Note: Descriptions are shown in the official language in which they were submitted.
Aldrich Case 23
i73S~
This invention relates to novel aqueous dispersions of
fortified rosin. Particularly, this invention relates to aqueous
dispersions which consist essentially of finely-divided fortified
rosin particles~ a water-soluble cationic dispersing agent for
, .
the finely-divided rosin particles, and water. The dispersing
agent will be detailed more ~ully hereinafter. The novel forti~
fied rosin dispersions of this invention are used to size paperG
. :.
.~ Internal sizing of paper with rosin is discussed by
. Casey, Pulp and Paper, Second Edition, Volume II: PapermakingO
.
Chapter XIII, pages 1043-1066~ reference to which is hereby madeO
At page 1048 Casey discusses forti~ied rosin size and
......... states that fortified rosin sizes are made by reacting maleic
':~ anhydride or other dienolphiles with rosin to increase the num
. ber of carboxylic acid groups. Casey also states that a typical
.;........ fortified size may contain about 1% to 30% of maleopimaric ac.id
. anhydride.
. Casey, at page 1047, under the heading "Free Rosin Size"~
: states that the relative merits of high free rosin size and low
: free rosin size has been a controversial subject for many years
but that it is now pretty generally recognized that high free
. rosin size results in better sizing and uses less alum~
.. At page 1050, under the heading "Protected Rosin Size"0
. . ~
: Casey states that by using a protective colloid it .is possible
to prepare highly stable size containing as high as 90% free
;.. ~ rosin. At page 1051 Casey discusses the Bewoid process ~or
preparing a high free rosin s.ize and states that Bewoid sizet
as usually prepared, contains about 90% free rosin dispersed
~......... in a small amount of rosin soap and stabilized by the presence
.~ of about 2% casein or other protein. The casein is used as
;.. 30 a protective colloid to prevent growth of rosin particles D` .:.-'
thereby maintaining them in a state of fine subdivisionO
Casey, at pages 1051 and 1052, discusses the Prosize
. :~
~.- process for producing a protected size containing a high free
. .
: rosin contentG The rosin particles are prevented from growing
'~t~
''
` 1~4S~35
into l?rger aggregates by the presence o a sur~ace-active protein such as
soybean protein.
German patent 1,131,348 to Wieger et al states that free rosin
: sizes are dispersions of unsaponified resin acids with a certain percentage
, of rosin soap. It is also stated that the dispersions are prepared by a
:
~ special process, that they are mostly used with free rosin content of 60% to
. . .
95% and contain besides rosin auxiliary emulsifiers and stabilizers such as
stearates, triethanolamine, casein, and waxes.
.
' German patent 1,131,348 further states that, heretofore, the
fortified rosins have not been suitable for the preparation of dispersions
.~ .
~` since they have mostly too high melting points, have a tendency to crystalliz-
",
ation, or form, during dispersing, fine crusts which lead to sedimentation
phenomena. German patent 1,131,3~8 discloses and claims a paper size and
.,
a process for the preparation of a paper size in the form of an aqueous
dispersion with a high free rosin content from fortified rosin characterized
~ in that the fortified rosin is mixed with fatty acids, fatty acid mixtures,
.; .
and/or naphthenic acids at elevated temperatures and that the dispersion is
carried out in a known manner.
U.S. Patent 3,565,755 to Davison discloses a substantially
~,~ 20 homogeneous stable aqueous suspension of rosin-base material in a state of
. ,... : .
fine subdivision. The rosin-base material can be all fortified rosin or it
can be a rosin-fortified rosin mixture. A very small amount of the rosin-
., .
; base material is saponified and functions as a dispersing agent Eor the
rosin-base particles. This composition, which consists essentially of the
., .
` rosin-base material, the saponified rosin-base material, and water, is used
i,.,
in the sizing of paper. The size of patent 3,565,755 is a high free rosin
;; size in that it contains only a very small amount of saponified rosin-base
'n material. ~urther, it has good stability ~good shelf life) for prolonged
~~ periods of time and does not require the use of the stabilizers hereto-fore
..~.,:
. .
^ 3 -
:' '
~`r.,
.- ';
'.'':'':;;;
r:, !
~ . . . .
1. ,'" .
. ~
73~
" used in the preparation of stable high free rosin sizes such, for example, as
.
casein and soybean protein.
.:
In accordance with this invention there are provided a~ueous dis-
persion of fortified rosin for use in the sizing of paper. The aqueous dis-
.~ persions of this invention have good stability and do not require the presence
;, . ,~
of rosin soap or fortified rosin soap. In addition the aqueous dispersions
of this invention do not require the use of stabilizers heretofore used in
the preparation of high free rosin sizes.
The aqueous fortified rosin dispersions of this invention consist
:
essentially of, be weight, (A) from abou~ 5% to about 50% of rosin based ma-
terial selected from fortified rosin, rosin and extender, said material com-
prising at least 25% by weight fortified rosin, (B) from about 0.5% to about
10% of water-soluble cationic resin dispersing agent, and (C) water to 100%,
-~ component (B) being selected from the group consisting of (i) a water-soluble
polyaminopolyamide-epichlorohydrin resin, (ii) a water-soluble alkylenepoly-
amine-epichlorohydrin resin and (iii) a water-soluble poly(diallylamine)-epi-
~':
;` chlorohydrin resin, said fortified rosin being the adduct reac~ion product of
rosin and an aeidic compound containing the >C=~-C=0 group. These rosin dis-
persions are essentially free of dissolved rosin. It is preferred to use (A)
from about 10% to about 40% of the rosin based material, and (B) from about 1%
to about 8% of the water-soluble cationic resin dispersing agent.
~ The invention also provides, in the method of sizing paper wherein
; fortified rosin is used in the sizing of the paper, the improvement wherein
~ .,
there is employed the aqueous fortified rosin dispersion deflned above.
. ",
~ The rosin based material of component (A) is fortified rosin, ex-
:,;: ;
!,'.,','',~ tended if desired by known ex*enders therefor such as waxes (particularly
. ~ ,,
paraffin wax and microcrystalline wax); hydrocarbon resins including those de-
rived from petroleum hydrocarbons and terpenes; and the like. This is accom-
plished by blending ~ith the fortified rosin from about 10% to about 100% by
` 30 weight based on the weight of fortified rosin of the fortified rosin extender.
;
~ Also blends of fortified rosin and rosin, and blends of fortified
;, ~
~ rosin, rosin and rosin extender can be used.
' .:
.~ .
. ;:',
35i
:.
Fortified rosin-rosin blends generally comprise about 25% to 95%
fortified rosin and about 75% to 5% rosin. Blends of fortified rosin, rosin,
and rosin extender generally comprise about 25% to 45% fortified rosin, about
, 5% to about 50% rosin, and about 5% to 50% rosin extender.
