EP0000778A1 - Procédé pour la préparation de polyamines de la série des diphénylméthanes - Google Patents
Procédé pour la préparation de polyamines de la série des diphénylméthanes Download PDFInfo
- Publication number
- EP0000778A1 EP0000778A1 EP7878100591A EP78100591A EP0000778A1 EP 0000778 A1 EP0000778 A1 EP 0000778A1 EP 7878100591 A EP7878100591 A EP 7878100591A EP 78100591 A EP78100591 A EP 78100591A EP 0000778 A1 EP0000778 A1 EP 0000778A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- weight
- ion exchangers
- styrene
- divinyl benzene
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920000768 polyamine Polymers 0.000 title claims abstract description 20
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 238000009833 condensation Methods 0.000 claims abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 12
- 230000005494 condensation Effects 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 239000003377 acid catalyst Substances 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 150000003142 primary aromatic amines Chemical class 0.000 claims abstract description 3
- 150000003336 secondary aromatic amines Chemical class 0.000 claims abstract description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 7
- 239000011973 solid acid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 abstract 3
- 239000011949 solid catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 20
- 150000002500 ions Chemical class 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 150000004982 aromatic amines Chemical group 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 description 2
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- VVAKEQGKZNKUSU-UHFFFAOYSA-N 2,3-dimethylaniline Chemical group CC1=CC=CC(N)=C1C VVAKEQGKZNKUSU-UHFFFAOYSA-N 0.000 description 1
- DWOBGCPUQNFAFB-UHFFFAOYSA-N 2-benzylaniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1 DWOBGCPUQNFAFB-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- CDEGDZUMZIYNRD-UHFFFAOYSA-N 2-cyclohexylaniline Chemical compound NC1=CC=CC=C1C1CCCCC1 CDEGDZUMZIYNRD-UHFFFAOYSA-N 0.000 description 1
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical group CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KEBXGLIHHLGNJH-UHFFFAOYSA-N n-methylsulfanylaniline Chemical compound CSNC1=CC=CC=C1 KEBXGLIHHLGNJH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
Definitions
- Polyamines of the diphenylmethane series are formed as condensation products from aniline and formaldehyde on acidic catalysts.
- aniline and formaldehyde react without catalysts to form N-alkyl compounds, which are referred to as precondensates.
- this precondensate rearranges into polyamines of the diphenylmethane series. This creates a mixture of 2,2'-, 2,4'-, 4,4'-diaminodiphenyl-methane and higher condensation products (trinuclear to hexahedral).
- the corresponding polyisocyanates of the diphenylmethane series are obtained, which are valuable starting materials in the production of polyurethane plastics, in particular polyurethane foams.
- polyurethane plastics in particular polyurethane foams.
- the proportion of ortho-standing isocyanate groups present in them in particular the proportion of 2,2'- and 2,4'-diisocyanatodiphenylmethane, is as low as possible. Accordingly, strives already in the aniline / formaldehyde condensation polyamine mixtures of the diphenylmethane series which meet these requirements with regard to the isomer distribution.
- hydrochloric acid When using hydrochloric acid as a catalyst, it is possible to keep the o-isomer content in the condensation mixture low, but the use of hydrochloric acid (or aniline hydrochloride) has the disadvantages of corrosiveness and the need for neutralization or elaborate removal of the catalyst connected by the reaction product. In principle, these disadvantages can be avoided by using heterogeneous acidic catalysts, such as ion exchangers, but it has so far not been possible to use these catalysts to produce polyamines of the diphenylmethane series which, for example, contain less than 12% of 2,4 ' -Diaminodiphenylmethane and have a content of less than 2% of 2,2'-diaminodiphenylmethane.
- heterogeneous acidic catalysts such as ion exchangers
- a polyamine mixture of the diphenylmethane series is obtained on organic acidic ion exchangers which contains 24-26% by weight of 2,4'- and approx. 2.8% by weight of 2,2'-diaminodiphenylmethane.
