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Structure of 1208-52-2
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
4.5
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Maria Hoppe ; Margit Gmeiner ; Petra Schmid ;
Abstract: Primary aromatic amines (PAAs) may be found in food contact materials and can potentially migrate from packaging material into the packed foodstuffs. Certain members of this substance class are of particular concern due to their toxicological properties. Legislators and authorities require a risk assessment regarding the transfer of PAAs into food. The evaluation of PAAs’ migration into food relies on migration or extraction tests using aqueous and acidic food simulants or solvents. However, PAAs exhibit stability issues in acidic media, which could lead to an underestimation of migration. Therefore, a systematic stability study was conducted for 28 PAAs in 3% acetic acid and water at different storage conditions. Standard solutions of 2 and 10 ng/ml of the amines in these media were prepared and stored under the following conditions: 2 h at 40 °C, 70 °C, and 100 °C, and 10 days at − 20 °C, 4 °C, 20 °C, 40° C, and 60 °C. The test solutions were analyzed using liquid chromatography coupled to mass spectrometry, and recovery was calculated against freshly prepared standard solutions. It was found that several PAAs undergo a loss of recovery under the investigated conditions; 7 of the substances were identified to be the most unstable: 3,3ʹ-dimethoxybenzidine, 3,3ʹ-dimethylbenzidine, 6-methoxy-m-toluidine, 4-methoxy-m-phenylendiamine, 2,6-toluenediamine, benzidine and 2,4-toluenediamine. It was concluded that both time and storage temperature play a pivotal role in the stability of PAAs. The experiments also demonstrated that PAAs exhibit greater stability in water than in 3% acetic acid.
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Keywords: Primary aromatic amines ; Food contact materials ; Migration and extraction testing ; PAA stability
Show More >
| CAS No. : | 1208-52-2 |
| Formula : | C13H14N2 |
| M.W : | 198.26 |
| SMILES Code : | NC1=CC=C(CC2=C(N)C=CC=C2)C=C1 |
| MDL No. : | MFCD01670227 |
| InChI Key : | UTNMPUFESIRPQP-UHFFFAOYSA-N |
| Pubchem ID : | 14580 |
| GHS Pictogram: |
|
| Signal Word: | Danger |
| Hazard Statements: | H301+H311+H331-H317-H319-H341-H410 |
| Precautionary Statements: | P261-P273-P280-P301+P310-P305+P351+P338 |
| Class: | 6.1 |
| UN#: | 2811 |
| Packing Group: | Ⅱ |
| Num. heavy atoms | 15 |
| Num. arom. heavy atoms | 12 |
| Fraction Csp3 | 0.08 |
| Num. rotatable bonds | 2 |
| Num. H-bond acceptors | 0.0 |
| Num. H-bond donors | 2.0 |
| Molar Refractivity | 64.7 |
| TPSA ? Topological Polar Surface Area: Calculated from |
52.04 Ų |
| Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
1.73 |
| Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
2.18 |
| Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
2.46 |
| Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
2.69 |
| Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
2.42 |
| Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
2.29 |
| Log S (ESOL):? ESOL: Topological method implemented from |
-2.9 |
| Solubility | 0.248 mg/ml ; 0.00125 mol/l |
| Class? Solubility class: Log S scale |
Soluble |
| Log S (Ali)? Ali: Topological method implemented from |
-2.91 |
| Solubility | 0.246 mg/ml ; 0.00124 mol/l |
| Class? Solubility class: Log S scale |
Soluble |
| Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-4.61 |
| Solubility | 0.00492 mg/ml ; 0.0000248 mol/l |
| Class? Solubility class: Log S scale |
Moderately soluble |
| GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
High |
| BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
Yes |
| P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
No |
| CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
Yes |
| CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
Yes |
| CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
Yes |
| CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
| CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
| Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-5.96 cm/s |
