CN103145981B - Polyhexamethylene guanidine phosphate and synthetic method thereof - Google Patents
Polyhexamethylene guanidine phosphate and synthetic method thereof Download PDFInfo
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Abstract
The invention provides a synthetic method for polyhexamethylene guanidine phosphate and poly hexamethylene guanidine phosphate synthesized by the method. The polyhexamethylene guanidine phosphate is obtained by the steps of reacting dicyandiamide and ammonium dihydrogen phosphate to synthesize an aminoguanidine dihydrogen phosphate salt, and then reacting the aminoguanidine dihydrogen phosphate salt with 1, 6-hexamethylene diamine. The method for synthesizing the polyhexamethylene guanidine phosphate is proper in selection of raw materials and technical process, simple in preparation method and low in cost, and is suitable for industrialized production. The prepared polyhexamethylene guanidine phosphate has the characteristics of no toxicity, no stimulation and no corrosion, and has very good killing effect for mildew.
Description
Technical field
The present invention relates to a kind of synthetic method of poly (hexamethylene), particularly relate to the polyhexamethylene guanidine phosphoric acid salt of the phosphatic synthetic method of a kind of polyhexamethylene guanidine and the method synthesis.
Background technology
Reporting a series of guanidine like polymer from the thirties in last century has had microbe killing properties since energy, this compounds obtains at the fungus and mildew resistance of medicine, plant protection, Industrial products, food and daily necessities and applies extremely widely, thus the research of guanidine like polymer more receives very high attention, wherein first ICI Americas Inc has prepared hexamethylene the seventies in last century, is the famous sanitas that makeup and textile industry have broad spectrum antibacterial activity.Zhang Chunchang etc. also disclose the toxicity test (" Chinese Disinfection magazine " of poly hexamethylene biguanide compound disinfectant, 25th volume the 1st phase in 2008,85 ~ 86 pages), report polyhexamethylene biguanidine hydrochloride and there is very high activity, can by bacterium, viruses adsorption, directly act on microorganism, microorganism is died of asphyxiation, and add chlorhexidine acetate the activity of guanidine can be made to be improved.
In recent years, some European countries such as Russian, Austrian research finds that polyhexamethylene guanidine is stronger compared with the fungicidal activity of poly hexamethylene biguanide, performance is more excellent, high-efficiency broad spectrum, for a long time antibacterial, non-corrosiveness, to have no side effect, belong to disinfection sanitizer of new generation, in industrial or agricultural, medical and daily life, have purposes extremely widely.Polyhexamethylene guanidine has been classified as novel guanidine class sterilizing agent by the Ministry of Health 2002 new edition " disinfection technology standard ", promotes the use of at home.
Polyhexamethylene guanidine is insoluble in water, general hydrochloric acid etc. make its ionogen form solvable salt, as Hu Yongcheng etc. discloses subacute toxicity research (the Tropical China medical science of Polyhaxemethylenguanidine Hydrochloride thimerosal Liquid soap, 7th volume the 9th phase in 2007,1700 ~ 1701 pages), prepared actual nontoxic level, the Polyhaxemethylenguanidine Hydrochloride disinfection hand cleanser of 0.3% concentration; Patent CN1390876A discloses a kind of preparation method of poly (hexamethylene) hydrochloride, and with salt acid imide urea and hexanediamine for raw material, tosic acid is catalyst preparing; Patent CN101289536A discloses the preparation method of poly (hexamethylene) hydrochloride, Guanidinium hydrochloride and hexanediamine is reacted, and the product polymerization degree prepared is high, the sterilization phase is long, and uses pH value range wide.
But poly (hexamethylene) hydrochloride water absorbability is strong, cannot make stable pulverulent solids; Be corrosive to some metals, therefore, production and use are all restricted simultaneously.Polyhexamethylene guanidine phosphoric acid salt has higher fungicidal effectiveness, especially suppresses algal grown ability better, is therefore highly suitable in the aqueous systems such as recirculated water, landscape water, oil field reinjection water and uses.
But there is not yet report about polyhexamethylene guanidine method for production of phosphate salt, only have company of SK Chemical of Korea S to produce in the world, therefore, domestic polyhexamethylene guanidine phosphate product depends on import substantially.Report according to available data, polyhexamethylene guanidine phosphoric acid salt is generally the product that polyhexamethylene guanidine phosphoric acid carries out ionogen and obtains, due to phosphoric acid and high molecular polymer react time, level of response is limited, guanidine and the phosphatase reaction of each repeating unit can not be realized, therefore product solubility property is not good, and sterilization activity is also restricted.
