Note: Descriptions are shown in the official language in which they were submitted.
The present invention relates to novel ampho-
ionic compounds and their production. More particularly,
it relates to novel ampho-ionic compounds which have a
cationic group and an anionic group in the ~orm of an inner
salt, possess characteristic chemical reactivity, surface
activity and electrochemical property and optionally include
one or more polymerizable unsaturated groups, and their
production.
The ampho-ionic compounds of the present invention
are representable by the formula:
R-C-CH2-B~ (I)
oso9
wherein R is a group of the formula:
11
CH2=C-Al-
wherein Rl is hydrogen or methyl and
Al is COOCH2 or 2 2 '
R2 is hydrogen or methyl; and
B~ is (a~ a group of either one of the formulas:
- ~R4, -~-R6, -~R7-CH and - ~ Rg
R5 R7 8
wherein R3, R4 and R5 are each alkyl,
alkenyl, hydroxyalkyl, mercaptoalkyl,
alkoxy, alkylthio, cyclic alkyl, phenyl
or substituted phenyl, these groups having
each not more than.7 carbon atoms, R6,
R7 and R8 are each alkylene, alkenylene,
..r,
~g~8
alkyleneoxy or alkylenethio, these groups
having each not more than 7 carbon atoms and
Rg is optionally substituted alkylidene of 4
to 10 carbon atoms,
(b) a group of the formula:
110
- ~-R
R12
wherein Rlo, Rll and R12 are each a sub-
stituent comprising as the major constituent
a hydrocarbon chain having 10 to 30 carbon
atoms, or
(c) a group of the formula:
13
\ / (A2-C=CH2)n
-N~
: (R14)3-n
wherein R13 is hydrogen or methyl, R14 is
a substituent comprising as the major con-
: stituent a hydrocarbon chain having 1 to
: 20 carbon atoms, A2 is -(CH2)mOCO-,
-(CH2)mNHCO- or -(CH2)m~ or when taken
together with a part or the whole of R14,
forms a heterocyclic structure, having not
more than 14 carbon atoms, which may option-
ally include an unsaturated double bond and/or
an oxygen or
- 2 -
-!
~ ?
11~9888
sulf ur atom, m is an integer of 1 to 4
and n is an integer of 1 to 3.
Among the ampho-ionic compound~ (I), there are
included the compounds of the formulas:
1 2 3
CH2-C-Al-C-CH2 1~6)R4 (Ia-l)
ls~ l5
1 12 R3
C~2-C-~l-c-cH2 ~ 6 (Ia-2)
R7
~1 R2 16
CH2=c-Al-c-cH2-N-~R7-cH (Ia-3)
OSO~ R8
and
Rl R2
CH2'C-Al-f CH2 ~ Rg (Ia-4)
osb2-
1' 1' R2~ R3~ R4~ Rs~ R6~ R7, R8 and Rg are each
as defined above.
There are also included the compounds of the
formula:
Rl R2 IRl o
CH2=C-Al-C)-cH2 N Rll lIb)
.~ S2 R12
-- n Al, Rl, R2, Rlo, Rll and R12 are each as defined
: above.
There are further included the compounds of the
formula:
-- 3 --
,,~,,
... . ..
1~8~8
CH2=1-Al-C-CH ~--'~A2~C-CH2) ~Ic~
lso~ (R14)3 n
1' A2~ Rl~ R2~ ~13~ R14 and n are each as defined
above.
The ampho-ionic compounds (I) are generally
produced by reacting an oxirane compound with sulfur dioxide
and a tertiary amine.
For instance, the compounds (Ia-l), (Ia-2), (Ia-
3), (Ia-4), ~Ib) a~d (Ic) are respectively produced by
reacting an oxirane compound of the formula:
Il j2
CH2=C-Al-C\ /C 2 (IIa)
O
wherein Al, Rl and R2 are each as defined above with sulfur
dioxide and a tertiary amine of the formulas:
IR3 l3 IR6~\ ~ :
N-R4, Nl-R6, ~-R~ CH or N ~ Rg,
R5 R7 R8'
(IIIa;l) (IIIa-2) (IIIa-3) (IIIa-4)
1 10
I 11 (IIIb)
R12
or
Rl 3
/(A2-C=CH2)
N ~IIIc)
14~3-n
-- 4 --
. ~, .
