CN103749478A - Formaldehyde releaser and treatment method - Google Patents

Abstract

The invention relates to a stable urea-formaldehyde composition which has a small smell and even has no smell. When combining with one or more biocides such as isothiazolono, the stable urea-formaldehyde composition slowly releases low-level formaldehyde.

Description

The method of formaldehyde releaser and processing

Technical field:

The method that the present invention relates to the stable composition of release formaldehyde and directly process with one or more biocides that comprise formaldehyde release composition.More particularly, the present invention relates to stable ureaformaldehyde composition, when being combined with one or more biocides that contain isothiazolone (isothiazolono), slowly discharge low-level formaldehyde.

Background technology:

The biocide that comprises isothiazolone is to merging they and slaine and formaldehyde stable usually the comprising of thermal degradation and storage degraded.Regrettably, result discharges a large amount of free formaldehydes and other VOCs odorous (VOC).Therefore be desirable to provide smell little and compatible with one or more biocides including isothiazolone, and discharge the stable concentrated formaldehyde release composition of low-level free formaldehyde and VOC.The open No.3 of US patent, 970,625 the method that discharges urea-formaldehyde concentrate of formulation fertilizer containing nitrogen as urea that provides has been provided.This concentrate is by merging the buffer solution of water-containing acetal and formic acid and urea in ammoniacal liquor, makes the mol ratio of formaldehyde/mol urea that gained mixture contains 4.4-7.3mol and prepares in two steps.The pH of mixture is adjusted to 8.8-9.5, adds hot mixt, by under reduced pressure distillation, remove water, so that concentrate to be provided.But urea-yuban product is odorous and also contains a large amount of free formaldehydes except other VOC.

Inventor has had been found that the one-step method of preparation low cost and the stable liquid urea-formaldehyde concentrate compatible with various biocides including isothiazolone.This concentrate is to have low smell and a high proportion of combination formaldehyde, thereby the clear solution of low-level free formaldehyde is provided.In addition, formaldehyde releaser concentrate has shown separately bio-killing activity, and is combined with one or more biocides, has observed collaborative bio-killing activity.Inventor also had been found that with separately and with the method for the formaldehyde releaser processing of one or more biocides (comprising isothiazolone) combinations.

Therefore, the invention provides and comprise urea, formaldehyde and paraformaldehyde, urea: the formaldehyde that formaldehyde mole ratio is 1: 3 discharges composition, wherein said composition is the density having lower than 1.3g/mL, lower than the VOC of 40wt% with lower than the colourless transparent liquid of the free formaldehyde level of 3wt%, based on the weight of said composition.

The present invention also provides and has comprised one or more isothiazolones and contain urea, formaldehyde and paraformaldehyde, urea: the formaldehyde that formaldehyde mole ratio is 1: 3 discharges the Biocidal composition of composition, wherein said composition has the density lower than 1.39/mL, lower than the VOC of 40wt% with lower than the free formaldehyde level of 3wt%, based on the weight of said composition.

The present invention also provides the method for producing formaldehyde release composition, comprises the following steps: water-containing acetal, sodium hydroxide, urea and paraformaldehyde to mix, and this mixture is heated to 90 ℃, until solid liquefaction, and pH is adjusted to 4-5.The method provides formaldehyde to discharge composition, and it is the density having lower than 1.3g/mL, lower than the VOC of 40wt% with lower than the colourless transparent liquid of the free formaldehyde level of 3wt%, based on the weight of said composition.

The present invention also provides the method for processing, comprise and add one or more isothiazolones and contain urea, formaldehyde and paraformaldehyde, urea: the formaldehyde that formaldehyde mole ratio is 1: 3 discharges the step of composition, wherein said composition has the density lower than 1.3g/mL, lower than the VOC of 40wt% with lower than the free formaldehyde level of 3wt%, based on the weight of said composition.

Term used herein refers to any system that contains water.Term VOC refers to VOC.Term volatility refers to the organic compound under atmospheric pressure with 100 ℃ or lower vapour pressure.Many VOCs can be by detecting because their steam forces down the smell of emitting.

Formaldehyde discharges (FR) composition and comprises urea: the mixture of urea, formaldehyde and paraformaldehyde that formaldehyde mole ratio is 1: 3.Typically, PR composition is clear, colorless liquid.FR composition has the density lower than 1.3g/mL, lower than the VOC of 40wt% with lower than the free formaldehyde level of 3wt%, based on the weight of said composition.FR concentrate has low smell, and a high proportion of combination formaldehyde is consistent with existing.Separately and with the FR composition of one or more biocides (comprising isothiazolone) combination provide formaldehyde in effective release.In addition, separately and can effectively control microbial growth with the FR concentrate of one or more biocides (comprising isothiazolone) combination.

The applicable example of biocide that can be effectively used according to the invention comprises as in US patent Nos.3,523,121; 3,761,488; 4,954,338; 5,108,500; 5,200,188; 5,292,763; 5,444,078; 5,468,759; 5,59 weights, 706; 5,759,786; 5,955,486 and specially tooth of Europe, No.EP 0 302 701; EP 0 490 565; EP 0 431 752; EP 0 608911; EP 0 608 912; EP0 608 913; Isothiazolone described in EP 0 611 522 and BP 0 648 414.

