Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
1999-07-06
2001-07-17
Killos, Paul J. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C260S66500B, C260S66500B, C536S060000
Reexamination Certificate
active
06262299
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a zwitterionic monomer having amino multicarboxylic acid functionality which is the reaction product of an amino-multicarboxylic acid and an amine containing monomer.
BACKGROUND OF THE INVENTION
Various carboxybetaines, sulfobetaines, homopolymers and copolymers thereof have been described in the prior art. U.S. Pat. Nos. 3,473,998 and 3,478,001 describe sulfobetaines and copolymers thereof with acrylonitrile. U.S. Pat. No. 3,497,482 describes homopolymers of sulfobetaines and copolymers with certain ethylenically unsaturated monomers. U.S. Pat. Nos. 2,777,872; 2,935,493; and 2,958,682 describe carboxybetaines and copolymers thereof with various ethylenically unsaturated compounds. U.S. Pat. No. 3,671,502 describes copolymers comprising units derived from carboxybetaines or sulfobetaines and units derived from hydroxyalkyl acrylates/methacrylates, polyalkylene glycol acrylateslmethacrylates or polyglycerol acrylates/methacrylates. U.S. Pat. No. 5,500,087 describes amino-multicarboxylate starch ether derivatives which are useful as retention and strength aids in papermaking.
However, the prior art does not describe multicarboxybetaine monomers or zwitterionic monomers having amino-multicarboxylic acid functionality. Moreover, the prior art does not describe preparing copolymers from such monomers.
SUMMARY OF THE INVENTION
The present invention provides a zwitterionic monomer having, amino-multicarboxylic acid functionality having Structure (I)
wherein R
1
is selected from the group consisting of H, an alkyl group having 1 to 6 carbon atoms; R
2
is (CH
2
)
n
where n is 2 to 12; R
3
and R
4
are independently an alkyl group having 1 to 6 carbon atoms; R
5
is (CH
2
)
m
where m is 2 or 3; R
6
and R
7
are independently selected from
wherein R
20
is selected from the group consisting of H, CH
3
, and COOY; R
21
is selected from H or CH
3
; X is oxygen or nitrogen; A is a halide; and Y is independently a cation;
said zwitterionic monomer is the reaction product of an amino-multicarboxylic acid and ar amine containing monomer, wherein the amino-multicarboxylic acid has Structure (II)
and the amine conitaining monomer has Structure (III)
wherein R
23
and R
24
are independently selected from
wherein R
27
is selected from the group consisting of H, CH
3
, and COOH; and R
28
is H or CH
3
.
The zwitterionic monomers of the invention have at least two carboxyl groups which are in close vicinity to each other in the monomer. The zwitterionic monomers may be polymerized alone or in combination with at least one other monomer to form a polymer having unique properties. Polymers prepared with the zwitterionic monomer are especially useful in hair treatment compositions to provide increased stiffness to hair, in coating formulations to increase the impact resistance, wet adhesion, and flexibility of the coating, especially wood coatings, and in mortar compositions to improve mortar compatibility, especially with redispersible powders.
DESCRIPTION OF THE INVENTION
The zwitterionic monomer having amino-multicarboxylic acid functionality is prepared by reacting an amino-multicarboxylic acid with an amine containing monomer. The zwitterionic monomer having amino-multicarboxylic acid functionality having Structure (I)
wherein R
1
is selected from the group consisting of H, an alkyl group having 1 to 6 carbon atoms; R
2
is (CH
2
)
n
where n is 2 to 12; R
3
and R
4
are independently an alkyl group having 1 to 6 carbon atoms; R
5
is (CH
2
)
m
where m is 2 or 3; R
6
and R
7
are independently selected from
wherein R
20
is selected from the group consisting of H, CH
3
, and COOY; R
21
is selected from H or CH
3
; A is a halide, preferably chloride or bromide; and Y is independently a cation, preferably H, alkali metal, alkaline earth metal, or ammonium.
