JPS62286905A - Mixed halogenating and/or halogen intermediate compound molecule addition reactant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention Field of Industrial Application The present invention relates to the instantaneous disinfection of water by contact, and in particular to the synergistically stabilized mixed form of halogenated and/or water disinfection. Or it relates to an interhalogen compound-added vinylpyridine resin.

BACKGROUND OF THE INVENTION Several techniques are known that use resins to kill bacteria in water. 12 which has a bactericidal effect on the ordinary method.
．． 8r2. and treatment of water with resins that release residual halogens, such as C-2.

Some methods also use polyhalide anion exchange resins. Still other water disinfection techniques use anion exchange resins loaded with insoluble triiodide (+3). The following patents are illustrative of such technology: U.S. Patent No. 3,316,173;
, No. 565,872: No. 3.817.860; No. 3.
No. 923゜665; No. 4.187.183: No. 4.1
No. 90.529: and No. 4,420,590.

Problems to be Solved by the Invention However, the resin according to the above technology releases halide and polyhalide ions and does not produce the most suitable halogen-hypohalous acid mixture for disinfection, which reduces its disinfection power. . U.S. Pat. No. 3,565,872 is not composed of an anion exchange resin, but has similar problems, and the decomposition of the resin is accelerated in an aqueous medium containing carbon, Brz, BrCJl, etc. There is a risk that the problem will be corrected.

Furthermore, any of the above anionic resins is No. 4,187.
No. 183 patent does not produce hypohalous acid when water with a large total dissolved amount of salts is treated, and U.S. Patent No. 4,187
, No. 183 is also very small (0221) under such circumstances.
) 11ml-101 > Only hypoiodic acid is produced. Hypoiodic acid is preferable because it has stronger bactericidal activity and virus eradication properties than iodine (I2). Previously, high levels of sub-iodic acid were produced using U.S. Patent No. 4.187.18.
No. 3, an iodinated anion exchange resin is used in combination with a scavenger system, or as described in U.S. Pat.
No. 3.716 and No. 3.161,588, external oxidizing agents such as chloramines were added.

The halogen intermediate compound resin of U.S. Pat.
It is not 2 HOI or Bl'2-HOBr.

Therefore, it provides an instant bactericidal effect upon contact in one pass, releases optimal bactericidal levels of halogens and hypohalous acid, does not release halides and polyhalides, and also lasts for a long time in an aqueous medium. There is a need in the water treatment technology for improved resins that provide stability.

Accordingly, the present invention provides a synergistically stabilized blended halogenated and/or interhalogenated polymeric vinylpyridine resin that fuses and simultaneously sterilizes water in a single pass. The purpose is to The invention also applies to bacteria, viruses.

and by the hydrolysis of halogens and hypohalous acids, for example, or by the reaction of halogens or interhalogen compounds with another halogen, which give a universal bactericidal action against amoeboid cells.
The purpose is to provide a bactericidal resin that forms an optimal bactericidal mixture consisting of ○[) and blanches. An object of the present invention is to provide a resin in which the eluate produced does not contain halide or polyhalide even when water with a relatively high salt concentration is treated. A further object of the present invention is to provide a resin that is stable for a long period of time in an aqueous medium.

SUMMARY OF THE INVENTION The present invention provides a halogenated and/or interhalogenated abase polyvinylpyridine resin with water sterilizing properties.The resin is passed through a column or bed system only once. It is used to instantly sterilize water contaminated with bacteria.

To achieve these objectives, the present invention provides pyridyl functional groups cross-linked with divinylbenzene, divinylpyridine, or other conventional cross-linking agents and covalently bonded to the vinyl polymer backbone through pyridyl No. 2 or 1N α4 carbons. A sterilizing medium for bacteria-containing water is obtained by treating granular or beaded polymeric vinylpyridine resins with halogens and/or interhalogen compounds. In the present invention, depending on the degree of loading of the halogen and/or interhalogen compound onto the vinylpyridine resin, it is possible to perform #2 bacteria by simply passing the halogen and/or interhalogen compound instantaneously, and in this case, residual halogen and hypochlorite can be removed. Halogen acid () (OBr or 1-
(01) is generated. If you want to reduce or remove this residual halogen and hypohalous acid, use l! ini
A subsequent scavenger column or activated carbon bed may be used.