| Lipinski? Lipinski (Pfizer) filter: implemented from |
0.0 |
| Ghose? Ghose filter: implemented from |
None |
| Veber? Veber (GSK) filter: implemented from |
0.0 |
| Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
| Muegge? Muegge (Bayer) filter: implemented from |
1.0 |
| Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
| PAINS? Pan Assay Interference Structures: implemented from |
1.0 alert |
| Brenk? Structural Alert: implemented from |
1.0 alert: heavy_metal |
| Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<1.0 |
| Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
1.48 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 44.5% | Stage #1: at 25 - 80℃; Stage #2: at 45 - 140℃; for 2.5 - 2.83333 h; Stage #3: With sodium hydroxide In water at 100℃; |
Example 1 a) Preparation of the polyamine mixture: In a stirred vessel, 2600 g of aniline were intimately mixed at 25°C with 1000 g of formalin (30 wt.percent aqueous solution), with stirring until the mixture warmed up to 60°C. The stirrer was stopped and the upper, aqueous phase was separated off. 68 g of 30 wt.percent aqueous hydrochloric acid were then admixed, with renewed stirring and cooling. The temperature was kept at 45°C. After stirring for a further 15 min at this temperature, the cooling was replaced by heating and the mixture was heated uniformly to 140°C over 120 min under 5 bar pressure and then kept at this temperature for 15 min. The mixture was then cooled to 100°C, let down to normal pressure and neutralized by adding 54 g of 50 wt.percent aqueous sodium hydroxide solution, with stirring. After the stirrer had been stopped, the phases were left to settle and the lower, aqueous phase was siphoned off. Excess aniline with residual water was then distilled off, initially under normal pressure, and the aniline residues were removed by distilling the resulting polyamine mixture at 100 mbar and 250°C. This yielded 1900 g of a polyamine mixture having the following composition: 4,4'-MDA: 60.1 wt.percent2,4'-MDA: 6.0 wt.percent2,2'-MDA: 0.2 wt.percenthigher-molecular polyamines: 33.7 wt.percent; Example 2 a) Preparation of the polyamine mixture: In a stirred vessel, 1800 g of aniline were intimately mixed at 30°C with 1000 g of formalin (30 wt.percent aqueous solution), with stirring. The mixture was warmed up to 80°C. The stirrer was stopped and the upper, aqueous phase was separated off. 23 g of 30 wt.percent aqueous hydrochloric acid were then admixed, with renewed stirring and cooling. The temperature was kept at 45°C. After stirring for a further 15 min at this temperature, the cooling was replaced by heating and the mixture was heated uniformly to 140°C over 150 min under 5 bar pressure and then kept at this temperature for 20 min. The mixture was then cooled to 100°C, let down to normal pressure and neutralized by adding 18 g of 50 wt.percent aqueous sodium hydroxide solution, with stirring. After the stirrer had been stopped, the phases were left to settle and the lower, aqueous phase was siphoned off. Excess aniline with residual water was then distilled off, initially under normal pressure, and the aniline residues were removed by distilling the resulting polyamine mixture at 100 mbar and 250°C. This gave 1880 g of a polyamine mixture having the following composition: 4,4'-MDA: 44.5 wt.percent2,4'-MDA: 7.3 wt.percent2,2'-MDA: 0.5 wt.percenthigher-molecular polyamines: 47.7 wt.percent |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 66.75 %Chromat. | Stage #1: at 38 - 90℃; Stage #2: With sodium hydroxide In water |
