GB971170A - Process for producing dimers and polymers of acetylenic compounds - Google Patents
Process for producing dimers and polymers of acetylenic compoundsInfo
- Publication number
- GB971170A GB971170A GB11739/61A GB1173961A GB971170A GB 971170 A GB971170 A GB 971170A GB 11739/61 A GB11739/61 A GB 11739/61A GB 1173961 A GB1173961 A GB 1173961A GB 971170 A GB971170 A GB 971170A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acetylenic
- cuprous salt
- amines
- butyne
- oxygen
- 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
- 150000001875 compounds Chemical class 0.000 title abstract 13
- 229920000642 polymer Polymers 0.000 title abstract 6
- 239000000539 dimer Substances 0.000 title 1
- 150000003839 salts Chemical class 0.000 abstract 9
- 239000002904 solvent Substances 0.000 abstract 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 6
- 150000002170 ethers Chemical class 0.000 abstract 6
- 239000001301 oxygen Substances 0.000 abstract 6
- 229910052760 oxygen Inorganic materials 0.000 abstract 6
- -1 ethynylpyridines Chemical compound 0.000 abstract 5
- 229930195733 hydrocarbon Natural products 0.000 abstract 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract 4
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 3
- 239000002253 acid Substances 0.000 abstract 3
- 150000001298 alcohols Chemical class 0.000 abstract 3
- 125000001931 aliphatic group Chemical group 0.000 abstract 3
- 150000001408 amides Chemical class 0.000 abstract 3
- 150000001412 amines Chemical class 0.000 abstract 3
- 229910052786 argon Inorganic materials 0.000 abstract 3
- 229910052799 carbon Inorganic materials 0.000 abstract 3
- 239000002738 chelating agent Substances 0.000 abstract 3
- 229910052802 copper Inorganic materials 0.000 abstract 3
- 239000010949 copper Substances 0.000 abstract 3
- 150000002148 esters Chemical class 0.000 abstract 3
- 239000011521 glass Substances 0.000 abstract 3
- 239000001307 helium Substances 0.000 abstract 3
- 229910052734 helium Inorganic materials 0.000 abstract 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 abstract 3
- 150000002576 ketones Chemical class 0.000 abstract 3
- 239000000203 mixture Substances 0.000 abstract 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract 3
- 239000011541 reaction mixture Substances 0.000 abstract 3
- 230000000630 rising effect Effects 0.000 abstract 3
- 150000003512 tertiary amines Chemical class 0.000 abstract 3
- PNXLPYYXCOXPBM-UHFFFAOYSA-N 1,3-diethynylbenzene Chemical compound C#CC1=CC=CC(C#C)=C1 PNXLPYYXCOXPBM-UHFFFAOYSA-N 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 abstract 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 230000001427 coherent effect Effects 0.000 abstract 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract 2
- CBYDUPRWILCUIC-UHFFFAOYSA-N 1,2-diethynylbenzene Chemical compound C#CC1=CC=CC=C1C#C CBYDUPRWILCUIC-UHFFFAOYSA-N 0.000 abstract 1
- ISJIEPHLMCICPJ-UHFFFAOYSA-N 1,2-diethynylnaphthalene Chemical class C1=CC=CC2=C(C#C)C(C#C)=CC=C21 ISJIEPHLMCICPJ-UHFFFAOYSA-N 0.000 abstract 1
- MVLGANVFCMOJHR-UHFFFAOYSA-N 1,4-diethynylbenzene Chemical compound C#CC1=CC=C(C#C)C=C1 MVLGANVFCMOJHR-UHFFFAOYSA-N 0.000 abstract 1
- LTLVZQZDXQWLHU-UHFFFAOYSA-N 1-bromo-4-ethynylbenzene Chemical group BrC1=CC=C(C#C)C=C1 LTLVZQZDXQWLHU-UHFFFAOYSA-N 0.000 abstract 1
- QTATYLSBJQTINJ-UHFFFAOYSA-N 1-chloroprop-2-ynylbenzene Chemical compound C#CC(Cl)C1=CC=CC=C1 QTATYLSBJQTINJ-UHFFFAOYSA-N 0.000 abstract 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 abstract 1
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 abstract 1
- JITPLZPWKYUTDM-UHFFFAOYSA-N 1-phenylprop-2-yn-1-one Chemical compound C#CC(=O)C1=CC=CC=C1 JITPLZPWKYUTDM-UHFFFAOYSA-N 0.000 abstract 1