According to one embodiment of the invention, can be used for isothiazolone of the present invention is NEOLONE 950,5-chloro-2-methyl-3-isothiazolone, 2-octyl group-3-isothiazolone, the chloro-2-cyclohexyl-3-of 4,5-bis-isothiazolone, the chloro-2-octyl group-3-of 4,5-bis-isothiazolone and their bond.

The example of other applicable bio-killing activity compositions comprises benzisothia oxazolone, di-bromonitrilopropiona,ide (DBNPA), 2-(thiocyanogen methyl mercapto) benzothiazole (TCMTB), iodine propargyl butyl carbamate (1PBC) and parabens.

Well known in the art, the performance of microbicide is usually by share to improve with one or more other microbicides.In fact, there is the collaborative example share of many biocides.We have found that, other known microbicides can advantageously discharge composition with formaldehyde of the present invention and share to process.

PR composition can be compatible with isothiazolone, and be used as the stabilizing agent of many isothiazolones.For example, when needs are packed isothiazolone and PR (using tank), the consumption of FR will be about 1% to about 25%.Isothiazolone can exist with body form, or packs or encapsulated by some mode, comprises slowly-releasing form.The ratio of FR and isothiazolone preferably about 1,5: 1 to 1: 7.

Optionally with solvent, dissolve isothiazolone, solvent comprises dissolving isothiazolone, adapts to the product purpose of plan, does not make isothiazolone remove any organic solvent stable and that do not react with isothiazolone or PR.Applicable solvent is including, but not limited to hydroxylic solvent, for example polyalcohol, and as ethylene glycol, polyethylene glycol, alcohols, ethers, polyethers and their bond.According to an embodiment independently, solvent also can be effective to prepare FR composition.

According to an embodiment independently, in mixture, can use a small amount of solvent, to contribute to form stable microemulsion.The exemplary of solvent comprises alcohols, for example methyl alcohol, ethanol and ethylene glycol, the mixture of water and alcohols, ethers, polyethers, and their bond.Can use hydroxylic solvent, for example polyalcohols, as glycols, the monoether of glycol, alcohols etc.Can also use hydroxyl coalescent, for example trimethyl-1,3-pentanediol mono isobutyrate.In some preparaton, hydro carbons (aliphatic series or aromatics) is effective solvent.Typical solvent also comprises dipropylene glycol, dihydroxypropane single-ethyl ether, dimethylbenzene, and white spirit.

At another independently in embodiment, use a small amount of benzylalcohol, benzyl acetate, pine tar, benzyl carbinol, dimethylbenzene, phenoxetol, butyl phthalate, 2 of being selected from, 2,4-trimethyl-1, one or more nonpolar, the immiscible solvent of water dissolves bio-killing activity composition or promotes microemulsion formation in 3-pentanediol mono isobutyrate and alkylbenzene, described solvent at room temperature can dissolve the biocide of at least 5 %.

Because isothiazolone biocide has such activity; so obtain stablize required low-level also make they with the combination of FR composition than many known biocide ideals; because required low-level under, they are not easy to disturb other components in the system needing protection or are not easy to disturb the system that puts on protected system.

Microbicide of the present invention (comprising isothiazolone) formaldehyde releaser bond can be used for many corrosion-resistant fields, comprise disinfectant, sanitizer, cleaning agent, deodorant, liquid soap, powder soap, rawhide remover (hidefemover), grease remover, food processing chemicals, breast chemicals processed, food preservative, animal feed preservative, wood preservation, polymer emulsion, paint, lazufes, colouring agent, mould inhibitor, hospital and medical preservative, medical device, metal working fluid, cooling water, air washing agent, Petroleum Production, paper processing, paper pulp and paper slurry (paporsluffy), paper mill slimicide, oil product, adhesive, textile, pigment slurries, latex, leather and rawhide processing, petroleum fuel, jet fuel, laundry sanitizer, agricultural preparaton, ink, mining, nonwoven, petroleum storage, rubber, sugar processing, tobacco, swimming pool, photograph rinsing liquid, cosmetics, Toiletries, medicine, chemical toilet, home laundry articles for use, diesel fuel additive, wax and polishing agent, field use, and many other application that wherein water contacts under the condition of the undesirable growth of microorganism of permission with organic substance.Other active components can be used as fungicide, miticide, insecticide and plant growth regulator.

Comprise for example recycle cooling device with the typical case of processing of the present invention, utilize the open recycle cooling device of evaporation as cooling source, closed-loop path cooling device, heat exchanger apparatus, reactor, for storing and the equipment of treat liquid, boiler and relevant steam generation device, radiator, flash distillation plant, refrigerating plant, reverse osmosis equipment, gas cleaning plant, blast furnace, paper and paper pulp process equipment, sugar evaporation equipment, steam power plant, geothermal device, nuclear cooling device, water treatment facilities, Food & Drink process equipment, pond EGR, mining path, closed-loop path heater, be used for such as drilling well, boring, grinding, fraising, drawing, broaching, turning, cutting, sewing, grind, screw chasing, be shaped, the machined liquid of the operation of spinning and roll-in and so on, hydraulic fluid, cooling fluid, oil exploitation device and drilling mud.

