U.S. patent application number 09/779261 was filed with the patent office on 2001-08-16 for amino-group-containing polymer (salt) and production process therefor.
This patent application is currently assigned to Nippon Shokubai Co., Ltd.. Invention is credited to Akasaki, Ichimoto, Saeki, Koichiro, Saeki, Takuya, Takagi, Masahito.
Application Number | 20010014722 09/779261 |
Document ID | / |
Family ID | 18558563 |
Filed Date | 2001-08-16 |
United States Patent
Application |
20010014722 |
Kind Code |
A1 |
Akasaki, Ichimoto ; et
al. |
August 16, 2001 |
Amino-group-containing polymer (salt) and production process
therefor
Abstract
The present invention provides a novel amino-group-containing
polymer (salt) and a production process therefor wherein the
amino-group-containing polymer (salt) is a product by a process
including the step of introducing amino groups into a grafted
polymer having a polyether skeleton, and can make good use of the
reactivity or cationic property of at least primary amino groups
and further, according to circumstances, secondary amino groups,
and further can display various performances, such as curability
useful for various uses and adsorbency onto films or fibers. The
novel amino-group-containing polymer (salt) is a product by a
process including the steps of: carrying out a graft polymerization
of a monoethylenically unsaturated monomer component onto a
polyether compound, wherein the monoethylenically unsaturated
monomer component includes an unsaturated carboxylic monomer as an
essential component, and wherein the polyether compound has a
specific repeating unit in a ratio of not less than 30 mol % and
has a number-average molecular weight of not less than 150; and
introducing amino groups by carrying out a ring-opening addition of
an alkylenimine to at least a part of carboxyl group portions of
the monoethylenically unsaturated monomer component which has been
graft-polymerized onto the polyether compound, wherein at least a
part of the amino groups might be neutralized with an acid.
Inventors: |
Akasaki, Ichimoto;
(Otsu-shi, JP) ; Takagi, Masahito; (Suita-shi,
JP) ; Saeki, Takuya; (Suita-shi, JP) ; Saeki,
Koichiro; (Suita-shi, JP) |
Correspondence
Address: |
ROBERT J JACOBSON PA
650 BRIMHALL STREET SOUTH
ST PAUL
MN
551161511
|
Assignee: |
Nippon Shokubai Co., Ltd.
|
Family ID: |
18558563 |
Appl. No.: |
09/779261 |
Filed: |
February 8, 2001 |
Current U.S.
Class: |
525/404 ;
525/403; 525/408; 525/523; 525/529; 525/530; 525/531; 525/532;
525/533; 528/403; 528/405; 528/421; 528/423; 528/424 |
Current CPC
Class: |
C08F 8/30 20130101; C08F
283/06 20130101; C08F 8/30 20130101; C08F 283/06 20130101 |
Class at
Publication: |
525/404 ;
525/403; 525/408; 525/523; 525/529; 525/530; 525/531; 525/532;
525/533; 528/403; 528/405; 528/421; 528/423; 528/424 |
International
Class: |
C08F 283/06; C08G
065/332; C08L 071/00; C08G 065/333 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 10, 2000 |
JP |
2000-034193 |
Claims
What is claimed is:
1. An amino-group-containing polymer (salt), which is a product by
a process including the steps of: carrying out a graft
polymerization of a monoethylenically unsaturated monomer component
onto a polyether compound, wherein the monoethylenically
unsaturated monomer component includes an unsaturated carboxylic
monomer as an essential component, and wherein the polyether
compound has a repeating unit of a general formula below in a ratio
of not less than 30 mol % and has a number-average molecular weight
of not less than 150; and introducing amino groups by carrying out
a ring-opening addition of an alkylenimine to at least a part of
carboxyl group portions of the monoethylenically unsaturated
monomer component which has been graft-polymerized onto the
polyether compound, wherein at least a part of the amino groups
might be neutralized with an acid; wherein the general formula is:
4wherein: R.sup.1, R.sup.2, R.sup.3 and R.sup.4 denote at least one
member selected from the group consisting of a hydrogen atom, alkyl
groups, alkenyl groups, and aryl groups, and these groups may
coexist in a molecule.
2. An amino-group-containing polymer (salt) according to claim 1,
wherein the alkylenimine is a compound having 2 to 8 carbon
atoms.
3. An amino-group-containing polymer (salt) according to claim 1,
wherein a part of the carboxyl group portions of the
monoethylenically unsaturated monomer component which has been
graft-polymerized onto the polyether compound remains in the
amino-group-containing polymer (salt), wherein at least a part of
the remaining carboxyl group portions are neutralized with a basic
compound.
4. An amino-group-containing polymer (salt) according to claim 2,
wherein a part of the carboxyl group portions of the
monoethylenically unsaturated monomer component which has been
graft-polymerized onto the polyether compound remains in the
amino-group-containing polymer (salt), wherein at least a part of
the remaining carboxyl group portions are neutralized with a basic
compound.
5. A production process for an amino-group-containing polymer
(salt), which comprises the steps of: carrying out a graft
polymerization of a monoethylenically unsaturated monomer component
onto a polyether compound, wherein the monoethylenically
unsaturated monomer component includes an unsaturated carboxylic
monomer as an essential component, and wherein the polyether
compound has a repeating unit of a general formula below in a ratio
of not less than 30 mol % and has a number-average molecular weight
of not less than 150; and carrying out a ring-opening addition of
an alkylenimine to at least a part of carboxyl group portions of
the monoethylenically unsaturated monomer component; wherein the
general formula is: 5wherein: R.sup.1, R.sup.2, R.sup.3 and R.sup.4
denote at least one member selected from the group consisting of a
hydrogen atom, alkyl groups, alkenyl groups, and aryl groups, and
these groups may coexist in a molecule.
6. A production process for an amino-group-containing polymer
(salt) according to claim 5, wherein the alkylenimine as used is a
compound having 2 to 8 carbon atoms.
Description
BACKGROUND OF THE INVENTION
[0001] A. Technical Field
[0002] The present invention relates to a novel
amino-group-containing polymer (salt) and a production process
therefor wherein the amino-group-containing polymer (salt) is a
product by a process including the step of introducing amino groups
into a grafted polymer having a polyether skeleton.
[0003] B. Background Art
[0004] Grafted polymers obtained by carrying out a graft
polymerization of unsaturated carboxylic monomers such as
(meth)acrylic acid onto polyether compounds are, for example,
utilized for uses, such as detergent builders, scale inhibitors,
lubricants, dyeing assistants, fiber-treating agents, and
dispersants for organic or inorganic particles, by taking advantage
of the hydrophilicity of the grafted polymers. Such hydrophilic
grafted polymers are, for example, disclosed in JP-A-208769/1996,
JP-A-208770/1996, and JP-A-053645/1995.
[0005] On the other hand, amino-group-containing polymers are known
to display excellent performances due to the presence of the amino
group, such as epoxy curability and reactivity to other functional
groups. For example, a curable resin composition comprising an
amino-group-containing acrylic resin is disclosed in U.S. Pat. No.
