CN102302039B - Dication quaternary ammonium complex iodine disinfectant, and application thereof - Google Patents
Dication quaternary ammonium complex iodine disinfectant, and application thereof Download PDFInfo
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- CN102302039B CN102302039B CN201110161961.7A CN201110161961A CN102302039B CN 102302039 B CN102302039 B CN 102302039B CN 201110161961 A CN201110161961 A CN 201110161961A CN 102302039 B CN102302039 B CN 102302039B
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Abstract
The invention provides a dication quaternary ammonium complex iodine disinfectant. The dication quaternary ammonium complex iodine disinfectant comprises the following ingredients in parts by weight: 10-200 parts of organic amine, 5-100 parts of trimethylamine hydrochloride, 5-150 parts of epoxy chloropropane, 1-50 parts of catalyst, 1-10 parts of buffering agent, 10-100 parts of leveling agent, 10-100 parts of iodine and 10-200 parts of de-ionized water. The preparation process of the disinfectant provided by the invention is simple and convenient; and the prepared disinfectant has the advantages of high efficiency, low toxicity, broad spectrum and less residue. The disinfectant provided by the invention can be widely applied to water disinfection of aquaculture and disease prevention of aquatic animals.
Description
Technical field
The present invention relates to a kind of novel dication quaternary ammonium salt chelated iodine disinfectant, its preparation method and application.
Background technology
Since nineteen thirty-five Domagk finds that after the bactericidal action of cationic surfactant, the research work of quaternary ammonium salt disinfectant has obtained major progress, in fields such as health care, oilfield exploitation, civilian and aquaculture sterilizations, obtained increasingly extensive application.Up to now, developed in the world four generation quaternary ammonium salt disinfectant.First generation product is zephiran, wherein alkyl chain length is product bactericidal effect the best of 12～16 carbon, second generation disinfectant is the derivative of first generation product, to obtain by the substitution reaction on phenyl ring or quaternary nitrogen, third generation product is Dialkyl dimethyl ammonium chloride, this generation product with front two generation product compare, there is synthesis technique simple, production cost is low, nonpoisonous and tasteless, the advantages such as bactericidal effect is good, and replace gradually old product, the quaternary ammonium salt bactericide best results that wherein in two alkyl, carbon number is 8～10, the 4th generation disinfectant be the compound of the first generation and third generation product, its bactericidal property exceeds 4～20 times than front three generation products.
At present, China has completed one, two liang of development and research for quaternary ammonium salt, and major product is 1227, and is widely used in the conventional sterilization sterilization in medicine, health, oil field.But because kind is single, caused resistance, be therefore badly in need of the new quaternary ammonium salt disinfectant of exploitation.China's three, four generations quaternary ammonium salt disinfectant is in development, have breakthrough at present, domestic conventional quaternary ammonium salt disinfectant mainly contains dodecyl benzyl dimethyl ammonium chloride (geramine or 1227), dodecyl dimethyl benzyl ammonium bromide (bromogeramine) and their joint product.Although they have brought into play good effect in disinfecting process, but its weak point also highlights day by day, be mainly reflected in bacterial spore, non-film virus killing effect undesirable, the medicament duration is short, bacterium easily develops immunity to drugs to it, and using dosage is large, and expense is high, and foam is many while using, easy-clear etc. not.
Summary of the invention
The present invention is intended to overcome the deficiency that existing disinfectant exists, and a kind of novel dication quaternary ammonium salt chelated iodine disinfectant is provided.
In order to realize the object of the invention, a kind of dication quaternary ammonium salt chelated iodine disinfectant of the present invention, it comprises the component by following weight portion: organic amine 10-200, trimethylamine hydrochloride 5-100, epoxychloropropane 5-150, catalyzer 1-50, buffer 1-10, levelling agent 10-100, iodine 10-100 and deionized water 10-200.
Preferred dication quaternary ammonium salt chelated iodine disinfectant of the present invention comprises the component by following weight portion: organic amine 50-100, trimethylamine hydrochloride 20-50, epoxychloropropane 10-100, catalyzer 10-30, buffer 2-5, levelling agent 20-50, iodine 20-60 and deionized water 10-150.