- polyamines of the diphenylmethane series are to be understood both as polyamine mixtures as they arise in the condensation of aniline itself with formaldehyde in the presence of acid catalysts, and as polyamine mixtures as they are through acid-catalyzed condensation on nitrogen or on the nucleus substituted anilines can be obtained with formaldehyde.
- the preferred polyamines of the diphenylmethane series according to the invention are the classic aniline / formaldehyde condensates.
- any primary or secondary arylamines to be regarded as substituted anilines can be used as starting materials in the process according to the invention.
- the only prerequisite for the suitability of the amines as starting material in the process according to the invention is that the substituents which may be present are inert under the reaction conditions of the process according to the invention and that the para-position which is unsubstituted to an aromatically bound amino group is present.
- Arylamines suitable as starting materials are accordingly N-methylaniline, N-ethylaniline, o-toluidine, o-chloroaniline, m-chloroaniline, o-anisidine, 2,3-xylidine, 3,5-xylidine, o-cyclohexylaniline, o-benzylaniline, ⁇ -naphthylaniline, methylmercaptoaniline or the aniline particularly preferred in the context of the present invention.
- the formaldehyde to be used as a reactant for the arylamine in the process according to the invention is preferably used as an aqueous formalin solution, although. in principle also gaseous formaldehyde or substances which release formaldehyde under the reaction conditions, e.g. Paraformaldehyde or trioxymethylene are suitable.
- the catalysts can be used in various external forms, e.g. in lumpy form, in the form of commercially available pearl granules or in a finely ground state. Activation of the catalyst can optionally be achieved in a manner known per se by acid treatment.
- the molar ratio of arylamine: formaldehyde is generally kept in the range from 3: 1 to 15: 1, preferably 5: 1 to 10: 1.
- the process according to the invention is carried out in such a way that the aqueous formaldehyde solution or the formaldehyde-releasing substance is added to the aromatic amine, care being taken to ensure thorough mixing and removal of the heat of reaction.
- the aromatic amine is expediently used immediately in the excess desired for the further conduct of the reaction and at the same time serves as a solvent for the N-substituted precondensate which forms, under certain circumstances. in any case, the reaction mixture must be saturated with water by the additional addition of water.
- the water-saturated reaction mixture is now using the above. Catalysts further reacted at elevated temperature, the process product according to the invention being formed from the precondensate and part of the amine present in excess.
- the process product according to the invention being formed from the precondensate and part of the amine present in excess.
- the process according to the invention is used in particular during the catalyzed rearrangement of the N-substi according to the invention tuated intermediates in the process products according to the invention at elevated temperatures generally carried out in the temperature range from 50 to 150 ° C.
- care must be taken to ensure that pressure and temperature ratios are chosen so that the water and condensation water introduced into the reaction mixture are not distilled off to any appreciable extent, so that it is always ensured that the catalyst is present in the water-saturated state. It is essential, therefore, that when working at temperatures above 100 ° C., a pressure preventing the water from distilling off is maintained.
- the formation of the N-substituted precondensates generally in the temperature range from 20 to 50 ° C. and the catalytic rearrangement of these precondensation products in the process products according to the invention in the temperature range from 50 to 120 ° C is done.
- the process according to the invention can be carried out continuously in a contact bed, a stirred tank or a stirred tank cascade, or batchwise in the stirred tank. Since it is not necessary to separate and recycle the catalyst in the contact bed, this type of procedure is recommended.
- reaction management in particular to remove the heat of reaction, it can also be expedient to have the reaction run in a plurality of stages connected in series, the heat of reaction formed in each case being able to be removed after the individual stages.
- the reaction mixture is preferably worked up by distillation, although in principle any other suitable separation process can be used.
- the lower boiling excess amine is distilled off overhead and returned to the process, while the polyamine mixture present as a distillation residue is immediately, e.g. can be further processed in known manner to a polyisocyanate mixture by phosgenation.
- reaction solution was separated off and the ion exchanger was reacted again with a new starting solution.
