CN105820333A - Preparation method of polyhexamethyleneguanidine hydrochloride - Google Patents
Preparation method of polyhexamethyleneguanidine hydrochloride Download PDFInfo
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Abstract
The invention discloses a preparation method of polyhexamethyleneguanidine hydrochloride. The method comprises the following steps: (1) polycondensation reaction: adding raw materials guanidine hydrochloride and 1,6-hexamethylenediamine into a reactor, stirring and heating to react in two stages, wherein the reaction is carried out for 2-10 hours after the material temperature is raised to 130-150 DEG C in the first stage, and the reaction is carried out for 1-5 hours after the material temperature is raised to 185-195 DEG C in the second stage; (2) saponification reaction: lowering the material temperature to 140-160 DEG C, adding a sodium hydroxide solution to regulate the pH value to 12 or above, and after finishing adding the sodium hydroxide solution, keeping the temperature at 90-120 DEG C for 1 hour or above; (3) skimming and washing: separating out the lower water layer of the reaction solution, and washing the upper layer with water to obtain water-insoluble polyhexamethyleneguanidine; (4) salification: dissolving the polyhexamethyleneguanidine in a hydrochloric acid solution, and regulating the pH value of the solution to obtain the polyhexamethyleneguanidine hydrochloride water solution; and (5) drying: drying the water solution to obtain the high-purity polyhexamethyleneguanidine hydrochloride product. The method has the advantages of mild reaction conditions and simple preparation process. The purity of the obtained product is 96% or above, the yield can reach 90% or above, and the product is suitable for large-scale production and application.
Description
Technical field
The invention belongs to high molecular polymer preparing technical field, the preparation method of a kind of Polyhaxemethylenguanidine Hydrochloride.
Background technology
Polyhaxemethylenguanidine Hydrochloride (PHMG) is broad-spectrum antimicrobial agent, is a kind of environment-friendly multipurpose New Cationic Polymer, soluble in water,
Aqueous solution colorless and odorless, has purposes the most widely in industrial or agricultural, medical and daily life.Its antibacterial mechanism is: owing to guanidine radicals has very
High activity, makes polymer become electropositive, easily by generally in electronegative each bacterioid, viruses adsorption, thus inhibits the division merit of bacterial virus
Can, make bacterial virus lose reproductive performance, and be polymerized organic guanidine and multiple guanidine radicals are concentrated on this effect that more strengthens on same a part；Meanwhile,
Owing to being high molecular polymer, the thin film that polymer is formed can block the respiration channel of microorganism, makes microorganism be choked to death rapidly.PHMG due to
The molecular structure of its uniqueness so that it is be provided with a lot of excellent performances, as low, still in broad-spectrum high efficacy, concentration, without Drug resistance, can drop by biology
The features such as solution, good water solubility so that it is become very promising class cosmetics of everyday use and a water treatment biocide." disinfection technology standard " (version in 2002)
Polyhexamethylene guanidine is classified as novel guanidine disinfectant, has promoted the use of at home.
The method preparing PHMG at present is mainly with guanidine hydrochloride and 1, and 6-hexamethylene diamine is raw material, uses thermal polycondensation technique to prepare.When PHMG product
Its bactericidal effect is the best in line style and time molecular weight is the biggest within the specific limits, and ideal product is mainly adjusted by thermal polycondensation technological parameter and obtains.Product
Molecular weight is generally measured product number-average molecular weight Mn by cohesion chromatograph and weight average molecular weight Mw characterizes, Mn with Mw is close to generally indicating that
Line style product is many, and narrow molecular weight distribution.If molecular weight of product too low (＜ 400), then product water dissolubility is strong, easily runs off, and absorption film-forming resists
Bacterium decreased effectiveness；If molecular weight too high (＞ 1600), then cross linked polymer is many, and the effective guanidine radicals playing antibacterial effect reduces, and product viscosity is big,
Poorly water-soluble, uses limited.Therefore it is generally acknowledged that molecular weight product has preferably antibacterial effect and have actual application value in the range of 800～1200.