"~,r
~988~
wherein A2, R3, R4, R5, R6, R7~ Rg, Rg~ Rlol Rll' R12' R13
and n are each as defined above.
Examples of the oxirane compound (IIa) are glycidyl
or methylglycidyl acrylate, glycidyl or methylglycidyl meth-
acrylate, all~l glycidyl or methylglycidyl ether, meth-
allyl glycidyl or methylglycidyl ether, glycidyl or methyl-
glycidyl der~vative of acrylamide, glycidyl or methyl-
glycidyl derivative of methacrylamide, etc.
As the amine (IIIa-l), there are exemplified tri-
methylamine, triethylamine, methyldiethylamine, dimethyl-
ethylamine, dimethylbutylamine, dimethylhexylamine, di-
methylethanolamine, dimethylbutanolamine, methyldiethanol-
amine, triethanolamine, dimethyl(2-methoxyethyl)amine,
dimethylthioethanolamine, dimethylcyclohexylamine, N,N-
dimethylaniline, dimethyl(p-methylphenyl)amine, etc.
Examples of the amine (IIIa-2) are N-methylaziridine, N-
methylpyrrolidine, N-methylpiperidine, N-ethylpiperidine,
N-methylmorpholine, N-ethylmorpholine, 4-methyltetrahydro-
thiazine, etc. Examples of the amine (IIIa-3) include
quinuclidine, etc. Examples of the amine (IIIa-4) include
pyridine, quinoline, methylpyridine, etc.
As the amine (IIIb), there may be exemplified
dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine,
dimethylmyristylamine, dimethylpalmitylamine, dimethyl-
stearylamine, methyldioctylamine, methyldidecylamine,
methyldilaurylamine, dimethyl(2-hydroxyoctyl)amine, dimethyl-
(2-hydroxydecyl)amine,~dimethyl(2-hydroxydodecyl)amine, di-
methyl(2-hydroxyhexadecyl)amine, dimethyl(2-hydroxylauryl)-
amine, dimethyl(2-hydroxymyristyl)amine, dimethyl(2-hydroxy-
palmityl)amine, dimethyl(2-hydroxystearyl)amine, methyl-
di(2-hydroxyoctyl~amine, methyldi(2-hydroxydecyl)amine,
-- 5 --
`Y !
. . .
~1~)9~388
methyldi(2-hydroxydodecyl)amin~, methyldit2-hydroxylauryl)-
amine, etc. In addition, the amine (IIIb) may be a dimethyl-
benzyla~ine having a substituent comprising as the major
constituent a hydrocarbon chain having 2 to 18 carbon atoms
on the benzene ring, a dimethylaniline having a substituent
comprising as the major constituent a hydrocarbon chain
having 2 to 18 carbon atoms on the benzene ring, a dimethyl-
~yclohexylamine having a substituent comprising as the
major constituent a hydrocarbon chain having 2 to 18 carbon
atoms on the cyclohexane ring, a pyridine having a substi-
tuent comprising as the major constituent a hydrocarbon chain
having 5 to 18 carbon atoms on the pyridine ring, an N-methyl-
pyrrolidine having a substituent compxising as the major
constituent a hydrocarbon chain having S to 18 carbon atoms
on the pyrrolidine ring, an N-methylpiperidine having a
substituent comprising as the major constituent a hydro-
carbon chain having 5 to 18 carbon atoms on the piperidine
ring, an N-methylmorpholine having a substituent comprising
as the major constituent a hydrocarbon chain having 5 to
18 carbon atoms on the morpholine ring or the like.
The term "a substituent comprising as the major
constituent a hydrocarbon chain" used in this specification
is intended to mean a straight or branched aliphatic, ali-
cyclic or aromatic hydrocarbon group, optionally having an
unsaturated group, a hydroxyl group, an ether linkage,
an ester group, a ~eto group, and/or the like.
As the amine (IIIc), there may be exemplified
dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
dimethylaminopropyl acrylate, dimethylaminopropyl meth-
acrylate, dimethylaminoethylacrylamide, dimethylaminoethyl-
L1~3
11~9&88
methacrylamide, dimethylallylamine, di~ethylmethallylamide,
vinylpyridine, N-methylvinylpyrrolidine, N-methylvinyl-
piperidine, N-methylvinylmorpholine, methyldi(acryloyloxy-
ethyl)amine, methyldi(methacryloyloxyethyl)amine, methyldi-
(acryloyloxypropyl)amine, methyldi(methacryloyloxypropyl)-
amine~ methyldiallylamine, methyldimethallylamine, tri-
(acryloyloxyethyl)amine, tri(methacryloyloxyethyl)amine,
triallylamine, trimethallylamine, etc.
