13680-35-8

Usage

Uses

Used in Polyurethane Industry:
4,4'-Methylenebis(2,6-diethylaniline) is used as a chain extender for polyurethanes (PU) to improve their mechanical and dynamic properties. Its incorporation into standard formulations results in enhanced performance characteristics that are not achievable with conventional methods.
Used in Epoxy Resin Industry:
In the epoxy resin industry, 4,4'-Methylenebis(2,6-diethylaniline) serves as an effective curing agent for epoxides (EP). Its use leads to the creation of epoxy resins with superior mechanical and dynamic properties, making them suitable for a wide range of applications.
Overall, 4,4'-Methylenebis(2,6-diethylaniline) is a valuable compound in the chemical industry, playing a crucial role in enhancing the properties of polyurethanes and epoxy resins, leading to improved performance and durability in various applications.

Flammability and Explosibility

Notclassified

Synthetic route

formaldehyd (50-00-0) + 2,6-diethylaniline (579-66-8) + 2-isopropyl-6-methylaniline (5266-85-3) → M-MIPADEA + methylene-1,1-bis(2-isopropyl-6-methylaniline) (16298-38-7) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8)

Conditions	Yield
With sulfuric acid In water; isopropyl alcohol at 60℃; for 5.5h; Product distribution / selectivity;
With sulfuric acid In water; isopropyl alcohol at 60℃; for 5.5h; Product distribution / selectivity;

formaldehyd (50-00-0) + 2,6-diethylaniline (579-66-8) + 2-isopropyl-6-methylaniline (5266-85-3) → M-MIPADEA + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8)

Conditions	Yield
With sulfuric acid In water; isopropyl alcohol at 60℃; for 5.5h; Product distribution / selectivity;

formaldehyd (50-00-0) + 2,6-diethylaniline (579-66-8) → 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8)

Conditions	Yield
Stage #1: 2,6-diethylaniline With hydrogenchloride In water at 50 - 55℃; for 0.5h; Inert atmosphere; Stage #2: formaldehyd In water at 90 - 95℃; for 2h; Temperature;

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) (106246-33-7)

Conditions	Yield
Stage #1: 4,4′-methylenebis(2,6-diethylaniline) With hydrogenchloride In water at 20℃; for 0.25h; Stage #2: With dihydrogen peroxide In water at 45 - 65℃; for 3h;	99.3%
With chlorine; acetic acid at 50 - 55℃; Reagent/catalyst; Temperature;	92.8%

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → bis-(3,5-diethyl-4-aminocyclohexyl)-methane (60469-05-8)

Conditions	Yield
With Ru/Al2O3; hydrogen In cyclohexane at 110℃; under 15001.5 Torr;

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + salicylaldehyde (90-02-8) → [(HOC6H4-o-C(H)=N-2,6-(CH3CH2)2(4-C6H2))2-4-CH2] (849704-38-7)

Conditions	Yield
toluene-4-sulfonic acid In methanol for 12h; Heating / reflux;	95%

3-tert-butyl-2-hydroxybenzaldehyde (24623-65-2) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → [(HO-(3-tert-butyl)C6H3-o-C(H)=N-2,6-(ethyl)2C6H2)2-4-CH2] (937721-14-7)

Conditions	Yield
toluene-4-sulfonic acid In methanol for 12h; Heating / reflux;	95%

maleic anhydride (108-31-6) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → di(3,5-diethyl-4-maleimido-phenyl)methane (105357-12-8)

Conditions	Yield
Stage #1: maleic anhydride; 4,4′-methylenebis(2,6-diethylaniline) In toluene Stage #2: With methanesulfonic acid In toluene for 1.5h; Reflux;	96%

formaldehyd (50-00-0) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → C66H90N6

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 100 - 150℃; for 12h;	99%

quinoline 2-carbaldehyde (5470-96-2) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → C41H40N4

Conditions	Yield
In ethanol at 20℃; for 24h;	50%

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + butanone (78-93-3) → N,N'-di-sec-butyl-4,4'-methylenebis(2,6-diethylbenzeneamine) (910915-05-8)

Conditions	Yield
With amberlyst-15; hydrogen; Pt(S)/C at 22 - 95℃; under 7224.57 Torr; for 3h; sulfonated divinylbenzene/styrene copolymer H ion form; Product distribution / selectivity; Autoclave;	94 %Chromat.
With amberlyst-15; hydrogen; Pt(S)/C In tetrahydrofuran at 22 - 120℃; under 5414.51 - 7224.57 Torr; for 5h; sulfonated divinylbenzene/styrene copolymer H ion form; Product distribution / selectivity; Autoclave;	86 %Chromat.

4-formyl-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (950-81-2) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → CH2[C6H2(C2H5)2NCHC3N2(CH3)2(C6H5)O]2 (1296869-06-1)

Conditions	Yield
With formic acid In methanol for 4h; Reflux; Inert atmosphere;	41.4%

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + butanone (78-93-3) → C25H36N2 + N,N'-di-sec-butylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) (910915-11-6)

Conditions	Yield
With Amberlist-15 In hexanes at 40℃; for 49h; sulfonated divinylbenzene/styrene copolymer H ion form; Heating / reflux;	A n/a B 94.7 %Chromat.