Patent WO99/54291 discloses the synthetic method of a kind of Polyhaxemethylenguanidine Hydrochloride, the method sintetics in two steps, and first first has carbon
Acid guanidine and ammonia chloride synthetic hydrochloric acid guanidine, second step reaction adds hexamethylene diamine and the Polyethylene Glycol as solvent, temperature reaction in two stages, first stage
150 DEG C of reaction 3h, second stage 180 DEG C reaction 1h, reaction cools down reactant liquor after terminating, and it is solvent layer that reaction terminates rear upper strata, and lower floor is product.
Owing to unreacted raw material and oligomer dissolubility in Polyethylene Glycol is relatively big, and it is substantially insoluble in product, thus product is played certain purification effect
Really.But this technique still has the deficiency of several aspect, and one is to use solvent to add cost, and after using cooling, the mode of natural layering has part molten
Agent remains in the product；Two is that after cooling down, lower floor's product condenses into hard solid, and blowing, stirring and dissolving are the most relatively difficult.
Patent CN101245141A refer to the preparation method of a kind of Polyhaxemethylenguanidine Hydrochloride solid, and its principle is by guanidine hydrochloride and triethylene two
Amine also adds initiator and is at high temperature polymerized, and initial polymer uses ion isolation exchange membrane separator, by hydrochloric polyhexamethylene after making aqueous solution
Guanidine is separated from solution, more isolated concentrated solution is dried to solid, then solid pulverizing is obtained product.Although this report refer to one
Separation method, but do not provide concrete technique and operating parameter, it is also suitable for using the method for membrance separation to prepare its production cost of solid product simultaneously
High.
Patent CN101289536A reports the preparation method of a kind of high polymerization degree Polyhaxemethylenguanidine Hydrochloride, and the method is with Polyethylene Glycol for catalysis
Agent, with guanidine hydrochloride and 1,6-hexamethylene diamine is raw material, and the Polyhaxemethylenguanidine Hydrochloride of synthesis is fluid product, and the degree of polymerization is more than 2000.But this report
The number average molecular weight distribution situation of road product is unknown, simultaneously the purification process of the most not mentioned product, and products application scope is limited.
" application chemical industry " the 1st phase of volume 43 in 2014, " synthesis of polyhexamethylene guanidine radicals hydrochlorate ", with hexamethylene diamine and guanidine hydrochloride as raw material,
Having investigated the impact on polymer molecular weight of each technological parameter, gained polyhexamethylene guanidine radicals hydrochlorate molecular weight product is 500～600.Owing to using
One elementary reaction, the products obtained therefrom degree of polymerization is on the low side.
The product that above method obtains is water aqua type, and the phase is low-boiling point material and the content of unhindered amina in minimizing system after the reaction, frequently with dragging down
The mode of vacuum, but the method is very limited to the degree improving product purity.The Polyhaxemethylenguanidine Hydrochloride can bought in the market is mainly
Aqueous solution type, working substance content is generally less than 40%, and product is without purification processes.Water aqua type product, when the transport of distance, can cause transport
Cost higher；Product without purification processes then product remain unreacted raw material completely, oligomer, reaction generate and the ammonia etc. that do not escapes
Impurity, can be restricted when being applied to the fields such as biological medicine, food, cosmetics of everyday use.
Patent CN102369944A, with hydrochloric acid carbotriamine, hexamethylene diamine as primary raw material, is added Polyethylene Glycol, toluene-4-sulfonic acid, is prepared for
A kind of effective active composition is the solid product of 100%.This technique is not engaged in polyreaction, reaction knot due to Polyethylene Glycol, toluene-4-sulfonic acid
Remain on after bundle in solid product, therefore make product quality be affected.
In sum, to prepare aqueous solution Polyhaxemethylenguanidine Hydrochloride product in prior art, produce at the preparation highly purified product of solid-state and raising
Can also improve in product quality and yield.
Summary of the invention
The technical problem to be solved in the present invention is: for present Polyhaxemethylenguanidine Hydrochloride mainly based on water preparation, has that content is low, impurity component is many
Problem, have developed the preparation method of the solid Polyhaxemethylenguanidine Hydrochloride of a kind of high-purity and high yield.