Summary of the invention
The phosphatic present situation of synthesis polyhexamethylene guanidine is there is no for domestic at present, the invention provides a kind of polyhexamethylene guanidine phosphoric acid salt synthesizing the phosphatic method of polyhexamethylene guanidine and use the method to synthesize, better to mould killing effect, preparation method is simple, and cost is low.
Therefore, first object of the present invention is to provide a kind of phosphatic method of synthesis polyhexamethylene guanidine, and synthesis step comprises:
Step 1, Dyhard RU 100 and primary ammonium phosphate react under 150 DEG C ~ 220 DEG C conditions, the amino guanidinesalt of synthesis biphosphate; Wherein, Dyhard RU 100 and primary ammonium phosphate mol ratio are preferably 1:(2 ± 0.5).
Step 2, the amino guanidinesalt of described biphosphate and the copolyreaction under initiator existence condition of 1,6-hexanediamine, obtain polyhexamethylene guanidine phosphoric acid salt.
Wherein, described initiator is the mixture with hydroxyl or amino, is preferably polyvalent alcohol, is more preferably and is selected from ethylene glycol, propylene glycol, glycerine, polyoxyethylene glycol; Described polyoxyethylene glycol comprises the polyoxyethylene glycol that number-average molecular weight is 200 ~ 6000.
In the method that the present invention is above-mentioned, described initiator accounts for (1 ± 0.1) ‰ of copolymer reactant gross weight.
In the method that the present invention is above-mentioned, in described copolyreaction process, temperature progressively heats up according to the order of 100 ± 10 DEG C, 150 ± 10 DEG C, 200 ± 10 DEG C, 250 ± 10 DEG C.
Wherein, preferred reaction 1 ~ 2h at 100 ± 10 DEG C of temperature.
Wherein, preferred reaction 1.5 ~ 2.5h at 150 ± 10 DEG C of temperature.
Wherein, preferred reaction 1.5 ~ 2.5h at 200 ± 10 DEG C of temperature.
Wherein, preferred reaction 0.5 ~ 1.5h at 250 ± 10 DEG C of temperature.
Second object of the present invention is to provide the polyhexamethylene guanidine phosphoric acid salt of a kind of aforesaid method synthesis, and it is characterized in that, backbone structure is as shown in structural formula (I), and wherein, n is the polymerization degree to structural formula (I).
（I）
The present invention synthesizes the phosphatic method of polyhexamethylene guanidine, and starting material and technical process are selected suitably, and preparation method is easy, cost is low, can carry out suitability for industrialized production, the polyhexamethylene guanidine phosphoric acid salt of preparation has nontoxic, non-stimulated, free from corrosion feature, simultaneously fine to the killing effect of mould; And stable powder can be made, all can widely use in fields such as weaving, plastics, daily use chemicals, water treatments.
Accompanying drawing explanation
Fig. 1 is that the present invention synthesizes polyhexamethylene guanidine phosphonate methods schematic flow sheet;
Fig. 2 adopts the present invention to synthesize the phosphatic C of polyhexamethylene guanidine prepared by polyhexamethylene guanidine phosphonate methods
13-NMR spectrogram;
Fig. 3 adopts the present invention to synthesize the phosphatic P of polyhexamethylene guanidine prepared by polyhexamethylene guanidine phosphonate methods
31-NMR spectrogram.
Embodiment
Below by specific embodiment, the polyhexamethylene guanidine phosphoric acid salt that the present invention synthesizes the phosphatic method of polyhexamethylene guanidine and the synthesis of use the method is described in detail and is described, consciousness better understands the present invention, but should be understood that, following embodiment does not limit the scope of the invention.
embodiment 1
Step 1, the amino guanidine of synthesis biphosphate
200 kilograms of Dyhard RU 100s and 550 kg of phosphoric acid ammonium dihydrogens join in impeller, mix 30 minutes, then start heating, stop heating, and remain on this temperature range 1 hour, obtain 660 kg of phosphoric acid dihydro aminoguanidine salt when temperature rises to 170 ~ 180 DEG C.
Step 2, the amino guanidinesalt of biphosphate and hexanediamine copolymerization
By 400 kg of phosphoric acid dihydro aminoguanidine and 330 kilogram 1,6-hexanediamine is put in reactor, after adding 0.8 kilogram of propylene glycol, progressively heat up by preset program 100 DEG C (being incubated 1h)-150 DEG C (insulation 2h)-200 DEG C (insulation 2h)-250 DEG C (insulation 0.5h), after reaction terminates, obtain polyhexamethylene guanidine phosphate polymer melt.
