GB2102426A - Process for the preparation of methacrylamide or acrylamide - Google Patents
Process for the preparation of methacrylamide or acrylamide Download PDFInfo
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- GB2102426A GB2102426A GB08222015A GB8222015A GB2102426A GB 2102426 A GB2102426 A GB 2102426A GB 08222015 A GB08222015 A GB 08222015A GB 8222015 A GB8222015 A GB 8222015A GB 2102426 A GB2102426 A GB 2102426A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/09—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/30—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by doubly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/68—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D521/00—Heterocyclic compounds containing unspecified hetero rings
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for the preparation of N-substituted amides of acrylic or methacrylic acid, wherein acrylic or methacrylic acid is reacted with the amine according to the following procedure: in a first step, the acid is reacted with the amine in a homogeneous phase, at about 75- 140 DEG C, and in a second step condensation is effected, with elimination of the water formed, at about 150-250 DEG C.
Description
SPECIFICATION
Process for methacrylamide or acrylamide preparation
The invention relates to a process for methacrylamide or acrylamide preparation and in particular to the preparation of industrially useful amides of acrylic and methacrylic acid by processes which start with readily obtainable starting materials.
Starting materials which are easily obtained include, for example, the nitriles and esters of acrylic and methacrylic acid and the acids themselves.
The reaction of organic carboxylic acids with alkylamines to form the alkylamides of the carboxylic acids, at temperatures of above 1000C and below 3500C, particularly at between 1 50 and 2500 C, has already been proposed in U.S. Patent No. 1 986 854. The amine is preferably in gaseous form and is added at atmospheric pressure to the acid which is in a molten state and the amide formed is removed from the reaction mixture by vacuum distillation. The amine should be added in a slight excess over the stoichiometric quantity required.
In U.S. Patent No. 2719177 it was shown that, using the process of U.S. Patent No. 1986854, for example, with dimethylamine as the gaseous amine component and acrylic acid in the molten state, no N,N-dimethylacrylamide is formed. Instead, U.S. Patent No. 2719177 discloses that a continuous gas phase reaction may be effected in a temperature range of between 250 and 5500C on dehydration catalysts. It states that it is advantageous to carry out the reaction on catalysts containing aluminium oxide, with retention times of between 1 and 7 seconds. The ratio of acid to amine is within the range from 1:1 to 1:2.5.
Similarly, a reaction in the gaseous phase with acrylic or methacrylic acid and primary or secondary aliphatic or aromatic amines at above 1 500C is discussed in German Auslegeschrift 1 043 320, using catalysts with a water-cleaving effect, containing phosphoric acid or phosphate.
When N,N-dialkyl-alkylenediamines are reacted with methacrylic acid, the stage in which the
Michael adduct, i.e. in this case N-(dialkylaminoalkyl)-2-methyl-p-alanine, is formed is deliberately included in the course of the reaction (U.S. Patent No. 3652671). The formation of the Michael adduct should thus occur at 1 00-1 500 C, and the subsequent elimination reaction to obtain the methacrylamide should be effected at temperatures of up to 2300 C, preferably at between 1 80 and 2200 C, with the exclusion of oxygen. The corresponding reaction with acrylic acid, on the other hand, gave totally unsatisfactory results.
The processes known from the prior art therefore leave much to be desired in various respects.
Either they are carried out as gas phase reactions at relatively high temperatures in the presence of catalysts or they are restricted to the thermal decomposition of certain types of Micheal adducts.
A problem therefore existed in providing a generally applicable process, starting from acrylic or methacrylic acid, for obtaining N-substituted acrylamides or methacrylamides as economically as possible, which is satisfactory in terms of both the quality of the product and the yield.
We have now found that N-substituted amides of acrylic and/or methacrylic acid, can be obtained in yields and at qualities which are largely satisfactory by a process in which a first step the acrylic or methacrylic acid is reacted in a homogeneous phase with the amine in stoichiometric quantities up to a small excess of the amine, at 75--1400C, under normal pressure, and in a second step condensation is effected at 150--2500C, with elimination of the water. Following the condensation reaction the product is generally worked up.