; 5 In preparing aqueous fortified rosin dispersions of this invention
., . ~
the fortified rosin ~including the extender or rosin or both if either or both
.~ are to be employed) is irst dissolved in a water-immiscible organic solvent
therefor such, for example, as benzene, xylene, chloroform and 1,2-dichloro-
` propane. Mix-
:
:' .
' :
';.
,;
: '~ '. '
: ..
"..,~
.;;,
; ",.,
"''''
:;:;:, .
.:
:.
.~:
.,, ' . .
.~'',:'';
. ~
';
.,
:: ~.
"
:1' .,:'
....
~',.~,;';
'~;`..~
: ,!
~ -4a-
., -
~, . . . .
573S
- tures of two or m~re solvents can be used if desired. The se=
, ~,,
lected solven-t will also be nonreactive to the components of the
aqueous dispersion to be subsequently preparedO
The organic solvent- fortified rosin solution is then
:
mixed with an a~ueous solution of cationic resin dispersing
.,
,,~i!~ agent to provide an emulsion which is essentially unstable and in
which the organic solvent-~fortified rosin solution forms the dis~
;~ persed phase. The essentially unstable aqueous emulsion is then
subjected to extreme shear to provide an essentially stable
aqueous emulsion O Extreme shear is conveniently accomplished by
'' ' -
means of an homogenizerO Thus passingD at least onceO the un
.., ~
stable aqueous emulsion through an homogenizer under a pressure
, ~, ,
- ~ of the order of from about 1000 p~s iOgO to about 8000 p s~iOg~0
. ~:
will provide an essentially stable emulsion. Subsequently, the
~- organic solvent component of the emulsion is removed from the
:, ,
~;~ emulsion and there is provided an essentially stable aqueous
dispersion of fortified rosin particlesO
.:: ,.,
The aqueous fortified rosin dispersions of this invention
` can be prepared by the inversion process as shown in Example 16~
;.,.- ~
; 20 The fortified rosin--organic solvent solution is admixed with an
aqueous solution of cationic resin dispersing agent in an amount
to provide a stable water-in-oil emulsion which is subse~uently
inverted to a stable oil-in-water emulsion by the rapid addition
of water with vigorous stirring. The organic solvent is subse~
';~ quently removed as by distillation under reduced pressure
: .
The rosin used to prepare the fortified rosin employed
. ~
- in this invention can be any oE the commercially available types
i.: ::
of rosin, such as wood rosin, gum rosin, tall oil rosin, and
, ', '
mixtures of any two or mored in their crude or refined state
Partially or substantially completely hydrogenated rosins and
, :.::.
polymerized rosins O as well as rosins that have been treated
~ to inhibit crystallization such as by heat treatmen-t or re-
,~ action with formaldehydeD can be employed~
~ The fortified rosin employed is the adduct reaction
~, ~ ..... ...
i ~ 5
,; ' ''
:, .. .
. : . ... .
' ~L~4L5;~735
' product o rosin and an acidic compound containing the ,C-~C-C~=0 group and
is derived hy reacting rosin and the acidic compound at elevated temperatures
of from about 150C. to about 210C.
The amount o acidic compound employed will be that amount which
will provide fortified rosin containing from about 1% to about 12% by weight
` ~ of adducted acidic compound based on the weight of the fortified rosin.
` Methods of preparing fortified rosin are disclosed and described in U.S.
Patents 2,628,918 to Wilson et al and 2,684,300 to Wilson et al, reference
` to which is hereby made.
.
Examples of acidic compounds containing the _ C=C-~=0 group that
can be used to prepare the fortified rosin include the alpha-beta-unsaturated
organic acids and their available anhydrides, specific examples of~which
include fumaric acid, maleic acid, acrylic acid, maleic anhydride, itaconic
.,
, acid, itaconic anhydride, citraconic acid, and citraconic anhydride.
Mixtures of acids can be used to prepare the fortified rosin if desired.
` Also mixtures of different fortified rosins can be used if desired. Thus,
~,: i';
for example, a mixture of the acrylic acid adduct of rosin and the fumaric
~, acid adduct can be used to prepare the novel dispersions of this invention.
Also fortified rosin that has been substantially completely hydrogenated
20 after adduct formation can be used.
.:
If rosin ~that is, unfortified rosin) is used in combination with
~ fortified rosin, it can be any of the commercially available types of rosin,
`- such as wood rosin, gum rosin, tall oil rosin, and mixtures of any two or
,, ~ ,;,; .
more, in their crude or refined state. Partially or substantially completely
hydrogenated rosins and polymerized rosins, as well as rosins that have been
,;'~? `
; ~ -treated to inhibit crystallization such as by heat treatment or reaction
:
. with formaldehyde, can be employed.
The dispersing agents used to prepare the substantially stable
aqueous dispersions of this invention are cationic polymeric resinous
30 materials that are water-soluble.
~," , ,~
~,~ Particularly suitable dispersing agents are the cationic
- 6 -
... .
^
.
~ ;'' ' . ' ` ~
thermosettable water-soluble aminopolyamide--epichlorohydrin resins disclosed
and described in patents U.S. 2,926,116 and 2,926,154 both to Keim. These
resins are water-soluble polymeric reaction products of epichlorohydrin and
an aminopolyamide. The aminopolyamide is derived by reaction of a dicarboxy-
- lic acid and a polyalkylene-polyamine in a mole ratio of polyalkylene-
polyamine to dicarboxylic acid of from about 0.8:1 to about 1.4:1.
Particularly suitable dicarboxylic acids are diglycolic 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 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 polyethylene
polyamines, polypropylene polyamines, polybutylene polyamines and the like
~ 20 can be employed. Polyalkylene polyamines can be represented as 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 to adjacent carbon atoms in the group -Cn~l2n- or to
.: .
carbon atoms farther apart, but not to the same carbon atom. Polyamines
:~ " ;
such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
~ and dipropylenetriamine, which can be obtained in reasonably pure form are
i' suitable for preparing water-soluble aminopolyamides. Other
,.: :
.. ,.. ~., .
i~ i
~ ~ 7 -
:'''. , .
, ~-
, ~
,
5735
polyalkylene polyamines that can be used lnclude methyl bis-
(3-aminopropyl)amine; methyl bis-(2-aminoethyl~amine; and 4,7-
dimethyltriethylenetetramine. Mixtures of polyalkylene poly-
amines 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 poly-
~10 alkylene 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
pressure. 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 in-
versely with reaction temperatures employed.
. i;
]0 In carrying out the reaction, it is preferred to use an
~ amount of dicarboxylic acid sufficient to react substantially
,~l completely with the primary amine groups of the polyalkylene
: ., .