Cooling, obtains 670 kilograms of polyhexamethylene guanidine phosphoric acid salt, packaging after pulverizing.
embodiment 2
Step 1, the amino guanidine of synthesis biphosphate
300 kilograms of Dyhard RU 100s and 820 kg of phosphoric acid ammonium dihydrogens join in impeller, mix 30 minutes, then start heating, stop heating, and remain on this temperature range 2 hours, obtain 990 kg of phosphoric acid dihydro aminoguanidine salt when temperature rises to 170 ~ 180 DEG C.
Step 2, the amino guanidinesalt of biphosphate and hexanediamine copolymerization
By 800 kg of phosphoric acid dihydro aminoguanidine and 660 kilogram 1,6-hexanediamine is put in reactor, after adding 0.8 kilogram of ethylene glycol, progressively heat up by preset program 100 DEG C (being incubated 1.5h)-150 DEG C (insulation 1.5h)-200 DEG C (insulation 1.5h)-250 DEG C (insulation 1h), after reaction terminates, obtain polyhexamethylene guanidine phosphate polymer melt.
Cooling, obtains 1340 kilograms of polyhexamethylene guanidine phosphoric acid salt, packaging after pulverizing.
embodiment 3
Step 1, the amino guanidine of synthesis biphosphate
320 kilograms of Dyhard RU 100s and 880 kg of phosphoric acid ammonium dihydrogens join in impeller, mix 30 minutes, then start heating, when temperature rises to 170 ~ 180 DEG C, stop heating, and remain on this temperature range 1.5 hours, obtain about 1000 kg of phosphoric acid dihydro aminoguanidine salt.
Step 2, the amino guanidinesalt of biphosphate and hexanediamine copolymerization
By 500 kg of phosphoric acid dihydro aminoguanidine and 400 kilogram 1,6-hexanediamine is put in reactor, after adding 0.8 kilogram of PEG200, progressively heat up by preset program 100 DEG C (insulation 2h)-150 DEG C (insulation 2.5h)-200 DEG C (insulation 2.5h)-250 DEG C (insulation 1.5h), after reaction terminates, obtain polyhexamethylene guanidine phosphate polymer melt.
Cooling, obtains 650 kilograms of polyhexamethylene guanidine phosphoric acid salt, packaging after pulverizing.
The phosphoric acid polyhexamethylene guanidine prepared by above-described embodiment carries out nuclear magnetic resonance spectroscopy, and nuclear magnetic spectrogram is basically identical, and Fig. 2 is C
13-NMR spectrogram, in figure, δ=155.63 ~ 156.70ppm be-C (=NH) in guanidine radicals-in carbon atom, δ=25.40 ~ 25.70ppm, 28.02 ~ 28.17ppm, 39.75 ~ 41.30ppm are respectively three kinds of carbon atoms in hexa-methylene chain; Fig. 3 is P
31, in figure, only to there is the phosphorus (P in phosphamide for 0.13ppm place in chemical shift (δ) in-NMR spectrogram
31) sharply unimodal.
Infrared spectrum analysis have also been obtained four charateristic avsorption bands of guanidine compound, and ν NH is at about 3300cm
-1, ν C=N is at about 1685 ~ 1650cm
-1, δ NH is at about 1640cm
-1and ν C-N is at about 1300cm
-1; The phosphoric acid hexa-methylene guanidine infrared spectrum synthesized in above-described embodiment is basically identical.
Can be found out by above-mentioned analysis, aforesaid method of the present invention has prepared the polyhexamethylene guanidine phosphoric acid salt shown in structural formula (I).
" disinfection technology standard " (the 2002nd edition) sterilized product toxicological experiment specification according to the Ministry of Health is tested, result shows, polyhexamethylene guanidine phosphoric acid salt toxicity prepared by the present invention is actual nontoxic level, and there is excellent sterilization effect, compared to commercially available prod, sterilization effect improves about 10%.
Those skilled in the art are it is understood that in foregoing of the present invention, and polyhexamethylene guanidine phosphoric acid salt is also referred to as phosphoric acid polyhexamethylene guanidine, and the two implication is the same.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (9)
1. synthesize the phosphatic method of polyhexamethylene guanidine, it is characterized in that, synthesis step comprises:
Step 1, Dyhard RU 100 and biphosphate ammonium salt react under 150 DEG C ~ 220 DEG C conditions, the amino guanidinesalt of synthesis biphosphate;
Step 2, the amino guanidinesalt of described biphosphate and the copolyreaction under initiator existence condition of 1,6-hexanediamine, obtain polyhexamethylene guanidine phosphoric acid salt;
Wherein, described initiator is polyvalent alcohol.