3,705,076 and JP-A-056549/1988 wherein the amino-group-containing
acrylic resin is obtained by carrying out a ring-opening addition
of an alkylenimine to carboxyl group portions of a
carboxyl-group-containing acrylic polymer; and a water-soluble
resin comprising an acid-neutralized salt of an
amino-group-containing acrylic resin is disclosed in U.S. Pat. No.
3,719,629 wherein the amino-group-containing acrylic resin is
obtained by carrying out a ring-opening addition of an alkylenimine
to carboxyl group portions of a carboxyl-group-containing acrylic
polymer; and an amino-group-containing acrylic polymer, obtained by
carrying out a ring-opening addition of an alkylenimine to a part
of carboxyl group portions of a carboxyl-group-containing acrylic
polymer and then neutralizing the rest of the carboxyl group
portions with basic compounds such as triethylamine, is disclosed
in U.S. Pat. No. 4,126,596; and a curable resin composition
obtained by Michael addition between a polyvalent amino compound,
such as polyamine or polyamide, and a polyvalent acryloyl group is
disclosed as an adhesive in JP-A-023615/1986; and a polymer with a
side chain amino group, which is obtained by carrying out a
reaction between a carboxyl group of a polymer and a polyamine, is
disclosed as a paint in JP-B-061321/1988 wherein the raw polymer is
obtained by carrying out a copolymerization of a
carboxyl-group-containing unsaturated monomer with another
copolymerizable unsaturated monomer and wherein the polyamine has
an aliphatic amino group or both an aliphatic amino group and at
least one ether group.
[0006] However, in consideration of the ionic aspect, it is a
conventional idea that a polyether skeleton having the nonionic
character is usually endowed with only either anionic or cationic
character by introducing either an anionic or cationic group as a
graft portion. It is difficult to lead to an idea of introducing an
anionic carboxyl group and then converting it into a cationic
group. Therefore, up to now, no polymers obtained by introducing
the carboxyl group and further an amino group into a graft portion
of a grafted polymer having a polyether skeleton have been studied,
and there have been no reports as to such polymers, either.
SUMMARY OF THE INVENTION
[0007] A. Object of the Invention
[0008] An object of the present invention is to provide a novel
amino-group-containing polymer (salt) and a production process
therefor wherein the amino-group-containing polymer (salt) is a
product by a process including the step of introducing amino groups
into a grafted polymer having a polyether skeleton.
[0009] B. Disclosure of the Invention
[0010] That is to say, an amino-group-containing polymer (salt),
according to the present invention, is a product by a process
including the steps of:
[0011] carrying out a graft polymerization of a monoethylenically
unsaturated monomer component onto a polyether compound, wherein
the monoethylenically unsaturated monomer component includes an
unsaturated carboxylic monomer as an essential component, and
wherein the polyether compound has a repeating unit of a general
formula below in a ratio of not less than 30 mol % and has a
number-average molecular weight of not less than 150; and
[0012] introducing amino groups by carrying out a ring-opening
addition of an alkylenimine to at least a part of carboxyl group
portions of the monoethylenically unsaturated monomer component
which has been graft-polymerized onto the polyether compound,
wherein at least a part of the amino groups might be neutralized
with an acid;
[0013] wherein the general formula is: 1
[0014] wherein:
[0015] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 denote at least one
member selected from the group consisting of a hydrogen atom, alkyl
groups, alkenyl groups, and aryl groups, and these groups may
coexist in a molecule.
[0016] A production process for an amino-group-containing polymer
(salt), according to the present invention, comprises the steps
of:
[0017] carrying out a graft polymerization of a monoethylenically
unsaturated monomer component onto a polyether compound, wherein
the monoethylenically unsaturated monomer component includes an
unsaturated carboxylic monomer as an essential component, and
wherein the polyether compound has a repeating unit of a general
formula below in a ratio of not less than 30 mol % and has a
number-average molecular weight of not less than 150; and
[0018] carrying out a ring-opening addition of an alkylenimine to
at least a part of carboxyl group portions of the monoethylenically
unsaturated monomer component;
[0019] wherein the general formula is: 2
[0020] wherein:
[0021] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 denote at least one
member selected from the group consisting of a hydrogen atom, alkyl
groups, alkenyl groups, and aryl groups, and these groups may
coexist in a molecule.
[0022] These and other objects and the advantages of the present
invention will be more fully apparent from the following detailed
disclosure.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The amino-group-containing polymer (salt), according to the
present invention, is a product by a process including the steps
of: carrying out a graft polymerization of a monoethylenically
unsaturated monomer component onto a polyether compound; and
carrying out a ring-opening addition of an alkylenimine to at least
a part of carboxyl group portions of the monoethylenically
unsaturated monomer component. More specifically, the
amino-group-containing polymer (salt) is a product by a process
including the steps of:
[0024] carrying out a graft polymerization of a monoethylenically
unsaturated monomer component onto a polyether compound, wherein
the monoethylenically unsaturated monomer component includes an
unsaturated carboxylic monomer as an essential component, and
wherein the polyether compound has a repeating unit of a general
formula below in a ratio of not less than 30 mol % and has a
number-average molecular weight of not less than 150; and
[0025] carrying out a ring-opening addition of an alkylenimine to
at least a part of carboxyl group portions of the monoethylenically
unsaturated monomer component which has been graft-polymerized onto
the polyether compound;
[0026] wherein the general formula is: 3
[0027] wherein:
[0028] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 denote at least one
member selected from the group consisting of a hydrogen atom, alkyl
groups, alkenyl groups, and aryl groups, and these groups may
coexist in a molecule.
[0029] A more specific mode for the amino-group-containing polymer
(salt), according to the present invention, is an
amino-group-containing polymer (salt) which is a product by a
process including the steps of: carrying out a graft polymerization
of a monoethylenically unsaturated monomer component onto a
polyether compound in order to obtain a grafted polymer, wherein
the monoethylenically unsaturated monomer component includes an
unsaturated carboxylic monomer as an essential component; and
carrying out a ring-opening addition of an alkylenimine to at least
a part of carboxyl group portions derived from the unsaturated
carboxylic monomer of the monoethylenically unsaturated monomer
component which forms a graft portion of the grafted polymer.
[0030] In addition, in the more specific mode for the present
invention, the above-defined grafted polymer in the present
invention may be a grafted polymer composition obtained by a
process including the step of carrying out a graft polymerization
of a monoethylenically unsaturated monomer component onto a
polyether compound, wherein the monoethylenically unsaturated
monomer component includes an unsaturated carboxylic monomer as an
essential component. This grafted polymer composition comprises the
above-mentioned grafted polymer as an essential component, and the
content of the grafted polymer is not especially limited. In a
preferred mode for the present invention, the
amino-group-containing polymer (salt) according to the present
invention can be obtained by a process including the step of
carrying out a ring-opening addition of an alkylenimine to the
grafted polymer composition.
