Note: Descriptions are shown in the official language in which they were submitted.
AMPHO~ERIC POLYELECTROLITE 9
AND METHOD FOR PRODUCTION THEREOF
BACK~ROUND OF THE INVENTION
Field o~ the Invention:
This invention relates to a novel amphoteric
polyelectrolite and a method for the production thereof.
The objects in which the amphoteric polyelectrolite of this
in~ention finds utility include antistatic agent for
synthetic ~ibers, synthetic resin film, and shaped article~
of synthetic resin; electroconductive agent for
electrostatic recording papers and electrophotographic
recording papers; yield impro~er for paper sheet filler;
paper strength enhancer; sizing agent; polymeric ~locculant
and dehydrater for sewage and refuse disposal; dehydrater
for ~arious colored waste waters including ~tained waste
water; sequestrating resin for heavy metals and ion-exchange
resin; component for such cosmetic goods as hair spray; rust
preventiv~; fungicide; mildewproo~ing agent; and
antifoggant~ for example.
Dsscr.iption of the Prior Art:
The amphoteric polyelectrolite which have been known
to the art inolude:
(1) Products obtained by Mannich reaction and the like
(Japanese Patent Laid-Open SHO 58t1983)-4,898 and Japanese
Patent Laid-Open SHO 58(1983)-104,299),
(2) Products obtained by Hoffman reaction (Japanese
Patent Laid-Open SHO 55(1980)-6,556),
(3) Products containing a quanternary ammonium group or
a tertiary amine group a~ a cationic group in the molecular
unit thereof (Japanese Patent Laid-Open-SHO 49(1974)-6,078
and Japanese Patent Laid~Open SHO 62(1987)-205,112), and the
amphoteric polyelectrolite obtained by aminoalkylating
reaction include:
Z()~69~
(4) Products aquated by aminoalkylating an acrylic ba~e
polymer and neutralizing the residual acid thereof with an
amine (Japanese Patent Publication SH0 55(1980)-35,422), ~nd
(5) Productq obtained by aminoalkylating an acryl type
base polymer with 1.0 to 1.1 equivalent weights, based on 1
equivalent weight of the acid of the base polymer, of an
alkylene amine and possessing the average value of n of the
suspended aminoalkyl group in the range of 1 to 1.2 (U.S.
Patent No. 3,372,149), for example.
Amphoterio polyele¢trolite have been heretofore
obtained by these known techni~ues. Those produced by
employing Mannich reaction and Hoffman decomposition
reaction are not stable because of gelation, for exampleO
An amphoteric polyelectrolite containing mainly a quaternary
ammonium group as a cationic component has been proposed as
a paper strength enhancer. Though the u3ability of thi~
amphoteric polyelectrolite as a flocculant i3 mentioned in
the pertinent patent specification, the polyelectrolyte i3
short of fulfilling the performanoe expected of the
~locculant. Moreover, the cationic monomer used therefor is
expensive~ When a amphoteric polyelectrolite is produced by
the known technique resorting to aminoalkylation7 it iq
unstable and vulnerable to gelation.
Heretofore, the disposal of various plant effluents
and the disposal of sewage and excrements have given ri~e to
sludge of polymeric flocced and sedimented particle~ and
excess sludge. As a dehydrater for the sludge of thi~ type,
an organic flucculant has come to Pind utility. In the
method~ for flocculation and dehydration of sludge, the
method which resorts to exclusive addition of a cationic
organic macromolecular flocculant and the method which
resorts to simultaneous addition of a cationic organic
polymeric flocculant and an anionic organic polymeric
flocculant have been famous.
The method which relies on the sole addition of a
cationic organic polymeric flocculant, however, is not fully
ef~ective in disposing thoroughly of the sludge an~ ~rl~ ging
about a satisfactory result in terms o~ cake content and
speed of filtration, for example.
Further, in case o~ the method relying on combined
use of a cationic organic polymeric flocculant and an
anionic organic polymeric flocculant, though it possibly
allows improvement in cake content and speed of filtration,
it has a disadvantage that the operation thereo~
necessitates installation of a plurality of flocculant
dissolYing tanks and flocculant reacting tanks, the
equipment therefor is expensive, and the disposal of sludge
calls for hea~y consumption of additives and boosts the cost
of chemicals.
In recent years, a method has been proposed which
uses a cationic organic macromolecular ~locculant and an
anionic organic macromolecular flocculant as di3solved
jointly in a solution with the pH of the solution controllQd
as disclosed in Japanese Patent Publication SHO 60(1985)-
43,800 and Japanese Patent Laid-Open SHO 58(1983)-216,706.
In the case of thi~ method, however, there is impo~ed a
restriction on the kind of the cationic organic polymeric
flocculant to be effectively usable for this method. Then,
in the case of an amphoteric organic polymeric ~locculant
using as a cationic component thereof a monomer oontaining a
tertiary amine or a quaternary salt as disclosed in Japanese
Patent Laid-Open SHO 62(1987)-205,112, a restriction is
imposed on the balance of composition of the flocculant.
When an organic polymeric flocculant containing both
a cationic and an anionic cumponent i~ u3ed a~ an organic
sludge dehydrater 9 the dehydrated cake content is smaller
than when a cationic ar an anionic flocculant is u3ed alone
as di~closed in Japanese Patent Publication SHO 60(1985~-
43,800, Japane~e Patent Laid-Open SHO 58(1983)-216,706, and
Japanese Patent Laid-Open SHO 63(1988)--205,112. The use
found for this flocculant, however, is limited.
2~ ;90
In the case of an amphoteric organic macromolecular
flocculant ha~ing as a cationic component thereof a monomer
containing a tertiary amine, since the balance of
composition is limited, the value of equi~alent weight of
cation, that of anion, and the equivalent weight ratio of
cation/anion have their own limits. An amphoterioc organic
sludge dehydrater which combines ability of flocculation and
ability of dehydration remains yet to be developed.
An object of this invention, therefore, is to
provide a no~el amphoteric polyelectrolite and a method for
the production thereof.
SUMMARY OF THE INVENTION
The objects described above are accomplished by a
amphoteric polyelectrolite represented by the general
formula I:
11 12 R3
~-CHz- f - ]a [- CH~ b L CH2
O(CH21H_I)nH~ntHY)
~4 R5
wherein n i9 an integer in ~he range of 1 to 5, providing
the average value o~ n i9 not le~s than 2, a, b, and c are
proportions ~uch that the sum; a ~ b ~ c is 1, or a ~ b is
1, R1, R2, ~3 and R4 are independently hydrogen atom or an
alkyl group3 R5 is hydrogen atom, an alkyl group, or an
alkyl group substituted with a ~-hydroxy group, HY is a
monobasic acid, and Z i an amide group represented by the
general formula II:
-CoNR6R7 (II)
wherein R6 and R7 are independently hydrogen atom or an
alkyl group, a hydroxyalkyl group represented by the general
formula m:
-4-
L06~
--COzfH-FHOH (m)
R8 R9
wehrein R8 and R9 are independently hydrogen atom or an
alkyl group, or a nitrile ~roup represented by the general
formula N:
-CN (IV)
These objects are further accornplished by a method
for the produotion of an amphoteric polyelectrolite
possessing an aminoalkyl group and a carboxyl group, which
method comprises either polymerizing in water at least one
anionic monomer (i) sele~ted from the group consisting of
acrylic acid and methacrylic acid or copolymerizing the
anionic monomer (i) with a nonionic monomer (ii)7 causing an
alkylene imine of an amount of not less than 1.2 mol~ per
mol of the anionic monomer (i) to react on the resultant
vinylic carboxylic acid polymer (iii) thereby
aminoalkylating the polymer (iii), and sub~equently
acidifying the aminoalkylated polymer with a monobasi¢ acid.
