CN102017979A - Poly-guanidine pyrithione acid salt antimicrobial and preparation method thereof - Google Patents
Poly-guanidine pyrithione acid salt antimicrobial and preparation method thereof Download PDFInfo
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- CN102017979A CN102017979A CN2009101767202A CN200910176720A CN102017979A CN 102017979 A CN102017979 A CN 102017979A CN 2009101767202 A CN2009101767202 A CN 2009101767202A CN 200910176720 A CN200910176720 A CN 200910176720A CN 102017979 A CN102017979 A CN 102017979A
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Abstract
The invention provides a poly-guanidine pyrithione acid salt antimicrobial and a preparation method thereof. The antimicrobial is prepared by the following steps of: a, mixing poly-guanidine inorganic acid salt or an organic acid salt aqueous solution and a hydroxyl sodium pyrithione aqueous solution and evenly stirring to obtain a mixture; and b, drying and crashing the mixture, wherein the mol ratio of guanidyl in the poly-guanidine inorganic acid salt or organic acid salt aqueous solution to hydroxyl in the hydroxyl sodium pyrithione aqueous solution is 1:0.1-4. The antimicrobial can hardly be dissolved in water, has high-efficiency sterilizing rate, can be widely used in the fields of antibacterial plastics, antibacterial coating, and the like, has simple preparation method and is convenient to industrialize.
Description
Technical field
The present invention relates to a kind of antibacterial agent and preparation method thereof.Specifically, relate to a kind of poly-guanidine pyrithione silicate antibiosis agent and preparation method thereof.
Technical background
Along with the enhancing of the raising of people's living standard and health consciousness and multiple infectious disease popular in recent years, make people improve constantly to various anti-biotic material product requirements.In recent years, a kind of polymer based on guanidine radicals (poly-guanidine) has become a research focus in antibiotic field because it is efficient, wide spectrum, nontoxic, non-stimulated, good stability, heat decomposition temperature are higher.The kind of poly-guanidine is more, comprises the inorganic acid salt and the organic acid salt of polyhexamethylene guanide; The inorganic acid salt of poly hexamethylene biguanide and organic acid salt; The inorganic acid salt of polyoxyethylene groups guanidine and organic acid salt; Also comprise some other inorganic acid salt and organic acid salt with guanidine radicals polymer of special construction; for example; the guanidine radicals polymer that has groups such as the acyl class of unsaturated double-bond or ester class on the strand that patent CN1111556C mentions has the guanidine radicals polymer of the group such as amide groups, alkyl, acyl group, amido of active group on the strand of mentioning among the patent CN1569923A.Recently, the researcher is on the one hand at the molecular weight (for example, patent CN101173041A) of making great efforts to improve the guanidine radicals polymer, to improve its bactericidal properties and stability; On the other hand, more as required, by choosing different predecessors, constantly adjust the guanidine radicals polymer molecular structure (CN1227219C for example, CN100366647C, US4831423).
When the poly-guanidine compound of major part is synthetic, all can use the inorganic acid salt of guanidine usually, for example therefore guanidine nitrate, guanidine hydrochloride, phosphoguanidine, guanidine carbonate etc. all can contain corresponding acid group (NO in final synthetic poly-guanidine compound
3 -, Cl
-, PO
3 -, CO
3 -Deng).Patent CN101037503 discloses a kind of preparation method of polyhexamethylene guanidine propionate, and it is big to have overcome hygroscopicity such as poly (hexamethylene) hydrochloride, makes the shortcoming of pulverulent solids difficulty, can improve the killing effect to mould simultaneously.Document Synthesis and antimicrobial activity of polymeric guanidine and biguanidine salts, Polymer 40 (1999) 6189-6198 reported polyhexamethylene (two) guanidinesalt hydrochlorate 80 ℃ down and the odium stearate prepared in reaction water-fast polyhexamethylene (two) guanidine stearate, and find that the two is under 280 ℃ temperature, polyhexamethylene (two) guanidinesalt hydrochlorate and polyhexamethylene (two) guanidine stearate still have the good sterilization effect to various bacteria and fungi, therefore can be used for polypropylene, the antimicrobial treatment of polymer such as nylon.
