ZA200107646B - Antimicrobial polymeric compositions. - Google Patents
Antimicrobial polymeric compositions. Download PDFInfo
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- ZA200107646B ZA200107646B ZA200107646A ZA200107646A ZA200107646B ZA 200107646 B ZA200107646 B ZA 200107646B ZA 200107646 A ZA200107646 A ZA 200107646A ZA 200107646 A ZA200107646 A ZA 200107646A ZA 200107646 B ZA200107646 B ZA 200107646B
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- South Africa
- Prior art keywords
- polymers
- propenal
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- 230000000845 anti-microbial effect Effects 0.000 title description 27
- 239000000203 mixture Substances 0.000 title description 26
- 238000012360 testing method Methods 0.000 claims description 10
- 230000001332 colony forming effect Effects 0.000 claims description 6
- 239000004443 bio-dispersant Substances 0.000 claims description 2
- 230000000813 microbial effect Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 67
- 229920000642 polymer Polymers 0.000 description 66
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 29
- 238000001994 activation Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000003115 biocidal effect Effects 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 230000002421 anti-septic effect Effects 0.000 description 6
- 239000000645 desinfectant Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229940064004 antiseptic throat preparations Drugs 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 150000001241 acetals Chemical group 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- -1 poly(2-propenal) Polymers 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 241001138501 Salmonella enterica Species 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000002599 biostatic effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002373 hemiacetals Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000272165 Charadriidae Species 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000001998 anti-microbiological effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Description
"ANTIMICROBIAL POLYMERIC COMPOSITIONS”
The present invention relates to antimicrobial polymeric compositions. More particularly, the antimicrobial polymeric compositions of the present invention contain compounds having a polyacrolein sub-unit with its aldehyde group in its free, hydrated, hemi-acetal or acetal form, and having biostatic and/or biocidal properties. The invention is directed to compositions containing these polymeric compounds and the biostatic and/or biocidal uses of these compositions.
The broad-based antimicrobial properties of polymers (hereinafter called the "subject polymers”) having the repeating polymeric unit:
A
C oe 0) H- 54 ; or this unit in its hydrated, hemi-acetal or acetal form, represented by the formulae: )
H
H H H J
0]
RO (@] 0]
RO OR RO” "07 “OR n OR H
DY H r ~ ~
H or Oo (@]
S¥bstitute Sheet (Rule 26) RO/AU wherein R is hydrogen or alkyl and n is an integer of one or more, have been demonstrated previously (Melrose et al., International Patent Publication WO 88/04671). The subject polymers described therein include poly(2-propenal, 2- propenoic acid).
It has also been noted previously (Melrose, International Patent Publication WO 96/38186) that poly(2-propenal, 2-propenoic acid) is formed when the aldehyde groups of poly(2-propenal) syn polyacrolein are partially auto-oxidised to carboxyl groups, by heating the dry polymer in air, to 100°C and preferably to between 80°C and 100°C. It was further noted that the resulting polymer is soluble in dilute aqueous bases, for example aqueous sodium carbonate.
An earlier disclosure (Werle et al, Australian Patent Application 11686/95, now lapsed) claimed solubility of the subject polymers in polyols — but not solubility in aqueous media, following heating to 75°C. It was further claimed that subsequent to the heating to 75°C, brief treatment with sodium hydroxide gave rise to aqueous solubility and apparently as a result, increased antimicrobial activity. :
To increase the stability of compositions containing the subject polymers, Melrose . & Huxham (International Patent Application PCT/AU99/00578) have formulated . compositions with anionic surfactants. Additionally, this prior art revealed that in
B basic compositions, in contrast to acidic compositions, the subject polymers have faster antimicrobial activity, but are less stable.
It is particularly desirable that the subject polymers should not be unstable, yielding acrolein, as this monomer is very irritating to the eyes, lungs, tissues and skin.
It is one object of the present invention to provide methods of preparing compositions, these methods producing a new configuration of the subject polymers and in particular of poly(2-propenal, 2-propenoic acid), and which have enhanced antimicrobial activity.