These objects are also a¢complished by an amphoterio
polyeleotrolite having aminoalkyl ~roup and a carboxyl group
and repre~ented by the general formula V:
71 72 73 710
[ CH2 - f ]d [-CH2- f, ~ CH2 f ]~ [ CH~_ C-l
C-O COOH A B
(CH2fH-N)nH n(HY) (v)
R4 R5
wherein n is an integer in the range of 1 to 5, d, e, f, and
g are proportions such that the sum, d ~ e + ~ + g, is 1,
or d + e ~ f is 1, R1, R2, R3, R4 and R10 are
independently hydrogen atom or an alkyl group, R5 is
hydrogen atom, an alkyl group, or an alkyl group substituted
zo~9o
with a ~-hydroxy group, HY is a monobassic acid, A is an
ester group represented by the general formula Vl:
-C02R 1 1 ( Vl )
wherein R11 is an alkyl group, an aromatic group, or an
alicyclic group, an unsubstituted or a p-substituted phenyl
group represented by the general formula ~:
~R12 (V~
wherein R12 is hydrogen atom, an alkyl group, or a hydroxy
group, or a nitrile group represented by the general formula
lV :
CN (IV)
B is an amide group represented by the general formula 11:
-CoNR6R7 (Il)
wherein R6 and R7 are independently hyrogen atom or an alkyl
group, a hydroxyalkyl group represented by the general
formula m:
-CO21H-fHOH
R8 R9
wherein ~8 and R9 are independen~ly hydrogen atom or an
alkyl group, or a nitrile group represented by the general
formula N:
-CN (~)
These objects are accomplished by a method for the
production of an amphoteric polyelectrolite having an
aminoalkyl group and a carboxyl group, which method
comprises either emulsion polymerizing in water at least one
anionic monomer (i) selected from the group consisting of
acrylic acid and methacrylic acid and a nonionic monomer
(iv) corresponding to A in the general formula V to be added
for the purpose of emulsification or -effecting in water the
emulsion polymerization in the presence of a nonionic
monomer (v) corresponding to B in the general formula V,
Z0~L069~)
causing an alkylene imine to react on the resultant vinylic
carboxylic acid polymer emulsion (vi) thereby
aminoalkylating the polymer emulsion, and subsequently
acidifying the aminoalkylated polymer emul~ion with a
monobasic acid.
These object~ are further accomplished by a water-
in-oil type amphoteric copolymer emul~lon oontaining an
amphoteric polylelectrolite represented by the general
t`ormula ~:
R1 R2 ~3
[-C~2- I-]a [ CH2- f - ]b [ CH2- I-]c
C-O COOH Z
(vm)
O(CH2fH-N)nH n(HY)
R4 R5
wherein n is an integer in the range oY 1 to S, providing
the average value of n is not less than 2, a, b, and c are
proportions ~uch that the ~um, a + b ~ c iq 1 or a ~ b is
1, R1, R2, R3, and R4 are .independently hydrogen atom or an
alkyl group, R5 is hydrogen atom, an alkyl gr-oup, or an
alkyl group substituted with a ~-hydroxy group, HY i~ a
monobasic acid, and Z i9 an amide group represented by the
general formula 11:
-CoR6R7 ~II)
wherein R6 and R7 are independently hydrogen atom or an
alkyl group, hydroxyalkyl group represented by the general
formula m:
--C02fH-CHOH (~
R8 R9
wherein R8 and R9 are independently hydrogen atom or an
alkyl group, a nitrile group represented by the general
formula N
-CN ~N)
~ L069~
or an ester group represented by the general formula ~:
-CO2R10 (~)
wherein R10 is an alkyl group, an aromatic group, or an
alioyclic group.
These objects are also accomplished by a method for
the production of a water-in-oil type amphoteric
polyelectrolite emulsion having an aminoalkyl group and a
carboxyl group, which method comprises emulsifying either at
least one anionic monomer (i) selected from the group
consiqting of acrylic acid and methacrylic acid or a mixture
of the anionic monomer ti) with a nonionic monomer (ii) in
water-in-oil form in the presence of water, a surfaotant,
and a hydrophobic organic solvent, causing an alkylene imine
to react on ~he resultant water-in-oil form vinylic
carboxylic acid emulsion (vii) resulting from the
polymerization or copolymerization by the use of a radical
polymerization catalyst thereby aminoalk~lating the
emulsion, and subsequently acidifying the amlnoalkylated
emulsion wiSh a monoba~ic acid.
The amphoteric polyelectrolite o~ this lnventior
finds utility for antistatic agent for synthetic fibers,
synthetic resin film~ and shaped articles of synthetic
resin; electroconduotive agent for electrostatic recording
papers and electrophotographic recording papers; yield
improver for paper sheet filler; paper strength enhancer;
sizing agen~; macromolecular flocculant and dehydrater for
sewage and re~use disposal3 dehydrater for various colored
waste waters including stained waste water; sequestrating
resin for heavy metals and ion-exchange resin; component for
such cosmetic goods as hair spray; rust preventive;
fungicide; mildewproofing agent; and antifoggant, for
example.
EXPLANATION OF THE PREFERRED EMBODIMENT
First, the amphoteric polyelectrolite represented by
the general formula I will be described below. The
subscript, n, is an integer in the range of 1 to 5,
;~0~ 90
preferably 1 to 3, providing that the average value of n
precede 2 and preferably falls in the range of 2 to 3. The
proportions of a, b, and c are such that the 3um a ~ b + c
is 1 or a ~ b is 1 and the ratio a : b : c is in the range
of 0.2-0.999: 0,001-0.2:0-0.6, preferably 0.4-0.99:0.01-
0.1:0-0.5 R1, R2, ~3, and R4 are independingly hydrogen atom
or an alkyl group. The number of carbon atoms of the alkyl
group is preferable to fall in the range of 1 to 2. R5 i~
hydrogen atom, an alkyl group, or an alkyl group substituted
with a ~-hydroxy group. The number of carbon atoms of the
alkyl group is preferable to fall in the range of 1 to 2.
NY is a monobasic acid.
Z is an amide group represented by the general
formula II, -CoNR6R7? a hydroxyalkyl group represented by
the general formula ~,
--C02fH-CHOH
R8 R9
,or a nitrile group represented by the general formula ~, -
CN. R6, ~7, R8, and R9 are independently hydrogen atom or an
alkyl group. The number of carbon atoms of the alkyl group
is preferable to fall in the range of 1 to 2.
The amphoteric polyelectrolite represented by the
general formula I is produced by either polymerizing in
water at least one anionic monomer (i) selected from the
group consisting of acrylic aoid and methacrylic acid or
copolymerizing the anionic monomer (i) with a nonionic
monomer (ii), causing an alkylene imine of an amoun't of not
leqs than 1.2 mols per mol of the anionic monomer (i) to
react on the resultant vinylic carboxylic acid polymer (iii)
thereby aminoalkylating the polymer (iii3, and subsequently
acidifying the aminoalkylated polymer with a monobasic acid.
The anionic monomer (i) is preferable to be acrylic
acid or methacrylic acid~ The nonionic monomer (ii) is
required to be selected in consideration of the
)69~
characteristic of acid dissociation. The acid dissociation
indexes of acrylic acid and methacrylic acid at 25C are 4.3
and 4.7 respectively. Though acrylic acid or a salt thereof
in water of a pH value of not more than 4.3 or meth~crylic
acid or a salt thereo~ in water of a pH value of not more
than 4.7 assumes ionic form, the proportion of its ion
sharply decreases below the indicated pH value. The
monomers both are in ~ubstantially undissociated form in
water of a pH value of not more than 3.5. Xn the case of an
anionic monomer possessing a sulfonic acid group of a small
dissociation acid index, since the amount of ion ~eeds
present is large even in a low pH region approximately in
the range of 2 to 3, the outstanding effect of this
invention cannot be attained by using this monomer.
The nonionic monomer ~ii) may be any nonionic
monomer copolymerizable with the monomer (i) mentioned
above. For example 7 a vinylic monomer possessing an amide
group represented by the general formula X can be used.
CH2
R3-C-C -N /R7 tX)
Il \R
o
In the general formula X, ~37 R6, and R7 are
independently hydrogen atom or an alkyl group as described
aboveO The vinylic monomers of the general formula X
include acrylamide, methacrylamide, N,N-dimethyl acrylamide,
N,N-dimethyl methacrylamide, N,N-diethyl acrylamide, and
N,N-diethyl methacrylamide, for example.
