Note: Descriptions are shown in the official language in which they were submitted.
This invention relates to cationic, water-soluble, amine-epichloro-
hydrin polymer compositions and to the uses of these polymers in the pulp and
paper industry to improve drainage, provide retention of fiber fines, dyes,
pigments, filler3, starch, and gum and increase strength. In a~ditlon, said
polymers are useful as resins in the manufacture of electroconductive paper and
: the sizing of paper and paperboard as well as the separation of minerals ln ore
processing operations.
The cationic polymers of thls invention can also be used~to lmprove
aqueous adhesive formulations, as flocculants for the purificatlon of wa~er and
the processing of wastes, to improve dye~bility and color fas~ness in textiles,
and to increase the adhesion of water-proofin~ and flame-proofing finislles to
fabric~. The cationic polymers of this invention are also effPctive in con-
trolling the growth of algae, bacteria and fungi in swimming pools and in
commercial and industrial coolin~ and proce~s water.
C~tionic polymers have been used in the past ~n the pulp ~nd paper,
¦textile, and water treating industrie~ for the uses de~cribed in tllis invcntion;
put none, however, are entirely ~atisfac~ory. Some are use~ul as retention a~cls
~nd flocculants but do not provlde any of the othcr desired benefits. Ionene-
~ype polymers whlch are prepared by reactins di-tertiaryamine~q with dihalo
~ompoullds are typically products wlth relatively low molecular wei~h~s. The~e
.
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products may be effective for controlling microorgani~ms, but their use as
flocculants i~ limited. The most versatile cationic polymers are the poly-
ethylenlmines which can ~e manufactured in various molecular weight ranges by
the selection of different catalysts and the use ol. cross-linking reagQn~s.
S l one of the polyethylenimines are good microbicides. In addltion, the manu-
; ¦ facture of polyethylenimlnes requires tbe use of the very toxic monomer
¦ethylemi~ine which, in recent years, has been described as a carcinogen, and
severe restrictions have been placed on the handling of the monomcr in com-
mercial and industrlal plants by ~overnment regulatory agencles.
¦ It iB, therefore, a princip~l ob~ect of this invention to provide
novel cationic, water-soluble, amlne-epichlorohydrin polymers.
It is another ob~ect of our invention to provide methods for improving
drainage and increasing retention of fines, dyes, pi~ments, fillers and s~arch
in the papermaking process as well as increasing s~ren~th, improving sizing and
l 15 increaZl~ing electrical conductivity of paper and paperboard.
i It 18 yet another ob~ect of our invention to provlde methods for
,~ improving aqueous adheslve formulatlons.
It i~ yet another ob~ect of our invention to'provide methods of floc-
culatin~ impurities in water and methods of improving processing of wastes.
It i~ yet another object of our invention to provide methodZZ3 of
i improving dyeability and color fastness in textiles and of lncreasing the
Z adheZZ310n of water-proofing and flame-proofing ~inishes to fabrics.
Z~ ~ ; It i9 yet another object of our lnvention to provlde methods of con-
l ~ troIling the growth of algae, bacteria, and fungi in ~wimmin& pools and ln com-
Z 2S mercial and $ndustrlal coollng and process water.
~, These and other objects and advantages of the novel compositlons and
method~ of this inventlon will become apparent as the descr$ption proceeds.
~ ' . ~; ~': :
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To the accompli~hment o the foregoing and related ends,
this invention then comprise~ the features hereina~ter fully
;described and particularly pointed out in the claim~, the
following description setting forth in detail certain illustra-
5 tive embodLments of the invention~ these beiny indicative, :
however, of but a few of the various ways in which the .:.
principles of the invention may be employed.
The novel cationic, water-soluble~ amine-epichlorohydrin
~ .. . .
: polymer compositions have the structure: : :
10~H ~H
: A- -CH2 - C~ - CH2 - B- - CH2 - ~H - CH2 - A
; ,. ~ ,, ~ . .
wherein n as used herein and throughout the specification and
claim represents an integer; A repre~ents
15 R' R" R'l RU R"
~ R' - ~ -J -~ - X - T -~ - x -~N - Y,
~ Cl ~ , Cl~R" R" Cl ~ " Cl ~ "
. ~ A .
~: N ~ , or ~ - C~ - C ~ - 3 N~ ;
~:- 20 Cl R~
R R
B represen~s - N- or -I ~ thereby providing ~or branching ~n
~; the polymer chain7
PolYmefh /e~e ;
- B~ 25 X represents a ~ group containing I to 12 carbon atoms,
CH2 ~H CH2 -~ - C~2 - CH2 - O - CH2 - C~2 -, or
OH `-
:; - C~ - C~ - CH - CH2 -; : ::
H : 1 OH
30 Y represent~ t CH2 - CH - CH2 - B- - C~2 - CH - C~ A . :
n ; :
. .
R represent~ a ~traight or branched chain aliphatic g~oup
:` A~ ~3~ .
- . .... - :. . . , . . .. ,....... -
~ ,L7d~
containing 1 to 20 carbon atoms a~d 0 to 2 carbon to carbon
double bonds, a straight or branched chain aliphatic group con-
taining 1 to 6 carbon atoms and one or more hydroxyl or chloro
substituents, an alicyclic group or an alkaryl group.
Each ~f the R' groups independently represents a straight
or branched chain aliphatic group containing 1 to 20 carbon atoms
and 0 to 2 oarbon to carbon double bonds, a straight or branched
chain aliphatic group containing 1 to 6 carbon atom~ and one or
more hydroxyl substituents, an alicyclic group, an alkaryl group,
or an aryl group:
R" repre~ent~ a stralght chain aliphatic group containing
1 to 6 carbon atoms.