Wherein, described organic amine is Dodecyl Dimethyl Amine, myristyl dimethyl tertiary amine, two eight alkyl methyl tertiary amines, two ten alkyl methyl tertiary amines or their mixture.
Described catalyzer is DDAO, cocamidopropyl propyl amide amine oxide or their mixture.
Described buffer is the phosphate solution of sodium dihydrogen phosphate and sodium hydrogen phosphate 2 grams per liters that 1:1 prepares by weight.
Described levelling agent is ethylene glycol, 1.2-propane diols, dipropylene glycol methyl ether or their mixture.
The present invention also provides the preparation method of above-mentioned dication quaternary ammonium salt chelated iodine disinfectant, comprise the following steps: 1) deionized water is placed in to the reactor with reflux condenser, stir, temperature is controlled to 30-40 ℃, then trimethylamine hydrochloride, epoxychloropropane, catalyzer are dropped in reactor, back flow reaction to reactant liquor is after pellucidity, add organic amine, then be warming up to 55-65 ℃, reaction 1-2 hour, be warming up to again 75-85 ℃, react and be pellucidity to reactant liquor in 2-3 hour; 2) above-mentioned reaction system is cooled to 50-68 ℃, levelling agent and iodine are added in reactor, react to reactant liquor and be pellucidity, be then cooled to 40-45 ℃, add buffer reaction 22-30 minute, standing, discharging and get final product.
Aforesaid method, preferred reactor is enamel reaction still.
Further provide above-mentioned dication quaternary ammonium salt chelated iodine disinfectant at water body disinfection, especially the application in aquaculture system sterilization.
The present invention relates to utilize the advanced technologies of crosslinking agent and organic amine, under the effect of catalyzer, generate and take dication quaternary ammonium salt as main ultralow interfacial tension surfactant, be mixed with dication quaternary ammonium salt chelated iodine disinfectant with iodine complexing simultaneously.In process for preparation, use buffer to guarantee the stability of product, add levelling agent simultaneously, effectively avoid the bonding of product under low-temperature condition.
Disinfectant of the present invention had both retained the advantages such as quaternary ammonium salt is non-stimulated, corrosion-free, noresidue, pollution-free, effective time long and can not develop immunity to drugs, and had overcome again the poor shortcoming of quaternary ammonium disinfectant Disinfection Effect; Simultaneously, both retained the effective advantage of iodine kill virus, overcome again the shortcoming that iodine excitant is large, corrosivity is strong, volatile and effective time is short, make quaternary ammonium salt and iodine " strong combination ", become a kind of desirable disinfectant, can be widely used in culture fishery sterilization, product can be applied within the scope of wider pH value, be not subject to the impact of water hardness, the ability that has stronger anti-organic matter to disturb.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
If do not specialize, the conventional means that in following examples, technological means used is well known to those skilled in the art, agents useful for same and raw material are commercial goods, and raw material umber is all by weight.
Embodiment 1
The preparation of dication quaternary ammonium salt chelated iodine disinfectant, comprises step:
(1) by 50 parts of enamel reaction stills that are placed in reflux condenser of deionized water, stir, temperature is controlled to about 30-40 ℃, then by 30 parts of trimethylamine hydrochlorides, 60 parts of epoxychloropropane, 10 parts of input reactors of DDAO, back flow reaction to reactant liquor is pellucidity.Add 50 parts of 12/myristyl dimethyl tertiary amines, be warming up to 55-65 ℃, reaction 1-2 hour, then is warming up to 75-85 ℃, reacts and is pellucidity to reactant liquor in 2-3 hour.
(2) be cooled to 50-68 ℃, 20 parts of ethylene glycol are mixed and added in reactor with 30 parts of smart iodine, react to reactant liquor and be pellucidity.Being cooled to 40-45 ℃, adding 2 grams per liter sodium dihydrogen phosphates and sodium hydrogen phosphate 1:1(weight ratio) 2 parts of water solution mixtures react 22-30 minute, and standing, discharging, obtains rufous thick liquid product.
