N,N-Methylenebismorpholine containing biocidal products are used as bactericides for the preservation of fuels and metal working fluids which are prone to bacterial decay.
Two out of seven studies submitted were suitable for proof of preservation, whereas the remaining five studies, which also covered mycobacteria and fungi, were rather suitable for proof of disinfection properties.
N,N-Methylenebismorpholine is a formaldehyde-releaser.
The biocidal activity of Methylene bis morpholine is due to the interaction of the released formaldehyde with protein, DNA and RNA.
The interaction with protein results from a combination with the primary amide and the amino groups. It reacts with carboxyl, sulfhydryl and hydroxyl groups.
As formaldehyde is not specific for one cellular target the development of resistances is not to be expected.
Methylenebismorpholine is intended to be incorporated by industrial users into fuels during the formulation process, which is carried out automatically, to act as a preservative with bactericidal activity.
Formulation is performed in closed systems and high degree of automation resulting in a final concentration of MBM of concentration of 0.01-0.1% in the fuel.
As Metalworking fluid preservative, Methylenebismorpholine is intended to be incorporated by professional users into water based emulsifiable metalworking fluids (MWF) to act as a preservative with bactericidal activity.
The lubricant concentrate,intended for the preparation of water based emulsifiable metal working fluids, contains Methylenebismorpholine at a concentration of 3% w/w.
The use concentration of Methylenebismorpholine in metalworking fluids is typically 0.15% w/w.
Methylenebismorpholine has to be regularly or occasionally re-dosed if a.s. is below effective concentration of 0.15% w/w.
The assessment of the biocidal activity of Methylenebismorpholine demonstrates that it has a sufficient level of efficacy against gram negative bacteria such as Citrobacter freundii, Alcaligenes faecalis, Pseudomonas aeruginosa and Enterobacter aerogenes.
The active substance Methylenebismorpholine is used for the preservation of fuels.
Most sites apply Methylenebismorpholine in closed systems using automatic dosage during formulation of fuels.
As fuels represent mainly an organic matrix and no addition of water is intended, hydrolysis of Methylenebismorpholine and formation of formaldehyde and exposure to formaldehyde is expected to be of minor relevance.
Therefore, exposure to the hydrolysis product formaldehyde was not considered regarding this use.
Formulation of fuels is not performed by non-professionals, therefore, human exposure of the general public via this application is considered to be not relevant.
Anyhow professional and non-professional contact with the active substance might take place during refuelling of engines.
Further exposure is not expected due to the combustion of Methylenebismorpholine within the engines.
Also combined exposure, as well as aggregate exposure were assessed/regarded.
Cumulative exposure which covers concurrent exposure to the same active substance from different biocidal products was not evaluated at present for Methylenebismorpholine.
The area primary exposure of professionals covers workers, who prepare lubricant concentrates and workers, who prepare/apply metal working fluids.
Referring to the identified tasks, inhalation and dermal exposures of workers are considered to be relevant.
The lubricant concentrates and the metalworking fluids contain significant amounts of water and Methylenebismorpholine hydrolyses quickly, therefore, total transformation of Methylenebismorpholine to formaldehyde and morpholine seems to be an acceptable assumption.
Methylenebismorpholine (MBM) as manufactured, is intended to be used as preservative for water based emulsifiable metal working fluids by industrial users.
According to the Intended Use the ready to use metalworking fluid contains 0.15% w/w N,N’-Methylenebismorpholine/kg metal working fluid.
Molecular Formula: C9H18N2O2
Molecular Weight: 186.251
Biocide for Use as In-can preservative
Identity of Active Substance
The active substance N,N-Methylenebismorpholine (short: MBM) is attributed the CAS-No: 5625-90-1 and the EC-No 227-062-3. The molecular formula is C9H1aN202, and the molecular weight is 186.26 g/mol. The minimum degree of purity is 92.10/ow/w.
MBM is a pale yellow liquid, has a slightly amine like odour.
Its melt ing point range is 18- 21°C, and the boiling point is 266.4°C.