The polymer~ of this invention are prepar~d using a two-
stage reaction procedure. In the first stage, one ~ole of a
primary amine i~ reacted with two mo}es of epichlorohydrin or one
mole of ammonia is reacted with three moles of epichlorohydrin to
produce the polymeric precursor. Similar reaction~ are described
in the chemical literature using water as solvent. ~owever, when :
- water may be used, an ill-defined polymeric substance i~ obtained,
20 and the ionic chloride de~eloped in the reaction cannot be corre- ~;
lated with the expected products~ The reaction is best conducted
in the presence of polar solvents ~uch as methanol, ethanol, ~:
l-propa~ol or 2-propanol. Som~ water may be present, but the .
: amount o~ water should be lesæ than the amount of the organic ~ol- :
.
: 25 vent. During the addition of the f~ ~t mole o~ epichlorohy~rin
to the amine solution, the reaction tem~erature ~hould be below
30D C. The remainder of the reaction may then be conducted at .
tem~eratures as high a~ 60 or 70 C. Primary amine~ other than ;.
th~ lower alkyl amines require higher temperature~ fo:r co~pletion
o~ the reaction. The compound ~irst *ormed in this rleaetion is
~ .~ .
~ ~ ~4~ ~ ~
a tertiary amine containing at least two 3-chloro-2-hydroxy-
propyl substituents. Since compound~ of this type contain at
least two reactive organic chlorine atoms and a tertiary -~
nitrogen atom, these a~ines will react with themselves to form
branched polymeric quaternary ammonium compounds. This poly-
merization will occur even at room temperature ~nd is
accelerated if the xeàction mixture is kept warm. Conventional
analytical procedures can be used to follow the decrease in
tertiary amine content, and the corre-
' .'~
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10~69Z
¦spondlng increase in ionic chloride a.s the quaternary ~mmonium compound is forme .
¦ The tertiary amilles formed from one mvle of primary amine and two moles
¦of epichlorohydrin or from ammonia and three mole3 of epichlorohydrin contain at
lleast two active chlorine atoms and only one nitro~,en atom. As thQ quaterniza-
¦tion reaction occurs, the polymeric precursor will thu~ still have available hal
~to two-third~ of the active clllorine atoms f~r further reaction. In this invan-
¦tion, we have found that ehi3 polymerlc precursor will react with tertiary amine
to produce useful wa~er-soluble polymers.
I ~nten the precursor 18 reacted with compounds containing only one
tertiary nitrogen, no further polymerization occurs during the-second stage 3ince
¦the reaction involves conversion of end group chlorine to quaternary nitrogen
~hloride. The quantity of monotertiary amine to add will depend on the amount
¦ f o~gablc chlorine still available. ~hen a di-tertiary amine is reacted with
I he polymeric precursor, two or more of the precursor molecules will be ~oined ¦
ogether when both nitrogen atoms o the di-tertiary amine are quaternized. The
~, ~ ount of branching or crosR-llnking can be con~rolled by varying ehe amoun~ of
¦ he di-tertiary a~ine added. If the stolchiometric ratio of tcrtiary nitrop.en ¦
¦ toms to precursor monomer is one or greater than one, less branch'in~ or cros~-
linking will occur. We have found that hi~h molecular weight polymers are pro-
l uced whet the molar ratio of di-tertiary amine to bls~3-chloro-2-hydroxypropyl)
~mine calculnted as the monomer i8 less than 0,95 to 1. ~ten equimolar ratios
~re used,-lower molecular veight polymers are produced. However, the addition
~f polymeric precursor to these lower molesular weight polymers to provl~e a
~light molar exce~ of the precursor will increase the moIecular weight of tlte
; ! 25 ~inal product.
I ¦ The reaction of the polymeric precur~or with the tertiary amines iæ
, onducted at temperatures between 50 and 100 C. in squeous solution~ The
coholic solYent used in the precursor reaction may be left ln the reaction
ixture, but we have obtained our best produces by removtng the solvent by dis-
~illatlon a~ the reacti~n proceeds,
~1 ~ I , .
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1 ~176~2
When di-~ertiary amines are reac~ed with the precursor as described
¦ herein before, the deslred molecular weight wlll be obtained while unreflcted
¦ tertiary smlne groups are still present. Thus, polymerization will con~inue to
l occur even at room temperature over a period of several days. We have found
¦ that the polymeri~ation can be stopped at the desiLred molecular wei~ht by the
I addition of mineral acids to form a salt of the unreacted tertiary amine.
¦ We have found that the reaction of the yolymeric precursor with a
l-tertiary amine is fac~litated when the reactant:s are maintained in high
concentration. ~s the polymerization proceeds and the viscosity increases,
ater i~ added while heating i3 continued until the desired vlscosity and
oncentrstion are obtained. Reaction iB stopped by addin~ sufflcient mineral
cid to convert all of the unreacted tertiary amine to a salt.
A~ a further aid for a clear understanding of the nature of thc
vention, a listing of speclfic primary amines, tertiary amines containing
( 15 ~e tertiary nitrogen and tertiary amines containing two tertiary nitrogen
i ; toms suitable for use in the invention will be given. It should be under-
tood, however, that this listing is merely for the purpose of illustration;
~nd that our invention, as will be apparent to those skilled in th,e art, i9
, t limited to the use of the specific smines listed.