According to one aspect of the invention we provide a process for the preparation of an Nsubstituted amide of acrylic or methacrylic acid which process comprises reacting acrylic or methacrylic acid in a homogeneous phase with a primary or secondary amine at temperatures of from about 75 to 1 400C, suitably at substantially atmospheric pressure, and, in a subsequent condensation step, eliminating water at a temperature of from about 150 to 2500C.
The process of the invention is particularly suitable for the preparation of acid amides of formula (I)
wherein R, represents a hydrogen atom or a methyl group;
R2 represents a hydrogen atom or a saturated or unsaturated, optionally branched, optionally substituted, alkyl group or an optionally substituted aryl group; and
R3 represents a saturated or unsaturated, optionally substituted, optionally cyclic, alkyl group or an optionally substituted aryl or aralkyl group or an alkenylcarboxamidoalkyl- or alkenylcarboxamidoaryl-group; or the group -NR2R3 represents a heterocyclic ring bounded at a nitrogen atom, in which an acid of formula (II)
wherein R, is as hereinbefore defined, is reacted with an amine of formula (III)
wherein R2 and R3 are as hereinbefore defined, according to the following procedure: in a first step, in a homogeneous phase of the acid of formula II is reacted with the amine of formula (III), preferably in stoichiometric quantities, up to a slight excess of the amine, at about 7 5--1 40 OC, preferably 80 to 1300C, under substantially atmospheric pressure; and in a second step condensation is effected, with removal of the water formed, at about 1 50--2 500C, preferably 1 60--2400 C.
For working up, the unreacted acid of formula (II) and the Michael adduct of the amine with the "B-unsaturated acid are preferably converted with a suitable base, such as calcium oxide, calcium carbonate, potassium hydroxide or sodium hydroxide, for example, to form the salts thereof and then the amide of formula (I) is preferably obtained from the reaction mixture by distillation.
Generally, the desired product of formula (I) is the lower-boiling fraction, whilst the higher-boiling fractions contain the Michael adduct of the amine with the a,P-unsaturated acid or the n,- unsaturated amide.
The definition of the substituent R2 in the amine of formula (III) includes a saturated or unsaturated, optionally branched, optionally substituted alkyl group with 1 to 18 carbon atoms, or an optionally substituted aryl group, more particularly a phenyl or naphthyl group, whilst the definition of
R3 includes a saturated or unsaturated, optionally substituted, optionally cyclic alkyl group with 1 to 18 carbon atoms or an aralkyl group or an optionally substituted aryl group, more particularly a phenyl or naphthyl group or the group -NR2R3 may together represent a heterocyclic ring bonded at the nitrogen atom and optionally containing as further heteroatoms one or more nitrogen, oxygen or sulphur atoms.
Examples of substituents which the groups R2 and R3 may in turn contain include, in particular, carboxy, alkoxycarbonyl (alkyl)-carbamoyl, sulpho, sulphonamido and especially (aikyl)-amino group. If the substituents contain alkyl or alkylene groups, these are preferably alkyl or alkylene groups with 1 to 6 carbon atoms.The amines of formula (III) may include compounds of the narrower formula formula (Ill)'
wherein R3 is as hereinbefore defined; A represents a (CR4R5) group or a cyclohexylene, phenylene or naphthylene group, in which R4 represents a hydrogen atom a C1~6 alkyl group or a phenyl group, R5 represents a hydrogen atom or a Cis alkyl group and n represents an integer from 1 to 18 and X represents a hydrogen atom or group O0H, -C0NR6R7, -000 R5, -SO3H, - SO2NR6R7 or NR6R7, group in which R6 and R7 and R'6 and R'7 independently of one another represent hydrogen atoms or C,~6 alkyl groups with the proviso that if X represents -NR6,R7,, n represents an
integer of from 2 to 18; or A and X together represent an allyl, alkenylcarboxamido alkyl for alkenylcarboxamide-aryl group.
