GB651315A - Improvements in and relating to processes for the polymerisation of ethylenically unsaturated compounds - Google Patents
Improvements in and relating to processes for the polymerisation of ethylenically unsaturated compoundsInfo
- Publication number
- GB651315A GB651315A GB17157/48A GB1715748A GB651315A GB 651315 A GB651315 A GB 651315A GB 17157/48 A GB17157/48 A GB 17157/48A GB 1715748 A GB1715748 A GB 1715748A GB 651315 A GB651315 A GB 651315A
- Authority
- GB
- United Kingdom
- Prior art keywords
- alpha
- carbamylazo
- methyl
- gamma
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Polymers or copolymers of an ethylenically unsaturated organic compound are made by polymerizing in the presence of a carbamylazo compound, e.g. one containing the group H2N.CO.N=N-. Preferred compounds have the formula H2N.CO.N=N.CA.R.R1, where A is a nitrile or carbamyl or carbalkoxy group in which the alkyl group contains from one to six carbon atoms and R and R1 are aliphatic, cycloaliphatic or aromatic radicals, or radicals which together form a cycloaliphatic ring. Specified monomers are ethylene, isobutylene, styrene, butadiene; vinyl chloride, vinyl fluoride, vinyl acetate, vinyl propionate, vinylidene chloride and fluoride; vinyl butyl ether, methyl vinyl ketone; acrylonitrile, methyl methacrylate, methacrylamide; tetrafluorethylene, trifluorochloroethylene 1,1-difluoro-2,2-dichloroethylene; monovinylacetylene; tetraethylene glycol dimethacrylate, diallyl diglycollate, diallyl carbonate, diallyl phthalate, ethylene bis-(allyl maleate); chloroprene and fluoroprene and esters and anhydrides of maleic and fumaric acid. Specified carbamylazo compounds are alpha-(carbamylazo)-isobutyramide, methyl alpha - (carbamylazo) - isobutyrate, n-hexyl alpha-(carbamylazo)-isobutyrate, alpha-(carbamylazo) - alpha - methylenanthronitrile, alpha - (carbamylazo) - alpha - phenylpropionitrile; alpha - (carbamylazo) - alpha, cyclopropylpropionitrile; alpha - (carbamylazo) - cyclohexanecarbonitrile, alpha - (carbamylazo) - alpha, gamma - dimethylvaleramide, methyl alpha - (carbamylazo) - alpha, gamma-dimethylvalerate, alpha - (carbamylazo) - alpha, alpha1 - dicylohexylacetonitrile. The polymerization may be effected in bulk, or solution, e.g. in water, tertiary butyl alcohol, benzene, cyclohexane or using granular or emulsion techniques. High pressure and increased temperature may be used. Polyvinyl alcohol may be prepared from polyvinyl acetate produced by the process by alkaline methanolysis. Specifications 622,374, 623,472, 626,155, 631,225, 634,757, 641,679 and 649,934, are referred to.ALSO:Compounds containing a carbamylazo group, i.e H2N.CON=N- and preferably conforming to the general formula H2N.CON=N.CA.RR1, where A is a nitrile or carbamyl or carbalkoxy group in which the alkyl group contains from one to six carbon atoms and R and R1 are aliphatic, cycloaliphatic or aromatic radicals are suitable for use as polymerization catalysts. The compounds may be made by adding hydrogen cyanide to the semicarbazone of a ketone, and oxidizing the resulting nitrile with potassium permanganate. Following this procedure alpha-(carbamylazo) isobutyronitrile is made from acetone, alpha-(carbamylazo)-alpha-cyclopropylpropionitrile M.P. 61-63 DEG C. from methyl cyclopropyl ketone, alpha-(carbamylazo)-alpha, gamma-dimethylvaleronitrile M.P. 42 DEG to 46 DEG C. from methyl isobutyl ketone and carbamyloazo - 1 - cyclohexanecarbonitrile M.P. 135 DEG C. from cyclohexanone. If desired, the nitrile groups of the carbamylazonitriles may be converted to carbalkoxy groups by reacting with alcoholic hydrogen chloride followed by mild hydrolysis and the carbalkoxy groups converted to amide groups by reaction with ammonia. Other specified carbamylazo compounds are alpha-(carbamylazo)-isobutyramide, methyl alpha - (carbamylazo) - isobutyrate, n-hexyl alpha-(carbamylazo)-isobutyrate, alpha-(carbamylazo) - alpha - methyleneanthronitrile, alpha - (carbamylazo) - alpha - phenylpropionitrile; alpha - (carbamylazo) - alpha, gamma - dimethylvaleramide, methyl alpha-(carbamylazo) - alpha, gamma dimethylvalerate, and alpha - (carbamylazo) - alpha, alpha1-dicyclohexylacetonitrile. Specifications 622,374, 623,472, 626,155, 631,225, 634,757, 641,679, [all in Group IV (a)], and 649,934 are referred to.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US651315XA | 1947-06-27 | 1947-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB651315A true GB651315A (en) | 1951-03-14 |