' polyamine but insufficient to react with the secondary amine
,, " i
groups and/or tertiary amine groups to any substantial extent.
l'his will usually re~uire a mole ratio of polyalkylene poly-
; amine to dicarboxylic 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 descrlbed, is react-
~ ed with epichlorohydrin at a temperature of from about 45C.
,~ to about 100C., and preferably between about 45C. and 70C.,
~'30 until the viscosity of a 20~ solids solution in water at
';l25C. 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 adjustment is usually
not necessary. However, since the pH decreases during
~~ - 8 -
','~', ~
,573~i
the polymeri~ation phase of ~he reactionO it may be desirableO
in some cases D 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 de0
sired amountO usually from about 2% to about 50%0
In the aminopolyamide--epichlorohydrin reactionO 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 reactionO if de~
sired. A monofunctional alkylating agent can be first reacted
with the aminopolyamide followed by reacticn of the aminopoly~
amide--alkylating agent reaction product with epichlorohydrinO
or the alkylating agent can be reacted wi-th the aminopolyamide~
epichlorohydrin reaction product. Thuso for exampleO epichloro
: ..
hvdrin can be added to an aqueous solution of the aminopolyamide
at a temperature from about 45Co to 55Co The reaction mixture
20 is then heated at a tempera~ure from about 50C. to 100Co o and
preferably from about 60C. to 80C., depending upon the rate of
reaction desired. After a suitable time at this temperatureO
i.e., from about 10-100 minutes, and preferably until the vis~
cosity of an approximately 25% solids solution of the reaction
mixkure at 25Cq is from A to B on the Gardner-Holdt scaleO at
which time most of the epoxy groups of the epichlorohydrin have
', reacted with the amine groups of the aminopolyamide, a mono~
, functional alkylating agent is added and the reaction mixture
~; ~ heated~ preferably at a temperature from about 60C. to about
; 30 80C., until the viscosity of an approximately 25% solids
solution at 25Co 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% 501idSo or reaction at a lower level followed
: ' :
~ g =
;.
.:
, ~ , . . .
.
5735
by concen-tration at less than 40~Co and under reduced pre~ssure
: to 25% solids~ Lower alkyl e~ters of mi.nexal acids such as the
~.
halidesD sulfates and phosphates0 substituted alkyl halides0 and
the like are suitable monofunctional alkylat.ing agent~= Illus~
trative of the compounds which can be used are dimethyl0 d.iethyl
. . .
and dipropyl sulfate~ methyl chlorideO methyl iodide) ethyl
iodide; methyl bromide~ propyl bromide0 and the mono~O0 di or
.. ..
... tri-methylO ethyl and propyl phosphatesO Certain aromatic com~
''. pounds such as benzyl chloride and methyl p~toluene sulfonate can
: ::
be usedO From about 0Ol mole to about 0~9 mole of mono~functicn~
al alkylating agent for each amine group can be usedO
In the examples that follow~ all parts and percentages
~,
.. .. .
~ are by weight unless otherwise specifiedO Sizing results are
" ~
.,,'- set forth in some of the examplesO Sizing results are determined
. . on the Hercules Sizing Tester~ The sizing test determines the
resistance of a sized sheet of paper to penetration by ~o, 2
,, j
~, Test SolutionO (an aqueous solution of0 by weight~ 100% formic
", ,
~`;, acid and 1025% naphthol Green B)~ The time necessary for ink
penetration to reduce light reflectance either 80% or.85% (as
indicated in the examples) of the sheet~s in.itial value is used
':j~'!;~ j
. to represent the degree of sizing~
~- The following example is illustrative of the preparati.on
o an aminopolyamide--epichlorohydrin resin that is particularl~
'~ useful as a cationic resin dispersing agent for use in t.h.is
, .. . .
nventlonO
; Ex~ple A
~ An aminopolyamide is formed by add.ing 21.903 parts of
.,~ adipic acid slowly0 with stirringD to 151.3 parts of diethylene~
triamine in a flask fitted with a stirrer and a co~denser for
collecting water distillate. The reaction mixture .LS stirred and
, . "~
7''''''' heated at 170-180Co under a nitrogen blanket until amide forma
; tion is completeO After air cooling to approximately 140Co o
'`'`` .
, hot water is added with stirring to provide a 50% solids ~olu~
~;: tion of polyamide resin with an intrinsic v.i.scosity of 00140
~'
. . '
.
i73~ii
~easured by using a 2% solution in 1 N NH4Clo An epichloro~
hydrin 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 14.0 parts (0.157 mole) of epichloro-
~ hydrin. 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 reaction mixture is diluted with
water to a solids content of about 1205%.
~s Other suitable dispersing agents that can be used in thLs
:,' .; ,
invention are the water-soluble alkylene polyamine--epichloro~
hydrin resins which are water-soluble polymeric reaction prod~
ucts of epichlorohydrin and an alkylene polyamineO
-~ Alkylene polyamines which can be reacted with epichloro
~ hydrin have the formula H2~(CnH2n~H)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 di-
amines such as ethylenediamine; propylene diamine-1~2, propylene
diamine-1,3; tetramethylenediamine; and hexamethylenediamine.
The polyalkylene polyamines such as the polyethylene polyaminesO
polypxopylene polyamines, polybutylene polyamines and the like
are e~amples of alkylene polyamines that can be used. Specific
examples of these polyalkylene polyamines include diethylene~
. .
triamine, triethylenetetramine~ tetraethylenepentamineO and
dipropylenetriamine~ Other polyalkylene polyamines that can be
used include methyl bis(3 aminopropyl)amine; methyl bis(2-amino-
ethyl)amine; and ~7-dimethyltriethylenetetramine. Mixtures of
alkylene polyamines can be used if desired.
The relative proportions of alkylene polyamine and
l ~ epichlorohydrin employed can be varied depending upon the par-~
s 30 ticular alkylene polyamine used. In generalO it is preferred
that the molar ratio of epichlorohydrin to alkylene polyamide
; be in excess of 1:1 and less than 2:10 In the preparation of
~,:
a ~ater-soluble resin from epichlorohydrin and tetraethylene-
pentamineO good results are obtained at molar ratios of from
:~
~; .
,::
~ " , . ,
t
735
~-~, ut 104 1 to 10~4 lo Re~ction temperatur~ i.s pref~rably in the
Lange of from about 40C. to about 60C~
` . The following example illustrates the preparation of a
;.- dispersing agent of th~ above ~yp2
.:
: Example B
To a mixture of 29O2 parts triethylenetetramine and
70 parts water is added 44~4 parts epichlorohydrin over a period
.. . .