The amines of formula (III) thus include, for example, amino acids, the esters and amides thereof, such as glycine and alanine, and alkenediamines, for example, ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, neopentylenediamine and dimethylaminoneopentylamine and sarcosine. If compounds of formula (Ill) which contain a second primary or secondary amino group, e.g. alkylenediamines, are used within the scope of this invention, a reaction with two molecules of the cr,-unsaturated acid of formula (II) is possible. This type of reaction to form a bis-amido compound is also included in the protection sought.
It is particularly preferred to effect the reaction starting from compounds of methacrylic acid (R,=methyl) and from compounds of formula (III) wherein R2 does not represent hydrogen, and to effect a reaction, starting from acylic acid (R1=hydrogen), with the amines of formula (Ill), and to react both types of starting compound of formula (II) with unsaturated amines of formula (III), particularly the allylamine and the diallylamine.
These reactions have proved particularly advantageous since the alternative methods of preparing the end products of formula (I) present problems or do not produce a sufficiently pure product or have low yields or are generally uneconomical.
Reaction with branched alkylamines of formula (III), for example isopropylamine, is also particularly advantageous. The reaction of the components of formula (II) and (Ill) is preferably effected with a ratio of 1 mole of acid to 1.2 mole of amine.
To prevent polymerisation losses, it is advisable to carry out the reaction and work up the reaction product in the presence of polymerisation inhibitors such as, for example, phenothiazine, hydroquinone, aromatic diamines such as, for example, N,N'-diphenyl-p-phenylenediamine, iron compounds such as
iron (III) acetylacetonate, and copper compounds such as copper oleate (vide. German
Offenlegungsschrift 2 809 102).
In the reaction according to the invention carried out under substantially atmospheric pressure, there are at least two distinct reaction steps, which are characterised by a specific temperature level. In the first step, which generally takes place at between 750C and 1 400C, preferably between 800C and 1 300C, it can be assumed that some of the amine is added to the a,-unsaturated acid of formula (II).
It appears to be particularly important that the reaction in this first step should be effected in a homogeneous phase; in other words, there should be no crystal slurry.
The reaction may be effected in the presence of one or more solvents, such as xylene, mesitylene, isobutylbenzene, diisoamylether, dichlorobenzene, Decalin, cresol, 1-bromo-4-chlorobenzene, nitrobenzene, resorcinol diethyl ether, but is preferably carried out without a solvent. In the first phase of the reaction, as a rule, the acid is mixed with the amine, preferably in the presence of the stablising agents. The duration of the reaction naturally depends on the quantity of mixture. As a guide, it may be from half an hour to about two and a half hours.
In a transitional phase, the reaction mixture is heated to the temperature of the second step of the reaction, i.e. to about 1 650C, whilst conveniently a weak current of gas, e.g. nitrogen, is passed through in order to remove the water forming during the condensation. The reaction is continued, possibly with the introduction of a gas, at the temperature of the second step of the reaction, whilst the temperature may be left within the range 160-1 800 C, suitably at 1 650C, for some hours, e.g. for more than 3 hours. In the second stage of the reaction, the water formed is conveniently eliminated by distillation. To complete the reaction, the mixture may finally be heated to a higher temperature, for example to about 2300C.
Alternatively, after the amine has been added, the reaction mixture may be heated gradually, i.e.
over a period of some hours (e.g. three hours), from about 1 650C to the upper temperature used, i.e. to the range from 210 to 2300C. However, excessively long treatment at temperatures above 2100C should be avoided.
At the beginning of the working up, it is advisable to bind any acid still present, for example by adding suitable bases such as calcium oxide, calcium hydroxide, potassium hydroxide or the like.
The desired amides of formula (I) are preferably isolated by fractional distillation, more particularly vacuum distillation. Working up by flash vacuum distillation or using a thin layer evaporator has also proved satisfactory. The lower-boiling components are generally the desired amides, whilst the high-boiling components are any remaining Michael adducts with the unsaturated acids of formula (Il) or the unsaturated amides of formula (I).
