US2743247A - Method of polycondensation of alkylene-alkylidene- and aralkylidene-bishalogen substituted carboxylic acid amides - Google Patents
Method of polycondensation of alkylene-alkylidene- and aralkylidene-bishalogen substituted carboxylic acid amides Download PDFInfo
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- US2743247A US2743247A US328141A US32814152A US2743247A US 2743247 A US2743247 A US 2743247A US 328141 A US328141 A US 328141A US 32814152 A US32814152 A US 32814152A US 2743247 A US2743247 A US 2743247A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
Definitions
- This invention relates to polycondensation, and more particularly to methods of'preparing polycondensates from bls-halogen substituted-carboxylic acid amides, as' well as the intermediates and end products obtained by the said methods.
- a still further object of the invention is to provide a variety of processes for converting bis-halogen substitutedcarboxylic acid amides intopolycondensates adapted for a variety of uses in the field of plastics.
- Yet another object of the invention is to devise methods of the kind referred to which eliminate decomposition 7 2,143,241 Patented Apr. 24, 1956 termediate products obtained in the first stage of the process, are treated by adding thereto from about 0.1 to about 3%, calculated on the weight of the intermediate product, of hydroxides, hydrosulfides or carbonates of alkali metals or alkali earth metals, thereafter melting the intermediate product with the said addition, under normal pressure while introducing nitrogen, and then heating in vacuo, to a temperature ranging from 100 to 250 C., and preferably within the range from 130 to 200 C.
- this procedure is the preferred embodiment of the invention.
- liquid ammonia is caused to act in the autoclave, at room temperature, for a period of up to 20 hours, on methylene-bis-chloropropionic acid amide, in the course of which treatment the pressure remains at about 8-10 mm, corresponding to this temperature, a corresponding monoamino compound of the following formula is obtained.
- This compound has a melting point of 240 C. If this monoamine is treated in a vacuum of 0.5 mm. Hg, and at a temperature of 115 C. in a current of nitrogen, there is obtained while HCl is split oif quantitatively in the distillation vessel a light colored polycondensation product which is useful for the production of plastic masses.
- the invention contemplates further treating the intermediate products obtained in the first stage of the process, by a second step with unlike the first step which is common to all embodiments ofthe invention, may be any one of a variety of procedures, as set out hereafter.
- the intermediate product obtained in the first, stage may undergo further treatment by beingheated, in a current of nitrogen, at temperatures up to about 250 C.v
- Another embodiment of the invention involves reacting the intermediate product obtained in the first stage, with an aliphatic or aromatic diearboxylic acid such as adipic acid, for example.
- an aliphatic or aromatic diearboxylic acid such as adipic acid, for example.
- the intermediate product is heated, in vacuo, above its melting point.
- the diamine thus obtained which has a melting point of 140 C., can be condensed with adipic acid and yields a polycondensate having a linear structure. It is excellently suited for the production of plastic masses.
- Example 1 200 grams of methylene-bis-chloropropionic acid amide are treated, in the autoclave and at normal temperature, with 1000 cc. of liquid ammonia. The reaction may last up to 20 hours. A homogeneous solution is formed which after evaporation of excessive ammonia, leaves a semisolid mass. After working down and purificationthere polycondensates particularly is obtained the corresponding monoamino compound of the following formula Cl.(CH2)2.CO.NH.CH2.NH.CO.(CH2) aNHz remaining in the distillation vessel when the reaction is completed, lends itself to the production of plastic masses.
- liquid ammonia are heated in the autoclave for up to hours at a pressure of up to about 20 atrn. and a temperature of about 60 C. A homogeneous liquid is formed. Upon evaporation of excessive ammonia and after removal of inorganic reaction products, a solid product is obtained which has a melting point of 140 C. and is the diamine of the methylene-bis-chloropropionic acid amide.
- Example III 20 grams of this compound are melted while introducing nitrogen at normal pressure, and thereafter are further condensed under reduced pressure (about 0.5 mm. Hg). After the reaction has proceeded for 3-5 hours there remains in the distillation vessel, a lightly colored polycondensation product which is eminently suitable for the manufacture of plastic materials.