;~ 20 The primary amines which have béen found to be satisactory for the
eaction with epichlorohydrin to form the poIymeric precursor include aliphatic,
llcycllc, and alkylaromatic amlnes which may be substituted by hydroxyl or
hloro groups or contain carbon to carbon double bonds. The aliphatlc groups in
he~e amines may be straight or branched chains. Examples of these amines are
æ3 follows:
methyla71ne t-octylamine
ethylamine stearyla~ine
n-propylamlne cyclohexylamine
n-hexylamine 3-chloro-2-hydroxypropyla~ine
~ ,
. : ~ .~.
~, : ; ',
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~0~76gZ
isopropylamine benzylamine
.~ . n-butylamine tris~llydroxymethyl)me~hylamine
~-butylamine ethanolamine
. isobutylamine 3-hydro~y-2 me~hylpropylamine
: 5 t-butylamine i~opropanolamine
. Tertiary amines containing ~ne ter~iary nitro~en atom which can be
:~ react~d with the polymeric precursor include allphatic, alicyclic, alkyl-
ar~matlc, aromatlc and heterocyclic amines. The aliphatic ~roups may contain
one or more carbon to carb~n double bonds and may be substituted with hydroxyl
10 groups. Examples of these amines are a~ follows: ~:
. trimethylamine didecylmethylamine
, triethylamine dimethylmyristylamine
.I dimethylstearylamine . N,N-dimethylaniline .
dimethyldecylamine pyridine
dimethyloleylamine N,N-dimethylbenzylamine ::
~ethyldistearylamine triethanolamine
(3-chloro-2-hydroxypropy}) N,N-dime~hyletllanolamine
dimethylamlne
i Tertiary amines con~aining ~wo tertiary nitrogen atoms which can be ::
: 20 reacted with the polymeric precursor include the fallowing amine3: .
, N,N,N',N'-tetramethyl-1,2-diaminoethane
i N,N,N',N'-tetramethyl-1,3-dlaminopropane
N,N,N',N'-te~r~methyl-1,3-diaminobutane
N,N,N',N'-tetramethyl-1,4-dlaminobutane '
~:~1 N,N,N',N'-tetramethyl-1,6-diaminohexane -
N,N9N',N'-tetramèthyl-1,3-dlamino-2-propanol . .
I ~ N,N,N',U'-tetraoethyl-114-dlaminobutene-2 - .
. N,N,N',N'-tetramethylmethylenediamlne
bl beta-dlmethylamlDo~thyl)ether
. ' .
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¦ Suitable solvent3 that can be used in the preparation of the poly-
meric precursor are methanol, ethanol, l-propanol, 2-propanol, and other polar
¦solvents includ~ng mixtures l~ith water. If one wishes to lsola~e the polymeric
precursor, solvents such as hexane, ben~ene, toluene, or xylene can be used. llle
polymeric precursor will precipitate and can be removed by filtrà~ion.
¦ The catiGnic polymers of ~his invention are ~oluble in water or other
I ¦ polar solvents such as alcohols ~nd dimethylformamide. The molecular weights
¦ ill vary wldely depending on the reaction sequence followcd and t:he end use
1 ~f the product. For example, the reactivn products involving polymeric precursor
1 and mono-tertiary ~minea may be as low as 500 whereas the polymers made with
¦ d~-tertiary amlnes may have molecular weights as hlgh as 50,000 to 500,000.
¦ ~li9 lnvention provides a process for the preparation of paper or
aperboard wherein an aqueous fluid contalning cellulo9ic pu1p and other paper-
I aking lngredients is formed into a slleet on a fourdrinier wire cloth, one or
' 15 ¦ ore of the polymers of this invention being added to the aqueous fluid before
he furn~sh contacts the fourdrinier wire cloth. Thus, the polymeric composi-
ions of our invention are useful as drainage aidq7 fonnation aids, re~en~ion
ids, sizing agents, and as strength improving agents for paper and paperboard
1 8 well as resins. I~hen these polymers are used as pap~rmaklng aids for manu-
¦ acture of electroconductive paper, one ~r more of them may, for example, be3dded continuously to the paper machine system at ~uitable location.q such as the
¦ ac!!ine;cheat, the fan pump, or the headbox a~ concentrations ranging from 0.05
o 2 percent based on the weight of the dry pulp. The desirable results obtained
I y using these processe~ may be summarlzed as follows:
l 1. Increased production per unlt of equlpment;
¦ 20 Improved formation and c~rength properties of paper and
¦ paperboard;
¦ 3. Increase in overall mill efficiency in that losse9 of
~ dyes, flne flbers, pigments, fillers, starch, and otller
~, I . , '.
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.
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paper components ara minimized by lncreasing retention
; of these products ln paper and paperboard; and
4. Alleviation oE water pollution problem~ by usin~ the
polymers in ~hc recovery of the valuable materials
S remaining in the process waters of paper ~nd pulp
; manufacture.
These polymeric compositions can also be used to remove dissolved or
¦~olid particulatc matter remaining in the water before lt i~ dischar2ed even
¦~hough such matter is not of a character suitable for use but mu~t be disposed
;; 10 ¦of by microbiologlcal decomposi~ion or combustion, or buried in a ~anitary fill.
I ¦ These polymeric composition~ according to the invention are also usefu
¦in the treatment of incomin~ water supplies. These composit:Lons are fast-acting
¦flocculants nnd will achieve a reduction ln process time in addition to the
desired degree oP completeness in the removal of flnely dlvided or dlssolved
lS l solldA. S~r~lar princlpleY apply to the removal of dissolved and particulate
atter from water discharged a~ indu~tri~l or municipal effluents.