A vinylic monomer possessing a hydroxyalkyl group
repre~ented by the general formula XI is also usable.
In the general formula XI~ R3, R8, and R9 are
independently hydrogen atom or an alkyl group. The vinylic
monomers of the general formula XI include hydroxyethyl
acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate,
-10-
CH2 2(~10690
Il
Il ~8 R9 (XI)
and hydroxypropyl methacrylate, ~or example. Acrylonitrile
and methacrylonitrile may be also cited.
It should be noted that the nonionic monomer (ii) is
used herein ~or the purpose of adjusting the molecular
weight and ion equi~alent weight of the macromolecular
ampholyte. Generally, it is preferable to account for a
proportion in the range of 0 to 60 mol%, preferably 0 to 50
mol%, in the vinylic carboxylic acid polymer (iii).
In the production of the amphoteric polyelectrolite
by the method of this invention, the amount o~ the anionic
monomer (i) and that of the nonionic monomer (ii) to be used
in the polymerization of the vinylic carboxylic acid polymer
(iii) must be fixed so that the produced amphoteric
polyelectrolite may acquire a cation equivalent weight
value, Cv, in the range o~ 0.8 to 7.0 me~/g, an anion
equivalent weight value, Av, in the range o~ 0.1 to 4.0
meq/g, and a Cv/Av ratio in the ran~e of 1.0 to 25Ø
Further, preparatory to the aminoalkylation, it is
necessary to fix the amounts of the vinylic carboxylic aci~
polymer (iii) and the alkylene imine to be used for the
aminoalkylation.
If the cation equivalent weight value, Cv, is less
than 0.8 meq/g, the produced amphoteric polyelectrolite
manifests its characteristics only with difficultyO If the
cation equivalent weight value, Cv, exceeds 7.0 meq/g, the
produced amphoteric polyelectrolite does not ea~ily manifest
its characteristics. If the anion equivalent weight value,
Av, is less than 0.1 meq/g9 the produced amphoteric
polyelectrolite manifests its characteristiQs only with
difficulty. Conversely, if the anion equivalent weight
value, Av, exceeds 4.0 meq/g, there arises a disadvantage
-11-
9~
that the produced amphoteric polyelectrolite tends to quffer
a decrease in its solubility in water.
If the Cv/Av ratio is less than 1.0 and the anion
equivalent weight value is unduly large proportionately,
there ensues a disadvantage that the effect of the cationic
group i9 degraded. If the Cv/Av ratio exceeds 25 and the
proportion of the anionic group is unduly small ? the
produced amphoteric polymer cannot be expeoted to manifest
its action sufficiently.
Preparatory to the initia~ion of the polymerization
in this invention, the total amount of` the anionic monomer
(i), the nonionic monomer (ii), and the vinylic carboxylic
acid polymer (iii~ (hereinafter re~erred to as "total amount
of monomersl'3 in the aqueous solution is pre~erable ~o
account for a concentration approximately in the range of 10
to 80% by weight. If this concentration i~ less than 10% by
weight, there is a disad~antage that the productivity of the
polymerization is inferior. Conversely, if this
concentration exceeds 80% by weight, there iq a disadvantage
that the polymerization produoes a large amount of heat and
the temperature of the polymerization system rises
excessively.
During the production of the vinylic carboxylic acid
polymer (iii) by the polymeri~ation in water of at least one
anionic monomer (i) selected from the group con~isting of
acrylic acid and methacrylio acid or the copolymerization of
the anionic monomer (i) with the nonionic monomer (ii), it
is permissible to use, when necessary, a radical
polymerization initiator of the redox type or the azo type,
for example. The redox type polymerization initiator~
include combinations between such oxidizing agents as
ammonium persulfate, potassium persulfate, hydrogen
peroxide, and cumene hydroperoxide and such reducing agents
a~ formaldehyde sodium ~ulfoxylate, thioglycolic acid, L-
ascorbic acid, dimethylaminopropionitrile, sodium hdyrogen
sulfite, ~-mercapto ethanol, and divalent iron salts, for
-12-
069~
example. The azo type polymerization initiators usable
herein include azobisisobutyronitrile, 2,2'-azobis(2-
amidinopropane)dihydrochloride, 2,2'-azobis(2,4-
dimethylvaleronitrile), and 4,4'-azobis(4-cyanopentanoic
acid) 7 for example. It is permissible to use a redox type
polymerization initiator and an azo type polymerization
initiator in combination. The amount of the polymerization
initiator is in the range of 0.001 to 10 ~ by weight,
preferably 0.01 to 5 % by weight, based on the total amount
of monomers.
The polymerization may be carried out in an
adiabatic qystem, with the initial polymerization
temperature kept approximately in the range of 10 to 4~C.
The sheet polymerization method may be used in properly
modified form, with the polymeri~ation temperature
externally controlled at a fixed level approximately in the
range of 30 to 100C, preferably 40 to 80C .
Though the polymerization time i~ variable with the
concentration of monomers, the polymerization temperature~
the polymerization degree aimed at~ and the like, it i~
generally in the range of 10 minutes to 10 hours, preferably
1 to 7 hours.
The aminoalkylation reaction can be carried out by
cau~ing an alkylene imine to react on the vinylic carboxylic
acid copolymer (iii). Preferably, the aminoalkylation
reaction is carried out at a temperaturs not exceeding about
65C~ preferably falling approximately in the range of 35 to
55C.
The aminoalkylation is effected by causing reaction
of the acid group of the vinyl type carboxylic acid polymer
(iii) with the alkylene imine as indicated below. The
reaction with 1,2-alkylene imine, for example, i~ indicated
by the following general formula.
6~C~
-C -OH ~ H2C- CH-R4
l N
R5
-C -O-CH2- CH-R4 _ f _o_fH - IH2
o NH or O R NH
R5
In the formula, R4 is hydrogen atom or an alkyl
group and R5 is hydrogen atom, an alkyl group, or an alkyl
group sub~tituted with a ~-hydroxy group.
The alkylene imine for exchanging the free carboxyl
group of the vinylic polymer for an aminoe3ter group is a
1,2-alkylene imine (aziridine). Among other 1,2-alkylene
imines, 1,2-propylene imine and ethylene imine prove to be
particularly desirable because of their ready availabilîty
and relatively low prices. Optionally, n-alkyl-~ub~tituted
or unsubstituted l,3~alkylene imine~ ~azetidine) are u~able
because their imine~ 9 in forming an aminoester group 9
exhibit chemical reactivity and other properties similar to
those o~ 1,2-imin0s. Such compounds u~able herein include
2-methyl aziridine, 2-ethyl aziridine, 2-n-propyl aziridine 9
2 i~opropyl aziridine, 2-n-butyl aziridine, 2-isobutyl
aziridine; 2-sec-bu~yl aziridine, 2-(1-methylbutyl)
aziridine, 2(2-methylbutyl) aziridine, 2-(3~methylbutyl)
aziridine, 2-n-pentyl aziridine, 2-(methylpentyl) aziridina,
2-(methylpentyl) aziridine, 2-(4-methylpentyl) aziridine,
2(3-ethylpentyl) aziridine, 2-(2-isopropylpentyl) aziridine,
2-n-hexyl aziridine, 2-n-(heptylaziridine), 2-n-octyl
aziridine, 2,3-dimethyl aziridine 9 2,3-di(2-methylbutyl)
aziridine, 2-ethyl-3-n~hexyl aziridine, 3-n-octyl-3-propyl
aziridine, 2-hydroxyethyl aziridine, and azetidine~
corresponding thereto such as, for example, 2-methyl
azetidine, 2-ethyl azetidine, 2-n-propyl azetidine, 2,4-
-14-
2~06~30
dimethyl azetidine, 2,4-dioctyl azetidine, and 2,3-di(2-
methylbutyl) azetidine, for example.
Ths acidification of a suspended aminoalkyl group i5
effected with a monobasic acid, which is used in an amount
in the range of 50 to 100 mol% (preferably 60 to 90 mol~),
based on the amount of the added alkylene imine. The
addition of the monobasic acid to the reaction system i~
carried out either collectively or peacemeal during the
course of the aminoalkylation. The monobasic acid is
selected from among hydrochloric aicd, nitric acid, etc.