- Example IV 250 grams of methylene-bis-chloropropionic acid amide are treated with 1250 cc. of liquid ammonia for up to about 20 hours, at ordinary temperature, in the autoclave. A homogeneous solution results which on evaporation of the excess of ammonia, yields a semi-solid mass; When worked up and cleaned, this in turn yields a monoamino compound corresponding to the starting material and having a melting point of 240 C. 0.5 grams of solid NaOH are added to this intermediate product which is then molten, at normal pressure, while introducing nitrogen, and then heated in vacuum of 2 mm. Hg for a period of about 3 hours, to a temperature of about 130-140 C. In the course of condensation hydrochloric acid is split off. Once the reaction is completed there remains behind,
- Example V The. methylene-bis-chloropropionic acidamide of Example-IV is replaced by an identical quantity of methylenebis-bromopropionic acid amide, and treated. exactly as described inEXample 1V. Here also av lightly colored condensation product of excellent plastic properties is obtained.
- Example V1 250 grams of ethylidene-bis-chloropropionic acid amide are treated with 1300 cc. of. liquid ammonia for up to about 20 hours, at room temperature, in the autoclave. A homogeneous solution results which after evaporation of any excessive ammonia, forms a semi-solid mass which is worked up and cleaned, to yield a monoamino compound corresponding to the starting material and having a melting point of 185-490" C.
- This compound after 1 gram of solid NazCOs has been added thereto, is molten at normal pressure while introducing nitrogen, to be then heated in a vacuum of 2 mm. Hg. for 3 hours, to 130- 140 C. Hydrochloric acidis split off during the condensation. When the reaction is completed, a lightly .colored condensation product remains in the distillation vessel which is highly useful as aplastic material.
- Example VII 50 grams of benzylidene-bis-bromopropionic acid amide of the formula are reacted with 200 cc. of liquid ammonia, at ordinary temperature and in the autoclave, for about 12 hours. A semi-solid mass is obtained which solidifies upon evaporation of excessive ammonia. This substance still contains ammonium bromide and therefore is thoroughly washed with water and, if desired, recrystallized once in methanol. 1 gram of solid calcium hydroxide is then added to this intermediate product which is molten at normal pressure, with a continuous supply of nitrogen. This is followed by heating in a vacuum of 0.5 mm. Hg, for 4-6 hours, to a temperature up to 200 C. In the course of heating HBr is split'otr'. The lightly colored condensation product obtained when the reaction is completed, has particular utility as a plastic.
- Example VII is replaced by the same quantity of trichloroethylidene-bis-chloropropionic acid amide of the formula which is reacted and treated as described in- Example VII.
- the temperature for the condensation within the range of from about to about 250' C.,'and the preferred range from about to about 200 C., should not be raised substantially above the melting point of the products so as to avoid any risk of even slight decomposition and consequent discoloration which may be observed occasionally with some other method; Inasmuch as the melting points of the various compounds contemplated by the invention vary materially, the temperature must be varied accordingly so as to be best adapted for any particular compound. Additional examples of substances added to the intermediate products are 0.l"-0".5 gram'of NaSI-I, and a mixture of 0.05 gram of NaOH' and 0.3 gram ofCaCOs.
- condensation products obtained according to any of the several methods described herein are very good plastic materials
- the condensation products yielded by the methodillustrated by Examples IV to VIII are particularly distinguished by being highly resistant to chemicals. readily susceptible to being dyed, and not exposed to even the slightest decomposition and discoloration phenomena.
- they share the advantageous characteristics of all condensation products obtained according to the invention, to wit: comparatively high softening or melting points and economic, simple mode of manufacture inasmuch as the starting materials are obtained readily and in excellent yields, for example from a single stage process reacting acrylonitrile, formaldehyde and HCl and HBr.
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Description
NIETHOD OF POLYCONDENSATION F ALKYL- ENE-ALKYLIDENE- AND ARALKYLIDENE-BIS- IZIALOEGSEN SUBSTITUTED 'CARBOXYLIC ACID Rudolfl otz, Klingenberg (Main), Germany, assignor to Veremrgte Glanzstolf-Fabriken A. G., Wuppertal-Elberfeld, Germany Application December 26, 1952, Serial No. 328,141
Claims priority, application Germany December 31,'1951 7 Claims. 01. 260-2) No Drawing.
This invention relates to polycondensation, and more particularly to methods of'preparing polycondensates from bls-halogen substituted-carboxylic acid amides, as' well as the intermediates and end products obtained by the said methods. v
This application is a continuation-in-part of my copending application for U. S. Letters Patent Serial Number 299,734, filed July 18, 1952.