Example 1:; Hydrochloric acid (a concentration percentage by weight is 30.8percent, this hydrochloric acid is a by-product from MDI apparatus) from storage tank 2 and aniline from storage tank 3 are fed into venturi mixer 5 by a pump 6 with a molar ratio of hydrochloric acid/anilin=0.36:1, for mixing and reacting with each other to produce aniline hydrochloride which is then pumped into circulation pipes and mixed with a circulation solution coming from a condensation stirred vessel 1 to obtain a mixed solution. The obtained mixed solution is introduced into a heat exchanger 7 to remove the reaction heat, and the mixed solution, which is cooled to 38°C and left the heat exchanger 7, is introduced into a feeding port of the high gravity rotating bed reactor 8 of rotating packed bed type. Formaldehyde solution (a concentration percentage by weight is 37 wtpercent) stream from storage tank 4 is fed through another feeding port of the high gravity rotating bed reactor 8, the ratio of formaldehyde to aniline is controlled at 0.40:1. The formaldehyde solution is mixed sufficiently with the previously mixed solution phase and conducted a pre-condensation reaction in the high gravity rotating bed reactor 8, the reaction temperature is controlled at 35°C, the reaction time is 0.5 sec, and the rotation speed of the rotor of high gravity rotating bed reactor is 1000rpm. Then the mixed reaction solution flows into the condensation reaction vessel 1 to proceed with the pre-condensation reaction, the temperature of reaction solution is controlled at 42°C, the stirring speed is about 110rpm, and the reaction residence time is about 20 min. Then the temperature of reaction solution is elevated to over 90°C to conduct a molecular rearrangement reaction, the residence time for molecular rearrangement reaction is about 2 hours. Finally a solution of diphenylmethylene diamine hydrochloride and polymethylene polyphenyl polyamines hydrochloride is obtained. 92 vol percent of the reaction mixture from the condensation reaction vessel 1 returns to the circulation pipes, as circulation solution, and flows to heat exchanger 7, the other 8 vol percent of the reaction mixture is discharged and neutralized with a sodium hydroxide solution at a concentration of 42 wtpercent. The salt water phase is separated from the polyamine organic phase, and the polyamines are washed with water and purified to finally obtain a mixture of diphenylmethylene diamine and polymethylene polyphenyl polyamines. The composition of products is listed in table 2. |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With hydrogenchloride; at 35 - 103℃; for 11.0833h;Heating / reflux; | Methanol and water were separated from this mixture by distillation. The remaining distillation bottom product (479.0 g) was tempered in a glass stirring apparatus with superimposition of nitrogen at 35 C. At this temperature, 11.4 g of 32.7% hydrochloric acid were added dropwise within 5 min. During this process the temperature was kept at 35 C. by an ice bath and stirring was continued at this temperature for 30 min. The mixture was then heated to 60 C. and stirring continued at this temperature for a further 30 min. The reaction charge was then heated to boiling and refluxed at boiling temperature (103 C.) for 10 h. 14.9 g 32% sodium hydroxide solution and 100 g of distilled water were then added and the two-phase mixture formed was thoroughly intermixed for 15 minutes. The phases were then separated and the organic phase was extracted twice more with 100 g distilled water each time. Excess aniline and also water and nitrobenzene were distilled off from the organic phase in a vacuum (0.1 mbar). The bottom temperature at the end of distillation was 215 C. The MDA produced (=distillation bottom product, 75.0 g) had the following composition: Wt. % Aniline - Nitrobenzene - 4,4'-MDA 38.6 2,4'-MDA 4.46 2,2'-MDA 0.3 N-methyl-MDA 0.65 3-core-MDA 19.9 4-core-MDA 11.2 Higher MDA oligomers 15.3 Other secondary components and unknown 9.59 |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 33.7 - 47.7%; 6.0 - 7.3%; 0.2 - 0.5%; 44.5 - 60.1% | Example 1 a) Preparation of the polyamine mixture: In a stirred vessel, 2600 g of aniline were intimately mixed at 25C with 1000 g of formalin (30 wt.% aqueous solution), with stirring until the mixture warmed up to 60C. The stirrer was stopped and the upper, aqueous phase was separated off. 68 g of 30 wt.% aqueous hydrochloric acid were then admixed, with renewed stirring and cooling. The temperature was kept at 45C. After stirring for a further 15 min at this temperature, the cooling was replaced by heating and the mixture was heated uniformly to 140C over 120 min under 5 bar pressure and then kept at this temperature for 15 min. The mixture was then cooled to 100C, let down to normal pressure and neutralized by adding 54 g of 50 wt.