CN85103016A - Many mould clean preparations and application - Google Patents

Abstract

Many mould clean (chemical name is 4-isothiazoline-3-ketone, i.e. 3-hydroxyl isothiazole) (I), structural formula is

Description

Many mould clean preparations and application

The invention belongs to the sterilant class.

Synthetic 4-isothiazoline-3-ketone (I) is if according to literature method ⁽¹⁾, its 3,3 '-mole ratio of dithio dipropyl acidamide (II) and chlorine reaction is 1: 3.5, yield is 75%.The synthetic method of its intermediate (II) is according to patent US3, and 769, be to adopt the bigger hydrogen sulfide of toxicity to participate in reaction 319(1973), yield is 72%.Reaction formula is:

The objective of the invention is to improve operational path, improve yield, reduce cost, reduce toxicity, be convenient to suitability for industrialized production and apply.

With the inventive method when synthetic (I), be to adopt (II) and chlorine reaction, its mole ratio is 1: 3.05, and the solvent that uses is taked the way of segmentation recycling use, and be to adopt acrylamide and sodium polysulphide reaction when synthetic (II), its route is:

Yield brings up to 83% because of after mole ratio changes 1: 3.05 into for (I) synthetic, and solvent can be recycled, and its solvent recovering rate is more than 90%, does not influence product yield and content, reduces cost greatly for suitability for industrialized production provides condition ， And.Synthetic (II) needn't use the hydrogen sulfide toxic gas, be convenient to produce, and raw material is cheap and easy to get.And (I) has antimycotic, bacterial activity, can be used for industrially as industrial biocide mildewcide, as is used for aspects such as electrocoating paint, machine tool coolant, sensitive film, opticinstrument, paste, recirculated water and paint and uses.

Example 1

3,3 '-preparation of dithio dipropyl acidamide

Take by weighing 62.4 grams (0.26 mol) and contain the sodium sulphite of 9 crystal water and the sulphur of 20.8 grams (0.65 mol), the beaker of packing into is heated with stirring to and boils, and the transparent liquid of reddish-brown that generate this moment is sodium polysulfide solution, puts cold standby.

In 500 milliliters of four-hole bottles, add 35.5 gram (0.5 mol) acrylamides (also available industrial acrylamide solution), 42 gram (0.5 mol) sodium bicarbonate and 320 ml waters, fully stir, the frozen water cooling slowly drips the sodium polysulfide solution for preparing above, continue to stir 5 hours, filter the gained solid and be many sulphur thing, take advantage of and wet the step to handle.

Many sulphur of gained thing to be handled with the sodium sulfite aqueous solution of about 300 milliliter of 1 molconcentration, filtration drying promptly get 3,3 '-dithio dipropyl acidamide 44.5 restrains.Fusing point 176-180 ℃, content 97%, pure yield 83%.

(product content is through high pressure liquid chromatographic analysis)

Crude product is through the ethanol/water recrystallization.Fusing point 176-178 ℃

Ultimate analysis: analytical value S% 30.42 N% 13.36

30.47 13.56

Calculated value 30.77 13.46

Spectrum (acetone soln) ν _S-S510cm ^-1ν _C-S658cm ^-1

Example 2

The preparation of 4-isothiazoline-3-ketone (promptly how mould clean)

Adding content is (II) 44.1 gram (0.2 mol) and 200 milliliters of exsiccant ethyl acetate of 94% in 500 milliliters of four-hole bottles, heat is to about 40 ℃, feed chlorine, temperature of reaction remains on 45-50 ℃, reaction later stage hydrogen chloride gas is emitted rapidly, after reacting completely, forms uniform cream-colored suspension, commonly go into chlorine 43.2 grams (0.61 mol), be chilled to room temperature, filter.Again with solid suspension in 150 milliliters of ethyl acetate, being neutralized to ph value of aqueous phase with 20% aqueous sodium hydroxide solution is about 4.5 down in cooling, tell organic layer, dry, desolventizing promptly gets product, weigh 34.1 gram content 98.3%(through high pressure liquid chromatography, thin layer scanning or gc analysis all can), yield 83%, the sherwood oil recrystallization gets white needle-like crystals, fusing point 72.5-73 ℃

Ultimate analysis: analytical value S% 31.39 N% 13.66

31.56 13.86

Calculated value 31.68 13.86

Example 3

The recycling use method of solvent ethyl acetate

The ethyl acetate that logical one step of chlorine is filtered the acid gas-containing of back gained is heavily steamed, be used further to logical one step of chlorine.The ethyl acetate of final product desolventizing gained is directly used in one step of alkaline purification.