[0031] In the present invention, the polyether compound is a
compound having the repeating unit represented by the above general
formula in a ratio of not less than 30 mol %, preferably not less
than 50 mol %, of the entirety of the polyether compound. Such a
polyether compound is, for example, obtained by a process including
the step of polymerizing a cyclic ether by such as conventional
methods in the presence of a reactant which serves as a
polymerization initiation site, wherein the cyclic ether comprises
at least one alkylene oxide selected from the group consisting of
such as ethylene oxide, propylene oxide, 1-butene oxide, 2-butene
oxide, styrene oxide, epichlorohydrin, glycidol, methyl glycidyl
ether, ethyl glycidyl ether, iso-butyl glycidyl ether,
methoxypolyethylene glycol monoglycidyl ether, phenoxypolyethylene
glycol monoglycidyl ether, allyl glycidyl ether, phenyl glycidyl
ether, and .alpha.-olefin oxide as an essential component and, if
necessary, further comprises another alkylene oxide which is
copolymerizable with those alkylene oxides. Particularly, it is
preferable to use ethylene oxide and/or propylene oxide as the
essential component of the cyclic ether in consideration of the
grafting efficiency of the monoethylenically unsaturated monomer
component. Furthermore, the ethylene oxide and/or propylene oxide
is preferably used in a ratio of not less than 30 mol %, more
preferably not less than 50 mol %, of the entirety of the polyether
compound. In addition, examples of other alkylene oxides include
tetrahydrofuran and oxetane.
[0032] The above reactant is a compound which serves as an
initiation site of the polymerization of the cyclic ether, and is
not especially limited in such as its kind and molecular weight.
Examples of the reactant include: water; hydrogen; alcohols;
phenols; hydrogen halides; ammonia; amines; hydroxylamine;
carboxylic acids; acid halides; lactones; and aldehydes. These can
be used either alone respectively or in combinations with each
other. Of them, at least one member selected from the group
consisting of water, alcohols, phenols, and amines is preferable as
the reactant.
[0033] Examples of the above-mentioned alcohol include: primary
aliphatic alcohols having 1 to 22 carbon atoms, such as methanol,
ethanol, n-propanol, and n-butanol; aromatic alcohols, such as
phenol, cresol, ethylphenol, cumylphenol, xylenol, octylphenol,
tert-butylphenol, nonylphenol, and naphthol; secondary alcohols
having 3 to 18 carbon atoms, such as iso-propyl alcohol and
alcohols obtained by a process including the step of oxidizing
n-paraffin; tertiary alcohols, such as tert-butanol; diols, such as
ethylene glycol, diethylene glycol, propanediol, butanediol, and
propylene glycol; triols, such as glycerin and trimethylolpropane;
and polyols, such as sorbitol. These can be used either alone
respectively or in combinations with each other.
[0034] Examples of the above-mentioned amine include: aromatic
amines, such as aniline and naphthylamine; alkylamines having 3 to
22 carbon atoms, such as dodecylamine and stearylamine; and
alkyldiamines, such as ethylenediamine. These can be used either
alone respectively or in combinations with each other.
[0035] The reaction form of the polymerization of the cyclic ether
is not especially limited, but, for example, may be any one of: (1)
anionic polymerization by use of basic catalysts such as strong
alkalis (e.g. hydroxides and alcoholates of alkaline metals) and
alkylamines; (2) cationic polymerization by use of catalysts, such
as metal halides, semi-metal halides, mineral acids, and acetic
acid; and (3) coordination polymerization by use of combinations of
such as metal (e.g. aluminum, iron, zinc) alkoxides, alkaline earth
compounds, and Lewis acids.
[0036] The polyether compound may be a derivative from the
polyether obtained by the above-mentioned polymerization. Examples
of such a derivative include: terminal-group-converted compounds
obtained by a process including the step of converting a terminal
functional group of the polyether; and crosslinked products
obtained by a process including the step of reacting the polyether
with a crosslinking agent having a plurality of groups such as
carboxyl group, isocyanate group, epoxy group, acid anhydride
group, and halogen group. Preferable of the
terminal-group-converted compounds are as follows: products by a
process including the step of esterifying at least one terminal
hydroxyl group of the above-mentioned polyether with fatty acids
having 2 to 22 carbon atoms or anhydrides thereof (such as acetic
acid and acetic anhydride) or with dicarboxylic acids (such as
succinic acid, succinic anhydride, and adipic acid); and products
by a process including the step of mono- or dietherifying at least
one terminal hydroxyl group of the above-mentioned polyether by
what is called Williamson (A. W. Williamson)'s synthesis of ether
process (process comprising the step of etherifying an alcoholic
hydroxyl group with an alkali and an alkyl halide).
[0037] In the present invention, the number-average molecular
weight of the polyether compound is not less than 150. The upper
limit of the number-average molecular weight is not especially
limited, but is preferably not more than 100,000. In the case where
the number-average molecular weight is less than 150, there are
problems in that the grafting ratio is so low that a large amount
of polyether compound remains unreacted. In the case where the
number-average molecular weight exceeds 100,000, the viscosity
tends to be high and it is therefore difficult to handle the
polyether compound during the polymerization.
[0038] The number of the repeating units of the above general
formula in the polyether compound is not especially limited, but is
preferably not smaller than 2, more preferably not smaller than 3,
in the polyether compound. As to R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 in the above general formula representing the repeating
unit, at least one thereof is preferably a hydrogen atom.
[0039] In the present invention, the monoethylenically unsaturated
monomer component includes the unsaturated carboxylic monomer as an
essential component and, if necessary, may further include another
unsaturated monomer which is copolymerizable with the unsaturated
carboxylic monomer.
[0040] Examples of the unsaturated carboxylic monomer include
ethylenically unsaturated carboxylic acids, such as (meth)acrylic
acid, itaconic acid, maleic acid, fumaric acid, and maleic
anhydride. These can be used either alone respectively or in
combinations with each other. Of them, at least one member selected
from the group consisting of (meth)acrylic acid, maleic acid,
fumaric acid, and maleic anhydride is preferable in consideration
of polymerizability.
[0041] There is no especial limitation in the above other
unsaturated monomer copolymerizable with the unsaturated carboxylic
monomer if it is a monomer other than the unsaturated carboxylic
monomer. Examples thereof include: alkyl (meth)acrylates obtained
by a process including the step of esterifying (meth)acrylic acid
with alcohols having 1 to 18 carbon atoms, such as methyl
(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and
cyclohexyl (meth)acrylate; amide-group-containing monomers, such as
(meth)acrylamide, dimethylacrylamide, and isopropylacrylamide;
vinyl esters, such as vinyl acetate; alkenes, such as ethylene and
propylene; aromatic vinyl monomers, such as styrene and
styrenesulfonic acid; maleimide and derivatives therefrom such as
phenylmaleimide and cyclohexylmaleimide; nitrile-group-containing
vinyl monomers, such as (meth)acrylonitrile;
aldehyde-group-containing vinyl monomers, such as (meth)acrolein;
sulfonic-acid-group-containing monomers, such as
2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid,
vinylsulfonic acid, 2-hydroxy-3-allyloxy-1-propanesul- fonic acid,
and 2-hydroxy-3-butenesulfonic acid; alkyl vinyl ethers, such as
methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; and
other-functional-group-containing monomers, such as vinyl chloride,
vinylidene chloride, allyl alcohol, and vinylpyrrolidone. These can
be used either alone respectively or in combinations with each
other.
[0042] The ratio of the unsaturated carboxylic monomer in the
monoethylenically unsaturated monomer component is not especially
limited, but is preferably not less than 30 weight %, more
preferably not less than 40 weight %, most preferably not less than
50 weight %, per 100 weight % of the monoethylenically unsaturated
monomer component in consideration of reactivity in the
below-mentioned ring-opening addition of the alkylenimine.