The reaction of the oxirane compound with
sulfur dioxide and the tertiary amine may be carried out
in the presence or absence of an appropriate solvent under
atmospheric or elevated pressure. Examples of the appro-
priate solvent are methanol, ethanol, ethyleneglycol mono-
methyl ether, acetonitrile, benzene, dimethylsulfoxide,
dimethylformamide, etc. The proportion of the o~ira~e
compound, sulfur dioxide and the tertiary amine may be
usually in a equivalent molar ratio. The reaction temper-
ature is usually from -40 to 200C, preferably from -20 to
100C. The reaction time is ordinarily from 10 minutes to
100 hours, favorably from 30 minutes to 10 hours. Al-
though no limitation is present on the reaction mode, it
is usually preferred first to mix the oxirane compound and
sulfur dioxide, if desired, in an appropriate solvent and
then to add the tertiary amine to the resulting mixture.
If necessary, a polymerization inhibitor such as hydroquinone
may be introduced into the reaction system for prevention of
the undesirable polymerization of polymerizable unsaturated
groups.
The ampho-ionic compounds (I) of the invention
have a cationic group (-N~) and an anionic group (-OSO~
-- 7 --
,~ i~,;
~1~9888
separately in their molecules and exert generally advan-
tageous properties due to those groups. Further, they
exhibit various characteristics in chemical reactivity,
surface activity, electrochemical property and biochemical
property. In addition, each of those compounas shows
Epecific and peculiar propexties.
For instance, the compounds (Ia-l), (Ia-2),
~Ia-3) and (Ia-4) obtained in the form of solid, semi-
solid or viscous liquid can be and are generally hygro-
scopic. They may be used monomers for production of highpolymeric materials, which are provided with said advan-
tageous properties.
The compounds (Ib) have a hydrocarbon group which
is hydrophobic and an ammonium group and a sulfite group
which are hydrophilic in their molecules, and there~ore they
exhibit a function as a surfactant. Further, they do not
have any low moleculax counter ion while they are ampho-
ionic. Because of this reason, they show characteristic
surface activity, particularly favorable in emulsion poly-
merization. In other words, they can serve not only as amonomeric component but also as a surfactant in emulsion
polymerization.
The compounds tIc) are ampho-ionic and have a
high stability. They are water-soluble or water-dispersible
and can be used as a crosslinking agent in paint composi-
tions t adhesive compositions and plastic compositions
comprising water-soluble or water-dispersible resins.
Practical and presently preferred embodiments of
this invention are illustratively shown in the following
Examples.
~ - 8 -
. . ~
~1~98~
In these Examples, reference is made to the
accompanying drawings, in which Figs. 1-20 are the NMR
spectra of compounds referred to.
Example l
In a reactor equipped with a stirrer, glycidyl
methacrylate (245.5 g; 1.73 mol) and hydro~uinone (0.49 g)
are charged while cooling at -50C, and sulfur dioxide
(110.5 g; 1.73 mol) is added thereto while maintaining the
temperature of the system below -20C. Then, trimethylamine
(102 g; 1.73 mol) is introduced therein while maintaining
the temperature of the system below -20C. Thereafter, the
temperature of the system is gradually elevated up to 75C
so as to effect the reaction. The reaction is completed in
100 minutes. The reaction product having the following
structure is obtained as white solid:
ICH3 1 3
CH2-C-CC~2-fH-C~l2 N, CH3
2 3
The NMR chart of the said product obtained by the use of an
apparatus'(100 MHz) manufactured by Nippon Denshi Co., Ltd.
and using d4-methanol as a solvent is shown in Fig. i of the
accompanying drawings.
Example 2
In the same manner as in Example l, allyl glycidyl
ether (76.4 g; 0.67 mol), sulfur dioxide (46.1 g; 0.72 mol)
and trimethylamine (42.5 g; 0.72 mol) are subjected to
reaction in the presence of hydroquinone (0.15 g) at 75C,
the reaction is completed in lO0 minutes. The reaction
product having the following structure is obtained as pale
brown solid:
f ,H~3
CH =CH-CH2QCH2-CH-CH -N~'CH3
' 2 3
1109888
The NMR chart of the said product obtained as in Example 1
is shown in Fig. 2.