Specifically to effect the aminoalkylation, the
vinylic carboxylic acid polymer (iii) and the alkylene imine
added thereto in an amount of 50 mol~., based on the mol
equivalent of the aninonic monomer (ii) contained in the
polymer (iii) are stirred for a period in t~e range of 5 to
60 minutes. Then ? the resultant mixture and a neutral acid
added thereto in an amount proportionate to the amount of
the alkylene imine added are stirred continuously for a
period in the range of 5 to 60 minutes. To the stirred
mixture, the remaining part of the alkylene imine is
gradually added over a period in the range of 5 to 60
minutes. Thereafter, the resultant mlxture and the
remaining part of the neutral acid added thereto are stirred
for a period in the range of 5 to 60 minutes. During the
course of the reaction, the reaction temperature must be
kept at a level in the range of 30 to 65C, preferably 35
to 55C.
If the reaction temperature exceeds 65C, the
reaction mixture is gelled during the course of the reaction
and the product of the reaction is opacified with suspended
insoluble particles. Conversely, if the temperature is le~
than 30C, the reaction itself becomes meaningless because
the reaction time is elongated infinitely.
In the production of the amphoteric polyelectrolite
by the method of this invention, not only the cation
equivalent weight value and the anion equivalent weight
-15-
20~69~
value mentioned above but also the molecular weight i~
preferable to be suitably controlled. The composition of
the component monomers~ the polymerization time, and the
like are preferable to be suitably set so that thi~
molecular weight a~ expressed by the molecular weight of the
vinylic carboxylic acid polymer (iii) may be in the range of
10,000 to 1,000,000, preferably 100,000 to 800,000~
By carrying out the polymerization in water and ths
reaction under the conditlons mentioned above, there is
obtained an aqueous solution of the amphoteric
polyelectrolite.
The amphoteric polyelectrolite represented by the
general formula VIII is in the Eorm of water-in-oil type
amphoteric copolymer emulsion. This emulsion is produced by
emulsifying in water-in-oil form either the anionic monomer
(i) or the mixture of the anionic monomer with the nonionic
monomer ~ii) in the presence of water, a surfactant, and a
hydrophobic organic sol~ent, then polymerizing or
copolymerizing the emulsi~ied monomer or monomers through
the agency of a radical polymerization cataly~t thereby
producing a water--in-oil form vinyl type carboxyllc acid
emulsion (vii), causing the alkylene imine to reactor on the
carboxylic acid emulsion thereby aminoalkylating it, and
subsequently acidi~ying the aminoalkylated emulsion with the
monobasic acid.
The anionic monomer (i) i9 used as already
described. The anionic monomer (i), however, is preferable
to be used as neutralized with a b~ae such as, for example,
sodium hydroxide, potassium hydroxide, or ammonia. The
neutralization ratio of the anionic monomer (i) in this case
i3 in the range of 5 to 100 mol%, preferably 20 to 95 mol%.
The compounds which are usable as the nonionic
monomer (ii) include, in addition to the compound~
represented by the aforementioned general formulas X and XI
and acrylonitrile and mechacrylonitrile, the compounds
repre~ented by the following general formula XII.
CH2
R~-C - C -O-R10 (XII)
wherein R3 ishydrogen atom or an alkyl group and R10 is an
alkyl group, an aromatic group, or an alicyclic group,
providing that the number of carbon atoms of the alkyl group
is in the range of 1 to 6, the number of carbon atom~ of the
aromatic group in the range of 6 to 9, pre~erably 6 to 8,
and the number of carbon atoms of the alicyclic group in the
range of 4 to 8, preferably ~ to 7. The compound~ o~ the
general formula XII include methyl acr~late, n-propyl
acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl
acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl
acrylate, methyl methacrylate, ethyl methacrylate, n-butyl
methacrylate, 2-ethylhexyl methacrylate, cyolohexyl
methacrylate, and phenyl methacrylate, for example.
The nonionic monomer (ii) i~ used herein for the
purpose of adjusting the molecular weight and ion equivalent
weight of the water-in-oil type amphoteric ¢opolymer
emul~ion.
For the water-in-oil type amphoteric type copolymer
emulsion to be produced b~ the method of this invention, the
amounts of the anionic monomer (i) and the nonionic monomer
(ii) to be u~ed during in the polymerization of the water~
in-oil form vinylic carboxylic acid polymer emulsion (iv)
must be fixed so that the produced copolymer emulsion may
acquire a cation equivalent weight value, Cv, in the range
o~ 0.8 to 10.0 meq/g, and an anion equivalent weight ~alue,
Av, in the range of 0.1 to 6.0 meq/g.
When at least one anionic monomer (i) ~elected from
the group consiqting of acrylic acid and methacrylic acid or
a mixture of the anionic monomer (i) with a nonionic monomer
(ii) is to be emulsified in water-in-oil form in the
presence of water, a surfactant, and a hydrophobic organic
2~ 69()
solvent, the surfaotant may be a nonionic surfactant in
popular use. The nonionic surfactants which are usable
herain include sorbitan monooleate, sorbitan monostrearate,
sorbitan monolaurate, polyoxyethylene sorbitan monostearate,
polyoxyethylene sorbitan monooleate, polyoxyethylene sorbin
monolaurate, polyoxyethylene nonylphenyl ether,
polyoxyethylene lauryl ether, glycerol monostearate, and
glycerol monooleate, ~or example. These nonionic
surfactants may be used either singly or in the form o~ a
mixture of two or more members~
Optionally, the nonionic surfactant may be used in
combination with an anionic and a cationic surfactant of
ordinary grade.
The hydrophobic organic solvents which are usable
herein include hydrophobic aliphatic and aromatic
hydrocarbons, ~egetable and animal oils, and modified
products of such oils, for example. Typical examples are
normal paraffin, isoparaffin, cyclohexane, toluene, xylene,
kerosine, mineral oils, and lamp oil, eto.
The total amount of the anionic monomer (i) and the
nonionic monomer (ii~ to be used herein ls preferable to
account ~or a corcentration in the range of 20 to 80~ by
weight, based on the amount of water. The concentration o~
the sur~actant to be used is preferable to be in the range
of 5 to 30% by weight~ based on the amount of the
hydrophobic organic solvent. The ratio of the hydrophobic
organic solvent to the water is in the range of 1 : 10 to 10
:1, preferably 1 : 5 to 3 : 1.
When the water-in-oil form monomer emulsion obtained
by emulsifying in water-in-oil form at least one anionic
monomer (i) selected from the group consisting of acrylic
acid and methacrylic acid or a mixture of the anionic
monomer (i) with a nonionic monomer ~ii) in the presence of
water, a surfactant, and a hydrophobic organic solvent i9 to
be polymerized or copolymerized, a redox type or azo type
radical polymerization initiator may be used as occasion
-18-
ZO~)69~:D
demands. The kinds of the redox type and azo type radical
polymerization initiator and the amount of addition of the
radical polymerization initiator are as already described.
It is also permissible to add to the polymerization
system a well-known chain transfer agent such as isopropyl
alcohol, erythorubic acid, or 2-mercapto ethanol.
The polymerization temperature is preferable to be
externally controlled, during the initial phase of the
polymerization, in the range of 10 to 60C, preferably 20
to 60C and, during the normal phase of the polymeri~ation,
in the range of 30 to 100C, preferably 40 to 80C.
Though the polymerization time is variable with the
concentration of monomers, the polymerization temperature~
and the polymerization degree aimed at, for example 9 it is
generally in the range of 10 minutes to 10 hours, preferably
1 to 7 hours.
The reaction of aminoalkylation can be effected by
causing an alkylene imine to react on the water-in-oil form
vinylic carboxylic acid polymer emulsion (iv).
Preparatory to the aminoalkylatlon, it is necessary
to fix the amounts of the water-in-oil form vin~lic
carboxylic aoid polymer emulsion (iv) and the alkylene imine
to be used.
