US4012437A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Method of producing betaines, monomers and polymers containing betaine-type units and novel and useful copolymers thereby obtained
Assignee: Rohm and Haas Co
•
Filing: 1972-02-07
•
Granted: 1977-03-15
•
Expires: 1992-02-07
Abstract
Abstract An improved method is provided for producing polymers of organic compounds, such as ethylenically unsaturated monomers, containing a betaine-type group of the formula: ##STR1## The method involves the reaction of acrylic acid or aqueous methyl acrylate and an aminoalkyl (meth)acrylate or an N-amino-alkyl (meth)acrylamide having a basic tertiary nitrogen atom in the presence of a free radical initiator. The monomers undergo vinyl addition polymerization to form valuable polymers having a wide variety of uses, such as flocculants, retention aids in the deposition of polymers, pigments, etc. on the fibers in a paper pulp, e.g., in the formation of mineral-filled papers.
Inventors
- 👤 Norman Shachat
- 👤 Richard A. Haggard
- 👤 Sheldon N. Lewis
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 10:30
CPC Classifications
C; C07; C07D; C07D295/00; C07D295/04; C07D295/14; C07D295/145; C07D295/15; B; B01; B01D; B01D21/00; B01D21/01; C08; C08F; C08F20/00; C08F20/02; C08F20/10; C08F20/34; C08F20/36; C08F20/52; C08F20/54; C08F20/60
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
152 words
A method for producing a betaine-type product which comprises reacting, at a temperature of about 0° C. to about 100° C., 1. acrylic acid with a tertiary amine of the formula ##STR6##wherein R is (C 1 -C 24 ) alkyl, allyl, benzyl, vinylbenzyl, hydroxyalkyl having 2 to 24 carbon atoms, (C 1 -C 8 )-alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido, alkoxyalkyl having 3 to 24 carbon atoms, or a poly(alkoxy)alkyl group having 2 to 6 oxygen atoms and 2 to 3 carbon atoms in all except one of the terminal alkyl groups, the latter having 1 to 8 carbon atoms; R' is a (C 1 -C 8 ) alkyl group; R° is a (C 1 -C 8 ) alkyl group, or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino or 2.
Claim 2
Independent Claim
152 words
A method for producing a betaine-type product which comprises reacting, at a temperature of about 0° C. to about 100° C., 1. acrylic acid with a tertiary amine of the formula ##STR6##wherein R is (C 1 -C 24 ) alkyl, allyl, benzyl, vinylbenzyl, hydroxyalkyl having 2 to 24 carbon atoms, (C 1 -C 8 )-alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido, alkoxyalkyl having 3 to 24 carbon atoms, or a poly(alkoxy)alkyl group having 2 to 6 oxygen atoms and 2 to 3 carbon atoms in all except one of the terminal alkyl groups, the latter having 1 to 8 carbon atoms; R' is a (C 1 -C 8 ) alkyl group; R° is a (C 1 -C 8 ) alkyl group, or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino or 2.
Claim 3
Dependent Claim
68 words
acrylic acid with a polymer containing tertiary amine groups, of the formula above where R is (C 1 -C 8 ) alkyl substituted by acryloxy, methacryloxy, acrylamido or methacrylamido, and R' and R° are as defined above, or 3. acrylic acid with a mixture of a tertiary amine as defined in (2) and (b) a polymer of said tertiary amine, the molar ratio of acid to amine in
Claim 4
Dependent Claim
68 words
acrylic acid with a polymer containing tertiary amine groups, of the formula above where R is (C 1 -C 8 ) alkyl substituted by acryloxy, methacryloxy, acrylamido or methacrylamido, and R' and R° are as defined above, or 3. acrylic acid with a mixture of a tertiary amine as defined in (2) and (b) a polymer of said tertiary amine, the molar ratio of acid to amine in
Claim 5
Dependent Claim
32 words
the mixtures (1), (2), and (3) being from 0.1:1 to 10:1. 2. A method according to claim 1 in which the molar ratio of acid to amine is about 1:1 to 5:1.