The amino-multicarboxylic acid has Structure (II)
wherein R
5
is (CH
2
)
m
where m is 2 or 3; R
23
and R
24
are independently selected from
wherein R
27
is selected from the group consisting of H, CH
3
, and COOH; R
28
is H or CH
3
, A is a halide, preferably chloride or bromide.
The amino-multicarboxylic acid is preferably prepared by a Michael reaction between an amine of an aminoalcohol, preferably a primary amine, and an olefin containing ester followed by halogenation with any halide and preferably chlorination or bromination. More preferably chlorination is used. The chlorination may be carried out using chloride compounds such as thionyl chloride or phosphorus oxychloride. Purification such as by steam stripping or recrystallization from isopropanol or other suitable solvents may be employed.
The amino alcohol used in preparing the amino-multicarboxylic acid has structure (IV):
wherein R
10
is H or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, m is 2 or 3.
The olefin containing ester has Structure (V):
wherein R
25
is selected from H, CH
3
, or COOR
22
; R
26
is selected from H or CH
3
; and R
22
is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Preferably, the olefin containing ester is selected from alkyl acrylates, alkyl methacrylates, alkyl crotonates, dialkyl maleate, or dialkyl fumarate.
In one embodiment of the invention where R
10
is hydrogen then any olefin containing ester is acceptable for the reaction. If R
10
is an alkyl group then the olefin containing ester must be a diester. Preferred diesters are dialkyl maleate and dialkyl fumarate, wherein the alkyl group has 1 to 6 carbon atoms.
In one embodiment of the invention, the amino-multicarboxylic acid is prepared by reacting ethanolamine with methyl acrylate followed by chlorination with thionyl chloride and hydrolysis to provide the aminodicarboxyl containing reagent, 2-chloroethylaminodipropionic acid. A preferred reaction scheme is as follows:
An amine containing monomer is reacted with the amino-multicarboxylic acid to form the zwitterionic monomer having amino-multicarboxylic acid functionality. The amine containing monomer has Structure (III):
wherein R
1
is selected from the group consisting of H, an alkyl group having 1 to 6 carbon atoms; R
2
is (CH
2
)
n
where n is 2 to 12; R
3
and R
4
are independently an alkyl group having 1 to 6 carbon atoms; and X is oxygen or nitrogen.
The formation of the zwitterionic monomer having amino-multicarboxylic acid functionality involves reacting the amine containing monomer with the amino-multicarboxylic acid in an aqueous medium at a temperature of from about 10° C. to 95° C., preferably from about 20° C. to 50° C. The reaction is carried out under alkaline conditions at a pH of from about 8.5 to 13, more particularly from about 9.5 to 12.5. The pH is conveniently controlled by the periodic addition of a dilute aqueous solution of sodium hydroxide or other common base including potassium hydroxide, calcium hydroxide, sodium carbonate, ammonium hydroxide, tetramethylammonium hydroxide, etc. The preferred bases are sodium and potassium hydroxide.
The amino-multicarboxylic acid may be added to the reaction mixture as a solid or an aqueous solution. The preferred concentration of the solution is 20 to 50% by weight, based on the weight of the reagent. In an alternative method, the amino-multicarboxylic acid solution is brought to the desired alkaline pH prior to its addition to the amine containing monomer. In this alternative method, the reagent is in the form of a salt rather than an acid or partially neutralized acid when it is introduced to the reaction mixture.
Reaction time will vary from about 0.2 to 24 hours depending on such factors as the stability and reactivity of the amino-multicarboxylic acid employed, the temperature, pH, the scale of the reaction. In general, the preferred range of reaction time is from about 1 to 16 hours.
After completion of the reaction, the pH of the reaction mixture is adjusted to from about 3 to 9 with any commercial acid such as hydrochloric acid, sulfuric acid, acetic acid, etc. Such acids may be conventionally added as a dilute aqueous solution. D
Tsai John
Wanigatunga Sirisoma
Killos Paul J.
National Starch and Chemical Investment Holding Corporation
Roland Thomas F.
Zitomer Fred
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