If the cation equivalent weight value, C~, is less
than 0.8 meq/g, the produced amphoteric macromolecule
manifests its characteristics only with difficulty. If the
cation equivalent weight value, Cv, exceed~ 10.0 meq/g, the
produced amphoteric polyelectrolite does not easily manifest
its characteristics. If the anion equivalent value, Av, is
less than 0~1 meq/g, the produced amphoteric macromolecule
manifests its characteristics with difficulty. If the anion
equivalent weight value, Av, exceeds 6.0 meq/g, there is
disadvantage that the produced amphoteric polyelectrolite
tends to exhibit inferior ~olubility in water.
The acid group of the water-in-oil form vinylic
carboxylic acid polymer emulsion (iii) is cau~ed to react
-19-
201~90
with the alkylene imine in the conventional manner indicated
below for the aminoalkylation. The reaction with a 1,2-
alkylene imine is performed as already described. Typical
examples of the alkylene imine and the amount of the
alkylene imine to be used are as already de~cribed. The
reaction of aminoalkylation i9 per~ormed as already
described.
For the water-in-oil form amphoteric copolymer
emulsion to be obtained by the method o~ this invention, it
is preferable to control suitably t;he molecular weight
thereof in addition to the cation equivalent weight and the
anion equivalent weight value mentioned above. With
intrinsic viscosity as an index to molecular weight, the
composition of the component monomers, the polymerization
conditions, etc. are preferable to be suitably set so that
the produced water-in-oil form amphoteric copolymer emul~ion
may aquire intrinsic viscosity [~] in the range of 0.1 to 25,
preferably 1 to 15.
Now, the amphoteric polyelectrolite repre~ented by
the general formula V will be described. The subscript n i9
an integer in the range o~ 1 to 5, preferably 2 to 3. The
proportions d, e, f, and g are such that the sum, d + e ~
P ~ g? or d + e -t f is 1, is 1 and the ratio, d : e : f :
g~ is 0.2-0.999: 0.001-0.2~ 0.01-0.2: 0-0.8, pre~erably 0.4-
0.99: 0.01 0.1: 0.1-0.2: 0-0.7. R1, R2, R3 and R10 are
independently hydrogen atom or an alkyl group, providing
that the number of carbon atoms of the alkyl group i~ in the
range of 1 to 2. R5 is a hydrogen atom, ~n alkyl group, or
an alkyl group substituted with a ~-hydroxy group, providing
that the number of carbon atoms of the alkyl group i~ in the
range of 1 to 6, preferably 1 to 3. HY is a monobasic
acid. A is an ester group represented by the general
formula VI, -C02R11 wherein R~ an alkyl group, an
aromatic group, or an alicyclic group, providing that the
number of carbon atoms of the alkyl group is in the range of
1 to 6, preferably 1 to 3, the number of carbon atoms of the
-20-
aromatic group in the range of 6 to 9, preferably 6 to 8,
and the number of carbon atoms oP the alicyclic group in the
range of 4 to 8, preferably 5 to 7, an unsubstituted or p-
substituted phenyl group represente~ by the general formula
~m
_~R12 (~)
wherein R12 is hydrogen atom, an alkyl group, or an
hydroxide hydroxyl group, providing that the number of
carbon atoms of the alkyl group is in the range o~ 1 to 2,
or a nitrile group represented by the general formula IY. B
stands for an ester group represented by the general formula
III or a nitrile group represented by the general formula
IV.
The ampho~eric polyelectrolite represented by the
general formula V is produced by either e.mulsion
polymerizing in water at least one anionio monomer (i)
selected from the group consisting of acrylio aoid and
methacrylic acid and a nonionic monomer (iv) aorre~ponding
to A in the general ~ormula V to be added to the anionic
monomer (i) for the purpose of emulsification with the
anionic monomer or e~fecting this emulsion polyemerization
in water in the presence of a nonionic monomer (v)
corresponding to B in the general ~ormula V 9 aminoalkylating
the resultant vinylic carboxylic acid polymer emulsion (vi)
~by the reaction thereof with an alkylene imine, and
subsequently acidifying the aminoalkylated polymer emulsion
with a monobasic acid.
The anionic monomer (i) to be used herein is as
already described.
The nonionic monomer (iv) may be any nonionic
monomer which is emulsifiable and, at the same time,
copolymerizable with the aforementioned monomer (i). The
nonionic monomers which are usable herein include vinylic
monomers pos~e~ing an ester group repre~ented by the
-21-
general formula Xll. Typical examples are as alr2eQ ~ ~ d.
Further, vinyl compounds posses~ing an unsubstituted or p-
substituted phenyl represented by the general formula ~ m:
CH2
R~C~R12 ( X 111 )
wherein R3 and R12 have the meanings defined above, are also
usable~ Typical examples are styrene, p-methylstyrene~ and
p-vinylphenol. Acrylonitrile may be cited as another
example.
The nonionic monomer (v) is used herein for the
purpose of enabling the vinylic carboxylic acid polymer
emulsion (vi) to be obtained as an emulsion po~se~sing low
viscosity and allowing an increase in molecular weight.
Generally it is added in an amount of not more than 20 mol%,
based on the amount of the vinylic carboxylic acid polymer
emulsion (vi). If this amount exceeds 20 mol%, there ari~es
a disadvantage that the produced amphoteric polyelectrolite
exhibits inferior solubility in water.
As the nonionic monomer (v), any o~ the nonionic
monomers which are copolymeriæable with the aforementioned
monomers ~i) and (iv) can be used. These nonionic monomers
include the vinylic monomers possessing an amide group a~
represented by the general formula X and the vinylic
monomers possessing a hydroxyalkyl group a repre~ented by
the general formula XI, for example. Typical examples o~
these monomers are as already cited. Besides, acrylonitrile
and methacrylonitrile are also usable.
The nonionic monomer (v) is used for the purpose of
adjusting the molecular weight and ion equivalent weight of
the amphoteric polyelectrolite. Generally, it is preferable
to be u~ed in an amount of not more than 70 mol~ based on
the amount of the vinyl type caboxylic acid polymer emulsion
(vi) .
For the amphoteric polyelectrolite to be produced by
the method of this invention, it is necessary to fix the
-~2-
20~)6~0
amounts of the anionic monomer (i) and the nonionic monomers
~iv) and ~v) to be used in the polymerization of the vinylic
carboxylic acid polymer emulsion (vi) so that the produced
amphoteric polyelectrolite may acquire a cation equivalent
weight value, Cv, in the range o~ 0.8 to 10.0 meq/g and an
anion equivalent weight value, Av, in the range of 0.1 to
6.0 meq/g. The amounts of monomers [the total amount of the
anionic monomer (i) and the nonionic monomers (iv) and (v)
(hereinafter referred to as "total amount of monomers")] are
preferable to account for a concentration approximately in
the range of 10 to 80% by weight. If the concentration i~
less than 10~ by weight, there arises a di~advantage that
the polymerization betrays poor productivityO Conversely,
if the concentration exceeds 80~ by weight, there ensure at
disadvantage that the polymerization generates a large
volume of heat and the polymerization system suffers from
undue rise of temperature.
In emulsion polymerizing in water at least one
anionic monomer (i) selected from the group consisting of
acrylic acid and methacrylio acid and a nonionic monomer
(iv) correqponding to A in the general ~ormula V to be added
for the purpose of emulsification with the anionic monomer
or in effecting the emulsion polymeri~ation in the presence
of a hydrophilic nonionic monomer (v) corresponding to B of
the general formula V, it is permissible to use a surfactant
Por the purpose of ensuring thorough di~persion of the
monomers (i), (iv), and (v). Though the surfactant to be
used is not ~pecifically defined, it is preferable to
possess relatively high hydrophylicity enough for the
formation of an 0/W ~orm emulsion in consequence of the
emulsification. The surfactants which are usable herein for
this purpose include nonionic surfactants such
polyoxyethylene nonylphenyl ether and polyoxyethylenestearyl
ether, anionic surfactants such as sodium lauryl sulfate and
polyoxyethylene nonylphenyl ether sodium sulfate, and
cationic surfactants such as stearyl amine acetate and
-23-
2C~1069~
stearyl trimethyl ammonium chloride, for example. The
amount of the surfactant to be used is in the range of 0.01
to 10% by weight, preferably 0.1 to 5% by weight, based on
the total amount of monomers.