[0043] When the graft polymerization of the monoethylenically
unsaturated monomer component onto the polyether compound is
carried out, the monoethylenically unsaturated monomer component is
preferably used in a ratio of 0.02 to 4 parts by weight, more
preferably 0.1 to 2 parts by weight, per part by weight of the
polyether compound. In the case where the ratio of the
monoethylenically unsaturated monomer component is less than 0.02
parts by weight per part by weight of the polyether compound, it is
difficult to exhibit properties derived from the amino group. On
the other hand, in the case where the ratio of the
monoethylenically unsaturated monomer component is more than 4
parts by weight per part by weight of the polyether compound, it
tends to be difficult to structurally design the desired
properties, such as balance between hydrophilicity and
hydrophobicity of the polymer, on the basis of the polyether
skeleton.
[0044] When carrying out the graft polymerization of the
monoethylenically unsaturated monomer component onto the polyether
compound, an organic peroxide is preferably used as a
polymerization initiator. Examples of the organic peroxide
include:
[0045]
[0046] ketone peroxides, such as cyclohexanone peroxide, methyl
ethyl ketone peroxide, methylcyclohexanone peroxide,
methylacetoacetate peroxide, and 3,3,5-trimethylcyclohexanone
peroxide;
[0047] peroxyketals, such as
1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcycl- ohexane,
1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3-
,3,5-trimethylcyclohexane,
1,1-bis(tert-butylperoxy)-2-methylcyclohexane,
1,1-bis(tert-butylperoxy)cyclohexane,
2,2-bis(tert-butylperoxy)butane,
n-butyl-4,4-bis(tert-butylperoxy)valerate, and
2,2-bis(tert-butylperoxy)o- ctane;
[0048] hydroperoxides, such as p-menthane hydroperoxide,
diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl
hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide,
tert-butyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide
and 2-(4-methylcyclohexyl)propane hydroperoxide;
[0049] dialkyl peroxides, such as
.alpha.,.alpha.'-bis(tert-butylperoxy)-p- -diisopropylbenzene,
dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylpero- xy)hexane,
tert-butylcumyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, and
.alpha.,.alpha.'-bis(tert-butylperoxy)-p-isopropylhexyne;
[0050] diacyl peroxides, such as isobutyryl peroxide,
3,3,5-trimethylcyclohexanoyl peroxide, octanoyl peroxide, lauroyl
peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl
peroxide, benzoyl peroxide, acetyl peroxide, decanoyl peroxide, and
2,4-dichlorobenzoyl peroxide;
[0051] peroxydicarbonates, such as di-n-propyl peroxydicarbonate,
di-isopropyl peroxydicarbonate, bis-(4-tert-butylcyclohexyl)
peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate,
di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl
peroxydicarbonate, di-sec-butyl peroxydicarbonate,
di(3-methyl-3-methoxybutyl) peroxydicarbonate, dimyristyl
peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, and
di-allyl peroxydicarbonate;
[0052] peroxyesters, such as
.alpha.,.alpha.'-bis(neodecanoperoxy)diisopro- pylbenzene, cumyl
peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate,
1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl
peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-hexyl
peroxypivalate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl
peroxy-2-ethylhexanoate,
2,5-dibutyl-2,5-bis(2-ethylhexanoylperoxy)hexane- ,
1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, tert-hexyl
peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate,
tert-butyl peroxyisobutyrate, tert-hexyl
peroxyisopropylmonocarbonate, tert-butyl peroxymaleic acid,
tert-butyl peroxy-3,5,5-trimethylcyclohexanoate, tert-butyl
peroxylaurate, 2,5-dibutyl-2,5-bis(m-tolylperoxy)hexane, tert-butyl
peroxyisopropylmonocarbonate, tert-butyl
peroxy-2-ethylhexylmonocarbonate, tert-hexyl peroxybenzoate,
2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-butyl
peroxyacetate, tert-butyl peroxy-m-tolylbenzoate, tert-butyl
peroxybenzoate, bis(tert-butylperoxy)isophthalate, cumyl
peroxyoctanoate, tert-hexyl peroxyneohexanoate, and cumyl
peroxyneohexanoate; and
[0053] other organic peroxides, such as tert-butyl
peroxyallylcarbonate, tert-butyl trimethylsilyl peroxide, and
acetylcyclohexylsulfonyl peroxide. These can be used either alone
respectively or in combinations with each other.
[0054]
[0055] The amount of the organic peroxide as used is not especially
limited, but is preferably in the range of 0.1 to 30 weight %, more
preferably 0.5 to 20 weight %, of the monoethylenically unsaturated
monomer component. In the case where the amount is smaller than 0.1
weight %, the ratio of grafting onto the polyether compound tends
to be low. On the other hand, in the case where the amount exceeds
30 weight %, there are economical disadvantages because the organic
peroxide is expensive. It is preferable that the organic peroxide
is added simultaneously with addition of the ethylenically
unsaturated monomer component and separately from the polyether
compound without being premixed with the polyether compound.
However, the organic peroxide may beforehand be added to either the
polyether compound or monoethylenically unsaturated monomer
component.
[0056] When the graft polymerization of the monoethylenically
unsaturated monomer component onto the polyether compound is
carried out, either a catalyst for decomposing the organic peroxide
or a reducible compound may be used together with the organic
peroxide.
[0057] Examples of the catalyst for decomposing the organic
peroxide include: metal halides such as lithium chloride and
lithium bromide; metal oxides such as titanium oxide and silicon
dioxide; metal salts of inorganic acids such as hydrochloric acid,
hydrobromic acid, perchloric acid, sulfuric acid, and nitric acid;
carboxylic acids, such as formic acid, acetic acid, propionic acid,
butyric acid, isobutyric acid, and benzoic acid, and their esters
and metal salts; and heterocyclic amines, such as pyridine, indole,
imidazole, and carbazole, and derivatives therefrom. These can be
used either alone respectively or in combinations with each
other.
[0058] Examples of the reducible compound include: organometallic
compounds such as ferrocene; inorganic compounds which can generate
metal ions (e.g. iron, copper, nickel, cobalt, manganese), such as
iron naphthenate, copper naphthenate, nickel naphthenate, cobalt
naphthenate, and manganese naphthenate; inorganic compounds, such
as trifluoroborate-ether adduct, potassium permanganate, and
perchloric acid; sulfur-containing compounds such as sulfur
dioxide, sulfite salts, sulfate esters, bisulfite salts,
thiosulfate salts, sulfoxylate salts, and aromatic sulfonic acid
homologues (e.g. benzenesulfonic acid, its substituted products,
and p-toluenesulfonic acid); mercapto compounds, such as
octylmercaptan, dodecylmercaptan, mercaptoethanol,
.alpha.-mercaptopropionic acid, thioglycolic acid, thiopropionic
acid, sodium .alpha.-thiopropionate sulfopropyl ester, and sodium
.alpha.-thiopropionate sulfoethyl ester; nitrogen-containing
compounds, such as hydrazine, .beta.-hydroxyethylhydrazine and
hydroxylamine; aldehydes, such as formaldehyde, acetaldehyde,
propionaldehyde, n-butyraldehyde, isobutyraldehyde, and
isovaleraldehyde; and ascorbic acid. These can be used either alone
respectively or in combinations with each other.