:~. of a~out 12 minutes with periodic cooling~ After the epichloro0
hydrin addition is completea the reaction mixture is heated to
75C. and maintained at a temperat-ure of from absut 70Co to
;: about 77Co for about 33 minute~0 at which point the Gardner
`~ Holdt viscosity reached about Io The resulting mass is di.luted
;- with 592 parts water to provide an aqueous solution that has a
. " "; . . ..
~; ; solids content of about 1107% and a pH o about 603.
Another suitable dispersing a~ent for use in this in~
vention is a poly(di~llylamine)- epihalohydrin resin. Resi.ns of
. t~is type can be prepared in accordance with the t~achings
. U.S. patent 3,700,k2~ t~ Keim, refer~nc~ to ~ic~ i~ here~y m~de.
; . A poly(diallylamine)-~epihalohydrin resin is the resinous
. . . :
;; 20- reaction product of (A) a linear polymer having units of the
:.~ , . .
, formula
~ ~ ~ CH\ R
;i, tI) ~I2C - C C
" ,, H2C ~ ~CH2
,.."
-~ R'
.` . where R is hydrogen or lower alkyl and R' is hydrogenO alkyl or
. ~ a substituted alkyl group and ~B) an epihalohydrin7
; ; In the above formulaO each R can be the same or differ~
; ~ ent and, as statedO can be hydrogen or lower alkylO The alkyl
groups contain rom l to 6 carbons and are preferably methylO
ethyl, isopropyl or n-butyl. R' of the formula represents
. hydrogen, alkyl or substitut~d alkyl groups. The R~ alkyl
. . groups will contain from l to 18 carbon atoms (preferably from
., j.~,: . , .
~ ......... l to 6 carbon atoms) such as m~thylO ethylO pxopylO isopropylO
~,i,, ' ' I
~, ,. i_,
,.:
5'7~i
Jutyl, tert-butyl, hexyl, octyl, decyl, dodecyl, t~tradecyl, and
- octadecyl. R' can also be a substituted alkyl group. Suitable
> substituents include, in general, any group which will not inter-
fere with polymerization through a vinyl double bondO Typically,
- the substituents can be carboxylate, cyano, ether, amino (pri-
; mary, secondary 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) CH2 llH2
R-C C-~
-, I I
:: CH2 CH2
N ~'
~- R'
'~ ~ where R and R' are as indicated above, either alone or as a
mixture with other copolymerizable ingredients~ in the presence
o~ a ~ree radical catalyst and then neutralizing the salt to
give the polymer free base.
:
Speci~ic hydrohalide salts of the diallylamines which
can be polymerized to provide the polymer units o~ the inven-
20 tion include diallylamine hydrochloride; N-methyldiallylamine
hydrochloride; N-methyldiallylamine hydrobromide; 2,2'dimethyl-
N-methyldiallylamine hydrochloride; N-ethyldiallylamine hydro-
~ .
;~ bromide; N-isopropyldiallylamine hydrochloride; N-n-butyl-
diallylamine hydrobromide; M-tert-butyldiallylamine hydro-
chloride; N-n-hexyldiallylamine hydrochloride; N-octa-
decyldiallylamine hydrochloride; N-acetamidodiallylamine
hydrochloride; M-cyanomethyldiallylamine hydrochloride; N-~ -
.:.
propionamidodiallylamine hydrobromide; N-carboethoxymethyl-
diallylamine hydrochloride: N-~ -methoxyethyldiallylamine
hydrobromide: N-~ -aminoethyldiallylamine hydrochloride; N-
hydroxyethyldiallylamine hydrobromide; and N-acetohydrazide
~;~ substituted diallylamine hydrochloxide.
~- Diallylamines and N-alkyldiallylamines, used to prepare
,:. '
; the polymers employed in this inventionO can be prepared by the
... . ~
13 -
~:. ' ....
~, ~"' ,
i73~
~ -eaction of ammonia or a primary amine with an allyl halide
.
employing 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~
erric bromide, zinc chloride0 mercuric iodide, mercuric nitrate~
mercuric bromide, mercuric chloride, and mixtures of two or more.
.
; Thus, for example, N-methyldiallylamine can be prepared by re-
action of two moles of an allyl halide, such as allyl chloride,
.'.
s with one mole of methylamine in the presence of an ionization
~ ...
10 catalyst such as one of those enumerated abovep
In preparing the homopolymers and copolymers~ reaction can
be initiated by redox catalytic system~ In a redox system, -the
~ catalyst is activa-ted by means of a reducing agent which produces
;, free radicals without the use of heat~ Reducing agents commonly
used are sodium metabisulfite and potassium metabisulfi-te.
Other reducing agents include water-soluble thiosulfates and
bisulfites; hydrosulfites and reducing salts such as the sulfate
of a metal which is capable of existing in more than one valence
, state such as cobalt, irone manganese and copper. A specific
` 20 example of such a sulate is ferrous sulfate. The use of a re-
dox initiator system has several advantages, the most important
;. ,~
` of which is efficient polymarization at lower temperatures.
Conventional peroxide catalysts such as ter-tiary-butyl hydro-
peroxide, potassium persulfate, hydrogen pero~ide, and ammonium
: persulfate 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
..:..;
units of formula (I) and/or contain units of one or more other
copolymerizable monomers. TypicallyO the comonomer is a differ-
-~ ent diallylamine~ a monoethylenically unsaturated compound con-
-; taining a single vinyl or vinylidene group or sulfur dioxide,
';~ and is present in an amount ranging from 0 to 95 mole % of the
,. .":
polymer. Thus the polymers of diallylamine are linear polymers
~':..... :
r ................................... 14
~5
;"
~C~4573~i
~herein from 5% to 100% o~ the recurring units have the formula
(I) and from 0 to 95% of the recurxing units are monomer units
derived from (1) a vinylidene monomer and/or (2) sulfur dioxide~
Preferred comonomers include acrylic acidO methacrylic aci~,
methyl and other alkyl acrylates and methacrylates, acrylamide D
methacrylamide, acrylonitrile, methacrylonitrileO vinyl acetate,
vinyl ethers such as the alkyl vinyl ethers, vinyl ketones such
as methyl vinyl ketone and ethyl vinyl ketone, vinyl sulfonamideO
. ,.
sulfur dioxide or a different diallylamine embraced by the above
~r~ 10 formula (II)o
` ` Specific copolymers which can be reacted with an epi-
halohydrin include copolymers of N-methyldiallylamine and sulfur
, ,
dioxide; copolymers of N-methyldiallylamine and diallylamine;
copolymers of diallylamine and acrylamide; copolymers of
diallylamine and acrylic acid; copolymers of N-methyldiallyl-
amine and methyl acrylate; copolymers of diallylamine and acrylo-
,
~; nitrile; copolymers of N-methyldiallylamine and vinyl acetate;
copolymers of diallylamine and methyl vinyl ether; copolymers of
N-methyldiallylamine and vinylsulfonamide, copolymers o~ ~-methyl-
diallylamine and methyl vinyl ketone; terpolymers of diallyl-
amine, sulfur dioxide and acrylamide, and terpolymers of ~-
.. .methyldiallylamine, acrylic acid and acrylamide.