Claim 6
Independent Claim
149 words
A method for producing a betaine-type product which comprises reacting, in an aqueous medium at a temperature of about 0° to about 80° C. acrylic acid with a tertiary amine of the formula, ##STR7##wherein R is (C 1 -C 24 ) alkyl, allyl, benzyl, vinylbenzyl, hydroxyalkyl having 2 to 24 carbon atoms, (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido, alkoxyalkyl having 3 to 24 carbon atoms, or a poly(alkoxy)alkyl group having 2 to 6 oxygen atoms and 2 to 3 carbon atoms in all except one of the terminal alkyl groups, the latter having 1 to 8 carbon atoms; R' is (C 1 -C 8 ) alkyl; R° is (C 1 -C 8 ) alkyl, or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino.
Claim 7
Independent Claim
149 words
A method for producing a betaine-type product which comprises reacting, in an aqueous medium at a temperature of about 0° to about 80° C. acrylic acid with a tertiary amine of the formula, ##STR7##wherein R is (C 1 -C 24 ) alkyl, allyl, benzyl, vinylbenzyl, hydroxyalkyl having 2 to 24 carbon atoms, (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido, alkoxyalkyl having 3 to 24 carbon atoms, or a poly(alkoxy)alkyl group having 2 to 6 oxygen atoms and 2 to 3 carbon atoms in all except one of the terminal alkyl groups, the latter having 1 to 8 carbon atoms; R' is (C 1 -C 8 ) alkyl; R° is (C 1 -C 8 ) alkyl, or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino.
Claim 8
Independent Claim
83 words
A method for producing a betaine-type product which comprises reacting, in an aqueous medium at a temperature of about 0° to about 80° C., 1. acrylic acid, with a polymer containing tertiary amine groups of the formula ##STR8##wherein R is (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido R' and R° are (C 1 -C 8 ) alkyl, or R' and R° are joined together with the N atom to form morpholino, thiomorpholino, N-alkylpiperidino or piperzino or
Claim 9
Independent Claim
83 words
A method for producing a betaine-type product which comprises reacting, in an aqueous medium at a temperature of about 0° to about 80° C., 1. acrylic acid, with a polymer containing tertiary amine groups of the formula ##STR8##wherein R is (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido R' and R° are (C 1 -C 8 ) alkyl, or R' and R° are joined together with the N atom to form morpholino, thiomorpholino, N-alkylpiperidino or piperzino or
Claim 10
Dependent Claim
38 words
acrylic acid with a mixture of (a) a tertiary amine of the formula as defined above in (1) and (b) a polymer of said teritary amine, the molar ratio of acid to amine being from 0.1 to 10:1.
Claim 11
Dependent Claim
38 words
acrylic acid with a mixture of (a) a tertiary amine of the formula as defined above in (1) and (b) a polymer of said teritary amine, the molar ratio of acid to amine being from 0.1 to 10:1.
Claim 12
Dependent Claim
22 words
A method according to claim 1 in which the reaction is effected at a temperature of about 10° C. to 40° C.
Claim 13
Independent Claim
145 words
A method for producing a betaine-type product which comprises reacting, at a temperature of about 0° C. to about 100° C., acrylic acid with a tertiary amine of the formula ##STR9##wherein R is (C 1 -C 24 ) alkyl, allyl, benzyl, vinylbenzyl, hydroxyalkyl having 2 to 24 carbon atoms, (C 1 -C 8 )-alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido, alkoxyalkyl having 3 to 24 carbon atoms, or poly(alkoxy)alkyl having 2 to 6 oxygen atoms and 2 to 3 carbon atoms in all except one of the terminal alkyl groups, the latter having 1 to 8 carbon atoms; R' is (C 1 -C 8 ) alkyl; R° is a (C 1 -C 8 ) alkyl group, or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino.