[0059] The graft polymerization is preferably carried out
substantially in the absence of solvent, but a solvent may be used
in an amount of not larger than 20 weight % of the entirety of the
reaction system. In the case where the amount of the solvent
exceeds 20 weight % of the entirety of the reaction system, the
grafting ratio of the monoethylenically unsaturated monomer
component tends to be low. In the case where the reaction system
has high viscosity, the use of a small amount of solvent might be
preferable for handling, and the solvent may be distilled off after
being added.
[0060] The above solvent is not especially limited, but it is
preferable to use, for example, a solvent such that the constant of
chain transfer thereto of the monomer as used is as small as
possible, or a solvent which has a boiling point of not lower than
80.degree. C. so as to be usable for a reaction under normal
pressure. Examples of such a solvent include: water; alcohols, such
as iso-butyl alcohol, n-butyl alcohol, tert-butyl alcohol, ethylene
glycol, diethylene glycol, triethylene glycol, propylene glycol,
ethylene glycol monoalkyl ether, and propylene glycol monoalkyl
ether; diethers, such as ethylene glycol dialkyl ether and
propylene glycol dialkyl ether; and acetic compounds, such as
acetic acid, ethyl acetate, propyl acetate, butyl acetate, ethylene
glycol monoalkyl ether acetate, and propylene glycol monoalkyl
ether acetate. These can be used either alone respectively or in
combinations with each other. Examples of alkyl groups in the
above-mentioned alcohols and diethers include methyl group, ethyl
group, propyl group, and butyl group.
[0061] The temperature of the graft polymerization is not
especially limited, but is preferably not lower than 80.degree. C.,
more preferably in the range of 90 to 160.degree. C. In the case
where the temperature is lower than 80.degree. C., the graft
polymerization is so difficult to proceed that the grafting ratio
of the monoethylenically unsaturated monomer component tends to be
low. On the other hand, in the case where the temperature exceeds
160.degree. C., thermolysis of the polyether compound and the
resultant grafted polymer might occur.
[0062] When carrying out the graft polymerization, it is preferable
to charge a portion or the entirety of the polyether compound in
the initial stage. For example, in the case where at least one
monomer (A) selected from the group consisting of maleic acid,
fumaric and, and maleic anhydride is graft-polymerized together
with (meth)acrylic acid as the monoethylenically unsaturated
monomer components onto the polyether compound, it is preferable
that: not less than half the monomer (A) is premixed with the
polyether compound, and the resultant mixture is heated to not
lower than 80.degree. C., and then the residual monoethylenically
unsaturated monomer components and the organic peroxide are
separately added to the heated mixture to carry out the graft
polymerization. Such a process enables to easily control the
molecular weight of the resultant grafted polymer.
[0063] The amino-group-containing polymer (salt), according to the
present invention, is a product by a process including the step of
carrying out a ring-opening addition of an alkylenimine to carboxyl
group portions of the graft-polymerized monoethylenically
unsaturated monomer component. As to this amino-group-containing
polymer (salt) according to the present invention, it is enough
that the ring-opening addition of the alkylenimine to the carboxyl
group portions of the graft-polymerized monoethylenically
unsaturated monomer component is made to at least a part of the
carboxyl group portions of the graft-polymerized monoethylenically
unsaturated monomer component, and, as is mentioned below, the
amino-group-containing polymer (salt) may be that in which a part
of the carboxyl group portions of the graft-polymerized
monoethylenically unsaturated monomer component are neutralized
with a basic compound, and in which the alkylenimine is
ring-opening-added to at least a part of the residual unneutralized
carboxyl group portions. In this case, a part or all of the
residual carboxyl group portions in the amino-group-containing
polymer (salt) are in the form neutralized with the above basic
compound. In this way, the carboxyl group of the monoethylenically
unsaturated monomer component can be converted into an amino group
by carrying out the ring-opening addition of the alkylenimine.
[0064] Examples of the alkylenimine include ethylenimine,
propylenimine, butylenimine, and N-(2-hydroxyethyl)aziridine. In
addition, N-(aminoalkyl)-substituted alkylenimines, such as
N-(2-aminoethyl)aziridi- ne, N-(3-aminopropyl)aziridine, and
N-(2-aminopropyl)propylenimine, can also be used likewise.
Furthermore, alkylenimine compounds obtained by Michael addition of
alkylenimines to acryloyl-group-containing compounds, such as
methyl 3-aziridinopropionate obtained by addition of ethylenimine
to the acryloyl group of methyl acrylate and
N-(2-cyanoethyl)aziridine obtained by addition of ethylenimine to
the double bond of acrylonitrile, can also be used likewise. In the
present invention, when a compound having 2 to 8 carbon atoms is
used particularly of the alkylenimines, there are advantages also
in respect to production cost because plenty of amino groups can be
introduced by use of a small amount of alkylenimine and because the
ring-opening addition can be carried out in a short time due to
high reactivity.
[0065] The method for carrying out the ring-opening addition of the
alkylenimine is not especially limited, but, for example, the
ring-opening addition can easily be carried out by mixing the
carboxyl-group-containing grafted polymer or the monoethylenically
unsaturated monomer component with the alkylenimine by stirring
them under temperature conditions of 10 to 150.degree. C.,
preferably 40 to 100.degree. C. Incidentally, this ring-opening
addition reaction may be carried out in the absence of solvent, or
can be carried out by use of the aforementioned solvent usable in
the graft polymerization reaction.
[0066] When carrying out the ring-opening addition of the
alkylenimine, the amount of the alkylenimine as used is preferably
in the range of 0.1 to 10 mols per mol of the carboxyl group of the
monoethylenically unsaturated monomer component. In the case where
the amount of the alkylenimine is smaller than 0.1 mol, it is
difficult to exhibit properties derived from the amino group. On
the other hand, in the case where the amount of the alkylenimine
exceeds 10 mols, storage stability of the resultant
amino-group-containing polymer (salt) tends to be inferior.
[0067] The conversion of the carboxyl group of the
monoethylenically unsaturated monomer component into the amino
group by carrying out the ring-opening addition of the alkylenimine
may fitly be selected so as to display properties according to use
purposes. However, it is preferable that not less than 10 mol % of
the carboxyl group of the monoethylenically unsaturated monomer
component is converted into the amino group. In the case where this
conversion is less than 10 mol %, it is difficult to display
properties derived from the amino group.
[0068] The amino-group-containing polymer (salt), according to the
present invention, preferably has an amine value of 0.1 to 12
mmols/g in terms of solid content by colloidal titration with
poly(potassium vinyl sulfate). In the case where the amine value
exceeds this range, the storage stability tends to be inferior. On
the other hand, in the case where the amine value is lower than the
above range, it is difficult to display properties derived from the
amino group.