Substitute Sheet (Rule 26) RO/AU
It is a further object of the present invention to provide methods of preparing compositions, these methods producing a new configuration of the subject polymers and in particular of poly(2-propenal, 2-propenoic acid), and which better retain antimicrobial activity.
S Itis a still further object of the present invention to provide methods of preparing compositions, these methods producing a new configuration of the subject polymers and in particular of poly(2-propenal, 2-propenoic acid), and which contain less free acrolein.
It is a yet still further object of the present invention to provide compositions containing a new configuration of the subject polymers and in particular of poly(2- propenal, 2-propenoic acid) which are efficacious disinfectants or antiseptics.
Throughout the specification, unless the context requires otherwise, the word “comprise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
In accordance with the present invention there is provided a method for the : preparation of polymers derived from acrolein and including poly(2-propenal, 2- propenoic acid), characterised in that the polymers are exposed to the presence of water, whereby such polymers exhibit increased antimicrobial activity.
Preferably. the polymers are heated in the range of 40 to 150°C.
Stilt preferably, the polymers are heated in the range of 40 to 115°C.
Still further preferably, the polymers are heated in the range of 70 - 90°C.
Substitute Sheet (Rule 26) RO/AU
Preferably, the polymers ere heated for a period of between 1 to 1,400 hours, thereby increasing antimicrobial activity of the polymers.
Still preferably, the polymers are heated for a period of between 10 to 60 hours.
In one form of the invention the polymers are heated in the presence of one or more of polyethylene glycol, polyol! or alkanol, thereby providing one or both of enhanced stability or enhanced antimicrobial activity. Water is invariably present in these alcohols.
Preferably, polyethylene glycol is present during the preparation of the polymers in the amount of between 50 and 99% by weight.
Still preferably, polyethylene glycol is present during preparation of the polymers in the amount of between 64 and 95% by weight.
In a further form of the invention, base or alkali is added to the polymers before and/or during heating, thereby enhancing the antimicrobial activity of the polymers.
Preferably. the addition of the base or alkali brings the pH of the polymers to between 7 and 9. : Still preferably, the pH is about 8. Sodium hydroxide may be the base added.
In a still further form of the invention, the release of free acrolein monomer is ; inhibited. thereby the polymers are less likely to present a source of tissue or dermal irritation.
Preferably, the polymer is initially heated, predominantly in the dry state, to between 80 and 100°C.
Still preferably, the polymer is initially heated to about 85°C.
Substitute Sheet (Rule 26) RO/AU
In accordance with the present invention there is further provided an antimicrobial compound or composition prepared by one or more of the methods described hereinabove.
In accordance with the present invention there is still further provided a
S preservative compound or composition prepared by one or more of the methods described hereinabove.
In accordance with the present invention there is yet still further provided a disinfectant or antiseptic compound or composition prepared wholly or in part by the methods described hereinabove.
Preferably, the disinfectant or antiseptic compound or composition has a pH greater than 6, thereby enhancing antimicrobial activity.
In accordance with the present invention, there are provided methods for the preparation of a new configuration of the subject polymers including poly(2- propenal, 2-propenoic acid) and of compositions therefrom, whereby the compositions exhibit increased antimicrobial activity, and/or increased stability and/or contain less free acrolein, thus making the polymers and/or their . compositions more suitable as preservatives, and/or active ingredients in disinfectants and/or, antiseptics, under acidic or basic conditions. :
Since the prior art recorded some instability of poly(2-propenal, 2-propenoic acid), as evidenced by loss of antimicrobial activity of its compositions, the routine procedure in industry was then followed in our laboratories, of quantitatively determining this instability by standard “accelerated ageing” at elevated temperature. ie. at 40°C. However, to our greatest surprise, the elevated temperature of “ageing” poly(2-propenal, 2-propenoic acid) in aqueous or in aqueous-polyethylene glycol solutions at 40°C, not only slowed the decrease in antimicrobial activity — but in fact, actually increased antimicrobial activity of the
Substitute Sheet (Rule 26) RO/AU poly(2-propenal, 2-propenoic acid), see Example 2(a) and (b). This finding is totally contradictory and unexpected in view of the prior art which predicts that the rise in temperature should lead to “accelerated ageing”, ie. accelerated loss of antimicrobial activity.