It is an object of this invention to prepare polycondensates from bis-halogen substituted-carboxylic acid amides which are eminently useful plastic materials.
It is another object of the presentinvention to treat bis-halogen substituted-carboxylic acid amides to obtain intermediates susceptible to polycondensation.
A still further object of the invention is to provide a variety of processes for converting bis-halogen substitutedcarboxylic acid amides intopolycondensates adapted for a variety of uses in the field of plastics.
, Yet another object of the invention is to devise methods of the kind referred to which eliminate decomposition 7 2,143,241 Patented Apr. 24, 1956 termediate products obtained in the first stage of the process, are treated by adding thereto from about 0.1 to about 3%, calculated on the weight of the intermediate product, of hydroxides, hydrosulfides or carbonates of alkali metals or alkali earth metals, thereafter melting the intermediate product with the said addition, under normal pressure while introducing nitrogen, and then heating in vacuo, to a temperature ranging from 100 to 250 C., and preferably within the range from 130 to 200 C. For reasons explained below, this procedure is the preferred embodiment of the invention.
The end products obtained in any of the several processes enumerated above are recovered as will be set out belowin detail, and are all useful as plastics.
If, for example, liquid ammonia is caused to act in the autoclave, at room temperature, for a period of up to 20 hours, on methylene-bis-chloropropionic acid amide, in the course of which treatment the pressure remains at about 8-10 mm, corresponding to this temperature, a corresponding monoamino compound of the following formula is obtained.
Cl, (CH2) 2.CO.NH.CH2.NH.CO. (CH2) 2.NH2
This compound has a melting point of 240 C. If this monoamine is treated in a vacuum of 0.5 mm. Hg, and at a temperature of 115 C. in a current of nitrogen, there is obtained while HCl is split oif quantitatively in the distillation vessel a light colored polycondensation product which is useful for the production of plastic masses.
and discoloration phenomena observed occasionally with 118.1.(0112) ..o o.NH.oH. H.o 04cm) mun wherein R stands for hydrogen, or an alkylor andgroup, Hal. stands for halogen, and n is an integer from 1 too, with liquid ammonia, in an autoclave and at normal or slightly elevated temperature. This first step of the treatment accordingto invention, yields intermediate products which are either monoor diamino compounds ofthe particular bis-halogen substituted-carboxylic acid amide used in the reaction. Their characteristics depend on the prevailing conditions of reaction.
The invention contemplates further treating the intermediate products obtained in the first stage of the process, by a second step with unlike the first step which is common to all embodiments ofthe invention, may be any one of a variety of procedures, as set out hereafter.
According to one embodiment of the invention, the intermediate product obtained in the first, stage may undergo further treatment by beingheated, in a current of nitrogen, at temperatures up to about 250 C.v
Another embodiment of the invention involves reacting the intermediate product obtained in the first stage, with an aliphatic or aromatic diearboxylic acid such as adipic acid, for example. i '7 According to another embodiment of the invention, the intermediate product is heated, in vacuo, above its melting point. p
In a still further embodiment of the invention, the m- If methylene-bis-chloropropionic acid amide is reacted in the autoclave, at a temperature of about 60 C., with liquid ammonia for a period of about 20 hours, a corresponding diamine is formed in accordance with the following equation Cl. (CH2) 2.CO.NH.CH2.NH.CO. (CH2) 2.Cl+2NH3- NHz. (CH2) 2.CO.NH.CH2.NH.CO. (CH2) 2.NH2+2HC1 The diamine thus obtained, which has a melting point of 140 C., can be condensed with adipic acid and yields a polycondensate having a linear structure. It is excellently suited for the production of plastic masses.
If 1nethylene-bis-chloropropionic acid amide is reacted, in the autoclave at normal temperature, with liquid ammonia for a period of about 20 hours, the monoamine of the formula Cl. (CH2)2.CO.NH.CH2.NH.CO. (CH2)2.NH2
and the melting point of 240 C., is obtained. A smail quantity of NaOH is added and the compound, with this addition, is molten under normal pressure While introducing nitrogen, whereupon it is heated in vacuo to a temperature of -140" C. HCl is split oif in the course ofthe condensation, and the light colored condensation product remaining in the distillation vessel is eminently suitable for use as a plastic.