The epihalohydrin which is reacted with the polymer of a
diallylamine can be any epihalohydrin, i O eO, epichlorohydrin,
~; epibromohydrin~ epifluorohydrin or epiiodohydrin and is prefer-
ably epichlorohydrin. In general~ the epihalohydrin is used in
an amount ranging from about 0~5 mole to about 1.5 moles and
~i preferably about 1 mole to about 1.5 moles per mole of secondary
; plus tertiary amine present in the polymer.
;~ 30 The poly(diallylamine)--epihalohydrin resin can be pre-
^ pared by reactin~ a homopolymer or copolymer of a diallylamine
as set forth above with an epihalohydrin at a temperature of
from about 30C. to about 80C, and preferably from about 40Co
` ~ to about 60C. until the viscosity measured on a solution con-
. .
*. 15
. , ,
.: .:
''', ' ~ : ' '~'
. .
aining 20% to 30% solids a-t 25Co has reached a range of A -to E
. and preferably about C to D on the Gardner Holdt scaleO The re-.~- action is preferably carried out in aqueous solution to moderate
the reaction, and at a pH of from about 7 to about 9O 5~
i When the desired viscosi-ty is reached, sufficient water
, . .
;: is added to adjus-t the solids content of the resin solution to
. about 15% or less and the product cooled to room temperature
, (about 25C.).
The poly(diallylamine)~-epihalohydrin resin can be sta-
~ 10 bilized against gelation by adding to the aqueous solution there-
s: of sufficient water-soluble acid (such as hydrochloric acid and
`?,' ' . .
sulfuric acid) to obtain and maintain the pH at about 2.
................. The following example illustrates the preparation of a
.~ poly(diallylamine)-~epichlorohydrin resin.
. .
-~ A solution of 69.1 parts of methyldiallylamine and 197
parts of 20 Be hydrochloric acid in 111.7 parts of demineralized
water is sparged with nitrogen to remove air O then treated with
0.55 part of tertiary butyl hydroperoxide and a solution of
20 0.0036 part of ferrous sulfate in 0.5 part of waterO The re-
. sulting solution is allowed to polymerize at 60-69C. for 24
,: ~
hours to give a polymer solution con-taining about 52.1% solids
with an RSV of 0.22. 122 parts of the above solution is ad-
, - ~ .
. justed to pH 8.5 by the addition of 95 parts of 3.8% sodium,:;
~: hydroxide and then diluted with 211 parts of water and combined
. ~, .
. with 60 parts of epichlorohydrin~ The mixture is hea-ted at
~ 45-55C. for 1.35 hours until the Gardner-Holdt viscosity of a
,? sample cooled to 25C. reached B-~ The resulting solution is
: acidified with 25 parts of 20 Be hydrochloric acid and heated
5 .. : ,:, 30 to 60C. until the pH becomes constant at 2O0~ The resulting
~;...~.,
~: resin solution has a solids content of 20.8% and a Brookfield
~ .,. .,:
viscosity = 77 cp. (measured using a Brookfield Model LVF
.~. Viscometer, ~o. 1 spindle at 60 r~p mO with guard).
16 =
~?
:'' .:
~10 45735
..
This example illustrates the preparation of fumaric acid
~ ,.
fortified rosin. Fumaric acid~ 6.5 parts9 is adducted, at a
temperature of about 205C. with formaldehyde treated tall oil
rosin, 93.5 parts. The fumaric acid dissolves in the fused tall
oil rosin and reacts therewith to provide fumaric acid fortified
tall oil rosin. After substantially all the ~umaric acid has
reacted with the tall oil rosin, the fortified rosin is cooled to
room temperature (about 23C1)O The fortified rosin contains
6~5% fumaric acidD substantially all of which is in the combined
or adducted form.
Examplel
A solution is prepared by dissolvin~ 300 parts of a forti-
fied rosin as prepared in Example D in 300 parts benzene~ This
solution is thoroughly mixed with 400 parts (50 parts solids) of
:, .
an aminopolyamide -epichlorohydrin resin solution prepared as in
Example ~ diluted with 350 parts of water providing a premix
which is homogenized twice at 2000 p.sOi.g. The resulting prod
uct is a stable oil-in~water emulsionO Substantially all of the
benzene is removed from the emulsion by distillation under re-
duced pressure with the pot temperature at about 40C. The
,;,
solids content of the resulting dispersion is about 35%O Of the
solids content about 30% is fortified rosin and about 5% is
:.
` epichlorohydrin aminopolyamide--epichlorohydrin resin. The
~: .
dispersion is stable for a period oE about 6 months.
-
Example 2
Example 1 is repeated using 200 parts fortified rosin
prepared as in Example D dissolved in 200 parts benzene with 150
; parts aminopolyamide--epichlorohydrin resin (18.8 parts solids)
. ~.
blended with 550 parts water~ The solids content of the result-
::
~ ing aqueous dispersion is about 24%~ Of the solids content about
; 22% is forti~ied rosin and about 2% is aminopolyamide--epichloro-
~ hydrin resin. The dispersion has yood stability~
''' '
~ 17 =
.~'-.
,...
L573~i
.,
EX~mE~3
.. Example 1 is repeat.ed using 750 parts aminopolyamide~
:. epichlorohydrin resin (93O8 parts soLlds) wi-th 750 parts water.
,i The solids content of the resulting aqueous di~persion is about
22%o 0f the solids conter.t about 17% is fortified rosin and
-. . .
;.......... about 5% is aminopolyamide~epichlorohydrin resinO The disper~ :
sion has good stabilityO
_a
. Example 1 is repeated using 500 parts aminoamide~epichlorohydrin resin [62O5 parts solids) wit:h 250 parts waterO
The solids content of the resulting aqueous d.ispersicn is about
35%. 0f the solids content about 29% is fortified rosin and
.~ about 6% is aminopolyamide~=~epichlorohydrin res.inO The disper~
sion has good stability~
ExamE~
Example 1 is repeated using only 150 parts benzene to
,;
,~ dissolve the fortified rosin and only 250 parts water to dilute
'~?'""'` the aminopolyamide~epichlorohydr.in res.inO The total solids of
~ , the resulting aqueous dispersion is about 37~5%O 0f the solids
:, ,.,;
.. 20 content about 32% is fortified rosin and about 5O5% is am.ino=
polyamide -epichlorohydrin resinO The dispersion has good
:
.; stability.
le 6
Example 1 is repeated ~Is.ing 600 parts benzene -to dissolve
`' the fortified rosinl The total solids of the resulting a~ueous
;.. :, dispersion is about 35%, Of the solids content about 30% is
~` fortified rosin and about 5% is aminopolyamide~-eplchlorohydrin
:, '.'.:
. ~ resin. The dispersion has good stabilityO
... .