- the reaction solution was saturated with water in each case, which could be recognized by clouding the reaction solution or by forming a separate water phase.
- the reaction solution after dist. Separation of the aniline examined by high pressure liquid chromatography.
- the polyamine mixture contained 0.6% by weight of 2,2'-, 10.8% by weight of 2,4'- and 75.3% by weight of 4,4'-diaminodiphenylmethane, the rest consisted of 3- or 4-core connections.
- Example 1 is repeated with the only difference that an appropriate amount of a water-moist, macroporous ion exchanger which is crosslinked with 18% by weight of divinylbenzene based on divinylbenzene-styrene copolymer was used.
- the polyamine mixture obtained consisted of 0.6 wt .-% 2,2'-, 8.0 wt .-% 2.4 1 and 73.2 wt .-% of 4,4'-diaminodiphenylmethane and polynuclear compounds together .
- the tests were carried out as in Example 1 for 3000 h without any change in conversion or selectivity.
- Example 1 is repeated, with the only difference that a gel-shaped, water-moist ion exchanger crosslinked with 4% by weight of divinylbenzene based on divinylbenzene-styrene copolymer was used.
- the polyamine mixture obtained was composed of 1.1% by weight of 2,2'-, 14.6% by weight of 2,4'- and 57.2% by weight of 4,4'-diaminodiphenylmethane. Almost 20% by weight consisted of 3- and higher-core compounds.
- Example 1 is repeated with the only difference that. that a gel-shaped, water-moist, with 8 wt .-% divinylbenzene based on divinylbenzene-styrene copolymer ver networked ion exchanger was used.
- the polyamine mixture formed contained 3.4% by weight of 2,2'-, 16.5% by weight of 2,4'- and 54% by weight of 4,4'-diaminodiphenylmethane. The rest consisted of higher core connections. The experiments were carried out up to a total of 3000 h without a product corresponding to Examples 1 and 2 being obtained by changing reaction parameters, such as aniline / formaldehyde molar ratio, temperature or residence time.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772736862 DE2736862A1 (de) | 1977-08-16 | 1977-08-16 | Verfahren zur hestellung von polyaminen der diphenylmethanreihe |
| DE2736862 | 1977-08-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000778A1 true EP0000778A1 (fr) | 1979-02-21 |
| EP0000778B1 EP0000778B1 (fr) | 1980-07-23 |
Family
ID=6016494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100591A Expired EP0000778B1 (fr) | 1977-08-16 | 1978-08-04 | Procédé pour la préparation de polyamines de la série des diphénylméthanes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0000778B1 (fr) |
| JP (1) | JPS5432461A (fr) |
| BR (1) | BR7805250A (fr) |
| DE (2) | DE2736862A1 (fr) |
| ES (1) | ES472514A1 (fr) |
| IT (1) | IT1106878B (fr) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0043933A1 (fr) * | 1980-07-12 | 1982-01-20 | BASF Aktiengesellschaft | Procédé pour la préparation de mélanges de polyamines ayant un taux élevé de 4,4'-diaminodiphénylméthane |
| EP0078414A1 (fr) * | 1981-10-27 | 1983-05-11 | Chemie Linz Aktiengesellschaft | Procédé pour la préparation de diamines de la série de diphényl méthane |
| WO2009144148A1 (fr) * | 2008-05-27 | 2009-12-03 | Evonik Degussa Gmbh | Procédé pauvre en chlore en plusieurs étapes, pour la préparation de diisocyanates cycloaliphatiques |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009129286A1 (fr) * | 2008-04-16 | 2009-10-22 | Dow Global Technologies Inc. | Procédé pour la production de méthane à base de polyaminopolyphényle utilisant un système catalyseur d’acide solide mixte |