In the production of the vinylic carboxylic acid
polymer emulsion (vi), it is permissible to use a redox type
or azo type radical polymerization initiator, as occasion
demands. The kinds of the polymerization initiator and the
amount of the polymerization initiator to be used are as
already described.
The polymerization temperature i~ required to be
controlled externally, during the initial phase of the
polymerization, in the range of 10 to 40C, preferably 20
to 40C, and, during the normal course of the
polymerization, in the range of 30 to 100C, preferably 40
to 80C.
Though the polymerization time is variable with the
concentration of the monomers, the pol~merization
temperature, and the polymerization degree aimed at, for
example, ik is generally in the range of 10 minute~ to 10
hours, pre~erably 1 to 7 hours.
Preparatory to the reaction of aminoalkylation, it
i~ necessary to ~ix the amounts of the vinylic oarboxylic
acid polymer emulsion (Yi) and the alkylene imine.
I~ the cation equivalent weight value, Cv, is les~
than 0.8 meq/g, the produced amphoteric polyelectrolite does
not manifest its characteristics easily. Conversely, if the
cation equivalent weight value, Cv, exceeds 10.0 meq/g, the
characteristics expected of the produced amphoteric
polyelectrolite do not easily manifest themselves~ If the
anion equivalent weight value, Av, is less than 0.1 meq/g,
the produced amphoteric polyelectrolite mani~ests its
characteristics only with difficulty. I~ this ~alue exceeds
6.0 meq/g, there is a disadvantage that the produced
amphoteric polyelectrolite tends to exhibit inferior
solubility in water.
-24-
Z~06go
The aminoalkylation can be carried out by causing
the vinylic carboxylic acid copolymer emulsion (vi) to be
acted upon by an alkylene imine.
Specifically, the aminoalkylation i~ conventional
manner as described above between the carboxylic acid group
of the vinylic carboxylic acid polymer emulsion (vi) and the
alkylene imine~ The typical examples of the alkylene imine
and the amount of the alkylene imine to be used are a~
already described~ The conditions ~or the aminoalkyl~tion
are also as described above.
In the production of the amphoteric polyeleotrolite
by the method o~ this invention, it is pre~erable to control
suitably the molecular weight thereof in addition to the
cation equivalent weight value and the anion equivalsnt
weight value mentioned above. With intrinsic viscosity a~
an index to molecular weight, the composition of the
component monomers, the polymerization conditions, etc. are
pre~erable to be suitably set so that the produced
amphoteric polyelectrolite may acquire intrinsic viscosity
~] in the range oY 0.1 to 25, preferably 1 to 15.
By carrying out the polymerization and reaction in
water under the conditions described above, the amphoteric
polyelectrolite can be produced~
Now, the present invention will be described more
specifically below with reference to working examples. It
should be noted, however, that the present invention is not
limited in any sense by these examples.
In the following Examples and Controls, the
abbreviation are as follows:
AA~ acrylic acid
AAm: acrylamide
HEA: 2-hydroxyethyl acrylate
AN: acrylonitrile
MAm: methacrylamide
AI: alkylene imine
EI: ethylene imine
-25-
)6~1
PI: propylene imine
St: styrene
MA: methyl acrylate
BA: butyl acrylate
MMA: methyl methacrylate
MAA: methacrylic acid
Referential Examples 1 to 6 [Production of vinylic
carboxylic acid polymer (iii)~
A varying vinylic carboxylic acid polymer (iii) was
obtained by placing in a reactor a mixture compri~ing
monomers of amounts forming an indicated weight ratio and
totalling a proportion of 20% by weight, di~placing the air
en~rapped in the reactor with nitrogen ga~, and e~fecting
polymerization of the monomer mixture by keeping the monomer
mixture at 50C and adding thereto 0.2% by weight each,
based on the total amount of monomers, of ammonium
per~ulfate (APS) and sodium hydrogen sul~ite (SB).
Tablel
_--~
Referential Compo3ition ratio of monomers
E~ample
., _ , , ~
1 AAtAAm = 100/0
2 AA/AAm = 80/20
_ _ _
3 AA/AAm = 60/40
4 AA/HEA = 60/40
AAlAAmlAN = 6313515
6 AA/MAm = 60/40
. __. ____
Exampl~ 1
In a reactor, 1,000 g of the vinylic carboxylic acid
polymer ~ynthesized in Referential Example 1 wa9 placed,
heated to 50C, kept at this temperature throughout the
whole course o~ reaction and, after dropwise addition of
59.7 g of ethylene imine thereto, ~tirred with the added
-26-
2~0~g~
ethylene imine for 30 minutes. The amount of the ethylene
imine thus added dropwise to the polymer accounted for 50
mol%, based on the mol equivalent of the carboxylic acid in
the charged vinylic carboxylic acid polymer. Then, the
resultant reaction mixture was stirred for 30 minutes with
143 g of an aqueous 61 wt% nitric acid solution, i.e. an
amount proportionate to the amount of the dropwise added
ethylene imine. The ensuant mixture was stirred for 30
minutes with the balance, or 140.3 g, of ethylene imine.
The resulting mixture, after dropwise addition thereto of
193 g of an aqueous 61 wt% nitric acid solution, was stirred
with the aqueous solution for 30 minutes, to obtain an
amphoteric polyelectrolite. The reaction conditions
involved herein and the appearance of the reaction product
were as shown in Table 2.
Examples 2 to 9
The procedure of Example 1 was repeated, except that
the conditions indlcated in Table 2 were used instead. The
physical properties of the reaction product~ were as ~hown
in Table 2.
Controls 1 to 5
The procedure of Example 1 was repeated, except that
the conditions indicated in Table 2 were used instead. The
physical properties of the reaction products were as shown
in Table 2.
The cation equivalent weight values, the anion
equivalent weight values, and the average values of n
indicated in Table 2 were determined by the following
methods (which similarly apply hereinafter).
(1~ Cation equivalent weight value
Thi~ property was determined by placing 95 ml of
distilled water in a beaker, adding thereto 5 ml of a
solution of 1,000 ppm of a given sample, adju~ting the pH
value of the resultant solution to 7.0 by addition of either
1% HCl or 1% NaOH, qtirring the solution for about 1 minute,
then adding two or three drops of toluidine blue indicator
-27-
069~
solution, and titrating the ~olution with N/400 PVSK
(polyvinyl sulfate potassium solution) at intervals of 2 ml.
The time at which an interval of at least 10 seconds elapsed
after the color of the sample water had changed from blue to
reddish purple was taken as the end point of thi~ titration.
Cation equivalent weight value (CY) (meq/g) =
(Amount of titrant [ml] for sample - amount of
titrant [ml] for blank) x F/2 x (concentration o~
effective component (ppm) in sample)
The term "effective component" as used herein refer~
to the component remaining after removal of neutralizing
acid from the solids of the sample.
(2) Anion equivalent weight value
This property was determined by placing 50 ml of
distilled water in a beaker, adding thereto about 0.3 g of
accurately weighed sample, stirring the resultant solution,
and titrating this solution with a N/10 NaOH solution to
obtain the scale reading of electrocondcutivity. l'he ~cale
reading of titration oorresponding to the last (the point at
which neutralization of the whole acid present was
completed) of several points of in~lection was taken for
reporting.
Anion equivalent weight value (Av) (meq/g) =
0.1 x F x (Amount of titrant [mll for N/10 NaOH) -
(number of m.mols of neutralizing acid used in
accurately weighed sample [meq]/(concentration of
amount of effective component [ppml in ~ample)
(3) Average value of n
Average value of n - Cr/Ar
wherein Cr is number of m.mols of alkylene imine (meq/g) in
effective component of polyelectrolyte and Ar i~ number of
m.mol~ of anionic monomer (i) (meq/g) in ef~ective component
of polyelectrolyte minu~ anion equivalent weight value
(meq/g).