Henceforth, the process of providing increased antimicrobiological activity by the formation of a new configuration of the subject polymers including poly(2-propenal, 2-propenoic acid), is referred to as “super-activation” and the polymers referred to as “super-activated polymers”.
Even more surprising, in view of prior art, the inventors have found super- activation in aqueous polyethylene glycol solution is promoted by basic conditions, see Example 2(c).
Also, super-activation is promoted by heat and moisture, alone, see Example 4.
Additionally, it has been found that priar, dry heating of the subject polymers between 80-85°C gives polymers, see Example 1, which are soluble in aqueous media and suitable for subsequent super-activation.
Super-activation is facilitated by the presence of polyethylene glycols or polyols or : alkanols see Example 3, — we believe, since the presence of the polyethylene glycol or polyol or alkanol protects and stabilises the carbonyl groups of the polymers, possibly by formation of acetals, from alkaline degradation by the ]
Cannizarro reaction.
An added advantage of super-activation is that it gives rise to less, contaminant acrolein which is a source of tissue and dermal irritation, see Example 6.
It is emphasised that super-activation is quite distinct and additional to any increase of antimicrobial activity which may result, merely from more polymer being available in any aqueous test-medium as the result of increased
Substitute Sheet (Rule 26) RO/AU hydrophillicity of the polymer such as was demonstrated in lapsed Australian
Patent Application AU-A-11686/95 (hereinafter “1 1686/95"). The inventors have repeated exactly the method described in 11686/95 and then, following, found that subsequent super-activation of the partially soluble polymer demonstratively gave rise to additional, substantial antimicrobial activity, see Example 5. It should be noted that even super-activation did not render the polymer from 11686/95 completely soluble — in contrast to super-activation beginning with polymer firstly heated between to 80 — 85°C.
The optimum time to achieve super-activation of solutions of poly(2-propenal, 2- propenoic acid) depends inversely upon the temperature, see Example 7. It will be apparent that even ageing at room temperature may be used for super- activation, especially when facilitated in the presence of hydroxylic solvent and/or base, but obviously, this may be impractical due to the longer time periods required.
The inventors have found polymers super-activated as described herein, suitable for preservatives in water-based products or processes, and as well, as active ingredients in disinfectants or antiseptics having the advantage of enhanced antimicrobial activity, see Example 8. Furthermore, the inventors found that the d antimicrobial activity of such disinfectants or antiseptics was increased by increase in their pH, for example above pH 6, see again Example 8. :
The invention will now be described with reference to several Examples, which should not be construed as limiting the scope thereof.
BIOCIDAL TEST
Dilute sample with 1% aqueous sodium bicarbonate to obtain the required concentration (unless specified to the contrary, 0.125% in polymer). Weight 19.9¢ of diluted sample into a sterile jar and inoculate with 0.1 mL of 107 — 10° suspension of Ps.aeruginosa and mix. At specified time-intervals, transfer 1 mL of
Substitute Sheet (Rule 26) RO/AU inoculated sample to 9 mL of letheen broth and vortex. Plate out serial 1 in 10 dilutions. Pour with trypton= sova agar. Incubate 3 days at 37°C.
EXAMPLE 1
Water (720 mL at ambient temperature, about 20°C) and acrolein (60g; freshly distilled, plus hydroquinone added to 0.25%w/w) were placed in an open beaker, within a fume cupboard, and very vigorously stirred, mechanically. Then, 0.2 M aqueous sodium hydroxide (21.4 mL) was added to bring the pH to 10.5 — 11.0.
The solution immediately turned a yellow typical of the hydroquinone anion and within a minute, the colour had disappeared and the clear solution became milky.
About 1 minute later, precipitation of a white crystalline, flocculent polymer began, and appeared complete within 15 — 30 minutes. The precipitate was filtered and washed with water (250 mL), dried at room temperature upon filter papers for 2 days (yield 25g), then spread as a thin layer in glass petri dishes and heated at 40°C/8 hours. This heating was continued at the following schedules : 50°C/15 hours; 65°C/4 hours; 75°C/18 hours; 84°C/24 hours.