'~ ¦ ~ccordlng to ~ further feature of the in~ention, there i9 provided
l ~ I a method o flocculating Aolids from ~n aqueous ~ystem which comp~iseA addin~
to the a~ueous system one or more of these polymersj as herein before describcd,
¦in an amount sufflcien~ to cause flocculation of the solids. One or more of
I l the water-soluble polymers may be added to a given aqueous suspension with
~ufficient agltation to in~ure~unlform distribution. Follo~ing this treatment,
the flocculated AggregAtes will settle. ~le amount of the water-soluble
oIy~erA necesAary to protuce the desired resul~ is highly variAble depending
;25 ~j I n the~amouDt and nature of the particulate matter on which an effect ls
~ ¦ eeded as vell a~ the other components of -the ionlc environment in which the
I ~ 1 olymers and particulate matter~are present. Suitable quantlties of the
olymers of thlA ~nvention ~y vary from a8 low~as 0.1 part per~ ~illion, based
_9_
10~76~32
lon the ~otal weight of wa~er and particulate matter, to as higll as 25 parts per
: ¦million on the 3ame basl~ with a preferred range of from 0.5 to 5 p~rts p~r ~:~
¦million. j . . ::
¦ In modern sewage trcatment plants and in other industrial proce~ses,
¦it $g often necessary to ~eparate organlc and/or inor~anlc solids from aqueous
¦solutions by filtratlon. Most often the suspended solids in these systems bear
la negative charge. Therefore, the highly cationic polymers of this invention
- ¦are readily adsorbed on the particles and cause flocculatlon and agglomeration
f the ~u~pended solids, thus facilitating the separation of tllese solids
Ifrom the water.
¦ Tl~e cationic nature of the water-soluble polymers also serve to
¦provide increased effectivenes~ in aqueous atlhesive formulations. This i8
accomplished by utillzing the strong positive char~e of the polymers in
¦ electrostatic bond~ or by utilizin~ the non-polar bonding characteristics
¦ of the polymers to adheslve material$ and surfaces that do not actually bear
charges ~trong enough to form electrosta~ic bonds. For e~ample, the adhesive
~ ¦ ond of polyethylene to paper 19 sign$flcan~1y increased by treatine the
;~ I dhe~tive that is applled to the paper with small atnounts of the cationic
olymers of this invention.
¦ In the textile industry, the same effects that make these polymers
¦ seful in paper manufacture apply to various operations used for the processing
f cotton textlles. The affinity of the polytners or ttle cellulose as well as
for varlous dyes, pigments and finishes will improve the retention to the
fibers as well as incre~se the resistance of tho treated fa~ric to leachin~
and other processes which reduce the effectivenes~ of the cotton additive.
The polymers are les~ effective in~providine these effects with synthetic fibers
ut the polymers of the~ invention still possess some utility. In partlcular,
the cstionic poly~ers are u~eful in provldlng antlstatic propertles to -~
yFthetlc textile products as ~-ll a~ fabFics made from natural flber~.
: : '' ' "'''.~: '
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. .
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The degradative e~fect of microorganisms on organic
materials is well known. Elimination or inhibition of growth
of bacteria, fungi and algae has been the objective of a
large number of research projects and patents. Quaternary
ammonium compounds and ionene polymers have found utility for
; the treatment of water used in various commercial and
industrial cooling systems and in swimming pools. We have ~ ~
found that the cationic polymers of this invention are -
effective against bacteria, fungi and algae in water systems
even ~hen used in very low concentrations. The polymers
provide excellent effectiveness against microorganisms without
excessive foaming. The products are readily water soluble and ;
.
can be diluted with water to any desired concentrations.
Other advantages of these polymers are the long shelf life,
the lack of corrosiveness and the relatively low toxicity to
warm-blooded animals and humans. Concentrations which are
suitable for the control of microorganisms vary from 0.5 to
500 parts per million based on the weight of the water being
. ~ ~
treated O "
~- ~ 20 The polymers are also useful in increasing the
f ~ ~ adhesive properties of water-so~luble adhesives.
In order to disclose the nature of the present inven-
i
tion still more clearly, the following illustrative examples ~
'1 '
fi will be given. It is to be understood, however, that the
invention is not to be limited to the specific conditions or -
details set~forth in these examp;les except~insofar as such
m~Ltations are speclfied in~the ~appended claims.
EXAMPLE l ~ ~
f ~ A 100-gallon;glass-lined jacketed reactor was charged ~ -`
;~f ;~ ~ 30 with 210 pounds of~methanol and~75;pounds of an aqueous
solutlon containinq~S0 percent monometh~lamine. The reactor
was sealed, the agitator started, and full cooling applied to
I ~ ~
~ the jacket using ambient~temperature (10-20 C.~ water.
10~769~2
Epichlorohydrin, 224 pounds, was charged to the reactor at
such a rate that the reaction temperature was maintained
between 20 and 40 C. The temperature of the reactor......
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contents was maintained between 20 and 40 C. for twelve ho~rs after the
epichlorohydrin addit$on wa9 completed. The ~olution w~ analyzed for lonic
chloride following the epichlorohydrin addition and was found to increase from
.7 percent to 3.4 percent durlng the twelve hours at 20 to ~0 C. The total
chloride content of the 301ution was calculated to be 33.78 percent with one-
alf of this or 16.89 percent ~vailable as ionic chloride. The methanol
olution of the partially polymerized bis(3-chloro-2-hydroxypropyl)methylamine
was cooled to 25 C. and was ready for use in subsequent re~c~ions. The product
escribed in this example i8 typical of the polymeric precursor discussed in the
ody of the patent.