[0069] When a part of the carboxyl group portions of the
monoethylenically unsaturated monomer component which has been
graft-polymerized onto the polyether compound remains or is
intentionally made to remain in the amino-group-containing polymer
(salt) according to the present invention, the
amino-group-containing polymer (salt) may be in the form of a salt
in which at least a part of the remaining carboxyl group portions
are neutralized with a basic compound. Examples of the basic
compound, which is used to neutralize the carboxyl group portions,
include: inorganic basic compounds, such as sodium hydroxide and
potassium hydroxide; ammonia; and organic basic compounds, such as
methylamine, dimethylamine, trimethylamine, ethylamine,
diethylamine, triethylamine, monoethanolamine, diethanolamine,
triethanolamine, dimethylaminoethanol, and aniline. These can be
used either alone respectively or in combinations with each
other.
[0070] The amino-group-containing polymer (salt), according to the
present invention, may be in the form of a salt in which at least a
part of the amino groups are neutralized with an acid. Such an
amino-group-containing polymer salt is obtained by a process
including the step of neutralizing the resultant
amino-group-containing polymer with an acid compound.
[0071] Examples of the above acid compound include: inorganic
acids, such as hydrochloric acid, hydrobromic acid, phosphoric
acid, and sulfuric acid; organic acids, such as formic acid, acetic
acid, propionic acid, citric acid, lactic acid, (meth)acrylic acid,
oxalic acid, succinic acid, maleic acid, poly((meth)acrylic acid)
or its partial salts. These can be used either alone respectively
or in combinations with each other. The amount of the acid compound
as used may fitly be set according to uses and is not especially
limited, but is preferably not larger than 5 mols per mol of the
amino groups of the amino-group-containing polymer. In the case
where the amount exceeds 5 mols per mol of the amino groups of the
amino-group-containing polymer, there are disadvantages in that the
pH might be so low as to deteriorate the stability.
[0072] The process for the neutralization with the acid compound is
not especially limited, but, for example, the
amino-group-containing polymer and the acid compound may be mixed
together by stirring them in the range of 0 to 120.degree. C.,
preferably 10 to 80.degree. C. Incidentally, the neutralization may
be carried out either in the absence of solvent or in the presence
of a solvent which is, for example, usable in the aforementioned
graft polymerization reaction.
[0073] As to the amino-group-containing polymer (salt) according to
the present invention, it is easy to structurally design its
desired properties, ranging from hydrophilicity to hydrophobicity
or from softness to rigidness, due to possession of the polyether
skeleton, and further it is possible to display various
performances, such as curability useful for various uses and
adsorbency onto films or fibers, due to possession of the amino
group. In addition, the amino groups of the amino-group-containing
polymer (salt) according to the present invention can include at
least primary amino groups and further, according to circumstances,
secondary amino groups, so it is possible to easily add thereto
further such as epoxy compounds, isocyanate compounds, acid
anhydrides, acyl halide compounds, and acryloyl compounds, and the
resultant product can also be a raw material for various
derivatives. Therefore, the amino-group-containing polymer (salt),
according to the present invention, can favorably be utilized for
the wide range of uses such as epoxy curing agents, solid
electrolytes for cells, enzyme fixers, water-retaining agents,
sludge flocculants, flocculants, heavy metal collectors, soot
collectors, chelating agents, ion-exchange resins,
excavated-soil-treating agents, viscosity-adjusting agents,
drilling mud additives for construction work and oil well drilling,
pressure sensitive adhesives, sealants, paints, adhesives, anchor
coating agents, primers, surface-treating agents, inks (e.g.
gravure inks, offset inks), ink jet inks, ceramic binders,
anticorrosives, adsorbents, odor eaters, paper strength
reinforcements, yield modifiers, water filterability modifiers,
binders for pigment coating, dispersants for papermaking, deinking
agents, hairdressings, cosmetic base agents, cosmetic additives,
detergent additives, builders for powdery and liquid detergents,
surfactants, emulsifiers, bubble conditioners, deemulsifiers, scale
inhibitors, inorganic substance dispersants, pigment dispersants,
cement dispersants (e.g. AE agents, water-reducing agents for
cement), flotating agents, oil additives (e.g. viscosity index
enhancing agents, cleaning agents), fiber-treating agents, dyeing
modifiers, antistatic agents, fiber softeners, and crosslinking
agents.
[0074] (Effects and Advantages of the Invention):
[0075] The amino-group-containing polymer (salt), according to the
present invention, can make good use of the reactivity or cationic
property of the primary amino group and further can display various
performances, such as curability useful for various uses and
adsorbency onto films or fibers. Specifically, antistatic effects,
or effects such as the improvement of slippability and the
endowment of hydrophilicity and surface activity, upon films or
fibers are obtained. Particularly, this polymer (salt) is
applicable also to conversion of such as polyester fibers into
hydrophilic ones. Therefore, the amino-group-containing polymer
(salt), according to the present invention, can favorably be
utilized for the wide range of uses such as epoxy curing agents,
solid electrolytes for cells, enzyme fixers, water-retaining
agents, sludge flocculants, flocculants, heavy metal collectors,
soot collectors, chelating agents, ion-exchange resins,
excavated-soil-treating agents, viscosity-adjusting agents,
drilling mud additives for construction work and oil well drilling,
pressure sensitive adhesives, sealants, paints, adhesives, anchor
coating agents, primers, surface-treating agents, inks (e.g.
gravure inks, offset inks), ink jet inks, ceramic binders,
anticorrosives, adsorbents, odor eaters, paper strength
reinforcements, yield modifiers, water filterability modifiers,
binders for pigment coating, dispersants for papermaking, deinking
agents, hairdressings, cosmetic base agents, cosmetic additives,
detergent additives, builders for powdery and liquid detergents,
surfactants, emulsifiers, bubble conditioners, deemulsifiers, scale
inhibitors, inorganic substance dispersants, pigment dispersants,
cement dispersants (e.g. AE agents, water-reducing agents for
cement), flotating agents, oil additives (e.g. viscosity index
enhancing agents, cleaning agents), fiber-treating agents, dyeing
modifiers, antistatic agents, fiber softeners, and crosslinking
agents.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0076] Hereinafter, the present invention is more specifically
illustrated by the following examples of some preferred embodiments
in comparison with comparative examples not according to the
invention. However, the invention is not limited thereto.
[0077] Incidentally, the acid value of the
carboxyl-group-containing polymer in terms of solid content was
measured by neutralization titration with an alkaline reagent; and
the residual acid value of the amino-group-containing polymer in
terms of solid content was measured by inverse colloidal titration
involving addition of a certain amount of chitosan solution and use
of poly(potassium vinyl sulfate); and the amine value of the
amino-group-containing polymer in terms of solid content was
measured by colloidal titration with poly(potassium vinyl
sulfate).
EXAMPLE 1
[0078] A glass reactor, as equipped with a thermometer, a stirrer,
a nitrogen-introducing tube, and a reflux condenser, was charged
with 85 parts by weight of phenoxypolyethylene glycol having a
number-average molecular weight of 530 (as obtained by an addition
reaction of 10 mols on average of ethylene oxide to phenol), and
then the charged material was heated to 128.degree. C. while being
stirred under a nitrogen gas stream. Next, 15 parts by weight of
acrylic acid and 1.5 parts by weight of Perbutyl-Z (tert-butyl
peroxybenzoate content: 98 weight %, made by NOF CORPORATION) were
dropwise added separately and continuously over a period of 1 hour
while maintaining the temperature in the range of 125 to
131.degree. C. Thereafter, stirring was continued for 1 hour, thus
obtaining a carboxyl-group-containing polymer as a grafted polymer.