The following Examples serve to illustrate the process according to the invention. Percentages are by weight unless otherwise specified.
Examples
Example 1
In a 1 litre four-necked flask, 4 mol of methacrylic acid, 2 g of phenothiazine and 0.5 g of hydroquinone were mixed with 4 mol of n-hexylamine at 900C over 45 minutes. Under a weak current of nitrogen (as water entrainer) the reaction mixture was then heated to 1 650C, kept at this temperature for three hours and the water of reaction thus formed was distilled off. The temperature at the bottom was then increased to 2300C whilst at the same time more water was eliminated.
Fractional distillation of the reaction mixture in vacuo produced N-hexyl-methacrylic acid amide in a 72% yield.
Examples 2-5 Methacrylic acid was reacted with various amines in the presence of 50 ppm of hydroquinone and 500 ppm of iron (III) acetylacetonate or copper oleate as stabilisers, in a manner analogous to that of Example 1. The yields of the N-substituted methacrylamides obtained are listed in Table 1.
Any unreacted methacrylic acid can readily be bound as a salt (e.g. with CaO or KOH) before the distillation, and in this way the methacrylamides formed can very easily be isolated in extremely pure form by distillation.
Table 1
Feed Reaction Yield of
Example Amine of temp. time at amide
No. Formula II ( C) 165-230 OC (h) (% of theory)
2 Methylamine 100 3 57
3 Isopropyiamine 130 10 75
4 Allylamine 110 6 58
5 Diallylamine 120 20 31
Example 6
9 mol of acrylic acid, 24 g of iron (III) acetylacetonate and 2 g each of hydroquinone monomethylether, phenothiazine and N,N'-diphenyl-p-phenylenediamine at 1 10--1300C were mixed with 9 mol of dimethylaminopropylamine. After all this latter compound had been added (2 h) the mixture was heated from 1 65 OC to 2 1 5 OC for 3 hours and the water formed was distilled off.The reaction mixture was fractionally distilled in vacuo. Yield of N-(dimethylaminopropyl)-acrylic acid amide: 53% of theory.
Examples 7-9 2 mol of acrylic acid were heated to 800C with 5 g of iron (III) acetylacetonate and 0.5 g of phenothiazine and at 80 to 1 200C 2 mol of aniline were added within 30 minutes. The reaction mixture was then heated to from 1 60 to 240 C within 4 hours and the water of reaction formed was distilled off Acrylic acid anilide was isolated in a 42% yield.
The same reaction in the presence of 0.1 mol of lithium hydroxide (Example 8) gave a yield of 46% of theory and the same reaction in the presence of 0.1 mol of aluminium isopropoxide (Example 9) gave a yield of 44% of theory.
Example 10
4 mol of methacrylic acid, 5 g of copper oleate and 0.5 g of hydroquinone were placed in 1 litre of mesitylene and, at 750C, 4 mol of allylamine were added within 10 minutes. The water of reaction formed was then eliminated azeotropically (in admixture with methacrylic acid and some amine) at boiling temperature (bottom temperature: 160-1 650C). After 5 hours' reaction, 40% of theory of Nallylmethacrylamide had formed.
Example 11
Methacrylic acid was reacted with methylamine in a manner analogous to Example 2 and the product was worked up by flash vacuum distillation to produce N-methylmethacrylic acid amide in a 65% yield.
Claims (12)
1. A process for the preparation of an N-substituted amide of acrylic or methacrylic acid which process comprises reacting acrylic or methacrylic acid in a homogeneous phase with a primary or secondary amine at a temperature of from about 75 to 1 400C and, in a subsequent condensation step, eliminating water at temperatures of from about 1 50 to 2500C.
2. A process as claimed in claim 1 wherein the reaction in the said homogeneous phase is effected under substantially atmospheric pressure.