Example 3
In the same manner as in Example 1, glycidyl
methacrylate tl64 g; 1.15 mol), sulfur dioxide (74 g; 1.16
mol) and dimethylethanolamine (103 g; 1.16 mol) are subjected
to reaction in the presence of hydroquinone (0.33 g) at
50C, the reaction is completed in 200 minutes. The
reaction product having the following structure is obtained
as viscous liquid:
Cl 3 fH 3
CH2=C-COOCH2-fH-CH2-NI-CH2CH20H
S2 CH3
The NMR chart of the said product obtained as in Example 1
is shown in Fig. 3.
E~amp~le 4
; In the same manner as in Example 1, allyl glycidyl
ether (136.8 g; 1.2 mol), sulfur dioxide (76.8 g; 1.2 mol)
and dimethylethanolamine (106.8 g; 1. 2 mol) are subjected to
reaction in the presence of hydroquinone (0.3 g) and
methanol (38.4 g) at 60c, the reaction is completed in 200
minutes. The reaction product having the following struc-
ture is obtained as pale brown solid:
H3
=cH-cH2ocH2-fH-cH2- ~CH2cH2OH
S2 CH3
The NMR chart of the said product obtained as in Example 1
is shown in Fig. 4.
,i ~
.~ Example 5
. ..
~7 _ ~/_
11~988~3
In the same manner as in Example 1, glycidyl
methacrylate (113~6 g; 0.8 mol), sulfur dioxide (51.2 g; 0.8
mol) and N-methylpiperidine (79.3 g; 0.8 mol) are subjected
to reaction in the presence of hydroquinone (O.Z3 g) and
acetonitrile (65.6 g) at 60C, the reaction is completed in
200 minutes. The reaction product having the following
structure is obtained as white solid:
CH3 CH
CH2=C-COOCH2-fH-CH _l0 ~ 2 CH
OSO~ CH2-CH2
The N~R chart of the said product obtained as in Example l
is shown in Fig. 5.
Example 6
in the same manner as in Example l, glycidyl meth-
acrylate (113.6 g; 0.8 mol), sulfur dioxide (51.2 g; 0.8
mol) and methyldiethylamine (69.6 g; b.8 mol) are subjected
to reaction in the presence of hydroquinone (0.23 g) at
70C, the reaction is completed in 150 minutes. The'reac-
tion product having the following s~ructure is obtained as
pale brown solid:
fH3 CH3
CH2=C-COOCH2-fH-CH2- IN-CH2CH3
OSO~ CH CH
The NMR chart of the said product obtained as in Example l
is shown in Fig. 6.
Example 7
In the same manner as in Example 1, allyl glycidyl
ether (125.8 g; l.l mol), sulfur dioxide (70.4 g; l.l mol)
and 4-methylmorpholine (111.3 g; 1.1 mol) are subjected to
reaction in the presence of hydroquinone (0.25 g) and
A,7
~1~9888
ethyleneglycol monomethyl ether ~83.7 g) at 70C, the reac-
tion is completed in 200 minutes. The reaction product
having the following structure is obtained as pale brown
solid:
CEI3
CH2=cE~-cH2ocH2-cH-cH2-N6~
S2 \ CH2-CH2
The NMR chart of the said product obtained as in Example 1
is shown in Fig. 7.
Example 8
In the same manner as in Example 1, glycidyl
methacrylate (124.4 g; 0.875 mol), sulfur dioxide ~56 g;
0~875 mol) and triethylamine (88.4 g; 0.875 mol) are
subjected to reaction in the presence of hydroquinone (0.25
g) at 70C, the reaction is completed in 240 minutes. The
reaction product having the following structure is obtained
as pale brown solid:
CH3 CH2CH3
2=1-CCH2-fH-CH2 N~ C 2 3
S2 CH2C~3
The NMR chart of the said product obtainecl as in Example 1
is shown in Fig. 8.
In the same manner as in Example 1, glycidyl
methacrylate (118.4 g; 0.833 mol), sulfur dioxide (53.3 g;
0.833 mol) and pyridine (65.9 g; 0.833 mol) are subjected to
reaction in the presence of hydroquinone (0.22 g) at 40C,
the reaction is completed in 40 minutes. The reaction
product having the following structure is obtained as pale
brown solid:
~,~
ll~g8~8
IH3 ~CH-CH~
CH2=C-COOCH2-CI H-CH2 ~ \CH=CH~
oSo~'
The NMR chart of the said product obtained in Example 1 is
shown in Fig. 9.