It is envisaged that this method may be scaled-up to include, eg the stepwise - addition of acrolein, in a closed vessel, and followed by more rapid drying. . Typically, a solution of the resulting poly(2-propenal, 2-propenoic acid) was prepared by adding 2g of the subject polymer, with stirring over 15-30 minutes, to a 1% w/w aqueous sodium carbonate solution (100 mL), and then diluted as required. Such solutions were perfectly clear — in contrast to attempted dissolutions, using alternatively, polymer derived from Example 5 of 11686/95; compare Example 5, hereinafter.
EXAMPLE 2 (a) 5g of poly(2-propenal, 2-propenoic acid) was dissolved in 64g polyethylene glycol ("PEG") 200 and combined with 31g of a 0.71% solution of sodium carbonate. A portion of the solution (apparent pH=5.8) was retained at room
Substitute Sheet (Rule 26) RO/AU temperature while the remainder was heated at 60°C for periods of 12 or 25 days.
Samples were diluted with 1% sodium bicarbonate and submitted for biocidal testing at polymer concentrations of 0.125% w/w. Surprisingly, the samples which had undergone “accelerated ageing” showed improved antimicrobial activity, as 5S can be seen by reference to Table 1:
Table 1 ] Ctu/mi * (Pseudomonas aeruginosa) 25 days at room temperature i 78x10%° | 41x10%° | 6.1x10° | 9.8x10* <10 12 days at 60°C 1.4x10° | 9.8x 10° <10 25 days at 60°C 1.0x10" | 1.3x10° | 6.6 x 10° * Colony forming units/mL (b) 1g poly(2-propenal, 2-propenoic acid) was dissolved in 200 ml of 0.1%
Na,CO0s and allowed to stand overnight. Sodium lauryl sulphate was introduced at } a level of 0.05% and the solution was acidified with HCI to pH 5.9. Portions were stored at both room temperature and 60°C. Biocidal Tests were carried out on . 0.125% polymer solutions, with 1% NaHCO; used as the diluent. The “aged” sample showed a surprising improvement in performance, as can be seen by reference to Table 2:
Substitute Sheet (Rule 26) RO/AU
Table 2
Sample Cfu/ml * (Pseudomonas aeruginosa) 20 days at room temperature 9.0 x 10° 51x10° | 6.8x 10? (RT) . 9.0x 10 1.2x 102 <10 <10 7 days at 60°C + 13 days at
RT
* Colony forming units/mL (c) A 5% solution of super-activated polymer was prepared as in example (2a) but replacing PEG200 with PEG1000. A portion of this solution was treated with conc. NaOH to pH 8.1. Samples were heated at 60°C and submitted for biocidal testing. The sample exposed to more basic conditions unexpectedly gave superior biocidal performance, as can be seen by reference to Table 3:
Table 3 } ] Ctu/mi * (Pseudomonas aeruginosa)
PH538, 12days60°C | 3.8x10° | 27x10° | 1.5x10° | 3.3x10° | <10 pH 8.1, 17 days 60°C | 8.3x 10° | 3.3x10° | 1.3x 102 * Colony forming units/mL
EXAMPLE 3 (@) 5% solutions of polymers of a range of degrees of super-activation, apparent pH 5.7, were prepared similarly to Example 2(a), but varying the percentage of PEG 200.
Substitute Sheet (Ruie 26) RC/AU
Samples were heated at 60°C and stabilities were monitored over time. Physical stability was considered to have failed with the occurrence of precipitation or gelling. UV measurements were made on a 0.01% polymer concentration in 1% sodium carbonate solution. A decrease of the ratio of absorption at 268 nm : 230 nm is considered synonymous with a decrease in chemical stability. Results are shown in Table 4:
Table 4
Chemical Stability Ratio 260 — 270 peak absorbance 228 — 235 peak absorbance me | oa [8 J o To 4 days 60°C 1.04 i 1.21 1.27 ;
Both physical and UV spectral results demonstrate the positive effect of PEG on stability; higher PEG content results in greater physical and chemical stabilities.