-28-
- ~ c~ c`~ c`~ ci c'~ ~> ~ l ~ l o ~ ~ l c~ - l
~ -- - - - - - - - ~-- - -
-o ~ c~ ~p c~ ~ ~-~ -~ t~- c~- u-~l co
~ --- - - - -- -- - - - ~ - - -
~
~ ~ u~. o u~ o~ ~o ~o o 3 ~ o
.~ ~ _ _ _. _ __ _ ___
~ ~)~ ~ ~ ~, ~ ~ ~ ~ ~ ~r ~
1 ~
,0 ~ U~ U~ U~ ~O O 10 10 U~ O c- r t- t- t-
',~0~- _ _. _ .- __ _ ___ _
n ~ ~ ~
~3 ~3 g a~ aao3 ~ co a o P~ ~o to Si O ~ ~; a~ _
~3 ~ ~ ~ t o t-- t~ N 1- CD tO tO O O
~ _ O _ ~ _ ~ _ O ~ --~ ~ _ ~
~ 1~ 1~ ~ ~y ~ ~ 1~1 1~ ,i~3 1~--1~ ~Y 5:
~ ~1 ~ ~
-29-
z~o~9o
Referential Example 7 [Method for production of water-in-
oil form vinylic carboxylic acid polymer emulsion (vii)]
In a four-neck flask fitted with a ~tirrer, a
thermometer, a condenser9 a dropping funnel, and a nitrogen
gas inlet tube, 100 g of Isoper M (isoparaffin solvent
produced by ~xxon Chemical) wa~ placed and 11.6 g of
sorbitan monooleate was dissolved therein and the resultant
mixture was emulsified by gradual adclition thereto o~ a
mixed solution prepared as an aqueous monomer solution by
the combination of 80 g of acrylic acid, 20 g o~ acrylamide,
52.9 g of aQueous 28 wt% ammonia solution, and 33.9 g of
deionized water. After the internal gas of the reaction
system had been thoroughly displaced with nitrogen gas, the
reaction mixture was heated to 60C and, in the pre~ence of
0.7 g of azobis(dimethyl valeronitrile) added thereto ag a
catalyst, was heated at 60C and, at the same time, stirred
for 4 hours. Consequently, there was obtained a water-in-
oil form vinylic carboxylic acid polymer emulsion.
Referential Examples 8 to 11
Water-in-oil form vinyl type carboxylio acid polymer
emulsions were obtained by ~ollowing the procedure of
Referential Example 1, except that varying hydrophoblc
organio solvent, surfactants, and monomer compositions
indicated in Table 3 were used instead.
Referentlal Examples 12 and 13
Aqueous solution form vinylic carboxylic acid
polymers were obtained by polymerizing in water monomers of
amounts forming weight ratios indicated in Table 3 and
totalling a proportion of 33~ by weight.
-30-
Z ~ ~0 69
T~ble3
_ ~
Refer~ntial Weight ratio Hydrophobic
Example of n~onomersorgani~ solvent Surfactant
. _ , ~
8 AA/AAm = 100/0isoparaf~m sorbitan mono~tear1te
. ~
9 AA/AAm = 60/40n-parafflm sorbitan monolauro.te
_ ~ __ _~
AA/HEA = 60/40 kerosen glyc~rol monost~arate
~ __ ~ _~
11 AA/MAm = 60/40 tolu~ne sorbitan mono~tearate +
polyoxyethelene nonyl phenyl ether
_ ~ _. _~
12 AA/AAm = 80/20
_~ . .~ _
13 A~UAAm =100/0
_ ~ __ ~ ~_
Example 10
In a reactor, 200 g of the water-in-oil form vinylic
carboxylic acid polymer emulsion synthesi2ed in Referential
Example 7 was placed, heated to 50C and kept at thi~
temperature throughout the course of reaction ancl, a~ter
dropwise addition thereto of 16.0 g of ethylene imine,
stirred with the added ethylene imine for 30 minute~. Then,
the resultant mixture and 38.4 g of an aqueous 61 wt% nitric
acid solution added thereto were stirred for 30 minutes.
Subsequently, the resulting reaction mixture and 50.8 g of
ethylene imine added dropwise thereto were stirred for 30
minutes. Then, the ensuing stirred mixture and 73.9 g of an
aqueous 61 wt% nitric acid solution added thereto were
stirred for 30 minutes. Consequently 5 ~here was obtained a
water-in-oil form amphoteric copolymer emulsion. The
reaction conditions and the physical properties of the
reaction product were as shown in Table 4.
Examples 11 to 17
The procedure of Example 10 was repeated, except
that the conditions shown in Table 4 were used instead. The
-31-
Z~ 90
physical properties of the reaction product were as shown in
Table 4.
Controls 6 and 7
Reactions were carried out by following the
procedure of Example 10, except that the aqueous solution
form vinylic carboxylic acid polymers obtained in
Referential Examples 12 and 13 were respectively used
instead. The physical properties of the reaction products
were as shown in Table 4.
The intrinsic viscosity was determined by the
following method (which applies similarly hereinafter).
(3) Intrinsic viscosity (dl/g)
In 100 parts by volume of water 9 0.2 part by weight
of a sample polymer was dissolved and adjus~ed to p~ 4 with
hydrochloric acid. In a conical flask fitted with a ground
stopper, 50 ml of the resutlant solution was placed and
gently stirred with 50 ml of 2N-NaN03 ~or thorough solution.
Then, the resultant solution was diluted with 1N-NaN03 to
concentrations o~ 0.02%, 0,OL~%, 0.06%, and 0.08%, diluted
solutions were adjusted to pH 4.
In a constant temperature bath adjusted to 30C ~
0.1C and fitted with a Canon Fenske viscosimeter, tO ml of
a sample was placed in the visco~imeter and allowed to flow
down spontaneously. The time required for the sample to
pass through the distance between the vertically separated
marks on the measuring bul~ was measured. This procedure
was repeated at least three times to determine the intrinsic
viscosity as the average. A blank test was performed with
an aqueous solution of 1N-NaN03.
This prooedure was performed on each o~ the 0.02 to
0.08~ solutions mentioned above.
The reduced viscosity was calculated as follows.
Relative viscosity ~rel = t/to
Specific viscosity ~sp = (t - to)/to = ~rel ~
Reduced viscosity ~sp/c
-3~-
Z0~9~
wherein to i5 the time for downward flow of 1N-NaN03, t is
the time for downward flow of sample solution, ~rel is the
relative viscosity, ~sp is the specific viscosity, and c is
the concentration of sample solution.
On a graph having the horizontal axis graduated for
sample conc~ntration and the vertical axis for reduced
~iscosity, the numerical values obtained by the measurement
described above were plotted and straight line~ were drawn
across the points. The reading of the vertical axis against
whiah the sample concentration was O was taken as the
intrinsic viscosity of the sample.
to = the time required for 1N-NaN03
t - the time required for the sample soln.
c = the concentration of the sample soln.
-33-
21D1~6
_ __ _ _ . _ . _ _ _
c ~ `~ c~ u~ ~ ~ a:) u~ ~ r ,- o
~-~= j L5- -I
~ ¢~ o ~o O c~, O ~o o ~o ~o ~r
~ _ . . ~ .
~ cn c~, ~ ~ c~ a~ c~ ~
_ 3~C~ _ _ . _ _ _ _ _
~ ~ r o o o o r r r o r
Z ~ _ _ _ _~ _ _ _ __
.~ _ ~. _ _ __ _ _ ~ __
~3 ' o~ ~ a~ ,, ~D, r o~ ~ a~ ~rO
_ _._ _ __ . _ _ _ _.