The acid value of this carboxyl-group-containing polymer was 1.91
mmols/g in terms of solid content.
[0079] Next, 125 parts by weight of propylene glycol monomethyl
ether and 25 parts by weight of deionized water were added to 50
parts by weight of the resultant carboxyl-group-containing polymer
under stirred conditions in order to obtain a uniform solution.
Thereafter, 4.4 parts by weight of ethylenimine (carboxyl
group/imino group=1.0 in molar ratio) was added to the solution
over a period of 10 minutes at room temperature. After being
stirred for 1 hour in the range of 25 to 30.degree. C., the
resultant reaction mixture was heated to 85.degree. C., and then
stirring was continued for 5 hours while maintaining the
temperature in the range of 82 to 88.degree. C. Thereafter, the
resultant reaction mixture was cooled, thus obtaining an
amino-group-containing polymer.
[0080] The residual acid value of the resultant
amino-group-containing polymer was 0.23 mmols/g in terms of solid
content. From this result, it was inferred that about 87% of the
carboxyl groups had been converted by the ethylenimine. In
addition, the amine value was 1.50 mmols/g in terms of solid
content by colloidal titration. Incidentally, the resultant
amino-group-containing polymer was analyzed by gas chromatography
of which the detection limit was 1 ppm. As a result, no unreacted
ethylenimine was detected.
EXAMPLE 2
[0081] A glass reactor, as equipped with a thermometer, a stirrer,
a nitrogen-introducing tube, and a reflux condenser, was charged
with 70 parts by weight of phenoxypolyethylene glycol having a
number-average molecular weight of 970 (as obtained by an addition
reaction of 20 mols on average of ethylene oxide to phenol) and 12
parts by weight of maleic acid, and then the charged materials were
heated to 145.degree. C. while being stirred under a nitrogen gas
stream. Next, 18 parts by weight of acrylic acid and 1.5 parts by
weight of Perbutyl-D (di-tert-butyl peroxide, made by NOF
CORPORATION) were dropwise added separately and continuously over a
period of 2 hours while maintaining the temperature in the range of
140 to 145.degree. C. Thereafter, stirring was continued for 1
hour, thus obtaining a carboxyl-group-containing polymer as a
grafted polymer. The acid value of this carboxyl-group-containing
polymer was 3.40 mmols/g in terms of solid content.
[0082] Next, 90 parts by weight of propylene glycol monomethyl
ether and 45 parts by weight of deionized water were added to 45
parts by weight of the resultant carboxyl-group-containing polymer
under stirred conditions in order to obtain a uniform solution.
Thereafter, 4.7 parts by weight of ethylenimine (carboxyl
group/imino group=0.7 in molar ratio) was added to the solution
over a period of 10 minutes at room temperature. After being
stirred for 1 hour in the range of 25 to 30.degree. C., the
resultant reaction mixture was heated to 85.degree. C., and then
stirring was continued for 4 hours while maintaining the
temperature in the range of 82 to 86.degree. C. Thereafter, the
resultant reaction mixture was cooled, thus obtaining an
amino-group-containing polymer.
[0083] The residual acid value of the resultant
amino-group-containing polymer was 1.2 mmols/g in terms of solid
content. From this result, it was inferred that about 61% of the
carboxyl groups had been converted by the ethylenimine. In
addition, the amine value was 1.61 mmols/g in terms of solid
content by colloidal titration. Incidentally, the resultant
amino-group-containing polymer was analyzed by gas chromatography
of which the detection limit was 1 ppm. As a result, no unreacted
ethylenimine was detected.
EXAMPLE 3
[0084] A glass reactor, as equipped with a thermometer, a stirrer,
a nitrogen-introducing tube, and a reflux condenser, was charged
with 80 parts by weight of methoxypolyethylene glycol having a
number-average molecular weight of 2,000 (reagent made by Aldrich),
and then the charged material was heated to 145.degree. C. while
being stirred under a nitrogen gas stream. Next, 20 parts by weight
of acrylic acid and 2.0 parts by weight of Perbutyl-D
(di-tert-butyl peroxide, made by NOF CORPORATION) were dropwise
added separately and continuously over a period of 2 hours while
maintaining the temperature in the range of 140 to 145.degree. C.
Thereafter, stirring was continued for 1 hour, thus obtaining a
carboxyl-group-containing polymer as a grafted polymer. The acid
value of this carboxyl-group-containing polymer was 2.65 mmols/g in
terms of solid content.
[0085] Next, 200 parts by weight of propylene glycol monomethyl
ether and 100 parts by weight of deionized water were added to 100
parts by weight of the resultant carboxyl-group-containing polymer
under stirred conditions in order to obtain a uniform solution.
Thereafter, 17.9 parts by weight of ethylenimine (carboxyl
group/imino group=1.5 in molar ratio) was added to the solution
over a period of 20 minutes at room temperature. After being
stirred for 1 hour in the range of 25 to 30.degree. C., the
resultant reaction mixture was heated to 85.degree. C., and then
stirring was continued for 5 hours while maintaining the
temperature in the range of 82 to 84.degree. C. Thereafter, the
resultant reaction mixture was cooled, thus obtaining an
amino-group-containing polymer.
[0086] The residual acid value of the resultant
amino-group-containing polymer was 0.18 mmols/g in terms of solid
content. From this result, it was inferred that about 92% of the
carboxyl groups had been converted by the ethylenimine. In
addition, the amine value was 2.92 mmols/g in terms of solid
content by colloidal titration. Incidentally, the resultant
amino-group-containing polymer was analyzed by gas chromatography
of which the detection limit was 1 ppm. As a result, no unreacted
ethylenimine was detected.
EXAMPLE 4
[0087] A glass reactor, as equipped with a thermometer, a stirrer,
a nitrogen-introducing tube, and a reflux condenser, was charged
with 80 parts by weight of methoxypolyethylene glycol having a
number-average molecular weight of 500, and then the charged
material was heated to 145.degree. C. while being stirred under a
nitrogen gas stream. Next, 24 parts by weight of acrylic acid, 6
parts by weight of maleic acid, and 2.0 parts by weight of
Perbutyl-D (di-tert-butyl peroxide, made by NOF CORPORATION) were
dropwise added separately and continuously over a period of 2 hours
while maintaining the temperature in the range of 140 to
145.degree. C. Thereafter, stirring was continued for 1 hour, thus
obtaining a carboxyl-group-containing polymer as a grafted polymer.
The acid value of this carboxyl-group-containing polymer was 3.80
mmols/g in terms of solid content.
[0088] Next, 50 parts by weight of propylene glycol monomethyl
ether was added to 50 parts by weight of the resultant
carboxyl-group-containing polymer under stirred conditions in order
to obtain a uniform solution. Thereafter, 8.0 parts by weight of
ethylenimine (carboxyl group/imino group=1.0 in molar ratio) was
added to the solution over a period of 30 minutes at room
temperature. After the addition had been completed, the resultant
reaction mixture was heated to 50.degree. C., and then stirring was
continued for 8 hours while maintaining the temperature in the
range of 48 to 52.degree. C. Thereafter, the resultant reaction
mixture was cooled, thus obtaining an amino-group-containing
polymer.
