CA1109888A - Ampho-ionic compounds and their production - Google Patents
Ampho-ionic compounds and their productionInfo
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- CA1109888A CA1109888A CA317,352A CA317352A CA1109888A CA 1109888 A CA1109888 A CA 1109888A CA 317352 A CA317352 A CA 317352A CA 1109888 A CA1109888 A CA 1109888A
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Abstract
Abstract of the Disclosure An ampho-ionic compound of the formula:
wherein R is a group of the formula:
wherein R1 is hydrogen or methyl and A1 is -COOCH2- or -CH2OCH2-, R2 is hydrogen or methyl; and B? is (a) a group of either one of the formulas:
wherein R3, R4 and R4 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, alkyleneoxy or alkylene-thio, 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:
wherein R10, R11 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:
wherein R is a group of the formula:
wherein R1 is hydrogen or methyl and A1 is -COOCH2- or -CH2OCH2-, R2 is hydrogen or methyl; and B? is (a) a group of either one of the formulas:
wherein R3, R4 and R4 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, alkyleneoxy or alkylene-thio, 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:
wherein R10, R11 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:
Description
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:
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 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:
- ~-R
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:
\ / (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
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:
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 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:
- ~-R
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:
\ / (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:
CH2-C-Al-C-CH2 1~6)R4 (Ia-l) ls~ l5 C~2-C-~l-c-cH2 ~ 6 (Ia-2) ~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:
,,~,, ... . ..
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-
~ ?
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:
CH2-C-Al-C-CH2 1~6)R4 (Ia-l) ls~ l5 C~2-C-~l-c-cH2 ~ 6 (Ia-2) ~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:
,,~,, ... . ..
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) I 11 (IIIb) or Rl 3 /(A2-C=CH2) N ~IIIc) 14~3-n . ~, .
"~,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, `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~
,~ 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:
CH2-C-CC~2-fH-C~l2 N, CH3 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 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
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:
=cH-cH2ocH2-fH-cH2- ~CH2cH2OH
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:
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:
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:
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 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:
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, 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 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 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:
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 :
.: '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 --~,~
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) I 11 (IIIb) or Rl 3 /(A2-C=CH2) N ~IIIc) 14~3-n . ~, .
"~,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, `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~
,~ 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:
CH2-C-CC~2-fH-C~l2 N, CH3 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 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
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:
=cH-cH2ocH2-fH-cH2- ~CH2cH2OH
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:
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:
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:
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 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:
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, 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 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 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:
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 :
.: '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 --~,~
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An ampho-ionic compound of the formula:
wherein R is a group of the formula:
wherein R1 is hydrogen or methyl and Al is -COOcH2- or -CH2OCH2 R2 is hydrogen or methyl; and B? is (a) a group of either one of the formulas:
and 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, alkyleneoxy or alkylene-thio, these groups having each not more than 7 carbon atoms and R9 is optionally substituted alkylidene of 4 to 10 carbon atoms, (b) a group of the formula:
wherein R10, R11 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:
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)mOC0-, -(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 optionally include an unsaturated double bond and/or an oxygen or sulfur atom, m is an integer of 1 to 4 and n is an integer of 1 to 3.
wherein R is a group of the formula:
wherein R1 is hydrogen or methyl and Al is -COOcH2- or -CH2OCH2 R2 is hydrogen or methyl; and B? is (a) a group of either one of the formulas:
and 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, alkyleneoxy or alkylene-thio, these groups having each not more than 7 carbon atoms and R9 is optionally substituted alkylidene of 4 to 10 carbon atoms, (b) a group of the formula:
wherein R10, R11 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:
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)mOC0-, -(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 optionally include an unsaturated double bond and/or an oxygen or sulfur atom, m is an integer of 1 to 4 and n is an integer of 1 to 3.