¢ ~ ~ ~ ~ ~ ~ ~ ~ ~ a
_ _ _ _ _ _ _ ~ _
~ ' ~ i r ~ e j ~
~.~
1 _ L~ - I ~ L~ L L L~ ~ L 1
- 34
Z~06go
Referential Example 14 ~Production of vinylic carboxylic
acid polymer emulsion (~
In a four-neck flask fitted with a stirrer, a
thermometer~ a condenser, a dropping funnel, and a nitro~en
gas inlet tube, 820 g o~ deionized water and 0.8 g of sodium
lauryl sulfate were stirred for thorough solution. To the
resultant solution, Z5.6 g of acrylic acid (AA), 3.2 g of
acrylamide ~AAm), and 3.2 g of styrene (St) were added. The
reaction mixture was kept stirred and the internal gas of
the reaction system was thoroughly displaced with nitrogen
gas. After the nitrogen displacement, the reaation mixture
was heated to 50C and 0.288 g of ammonium persulfate (APS)
and 0~288 g of sodium hydrogen sulfite were added as
catalyst thereto. Immediately, 102.4 g of acrylic acid
(AA), 12.8 g of acrylamide (AAm), and 12.8 g of styrene (St)
were added dropwlse through the dropping funnel to the
reaction mixture over a period of 2 hours, with the
temperature kept at 50C. The resultant mixture was left
aging for 2 hours. Consequently, there was obtained a
vinylic carboxylic acid polymer emulsion. The visco~ity of
this polymer emulsion was 2850 cps. When this polymer
emulsion was neutrali~ed with sodium hydroxide to effect
thorough ~olution of the emulsion and the solids content of
the resultant solution was adjusted to 1% by weight, the
viscosity of the solution was 130 cps.
Referential Examples 15-19
~ inylic carboxylic acid polymer emulsions (vi) were
obtainad by following the procedure of Referen~ial Example
14, except that the composition of monomers was varied as
indicated in Table 5.
-35-
2~
Table~
.... ~ , _ ~ __~___ _ . .
Vi~cos~y Viscosityof
Re~erential Weightratioo~monomer (2~C,CPS) l%solution
____
1~ AAlAAmlSt = 80/15/5 3,500 140
_.
16 AAlAAmlBA = 80/10/10 3,100 120
17 AA/HEA/MMA = 60/30/10 3,600 113
__. ___
18 AAIMAlVSt=65l30l5 6,200 83
_ ~______
19 AA/HAm/MA = 80/10/10 2,800 105
_ ~
AAJAAm = 100/0 35,000 75
~__ ___
21 AA/AAm = 80/20 28,000 80
~ ~ ,____
Example 18
In a reactor, 500 g of the vinylic carboxylic acid
polymer emulsion (vi) synthesized in Referentia~ Example 14
was placed and heated 50C and kept at this temperature
throughout the entire course of reaction and, after dropwise
addition of 19.1 g of ethylene imine thereto, was stirred
with the added ethylene imine for 30 minutes. The resultant
mixture and 45.9 g of an aqueous 61 wt~ nitric acid solution
added thereto were stirred for 30 minutes. Subsequently,
the ensuant mixture and 88.6 g of an aqueous 61 wt% nitric
acid solution ad~ed thereto were stirred for 30 minutes.
Consequently, there was obtained an amphoteric
polyelectrolite. The reaction conditions and the physical
properties of the reaction product were ~s shown in Table 6.
Examples 19 to 26
The procedure of Example 18 was repeated, except
that the conditions indicated in Table 6 were used instead.
The physical properties of the reaction products were as
shown in Table 6.
Controls 8 and 9
-36-
IL069~
The procedure of Example 18 was repeated, except
that the vinylic carboxylic acid polymers (vi) synthesized
in Referential Examples 20 and 21 were respectively used
instead. The physical properties of the reaction products
were as shown in Table 6.
lL0~9C~
I _ ~1 ,W ~ ~ ¦ ~ ¦ d ¦ ~ ¦ ~ I O co d .1 I O
_ _ _ _______ __ _
~o ~ CO ~O O, ~0 ~0 O ~0 O ~ U~ O
b _ _ _ _ _ _ _ _ __ _ _
~ ~ _~ a~, ,. ~ , ~, ,~ ~ u~ ~ ~ ~
_ _ _ _ ___ ____ __.
~ ~ o o o, o o r o o o o, o
~o 3 ~ ~ o~ co c~n ~ , o G~ ~ o~
:~ _ __ _ _ .._ _ _ _ _
~ ~ L~ ~ ~ ~3 ~ ~:d ~3 P~ E~ ~ g
_ _, _ l ____ ~ _ ~m
;~ ~
c
-3~-
zo~o~9~
Examples 27 to 35
The amphoteric polymer dehydraters abtained in
Examples 1 to 9 were tested for flocculation property on a
mixed raw sludge (having a solids content o~ 2.2% by weight)
from a sewage disposal plant. The results were as shown in
Table 7.
Controls 10 to 12
DAM (N,N-dimethylaminoethyl methacrylate) type
polymer dehydraters indicated in Table 7 were tested for
flocculation property on a mixed raw sludge (having a solids
content of 2.2% by weight) from a sewage disposal plant.
The results were as shown in Table 7.
Control 13
The amphoteric polymer dehydrater obtained in
Example 10 was tested for flocculation property on a mixed
raw sludge (having a solids content of 2.2% by weight) from
a sewage disposal plant. The results were as shown in Table
7.
Control 14
The amphoteric DAM (N,N-dimethylaminoethyl
methacrylate) type polymer dehydrater indicated in Table 7
was tested for flocculation property on a mixed raw sludge
(having a solids content of 2.2% by weight) from a sewage
disposal plant. The results were as shown in Table 7.
~Flocculation te3t]
In a beaker having an inner volume of 300 ml, 150 ml
of sludge was placed and a stated amount of an aqueous 0.2
wt% solution of a polymer dehydrater indicated in Table 7
was added thereto. After the addition, the sludge and the
dehydrater were stirred at 150 rpm for 2 minutes with a jar
tester. The flocs of sludge consequently obtained were
passed through a 100-mesh nylon filter cloth under 400 mmHg
in a vacuum filtrating device (leaf tester) to determine the
average specific resistance of filter cake as an index to
water-filtrating property. The cake resulting from the
vacuum filtration was nipped between two filter cloths
-39-
2~0~g~
having a surface area of the square of 10 cm, pressed under
0.~ kg/cm2 for 10 minutes, and then tested for water
content.
The amount of the amphoteric polymer dehydrate added
to the sludge was 15% by weight as effective component,
based on the amount of the solids of the sludge slurry.
The water content of the dehdyrated cake wa~
calculated from the weight of the cake after the dehydration
with the pre~s and the weight of the sludge solids remaining
after 2 hours' drying at 110C.
The average specific resistance, a, of the cake
indicates that the desirability of water filtering property
increases in proportion as the average specific resistance
decreases.
The average specific resistance~ a, of the cake was
found by plotting the found functions of ~/V and V on a
graph and calculating Routh's filtration constant K and
filtration constant.
The average specific re~i~tance, a, of the ¢ake and
the resistance coefficient of the filter material were
calculated by plotting the function~ of H/V and V on a graph
paper and calculating Routh's filtration constant K and
filtration constant C.
The Routh'~ theoretical formulas convering th~
constant pressure filtration are as follows:
v2 + 2VC = K~
K - 2 P qc A2 k/a~
C = A km k /a
a = 2 P qc A2 k~K~
km = C a/A k
V: amount of filtrate (m3)
~: time of filtration (s)
K: Routhls filtration constant (m3/s)
C: Routh's filtration constant (m3)
p: pressure difference ~kgw/m3)
A: filtration area (m2)
-40-
~O~
~: viscosity of filtrate (kg~m . s)
(assured to be 0.001 kg/m s)
a: specific resistance of cake (m/kg)
km: resistance coefficient of filter material (1/m)
k: amount of filtrate per unit m~ss of dried cake (m3/kg)
= 0.00~ - m s/p . 3
m: mass ratio of wet cake dry cake
s: sludge concentration (mass ratio of solids to sludge)
p: density of filtrate (kg~m3)
(= 1000 kg/m3)
qc. coefficient for conversion of qravity (kg ~ m/kgw ~2)
-41-
I ~ 1~ 1~ ~ ~ ~ ~ Z 106 0
L~ SX s so o ~ ~ ~o ~x ~o ~x Sx o x I
m ¦~ ¦~ m _ L m _ m ¦_ _ ¦_ ~ ~ _ ¦
~i 2 m m o _ r m m m ¦_ _ ¦_ m o:~ j o m
6 ~ o ~ o o o o o o ~ ' ~ ~ ' s .
_ 42 --