In a reactor equipped with a stirrer, glycidyl
methacrylate (103.7 g; 0.73 mol) and hydroquinone (0.2 g)
are charged while cooling at -50C, and sulfur dioxide (47.0
g; 0.73 mol) is added thereto while maintaining the temper-
ature of the system below -20C. Then, dimethyllaurylamine
(155,5 g; 0.73 mol) is introduced therein while maintaining
the temperature of the system below -20C. Thereafter, the
temperature of the system is gradually elevated up to 70C
so as to effect the reaction. The reaction is completed in
10 hours. By removal of unreacted materials under reduced
pressure, the reaction product having the following struc-
ture is obtained as brown cream:
fH3 1 3
2 C COOCH2-fH-CH2-N-C12H25
S2 CEI3
The NMR chart o~ the said product obtained by the use of an
apparatus ~100 ~Hz),manufactured by Nippon Denshi Co., Ltd.
~ and using d4-methanol as a solvent is shown in Fig. 10 of
- the accompanying drawings. In ihe IR spectrum, character-
istic absorptions are seen at 1040, 3430 and 1630 cm 1.
' Examp'l'e_ll
In the same manner as in Example 10, allyl
glycidyl ether (97.0 g; 0.85 mol), sulfur dioxide (54.5 g;
0.85 mol) and dimethyllaurylamine (181.1 g; 0.85 mol~ are
,A~ .~
11098~3
subjected to reaction in the presence of hydroquinone (0.2 g)
and dimethylformamide (40.0 g) at 70C, the reaction is
completed in 8 hours. The reaction product having the
following structure is obtained as yellow viscous liquid:
CH3
CH2=cH-cH2acH2-cH CH2 ~ C12 25
lS2 CH3
The NMR chart of the said product obtained as in Example 10
is shown in Fig. 11. In the IR spectrum, characteristic
absorptions are seen at 1040, 3430 and 1630 cm 1.
Example 12
In the same manner as in Example 10, glycidyl
methacrylate (120.9 g; 0.85 mol), sulfur dioxide (54.5 g;
0.85 mol) and dimethylstearylamine (252.5 g; 0.85 mol) are
sub~ected to reaction in the presence of hydroquinone (0.2 g)
at 70C, the reaction is completed in 8 hours. The reac-
tion product havlng the following structure is obtained as
yellow cream:
C,H3 CH3
CH2=c-cooc~I2-f~ CH2 ,N C18 37
OS ~ CH3
The NMR chart of the said product obtained as in Example 10
is shown in Fig. 12. In the IR spectrum, characteristic
absorptions are seen at 1040, 3430 and 1630 cm 1.
Example 13
In the same manner as in Example 10, allyl glycidyl
ether (32.1 g; 0.28 mol), sulfur dioxide (18.0 g; 0.28 mol)
and dimethyl(2-hydroxydodecyl)amine (64.1 g; Q.28 mol) are
sub~ected to reaction in the presence of hydroquinone (0.06
g) and ethyleneglycol monomethyl ether (10.7 g) at 70C,
888
the reaction is completed in 6 hours. The reaction product
having the following structure is obtained as pale yellow
viscous liquid:
fH3
CH2=CH-CH20CH2-fH-CH2- 1 -CH2-fH-CloH21
OSO~ CII3 OH
The NMR chart of the said product obtained as in Example 10
is shown in Fig. 13. In the IR spectrum, characteristic
absorptions are seen ati1040, 3430 and 1630 cm 1.
Example 14
In the same manner as in Example 10, glycidyl
methacrylate (46.8 g; 0.33 mol), sulfur dioxide (21.1 g;
0.33 mol) and dimethyl(2-hydroxyhexadecyl)amine (103.3 ~;
0.33 mol) are subjected to reaction in the presence of
hydroquinone (0.1 g) and ethyleneglycol monomethy]. ether
(50.0 g) at 70C, the reaction is completed in 8 hours.