... x~ E
This example i.llustrates the p.reparation of fumaric acid
. ,~
: fortified rosin. Fumaric acidD 14 parts0 is adductedO at a
temperature of about 205Co with formaldehyde treated tall oil
. rosin~ 86 parts~ The fumaric acid dissolves in th.e fused tall
oil rosin and reacts therewith to provide fumarlc acid fortified
~ ~ 18
'' . ~
~915~73~i
~: ~11 oil rosin~ Af-ter subs-tantially all the fumaric acid has
reacted with the tall oil rosinO the fortified rosin is cooled
; to room temperature (about 23Co ) o The fortified rosin contains
14% fumaric acidO substantially all of which is in the combined
: ~ or adducted form~
Example 7
A solution is prepared by dissolving 128 ~ 5 parts of forti~
., fied rosin as prepared in Example Eo 210 5 parts formaldehyde
treated tall oil rosin and 150 parts of a copolymer of vinyl
toluene and ~-methyl styrene which hai, a molecular weight of
about 1400V a ring and ball softening point of about. 120Co o and
.~ an acid number less than 1 in 300 parts benzeneO This solution
is thoroughly mixed with 400 parts (50 parts solids) of an amino~
'j/ polyamide--epichlorohydrin solution prepared as in Example A di-
.'' luted with 350 parts of water providing a premix which is homo-
~; genized twice at 3000 posoi~ The resulting product is a stable
.. oil-in-water emulsion from which substantially all of the benzene
`~ : is subsequently removed by distillation under reduced pressure
' .,
, "~~, with the pot temperature at about 40Co The solids content of,,", .; ... .
'. ~ 20 the dispersion is about 33%o Of the solids content about 1402%
'~ ~ is vinyl toluene-- d-methyl styrene copo.lymerO about 408% is; ~
~.;." aminopolyamide--epichlorohydrin resinD and about 109% is combined
"-.~ fumaric acid.
. Example 8
~, Example 7 is repeated using 134 parts formaldehyde
treated tall oil rosin and 3705 parts vin~l toluene~ ~ ~methyl
~ styrene copolymer. The solids content of the resulting disper~
i sion is about 34%1 Of the solids content about 3 o 6% is co
,
polymer~ about 408% is aminopolyamide~-epichlorohydrin resin
', 30 and about 1.9% is combined fumaric acid. The dispersion has
: .
good stabilityO
, Example 9
A solution is prepared by dissolving 12805 parts of
. fortified rosin as prepared in Example Eo 2105 parts formaldehyde
t ,
';-~ '
~',. r~,
, . ~ 1 9
: .
~'' ;' , . ' ~ ' :
4~i~735
reated tall oil rosin and 150 parts of a fully refined paraffin
wax (mOpO about 145Fo) D in 300 parts benzene by mixing and
warming at about 60Co to dissolve the paraffin waxO This solu~
tion is thoroughly mixed with 400 parts (50 parts solids) of an
aminopolyamide--epichlorohydrin resin solution prepared as in
Example A diluted with 350 parts of waterO Before mixing the
two solutions, the diluted aminopolyamide-~epichlorohydrin resin
is warmed to about 60C~ The warm premix is homogenized twice
at 4000 pos~i. in an homogenizer which is preheated to about 60Co
The resulting product is a stable oil in~water emulsion from
;
i- which substantially all of the benzene is removed by distilla~
:.':.:; tion under reduced pressure with the pot temperature at 40C~ to
,. 50Co The total solids of the aqueous dispersion is about 31%o
:~ Of the solids about 13 o 8% is wax~ about 4O4% is aminopolyamide~
... epichlorohydrin resin and about 1~8% is combined fumaric acid.
. The dispersion has good stabilityO
~ Example 10
.. Example 9 is repeated using 14.5 parts formaldehyde
,~: treated tall oil rosin and 30 parts fully refined paraffin waxO
. 20 The total solids of the resulting aqueous dispersion is about
:; 36%. Of the solids about 3.1% is waxO about 502% is aminopoly
amide--epichlorohydrin resin and about 2% is combined fumaric
,....
. acid. The dispersion has good stability.
.i, Example F
.....
: A reaction kettle fitted with a steam ~et vacuum system
is charged with 704 parts water and 476 parts epichlorohydrinO
The steam jet vacuum system is turned on to exhaust vapors
through a condenser and prevent them from escaplng through the
. open manholeO 420 parts of Amine 248 is added with agitation in
;,.:;.: .
. 30 35 minutes while the temperature is allowed to rise to 70Co
;: Cooling water is required to limit the temperature rise to 70Co
: After the amine addition is complete the resulting mixture has
;~
-: a pH of 708 and an A viscosity by Gardner HoldtO Six parts of
20% NaOH is added to speed the reactionO After two hours and
. .,
20 -
.
. .,
-' 10~35
rO minutes at about 70Co o the visco~ity reached a ~ viscosity
and the resin solution is di].wted w.ith 640 paxts of water which
reduces the viscosity to abou-t C--O A tot.al of 44 parts 20% ~aO~
.~ is added in four separate additions during 1~3j4 period to speed
reaction. An S ~iscos.ity is reached after three hours and 35
minutes~ and the reaction is killed and diluted with 26 parts
concentrated sulfuric acid .in 1345 parts waterO This gives an
', aqueous solution having a solids content of 23O3%~ a D viscosi-ty
.` and a pH of 4~4O Additional H2SO4 and water are added to provide
: : 10 a solution having a pH of 4 and a solids content of 22O5%o The
resin solution is filtered thru 100~ filter cartridges to give
a total of 3336 parts productO Amine 248 is a commercially
,.~ available liquid mixture of long chain aliphatic pclyamine~s,
~'.. At least 75% of Amine 248 consists of bis~hexamethylene)
- triamine and higher homologues n The remainder consists of lower
,~.. ., molecular weight amines~ nitr.iles0 and lactamsO
- Example 11
~., A solution is prepared by d.issolving 300 parts of forti-
f~ fied rosin as prepared .in Example D in 300 parts benzene. This
',j' 20 solution is thoroughly mixed with 217O4 parts (50 parts solids)
,~ ~
of the epichlorohydrin-polyamine reaction prcduct prepared as in
. Example F and diluted with 533 parts of watex providing a premix
.. ' ~ .