Claim 14
Independent Claim
145 words
A method for producing a betaine-type product which comprises reacting, at a temperature of about 0° C. to about 100° C., acrylic acid with a tertiary amine of the formula ##STR9##wherein R is (C 1 -C 24 ) alkyl, allyl, benzyl, vinylbenzyl, hydroxyalkyl having 2 to 24 carbon atoms, (C 1 -C 8 )-alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido, alkoxyalkyl having 3 to 24 carbon atoms, or poly(alkoxy)alkyl having 2 to 6 oxygen atoms and 2 to 3 carbon atoms in all except one of the terminal alkyl groups, the latter having 1 to 8 carbon atoms; R' is (C 1 -C 8 ) alkyl; R° is a (C 1 -C 8 ) alkyl group, or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino.
Claim 15
Dependent Claim
39 words
A method according to claim 1 ##STR10##wherein R is (C 1 -C 8 ) alkyl substituted by acryloxy, methacryloxy, acrylamido or methacrylamido, R' is (C 1 -C 4 ) alkyl, and R° is (C 1 -C 4 ) alkyl.
Claim 16
Dependent Claim
27 words
A method according to claim 1 in which the tertiary amine is dimethylaminoethyl acrylate dimethylaminoethyl methacrylate, N-dimethylaminoethyl acrylamide or N-dimethylaminoethyl methacrylamide or a polymer containing units thereof.
Claim 17
Dependent Claim
22 words
A method according to claim 3 in which the reaction is effected at a temperature of about 10° C. to 40° C.
Claim 18
Dependent Claim
39 words
A method according to claim 3 wherein R is (C 1 -c 8 ) alkyl substituted by acryloxy, methacryloxy, acrylamido or methacrylamido; R' is (C 1 -C 4 ) alkyl and R° is (C 1 -C 4 ) alkyl.
Claim 19
Dependent Claim
26 words
A method according to claim 3 wherein the tertiary amine is dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, N-dimethylaminoethyl acrylamide or N-dimethylaminoethyl methacrylamide or a polymer containing said amines.
Claim 20
Dependent Claim
26 words
A process according to claim 3 for preparing a betaine-type product having the formula ##STR11##which comprises reacting acrylic acid with β-N, N-dimethylaminoethyl methacrylate at 25° C.
Claim 21
Independent Claim
141 words
A method for producing a betaine-type product which comprises reacting, in an aqueous medium at a temperature of about 0° to about 80° C., a lower alkyl ester of acrylic acid with a tertiary aliphatic amine of the formula ##STR12##wherein R is (C 1 -C 24 ) alkyl, allyl, benzyl, vinylbenzyl, hydroxyalkyl having 2 to 24 carbon atoms, a (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido group, alkoxyalkyl having 3 to 24 carbon atoms in all except one of the terminal alkyl groups, the latter having 1 to 8 carbon atoms; R' is (C 1 -C 8 ) alkyl; R° is (C 1 -C 8 ) alkyl, or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino.
Claim 22
Independent Claim
141 words
A method for producing a betaine-type product which comprises reacting, in an aqueous medium at a temperature of about 0° to about 80° C., a lower alkyl ester of acrylic acid with a tertiary aliphatic amine of the formula ##STR12##wherein R is (C 1 -C 24 ) alkyl, allyl, benzyl, vinylbenzyl, hydroxyalkyl having 2 to 24 carbon atoms, a (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido group, alkoxyalkyl having 3 to 24 carbon atoms in all except one of the terminal alkyl groups, the latter having 1 to 8 carbon atoms; R' is (C 1 -C 8 ) alkyl; R° is (C 1 -C 8 ) alkyl, or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino.
Claim 23
Dependent Claim
34 words
A method according to claim 13 wherein R is (C 1 -C 8 ) alkyl substituted by acryloxy, methacryloxy, acrylamido or methacrylamido the molar ratio of acid to amine being from 0:1 to 10:1.