| DE102008001469A1 (de) * | 2008-04-30 | 2009-11-05 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Diaminodiphenylalkanen |
| DE102008001492A1 (de) * | 2008-04-30 | 2009-11-05 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Diaminodiphenylalkanen |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1179945B (de) * | 1962-12-11 | 1964-10-22 | Basf Ag | Verfahren zur Herstellung von 4, 4'-Diaminodiphenylmethanen |
| US3367969A (en) * | 1965-03-08 | 1968-02-06 | Du Pont | Process for the preparation of 4, 4'-methylenedianiline |
| DE2037550A1 (de) * | 1969-07-31 | 1971-02-11 | Kaiser Aluminum & Chemical Corp., Oakland. Calif (VStA) | Verfahren zur Herstellung aromatischer Polyamine |
| DD109615A1 (fr) * | 1972-08-14 | 1974-11-12 | ||
| US3971829A (en) * | 1974-11-18 | 1976-07-27 | Jefferson Chemical Company, Inc. | Preparation of methylene-bridged polyphenylpolyamine mixtures |
| FR2370032A1 (fr) * | 1976-11-06 | 1978-06-02 | Elprochine Ag | Procede pour l'obtention de polyarylamines possedant des ponts methylenes |
-
1977
- 1977-08-16 DE DE19772736862 patent/DE2736862A1/de not_active Withdrawn
-
1978
- 1978-08-04 EP EP78100591A patent/EP0000778B1/fr not_active Expired
- 1978-08-04 DE DE7878100591T patent/DE2860072D1/de not_active Expired
- 1978-08-11 ES ES472514A patent/ES472514A1/es not_active Expired
- 1978-08-11 IT IT50728/78A patent/IT1106878B/it active
- 1978-08-14 JP JP9828478A patent/JPS5432461A/ja active Pending
- 1978-08-15 BR BR7805250A patent/BR7805250A/pt unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1179945B (de) * | 1962-12-11 | 1964-10-22 | Basf Ag | Verfahren zur Herstellung von 4, 4'-Diaminodiphenylmethanen |
| US3367969A (en) * | 1965-03-08 | 1968-02-06 | Du Pont | Process for the preparation of 4, 4'-methylenedianiline |
| DE2037550A1 (de) * | 1969-07-31 | 1971-02-11 | Kaiser Aluminum & Chemical Corp., Oakland. Calif (VStA) | Verfahren zur Herstellung aromatischer Polyamine |
| DD109615A1 (fr) * | 1972-08-14 | 1974-11-12 | ||
| US3971829A (en) * | 1974-11-18 | 1976-07-27 | Jefferson Chemical Company, Inc. | Preparation of methylene-bridged polyphenylpolyamine mixtures |
| FR2370032A1 (fr) * | 1976-11-06 | 1978-06-02 | Elprochine Ag | Procede pour l'obtention de polyarylamines possedant des ponts methylenes |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0043933A1 (fr) * | 1980-07-12 | 1982-01-20 | BASF Aktiengesellschaft | Procédé pour la préparation de mélanges de polyamines ayant un taux élevé de 4,4'-diaminodiphénylméthane |
| EP0078414A1 (fr) * | 1981-10-27 | 1983-05-11 | Chemie Linz Aktiengesellschaft | Procédé pour la préparation de diamines de la série de diphényl méthane |
| WO2009144148A1 (fr) * | 2008-05-27 | 2009-12-03 | Evonik Degussa Gmbh | Procédé pauvre en chlore en plusieurs étapes, pour la préparation de diisocyanates cycloaliphatiques |
| US8536370B2 (en) | 2008-05-27 | 2013-09-17 | Evonik Degussa Gmbh | Low chlorine, multi-staged method for producing cycloaliphatic disocyanates |
Also Published As
| Publication number | Publication date |
|---|---|
| ES472514A1 (es) | 1979-02-16 |
| EP0000778B1 (fr) | 1980-07-23 |
| DE2736862A1 (de) | 1979-03-01 |
| BR7805250A (pt) | 1979-04-24 |
| IT7850728A0 (it) | 1978-08-11 |
| JPS5432461A (en) | 1979-03-09 |
| IT1106878B (it) | 1985-11-18 |
| DE2860072D1 (en) | 1980-11-13 |
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