Water miscible poly-guanidines such as polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine propionate, after it is added plastics such as polypropylene, polyethylene, the antibiotic plastic that obtains has good antibacterial effect to bacteriums such as Staphylococcus aureus and Escherichia coli, but when it is dipped in the water, particularly in the hot water, after soaking the long period, the antimicrobial efficiency of antibiotic plastic will descend very big, even disappears.This explanation, water miscible poly-guanidine can be separated out from plastic substrate in hot water gradually, are diffused in the water, lose antibacterial effect gradually.Therefore, often contact the antibiotic plastic of large quantity of moisture, just need to add the poly-guanidine of hydrophobe as antibacterial agent for meeting.At present, the hard acid ester salt of water-insoluble polyhexamethylene (two) guanidine for known still can keep better anti-bacterial effect after poach.But, still the problem of Cun Zaiing is, the antimicrobial efficiency of the hard acid ester salt of polyhexamethylene (two) guanidine is far short of what is expected with respect to polyhexamethylene (two) guanidinesalt hydrochlorate or polyhexamethylene (two) guanidine propionate, need add double usually in plastics even more just can reach same antibacterial effect more than the former quality.Reason may be that the molecular weight of inorganic acid radicals such as hard ester acid group molecular weight ratio salt acid group of introducing and propionate is much bigger on the one hand; On the other hand, hard ester acid group may weaken the antibacterial action of poly-guanidine.
For some antibacterial product that often contacts with water, its resistance to water is very important, therefore, how can make poly-guanidine be insoluble in water, and the bactericidal effect that can keep or improve simultaneously poly-guanidine again is a very good problem to study.The method of patent CN1149926C antimicrobial compositions and its sterilization of use, disclose a kind of with 3-isothiazolone and the poly-compound coordination sterilization of six hexylidene guanidine phosphate, provide a kind of method that improves germicidal efficiency and sterilization broad spectrum activity, but this method can't solve the water miscible problem of poly-guanidine.
Summary of the invention
The inventor finds by great deal of experimental, guanidine radicals polymer and sodium pyrithione prepared in reaction are gone out the agent of a kind of poly-guanidine pyrithione silicate antibiosis, this antibacterial agent is insoluble in water, has the efficient sterilizing rate again, and it has had both the bactericidal effect of guanidine radicals and two kinds of groups of pyrithione acid.The preparation method of this antibacterial agent is simple simultaneously, is easy to industrialization.
Therefore the purpose of this invention is to provide the agent of a kind of poly-guanidine pyrithione silicate antibiosis, this antibacterial agent can be widely used in fields such as antibiotic plastic, antibiotic paint.
Another object of the present invention provides the preparation method of described poly-guanidine pyrithione silicate antibiosis agent.
Poly-guanidine pyrithione silicate antibiosis of the present invention agent gets by including the following steps preparation:
A, will gather the guanidine inorganic acid salt aqueous solution and sodium pyrithione aqueous solution, stir, obtain mixture;
B, with above-mentioned mixed liquor drying, pulverize;
Wherein said poly-guanidine inorganic acid salt is hexamethylene, poly hexamethylene biguanide nitrate, poly hexamethylene biguanide carbonate, poly (hexamethylene) hydrochloride, polyhexamethylene guanidine nitrate, polyhexamethylene guanidine carbonate, polyoxyethylene groups guanidinesalt hydrochlorate, polyoxyethylene groups guanidine nitrate or polyoxyethylene groups guanidine carbonate; Wherein said poly-guanidine organic acid salt is poly hexamethylene biguanide propionate, polyhexamethylene guanide propionate or polyoxyethylene groups guanidine propionate.
Guanidine radicals in the wherein said poly-guanidine inorganic acid salt or the organic acid salt aqueous solution and the sodium pyrithione mol ratio in the sodium pyrithione aqueous solution are 1: 0.1～4, be preferably 1: 0.5～and 3.
Wherein said sodium pyrithione is the commodity of knowing, and it is described as U.S. Pat 3159640 usually, is by 2-chloropyridine-N-oxide and NaSH and NaOH reaction are prepared.Sodium pyrithione is a kind of potent water-soluble fungusproof anti-corrosion agent, have efficient, wide spectrum, low toxicity, stable characteristics, it has been widely used in fields such as medicine, daily use chemicals, metal processing, agricultural product, anticorrosive paint, leather and fur products, weaving, papermaking.But, also can't be used for the antibiotic plastic of requirement resistance to water owing to its good water-solubility.
In the present invention, the concentration of the poly-guanidine inorganic acid salt or the organic acid salt aqueous solution and the concentration of the sodium pyrithione aqueous solution there are not strict restriction, if but excessive concentration can cause poly-guanidine viscosity excessive, can cause mixing inhomogeneous in stirring, make reaction insufficient; And concentration is crossed low meeting, and the waste of water and thermal source when causing drying simultaneously also can time expand, and therefore, preferably gathering guanidine aqueous solution percent concentration is 10%～60%, and sodium pyrithione aqueous solution percent concentration is 15%～70%.