The invention will'be more fully described by reference to the following specific examples. It should be understood, however, that the examples are given by way of illustration only and that the invention is not to be limited by the details set forth therein.
Example 1 200 grams of methylene-bis-chloropropionic acid amide are treated, in the autoclave and at normal temperature, with 1000 cc. of liquid ammonia. The reaction may last up to 20 hours. A homogeneous solution is formed which after evaporation of excessive ammonia, leaves a semisolid mass. After working down and purificationthere polycondensates particularly is obtained the corresponding monoamino compound of the following formula Cl.(CH2)2.CO.NH.CH2.NH.CO.(CH2) aNHz remaining in the distillation vessel when the reaction is completed, lends itself to the production of plastic masses. Example [I 200 grams of methylene-bis-chloropropionic acid amide and 1000 cc. of liquid ammonia are heated in the autoclave for up to hours at a pressure of up to about 20 atrn. and a temperature of about 60 C. A homogeneous liquid is formed. Upon evaporation of excessive ammonia and after removal of inorganic reaction products, a solid product is obtained which has a melting point of 140 C. and is the diamine of the methylene-bis-chloropropionic acid amide.
Thereafter, 188 grams of the diamine thus obtained, together with 146 grams of adipic acid, are heated with reflux in 2 liters of ethanol for 3 hours. When the reac tion is terminated and after suction filtering from a small residue of insoluble matter, the lightly colored condensation product is concentrated in vacuo. A polycondensate having a melting point of 2l5-220 C. is thus obtained.
Example III 20 grams of this compound are melted while introducing nitrogen at normal pressure, and thereafter are further condensed under reduced pressure (about 0.5 mm. Hg). After the reaction has proceeded for 3-5 hours there remains in the distillation vessel, a lightly colored polycondensation product which is eminently suitable for the manufacture of plastic materials.
Example IV 250 grams of methylene-bis-chloropropionic acid amide are treated with 1250 cc. of liquid ammonia for up to about 20 hours, at ordinary temperature, in the autoclave. A homogeneous solution results which on evaporation of the excess of ammonia, yields a semi-solid mass; When worked up and cleaned, this in turn yields a monoamino compound corresponding to the starting material and having a melting point of 240 C. 0.5 grams of solid NaOH are added to this intermediate product which is then molten, at normal pressure, while introducing nitrogen, and then heated in vacuum of 2 mm. Hg for a period of about 3 hours, to a temperature of about 130-140 C. In the course of condensation hydrochloric acid is split off. Once the reaction is completed there remains behind,
It is the i in the distillation vessel, a lightly colored condensation product which is eminently suited for the production of plastic masses.
Example V The. methylene-bis-chloropropionic acidamide of Example-IV is replaced by an identical quantity of methylenebis-bromopropionic acid amide, and treated. exactly as described inEXample 1V. Here also av lightly colored condensation product of excellent plastic properties is obtained.
Example V1 250 grams of ethylidene-bis-chloropropionic acid amide are treated with 1300 cc. of. liquid ammonia for up to about 20 hours, at room temperature, in the autoclave. A homogeneous solution results which after evaporation of any excessive ammonia, forms a semi-solid mass which is worked up and cleaned, to yield a monoamino compound corresponding to the starting material and having a melting point of 185-490" C. This compound, after 1 gram of solid NazCOs has been added thereto, is molten at normal pressure while introducing nitrogen, to be then heated in a vacuum of 2 mm. Hg. for 3 hours, to 130- 140 C. Hydrochloric acidis split off during the condensation. When the reaction is completed, a lightly .colored condensation product remains in the distillation vessel which is highly useful as aplastic material.
Example VII 50 grams of benzylidene-bis-bromopropionic acid amide of the formula are reacted with 200 cc. of liquid ammonia, at ordinary temperature and in the autoclave, for about 12 hours. A semi-solid mass is obtained which solidifies upon evaporation of excessive ammonia. This substance still contains ammonium bromide and therefore is thoroughly washed with water and, if desired, recrystallized once in methanol. 1 gram of solid calcium hydroxide is then added to this intermediate product which is molten at normal pressure, with a continuous supply of nitrogen. This is followed by heating in a vacuum of 0.5 mm. Hg, for 4-6 hours, to a temperature up to 200 C. In the course of heating HBr is split'otr'. The lightly colored condensation product obtained when the reaction is completed, has particular utility as a plastic.