The reaction product having the following structure is
obtained as pale yellow viscous liquid:
CE 3 IICI+ 3
f
S2 3
The NMR chart of the said product obtained as in Example 10
is shown in Fig. 14. In the IR spectrum~ characteristic
absorptions are seen at 1040J 3430 and 1630 cm 1.
Example i5
In the same manner as in Example 10, glycidyl
methacrylate (71.0 g; 0.5 mol), sulfur dioxide (32.0 g;
0.5 mol) and N-dodecylmorpholine (127.5 g; 0.5 mol) are
subjected to reaction in the presence of hydroquinone (0.2 g)
and dimethylformamide (65 g) at 70C, the reaction is
., /~
.~ - ~r -
completed in 8 hours. The reaction product having the
following structure is obtained as pale yellow viscous
liquid:
2 C COOC~2 CH CH2 E ~ O
The NMR chart of the said product obtained as in Example 10
is shown in Fig. 15. In the IR spectrum, characteristic
absorptions are seen at 1040, 3430 and 1630 cm 1.
Example 16
In the same manner as in Example 10, allyl glycidyl
ether (47.9 g; 0.42 mol), sulfur dioxide (26.9 g; 0.42 mol)
and methyldi(2-hydroxydodecyl)amine (167.6 g; 0.42 ~ol) are
subjected to reaction in the presence of hydroquinone (0.1 g)
and dimethylformamide (57 g) at 70C, the reaction is
completed in 10 hours. The reaction product having the
following structure is obtained as pale yellow viscous
liquid:
C~I3 OH
CH2=CH-CH20CH2-fH-CH2-~-CH2CH-
S`2 CH2fH-Cl oH
OH
The NMR chart of the said product obtained in Example 10
is shown in Fig. 16. In the IR spectrum, characteristic
absorptions are seen at 1040, 3430 and 1630 cm 1,
Reference Example 1
- In a 2 liter volume reactor equipped with a
stirrer, a cooler, a temperature controller and an inlet for
nitrogen gas, deionized water (450 g) is charged, and the
temperature is elevated up to 80C while introducing nitrogen
..,
1~988~
gas therein. Potassium persulfate (4.5 g) and sodium
hydrogen sulfite (1.5 g) are charged into the reactor, and
the reactlon product in Example 10 (20 g~, methyl meth-
acrylate (124 g), styrene (185 g), n-butyl acrylate (166 g)
and laurylmercaptan (5 g) are dropwise added thereto in 30
minutes. Further, potassium persulfate (1.5 g), sodium
hydrogen sulfite (0.5 g) and deionized water (70 g) are
added thereto, and the reaction is continued for 30 minutes,
whereby an emulsion of the produced polymer is obtained.
Reference Example 2
In a 2 liter volume reactor equipped with a
stirrer, a cooler, a temperature controller and an inlet for
nitrogen gas, deionized water (408 g) is charged, and the
temperature is elevated up to 80C while introducing
nitrogen gas therein. An aqueous solution of azobiscyano-
valeric acid (8 g) and dimethylethanolamine (4.8 g) is
charged into the reactor, and the reaction product in
Example 11 (16 g), methyl methacrylate (103 g), styr~ne (144
g) and n-butyl acrylate (137 g) are dropwise added thereto
in 40 minutes. After the dropwise addition is finished,
stirring is continued for 30 minutes, whereby an emulsion of
the produced polymer is obtained.
Example 17
In a reactor equipped with a stirrer, glycidyl
methacrylate (44.4 g) and hydroquinone (0.08 g) are charged
while cooling at -50C, and sulfur dioxide (20.0 g) is added
thereto while maintaining the temperature of the system
below -20C. Then, dimethylaminoethyl methacrylate (49.1 g)
is introduced therein while maintaining the temperature of
the system below -20C. Thereafter, the temperature of the
~1~9~38f~
system is gradually elevated up to 60C so as to e~fect the
reaction. The reaction is completed in 6 hours. By removal
o unreacted materials under reduced pressure, the reaction
product having the following structure is obtained as pale
yellow liquid:
fH3 fH3 iH3
CH2=C-COOCH2--fH--CE~2-N~CH2)20CO--C=CH2
2 3
The NMR chart of the said product obtained by the use of an
apparatus (lO0 MHz) manufactured by Nippon Denshi Co., Ltd.
and using d4-methanol as a solvent is shown in Fig. 17
of the accompanying drawings. In the IR spectrum, character-
istic absorptions are seen at 1040, 3430 and 1630 cm 1.