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + butanone (78-93-3) → N-sec-butyl-4,4'-methylenebis(2,6-diethylbenzeneamine) + N,N'-di-sec-butyl-4,4'-methylenebis(2,6-diethylbenzeneamine) (910915-05-8)

Conditions	Yield
With hydrogen; Pt(S)/C In toluene at 22 - 130℃; under 6448.83 Torr; for 19.5h; Product distribution / selectivity; Autoclave;	A 4 %Chromat. B 96 %Chromat.

6-(hydroxymethyl)picolinaldehyde (39621-11-9) + tetrakis(actonitrile)copper(I) hexafluorophosphate (64443-05-6) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → 2C35H40N4O2*2Cu(1+)*2F6P(1-)

Conditions	Yield
Stage #1: 6-(hydroxymethyl)picolinaldehyde; 4,4′-methylenebis(2,6-diethylaniline) In methanol at 20℃; for 0.5h; Stage #2: tetrakis(actonitrile)copper(I) hexafluorophosphate In methanol at 20℃; for 15h;	36%

pyridine-2-carbaldehyde (1121-60-4) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → 4,4'-methylene-N,N'-(2-pyridinylmethylene)-bis(2,6-diethylanil)

Conditions	Yield
With toluene-4-sulfonic acid In ethanol at 20℃; for 48h;	61%
In methanol

phenyl(pyridin-2-yl)methanone (91-02-1) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → 4,4'-methylene-N,N'-(phenyl-2-pyridinylmethlene)-bis(2,6-diethyl-anil)

Conditions	Yield
With tetraethoxy orthosilicate; sulfuric acid at 150℃; for 10h;	73%

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + acetone (67-64-1) → N-isopropylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) + N,N'-diisopropylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) (910915-14-9)

Conditions	Yield
With amberlyst-15 for 24h; sulfonated divinylbenzene/styrene copolymer H ion form; Molecular sieve; Heating / reflux;

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + 1-Chloromethylnaphthalene (86-52-2) → 4′-methylenebis(2,6-diethyl-N-(naphthalen-1-ylmethyl)aniline)

Conditions	Yield
With potassium carbonate In acetonitrile at 83℃; for 24h;

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + Phenyl glycidyl ether (122-60-1) → 1-{4-[3,5-diethyl-4-(2-hydroxy-3-phenoxy-propylamino)-benzyl]-2,6-diethyl-phenylamino}-3-phenoxy-propan-2-ol

Conditions	Yield
at 100℃; for 5h;

6-(hydroxymethyl)picolinaldehyde (39621-11-9) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → (6-{[(E)-4-(3,5-Diethyl-4-{[1-(6-hydroxymethyl-pyridin-2-yl)-meth-(E)-ylidene]-amino}-benzyl)-2,6-diethyl-phenylimino]-methyl}-pyridin-2-yl)-methanol

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 4-formyl-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (950-81-2) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → CH2[C6H2(C2H5)2NCHC3N2(CH3)2(C6H5)OPdCl2]2 (1296869-09-4)

Conditions	Yield
In acetic acid under N2, Schlenk techniques; proper 4,4'-methylene bis-(2,6-dialkylaniline), antipyrine-4-carboxaldehyde, PdCl2(COD) added to glacial CH3COOH, reflux (12 h), cooled to room temp.; pptd. (Et2O), solid washed (MeOH, ether); elem. anal.;

Upstream product

• 50-00-0 formaldehyd 
• 579-66-8 2,6-diethylaniline 
• 5266-85-3 2-isopropyl-6-methylaniline 

Downstream Products

• 910915-11-6 N,N'-di-sec-butylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) 
• 910915-05-8 N,N'-di-sec-butyl-4,4'-methylenebis(2,6-diethylbenzeneamine) 
• 1296869-06-1 CH₂[C₆H₂(C₂H₅)2NCHC₃N₂(CH₃)2(C₆H₅)O]2 
• 106246-33-7 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) 
• 105357-12-8 di(3,5-diethyl-4-maleimido-phenyl)methane 
• 937721-14-7 [(HO-(3-tert-butyl)C₆H₃-o-C(H)=N-2,6-(ethyl)2C₆H₂)2-4-CH₂] 
• 910915-14-9 N,N'-diisopropylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) 

Relevant academic research and scientific papers

Preparation method of 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline)

The invention discloses a preparation method of 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline). The preparation method comprises the following steps: (1) in a nitrogen protective atmosphere, carrying out reaction on raw materials 2,6-diethylaniline and hydrochloric acid to generate 2,6-diethylaniline hydrochloride, and dropwisely adding formalin to carry out condensation reaction; after the reaction finishes, neutralizing with liquid caustic soda, and carrying out water separation to obtain 4,4'-methylene-bis-(2,6-diethylaniline); (2) dissolving the product in the step (1) in a solvent, and introducing chlorine to carry out chlorination reaction; after the reaction finishes, neutralizing with liquid caustic soda, and carrying out water separation to obtain a 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) crude product; and (3) dissolving the product in the step (2) in a solvent, decolorizing with activated carbon, cooling to crystallize, filtering, and drying to obtain the final product. The method has the advantages of simple technique, accessible raw materials, low price and high product purity and yield, and can easily implement industrial production.

NOVEL CURING AGENTS

The invention relates to a resin curing agent having the formula (I), wherein R1 to R4 are each individually selected from linear or branched C1 to C5 alkyl, a process for its manufacture, blends of the reaction products, and two-component curable resin systems.