[0089] The residual acid value of the resultant
amino-group-containing polymer was 0.66 mmols/g in terms of solid
content. From this result, it was inferred that about 80% of the
carboxyl groups had been converted by the ethylenimine. In
addition, the amine value was 3.20 mmols/g in terms of solid
content by colloidal titration. Incidentally, the resultant
amino-group-containing polymer was analyzed by gas chromatography
of which the detection limit was 1 ppm. As a result, no unreacted
ethylenimine was detected.
EXAMPLE 5
[0090] First, 50 parts by weight of deionized water was added to 50
parts by weight of a carboxyl-group-containing polymer (as obtained
in the same way as of Example 4; acid value=3.80 mmols/g in terms
of solid content) under stirred conditions in order to obtain a
uniform solution. Thereafter, 8.0 parts by weight of ethylenimine
(carboxyl group/imino group=1.0 in molar ratio) was added to the
solution over a period of 30 minutes at room temperature. After the
addition had been completed, the resultant reaction mixture was
heated to 50.degree. C., and then stirring was continued for 8
hours while maintaining the temperature in the range of 48 to
52.degree. C. Thereafter, the resultant reaction mixture was
cooled, thus obtaining an amino-group-containing polymer.
[0091] The residual acid value of the resultant
amino-group-containing polymer was 0.87 mmols/g in terms of solid
content. From this result, it was inferred that about 73% of the
carboxyl groups had been converted by the ethylenimine. In
addition, the amine value was 2.90 mmols/g in terms of solid
content by colloidal titration. Incidentally, the resultant
amino-group-containing polymer was analyzed by gas chromatography
of which the detection limit was 1 ppm. As a result, no unreacted
ethylenimine was detected.
EXAMPLE 6
[0092] An autoclave, as equipped with a thermometer, a stirrer, and
a nitrogen-introducing tube, was charged with 74 parts by weight of
dipropylene glycol monomethyl ether and 1 part by weight of sodium
hydroxide powder, and the internal air of the autoclave was
displaced with nitrogen, and then the charged materials were heated
to 130.degree. C. Next, 426 parts by weight of ethylene oxide was
introduced into the autoclave over a period of 3 hours, and then
the resultant reaction mixture was aged at 130.degree. C. for 2
hours and then cooled, thus obtaining a dipropylene glycol
monomethyl ether-ethylene oxide adduct (number-average molecular
weight=1,000, average molar number of addition= 1.94).
[0093] Next, a glass reactor, as equipped with a thermometer, a
stirrer, a nitrogen-introducing tube, and a reflux condenser, was
charged with 85 parts by weight of the above-obtained dipropylene
glycol monomethyl ether-ethylene oxide adduct, and then the charged
material was heated to 145.degree. C. while being stirred under a
nitrogen gas stream. Next, 15 parts by weight of acrylic acid and
2.0 parts by weight of Perbutyl-D (di-tert-butyl peroxide, made by
NOF CORPORATION) were dropwise added separately and continuously
over a period of 2 hours while maintaining the temperature in the
range of 140 to 145.degree. C. Thereafter, stirring was continued
for 1 hour, thus obtaining a carboxyl-group-containing polymer as a
grafted polymer. The acid value of this carboxyl-group-containing
polymer was 2.71 mmols/g in terms of solid content.
[0094] Next, 100 parts by weight of propylene glycol monomethyl
ether and 50 parts by weight of deionized water were added to 50
parts by weight of the resultant carboxyl-group-containing polymer
under stirred conditions in order to obtain a uniform solution.
Thereafter, 6.0 parts by weight of ethylenimine (carboxyl
group/imino group 1.0 in molar ratio) was added to the solution
over a period of 10 minutes at room temperature. After being
stirred for 1 hour in the range of 25 to 30.degree. C., the
resultant reaction mixture was heated to 85.degree. C., and then
stirring was continued for 5 hours while maintaining the
temperature in the range of 82 to 88.degree. C. Thereafter, the
resultant reaction mixture was cooled, thus obtaining an
amino-group-containing polymer.
[0095] The residual acid value of the resultant
amino-group-containing polymer was 0.37 mmols/g in terms of solid
content. From this result, it was inferred that about 85% of the
carboxyl groups had been converted by the ethylenimine. In
addition, the amine value was 2.35 mmols/g in terms of solid
content by colloidal titration. Incidentally, the resultant
amino-group-containing polymer was analyzed by gas chromatography
of which the detection limit was 1 ppm. As a result, no unreacted
ethylenimine was detected.
EXAMPLE 7
[0096] While the temperature was controlled in the range of 30 to
40.degree. C., an aqueous hydrochloric acid solution was added to
the amino-group-containing polymer as obtained in Example 5 (amine
value=2.90 mmols/g in terms of solid content), wherein the amount
of the aqueous hydrochloric acid solution corresponded to 0.8 times
by mol of that of the amino groups of the amino-group-containing
polymer. As a result, a hydrochloric-acid-neutralized salt of the
amino-group-containing polymer was obtained.
EXAMPLE 8
[0097] While the temperature was controlled in the range of 30 to
40.degree. C., acetic acid was added to the amino-group-containing
polymer as obtained in Example 5 (amine value=2.90 mmols/g in terms
of solid content), wherein the amount of the acetic acid
corresponded to 2 times by mol of that of the amino groups of the
amino-group-containing polymer. As a result, an
acetic-acid-neutralized salt of the amino-group-containing polymer
was obtained.
EXAMPLE 9
[0098] While the temperature was controlled in the range of 30 to
32.degree. C., triethylamine was added to the
amino-group-containing polymer as obtained in Example 5 (residual
acid value=0.87 mmols/g in terms of solid content, amine value=2.90
mmols/g in terms of solid content), wherein the amount of the
triethylamine corresponded to 0.5 times by mol of the residual acid
value of the amino-group-containing polymer. As a result, a salt of
the amino-group-containing polymer in which a part of the residual
carboxyl groups were neutralized with the triethylamine was
obtained.
EXAMPLE 10
[0099] A mixture was prepared by well mixing 10 parts by weight of
the amino-group-containing polymer as obtained in Example 4 (solid
content=50%, amine value=3.20 mmols/g in terms of solid content)
and 3.1 parts by weight of bisphenol A type liquid epoxy resin
(Epikote 828, produced by Yuka Shell Epoxy Kabushiki Kaisha)
together, and the resultant mixture was coated onto a steel sheet
with an applicator and then dried by heating in a hot-air drying
oven of 150.degree. C. for 10 minutes to form a coating film. The
resultant coating film had the following properties:
[0100] dry coating film: 70 .mu.m
[0101] external appearance: transparent
[0102] pencil scratching test (JIS-K5400): HB
[0103] water resistance (rubbing test with deionized water):
good.
[0104] Various details of the invention may be changed without
departing from its spirit not its scope. Furthermore, the foregoing
description of the preferred embodiments according to the present
invention is provided for the purpose of illustration only, and not
for the purpose of limiting the invention as defined by the
appended claims and their equivalents.
* * * * *