Among the present invention, to gather the reaction of guanidine inorganic acid salt or organic acid salt and sodium pyrithione, make original acid group of poly-guanidine inorganic acid salt or organic acid salt be replaced by the pyrithione acid group wholly or in part, generate the antibacterial agent of hydrophobe, the mol ratio of guanidine radicals and the sour sodium of pyrithione is 1: 0.1～4 in poly-guanidine inorganic acid salt or the organic acid salt in reaction, be preferably 1: 0.5～and 3.If pyrithione acid sodium ratio is too high, can cause unnecessary waste; If pyrithione acid sodium ratio is low excessively, will be difficult to play the effect of detesting water.If the mol ratio of guanidine radicals and pyrithione acid sodium is lower than at 1: 1 o'clock in poly-guanidine inorganic acid salt or the organic acid salt, that will make the acid group in poly-guanidine inorganic acid salt or the organic acid salt is replaced by the pyrithione acid group fully, at this moment preferred interpolation is that the poly-guanidine inorganic acid salt or the organic acid salt aqueous solution are added in the excessive pyrithione acid sodium aqueous solution in proper order, can make like this to replace carry out more complete.If the mol ratio of guanidine radicals and pyrithione acid sodium is higher than 1: 1 in poly-guanidine inorganic acid salt or the organic acid salt, that will make the acid group in poly-guanidine inorganic acid salt or the organic acid salt partly is replaced by the pyrithione acid group, still has the original inorganic acid radical or the organic acid that are connected with guanidine radicals of part.But, what deserves to be mentioned is, even if the poly-guanidine pyrithione hydrochlorate that part replaces will have certain hydrophobe, and sterilization idiocratic that can the original poly-guanidine of reservation as much as possible, cost also can reduce.Therefore, the poly-guanidine pyrithione hydrochlorate that part replaces is in some purposes, and is more worth preferred.For the poly-guanidine pyrithione hydrochlorate that composite part replaces, it should be noted that in the building-up process, preferably pyrithione acid sodium is joined poly-guanidine inorganic acid salt gradually, and want vigorous stirring.
The preparation method of poly-guanidine pyrithione silicate antibiosis of the present invention agent is: will gather the guanidine inorganic acid salt or the organic acid salt aqueous solution and the sodium pyrithione aqueous solution and mix in described ratio, and then with the mixture drying, pulverize.
After the poly-guanidine inorganic acid salt aqueous solution and sodium pyrithione aqueous solution are even, directly carry out drying, obtain dried product exhibited.Dry method can be common drying means, comprises that nature dries, and oven for drying perhaps utilizes spray drying process to spray or the like altogether.
The above-mentioned dried product exhibited that obtains is pulverized, and breaking method does not limit yet.
Preparation method of the present invention is simple, can at room temperature carry out, and antibacterial agent of the present invention can have both the antibacterial and mouldproof effect of poly-guanidine and pyrithione acid, has wider broad-spectrum antibacterial property, application prospect light.
Embodiment
The invention will be further described below in conjunction with specific embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
One, the preparation of complex antimicrobials
Embodiment 1:
(Shanghai is high poly-, and F3000) 21.0g (0.098mol) joins in the 200mL deionized water solution, stirs and makes its dissolving to take by weighing the polyhexamethylene guanide propionate; Other take by weighing pyrithione sodium (Hangzhou ten thousand scapes, NPT) 20.0g (0.134mol) joins in the 200mL deionized water, stirs to make its dissolving; At room temperature (about 25 ℃) with the two mixing, and fully stirred 20 minutes, with the product drying, pulverize, the polyhexamethylene guanide pyrithione hydrochlorate that is replaced fully (
Antibacterial agent 1).
Embodiment 2:
(go up the Industrial Co., Ltd. of seamount, PHMB) 20g (0.091mol) joins in the 200mL aqueous solution, stirs to make its dissolving to take by weighing hexamethylene; Other take by weighing pyrithione sodium (Hangzhou ten thousand scapes, NPT) 35.0g (0.235mol) is added to the water, and stirs to make its dissolving; Under 40 ℃, the two is mixed stirring 10 minutes,, pulverize the product drying, the poly hexamethylene biguanide pyrithione hydrochlorate that is replaced fully (
Antibacterial agent 2).
Embodiment 3:
(Shanghai is high poly-, and F1000) 21.0g (0.133mol) joins in the 200mL aqueous solution, stirs and makes its dissolving to take by weighing poly (hexamethylene) hydrochloride; Other take by weighing pyrithione sodium (Hangzhou ten thousand scapes, NPT) 12.0g (0.080mol) is added to the water, and stirs to make its dissolving; At room temperature (about 25 ℃) with the two mixing, and fully stirred 20 minutes, with the product drying, pulverized, obtain the polyhexamethylene guanide pyrithione hydrochlorate that part replaces (
Antibacterial agent 3).