Formation of nonionic complexes with pyridyl functional groups of halogens and/or interhalogens, hydrolysis of interhalogens, and/or - in resin matrices between halogens or interhalogens and other halogens. The combination of the reactions at 1 and 2 causes the generation of halide ions (■- and Sr) and polyhalide ions (I3.

Br3, IzC [, etc.] tonoion exchange does not occur, and by minimizing the halide and polyhalide content in the eluate water, it is more bactericidal and more physiologically effective as aimed at in U.S. Pat. The result is a portable water sterilizer that is easily tolerated. U.S. Patent No. 3.5
No. 65,872; No. 3,187,866; and No. 4.
Prior art resins, such as No. 187.183, when used in water with an overall high concentration of dissolved salts, create problems with halide excess (more than 5-10 ppm) and replacement of polyhalide from the resin. However, such a problem does not occur with the resin according to the present invention.

In the present invention, nonionic complexes are formed, so in the preparation process, iodine salts and bromine J3! (e.g. Kl and 8r) are not required, which maximizes the bactericidal effect of the halogens and interhalogens as a whole. For example, the polyhalide resin Br3 of U.S. Pat. No. 3,462.363
- etc., 1/3 of the halogen is wasted just for bonding the negatively charged triiodide ion (Br3) to the positively charged anion exchange resin.

The resins obtained according to the invention can be used in swimming pool disinfection, emergency water disinfection kits 8 and small scale drinking water treatment systems, scavenge systems suitable for colanders, colanders and other water disinfection applications.

A feature of the present invention is that it solves a problem that was clearly overlooked in the prior art. These characteristics are not caused solely by the characteristics of vinylpyridine polymers;
This is due to the molecular addition reaction products of halogens and/or interhalogens in mixed forms that have not been previously prepared or tested. None of these produce a bactericidal effect upon contact. Furthermore, the synergistic stability of the mixed resin, which was previously unknown, was demonstrated. Moreover, none of the conventional resins is capable of forming an eluate containing an optimal halogen and hypohalous acid mixture.

The reasons for the synergistic stability of mixed-format resins are not fully understood, but are believed to be due to an inherent oxidation-reduction buffering phenomenon or "redox" equilibrium occurring within the resin matrix; It is also believed to occur to some extent with all mixed type resins. A similar redox equilibrium has been defined by Wright (T. Nis. Wright, Vol. 44, 103).
B (1972)), and an example is Lambert et al.
-Karesu 嘗-9 Volume 47.

915, (1975)) and Black and Whittle (Fumiji, W NaoA, Vol. 59, p. 607 (1967)
)It is described in.

No prior art, including U.S. Pat. .

Examples In the present invention, base-free compounds cross-linked with divinylbenvin, divinylpyridine, or other conventional cross-linking agents and containing a pyridyl functional group covalently bonded to the backbone at the second or fourth carbon of the pyridyl. A medium in which a vinyl polymer resin (in the form of granules or beads) is reacted with a halogen and/or an interhalogen compound, which instantly sterilizes water contaminated with bacteria by contact (in just one pass). is obtained. This instantaneous bactericidal action is produced by the production of relatively high concentrations of halogen and hypohalogen M (HOBr or Hot) on the surface of the grains or beads, so that this bactericidal action takes place within the resin head. If desired, residual halogens and hypohalous acids can be reduced or removed by a subsequent scavenger column such as Dt5 or an activated carbon bed.

Preparation of base-free crosslinked virgin materials (poly-2- and poly-4-vinylpyridine) is described in U.S. Pat.
It is described in No. 9.948 and is as follows.

h The 1-vinylpyridine crosslinked 2-vinylpyridine copolymer is formed into beads by suspended FIA polymerization in a sealed autoclave according to the following process. The following materials are added to the autoclave (seedlings are indicated by weight): 018 parts benzoyl peroxide dissolved in vinylpyridine 0405 parts tart-butyl perbenzoate dissolved in vinylpyridine 2-vinyl Pyridine 90 parts divinylbenzene (or U.S. Pat. No. 2,739°948)
2,4-divinylpyridine (prepared in No. 2) 10 parts Distilled water 200 parts Hydroxylated apatite (submicron particle size) 3 parts Monohelium oleate 0.03 parts The autoclave was then closed and placed in a temperature controlled bath at 90°C. The A polymer beads produced were washed with dilute hydrochloric acid to remove all the suspending agent, and then kept in diluted water for 7 hours with stirring using a rocking chamber, and then kept at 113-115°C for 3 hours. Hydrochloric acid adsorbed with sodium oxide is removed, washed with water, and then dried at 70°C for about 2 hours.