Embodiment 2
The preparation of dication quaternary ammonium salt chelated iodine disinfectant, comprises step:
(1) by 100 parts of reactors that are placed in reflux condenser of deionized water, stir, temperature is controlled to about 30-40 ℃, then by 40 parts of trimethylamine hydrochlorides, 80 parts of epoxychloropropane, 20 parts of input reactors of DDAO, back flow reaction to reactant liquor is pellucidity.Add 80 parts of 12/myristyl dimethyl tertiary amines, be warming up to 55-65 ℃, reaction 1-2 hour, then is warming up to 75-85 ℃, reacts and is pellucidity to reactant liquor in 2-3 hour.
(2) be cooled to 50-68 ℃, 30 parts of 1.2-propane diols are mixed and added in reactor with 40 parts of smart iodine, react to reactant liquor and be pellucidity.Being cooled to 40-45 ℃, adding 2 grams per liter sodium dihydrogen phosphates and sodium hydrogen phosphate 1:1(weight ratio) 3 parts of water solution mixtures react 22～30 minutes, and standing, discharging, obtains rufous thick liquid product.
Embodiment 3
The preparation of dication quaternary ammonium salt chelated iodine disinfectant, comprises step:
(1) by 150 parts of reactors that are placed in reflux condenser of deionized water, stir, temperature is controlled to about 30-40 ℃, and then, by 50 parts of trimethylamine hydrochlorides, 100 parts of epoxychloropropane, 20 parts of input reactors of cocamidopropyl propyl amide amine oxide, back flow reaction to reactant liquor is pellucidity.Add 100 parts of 12/myristyl dimethyl tertiary amines, be warming up to 55-65 ℃, reaction 1-2 hour, then is warming up to 75-85 ℃, reacts and is pellucidity to reactant liquor in 2-3 hour.
(2) be cooled to 50-68 ℃, 30 parts of 1.2-propane diols are mixed and added in reactor with 30 parts of smart iodine, react to reactant liquor and be pellucidity.Being cooled to 40-45 ℃, adding 2 grams per liter sodium dihydrogen phosphates and sodium hydrogen phosphate 1:1(weight ratio) 2 parts of water solution mixtures react 22-30 minute, and standing, discharging, obtains rufous thick liquid product.
Embodiment 4
The preparation of dication quaternary ammonium salt chelated iodine disinfectant, comprises step:
(1) by 80 parts of reactors that are placed in reflux condenser of deionized water, stir, temperature is controlled to about 30-40 ℃, and then, by 40 parts of trimethylamine hydrochlorides, 80 parts of epoxychloropropane, 10 parts of input reactors of DDAO, back flow reaction to reactant liquor is pellucidity.Add 60 parts of two eight/ten alkyl methyl tertiary amines, be warming up to 55-65 ℃, reaction 1-2 hour, then be warming up to 75-85 ℃, reacts and is pellucidity to reactant liquor in 2-3 hour.
(2) be cooled to 50-68 ℃, 30 parts of ethylene glycol are mixed and added in reactor with 20 parts of smart iodine, react to reactant liquor and be pellucidity.Being cooled to 40-45 ℃, adding 2 grams per liter sodium dihydrogen phosphates and sodium hydrogen phosphate 1:1(weight ratio) 2 parts of water solution mixtures react 22-30 minute, and standing, discharging, obtains rufous thick liquid product.
Embodiment 5
The preparation of dication quaternary ammonium salt chelated iodine disinfectant, comprises step:
(1) by 60 parts of reactors that are placed in reflux condenser of deionized water, stir, temperature is controlled to about 30-40 ℃, and then, by 30 parts of trimethylamine hydrochlorides, 60 parts of epoxychloropropane, 20 parts of input reactors of cocamidopropyl propyl amide amine oxide, back flow reaction to reactant liquor is pellucidity.Add 50 parts of two eight/ten alkyl methyl tertiary amines, be warming up to 55-65 ℃, reaction 1-2 hour, then be warming up to 75-85 ℃, reacts and is pellucidity to reactant liquor in 2-3 hour.
(2) be cooled to 50-68 ℃, 20 parts of dipropylene glycol methyl ethers are mixed and added in reactor with 20 parts of smart iodine, react to reactant liquor and be pellucidity.Being cooled to 40-45 ℃, adding 2 grams per liter sodium dihydrogen phosphates and sodium hydrogen phosphate 1:1(weight ratio) 3 parts of water solution mixtures react 22-30 minute, and standing, discharging, obtains rufous thick liquid product.