EX~MPLE 2 - ;
A 5-liter round-bottomed, 4-necked glass react$on flask equipped witll
external heating or coolin~, thermometer, a&itator, dry-ice cooled condenser andropplng funnel w~s charged with 1529 ~rams of methanol and 549 grams of an
queous ~olution contalning 50 percent monomethylamine. Epichlorohydrin, 855.3
rams, was added dropwise to the above solution at such a rate that the reaction ~ -
emperatùre was maintained between 10 and 30 C. Another 800 gra=s of epichloro-
~ l~ydrln was then adted at a rate that the reactlon ee=perature was~maintained
I etween 55 and 60 C. The agitat~ion was con~inued Por three hours af~er the
pichlorohydrin addition was completPd at a temperature of 55 ~o 60 C. ~le
, artlally palymerized methanol solution of bis(3-chloro-2-hydroxypropyl)methyl-
1, amine wa8 cooled to 2S C. and was ready for u~e in subsequ~nt reactions.
EXAMPLE 3
The procedure of Exa=ple 1 was followed wherein the organic solvent
25 ~ mployed was l-propanol. T~e polymeric precursor obtained from this solvent
aY c~mparable to that obtained ln Example 1 as sbown by lnfrared spectral
~ ~sls~
~ .. .
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¦ The procedure of Example 1 was followed with smaller quantities of
¦reagents and solvents wherein the org,anic solvents u~ed were ethanol, 2-propanol
¦and acetone. The polymeric precursor obtained from these solvents was comparable
S Ito that obtained in Example 1 a9 shown by infrared spectral analysis.
¦ EXA~IPLE 5
¦ ~le procedure of Example 2 was followed wherein the monome~hylamine
~as varied from 35 percent aqueous to 100 percent anhydrous monomethylamine.
I EXA~L~ 6
- 10 ¦ The procedure of Example 2 was followed ~ith smaller quantities of
¦reagents and solvents wherein the monomethylamine was replaced by ~he following
I minea:
¦ ethylamine cyclohexylamine
¦ n-propylamine ethanolamine
~5 ~ ¦ lso-propylamine benzylam~ne
¦ n-butylamine stearylamine
¦ t-butylamine ~ tris(hydroxymethyl)methylam~ne
t-octylamine 3-hydroxy-2-methylpropylamine
, ¦ n-hexylamine .~-chloro-2-hydroxypropylamine
`~20 ¦ EX~MPLE 7
¦ ;; ~ lQ0-gallon glass-lined ~ac~eted reactor was char~ed with 245 pounds
I f a methanol solution containing 51.4 percent of partially polymerized bis(3-
i ~ ~hloro-2-hydroxypropyl)methylamine (prepared a~ described in Example 1). The
eactor was set up for di3tillation under vacuum. The methanol (approximately
; 25~ O poundR~ wa~ dlstilled off under a reduced pressure of 122 mm. to 50 mm. of
nercury at the temperature of 40 to 50 C. The reactor was then charged with
~¦ 3 pound~ of water and 103 pound~ of an aqueous solutlon containing 59.14 percen
¦ ,N,N'~,N'-tetramethyl-1,2-diaminoethane. ~-e contents of the reactor were heate
t 75 to 95 C~ wlth agitation until the reaction mixture thickemed. Water, 430
~ ¦ ounds, was introduced over a period ol one hour in increments o~ 33 to 112
-'1 I : , '.".'
~'1 1 , . .
-13- -
1(~47~;9Z
pounds to dilute the reactor contents. The reactlon mass was allowed to thickcn
betw~en each incre~ental addition of water. The reaction temperature was main-
tained at 90 to 95 C. durin~ the addition of wuter. ~he reactor contents w~re
cooled to 30 to 35 C. after tl~e last addition of water. Ihe final product
viscosity ~as 1292 centipoises as measured by a ~rookfield viff3cosimetcr. The
solution viscoslty increased with time, notably to a viscosity of 3000 centi-
poi~es after 24 hours and finally to a complete gel in 4 days.
~XAMPLE 8
A l-liter round-bottomed, 4-necked glass reaction flask equlpped with
external heating, agitator, t1hermometer, condenser and addi~ion funnel was
charged with 260.5 grams of a methanol solution containing 49.75 percent
partially polymerized bis (3-chloro-2-hydroxypropyl)methylamine, 73.1 grams of
water, and 93.6 gra~s of an aqueous solution containing 67 percent N,N,N',N'-
tetramethyl-1,2-dia~inoethane. The reactor contents with agitation were heated
at reflux (75 to 90 C.) and 94.2 grams of methanol were removed by distillation1 ater, 320 grams, was added and the reactor contents maintained at 55 to 60 C.
f unti~ the solution vlscoslty, measured by a Brookfield viscosi~eter9 reached
lS00 centipoises and then 130 grams of water ~ere added. The reaction mixture
as cooled to 25 to 30 C. and the solution pH ad~usted to 4.0 with the addition
of concentrated aulfuric acid. l~le final viscosity was 1575 centipoises and
remained stable on prolonged standing.
EXAMrL~ 9
A one-liter, round-botto~ed~ 4-necked glass reaction flask equipped
ith heating mantle, agitator, thermometer, condenser and dropping funnel was
25 ~ charged with 132.2 gra~s of an aqueo~s solution containing 96.5 percent partiall~
olymer~zed bis (3-chloro-2-hydroxypropyl)rethyla~ine, 84.5 grams of water, and
12.8 grams of an aquecos-solution con alning 59.51 percent N,N,N',N'-tetra-
etùyl-1,2-diami~oethane, The reactor cont~nts w-re heated at 55 to 80 C. fcr
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-~- ¦two hour~ and then 250 grams of water were added over a pe~iod of 0.5 hour. The
¦reaction temperature was maintained at 75 to 80 C. for an ad~itlonal two hour~.