Force 0 Ha 1-4-Nylpyridine The process for preparing poly-2-vinylpyridine described above is substantially the same, but 2-vinylpyridine monomer is iNIMed with the same mole of 4-vinylpyridine monomer.

Poly-2- and poly-4-vinylpyridine (crosslinked) are also available from Riley Tar and Chemical Company as LX-101 and R-8050, respectively.

Resin Q according to the invention is a molecule I1 addition reaction product comprising a polymerized base-free pyridyl functional group and a halogen ([2 and 3r2) and/or an interhalogen compound (I
CI, IBr, and BrC2). In this case all or some of the pyridyl functions are complexed. The complex formation reaction between a polymerized salt-free pyridine resin (poly-4-vinylpyridine) and a halogen (2) and an interhalogen compound (IcI mixture) is represented by the following formula.

2ICI aII 3υ1 The first step in forming the complexed resin according to the invention is the addition of the necessary halogens and/or interhalogens to give the resin the required form and filling. m to a predetermined dry virgin resin material 151i. The appropriate halogen and/or interhalogen compound is then added to the fJ4 vessel with a compatible solvent such as methyl alcohol. A non-oxidizing solvent such as CHCe3) is used.

Once completely dissolved, the dry resin is then added directly to the alcohol solution. For about an hour, continuous mixing of the resin slurry is preferred to obtain a more homogeneous product;
Intermittent mixing every 3 to 5 minutes is sufficient. The slurry is allowed to stand overnight. The next day, excess alcohol is drained off or discarded by suction filtration. The resin is then washed batchwise or by column flow using 5 to 10 bed volumes of water.

Below are some examples of synergistically stabilized mixed format complexes according to the invention. Such examples are for the purpose of illustrating embodiments of the invention and are not intended to limit the scope of the invention. If the suspension described in this example is desired to be formed in the same way, it may be scaled up or changed as necessary, and the combination or degree of filling to be filled on the resin can be arbitrarily selected.

Example ■ 18.74 grams of dry virgin resin material (crosslinked poly-4-
Vinylpyridine or P4VP) (8.8meq/
grams), add 1256 grams of 12 and 8.03 grams of monochloride (ICfl) to about 100 mL of methyl alcohol. Once the I2 and 1cIl are dissolved, the resin is added and mixed, left to stand overnight and washed as described in the general preparation process section.

In this resin, 30% of the usable pyridyl seats are 12
or 30% is complexed with IC2.

Example ■ For virgin P4vP of 17.31 grams, 19.33
12 and 2.43 grams of bromine (Br2) about 1
9°I2 added to 00ml of methyl alcohol
After the and 8r2 are dissolved, the dry resin matrix is added, mixed, allowed to stand, and washed as described above. In this resin, 50% of the pyridyl sites are 12 and 10% are Br.
2 has been made into 111 bodies.

Example M The process is almost the same as Example (2), but Brz is replaced with 2.47 grams of IOC. This resin is 50% I2 and 10% I
ce (percentage of available seats of pyridyl functional group)
including.

Example ■ 17.3' For 1 gram of pyridine P 4 'V P, 12.17 grams of Brz and 1.76 grams of bromine chloride (BrC) are mixed with about 100 ml of chloroform (C
HCJ! 3) a B r 2 and BrCe added to C
After dissolving in HC23, add the dry resin matrix, mix, let stand and wash as described. This resin contains 50% Br2 and 10% BrC (percentage of available sites of pyridyl functionality).

Example V Similar process to Example 1, but replacing Brz with 1515 grams of iodine monobromide (IBr). This resin is 50%
of lBr and 10% of 8rCfl (percentage of available seats of pyridyl functionality).

Example V1 For 6.68 g of dry virgin poly-2-vinylpyridine (crosslinked) resin (8.5 meq/g):
721 grams of 12 and 0.92 grams of IC2 are approximately 1
Add to 00ml of methyl alcohol. I2 and Ice
After the and is dissolved, the resin is added, mixed, allowed to stand, and washed as described above. This resin has 50% 12 and 10% Ic
e (percentage of available seats of pyridyl functional group).