Embodiments more of the present invention are described in detail in following examples.Unless otherwise prescribed, all ratios, part and percentage represent by weight, and unless otherwise prescribed, whole reagent used has good commercial quality.

Embodiment 1 (formaldehyde discharges single tank preparation of composition)

In flask at the bottom of 2 liter of four neck garden that mechanical agitator, condenser, thermometer and pn meter are housed, add the formalin (37%wt./wt.) of 344g (34.4%).Stir this solution, then add the 50wt%NaOH aqueous solution of 8.5g (0.9%), to pH is increased to and is greater than 10.5.When stirring, urea solid (241.4g, 29.1%) is joined in this alkaline mixt, also add the paraformaldehyde resin as bead (90%) of 351.3g (35.1%).Under agitation the dense mixture of solid and liquid is heated to 90 ℃, this temperature is kept 1 hour.Solid liquefaction, the outward appearance of reactant becomes transparent from muddiness.Use 32wt% aqueous hydrochloric acid solution (4.8g, 0.5%) that the pH of reactant is adjusted to 4-5, then reactant is heated other 1 hour.Cooling solution, has obtained the product (PR2) with the following performance as summed up at table 1.

Table 1 formaldehyde discharges (FR) composition

The stability test of embodiment 2 (FR with CM1/UI combination) 5-chloro-2-methyl isothiazoline-3-ketone/2-methyl isothiazoline-3-ketone mixes with 14wt% Active principals (A1) 3: 1 mixtures of 5-chloro-2-methyl isothiazoline-3-ketone (CU1)/2-methyl isothiazoline-3-ketone (H1) with 49wt%FR.At 40 ℃ 4 weeks, and at 70 ℃ 1 week and after 2 weeks, measure the retention rate of AI.Measure AI with HPLC.Result is comparable to 3: 1 mixtures of 5-chloro-2-methyl isothiazoline-3-ketone (the CM1)/2-methyl isothiazoline-3-ketone (M1) stable with magnesium nitrate (15%).

Claims (9)

1. comprise urea, formaldehyde and paraformaldehyde, urea: the formaldehyde that formaldehyde mole ratio is 1: 3 discharges composition, wherein said composition has the density lower than 1.3g/mL, lower than the VOC of 40wt% with lower than the free formaldehyde level of 3wt%, based on the weight of said composition.

2. comprise one or more isothiazolones and contain urea, formaldehyde and paraformaldehyde, urea: the formaldehyde that formaldehyde mole ratio is 1: 3 discharges the Biocidal composition of composition, wherein said composition has the density lower than 1.3g/mL, lower than the VOC of 40wt% with lower than the free formaldehyde level of 3wt%, based on the weight of said composition.

3. according to the composition of claim 2, wherein isothiazolone is selected from NEOLONE 950,5-chloro-2-methyl-3-isothiazolone, 2-octyl group-3-isothiazolone, the chloro-2-cyclohexyl-3-of 4,5--isothiazolone, the chloro-2-octyl group-3-of 4,5-bis-isothiazolone and their bond.

4. according to the composition of claim 4, wherein this formaldehyde discharges composition and further comprises and be selected from ethylene glycol, polyalcohol, the monoether of glycol, trihydroxy-1,3-pentanediol, dipropylene glycol, the glycol in DPE and their bond.

5. produce the method for formaldehyde release composition, comprise the following steps: water-containing acetal, sodium hydroxide, urea and paraformaldehyde to mix, this mixture is heated to 90 ℃, until solid liquefaction, and pH is adjusted to 4-5, wherein gained mixture has the density lower than 1.3g/mL, lower than the VOC of 40wt% with lower than the free formaldehyde level of 3wt%, based on the weight of said composition.

6. the method for processing, comprises the step of the composition that adds one or more isothiazolones and claim 1.

7. according to the method for claim 6, wherein isothiazolone is selected from NEOLONE 950,5-chloro-2-methyl-3-isothiazolone, 2-octyl group-3-isothiazolone, the chloro-2-cyclohexyl-3-of 4,5-bis-isothiazolone, the chloro-2-octyl group-3-of 4,5-bis-isothiazolone and their bond.

8. according to the method for claim 6, wherein be selected from water treatment facilities, recycle cooling device, utilize the open recycle cooling device of evaporation as cooling source, closed-loop path cooling device, heat exchanger apparatus, reactor, for storing and the equipment of treat liquid, boiler and relevant steam generation device, radiator, flash distillation plant, refrigerating plant, reverse osmosis equipment, gas cleaning plant, blast furnace, paper and paper pulp process equipment, sugar evaporation equipment, steam power plant, geothermal device, nuclear cooling device, Food & Drink process equipment, pond EGR, mining path, closed-loop path heater, machined liquid, hydraulic fluid, cooling fluid, oil exploitation device and drilling mud.

9. according to the method for claim 6, wherein with the formaldehyde that contains one or more isothiazolones and claim 1, discharge the microemulsion processing of composition.