~: which is homogenized twice at 2000 p~S~io The resulting product
.: is a stable oil-in-water emulsion from which substantially all
, of t'he benzene is subsequently removed by di.sti.llation under
i reduced pressure at about 40CO The solids content of the re-
:. .
-; sul-ting dispersion is about 35%, Of the solids content about
.,. 30% is fortified rosin and about 5% is epichlorohydrin~polyamine
~": reaction productO The dispersion has good stabi.lity,
" 30 Fxample 12
t~'' A solution is prepared by dissolving 12B,5 parts forti-
; ~ fied rosin prepared as in Example E D 141O5 parts tall oil rosin
' . and 30 parts fully refined paraffin wax ln 300 par~s benzelle by
mixing and warming to 60Co to dissolve the paraffin waxO This
... ..
.,~, . .
.: ,: ,;
~ 21 -
.. "':,:
.,,,.: .
5'73~i
jolution is thoroughly mixed with 21704 parts (50 gO solids) of
the epichlorohydrin~polyamine reaction product prepared as in
Example F and diluted with 533 parts of water~ Before mixing
the two solutions, the diluted epichlorohydrin-polyamlne re~
action product is warmed to about 60C~ The warmed premix is
homogenized twice at 2000 po s o i o in an homogenizer preheated to
; :;
about 60C. The resulting product is a stable oil=in~water
` emulsion from which substantially all of the benzene is sub~
".~
sequently removed by distillation at atmospheric pressure during
which the product temperature increases from about 75C R to about
. "
~ 100C. The solids conten-t of the resulting dispersion is about
36. 0%o Of the solids content about 3 01% is paraffin waxO about
. ...
5.2% is epichlorohydrin--polyamine reaction product and about 2%
is combined fumaric acidO The dispersion has good stabilityO
~:,.. .
~ Example G
!,., ~ . .
, :~
To a solution of 26. 2 parts of iminobis(propylamine)O also
~ called bis(3-aminopropyl) amineO in 82 parts of water is added
f' "'.' 55.6 parts o epichlorohydrin in one portion~ The resulting
mixture is held between about 43Co and about 58Co by external
cooling for about 007 hourO until the exothermic phase of the
reaction is over. The mixture is then heated at about 70C.
for about 0~8 hourO during which the viscosity of the mixture
increases to a ~ardner Holdt viscosity in excess of ~0 The
' mixture is then diluted with 364 parts of water and adjusted to
: .~
p~I 4.5 with sul~uric acid. The resulting resin solution contain$
about 16.5% solids and has a Brookfield viscosity of 10 centi~
,.!"'' ' poises (#1 spindle~ 60 rpm.)~
l Example 13
,
,- Example 1 is repeated using 301 parts (50 parts solids)
~:
', ' 30 of an epichlorohydrin polyamine reaction product prepared as in
: :.
~`~ Example G with 300 parts of water as the aqueous phase~ The
premix is homogenized twice at 3000 pOSO io The total solids of
the resulting aqueous dispersion suspension is about 39%0 Of
~ "'':':: '
; ~~ the total solids about 5.6% is epichlorohydrin~polyamine reQ
... ;~: ~
i~ ~ 22 ~
', "':
0~5735
.ction product and about 33% is fortifled ro3inO The dispersl~sn
has good stabilityO
. Example EI
Seventy-four parts of epichlorohydrin is added to a
;. solution of 37.8 parts of tetraethylenepentamlne in 112 parts
i~ of waterO during a period of 15 minutesO The temperature rises
.. to about 55C3 The mixture is then heated externally and main~
..
tained at about 60C. for one-half hourO then at 70~Co for about
~.:
~ three hours D during which time the Gardner~Hol.dt v.iscoslty
: 10 reaches Bo The resulting resin solution is then cooled to room
: .,,: .,
- temperature (about 25Co) and aged for 11 daysO during which the
u resin solution reaches a Gardner~Holdt viscosity of ZO The resin
;.`~ solution is then diluted with 524 parts waterO The resulting
.- solution contains about 15.3% non-~vclatile solids and has a
!~ '
' Brookfield viscosity of 23 centipoises (Modél LVF viscometer0
; , #1 spindleO 60 rpm,0 25)~
: ~ ExamPle 14
Example 13 is repeated using 327 parts (50 parts sclids)
epichlorohydrin-polyamine reaction product prepared as in EX~3
. 20 ample H and 327 parts water as water phaseO The total solids
:~ of the resulting product is about 37%3 Of the total solids
. about 5.4% i9 epichlorohydrin~polyamine reactlon product and
:.: about 32% is fortified rosin3
,1 ,; ~m
,:
, To 250 parts of methyldiallylamine is added 31~wly 230
.. ;. parts 37% hydrochloric acid in about 240 parts demineraliYed
::~ water. The mixture is cooled as required to preve~t volatlliza~
,~: tion of materials due to the heat of reaction3 The pH of the
,:,.
i resulting mixture is then adjusted to 3Ol by addltion of addi~
. .
... 30 tional (19 parts~ methyldiallylamineO After the oxygen in the
~ reaction vessel is displaced with nitrogenD 2O2 parts t butyl
... hydroperoxide is added. This is followed by o0014 parts ferrous
~ sulfate hepta hydrata in 1.1 parts demineralized waterO When
:.
~ the reaction mixture is warmed to 60Co o there is a mild exo-
: '
:''.
~:- ~ 23
.~ ." -,
;:;
. . ,
'735~
_hermic reaction which carries the reaction temperiature briefly
to ahout 66C,-70C. For the xemainder of the 24 hour reaction
. .
.
. time the temperature is held at about 60C o After cooling to
~:. 25-30C., the total solids of the product is about 4804% and the
.
:~ RSV .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 parts water) to adjust the pX to abollt
8.5. The neutralized polymer solution is diluted with 366 parts
.- demineralized water and then heated to about 40Co To the wa.rm
solution is added 106 parts epichlorohydrin and the reaction
` warmed further to react the epichl.orohydrin at about 50 55Co
~ .- .,
~-. Reaction is continued until the reaction mixture reaches a
'- ';`:
Gardner viscosity of about B~ (about 107 hours)0 At this time
the reac-tion is quenched by the rapid addition of about 35 partis
37% hydrochloric acid to give a final pH of about 20 There is
:. .
~ obtained 859 parts of a product containing about 20O7% total
., .
.~ : solids. A series o~ runs are made approximately as described
above to give a total of about 73 95 parts of product with about
20..4% total solidsO
,':'., '
Exam~e 15
Example 13 is repeated using 245 parts (50 parts solids~
,. of a epichlorohydrin modified tertiary amine polymer prepared as
. . .