Example ■ Same process as Example ■, but replace IC2 with 0.91 grams of Brz. This resin is 50%I2 and 1o%Br
2 (percentage of available seats for pyridyl sensuality).

Example■ For dry virgin P4VP of 34.629, 15.46
3's 12 and 4.87 (j's B r 2 and approximately 1001
Add to methyl alcohol from step 1. After I2 and Brz are dissolved, dry resin material is added, mixed, allowed to stand, and washed as described above. This resin is 20% 12 and 10% Br2
(percentage of available pyridyl functional group).

Example IX Same process as Example ■, but 11.6g of 12 and 7.3
9 Br'2 is used. This resin is 15% 12 and 1
Contains 5% Br2 (percentage of available pyridyl functional groups).

Effects of the Invention Figure 1 shows the mixed-form halogenation and/or halogenation according to the present invention when three different types of feed water were treated and several eluate compositions of iodinated resins according to the prior art were treated in the same manner.
Or it is a figure of the table shown in comparison with the eluate composition of interhalogen compound addition resin.

The subscripts a- in FIG. 1 represent the following contents.

a-N The resin is poly-4-vinylpyridine (10x35 mesh) crosslinked with 2% divinylbenzene. This material is treated with appropriate amounts of halogen and/or interhalogen compounds to yield 1 q of the desired formulation. Each resin (6.0 ml) is placed in a glass column with an internal diameter of 1 cm and used at 24 mL/min (low force flow).

The percentage shown on the format side indicates the percentage of seats available for complex formation that have been converted to this format.

b-6 Analyzed using a modified version of the quasi-leuco crystal violet method.

C-Buffered to p)-17 by dropwise addition of dilute sodium carbonate.

d-Dechlorination of the water stream through a fresh granular activated carbon head.

Add e-NaCe to 412 mg/L distilled water and add subscript C.
Buffered as well.

f-Resin x is a mono-formal abasic resin according to U.S. Pat. No. 3,565,872.

Q-Resin Y is a triiodinated type anion exchange resin (20 x 40 mesh) according to U.S. Pat. No. 3,187,860.

h-Resin Z is a mixed polyhalide resin according to U.S. Pat. .

Br2. and/or HOBr. However, the residual components are indicated by HOI and 12.

j-1 This resin is a polycarbonate cross-linked with 2% divinylbenzene.
2-vinylpyridine. .

k - Same as subscript a except for 100 mL bed and flow rate of ~380 mL/min.

The mixed-format resins according to the invention shown in FIG. 1 were all prepared by the method described above.

The following results clearly show problems that were not recognized in the prior art.1. The last three resins (X, Y, Z) in the table of FIG. 1 release halide ions (■-) and polyhalide ions (+3) for three types of feed water. In contrast, none of the mixed-format halogenated and/or interhalogenated resins release 1-. Mixed-form halogenated and/or interhalogen addition resins are either iodine (I2) and hypoiodic acid, or bromine and hypobromite! (HOBr) and/or hypoiodic acid at equal or significant levels.

Monomorphic resin samples (in the Ce2, Br2, and BrCe-forms) according to U.S. Pat. It was discovered that After standing for one year in aqueous media, these resins were unable to release any detectable levels (<0.01 mg/L) of residual halogen. On the other hand, Br2 or BrC2 (Example II
, V, and ■), no resin decomposition was detected in the resin prepared according to the present invention containing
BrCe (fi combined type) has a level that is still effective for sterilization even if it is kept in water medium for one year (20,50IQ/L).
) could release halogen and/or hypohalous acid.

The previously unknown synergistic stability shown in Example IV, Example V, and Example VH is a characteristic advantage of the present invention, and is believed to occur to some extent with all blended resins. It will be done.

To further illustrate this non-obvious advantage of the present invention, the relationship between the degree of resin deterioration (swelling) and the elution composition is compared in the table of FIG. The medium letters a to d in FIG. 2 represent the following contents.

a- Bed volume 100 mL, flow m-~380 mL/
After one month of separation in an aqueous solution (deionized water), the feed water was mixed with ion-exchanged water (first
(See Figure Supplement C) d - Prepared according to U.S. Pat. No. 3,565.872.

Here, resins A and 8 were prepared according to U.S. Pat. No. 3,565.872. Resin A (15%+2) showed no degradation (no swelling) but is disadvantageous in that it releases iodide (l-). Resin B (15% Br2) shows significant swelling indicating decomposition of the resin. However, example ■ and d of Iχ
The mold resin does not show resin degradation and both release iodine and hypoiodic acid (HOI) (see table in Figure 1).
.