2. the phosphatic method of synthesis polyhexamethylene guanidine according to claim 1, is characterized in that, described initiator is for being selected from ethylene glycol, propylene glycol, glycerine, polyoxyethylene glycol.
3. the phosphatic method of synthesis polyhexamethylene guanidine according to claim 1 and 2, is characterized in that, described initiator weight accounts for (1 ± 0.1) ‰ of reactant gross weight.
4. the phosphatic method of synthesis polyhexamethylene guanidine according to claim 1, is characterized in that, in described copolyreaction process, temperature progressively heats up according to the order of 100 ± 10 DEG C, 150 ± 10 DEG C, 200 ± 10 DEG C, 250 ± 10 DEG C.
5. the phosphatic method of synthesis polyhexamethylene guanidine according to claim 4, is characterized in that, reacts 1 ~ 2h at 100 ± 10 DEG C of temperature.
6. the phosphatic method of synthesis polyhexamethylene guanidine according to claim 4, is characterized in that, reacts 1.5 ~ 2.5h at 150 ± 10 DEG C of temperature.
7. the phosphatic method of synthesis polyhexamethylene guanidine according to claim 4, is characterized in that, reacts 1.5 ~ 2.5h at 200 ± 10 DEG C of temperature.
8. the phosphatic method of synthesis polyhexamethylene guanidine according to claim 4, is characterized in that, reacts 0.5 ~ 1.5h at 250 ± 10 DEG C of temperature.
9. as described in above-mentioned any one claim, synthesize a polyhexamethylene guanidine phosphoric acid salt for the phosphatic method synthesis of polyhexamethylene guanidine, it is characterized in that, backbone structure is:
Wherein, n is the polymerization degree.
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| AT513858B1 (en) * | 2013-01-25 | 2014-08-15 | Sealife Pharma Gmbh | New bioactive polymers |
| CN103396546B (en) * | 2013-08-01 | 2015-09-30 | 湖南利洁科技有限公司 | The method of hexamethylene is prepared in a kind of suspension polymerization |
| CN104397006A (en) * | 2014-11-25 | 2015-03-11 | 苏州佑君环境科技有限公司 | Water-treated polyhexamethylene guanidine hydrochloride sterilizing agent and preparation method thereof |
| CN106075577A (en) * | 2016-07-21 | 2016-11-09 | 南京工业大学 | Based on organic guanidinesalt and the antimicrobial coating of Polyethylene Glycol |
| TWI626229B (en) * | 2016-09-22 | 2018-06-11 | 中國石油化學工業開發股份有限公司 | Synthesis of biguanid phosphate and bactericide |
| CN108069880A (en) * | 2017-12-04 | 2018-05-25 | 辽宁科技大学 | A kind of polyhexamethylene list guanidine nitrate preparation method |
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| CN114452348A (en) * | 2022-04-13 | 2022-05-10 | 深圳德荫堂生物科技有限公司 | Biological agent for inhibiting bad bacteria infection of private parts and production method thereof |
| CN115160527A (en) * | 2022-08-29 | 2022-10-11 | 江苏钟山新材料有限公司 | Preparation method of flame-retardant polyurethane foam containing guanidium phosphate polyether |
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| RU2142451C1 (en) * | 1998-06-30 | 1999-12-10 | Институт эколого-технологических проблем | Method of preparing antiseptic polyhexamethylene guanidine phosphate |
| RU2167167C1 (en) * | 2000-01-18 | 2001-05-20 | Закрытое акционерное общество "Специализированная промышленная компания Ир ИОХ" | Method of preparing polyhexamethyl guanidine phosphate and aqueous solution thereof |
| RU2214426C2 (en) * | 2001-10-11 | 2003-10-20 | Региональная общественная организация - Институт эколого-технологических проблем | Polyhexamethyleneguanidin phosphate preparation method |
| CN101245141B (en) * | 2007-02-16 | 2011-04-06 | 铜陵高聚生物科技有限公司 | Hydrochloric polyhexamethylene guanidine and preparation method thereof |
| CN101857540B (en) * | 2009-04-09 | 2013-04-17 | 宁波大学 | Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization |
| CN101715780A (en) * | 2009-11-09 | 2010-06-02 | 中国海洋石油总公司 | Novel preparation method of organic guanidine bactericide |
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