Substitute Sheet (Rule 26) RO/AU
(b) The following solutions A and B were prepared by dissolving 4g of poly(2- propenal, 2-propenoic acid) in 196 g 1% sodium bicarbonate and adjusting the pH to 7 (A) and 5.5 (B) with dilute HCI. Solution C was prepared by dissolving 50g of poly(2-propenal, 2-propenoic acid) in PEG 200 (640g) at 65° — 70°C. Then a solution of 4g sodium carbonate in water (306g) was added, the apparent pH being 7, and then 5.5 at the end of the treatment period of 31 days.
All samples were stored at 40°C. At various time intervals samples containing equivalent to 0.125% polymer were submitted for biocidal testing. Results are shown in Table 5:
Table 5
Time(days) Time for complete kill (minutes) <10 cfu/ml at 40°C Pseudomonas aeruginosa ] Solution A ! Solution B Solution C or oe |e : EL EE EE
EXAMPLE 4 1g of poly(2-propenal, 2-propenoic acid) was heated in either a dry or a humid, enclosed chamber, both at 60°C, for 3 days. Solutions of the dry polymer and the humidified polymer, respectively were prepared at 0.125% w/v (with correction for moisture content) and submitted for evaluation by the Biocidal Test :
Substitute Sheet (Ruie 26) RO/AU
Table 6
Ctu/ml * (Pseudomonas aeruginosa) . . ! . . . 0 min Smin © 10min 15 min 30 min 60 min
Polymer (dry) 49x 108 - 76x10° |59x10° |1.2x10?
Polymer 11x10" |6x10° [34x10° |3.7x10° |<10 - (humidified) * Colony forming units/mL
The polymers exhibited carbonyl! and/or carboxyl absorption in the LR. between 1700 ~ 1730 cm’, carbonyl groups (e.g. with Schiff's reagent) and have M,, = ca. 10000 and M. = ca.5000; titration shows carboxyl groups ca.5 mole %. These parameters are similar (but not the same) as those of poly(2-propenal, 2-propenoic acid).
EXAMPLE 5
In duplicate experiments, a sample of polymer was prepared and then dissolved in ethane diol, exactly as described in Example 5 of 11686/95. Half of this material a was further heated at 80°C for 24 hours (following which, solubility in aqueous media remained incomplete). The samples were compared for antimicrobial : activity, using the standard Biocidal Test. Both of the samples treated by heating, ie. super-activation showed a clear enhancement of antimicrobial activity, as shown in Table 7:
Substitute Sheet (Rule 26) RO/AU
Table 7
Cfu/ml * (Pseudomonas aeruginosa)
Treatment of Initial Count 10 min 15min | 30 min solution (2) None | 4.6 x 108 42x10° | 1.5x 102 10 | <10 (1) 24 hours 80°C | 4.6x 10° 3.7 x 10° <10 <10 <10 (2) 24 hours 80°C | 4.6 x 10° 8.0 x 10° * Colony forming units/mL
EXAMPLE 6 50g of poly(2-propenal, 2-propenoic acid) was dissolved in PEG 200 (640g) at 65° 70°C. Then, an aqueous solution of sodium carbonate (4g) in water (306g) was added. The sample was divided and either stood at room temperature or heated at 80°C for 24 hours. The acrolein content of the solution was determined over time. by reverse phase HPLC and results are shown in Table 8:
Table 8 i 10
Days stored at 20°C Acrolein Content (ppm)
Super-Activated | Not Super-Activated
EI EC
Substitute Sheet (Rule 26) RO/AU
EXAMPLE 7
Solutions of poly(2-propenal, 2-propenoic acid) were prepared as in Example 6 and treated at temperatures of 40, 60, 80, 100 and 115°C for varying time periods.
Samples were subjected to the standard Biocidal Test to confirm the increased kill rate and results are shown in Table 9.
Table 9
Super-activation Optimum Time Total Kill
Temperature (°C) Range (Hours) | Time (minutes)
Room Temperature >1400 <10 80 16 — 24 <10
The amount of time required for super-activation is seen to be inversely proportional to temperature. All solutions of polymers derived from the super- activation process were completely miscible, in all proportions, with agueous solvents.