% aqueous sodium hydroxide solution, with stirring. After the stirrer had been stopped, the phases were left to settle and the lower, aqueous phase was siphoned off. Excess aniline with residual water was then distilled off, initially under normal pressure, and the aniline residues were removed by distilling the resulting polyamine mixture at 100 mbar and 250C. This yielded 1900 g of a polyamine mixture having the following composition: 4,4'-MDA: 60.1 wt.%2,4'-MDA: 6.0 wt.%2,2'-MDA: 0.2 wt.%higher-molecular polyamines: 33.7 wt.%; Example 2 a) Preparation of the polyamine mixture: In a stirred vessel, 1800 g of aniline were intimately mixed at 30C with 1000 g of formalin (30 wt.% aqueous solution), with stirring. The mixture was warmed up to 80C. The stirrer was stopped and the upper, aqueous phase was separated off. 23 g of 30 wt.% aqueous hydrochloric acid were then admixed, with renewed stirring and cooling. The temperature was kept at 45C. After stirring for a further 15 min at this temperature, the cooling was replaced by heating and the mixture was heated uniformly to 140C over 150 min under 5 bar pressure and then kept at this temperature for 20 min. The mixture was then cooled to 100C, let down to normal pressure and neutralized by adding 18 g of 50 wt.% aqueous sodium hydroxide solution, with stirring. After the stirrer had been stopped, the phases were left to settle and the lower, aqueous phase was siphoned off. Excess aniline with residual water was then distilled off, initially under normal pressure, and the aniline residues were removed by distilling the resulting polyamine mixture at 100 mbar and 250C. This gave 1880 g of a polyamine mixture having the following composition: 4,4'-MDA: 44.5 wt.%2,4'-MDA: 7.3 wt.%2,2'-MDA: 0.5 wt.%higher-molecular polyamines: 47.7 wt.% |
[ 75-44-5 ]

[ 1208-52-2 ]
[ 6582-52-1 ]
[ 101-77-9 ]

[ 2536-05-2 ]
[ 5873-54-1 ]
[ 101-68-8 ]| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 35 - 48.2%; 0.2 - 0.5%; 5.5 - 7.2%; 44.1 - 59.3% | In chlorobenzene; at 0℃;Product distribution / selectivity; | b) Preparation of the polyisocyanate mixture: In another stirred reactor, the 1900 g of polyamine mixture were dissolved in 5700 g of chlorobenzene. In a second vessel, a 33 wt.% phosgene solution was prepared by dissolving 3800 g of phosgene in 7600 g of chlorobenzene, with cooling to 0C, and mixing the amine and phosgene solutions with vigorous stirring. The solid suspension formed was then heated slowly and the hydrogen chloride gas produced was withdrawn in appropriate manner. This gave a homogeneous solution of the polyisocyanate. The solvent was then separated off by distillation to give 2370 g of a polyisocyanate mixture having the following composition: 4,4'-MDI: 59.3 wt.%2,4'-MDI: 5.5 wt.%2,2'-MDI: 0.2 wt.%higher-molecular polyisocyanates: 35 wt.% This mixture had a crystallization point below 20C and was suitable for transportation in large barrels and tankers.; b) Preparation of the polyisocyanate mixture: The polyamine mixture was reacted with phosgene in chlorobenzene in the same manner as described in Example 1 to give the polyisocyanate mixture. This gave 2330 g of a polyisocyanate mixture having the following composition: 4,4'-MDI: 44.1 wt.%2,4'-MDI: 7.2 wt.%2,2'-MDI: 0.5 wt.%higher-molecular polyisocyanates: 48.2 wt.% This first polyisocyanate mixture was distilled in a pot still at 10 mbar pressure and 215C bottom temperature until 280 g of distillate had been obtained. This distillate was back-mixed with 420 g of the remaining bottom product. This gave 700 g of a second polyisocyanate mixture having the following composition: 4,4'-MDI: 57.4 wt.%2,4'-MDI: 9.0 wt.%2,2'-MDI: 0.5 wt.%higher-molecular polyisocyanates: 33.1 wt.% This mixture had a crystallization point below 20C and was suitable for transportation in large barrels and tankers. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Example 1; a) Production of a Mixture of Di- and Polyamines; 2,600 g of aniline was mixed intensively with 1,000 g of formalin (30 wt. % aqueous solution of formaldehyde, based on the weight of the solution) in a stirred vessel at 25 C., with stirring, during which the mixture heated up to 60 C. The stirrer was turned off and the aqueous phase settling out at the top was separated off. 680 g of 30 wt. % aqueous hydrochloric acid was mixed in, while stirring again and cooling, maintaining a temperature of 45 C. After stirring at this temperature for a further 15 min, the cooling was replaced by heating and the mixture was uniformly heated to 140 C. in the course of 120 min under 5 bar pressure, and was maintained at this temperature for 15 min. The mixture was cooled to 100 C., depressurized to normal pressure and neutralized by adding 540 g of 50 wt. % aqueous sodium hydroxide solution, while stirring. After turning off the stirrer, the phases were left to settle and the lower aqueous phase was removed by suction. Excess aniline was distilled off with residual water, initially under normal pressure, and the aniline residues were removed by starting to distil the polyamine mixture obtained at 100 mbar and 250 C. 1,900 g of a mixture of di- and polyamines of the following composition were obtained: 4,4-MDA: 60.1 wt. %, 2,4'-MDA: 6.0 wt. %, 2,2'-MDA: 0.2 wt. %, higher molecular weight polyamines: 33.7 wt. %, based on the weight of the mixture.; Example 2; a) Production of a Mixture of Di- and Polyamines; 1,800 g of aniline were mixed intensively with 1,000 g of formalin (30 wt. % aqueous solution of formaldehyde, based on the weight of the solution) in a stirred vessel at 30 C., with stirring, during which the mixture heated up to 80 C. The stirrer was turned off and the aqueous phase settling out at the top was separated off. 230 g of 30 wt. % aqueous hydrochloric acid were mixed in, while stirring again and cooling, maintaining a temperature of 45 C. After stirring at this temperature for a further 15 min, the cooling was replaced by heating and the mixture was uniformly heated to 140 C. in the course of 150 min under 5 bar pressure, and was maintained at this temperature for 20 min. The mixture was cooled to 100 C., depressurized to normal pressure and neutralized by adding 180 g of 50 wt. % aqueous sodium hydroxide solution, while stirring. After turning off the stirrer, the phases were left to settle and the lower aqueous phase was withdrawn by suction. Excess aniline was distilled off with residual water, initially under normal pressure, and the aniline residues were removed by starting to distil the polyamine mixture obtained at 100 mbar and 250 C. 1880 g of a mixture of di- and polyamines of the following composition were obtained: 4,4'-MDA: 44.5 wt. %, 2,4'-MDA: 7.3 wt. %, 2,2'-MDA: 0.5 wt. %, higher molecular weight polyamines: 47.7 wt. %, based on the weight of the mixture. | ||
| In a stirred vessel, 2600 g aniline were thoroughly mixed with 1000 g formalin (30 wt. % aqueous solution of formaldehyde, based on the weight of the solution) at 25 C., with stirring, during which the mixture heated up to 60 C. The stirrer was turned off and the aqueous phase settling out at the top was separated off. 68 g of 30 wt. % aqueous hydrochloric acid were then mixed in, while stirring again and cooling, maintaining a temperature of 45 C. After continuing to stir at this temperature for 15 min, the cooling was replaced by heating and the mixture was uniformly heated to 140 C. in the course of 120 min under a pressure of 5 bar, and was then kept at this temperature for 15 min.The mixture was then cooled to 100 C., depressurized to normal pressure and neutralized by adding 54 g of 50 wt. % aqueous sodium hydroxide solution while stirring. After turning off the stirrer, the phases were allowed to settle and the aqueous phase at the bottom was sucked off. Excess aniline was then distilled off with residual water that remained, initially under normal pressure, and the aniline residues were removed by incipient distillation, at 100 mbar and 250 C., of the polyamine mixture obtained.1900 g of a mixture of diamines and polyamines of the following composition were obtained:4,4'-MDA: 60.1 wt. %2,4'-MDA: 6.0 wt. %2,2'-MDA: 0.2 wt. %higher molecular weight polyamines: 33.7 wt. %, based in each case on the weight of the mixture. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| In chlorobenzene; at 0℃;Heating / reflux;Product distribution / selectivity; | b) Production of a Mixture of Di- and Polyisocyanates; The 1,900 g of the mixture of di- and polyamines obtained in Example 1 a) were dissolved in 5,700 g of chlorobenzene in another stirred reactor. In a second vessel, a 33 wt. % (based on the weight of the solution) phosgene solution was prepared by dissolving 3,800 g of phosgene in 7,600 g of chlorobenzene, while cooling to 0 C., and the amine and phosgene solutions were mixed while stirring intensively. The resulting suspension of solids was heated slowly with the formation of hydrogen chloride gas, which was withdrawn in a suitable manner. A homogeneous solution of polyisocyanate was formed during this process. The solvent was separated off by distillation, which resulted in 2,370 g of a mixture of di- and polyisocyanates of the following composition being obtained: 4,4'-MDI: 59.3 wt. %, 2,4'-MDI: 5.5 wt. %, 2,2'-MDI: 0.2 wt. %, higher molecular weight polyisocyanates: 35 wt. %, based on the weight of the mixture.; b) Production of the Polyisocyanate Mixture; The mixture of di- and polyamines obtained in Example 2 a) was reacted with phosgene in chlorobenzene in the same way as described in Example 1, with the same molar ratio of phosgene to amino groups as in Example 1, to form the polyisocyanate mixture. 2,330 g of a polyisocyanate mixture of the following composition were obtained: 4,4'-MDI: 44.1 wt. %, 2,4'-MDI: 7.2 wt. %, 2,2'-MDI: 0.5 wt. %, higher molecular weight polyisocyanates: 48.2 wt. %, based on the weight of the mixture. | |
| In chlorobenzene; at 0℃;Industry scale;Product distribution / selectivity; | In a stirred reactor, 1900 g of the mixture of diamines and polyamines obtained in Example 1 were dissolved in 5700 g chlorobenzene with a content of 200 ppm phosgene and 200 ppm MDI, based in each case on the weight of the solvent chlorobenzene. In a second vessel made of stainless steel (DIN 1.4571), a 33 wt. % (based on the weight of the solution) phosgene solution was prepared by dissolving 3800 g phosgene in 7600 g chlorobenzene while cooling to 0 C., and the amine and phosgene solutions were mixed while stirring intensively. The resulting suspension of solids was then heated slowly with the formation of hydrogen chloride gas, which was withdrawn by suitable means. During this process, a homogeneous solution of the polyisocyanate was formed. The solvent was now separated off by distillation, as a result of which 2370 g of a mixture of diisocyanates and polyisocyanates of the following composition was obtained:4,4'-MDI: 59.2 wt. %2,4'-MDI: 5.4 wt. %2,2'-MDI: 0.2 wt. %higher molecular weight polyisocyanates: 35.2 wt. %, based in each case on the weight of the mixture.Acidity (ASTM D 1638-74): 180 ppmIron content: 10 ppmExtinction of a 2% solution in chlorobenzene (wavelength 430 nm, film thickness 10 mm): 0.27 Example 3 (Production of a Mixture of Diisocyanates and Polyisocyanates Using Pure Solvent (According to the Invention))In a stirred reactor, 1900 g of the mixture of diamines and polyamines obtained in Example 1 were dissolved in 5700 g chlorobenzene with a content of 20 ppm phosgene and 20 ppm MDI, based in each case on the weight of the solvent chlorobenzene. In a second vessel made of stainless steel (DIN 1.4571), a 33 wt. % (based on the weight of the solution) phosgene solution was prepared by dissolving 3800 g phosgene in 7600 g chlorobenzene while cooling to 0 C., and the amine and phosgene solutions were mixed into this while stirring intensively. The resulting suspension of solids was then heated slowly with the formation of hydrogen chloride gas, which was withdrawn by suitable means. During this process, a homogeneous solution of the polyisocyanate was formed. The solvent was then separated off by distillation, as a result of which 2370 g of a mixture of diisocyanates and polyisocyanates of the following composition was obtained:4,4'-MDI: 59.3 wt. %2,4'-MDI: 5.5 wt. %2,2'-MDI: 0.2 wt. %higher molecular weight polyisocyanates: 35 wt. %, based in each case on the weight of the mixture.Acidity (ASTM D 1638-74): 