Example VII is replaced by the same quantity of trichloroethylidene-bis-chloropropionic acid amide of the formula which is reacted and treated as described in- Example VII.
Lightly colored condensation products having excellent properties for use as plastics, are obtained.
Referring to the preferred embodiment of the invention illustrated by Examples IV to VIII, the temperature for the condensation, within the range of from about to about 250' C.,'and the preferred range from about to about 200 C., should not be raised substantially above the melting point of the products so as to avoid any risk of even slight decomposition and consequent discoloration which may be observed occasionally with some other method; Inasmuch as the melting points of the various compounds contemplated by the invention vary materially, the temperature must be varied accordingly so as to be best adapted for any particular compound. Additional examples of substances added to the intermediate products are 0.l"-0".5 gram'of NaSI-I, and a mixture of 0.05 gram of NaOH' and 0.3 gram ofCaCOs.
While the condensation products obtained according to any of the several methods described herein, are very good plastic materials, the condensation products yielded by the methodillustrated by Examples IV to VIII are particularly distinguished by being highly resistant to chemicals. readily susceptible to being dyed, and not exposed to even the slightest decomposition and discoloration phenomena. Besides, they share the advantageous characteristics of all condensation products obtained according to the invention, to wit: comparatively high softening or melting points and economic, simple mode of manufacture inasmuch as the starting materials are obtained readily and in excellent yields, for example from a single stage process reacting acrylonitrile, formaldehyde and HCl and HBr.
While I have disclosed several embodiments of my invention and several modes of carrying it into effect, it will be readily apparent to those skilled in the art that the invention as illustrated in the foregoing specification, is susceptible to numerous variations without departure from the spirit of the invention or sacrifice of the advantages thereof. Accordingly, the scope of the invention is to be understood as limited solely by the appended claims.
I claim:
1. The process of preparing a light colored condensation product of a mono-amine of the general formula wherein Hal means halogen, n is an integer from 1 to 6, and R is a member of the group consisting of H, CH3, and CsHs, which comprises reacting a bis-amide of the formula where Hal, n, and R have the same meanings, respectively, with one mol of liquid ammonia at room temperature to form the mono-amine, separating the mono-amine, maintaining the mono-amine in molten condition in a current of gaseous nitrogen at a temperature from about 130 to 200 C. in the presence of from 0.1 to 3.0 per cent of a member of the group consisting of the hydroxides, carbonates, and hydrosulfides of the alkali and alkaline earth metals, and then heating the mono-amine further under reduced pressure to effect condensation of the amine and elimination of hydrogen chloride.
2. The process of claim 1, wherein the current of nitrogen gas is at normal pressure.
3. The process of claim 1, wherein the heating of the mono-amine to effect condensation is carried out at a pressure of from 0.5 to 2.0 mm. mercury for a period of from 3 to 6 hours.
4. The process of claim 1, wherein the bis-amide is methylene-bis-chlorpropionic acid amide.
5. The process of claim 1, wherein the bis-amide is ethylidene-bis-chlorpropionic acid amide.
6. The process of claim 1, wherein the bis-amide is benzylidene-bis-bromopropionic acid amide.
7. The process of claim 1, wherein the bis-amide is trichloroethylidene-bis-chlorpropionic acid amide.
References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Marvel et al.: J. Am. Chem. Soc., vol. 68 (1946), pages 1681-1686.
Braun et al.: Ber. Deut. Chem, vol. 70, (1937), pages 994-1000.
Hackhs Chemical Dictionary, 3rd edition, 664 and 665.