Example 18
In the same manner as in ~xample 17, allyl glycidyl
ether (97.1 g), sulfur dioxide (54.5 g) and dimethylamino-
ethyl methacrylate (133.7 g) are subjected to reaction in
the presence of hydroquinone (0.2 g) at 60C, the reaction
is completed in 6ihours. The reaction product having the
following structure is obtained:
CH3 ICH3
CH2=cH-cH2ocH2-fH-CH2-l (CH2)2O 2
_,
The NMR chart of the said product obtained as in Example 17
is shown in Fig. 18. In the IR spectrum, characteristic
absorptions are seen at 1040, 3430 and 1630 cm 1.
Example 19
In the same manner as in Example 17, glycidyl
methacrylate ~(42~2 g), sulfur dioxide (l9 g) and tri-
allylamine (40~7 g) are subjected to reaction in the
9_
11~988!3
presence of hydroquinone (0.1 g) and ethyleneglycol mono-
methyl ether (22.6 g) at 60C, the reaction is completed in
6 hours. ~he reaction product having the following struc-
ture is obtained:
C 3 CH2-CH=CH2
C~I2_C_coocH2_fH_cH2_N_cH2_cH=cH2
S2 CH2-CH=CH2
The NMR chart of the said product obtained as in Example 17
is shown in Fig. 19. In the IR spectrum, characteristic
absorptions are seen at 1040r 3430 and 1630 cm
Example 20
In the same manner as in Example 17, allyl glycidyl
ether (40.9 g), sulfur dioxide (23.0 g) and triallylamine
(49.2 g) are subjected to xeaction in the presence of hydro-
quinone (O.l,g) and ethyleneglycol monomethyl ether (13.7
g) at 60C, the reaction is completed in 6 hours. The
reaction product having the following structure is obtained:
CH2~CH=CH2
CH2=CH_CH2oCH2_CH_CH2_~CH2_CH=CH2
S2 CH2-CH=CH2
The NMR chart of the said product obtained as in Example 17
is sho~-n in Fig. 20. In the IR spectrum, characteristic
absorptions are seen at 1040, 3430 and 1630 cm 1.
In the same manner as in Example 17, allyl glycidyl
ether (57.0 g), sulfur dioxide (32.0 g) and 4-vinylpyridine
(52.5 g) are subjected to reaction in the presence of hydro-
quinone (0.1 g) and ethyleneglycol monomethyl ether (40.0 g)
at 60C, the reaction is completed in 6 hours. The reac-
tion product having the followins structure is obtained:
)~ ;,
88~
CH2=cH-cH2ocH2-cH-cH2-N~=~rcH=cH2
oso~
In the NMR analysis, characteristic peaks are recognized at
3.6 ~ and 3.6 ~. In the IR spectrum, characteristic ab-
so-rptions are seen at 1040l 3430 and 1630 cm 1
Example 22
In the same manner as in Example 17, glycidyl
methacrylate (71.0 g), sulfur dioxide (32.0 g) and dimethyl- .
allylamine (42.5 g) are subjected to reaction in the
presence of hydroquinone (0.1 g) and dimethylformamide (20
g) at 60C, the reaction is completed in 6 hours. The
reaction product having the following structure is obtained:
CjH3 CH3
CH2=C-COOCH2-Cl H-CH2-N-CH2-CH=CH2
. S2 CH3
In the NMR anaIysis, characteristic peaks are recognized at
3.6 ~ and 4.6 ~. In the IR spectrum, characteristic ab-
sorptions are seen at 1040, 3430 and 1630 cm 1.
Exam~le 23
In the same manner as in Example 17, allyl glycidyl
ether (57.0 g), sulfur dioxide (32.0 g) and dimethylallyl-
- amine (42.5 g) are subjected to reaction in the presence of
20 hydroquinone (0.1 g) at 60C, the reaction is completed in 6
hours. The reaction product having the following structure
is obtained:
C~H3
CH;2=C~-CH20CH2--CH~CH2-N-CH2-CH=CH2
S2 C~3
In the NMR analysis, characteristic peaks are recognized at
- 21 -
:
.: '1 . I ,
~1~98l3~
3. 6 ~ and 4 . 6 ~ . In the IR spectrum, characteri~tic a~-
sorptions are seen at ~040, 343û and 1630 cm 1,
.
- i -- 22 --
~,~