Family
ID=22060543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB17157/48A Expired GB651315A (en) | 1947-06-27 | 1948-06-25 | Improvements in and relating to processes for the polymerisation of ethylenically unsaturated compounds |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB651315A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4112211A (en) * | 1975-05-28 | 1978-09-05 | Hoechst Aktiengesellschaft | Process for the manufacture of homo- and copolymers of tetrafluoroethylene employing as the reducing agent in the redox catalyst an ayodicarboxylic acid, salt of ayocarboxylic acid, azodicarbonamide, or mixtures thereof |
| CN113248663A (en) * | 2021-07-05 | 2021-08-13 | 北京金隅水泥节能科技有限公司 | Early-strength functional monomer, early-strength polycarboxylate superplasticizer and preparation method thereof |
-
1948
- 1948-06-25 GB GB17157/48A patent/GB651315A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4112211A (en) * | 1975-05-28 | 1978-09-05 | Hoechst Aktiengesellschaft | Process for the manufacture of homo- and copolymers of tetrafluoroethylene employing as the reducing agent in the redox catalyst an ayodicarboxylic acid, salt of ayocarboxylic acid, azodicarbonamide, or mixtures thereof |
| CN113248663A (en) * | 2021-07-05 | 2021-08-13 | 北京金隅水泥节能科技有限公司 | Early-strength functional monomer, early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN113248663B (en) * | 2021-07-05 | 2022-03-18 | 北京金隅水泥节能科技有限公司 | Early-strength functional monomer, early-strength polycarboxylate superplasticizer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2520338A (en) | Azo compounds containing carboxyl and cyano groups | |
| US2383055A (en) | Polymerization of conjugated dienes | |
| US2594560A (en) | Low-temperature polymerization of ethylenic compounds using as initiators compositions comprising sodium azide and an oxidant | |
| GB893472A (en) | A process for the polymerisation of unsaturated compounds | |
| US2746944A (en) | Process for preparing vinyl halide copolymers and copolymers produced thereby | |
| GB723921A (en) | Process and catalyst for polymerizing halogen-substituted ethylenes | |
| US2847402A (en) | High pressure homopolymerization and interpolymerization of vinylene carbonate | |
| GB590816A (en) | Polymerisation products of ethylene | |
| GB690937A (en) | A process for copolymerising unsaturated monomers and the copolymers produced thereby | |
| US2846418A (en) | Process for the production of polymerisation products | |
| US3420807A (en) | Vinyl chloride polymerization | |
| US2519135A (en) | Polymerization process | |
| GB651315A (en) | Improvements in and relating to processes for the polymerisation of ethylenically unsaturated compounds | |
| US3249595A (en) | Aqueous emulsion polymerization process employing water-soluble peroxides | |
| US3222327A (en) | Peroxide catalysts and polymerization processes employing the same | |
| US2820026A (en) | Manufacture of fluorine containing polymers | |
| GB852611A (en) | Process for polymerizing vinyl compounds | |
| US2380591A (en) | Amino acids in emulsion polymerization | |
| US2717248A (en) | Polymerization of vinyl chloride with monopermalonate catalyst | |
| US2847401A (en) | Interpolymers of vinylene carbonate with halo-substituted ethylenes | |
| GB948998A (en) | Epoxy-containing copolymers | |
| US2581925A (en) | 1, 1-dichlorobutadiene-1, 3, its preparation and polymers | |
| US2457873A (en) | Vulcanizable copolymers of acrylonitrile, butadiene and maleic esters | |
| US2437421A (en) | Vulcanizable copolymers of acrylonitrile, butadiene, and vinyl ethers | |
| US4379901A (en) | Polyfluoroallyl ethers and their production and use |