Two, the preparation of polypropene composition
Embodiment 4:
Polypropylene (2007-15A of Sinopec Beijing Chemical Research Institute, copolymerization, melt index 7.0) 2000.0g, antioxidant (1010 and 168 composite, wherein 1010 and 168 weight ratio is 1: 1, Switzerland gas Ba Jiaji produces) 6.0g, (
Antibacterial agent 1) 8g, in homogenizer, stir, put into double screw extruder melt blending, cooling, pelletizing afterwards.Utilize injection machine to make antibiotic detection print with above-mentioned.
Before carrying out antibacterial test, elder generation in 50 ℃ of water, boils 16 hours with polypropylene specimen, and is standby.
Embodiment 5:
Remove with (
Antibacterial agent 2) the 8g replacement (
Antibacterial agent 1) outside the 8g, all the other are with embodiment 4.Test result such as table 1.
Embodiment 6:
Remove with (
Antibacterial agent 3) the 8g replacement (
Antibacterial agent 1) outside the 8g, all the other are with embodiment 4.Test result such as table 1.
Comparative Examples 1:
Remove with the polyhexamethylene guanide propionate (go up the Industrial Co., Ltd. of seamount, PHMB) 12g replace (
Anti- Microbial inoculum 1) outside the 8g, all the other are with embodiment 4.Test result such as table 1.
Comparative Examples 2
Remove with poly (hexamethylene) hydrochloride (go up the Industrial Co., Ltd. of seamount, PHMB) 12g replace (
Anti- Microbial inoculum 1) outside the 8g, all the other are with embodiment 4.Test result such as table 1.
Comparative Examples 3:
Remove with hexamethylene (go up the Industrial Co., Ltd. of seamount, PHMB) 12g replace (
Anti- Microbial inoculum 1) outside the 8g, all the other are with embodiment 4.Test result such as table 1.
Comparative Examples 4:
Remove with the polyhexamethylene guanide stearate (go up the Industrial Co., Ltd. of seamount, PHGS) 18g replace (
Anti- Microbial inoculum 1) outside the 8g, all the other are with embodiment 4.Test result such as table 1.
The antibacterial test step is tested with reference to antibiotic plastic examination criteria QB/T 2591-2003, and concrete steps are as follows: testing sample is handled with 75% ethanol disinfection and dried, and bacterial classification is standby with the bacteria suspension that sterile water is diluted to debita spissitudo.The bacteria suspension of getting 0.2ml drops in sample surfaces, and (4.0cm * 4.0cm) cover thereon makes bacteria suspension form uniform liquid film between sample and film with the thick polyethylene film of 0.1mm.Keep relative moisture 90% to cultivate 18～24 hours at 37 ℃.With sterile water bacterium liquid is washed, be diluted to suitable concentration gradient, get 0.1ml and be uniformly coated on the aseptic agar medium that has prepared.Cultivated observed result 18～24 hours in 37 ℃.Negative control replaces with aseptic plate, and other operations are identical.
As can be seen from the table, during without poach, the poly-guanidine sterilizing rate of different content can reach 99.9%, illustrates that the sterilizing rate effect of poly-guanidine is reasonable.But, behind poach, for polyhexamethylene guanide propionate, poly (hexamethylene) hydrochloride, hexamethylene, basically do not had antibacterial effect, though and polyhexamethylene stearic acid guanidine still possesses certain germicidal efficacy, antibiotic rate has decline to a certain degree.Comparatively speaking, no matter be the polyhexamethylene guanide pyrithione hydrochlorate and the poly hexamethylene biguanide pyrithione hydrochlorate that replace fully among embodiment 1 and the embodiment 2, still the bactericidal effect behind the polyhexamethylene guanide pyrithione hydrochlorate poach that part replaces among the embodiment 3 is all much better than relatively, illustrates that its bactericidal properties and resistance to water are all fine.
Claims (4)
1. poly-guanidine pyrithione silicate antibiosis agent gets by including the following steps preparation:
A, will gather guanidine inorganic acid salt or the organic acid salt aqueous solution and sodium pyrithione aqueous solution, stir, obtain mixture;
B, with above-mentioned mixed liquor drying, pulverize;
Wherein said poly-guanidine inorganic acid salt is hexamethylene, poly hexamethylene biguanide nitrate, poly hexamethylene biguanide carbonate, poly (hexamethylene) hydrochloride, polyhexamethylene guanidine nitrate, polyhexamethylene guanidine carbonate, polyoxyethylene groups guanidinesalt hydrochlorate, polyoxyethylene groups guanidine nitrate or polyoxyethylene groups guanidine carbonate; Wherein said poly-guanidine organic acid salt is poly hexamethylene biguanide propionate, polyhexamethylene guanide propionate or polyoxyethylene groups guanidine propionate;
The guanidine radicals in the wherein said poly-guanidine inorganic acid salt or the organic acid salt aqueous solution and the mol ratio of the sodium pyrithione in the sodium pyrithione aqueous solution are 1: 0.1～4.
