Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/08—Bridged systems
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
  • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
  • A01N47/14—Di-thio analogues thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C333/14—Dithiocarbamic acids; Derivatives thereof
  • C07C333/16—Salts of dithiocarbamic acids
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor

Definitions

• This invention relates, by way of a new product, to a composition for protecting all industrial products liable to biological deterioration.
• the invention prevents damage to liquid or wet paper pulp by microorganisms and forestalls or destroys the microbic ooze that forms in the water systems of paper mills.
• the invention also relates to the manner or methods of industrially using the composition.
• the inventors made the following unexpected discovery forming the basis of the invention: biological damage to industrial products, and particularly with regard to paper making treatments (damage to pulp, prevention or destruction of microbic ooze), can be avoided in a way that is at once advantageous and thorough by treating the products with a stabilized or unstabilized mixture of water soluble salts of at least one mono or dialkyl dithiocarbamic acid and of an alkylene-bis-dithiocarbamic acid.
• the soluble salts are particularly alkaline or alkaline earth salts, including ammonium or quaternary ammonium salts; the alkyl radical comprises one to three carbon atoms, and the alkylene comprises two or three carbon atoms.
• compositions of the invention when used for the purposes indicated, give rise to numerous advantages alongside their non-toxicness. 0n the one hand, the compositions do not leave toxic residues. On the other hand, the range of activity on the different bacterial or cryptogamous organisms is broadened. The action of the compositions increases normally with their concentration in the mass treated; that is, there are no inversion zones as there are with the constituents taken alone (the behavior of sodium dimethylthiocarbamate being well known).
• R is an alkyl group having a low molecular weight (equal to or less than C R is H or an alkyl group of low molecular weight;
• M is an alkaline or an alkaline earth cation or a quaternary ammonium
• alkylene-bis-dithiocarbamates having the formula MS-C--NH(CH2)nNHCSM l t where n is equal to 2 or to 3 and M has the same meaning as under (1).
• a composition which is especially effective, is a mixture of alkaline-dimethyldithiocarbamate and ethylene alkaline-bis-dithiocarbamate, the molecular proportions being varied from five to one or one to five.
• compositions obtained from the mixture are solutions that are generally stable under normal conditions for from two to six months. According to another object of the invention, their stability can be improved by adding the condensation product of ethylenediamine with methanal. Said product was prepared by Bischoif (Berichte 3l-32541898). The quantity added may amount to 25 of the dithiocarbamic salts. It is interesting to observe that, even in the very large quantities indicated, the weak action of the stabilizer has no unfavorable elfect on the activity of the composition.
• composition containing 10% to 25% of this additive remains stable for from 18 to 24 months under usual conditions.
• compositions of the invention are employed as aqueous solutions. They can be prepared either by mixing aqueous solutions of the various components of the composition, according the desired proportions, or by operating the reaction from a mixture of amines.
• compositions of the invention with the results obtained from their use compared with those obtained from the individual constituents.
• EXAMPLE 1 632 grams of 40% dimethylamine solution, 415 grams of 20% ethylenediamine solution, and 1090 grams of 30% caustic soda lye were loaded into a glass reactor furnished with means for agitation and reflux.
• composition of the invention can also be obtained by mixing corresponding amounts of solutions of sodium dimethyldithiocarbamate and sodium ethylene-bis-dithiocarbamate.
• the amine proportions can be varied. Broadly, from 0.2 to 0.5 of a mole of ethylenediamine are preferably used for from 0.8 to 0.5 of a mole of alkylamine.