2. The compound according to claim 1, wherein B? is the group (a).
3. The compound according to claim 1, wherein B? is the group (b).
4. The compound according to claim 1, wherein B? is the group (c).
5. A process for preparing a compound according to claim 1, which comprises any one of the following:
(a) reacting a compound of the formula:
wherein R1 is hydrogen or methyl, A is -COOCH2- or -CH20CH2- and R2 is hydrogen or methyl with sulfur dioxide and a tertiary amine of either one of the formulas:
and 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, alkyleneoxy or alkylenethio these groups having each not more than 7 carbon atoms and R9 is optionally substituted alkylidene of 4 to 10 carbon atoms;
(b) reacting a compound of the formula:
wherein R1 is hydrogen or methyl, A is -COOCH2-, CH2OCH2- or -CONHCH2- and R2 is hydrogen or methyl with sulfur dioxide and a tertiary amine of the formula:
wherein R10, R11 and R12 are each a substituent comprising as the major constituent a hydrocarbon chain having 10 to 30 carbon atoms, which may optionally include an unsaturated double bond and/or an oxygen or sulfur atom; or (c) reacting a compound of the formula:
wherein R1 is hydrogen or methyl, A is -COOCH2-, -CH2OCH2- or -CONHCH2- and R2 is hydrogen or methyl with sulfur dioxide and a tertiary amine of the formula:
wherein R13 is hydrogen or methyl, R14 is a sub-stituent comprising as the major constituent 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 of the whole of R14, forms a heterocyclic structure having not more than 14 carbon atoms, which may optionally include an unsaturated double bond and/or an oxygen or sulfur atom, m is an integer of 1 to 4 and n is an integer of 1 to 3.
(a) reacting a compound of the formula:
wherein R1 is hydrogen or methyl, A is -COOCH2- or -CH20CH2- and R2 is hydrogen or methyl with sulfur dioxide and a tertiary amine of either one of the formulas:
and 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, alkyleneoxy or alkylenethio these groups having each not more than 7 carbon atoms and R9 is optionally substituted alkylidene of 4 to 10 carbon atoms;
(b) reacting a compound of the formula:
wherein R1 is hydrogen or methyl, A is -COOCH2-, CH2OCH2- or -CONHCH2- and R2 is hydrogen or methyl with sulfur dioxide and a tertiary amine of the formula:
wherein R10, R11 and R12 are each a substituent comprising as the major constituent a hydrocarbon chain having 10 to 30 carbon atoms, which may optionally include an unsaturated double bond and/or an oxygen or sulfur atom; or (c) reacting a compound of the formula:
wherein R1 is hydrogen or methyl, A is -COOCH2-, -CH2OCH2- or -CONHCH2- and R2 is hydrogen or methyl with sulfur dioxide and a tertiary amine of the formula:
wherein R13 is hydrogen or methyl, R14 is a sub-stituent comprising as the major constituent 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 of the whole of R14, forms a heterocyclic structure having not more than 14 carbon atoms, which may optionally include an unsaturated double bond and/or an oxygen or sulfur atom, m is an integer of 1 to 4 and n is an integer of 1 to 3.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP159788/1977 | 1977-12-28 | ||
| JP15978877A JPS5492917A (en) | 1977-12-28 | 1977-12-28 | Polymerizable amphoteric compound |
| JP159789/1977 | 1977-12-28 | ||
| JP15978977A JPS5492918A (en) | 1977-12-28 | 1977-12-28 | Polymerizable amphoteric compound |
| JP34649/1978 | 1978-03-24 | ||
| JP3464978A JPS54128519A (en) | 1978-03-24 | 1978-03-24 | Amphoteric compound having plural polymerizable unsaturated groups |
| JP3465078A JPS54128520A (en) | 1978-03-24 | 1978-03-24 | Amphoteric ammonium compound |
| JP34650/1978 | 1978-03-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109888A true CA1109888A (en) | 1981-09-29 |
Family
ID=27459966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA317,352A Expired CA1109888A (en) | 1977-12-28 | 1978-12-05 | Ampho-ionic compounds and their production |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1109888A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6106940A (en) * | 1998-03-17 | 2000-08-22 | 3M Innovative Properties Company | Adhesive compositions with zwitterionic tackifiers and plasticizers |
| US6133391A (en) * | 1998-03-17 | 2000-10-17 | 3M Innovative Properties Company | Adhesive compositions and adhesive tapes comprising zwitterionic copolymers, and novel zwitterionic copolymers |
-
1978
- 1978-12-05 CA CA317,352A patent/CA1109888A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6106940A (en) * | 1998-03-17 | 2000-08-22 | 3M Innovative Properties Company | Adhesive compositions with zwitterionic tackifiers and plasticizers |
| US6133391A (en) * | 1998-03-17 | 2000-10-17 | 3M Innovative Properties Company | Adhesive compositions and adhesive tapes comprising zwitterionic copolymers, and novel zwitterionic copolymers |
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