; The solutlon vi6co~i~y was measured ~o be 90 centipoiseq. To thc reaction
nixture was added 6.6 gram~ of an aqueou~ solution containing 96.5 percent
artially polymerized bis ~3-cllloro-2-hydroxypropyl)methylamine and the reaction
temperature was maint~ined at 75 to 80 C. for four hours. Water, 96.6 grams,
as added and the reactor conten~s were maintained at 60 to 65 C. for 6.5 hours.
rhe solution pH was ad~usted to 4.0 with the addition of 19.6 grams of concen-
trated sulfurlc acid. The final solutlon viscosity was measured to be 2029
¦ centipoises.
EXAMPLE 10
j A one-liter round-bottomed, 4-necked glass reaction flask equipped witl
I eating msntle, agitator, thermometer, condenser and dropping funnel was charged
1th 134 grams of an nqueous solution contalnlng 97.5 percent pareially poly-
; arized bl~ (3-chloro-2-hydroxypropyl~methylamine (prepared as described in
l xample 1, with removal of the methanol by distillation); 123 gram~ of water,
;l and 63 grams of an aqueous ~olution containing~98.7 percent N,N,N',N'-tetra- ¦
~ethyl-1,2-diaminoethane. The reactlon mixture was heated at a ~e~perature of
0 to 7S C. for two l)our9 and then diluted with 320 grams of water. ~le
j 20 eaction mixture was heated at 60 C. for ten hours ant showed an increase in
rookfleld v~scosity rom 105 centipoises to 1865 centipoises. Water, 128 grams,
as added to dilute the reaction mixture an~ the resulting solutlon cool~d to
I O to 35 C. The ~olution pll was adjusted to 3.85 by the addition of 16.8 grams
f 96 pescent sul~ric acld. The final vi9c08ity of the product was 1280
~; 2S entipoiæes. ~
~i~ RXAMPL~.11
The procedure o ~xample 8 W9S used whereln the organic solvent
; emoved w~s ethanol,~l-propanol or 2-propsnol. As these solven~s Decessarily
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. ¦carry out water during their distillation, water equiva~en~ to tnat removed in
;~ ~ ¦the azeotrope wa~ added back to the reactor. The prOdUCC8 obt~ined rom use of
~:~ . ¦the~e solv&nt~ were comparable in all re~pect~ to ~he producl ~btained in
: . ¦Example 8.
¦ . ~X~LE 12
¦ The procedure of Example 8 was used wherein the polymer~c bis
- ¦(3-chloro-2-hydroxypropyl)methylamine was replaced by a ~omparable molar equiva-
lent of the following polymeric bi~ (3-chloro-2-hydroxypropyl)alkyl amlne~ where .
¦the alkyl group is as follow~:
10¦ ethyl stearyl :~
n-propyl benzyl
¦ iso-propyl cyclohexyl
. I n-butyl 3-hydroxy-2-methyl~ropyl
¦ t-butyl trls ~hydroxymethyl)metllyl ' :.
15¦ 3-chloro-2-hydroxypropyl 2-hydroxyethyi : .
. ¦ EXAMPLE 13
.j ¦ -The procedure of Example 8 was used wherein the N,M,N',N'-tetramethyl- :
: p,2-diaminoethane wa3 replaced by a comparable molar equivalent of'the following
~i-tertlary amines:
20 l bls ~beta-dimethylaminoethyl) ether
. ¦ N,N,N',N'-tetramethyl-1,3-diaminobutane
l . ¦~ N,N,N',N'-tetramethyl-1,4-diaminobutane . . .
¦ l N,N,N',N'-tetramethyl-1,6-diaminohexane :
¦ .~ N,N,W',N'-tetramethylmethylenediamine ~ ;.
~; 25~ ¦~ ~ .1,3-bis(dimethylamlno)-2-provanol ~
,N,N',~ r-~tl~ ~l,.-dl _l~ap-op e
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EXAMPLE 14
The procedure of Example 8 was used wherein the N,N,N',N~-tetramethyl-
1,2-diaminoethane was replaced by comparable molar quantitie3 of tertiary amines
equivalent to the available organlc chlorine content of the polymerie precursor.
The followlng tertiary amines are example~ of those used:
triethylamine
pyrldine
~' trimethylamine ! .
; trlethanol~mine
dimethyl ~18 to C22 alkylamine~3
dimethylbenzylamine
3-chloro-2-hydroxypropyldimethylamlne
EXA~IPL~ 15
A 3-liter round-bottomed, 4-necked gla99 reaction flask equipped with
~xternal cooling, agitator, thermometer, dry-ice cooled cond~nser and droppin~
funnel was charged ~ith 1200 ml. of methanol and 36.3 grams of anhydrou~
ammonia. Lpichloro}lydrin, 596 grams, was added slowly at 8uch a rate that the
temperature was maintained between 0 to 25 C. The reaction mdxture was ag~-
tated ovcrnight and allowed to slowly warm to room temperature. The partially
polymerized tris(3-chloro-2-hydroxypropyl)amine solution was ready for use in
~ ~ 3ubsequent reactions.
¦ ~ ~ EXA~PLE 16
A 250-ml. round-bottomed, 3-~lecked glass rcaction ~la~k equipped with
~' . ~ -
~xternal heating, agitator, thcrmometer and condenser was chargQd with 44.3
_ of cr (3-chloro-2-hydroxypropyl~Lmii,e, 30 gram~ oE w~te~ and 43.5 grams j
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11
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of an aqueou~i ~olution containing fin percent N,N,N',NI~etrame,~hyl-1,2-dlamino-
-- ethane. The reactor content3 were lleated at reflux for two hours when the
:~ content~ gelled to a soft t,~ater sQluble ~el.
