drum dried. Sizing
results are as follows:
Hercules Sizing Test
Example Seconds
28 212
29 303
336
31 510
~ 32 676
j 33 842
,Example 35 illustrates the preparation of a diqpercing
10 agent for use in this invention, the dispersing agent being a
water-soluble alkylenepolyamine--epichlorohydrin resin.
Example 35
A reaction vessel i~ charged with 704 parts water and 476
parts epichlorohydrin. A steam jet vacuum system is turned on to
exhaust vapors through a condenser and to prevent them from es-
caping through the open manhole. Four hundred twenty parts of
Amine 248 is added with agitation in 35 minutes while the tempera-
ture is allowed to rise to 70C. Cooling water is required to
~limit the temperature rise to 70C. After amine addition is
;320 complete, the reactor charge has a pH of 7.8 and an A viscosity
by Gardner Holdt. Six parts of 20% NaOH is added to speed reac-
tion. After 2 hours and 40 minutes at about 70C., the viscosity
reaches a U+ viscosity and the resin solution is diluted with 640
i~parts water which reduces the viscosity to about C-. A total of 44
part~ of 20% NaOH i8 added in four separate additions during 1-3/4
hour period to speea reaotion. An S viscosity i9 reached after 3
hours and 35 minut~s, and the rea¢tion i~ killed and diluted with
26 parts concentsated sul~uxic acid in 1345 parts water. This
glves an aqueous solutio~ of 23.3% total solids, a P visco~ity,
30 and a pH of 4.4. Further addition of H2S04 and wa~er give~ 22.5%
total solids, (113 cp, vi~c.) and 4.0 pH. The resin solution is
filtered through 10~ filtex cartridges to give a total of 3336
parts of product. Amine 248 i~ a dark, viscous liquid or pa~te
with a slight ammoniacal odor. At least 75% of Amine 248 consists
- 21 -
.
109Z738
of bis(hexamethylene)-triamine and higher homologues:
H2N- (CH2) 6-N- (CH2) 6-NH2
bis-(hexamethylene)-triamine
and
H2N [ ( CH2 ) 6NH ] ( 2 +N ) H
~ higher homologues
,^ The remainder consists of lower molecular weight amines, nitriles
and lactams. ~ -
Example 36 uses as a dispersing agent the resin of Example
35 and is a control for comparison with Examples 37-42.
Example 36 ;~
One hundred seventy four (174) parts of a 22.5% solids
solution of an alkylenepolyamine--epichlorohydrin reaction product
prepared in accordance with Example 35 and 506 parts water are
mixed and heated quickly to 90C. and added to the supply tank of
a Manton-Gaulin laboratory (15 gal. per hour) homogenizer. Two
hundred forty parts of fu~ed refined paraffin wax (m.p~ 140-145F.) ~
`~ is added to the hot solution in the ~upply tank with mixing by - ;-
`"
; ~ means of a propeller type stirrer. Before addition of the aqueous
resin solution to the supply tank, the homogenizer is preheated
by circulating water at about 85C. through the body of the homo- ~;
genizer and back to the supply tank where the water i~ heated by
blowing steam through a stainle~s steel coil brazed onto the out- `
; side of the tank. Thç mixtu~e i~ homogenized with two p~88e8 ~ ~
through the h~mog~nizex at 3000 psi, Th~ h~moge~lzed pX~duct i8 ." :`
collectod in a gla~ bQ~tle and coQled to room te~peratuxe by
: :~
placing the bottle in a ~old wateX ~a~h with ~tlrrin~ of the
product durin~ ~oli~. The pFodu~ i8 a blue-white a~ueou~ di~-
persion with 28~ total ~olids, 24~ wax ~nd ~ alkylenepolyamine
epichloxohydrin re~i~. A~ter s~a~ding ~ hou~, a ~mal~ amount
~ .
of undispersed wax pre~ent in the di~per~lon i~ ~qpaxated by ~
- tration throu~h a 100 me~h ~axeen. Thig i~ ~olIe~ted, dxied and
- 22 -
. :
~,: ~: . ., .... , . - .. .
109Z738
weighed to measure the percentage of the added wax which separate~
under these conditions. Longer term stability i~ mea~ured by
allowing about 235 parts of the filtered dispersion to stand for
about two weeks when it is filtered a second time through a 100
mesh screen. The separated wax is dried and weighed. Results are
shown in Table VI below.
s Examples 37-42
Example 36 is repeated using varying amounts of fatty acids
y (as indicated in Table VI below) to replace part of the paraffin
10 wax. The wax and fatty acids are first fused together to provide
a homogeneous blend thereof which blend is added, in the fused
state, to the hot solution in the supply tank. The fatty acids
are the same as used in Examples 5-7. Solids separation results
are set forth in Table VI below.
~` TAB~E VI
Parts Solids From
~3 Parts % Solids 235 Parts Filtered
;~ Fatty Parts Separated Dispersion After
~' Example Acids Wax (24 Hours) 2 Weeks Standing
36 (Control) 0 240 .36 .00
37 1.2 238.8 .63 .00
38 2.4 237.6 .57 .00
20 3g 4.8 235.2 .47 .00
9.6 231.4 .10 .00
' 41 16.9 223.1 .13 .00
42 24.0 216.0 .15 .00
The dispersions of Examples 37-42 can be satisfactorily
employed in the manufacture of sized paper.
~¦ Commercially available 8aturated ~atty aciA~ will often
contain 8mall amoUnts of u~saturated fatty acids. These fatty
¦ acids ¢an be empl~yeA in pxepa~ing the blends used in thi~ i~ven-
tion provided the un~aturated cQntent Aoes not exceed about 10%
by weight.
It i8 to be under~to~d that ~e above aesaription and
j 30
, working examples a~e illustrative of this inVention and not in
'~ limitation thereQf.
- 23 -
".. .. . .. . ...