• compositions Examples 1 and 2 remained stable for 12 weeks.
• the 1,3,6,8 diendomethylene 1,3,6,8 tetraazacyclodecane or 1,8,3,6 diendomethylene 1,3,6,8 tetraazacyclodecane had been prepared by the action of ethylenediamine on formaldehyde in aqueous solution.
• Diendomethylene tetraazacyclodecane can be prepared as follows:
• the clear yellow soltuion has pH equal to 8.7.
• the solution obtained was yellow-green, with a density 1.185 and containing 20% of combined carbon sulphide.
• the bacteriostatic threshold (the amount inhibiting growth in culture broth) and the bactericidal threshold (destruction in an agar-agar containing nutritive medium) were determined. Following a similar method, the fungistatic thresholds were also found.
• the tests were conducted on a broad range of microorganisms, among which were a mushroom (Aspergillus flavus), a Gram-positive bacterium (Staphylococcus aureus), and a Gram-negative bacterium (Pseudomonas aeruginosa)
• the tables show some of the results obtained with the products used.
• PR and PR respectively designate the compositions of Examples 1 and 3.
• the amounts of active substances are given in parts per million (ppm).
• Tables Ia Ib relate to the fungicidal and fungistatic thresholds on Aspergillus flavus.
• Tables H and III show the bacteriostatic and bacteri- (DMTCD). No control is obtained with product A. At cidal levels, respectively, with Staphylococcus aureus. p.p.m., the product B gives total control. The synergism A. STAPHYLOCOCCUS AUREUS is evident- Substance 40 20 10 5 1 0.1
• Control Suspension 2 In Table V, below, which is similar to Table IV, the of the Lamor screens, and on the walls of the back water product A consists of ethylene-bis-dithiocar-bamate and dibox. methyl dithiocarbamate.
• the product B consists of product
• the PR 3 mixture was continuously added in the Four- A+diendomethylene tetraazacyclodecane as stabilizer 75 drinier pit catching the water from the pulp, so that its concentration in the water was from O.2-to 1 p.p.m. The average number of breaks over a period of 15 days was reduced to one or two daily. Moreover, it must be noted that it was impossible to be certain that these breaks were caused by the formation of ooze.
• a bacteriostatic and bactericidal composition consisting essentially of (1) a water soluble salt selected from the group consisting of alkali metal and alkaline earth metal salts of alkyl dithiocarbamic acids, the alkyl group being of one to three carbon atoms, (2) a water soluble salt selected from the group consisting of alkali metal and alkaline earth metal salts of alkylene-bis-dithiocarbamic acids, the alkylene radical being of two to three carbon atoms, and (3) a stabilizer consisting essentially of 1,8,3,6 diendomethylene 1,3,6,8 tetraazacyclodecane, the molecular proportions between the alkyl dithiocarbamate and the alkylene-bis-dithiocarbamate varying from one to five and five to one by weight and the stabilizer being from to 25% of the weight of the composition.
• alkyl dithiocarbamate is of the formula where R is an alkyl group equal to or less than C R' is H or an alkyl group equal to or less than C and M is an alkali or alkaline earth metal substituent.
• composition of claim 1 wherein the alkylenebis-dithiocarbamate is of the formula where n is two or three and M is alkali or alkaline earth metal substituent.
• composition of claim 2 wherein the alkylene-bisdithiocarbamate is of the formula where n is two or three and M is as in claim 2.
• composition of claim 3 wherein a soluble salt of ethylene-bis-dithiocarbamic acid is employed.
• composition of claim 4 wherein there is a mixture of dimethyl dithiocarbamate and of ethylene-alkali metal-bis-dithiocarbamate.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=8791477

Family Applications (1)

Country Status (6)

Cited By (4)

Families Citing this family (3)

Family Cites Families (1)

• 1962
  • 1962-11-23 FR FR916456A patent/FR1356258A/fr not_active Expired
• 1963
  • 1963-11-19 FI FI632254A patent/FI47262C/fi active
  • 1963-11-21 SE SE12862/63A patent/SE324672B/xx unknown
  • 1963-11-22 DE DEP33041A patent/DE1287258B/de active Pending
• 1964
  • 1964-12-31 OA OA51394A patent/OA01212A/xx unknown
• 1968
  • 1968-04-08 US US719715A patent/US3577547A/en not_active Expired - Lifetime

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