Embodiment 6
The preparation of dication quaternary ammonium salt chelated iodine disinfectant, comprises step:
(1) by 120 parts of reactors that are placed in reflux condenser of deionized water, stir, temperature is controlled to about 30-40 ℃, then by 40 parts of trimethylamine hydrochlorides, 100 parts of epoxychloropropane, 20 parts of input reactors of DDAO, back flow reaction to reactant liquor is pellucidity.Add 80 parts of 12/myristyl dimethyl tertiary amines, be warming up to 55-65 ℃, reaction 1-2 hour, then is warming up to 75-85 ℃, reacts and is pellucidity to reactant liquor in 2-3 hour.
(2) be cooled to 50-68 ℃, 30 parts of dipropylene glycol methyl ethers are mixed and added in reactor with 30 parts of smart iodine, react to reactant liquor and be pellucidity.Being cooled to 40-45 ℃, adding 2 grams per liter sodium dihydrogen phosphates and sodium hydrogen phosphate 1:1(weight ratio) 4 parts of water solution mixtures react 22-30 minute, and standing, discharging, obtains rufous thick liquid product.
Embodiment 7
The preparation of dication quaternary ammonium salt chelated iodine disinfectant, comprises step:
(1) by 100 parts of reactors that are placed in reflux condenser of deionized water, stir, temperature is controlled to about 30-40 ℃, and then, by 30 parts of trimethylamine hydrochlorides, 60 parts of epoxychloropropane, 20 parts of input reactors of cocamidopropyl propyl amide amine oxide, back flow reaction to reactant liquor is pellucidity.Add 80 parts of two eight/ten alkyl methyl tertiary amines, be warming up to 55-65 ℃, reaction 1-2 hour, then be warming up to 75-85 ℃, reacts and is pellucidity to reactant liquor in 2-3 hour.
(2) be cooled to 50-68 ℃, 20 parts of dipropylene glycol methyl ethers are mixed and added in reactor with 30 parts of smart iodine, react to reactant liquor and be pellucidity.Being cooled to 40-45 ℃, adding 2 grams per liter sodium dihydrogen phosphates and sodium hydrogen phosphate 1:1(weight ratio) 2 parts of water solution mixtures react 22-30 minute, and standing, discharging, obtains rufous thick liquid product.
Embodiment 8
The preparation of dication quaternary ammonium salt chelated iodine disinfectant, comprises step:
(1) by 85 parts of reactors that are placed in reflux condenser of deionized water, stir, temperature is controlled to about 30-40 ℃, and then, by 30 parts of trimethylamine hydrochlorides, 75 parts of epoxychloropropane, 25 parts of input reactors of DDAO, back flow reaction to reactant liquor is pellucidity.Add 80 parts of 12/myristyl dimethyl tertiary amines, be warming up to 55-65 ℃, reaction 1-2 hour, then is warming up to 75-85 ℃, reacts and is pellucidity to reactant liquor in 2-3 hour.
(2) be cooled to 50-68 ℃, 30 parts of ethylene glycol are mixed and added in reactor with 25 parts of smart iodine, react to reactant liquor and be pellucidity.Being cooled to 40-45 ℃, adding 2 grams per liter sodium dihydrogen phosphates and sodium hydrogen phosphate 1:1(weight ratio) 3 parts of water solution mixtures react 22-30 minute, and standing, discharging, obtains rufous thick liquid product.
Experimental example
The dication quaternary ammonium salt chelated iodine disinfectant products that the present invention is made and commercially available common quaternary ammonium salt disinfectant product contrast discovery, and it is more obvious that dication quaternary ammonium salt chelated iodine disinfectant of the present invention is applied to the water body disinfection of aquaculture and the prevention from suffering from the diseases of aquatic animal and result for the treatment of.
1, the result for the treatment of to porgy disease
Vibrios (Vibrio natriegens) 1594 strains (purchased from Xin Yu medicine clinic test center of the Ministry of Agriculture) of floating are bathed and are infected after porgy with bacterium, difference dipping drug treatment, and result is as shown in table 1.
The result for the treatment of of table 1 pair porgy disease
Note: positive control be porgy bacterium bathe infect after drug treatment not, negative control is not infected porgy.