Claim 24
Dependent Claim
40 words
A method according to claim 13 wherein R is (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido; R' is (C 1 -C 4 ) alkyl, and R° is (C 1 -C 4 ) alkyl.
Claim 25
Dependent Claim
26 words
A method according to claim 13 wherein the tertiary amine is dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, N-dimethylaminoethyl acrylamide or N-dimethylaminoethyl methacrylamide or a polymer containing units thereof.
Claim 26
Independent Claim
26 words
A method according to claum 13 in which the reaction is conducted at a temperature in the range of from about 10° C. to 40° C.
Claim 27
Independent Claim
26 words
A method according to claum 13 in which the reaction is conducted at a temperature in the range of from about 10° C. to 40° C.
Claim 28
Dependent Claim
106 words
A method according to claim 13 wherein R is (C 1 -C 24 ) alkyl, allyl, benzyl, vinylbenzyl, hydroxyalkyl having 2 to 24 carbon atoms, alkoxyalkyl having 3 to 24 carbon atoms, or poly (alkoxy)alkyl having 2 to 6 oxygen atoms and 2 to 3 carbon atoms in all except one of the terminal alkyl groups, the latter having 1 to 8 carbon atoms; R' is (C 1 -C 8 ) alkyl; R° is (C 1 -C 8 ) alkyl, or R' and R° are joined together and form, with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino.
Claim 29
Independent Claim
96 words
A method for producing a betaine-type product which comprises reacting at a temperature of about 0°-100° C., a mixture of acrylic acid with a polymer of tertiary aliphatic amine groups of the formula: ##STR13##wherein R is allyl, vinylbenzyl, or (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido; R' is (C 1 -C 8 ) alkyl; R° is (C 1 -C 8 ) alkyl or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino.
Claim 30
Independent Claim
96 words
A method for producing a betaine-type product which comprises reacting at a temperature of about 0°-100° C., a mixture of acrylic acid with a polymer of tertiary aliphatic amine groups of the formula: ##STR13##wherein R is allyl, vinylbenzyl, or (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido; R' is (C 1 -C 8 ) alkyl; R° is (C 1 -C 8 ) alkyl or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino.
Claim 31
Dependent Claim
22 words
A method according to claim 19 in which the reaction is effected at a temperature of about 10° C. to 40° C.
Claim 32
Dependent Claim
39 words
A method according to claim 3 wherein R is (C 1 -C 8 ) alkyl substituted by acryloxy, methacryloxy acrylamido or methacrylamido; R' is (C 1 -C 4 ) alkyl and R° is (C 1 -C 4 ) alkyl.
Claim 33
Dependent Claim
94 words
The method of claim 3 in which a polymer of a tertiary aliphatic amine groups of the formula: ##STR14##wherein R is allyl, vinylbenzyl, or (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido; R' is (C 1 -C 8 ) alkyl; R° is (C 1 -C 8 ) alkyl or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpipereidino, or piperazino, is present during the reaction of the acrylic acid and the tertiary amine.
Claim 34
Dependent Claim
92 words
The method of claim 13 in which a polymer of a tertiary amine of the formula: ##STR15##wheren R is allyl, vinylbenzyl, or (C 1 -C 8 ) alkyl substituted by an acryloxy, methacryloxy, acrylamido or methacrylamido; R' is (C 1 -C 8 ) alkyl; R° is (C 1 -C 8 ) alkyl or R' and R° may be joined together and form with the N atom of the tertiary amine, a ring selected from morpholino, thiomorpholino, N-alkylpiperidino, or piperazino, is present during the reaction of the acrylic acid and the tertiary amine.
References Cited (Backward Citations)
US2777872A
Cited
FR1487622A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-03-14 | 1980-09-13 | 1981-03-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-03-14 | 1984-09-13 | 1985-03-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-03-14 | 1988-09-13 | 1989-03-15 | $7700.00 | Window Closed / Lapsed |