- PULPQOUKKDDVFR-UHFFFAOYSA-N 2-nitroethynylbenzene Chemical group [O-][N+](=O)C#CC1=CC=CC=C1 PULPQOUKKDDVFR-UHFFFAOYSA-N 0.000 abstract 1
- PZFBULOUMNPBFA-UHFFFAOYSA-N 3-chlorobut-1-yne Chemical compound CC(Cl)C#C PZFBULOUMNPBFA-UHFFFAOYSA-N 0.000 abstract 1
- OVNWORSPZLORHV-UHFFFAOYSA-N 3-ethyl-3-methylpent-1-yne Chemical compound CCC(C)(CC)C#C OVNWORSPZLORHV-UHFFFAOYSA-N 0.000 abstract 1
- USCSRAJGJYMJFZ-UHFFFAOYSA-N 3-methyl-1-butyne Chemical compound CC(C)C#C USCSRAJGJYMJFZ-UHFFFAOYSA-N 0.000 abstract 1
- MXYUEMWMHJSSSJ-UHFFFAOYSA-N 5-fluoropent-1-yne Chemical compound FCCCC#C MXYUEMWMHJSSSJ-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- XGABPYVCXHITQG-UHFFFAOYSA-N C#CCCCCCCCCC#C.C#CCCCCCC#C Chemical compound C#CCCCCCCCCC#C.C#CCCCCCC#C XGABPYVCXHITQG-UHFFFAOYSA-N 0.000 abstract 1
- 150000001335 aliphatic alkanes Chemical group 0.000 abstract 1
- 150000001454 anthracenes Chemical class 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- OTJZCIYGRUNXTP-UHFFFAOYSA-N but-3-yn-1-ol Chemical compound OCCC#C OTJZCIYGRUNXTP-UHFFFAOYSA-N 0.000 abstract 1
- GKPOMITUDGXOSB-UHFFFAOYSA-N but-3-yn-2-ol Chemical compound CC(O)C#C GKPOMITUDGXOSB-UHFFFAOYSA-N 0.000 abstract 1
- XRGPFNGLRSIPSA-UHFFFAOYSA-N butyn-2-one Chemical compound CC(=O)C#C XRGPFNGLRSIPSA-UHFFFAOYSA-N 0.000 abstract 1
- 238000005266 casting Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- VLARUOGDXDTHEH-UHFFFAOYSA-L disodium cromoglycate Chemical compound [Na+].[Na+].O1C(C([O-])=O)=CC(=O)C2=C1C=CC=C2OCC(O)COC1=CC=CC2=C1C(=O)C=C(C([O-])=O)O2 VLARUOGDXDTHEH-UHFFFAOYSA-L 0.000 abstract 1
- ZVDBUOGYYYNMQI-UHFFFAOYSA-N dodec-1-yne Chemical compound CCCCCCCCCCC#C ZVDBUOGYYYNMQI-UHFFFAOYSA-N 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- RSPZSDWVQWRAEF-UHFFFAOYSA-N hepta-1,6-diyne Chemical compound C#CCCCC#C RSPZSDWVQWRAEF-UHFFFAOYSA-N 0.000 abstract 1
- YFIBSNDOVCWPBL-UHFFFAOYSA-N hexa-1,5-diyne Chemical compound C#CCCC#C YFIBSNDOVCWPBL-UHFFFAOYSA-N 0.000 abstract 1
- BKWVBDLCGSFRKD-UHFFFAOYSA-N n-prop-1-ynylaniline Chemical compound CC#CNC1=CC=CC=C1 BKWVBDLCGSFRKD-UHFFFAOYSA-N 0.000 abstract 1
- DSOJWVLXZNRKCS-UHFFFAOYSA-N octa-1,7-diyne Chemical compound C#CCCCCC#C DSOJWVLXZNRKCS-UHFFFAOYSA-N 0.000 abstract 1
- IYDNQWWOZQLMRH-UHFFFAOYSA-N octadec-1-yne Chemical compound CCCCCCCCCCCCCCCCC#C IYDNQWWOZQLMRH-UHFFFAOYSA-N 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- MDROPVLMRLHTDK-UHFFFAOYSA-N penta-1,4-diyne Chemical compound C#CCC#C MDROPVLMRLHTDK-UHFFFAOYSA-N 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 abstract 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 abstract 1
- NGKSKVYWPINGLI-UHFFFAOYSA-N prop-2-ynylbenzene Chemical compound C#CCC1=CC=CC=C1 NGKSKVYWPINGLI-UHFFFAOYSA-N 0.000 abstract 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 abstract 1
- HCJTYESURSHXNB-UHFFFAOYSA-N propynamide Chemical compound NC(=O)C#C HCJTYESURSHXNB-UHFFFAOYSA-N 0.000 abstract 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 abstract 1
- 150000003222 pyridines Chemical class 0.000 abstract 1
- 150000003230 pyrimidines Chemical class 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
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
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
-
- 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