EX~LE 17
S A 500-ml. round-bottomed, 4-necked reaction flask equipped witb
external heating or cooling, agitator, thermome~er,, condenser and droppillg
funnel was charged with 16.0 grams of a methanol ~olution containlng 46.2 per-
cent tris(3-chloro-2-hydroxypropyl)amine, 152 grams of a me~.hanol solution
containing 39.37 percent bis(3-chloro-2-hydroxypropyl)dimethylammonium cl~loride,
46.3 grams of an aqueou,~i nolution conta~ning 59.51 percent N,N,N',N'-tetra-
methyl-1,2-diaminoethane and 76 grams of water. The reactor con~ents were
heated at 75 to 80 C. and 102 grams of methanol removed by distillatlon. The
~
reactor contents ~ere then heated at reflux or 3 hours and then cooled to 25
I -
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I EXA~I.E i8 -~
¦ Cstionic polymeric compositions of this invention were tested for their
¦ effectiveness in the retention of titanillm dioxide pigment ln a pulp pad follow-
¦ ~ng a method described by Britt, K.W., Mechanisms of Retention Durin~ Paper
¦ Forma~ion, TAppI 56(10), 46-50 (Oct. 1~73).
I ¦ The furnish used ln ~heYe test~ was a 70~30 blend of bleached hardwood
and bleached softwood kraft pulps beaten to a standard Canadian freeness of 370
~1. using a laboratory Valley beater. ~li8 slurry was then diluted to 0.6
¦ ercent consistency and mixed with tltanium dioxide at the rate of 10 percent
1 a~ed on the dry weight of the pulp.
; ¦ The apparatus used was a dynamic drainage ~ar whlch is equipped with
an agitator to provide controlled turbulence and high dynamic shear. The
ynamic drainage Jar consists of ~wo par~s. The 3ample to be te~ted is added
¦ to an upper chamber whlch has a capacity of one liter. The bottom chamber is
l an air chamber used to prevent the sample from leaving the upper chamber. Thc¦ two chambers are separated by a screen coated with electrodeposited nic~el
md containlng conical perforations of 0.003-inch diameter in such number as
¦ to provid`e 14.5 percent open area. The agitator in the upper chamber i5 a
two-inch propeller driven by a variable speed syncllronous motor. The speed of
1 the a~itator wa~ maintained at 1000 R.P.M~ in all of the test~.
¦ In these tests, 500 ml. of the 0.6 percent pulp-TiO2 slurry was mixed
ith tho required a~ount of polymeric retention aid in the upper chamber.
'~e mixture was agitated one minute and a stopper in the bottom chamber was
then remoYed. Tlle ~ample then filtered ~hrough the screen and after 150 ml.
;25 ¦ ad passed the screen, a sample wa~ collectcd for analysis. Thi3 filtrate
I ¦ contained pulp fines and TlO~ that was not retained on the screen One
; ¦ undred grams of the filtrate ~ample were filtered throu&h l~atman No. 42
aper and the TiO2 in the sample was determined by ashlng the filter paper.
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The percent improvement in retention wa~ c~lculated nslng t11c
¦ followlng formula:
~ I Percent retention = (Ash in treat~d san~ple, ~ sh in untreate~ s~mple, r,.)xlOC : .
: ¦ A~QII in untreated sample, ~. : ;~
. 5 ¦ Thl~ proce~ure wns u3ed to tes~ tlle polymeric material.q descrlbed in ¦ .
.~ . Examples 7t 8, 9, 12, and 13. The ~nrrease ln retention waQ significant in ev~r~
- ¦ case, and incre~ses were better or equal to tho~e obtained with con~lerical
¦ retention aids in mo_t inQtances. The re~ults are tabulatet in Table l.
¦ . Table l .
I ¦ I~provement in retention of t~tanium dioxide :
improvement
Po ~ mer varlable~ Use rate in reten~ion
R ~ Pound per ton Percent
~,. . I . of pulp ~ .~.
lS l CH3 ~ C~13 (CH2)20-5 19.2 .
:. ¦ C2H5 ~~ CH3 (CH2)2l.5 l4.4
. ¦ n-C3U7 ~- C113 (Cl12)2 1.5 24.7
i-C3H7 ~~ CH3 (CH2)21.5 6.5
n-C4Hg ~~ CH3 (cla2) 2 l 5 21.7
l t-C~Hg ~~ CH3 (CH2)21,5 '9.1 ~ ::
¦ n-Cl81137 ~~ CH3 tCH2)21;5 10.6 . .
~: : ¦ C6H5-C~12 ~ - Cl{3 ~C~2)20-5 lO.7
6Hl2 ~~ C~3 (CH2)21.5 14.5
¦ 110C~2Cl12 ~~ Cll3(CH2)2 l.5 27.3
2S I C~13 ~~ C113 ~C~12)4 1.5 20.4
i ¦ CH3~ ~~ CH3 ca2 1.5 3.9 : :.
~ : 1 CU3 cn3 (C}l2)3 1.5 28.~ -:~
; ~ 1 C~3 C13~(37 1.5 17.6
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EX~LE 19
The flocculatory properties of the catlonic polymers of thi~, invention
ere determined u~in~ a mixture of pulp and clay~ The proce~,ure was as follows:
An 800-ml. beaker was charged with 550 ml. of ~1ater, and 50
ml. of n slurry containing O.i ~ram of ground~ood 3pruce
pulp and 0.5 gram of kaolin clay. The pulp and clay had
been dispersed by agitating stock solutions with a ~aring
blender. A paddle ~urnin~ at lO0 R.P.M. was ~hen in~erted
lnto the beaker and a solution of polymer to be tested was
~ 10 ~dded to provide the desired concentration. The mixture
- was agitated for one minute and the paddles were then slowed
to lO R.P.M. Observatlons of the settlin~ rates of the clay
and pulp were made after one and five minutes. The paddles
were then stopped and the mixturc allowed to stand for ten
lS minutes before the final observations were made.