1944, pages
Claims (1)
1. THE PROCESS OF PREPARING A LIGHT COLORED CONDENSATION PRODUCT OF A MONO-AMINE OF THE GENERAL FORMULA
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2743247X | 1951-12-31 |
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| US2743247A true US2743247A (en) | 1956-04-24 |
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| US328141A Expired - Lifetime US2743247A (en) | 1951-12-31 | 1952-12-26 | Method of polycondensation of alkylene-alkylidene- and aralkylidene-bishalogen substituted carboxylic acid amides |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2864684A (en) * | 1955-09-15 | 1958-12-16 | Monsanto Chemicals | Herbicides |
| US3213819A (en) * | 1965-02-19 | 1965-10-26 | May Griffith | Boundary layer control assembly |
| US3981716A (en) * | 1973-05-24 | 1976-09-21 | Stauffer Chemical Company | Gem-bis amide herbicide antidote compositions and methods of use |
| US3982923A (en) * | 1973-05-24 | 1976-09-28 | Stauffer Chemical Company | Gem-bis amide herbicide antidote compositions and methods of use |
| US4338428A (en) * | 1981-08-14 | 1982-07-06 | The Upjohn Company | Novel polyamides from ketene-aminals |
| US6365706B1 (en) | 2000-06-21 | 2002-04-02 | Mississippi Chemical Corporation | Process for production of polyasparagine and the high nitrogen content polymer formed thereby |
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| US2109929A (en) * | 1937-03-15 | 1938-03-01 | Du Pont | Preparation of amino acids |
| US2176896A (en) * | 1938-08-04 | 1939-10-24 | Albert K Epstein | Quaternary ammonium derivatives of amides |
| US2279497A (en) * | 1938-08-12 | 1942-04-14 | Chem Ind Basel | Asymmetrical condensation products and process of preparing same |
| US2293388A (en) * | 1939-11-21 | 1942-08-18 | Du Pont | Polyamides and their preparation |
| FR882106A (en) * | 1939-05-11 | 1943-05-18 | Ig Farbenindustrie Ag | Di-beta-chloropropionic diamides, diacrylic diamides, polymerization products thereof and process for the preparation thereof |
| US2338177A (en) * | 1938-10-14 | 1944-01-04 | Chem Ind Basel | Condensation product and process of making same |
| US2356702A (en) * | 1939-05-11 | 1944-08-22 | Schlack Paul | Process for the production of synthetic linear condensation polyamides |
| US2436363A (en) * | 1944-01-19 | 1948-02-17 | Marvel Carl Shipp | Aminoamide resins |
| US2537689A (en) * | 1948-04-15 | 1951-01-09 | Monsanto Chemicals | Polyamide resins |
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- 1952-12-26 US US328141A patent/US2743247A/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2109929A (en) * | 1937-03-15 | 1938-03-01 | Du Pont | Preparation of amino acids |
| US2176896A (en) * | 1938-08-04 | 1939-10-24 | Albert K Epstein | Quaternary ammonium derivatives of amides |
| US2279497A (en) * | 1938-08-12 | 1942-04-14 | Chem Ind Basel | Asymmetrical condensation products and process of preparing same |
| US2338177A (en) * | 1938-10-14 | 1944-01-04 | Chem Ind Basel | Condensation product and process of making same |
| FR882106A (en) * | 1939-05-11 | 1943-05-18 | Ig Farbenindustrie Ag | Di-beta-chloropropionic diamides, diacrylic diamides, polymerization products thereof and process for the preparation thereof |
| US2356702A (en) * | 1939-05-11 | 1944-08-22 | Schlack Paul | Process for the production of synthetic linear condensation polyamides |
| US2293388A (en) * | 1939-11-21 | 1942-08-18 | Du Pont | Polyamides and their preparation |
| US2436363A (en) * | 1944-01-19 | 1948-02-17 | Marvel Carl Shipp | Aminoamide resins |
| US2537689A (en) * | 1948-04-15 | 1951-01-09 | Monsanto Chemicals | Polyamide resins |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2864684A (en) * | 1955-09-15 | 1958-12-16 | Monsanto Chemicals | Herbicides |
| US3213819A (en) * | 1965-02-19 | 1965-10-26 | May Griffith | Boundary layer control assembly |
| US3981716A (en) * | 1973-05-24 | 1976-09-21 | Stauffer Chemical Company | Gem-bis amide herbicide antidote compositions and methods of use |
| US3982923A (en) * | 1973-05-24 | 1976-09-28 | Stauffer Chemical Company | Gem-bis amide herbicide antidote compositions and methods of use |
| US4338428A (en) * | 1981-08-14 | 1982-07-06 | The Upjohn Company | Novel polyamides from ketene-aminals |
| US6365706B1 (en) | 2000-06-21 | 2002-04-02 | Mississippi Chemical Corporation | Process for production of polyasparagine and the high nitrogen content polymer formed thereby |
| US6562941B2 (en) | 2000-06-21 | 2003-05-13 | Mississippi Chemical Corporation | Process for production of polyasparagine and the high nitrogen content polymer formed thereby |
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