EXAMPLE 8 (a) 540g of poly(2-propenal, 2-propenoic acid) was dissolved in 2304g PEG200 at 65°C, prior to mixing with 43.29 of sodium carbonate in 712g of water. Then, the solution was heated to 100°C for 4 hours, and 36g sodium lauryl sulphate, 79
ECOTERIC T20 (nonionic detergent) and 2g lemon fragrance were added. The formulation, pH6, was diluted 1:30 with hard water and challenged against
Substitute Sheet (Rule 26) RO/AU
Staphylococcus aureus (a gram-positive bacterium, of particular significance regarding infections in hospitals), and Salmonella choleraesuis (a gram-negative bacterium, of particular significance regarding infections in food preparation areas), respectively using the Association of Agricultural Chemists Official
Methods of Analysis (1995) 991.47, 991.48, (Hard Surface Carrier Test Method).
Results are shown in Table 10:
Table 10
S aureus 2/60 | Pass
Lo
S.choleraesuis 1/60 | Pass
Adjustment of this formulation to higher pH?®, increases the antimicrobial activity, as monitored by the Biocidal Test. Results are shown in Tables 11(a) and 11(b):
Table 11 (a)
Activity against Staphylococcus aureus : Initial Count, 3 x 10° cfu/ml; polymer 350 ppm. ! 10 : 20 30 : 45 60 pH . minutes ~~ minutes minutes minutes minutes . cfu/ml cfu/ml cfu/ml cfu/ml cfu/ml 56 = 28x10° 4.4 x 10° 23x10° | 20 | <10 15 .
Substitute Sheet (Rule 26) RO/AU
Table 11(b)
Activity against Pseudomonas aeruginosa
Initial Count, 3.7 x 10° cfu/ml; polymer 350 ppm. 10 20 30 45 60 pH } minutes minutes minutes minutes minutes cfu/mi cfu/ml cfu/ml cfu/ml | cfu/ml 72 58x10° 9.1 x 10° 43x 10° <10 89 | 95x10° 105 | 45x10’ (b) 1200g of poly(2-propenal, 2-propenoic acid) was dissolved in 7680¢g of
PEG200 at 60°C and then 96g Na,CO; in 3024g water was added. The solution was heated at 100°C for 6 hours.
The formulation was added to the basin of an induced draft cooling tower, to a concentration of 300ppm (30ppm polymer) 3 times/week. Dosing was carried out - at evening to allow contact times of 8-12 hours before operation recommenced; residual concentration was expected to be halved every 3 — 6 hours of operation.
Recirculation water had on average, temperature 27°C, pH 8.5, conductivity 3000 uS. Microbial counts were determined and compared to an adjacent, identical, tower which was dosed with a biodispersant, daily. Results are shown in Table 12:
Substitute Sheet (Rule 26) RO/AU
Claims (1)
- Table 12 Treatment Time (days) Treated Tower 14 6.1 x 10° 2.6x 10° 16 5.1 x 10° 4.9 x 10° * Colony forming units/mL The data indicate the treatment programme maintained the microbial counts within the guidelines of AS/NZ Standard 3666.3(Int):1998 and below that in the adjacent tower, containing biodispersant (which was found to be unusually inadequate during the demanding conditions of the very hot, summer period of the test). Modifications and variation such as would be apparent to the skilled addressee are . considered to fall within the scope of the present invention.Substitute Sheet (Rule 26) RO/AU
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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ZA200107646A ZA200107646B (en) | 2001-09-17 | 2001-09-17 | Antimicrobial polymeric compositions. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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ZA200107646A ZA200107646B (en) | 2001-09-17 | 2001-09-17 | Antimicrobial polymeric compositions. |
Publications (1)
Publication Number | Publication Date |
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ZA200107646B true ZA200107646B (en) | 2002-11-27 |
Family
ID=27735359
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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ZA200107646A ZA200107646B (en) | 2001-09-17 | 2001-09-17 | Antimicrobial polymeric compositions. |
Country Status (1)
Country | Link |
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ZA (1) | ZA200107646B (en) |
-
2001
- 2001-09-17 ZA ZA200107646A patent/ZA200107646B/en unknown
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