Example 4

Many mould clean biological activitys to various industrial moulds, bacterium

How mould clean employing contain mould medium method and measure " " relative inhibition percentage to various common industrial moulds; Adopt " turbidimetry " to measure how mould clean minimal effective concentration and the results are shown in table one, table two various common industrial bacteriums.

How mould clean table one " " suppress percentage relatively to various industrial moulds

Mould title 250 100 50(PPM)

Aspergillus niger 100 87.5 85.0

Penicillium citrinum 100 88.3 86.6

Wood mould 100 81.6 55.0

Chaetomium globosum 100 85.0 68.0

Cladosporium herbarum 100 81.0 74.8

Paecilomyces varioti 100 100 80.5

How mould clean table two " " to various industrial bacterium minimum inhibitory concentrations

Thin mould title minimum inhibitory concentration PPM

Bacillus megaterium 6.25

Bacillus subtilus 6.25

Intestinal bacteria 50

Light pseudomonas 6.25

Streptococcus aureus 25

Example 5

How mould clean " " renderd a service the acrylic latex coating mildew-resistant

(5 * 5cm) is clean with solvent scouring with aluminium sheet, the acrylic latex coating that contains the finite concentration mould inhibitor is smeared on top, after paint film is done, lie in the incubator that contains the PDA substratum,, cover the ware lid then and be placed in the tube of preserving moisture with evenly spraying industrial mould spores suspension on the equal model of the mould device of spray, relative humidity is more than 95%, temperature remains in 26 ℃ the thermostat container, and month " Invest, Then Investigate " model degree that mildews the results are shown in Table three.

Grade scale

0 grade of mildew not

The local fragmentary little mildew of I level

II level mildew area is no more than 1/4

III level mildew area accounts for whole area about 1/2

The whole surface of IV level is covered with mildew

How mould table three is renders a service the acrylic latex coating mildew-resistant only

Medicament title concentration

0.2% 0.1% 0.05%

Many mould clean 00 I

N-54-D 0 Ⅰ Ⅱ

Contrast IV IV IV (level)

Example 6

How mould clean " " prevent the corrupt effectiveness of acrylic latex coating

Preparation contains the acrylic latex coating of finite concentration mould inhibitor, does contrast with not dosing.Add in the lacquer 1% cause the putrid various bacterium mixed solutions of emulsion paint.Be placed in 37 ℃ of thermostat containers and keep relative humidity more than 95%.With bacterium viable count colony counting method, count the viable count that the every gram emulsion paint of every processing contains after one month.The results are shown in Table four

How mould clean table four " " prevent the corrupt effect of acrylic latex coating

The viable count of the every gram emulsion paint of medicament title concentration

Many mould clean 0.1% 3 * 10 ⁴

N-54-D 0.1% 5.5×10 ⁴

Contrast-7.8 * 10 ⁴

Annotate: the mould inhibitor that (1) N-54-D provides for the U.S. big auspicious Mei Hua company limited.Chemical name: daconil M trade(brand)name: Nopcocide-N-54-D.

(2) used bacterial classification is respectively table one, the listed bacterial classification of table two.

Reference

〔1〕S·N·Lewis et al J·Heter Chem 1971 8（4）P571-80.

Claims (5)

1, a kind of with 3,3 '-dithio dipropyl acidamide (II) is a raw material with chlorine, with the ethyl acetate be solvent preparation " how mould clean " (

, (I)) method when it is characterized in that system (II), is to adopt following synthetic route;

2, how mould clean according to the method for the said manufacturing of claim 1 " " (I), when it is characterized in that synthesizing (II), the mole ratio of its each raw material is:

CH ₂＝CHCONH ₂∶Na ₂S _x∶NaHCO ₃∶Na ₂SO ₃＝2∶1∶2∶1.2

3,, it is characterized in that (II) and the mole ratio of chlorine are 1: 3.05, recyclable the recycling of solvent for use (ethyl acetate) according to the method for the said preparation of claim 1 (I).

4, how mould clean a kind of use " " as the method for industrial (as electrocoating paint, machine tool coolant, paste, recirculated water and various paint etc.) sterilization, mildew-resistant, it is characterized in that it is that how mould clean " " be dissolved on the Industrial products that need antimycotic antiseptic, gets final product to be made into minimum effective concentration.

5, the method that is used for industrial fungus and mildew resistance according to the said handle of claim 4 " how mould clean ", minimal effective concentration when it is characterized in that using is mould for aspergillus niger, Penicillium citrinum, wood, Chaetomium globosum, cladosporium herbarum, Paecilomyces varioti be 250(PPM), for bacillus megaterium, Bacillus subtilus and fluorescent pseudomonas is 6.25(PPM), for intestinal bacteria is 50(PPM), and be 25(PPM for streptococcus aureus).