;.. in Example J diluted with 505 parts water as the aqueous phaseO
.~
,' The total solids of the resulting stable a~ueous suspension iis
,....
~ about 33%o 0 the total solids about 4O 7% is tertiary amine
,
~:.. : polymer and about 28% is fortified rosinO
,,., ;.;:
,,,, ~e~
A solution i.s prepared by dissolving 300 parts fortified
rosin prepared as in Example D in 200 parts benzene in a suitable
:j. . . '
,!,;.:~ 30 vessel provided with excellent ayitation by means of an air motor
. driven propellor-type stirrer. To this well stirred solution is
~.;,.: added 400 parts (50 parts solids) of aminopolyamide-~epichloro
;" hydrin resin prepared as in Example A~ This results in a stable
.i;~ .: .
;~.......... water-in-oil emulsion which is inverted by the rapid addition of
i:
~,,,
~;: 2~ -
:~ .
~5~35
~0 parts cold (about 20C~ ) water whlle continuing vi.gorous
.
stirring. After addition of water is complete D stirring is con~
-tinued for about 23 minutes to ensure complete inversion to a
stable oil~in-water emulsion from which substantially all of the
... :. benzene is subsequently removed by distillation under reduced :
pressure with a pot temperature of about 40Co The total solids
. of the resulting stable aqueous suspension is abou-t 34%~ of the
.. total solids about 4~8% is aminopolyamide -epichlorohydrin resin
~` and about 29% is fortified rosinO
`;*, 10
.,~.~
:: To determine the sizing efficiency of the aqueous dis~
persion of Example 19 handsheets are prepared using the disper~
, :. ,
sion as the sole sizing agentO To prepare the handsheets~ a
50:50 blend of Rayonier bleached softwood kraft pulp and Weyer~
haeuser bleached hardwood kraft pulp is suspended in standard
hard water and beaten to 500 Canadian standard freeness in a
Noble and Wood cycle beaterO A 2-liter portion of the beater
. slurry, which has been diluted to 2~5% solids by weight are
... treated with sufficient alum to provide a pH of about 4O5 m e
: . 20 slurry is then diluted to a consistency of 0O27% .in the propor~ .
tioner, using acid-alum dilution water~
,.: .
:.......... The dilution water is prepared by reducing the pH of
i :~ water of moderate hardness to 5 0 with sulfuric acid~ then adding
~.......... enough alum to provide 5 p~p m. soluble aluminumO One--l.iter
; .;: -.
~:: portions of proportioner pulp slurry are treated with sufficient
~` of the size of Example 1 to give 0.4% size based on the dry
, . ,:: .;
..... ~ weight of pulp, They are diluted further with acid alum dilution
~ water to a deckle box consistency of 0~025% in order to form 40~ , ~
. ~ pound basis weight (24" x 36" ! 500 sheet ream) handsheet using
..,. 30 a ~oble and Wood sheetmaking apparatus~ A closed white water
system is employed~ Formed sheets are wet-pressed to 33% solids
, . .. .
;. ; content and then dried at 240Fo on a steam drum drierO All
;' !
. handsheets are conditioned for at least seven days at 72Fo and
50% relative humidity and are tested in this environment for size
.::.,,
,;,, ~
2 5
:,~
:: , .
, ~1 ,. . . .
~IL0~5735
pS`Dper~ies by usinq ~Iercules Sizing ~est. Using ~2 test solution
~o 803 refl~ctance the test time is about 139 seconds.
;` Example 18
.... .
~ o determine the sizing efficiency of the aqueous dis-
persion of Example 1 at pH 6.5 the handsheet making of Example
17 is repeated using only 0O4% alum with the pH of the system
.......
adjusted to pH 6.5 as required. The results of the Hercules Siz-
. .
ing Test in this case is 82 seconds.
Example 19
. . _ ,
To determine the sizing efficiency of the aqueous sus-
pension of Examples 2, 3, 4, 5, 13, 14 and 15 surface sizing
,.: .: '
experiments are performed using bleached kraft paper (40 lb. per
500 24" x 36" sheets) made at pH 6.5 with 0.5% added alum. The
sheets are treated using a small laboratory horizontal size
press by adding samples of the aqueous suspensions diluted to
about 0.54~ to the nip of t~.e size press and passing sheets of
paper through the solution before being saueezed by ~he rolls of
the size press. Under these conditions the sheets pick up about
; 70% of their weight of size press solution to give about 0.38%
size applied to the sheet. The sized sheets are dried about
:.: .
``~ 18 seconds on a laboratory drum dryer with the surface tempera-
, :. -
~ ture about 200F. The sheets are aged four days and then tested
;, using num~er two test solution with the Hercules Sizing Tes~ to
; , 85% reflectance. The following summarizes the results.
:;. . .
Hercules Sizing Test
Size o ExampleResults in Seconds
: :,.
; 2 280
3 366
4 372
411
;~ 13 339
` 14 305
245
Example 20
To determine the sizing efficiency of the aqueous
suspensions of Examples 7, 8, 9, 10, 11, and 12 surface sizing
.
is c~rried out as in Example 19 except the siæing solutions are
; A
..... . .
. ,
.;.~ ,. .... ,
~``,, . , - . , .
S~35
-- ly about 0.45'~ so th~ only about 0.32'~ of each siz~ is
~ppliedO
Hercules Sizin~ Test
`,: to 85~ P~eflectance
Size of Example Results in Seconds
7 183
: 8 311
`: 9 239
217
: 11 216
: 12 140
Example 21
: ., .
In another demonstration of sizing efficiency of the
aqueous suspension prepared as in Example 1, about 0.4% of the
' ~ solids of this suspension and about 0.4% alum are applied in
., .
'~ about 4.5~ Penford Gum 280 (ethoxylated corn starch) to the
: . .
~ ; surface of a 40 lb, bleach kraft water leaf sheet made at pH
: .
.` about 7.5. In this case ~2 test solution used in the Hercules
,:.,,~
Sizing Test to 80% reflectance gives 252 seconds.
~.. ,
,. . . .
.
.i.,,. . ,; ;,
,,. ;,. ~ . . . .
~ :;, . . .
i',; :~,. .
, .. .. .
... . . .
"
. . . .
.:.:.
:: ,',: ;;
; ,. ..
.~','. 1 .
~, ' ' , . .
,'~';' . .
;"j.'`~; ~ .
'~ ;.' ~ ' ' . ' _
~: ~7-
",~,.. . .
, ....
- ~ TRADE ~RK
,,.,~, ,~;
,~
~ `h
, .... . . ~ .` . .` ~
` - . . . . . .. . ~ `