The relative density is 1.05 at 20°C and the density is 1.0647 g/cm3 at 20°C.
The calculated vapour pressure of the active substance is 0.625 Pa at 25°C (EpiSuite) and 0.443 at 20°C.
The calculated Henry's law constant is 2. 72x10-s Pa m3 mo1-1 at 25°C.
Water solubility cannot be determined as the active substance is hydrolysable.
MBM is miscible in water in all proportions (at 10 - 30°C and at pH 5 - 9).
The dissociation constant (pKa) is calculated to be 7.39 and 2.98 at 20°C.
(MBM cannotbe isolated because of its hydrolysis properties and therefore determination of the single pKa values is not possible.)
The solubility of MBM is 2000 - 2500 mg/L in Heptan and MBM is completely miscible in DMSO, Toluene, Ethanol, n-Octanol, Acetone and partially soluble in Cyclohexane at 21-23 °C.
The active substance as manufactured does not contain any organic solvents.
The active substance MBM displays neither explosive nor oxidizing properties based on its structure.
Its flash point is 115°C. The substance can be safely handled up to its flash point (115°C).
It is not considered to be reactive to container material.
Morpholine is a hydrolysis product of the active substance N,N-Methylenebismorpholine
Selected literature data on physico–chemical properties were provided by the applicant:
Morpholine is an oily ,hygroscopic, colourless liquid; has a characteristic amine smell.
Its melting point range is -3,1 to -5°C, and the boiling point is 128°C.
The relative density is 1.0001 at 20°C.
The vapour pressure of morpholine are 1.1 kPa at 20°C; 3.2 kPa at 40°C and 1.34 kPa at 25°C
The literature data of Henry’s law constant are 49 Pa m3 mol-1(20°C); 244 Pa*m3*mol-1 and 0.012 Pa*m3*mol-1(25°C)
The structure of morpholine is confirmed by IR- spectra.
Morpholine is miscible with water and has a low soluble in alkaline aqueous solutions.
The dissociation constant (pKa) is to be 8.5 and 8.33 at 25°C.
Morpholine is completely miscible with, for instance, methanol, ethanol, acetone, diethyl ether, benzene, toluene,xylol.
The partition coefficient Octanol-Water is -0.86 (pH no data), and -2.55 (pH 7).
Morpholine is not surface active and the viscosity is 2.021 mPas at 25°C.
The hydrolysis product morpholine displays neither explosive nor oxidizing properties based on its structure.
Its flash point is 38°C- Open cup and 33°C - Closed cup.
Morpholine is a flammable liquid Category 3.
It is not considered to be reactive to container material (LDPE.).
N,N'-Methylenebismorpholine@100 μg/mL in Methanol
N,N'-Dimorpholinomethane / 4,4'-methylenedimorpholine / N,N'-Methylenbismorpholin
4,4'-Methylendimorpholin [German] [ACD/IUPAC Name]
4,4'-Methylenedimorpholine [ACD/IUPAC Name]
4,4'-Méthylènedimorpholine [French] [ACD/IUPAC Name]
Morpholine, 4,4'-methylenebis- [ACD/Index Name]
1,2,3,4-Tetrahydroquinoline [ACD/IUPAC Name]
4-27-00-00203 (Beilstein Handbook Reference) [Beilstein]
N,N'-Methylene-bis-morpholine, metilen bis morfolin, metilenbismorfolin,metilen bismorpholine, MBM, Metal işleme sıvısı için biyosit, bakterisit, fungusit,CAS 5625-90-1
N,N'-Methylene-bis-morpholine by Ataman is used in metalworking fluid compositions as preservative / biocide
N,N-Dimorpholinomethane; Morpholine,4,4-methylenebis-; Bis(4-morpholinyl)methane; N,N'-Methylenebismorpholine;
4,4'-methanediyldimorpholine; 4,4-methylenebis-Morpholine; N,N-Methylene-bis-morpholine; N,N'-DIMORPHOLINOMETHANE;
4,4'-methylenedi-morpholin; 4,4'-methylenedimorpholine; bis(morpholino-)methan; bismorpholinomethane; N,N'-Methylenebismorpholine;
N,N'-DIMORPHOLINOMETHANE; 4,4’-methylenedi-morpholin; 4,4’-methylenedimorpholine; bis(morpholino-)methan; bismorpholinomethane; N,N’-Methylenebismorpholine;
DIMORPHOLINOMETHANE; DIMORPHOLINOMETHONE;N,N'-Dimorpholinomethane;;N,N´-Methylene bismorpholine;Bis (morpholino-) methan; Bismorpholino methane;
4,4-Methylenedimorpholine; Morpholine, 4,4-methylenedi-
cas no : 5625-90-1
N,N'-Methylene-bis-morpholine helps to increase the life of metalworking fluid with maintaining the stable product function and preserving the fluid from bacteria and fungi.