3. A process for the preparation of acid amides of formula (I)
wherein R, represents a hydrogen atom or a methyl group;
R2 represents a hydrogen or a saturated or unsaturated, optionally branched, optionally substituted, alkyl group or an optionally substituted aryl group; and
R3 represents a saturated or unsaturated, optionally substituted, optionally cyclic, alkyl group or an optionally substituted aryl or aralkyl group or an alkenylcarboxamido-alkyl- or alkenylcarboxamidoaryl-group; or the group -NR2R3 together represents a heterocyclic ring bonded at a nitrogen atom, in which an acid of formula (II)
wherein R1 is as hereinbefore defined, is reacted with an amine of formula (Ill)
(wherein R2 and R3 are as hereinbefore defined) according to the following procedure: in a first step, in a homogeneous phase the acid of formula (II) is reacted with the amine of formula (III) at about 75 140 C, under substantially atmospheric pressure; and in a second step condensation is effected, with removal of the water formed, at about 1 50--2500C.
4. A process as claimed in either of claims 1 or 2 wherein the said primary or secondary amine is an amine of formula (II) as defined in claim 3.
5. A process as claimed in either of claims 3 and 4 wherein, at least one of the substituents R2 and R3 in the amine of formula (III) represents an unsaturated alkyl group.
6. A process as claimed in any one of claims 3 to 5 wherein at least R2 in the amine of formula (III) represents an allyl group.
7. A process as claimed in any one of claims 3 to 6 wherein R2 and R3 represent allyl groups.
8. A process as claimed in any one of claims 3 to 6 wherein at least one of the substituents R2 and R3 in the amine of formula (III) represents a branched alkyl group.
9. A process as claimed in claim 8 wherein at least one of the substituents R2 and R3 represents an isopropyl group.
10. A process as claimed in either of claims 3 and 4 wherein R2 is the amine of formula (III) represents hydrogen atom and R3 represents a Cio alkyl group.
11. A process as claimed in claim 10, wherein R2 in the amine of formula (Ill) is a hydrogen atom and R3 represents a methyl group.
12. A process as claimed in any one of the preceding claims wherein the said acid and the said amine are reacted together in from substantially stoichiometric quantities to quantities wherein the said amine is in slight excess.
1 3. A process as claimed in any one of the preceding clairns wherein following the condensation step the unreacted acid is converted with a base to the salt thereof and subsequently the N-substituted acid amide product is recovered from the reaction mixture by distillation.
1 4. A process as claimed in any one of the preceding claims carried out in the presence of polymerisation inhibitors.
1 5. A process for the preparation of an N-substituted amide of acrylic or methacrylic acid substantially as herein described in any one of Examples 1 to 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813130508 DE3130508A1 (en) | 1981-08-01 | 1981-08-01 | "METHOD FOR PRODUCING METHACRYL AND ACRYLAMIDES" |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2102426A true GB2102426A (en) | 1983-02-02 |
| GB2102426B GB2102426B (en) | 1985-08-21 |
Family
ID=6138360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08222015A Expired GB2102426B (en) | 1981-08-01 | 1982-07-30 | Process for the preparation of methacrylamide or acrylamide |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5826849A (en) |
| DE (1) | DE3130508A1 (en) |
| FR (1) | FR2510564A1 (en) |
| GB (1) | GB2102426B (en) |
| IT (1) | IT1156478B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008054612A1 (en) * | 2008-12-15 | 2010-06-17 | Evonik Röhm Gmbh | Process for the preparation of N-isopropyl (meth) acrylamide |