FIG. 3 is a table showing the contact and instant sterilization effects of various halogenated and/or interhalogen compound-added vinylpyridine resins according to the present invention. The medium-sized letters a to d in FIG. 3 represent the following contents.

a - Base resin is granular poly-4-vinylpyridine (10 x 35 mesh) crosslinked with 2% divinylbenzene. This material is treated with appropriate amounts of halogens and/or interhalogens to form the desired formulation. Each resin (~50+a
L) was placed in a glass column (3/4 inch inner diameter) and 1
Used at 40 m1/min (gravity flow).

The b-% format indicates the percentage of available seats for pyridine converted to that format.

C-Each column is used for approximately 100 ml of bacterial suspension washed with 100 ml of sterile buffered residual water. The last 50+++ of bacterial suspension used
Collected in a sterile bottle containing 10% thio[0 sodium with a L of 0.211. 1 mL of the spent eluate was tested for E. coli ArCC #8739.

d - The eluates of Examples I, I, and ■ contain a mixture of I2 and HOI. Example n, rv, and resin eluate of ■]2
and Brz or Hot.

Br2. and/or HOBr. Analysis is standard D
Based on PD method.

It is noteworthy that the untreated resin, i.e. the virgin granular crosslinked poly-4-vinylpyridine, has a particularly low bactericidal effect compared to other resins.

As shown in Figure 1'EL and Figure 2, iodine (I2) and hypoiodic acid (HOI >) or iodine and bromine (Br2) at a total active halogen level of about 8-10 ppm.
) occurs in the eluate, so Example 4 and Example 2 are preferred as examples. The iodine and/or bromine levels are adequate to completely disinfect moderately and heavily contaminated water. The molecules iodine (I2) and bromine (Br2) are most effective against amoeboid cells, and hypoiodic acid is preferred because it is more bactericidal and at least 40 times more effective at killing viruses than iodine.

The mixed type resin not only provides an instant contact membrane V1 but also provides protection against recontamination of sterile attack. If it is necessary to remove halogens and hypohalous acids for the final use of the treated water, the use of an activated carbon trailing scavenger column or bed in the water treatment system can effectively remove both. If it is desired to reduce the level of halogen and hypohalous acid in the eluate, the resin may be first treated with a low weight fraction of halogen and/or interhalous compound.

Furthermore, various embodiments are possible within the scope of the invention.

[Brief explanation of the drawing]

FIG. 1 shows the composition of several eluates of iodinated resins according to the prior art when treating three different types of feed water, and the mixed-form halogenation and/or composition according to the present invention when subjected to the same treatment.
2 is a table showing a comparison between the eluate composition of interhalogen compound-added resins; FIG. FIG. 2 is a table showing the instant sterilization effects of various halogenated and/or interhalogen compound-added vinylpyridine resins upon contact.

Claims (6)

[Claims] (1) A stable mixed halogenated and/or halogen intermediate compound molecular addition reaction product consisting of a copolymer of the form A/B-X, where X is crosslinked with about 2-25% divinylbenzene. containing polyvinylpyridine having a cyclic pyridyl functional group ring C_5H_5N, and A/B is I_2/ICl, I_
2/IBr, I_2/Br_2, I_2/BrCl, B
represents a combination of halogens and/or halogen intermediates selected from r_2/BrCl, Br_2/ICl, Br_2/IBr, BrCl/ICl, BrCl/IBr, ICl/IBr, and mixtures thereof, containing at least about 10% The pyridyl functional group has A to B of about 0.08 depending on the A/B combination.
A reaction product characterized in that it is complexed such that it is present in a molar ratio of about 0.92 from (2) The reaction product according to claim 1, wherein X is poly-4-vinylpyridine crosslinked with divinylbenzene. (3) The reaction product according to claim 1, wherein X is poly-2-vinylpyridine crosslinked with divinylbenzene. (4) The reaction product according to claim 1, wherein the A/B mixture comprises a combination of three halogens and/or interhalogen compounds. (5) The reaction product according to claim 1, wherein the A/B mixture contains a combination of four types of halogens and/or interhalogen compounds. (6) The reaction product according to claim 1, wherein the A/B mixture contains a combination of five halogens and/or interhalogen compounds.