It could be for metalworking fluid concentrate during manufacturing or for tank side treatment.
N,N'-Methylene-bis-morpholine - CAS 5625-90-1
Molecular Formula: C9H18N2O2
Molecular Weight: 186.251
N,N'-Methylene-bis-morpholine - Physico-chemical Properties
Molecular Formula C9H18N2O2
Molar Mass 186.251 g/mol
Boling Point 265.1°C at 760 mmHg
Flash Point 77.6°C
Vapor Presure 0.00935mmHg at 25°C
Refractive Index 1.496
Purity of Active Content
Boiling point ℃
Solubility in Water
Usage of MBM ( Methylene-bis-morpholine) :
1, a low toxicity broad spectrum fungicide for water-based metalworking fluid
2, anti-Bacteria and fungi effectively
3, fully meet with the requirements of water-based metalworking fluid: low skin irritation, mild odor, lowntoxicity; formulation compatibility, lasting bactericidal.
At higher concentrations, fungi and molds also have better inhibition.
Recommended addition amount (mass ratio): Recipe 2-3%, the working liquid 1-2‰;
6.Package: 25kg/ drums or 200kg/ drums
Application and Benefits of Methylene-bis-morpholine : Biocide ( Preservative ) in the the metal working fluid composition permits the efficient practice of cutting, grinding, form rolling, press working and plastic
working of metallic materials.
NO MORE FORMALDEHYDE !!
Formaldehyde occurs naturally in the environment as a
by-product of metabolic processes in humans, animals and
through the natural decay process of plant species.
Formaldehyde is even detectable in human breath at low
levels. Under the changes planned to the labelling of
certain chemicals, formalin-releasing species have been
re-classified according to their total potential to release
formaldehyde and not through actual measurement in use.
Research by several chemical manufacturers supports very
low levels, no higher than the surrounding environment,
when used well managed metalworking fluid systems.
Formaldehyde has long been classed as a category 1B
carcinogen. Formaldehyde Depots or ‘donors’ (FADs) have
been used to improve the sump life of soluble metalworking
New legislation now affects certain formalin- containing
biocides. Under the recent update to CLP regulation, ATP
(Adaptation to Technical Progress, review May 4th 2017),
any product or treated article which contains certain formalin-containing biocides (to protect the function of the
product) will need to be labelled as category 1B. Examples
of the biocides affected include methylene bis-morpholine
(MBM) and methylene bis[5-methyloxazolidine] (MBO).
Methylene bis-morpholine (MBM) is a low toxicity biocide developed for use in metal working concentrates. Nipacide MBM is effective against a wide range of microorganisms including
gram positive and gram negative bacteria, yeast and fungi. Microorganisms grow at a rapid rate and without use of the correct biocide, numbers can increase dramatically.
Methylene bis-morpholine (MBM)is recommended for preservation of metal working solution concentrates. N,N'-Methylene-bis-morpholine is effective against a wide range of spoilage
organisms and effective over a wide pH and temperature range.
Methylene bis morpholine should be evaluated in finished products at levels between 2.0% and 5.0%.