62 ppmIron content: 4 ppmExtinction of a 2% solution in chlorobenzene (wavelength 430 nm, film thickness 10 mm): 0.13Thus, when the results of Examples 2 and 3 are compared, it is shown that the use of purified solvent for the production of the amine solution in accordance with the process of the present invention results in an isocyanate being obtained with improved quality, which is expressed as a low acidity, a low iron content and a light color (low extinction). |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 4.30%Chromat.; 0.085%Chromat.; 66.75%Chromat. | Example 1:; Hydrochloric acid (a concentration percentage by weight is 30.8%, this hydrochloric acid is a by-product from MDI apparatus) from storage tank 2 and aniline from storage tank 3 are fed into venturi mixer 5 by a pump 6 with a molar ratio of hydrochloric acid/anilin=0.36:1, for mixing and reacting with each other to produce aniline hydrochloride which is then pumped into circulation pipes and mixed with a circulation solution coming from a condensation stirred vessel 1 to obtain a mixed solution. The obtained mixed solution is introduced into a heat exchanger 7 to remove the reaction heat, and the mixed solution, which is cooled to 38C and left the heat exchanger 7, is introduced into a feeding port of the high gravity rotating bed reactor 8 of rotating packed bed type. Formaldehyde solution (a concentration percentage by weight is 37 wt%) stream from storage tank 4 is fed through another feeding port of the high gravity rotating bed reactor 8, the ratio of formaldehyde to aniline is controlled at 0.40:1. The formaldehyde solution is mixed sufficiently with the previously mixed solution phase and conducted a pre-condensation reaction in the high gravity rotating bed reactor 8, the reaction temperature is controlled at 35C, the reaction time is 0.5 sec, and the rotation speed of the rotor of high gravity rotating bed reactor is 1000rpm. Then the mixed reaction solution flows into the condensation reaction vessel 1 to proceed with the pre-condensation reaction, the temperature of reaction solution is controlled at 42C, the stirring speed is about 110rpm, and the reaction residence time is about 20 min. Then the temperature of reaction solution is elevated to over 90C to conduct a molecular rearrangement reaction, the residence time for molecular rearrangement reaction is about 2 hours. Finally a solution of diphenylmethylene diamine hydrochloride and polymethylene polyphenyl polyamines hydrochloride is obtained. 92 vol% of the reaction mixture from the condensation reaction vessel 1 returns to the circulation pipes, as circulation solution, and flows to heat exchanger 7, the other 8 vol% of the reaction mixture is discharged and neutralized with a sodium hydroxide solution at a concentration of 42 wt%. The salt water phase is separated from the polyamine organic phase, and the polyamines are washed with water and purified to finally obtain a mixture of diphenylmethylene diamine and polymethylene polyphenyl polyamines. The composition of products is listed in table 2. |
Tags: 1208-52-2 synthesis path| 1208-52-2 SDS| 1208-52-2 COA| 1208-52-2 purity| 1208-52-2 application| 1208-52-2 NMR| 1208-52-2 COA| 1208-52-2 structure

A831836 [78525-34-5]
4,4',4'',4'''-(Ethene-1,1,2,2-tetrayl)tetraaniline
Similarity: 0.93

A831836 [78525-34-5]
4,4',4'',4'''-(Ethene-1,1,2,2-tetrayl)tetraaniline
Similarity: 0.93
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| P378 | |
| P380 | Evacuate area. |
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| P390 | Absorb spillage to prevent material damage. |
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| P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
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| P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
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| H411 | Toxic to aquatic life with long-lasting effects |
| H412 | Harmful to aquatic life with long-lasting effects |
| H413 | May cause long-lasting harmful effects to aquatic life |
| H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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