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/10—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkaline earth metals, zinc, cadmium, mercury, copper or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/122—Compounds comprising a halogen and copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Carbon is obtained by igniting a film of a polymeric, polyacetylenic compound obtained by oxidizing a compound containing at least two terminal acetylenic groups (-CCH) (see Division C3). In a preferred embodiment the polymer is derived from meta-diethynyl benzene; the polymer is dissolved in chlorobenzene, nitrobenzene or tetrachlorethane and cast on a glass plate and the solvent evaporated. The film decomposes above 180 DEG C. to leave a coherent carbon film.ALSO:Compounds containing two conjugated acetylenic linkages are obtained by reacting a compound containing a terminal acetylenic group (-CCH) with oxygen in the presence of a solution of a cuprous salt-tertiary amine complex, said cuprous salt being one for which a corresponding cupric salt exists. The acetylenic group may be attached to an aliphatic or aromatic radical which may contain as substituents, halogen, -OH, -OR, -OCOR, -COOR, -COR, -CONH2, -CONHR, -CONR2, -CH, -SH, -SR, -SSH, -SSR, -SOR, -NO2, -SO2R, -NH2, -NHR or -NR2 e.g. 5-fluoro-1-pentyne, 3-chloro-3-phenylpropyne, 3-bromopropyne, 3-chloro-1-butyne, ethynylpyridines, 3-butyne-1-ol, 2-propyne-1-ol, N-propynyl-aniline, propiolic acetate, propiolic amide, propiolophenone, 2-propynylamine, N,N-dimethylpropynylamine 2-propynyl sulphide, methyl-3-butynoate, 3-butyne-2-ol, 3-butyne-2-one, parabromophenylacetylene, nitrophenyl-acetylene and 1-ethynyl-cyclohexanol. The cuprous salt is preferably the chloride but others are specified and many tertiary amines are specified including heterocyclic amines and di-tertiary amines; preferably N-aryl amines are not used. Excess amine may be used to dissolve the complex and other solvents may be present, e.g. alcohols, ketones, hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, ether esters or sulphoxides. Oxygen is bubbled into the mixture as such or diluted with nitrogen, helium or argon or as air. The reaction mixture is cooled if necessary to prevent the temperature rising above 100 DEG C. and the reaction is terminated by addition of an acid by pouring into a non-solvent for the product or by adding a copper chelating agent.ALSO:Polymeric polyacetylenic compounds are obtained by reacting acetylene or a compound containing two or more terminal acetylenic groups (-C==CH) with oxygen in the presence of a cuprous salt-tertiary amine complex, the cuprous salt being one for which a corresponding cupric salt exists. The products are linear polymers formed for example according to the equation: [-C==C-R-C==C-]n <FORM:0971170/C3/1> where n is usually at least 10 and probably at least 50. Compounds containing two terminal acetylenic groups are preferred, compounds with one such group being added as a chain stopper if required; compounds with three or more acetylenic groups yield three-dimensional, cross-linked, insoluble, infusible polymers. The radical to which the acetylenic groups are attached may be aliphatic or aromatic, hydrocarbon or substituted hydrocarbon, e.g. 1,4-pentadiyne, 1,5-hexadiyne, 1,6-heptadiyne, 1,7-octadiyne, 1,8-nonadiyne 1,11-dodecadiyne, o-, m-, or p-diethynyl benzene, or diethynyl naphthalenes, anthracenes, pyridines or pyrimidines. The polymers and copolymers obtained from m-diethynyl benzene are soluble in chlorobenzene, nitrobenzene, or tetrachloroethane above 100 DEG C. and can be cast, e.g. on glass, to produce tough transparent films stable up to 180 DEG C. The cuprous salt is preferably the chloride but others are specified and many tertiary amines are specified including heterocyclic amines and di-tertiary amines; preferably N-aryl amines are not used. Excess amine may be used to dissolve the complex and other solvents may be present, e.g. alcohols, ketones, hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, ether esters or sulphoxides. Oxygen is bubbled through the mixture as such or diluted with nitrogen, helium