| US7906596B2 (en) | 2005-04-22 | 2011-03-15 | Basf Se | Processes for enzymatic synthesis of poly(oxyalkylene)acrylamides |
| EP2664611A1 (en) * | 2009-05-01 | 2013-11-20 | Idemitsu Kosan Co., Ltd | Method for producing alpha,beta-unsaturated carboxylic acid-N,N-disubstituted amide and method for producing 3-alkoxycarboxylic acid-N,N-disubstituted amide |
| CN112789341A (en) * | 2018-10-05 | 2021-05-11 | 日本曹达株式会社 | Adhesive composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3209800C2 (en) * | 1982-03-18 | 1990-03-08 | Chemische Fabrik Stockhausen GmbH, 4150 Krefeld | Process for the preparation of N- (tert. Aminoalkyl) acrylamides |
| JP2005060302A (en) * | 2003-08-12 | 2005-03-10 | Sumitomo Chemical Co Ltd | Method for producing n-methacryloyl-4-cyano-3-trifluoromethylaniline and method for stabilizing the same |
| US8445723B2 (en) * | 2008-08-19 | 2013-05-21 | Nalco Company | Processes for producing N-alkyl (alkyl)acrylamides |
| JPWO2022249994A1 (en) * | 2021-05-28 | 2022-12-01 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1986854A (en) * | 1931-10-24 | 1935-01-08 | Du Pont | Cellulose derivative compositions |
| US2719177A (en) * | 1953-03-18 | 1955-09-27 | Eastman Kodak Co | N-substituted acrylamides by vapor phase method using acrylic acids |
| DE1043320B (en) * | 1955-07-05 | 1958-11-13 | Basf Ag | Process for the production of acrylic acid amides substituted on nitrogen |
| GB1519112A (en) * | 1977-01-04 | 1978-07-26 | Shostkin Z Khim Reaktivov | Method of preparing dimethylacetamide |
| DE2809102C2 (en) * | 1978-03-03 | 1986-12-04 | Röhm GmbH, 6100 Darmstadt | Process for the preparation of α, β-unsaturated carboxamides |
| DE2941023A1 (en) * | 1979-10-10 | 1981-04-23 | Hoechst Ag, 6000 Frankfurt | METHOD FOR THE CONTINUOUS PRODUCTION OF DI-ACETYLENEDIAMINE |
-
1981
- 1981-08-01 DE DE19813130508 patent/DE3130508A1/en active Granted
-
1982
- 1982-06-11 FR FR8210190A patent/FR2510564A1/en active Granted
- 1982-07-19 IT IT67924/82A patent/IT1156478B/en active
- 1982-07-30 JP JP57132311A patent/JPS5826849A/en active Granted
- 1982-07-30 GB GB08222015A patent/GB2102426B/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7906596B2 (en) | 2005-04-22 | 2011-03-15 | Basf Se | Processes for enzymatic synthesis of poly(oxyalkylene)acrylamides |
| DE102008054612A1 (en) * | 2008-12-15 | 2010-06-17 | Evonik Röhm Gmbh | Process for the preparation of N-isopropyl (meth) acrylamide |
| EP2664611A1 (en) * | 2009-05-01 | 2013-11-20 | Idemitsu Kosan Co., Ltd | Method for producing alpha,beta-unsaturated carboxylic acid-N,N-disubstituted amide and method for producing 3-alkoxycarboxylic acid-N,N-disubstituted amide |
| US8748659B2 (en) | 2009-05-01 | 2014-06-10 | Idemitsu Kosan Co., Ltd. | Method for producing alpha,beta-unsaturated carboxylic acid-N,N-disubstituted amide and method for producing 3-alkoxycarboxylic acid-N,N-disubstituted amide |
| CN112789341A (en) * | 2018-10-05 | 2021-05-11 | 日本曹达株式会社 | Adhesive composition |
| US20210347726A1 (en) * | 2018-10-05 | 2021-11-11 | Nippon Soda Co., Ltd. | Adhesive composition |
| US11834390B2 (en) * | 2018-10-05 | 2023-12-05 | Nippon Soda Co., Ltd. | Adhesive composition |
| CN112789341B (en) * | 2018-10-05 | 2024-03-08 | 日本曹达株式会社 | Adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2102426B (en) | 1985-08-21 |
| IT8267924A0 (en) | 1982-07-19 |
| FR2510564B1 (en) | 1985-04-19 |
| FR2510564A1 (en) | 1983-02-04 |
| JPH039897B2 (en) | 1991-02-12 |
| JPS5826849A (en) | 1983-02-17 |
| DE3130508A1 (en) | 1983-02-17 |
| DE3130508C2 (en) | 1990-04-05 |
| IT1156478B (en) | 1987-02-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19920730 |