2. a kind of poly-guanidine pyrithione silicate antibiosis according to claim 1 agent is characterized in that the guanidine radicals in the described poly-guanidine inorganic acid salt or the organic acid salt aqueous solution and the sodium pyrithione mol ratio of the sodium pyrithione aqueous solution are 1: 0.5～3.
3. a kind of poly-guanidine pyrithione silicate antibiosis according to claim 1 agent is characterized in that described poly-guanidine inorganic acid salt or organic acid salt aqueous solution percent concentration are 10%～60%, and sodium pyrithione aqueous solution percent concentration is 15%～70%.
4. according to the preparation method of each described a kind of poly-guanidine pyrithione silicate antibiosis agent among the claim 1-3, be to gather the guanidine inorganic acid salt or the organic acid salt aqueous solution and the sodium pyrithione aqueous solution to mix in described ratio, with the mixture drying, pulverize then.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102657281A (en) * | 2012-04-12 | 2012-09-12 | 广汉隆达饲料有限公司 | Dispersion type liquid mildew inhibitor and preparation method thereof |
| CN103229778A (en) * | 2013-05-07 | 2013-08-07 | 江苏辉丰农化股份有限公司 | Cereal crop disease-preventive bactericide |
| CN104911914A (en) * | 2015-06-18 | 2015-09-16 | 周波香 | Durable odor-resistant anti-bacterial finishing process for garments |
| CN107501726A (en) * | 2017-08-22 | 2017-12-22 | 芜湖蓝天工程塑胶有限公司 | A kind of antibiotic polypropylene plastic and preparation method thereof |
| CN107541060A (en) * | 2017-08-22 | 2018-01-05 | 芜湖蓝天工程塑胶有限公司 | A kind of antiseptic and its preparation method and application |
| CN108069880A (en) * | 2017-12-04 | 2018-05-25 | 辽宁科技大学 | A kind of polyhexamethylene list guanidine nitrate preparation method |
| CN115363048A (en) * | 2022-02-11 | 2022-11-22 | 天津市科达斯实业有限公司 | Composite bactericide of nano platinum chelate and polyhexamethylene guanidine and preparation process thereof |
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| KR20080043557A (en) * | 2006-11-14 | 2008-05-19 | 에스케이케미칼주식회사 | Sterilization composition and sterilization method using the same |
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2009
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080043557A (en) * | 2006-11-14 | 2008-05-19 | 에스케이케미칼주식회사 | Sterilization composition and sterilization method using the same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102657281A (en) * | 2012-04-12 | 2012-09-12 | 广汉隆达饲料有限公司 | Dispersion type liquid mildew inhibitor and preparation method thereof |
| CN103229778A (en) * | 2013-05-07 | 2013-08-07 | 江苏辉丰农化股份有限公司 | Cereal crop disease-preventive bactericide |
| CN103229778B (en) * | 2013-05-07 | 2015-05-06 | 江苏辉丰农化股份有限公司 | Cereal crop disease-preventive bactericide |
| CN104911914A (en) * | 2015-06-18 | 2015-09-16 | 周波香 | Durable odor-resistant anti-bacterial finishing process for garments |
| CN104911914B (en) * | 2015-06-18 | 2017-01-11 | 周波香 | Durable odor-resistant anti-bacterial finishing process for garments |
| CN107501726A (en) * | 2017-08-22 | 2017-12-22 | 芜湖蓝天工程塑胶有限公司 | A kind of antibiotic polypropylene plastic and preparation method thereof |
| CN107541060A (en) * | 2017-08-22 | 2018-01-05 | 芜湖蓝天工程塑胶有限公司 | A kind of antiseptic and its preparation method and application |
| CN108069880A (en) * | 2017-12-04 | 2018-05-25 | 辽宁科技大学 | A kind of polyhexamethylene list guanidine nitrate preparation method |
| CN115363048A (en) * | 2022-02-11 | 2022-11-22 | 天津市科达斯实业有限公司 | Composite bactericide of nano platinum chelate and polyhexamethylene guanidine and preparation process thereof |
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Application publication date: 20110420 |