or argon or as air. The reaction mixture is cooled to prevent the temperature rising above 100 DEG C. and the reaction is terminated by adding an acid, by pouring into a non-solvent for the product or by adding a copper chelating agent.ALSO:Compounds containing two conjugated acetylenic linkages are obtained by reacting a compound containing a terminal acetylenic group (-C CH) with oxygen in the presence of a solution of a cuprous salt-tertiary amine complex, said cuprous salt being one for which a corresponding cupric salt exists. The acetylenic group may be attached to an aliphatic or aromatic radical e.g. acetylene, propyne, 1-butyne, 3-methyl-1-butyne, 3-phenylpropyne, 1 - pentyne, 3 - ethyl - 3 - methyl - 1 - pentyne, 1 - dodecyne, 1 - octadecyne, phenylacetylene, ethynylnaphthalenes, ethynylanthracenes. The cuprous salt is preferably the chloride but others are specified and many tertiary amines are specified including heterocyclic amines and di-tertiary amines; preferably N-aryl amines are not used. Excess amine may be used to dissolve the complex and other solvents may be present, e.g. alcohols, ketones, hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, ether esters or sulphoxides. Oxygen is bubbled into the mixture as such or diluted with nitrogen, helium or argon or as air. The reaction mixture is cooled if necessary to prevent the temperature rising above 100 DEG C. and the reaction is terminated by addition of an acid by pouring into a non-solvent for the product or by adding a copper chelating agent.ALSO:Clear, tough coatings on glass are obtained by casting a solution of a polyacetylenic compound containing meta-diethynyl benzene groups with or without para-diethynyl benzene or diethynyl alkane groups, i.e. containing the recurring structure [-CC-R-CC-]n, and evaporating the solvent. On heating above 180 DEG C. the film is converted to a coherent coating of carbon.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1918660A | 1960-04-01 | 1960-04-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB971170A true GB971170A (en) | 1964-09-30 |
Family
ID=21791877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB11739/61A Expired GB971170A (en) | 1960-04-01 | 1961-03-30 | Process for producing dimers and polymers of acetylenic compounds |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE1158272B (en) |
| GB (1) | GB971170A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3993711A (en) * | 1975-03-19 | 1976-11-23 | Hercules Incorporated | Carboxylated poly(arylacetylenes) |
| US4255535A (en) | 1974-12-30 | 1981-03-10 | Allied Chemical Corporation | Organic polymers with near-zero uniaxial thermal expansion coefficients |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3617365A (en) * | 1969-03-25 | 1971-11-02 | American Can Co | Composite coated with acetylene-oxygen polymers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR733663A (en) * | 1931-06-19 | 1932-10-10 | Du Pont | Improvements to acetylene reactions |
| FR829617A (en) * | 1936-11-21 | 1938-07-01 | Ig Farbenindustrie Ag | Process for the preparation of acyclic polymers of acetylene and catalysts suitable for carrying out this process |
-
1961
- 1961-03-29 DE DEG31939A patent/DE1158272B/en active Pending
- 1961-03-30 GB GB11739/61A patent/GB971170A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4255535A (en) | 1974-12-30 | 1981-03-10 | Allied Chemical Corporation | Organic polymers with near-zero uniaxial thermal expansion coefficients |
| US3993711A (en) * | 1975-03-19 | 1976-11-23 | Hercules Incorporated | Carboxylated poly(arylacetylenes) |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1158272B (en) | 1963-11-28 |
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