Not infected control group porgy is dead without appearance, after positive infection control group porgy 48h, starts to occur that mouth, tail fin and dorsal fin are hemorrhage, and eyes are outstanding, start to occur death.And disinfectant 100 μ g/ml dipping group porgy protective rates of the present invention are 83.3%, commercially available quaternary ammonium salt disinfectant 100 μ g/ml protective rates are only 70%.
2, the result for the treatment of to Chinese disease of prawn
Vibrios (Vibrio natriegens) 1594 strains (purchased from Xin Yu medicine clinic test center of the Ministry of Agriculture) of floating are bathed after infection of Chinese prawn with bacterium, difference dipping drug treatment, and result is as shown in table 2.
The result for the treatment of of table 2 pair Chinese disease of prawn
Note: positive control be prawn bacterium bathe infect after drug treatment not, negative control is not infected prawn.
Not infected control group prawn is dead without occurring, positively starts to occur that motoricity weakens after infecting control group prawn 48h, and foot is rubescent to be started to occur dead, and 144h is all dead.And disinfectant 100 μ g/ml dipping group lethality of the present invention are only 16.7%, commercially available quaternary ammonium salt disinfectant 100 μ g/ml lethality are up to 25%.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (4)
1. dication quaternary ammonium salt chelated iodine disinfectant, is characterized in that, described disinfectant comprises the raw material by following weight portion:
The preparation method of described disinfectant comprises the following steps:
1) deionized water is placed in to the reactor with reflux condenser, stir, temperature is controlled to 30-40 ℃, then trimethylamine hydrochloride, epoxychloropropane, catalyzer are dropped in reactor, back flow reaction to reactant liquor is after pellucidity, adds organic amine, then be warming up to 55-65 ℃, reaction 1-2 hour, then is warming up to 75-85 ℃, reacts and is pellucidity to reactant liquor in 2-3 hour;
2) above-mentioned reaction system is cooled to 50-68 ℃, levelling agent and iodine are added in reactor, react to reactant liquor and be pellucidity, be then cooled to 40-45 ℃, add buffer reaction 22-30 minute, standing, discharging and get final product;
Wherein, described organic amine is Dodecyl Dimethyl Amine, myristyl dimethyl tertiary amine, two eight alkyl methyl tertiary amines, two ten alkyl methyl tertiary amines or their mixture;
Described catalyzer is DDAO, cocamidopropyl propyl amide amine oxide or their mixture;
Described buffer is the phosphate solution of sodium dihydrogen phosphate and sodium hydrogen phosphate 2 grams per liters that 1:1 prepares by weight;
Described levelling agent is ethylene glycol, 1.2-propane diols, dipropylene glycol methyl ether or their mixture.
2. disinfectant according to claim 1, is characterized in that, described disinfectant comprises the raw material by following weight portion:
3. disinfectant according to claim 1, described reactor is enamel reaction still.
4. the application of the dication quaternary ammonium salt chelated iodine disinfectant described in claim 1 or 2 in water body disinfection.
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| US20090162359A1 (en) | 2007-12-21 | 2009-06-25 | Christian Klein | Bivalent, bispecific antibodies |
| CN105693534A (en) * | 2014-11-24 | 2016-06-22 | 天津博克尼科技发展有限公司 | Preparation method of cocamidopropyl betaine-iodine complex |
| CN112980612B (en) * | 2021-02-20 | 2022-05-31 | 南京邮电大学 | Washing disinfectant and preparation method thereof |
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| GB0311174D0 (en) * | 2003-05-15 | 2003-06-18 | Baker Brian F | Anti-viral cleaning composition |
| CN1331397C (en) * | 2004-07-16 | 2007-08-15 | 哈尔滨工业大学 | Bi-dodecyl double quaternary ammonium salt iodine attached bactericide |
| CN101040618A (en) * | 2007-04-07 | 2007-09-26 | 李安民 | Method for preparing fungicides esterquats compound Iodine |
| CN101066054A (en) * | 2007-06-05 | 2007-11-07 | 孙保兴 | Disinfectant |
| CN100542405C (en) * | 2007-06-05 | 2009-09-23 | 孙保兴 | Amine oxide iodine complex disinfectant |
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