~' , hi~ procedure W~5 used to test the polymerlc materials described in Examples
, 8, 9, i2, nnd 13 as flocculant~. The flocculating properties of all of the
, olymers were signiffcant and in most cases the results were better or equivalPnt
1: . , . ':'
~ ~ o those obtained with commercial eationic flocculatin~ agents.
; 1~ . 20 : EXAMPLE 20
, ; The effect of two of the cationic poiymers of thi~ invention on the
I inh~bitlon of the algae Chlorella p~renoidosa and Phormidium in~mdat~m was
eterminad using the procedure described in Example 2 of U.S. Pat. No. 3,771,989.
~ olymer A wa~ prepared by reacting monomethylamine with two moles of epichlorQ-
,~ ~25~ ~ hydrin to ;for~ the~precorsor polymer which w3s then reacted with 0.9 molar
qui~alent o N,N,N',Nr-tetramethyl-1,2 diaminoethane aa exemplifled by the
~ .
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product described in Example 7. Polymer B was prepared by :
reacting the monomethylamine-epichlorohydrin precursor
polymer with dimethyl tallow amine as exemplified in Example
14. The results are tabulated in Table 2. ::
Table 2
Inhibition of algae by polymer A and polymer B
after 7 days
Active ingredient Chlorella Phormidium
. concentration pyrenoidosa ~lnundatum
Parts per million A B A B
:: .
: 0 4 4 4 4
;. 1 0 0 4 2
3 0 0 1 0
0 0 0 0
,' 10 0 0 0 0
.~ 15 0 0 0 0
, 20 0 0 0 0
0 0
' "
EXAMPLE 21
The effect of the two polymers described in Example
20 on the inhibition of the Eungi Chaetomium globosum and
~, Penicillium roqueforti was determln:ed using the method ~:
described in U.S. Pat. Mo. 3,356,706 which was modified by :~:
.~ . .
using a mineral salt solution as substrate instead of paper .
: , . .
,~ pulp.: The mineral salt solution contains the following
ingredients:
Ingredients Grams per liter
, .
Ammonium nitrate 3.0
:i :
Potassium phosphate,~dibasic l.0
Potassium chloride~ 0.25
Magnesium sulfate 0.25
: Tween 80 (trade mark) O.5
Deionized water:: to lO00 ml.
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Tween 80 i9 a polyoxyalkylene derivative of 30rbitan monooleate ,.:
msnufactured by ICI ~merica, Wilmington, Delàware.
The results are t~bulated in Table 3.
Table 3 . :
Inhibltion of two fungi by two cationic polymers after 7 days
, Active ingredient
.~ Fungusconcentratian . _ `Growth
Parts per milllon Polymer A Polymer
. Chaetomium ~0 4 4
,.~ , io ~lobosum 1 0 ' . 4
`. 3 0 4 :
- 10 . 0 2
15 - ` 20 ' 0 ` 0 .
. : 25 ` ~ 0 o . -
Penicillium 0 ; 4 4 ~ ~
. roqueforti 1 2 4 ~.:
: 0 4 ` :
l 10 0 4 ::
.j 15 0 3 : ::
~0 2 :.:
EX~LE Z
The effect of~the ~two polymcrs described in Example 20 on the
I ~ ercentage ~ill of the bacterium Enterobacter aerogene~ was determined uslng
. . .
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the ~ethod describecl ln U.S. Pat. No. 2,881~070 which ~as modifled u~in~ a ba~.al
~ salts 601ution enriche~ witl~ glucose as substrate instead of paper pulp. llle
ba~al salts solutlon contai.ned the followin~ ingredient~:
In~redient Grnm~ per lit~r
¦ Sodlum phospha~e, dibasic 3.0
¦ Potassium phosphate, dibasic . 2.0
I Ammonium chloride 0.5
: ¦ Magne~lum ~ulfate 0.01
Ammonium sulfate 0.5
l ~lucose ` 4, 5
¦ ~ Deionize~ water . to 1000 ml.
.IThe solution was a~usted to the desired pll with 1 N sulfuric acid
¦ rlor to sterilization rather than by addi~ion of buffer ~alts.
¦The results are tabulated in Table 4.
15 ¦ Table 4
~ Percentage kill of Enterobacter aeror,enes in a basal ~al~
:l Isub~trate at pl~ 6.0 af ter 18 hours' contact by two cationic polymers I ; -
~ Active lngredient - : .
i I concentration Percent klll ,
! 20 ¦ . Parts per mlllion Polymer A,. Polymer B ~
l I 0.5 : . 69 13 :
2 9~ 56 .~ :~
. 25 1 4 ' 99'5 38 .- :
~ 6 . -- 50 :
~ I 8 99.9 57 .
., I 10 ~~ 95
I 30 1 20 100 99.99 ....
~ ~ 25 -- 100
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~ h~lile particular embodiments of the lnvention have been described, it
¦will be understood, of course, that the ~nvèntion iY not limited thereto slnce
¦many modificatlons may be made, and lt i8, therefore, contemplated to cover by
the appended claims any such modiflcations as fall ~ithln the ~rue splrit and
¦scope of the i~vention.
¦ The inventlon hsvlng thus been described, what is claimed and desiredto be ~ecu ed by Lett-r~ P-tent le:
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