The preparation method of a kind of Polyhaxemethylenguanidine Hydrochloride, comprises the following steps: (1) polycondensation reaction, first raw material guanidine hydrochloride and 1, and 6-hexamethylene diamine is thrown
Entering in reactor, stirring heats up and reacts in two stages, and the first stage raises material temperature and raises material temperature extremely to 130～150 DEG C of reactions 2～10h, second stage
185～195 DEG C are reacted 1～5h again,；(2) saponification, reduction material temperature, to 140～160 DEG C, adds sodium hydroxide solution and adjusts pH to more than 12,
Alkali liquor is incubated after adding at 90～120 DEG C of more than 1h；(3) separatory, washing, separates reactant liquor lower aqueous layer, and upper strata is washed, and is not dissolved in
The polyhexamethylene guanidine of water；(4) become salt, polyhexamethylene guanidine hydrochloric acid solution is dissolved, regulates pH value of solution, obtain Polyhaxemethylenguanidine Hydrochloride water
Solution；(5) it is dried, aqueous solution dried is i.e. obtained highly purified solid Polyhaxemethylenguanidine Hydrochloride product.
1,6-hexamethylene diamine and mol ratio=1.0～1.2: 1 of guanidine hydrochloride in step (1).
The alkali liquor that step (2) adds includes one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, solution of potassium carbonate.
The alkali liquor that step (2) adds is sodium hydroxide solution.
Step (4) hydrochloric acid solution dissolves, and regulation pH value of solution is to 6.0～7.5.
Step (5) uses and is spray-dried or vacuum drying mode.
The detailed step of the present invention is as follows:
1, polycondensation reaction
With guanidine hydrochloride and 1,6-hexamethylene diamine is raw material, n (1,6-hexamethylene diamine): n (guanidine hydrochloride)=1～1.2: 1, raw material is put into stirring intensification point in reactor
Two benches reacts, and the first stage raises material temperature and reacts 1～5h to 130～150 DEG C of reactions 2～10h, second stage rising material temperature again to 185～195 DEG C.
Reaction equation is as follows:
NH2-(CH2)6-NH2+NH2-C (=NH HCl)-NH2→H-[HN-(CH2)6-NH-C (=NH HCl)-NH]n-H+NH32, saponification
Reduction material temperature, to 140～160 DEG C, adds sodium hydroxide solution, and the Polyhaxemethylenguanidine Hydrochloride that the degree of polymerization is high reacts with alkali liquor, generates not
It is dissolved in the polyhexamethylene guanidine of the thick white shape of water.Alkali liquor is incubated after adding at 90～120 DEG C of more than 1h.Low molecular weight polycaprolactone is conducive under the conditions of alkalescence
Compound is polymerized further, improves the product degree of polymerization.Unreacted raw material completely and a small amount of oligomer composition are the most soluble in water.
System pH to be adjusted to more than 12 by the alkali liquor added in this step, and the alkali liquor of addition is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate
Aqueous solution Deng one or more in raw material.Preferably sodium hydroxide.
3, separatory, washing
Solution step 2 obtained filters, and washing, the water-fast paste of white obtained is polyhexamethylene guanidine.
4, salt is become
Polyhexamethylene guanidine aqueous hydrochloric acid solution is dissolved, regulates aqueous solution pH to 6.0～7.5, obtain Polyhaxemethylenguanidine Hydrochloride aqueous solution.
5, it is dried
Aqueous solution step 4 obtained carries out being spray-dried or being vacuum dried i.e. obtaining highly purified solid Polyhaxemethylenguanidine Hydrochloride product, and product can be
Powder or bulk.
The preparation method of the present invention has the advantage that
1, the product of the present invention is solid, has transport, storage, advantage easy to use.Product purity up to more than 96%, applied range.
2, using crude product direct alkaline saponification method in the technique of the present invention, simplify production technology, oligomer aggregates under alkali liquor effect further simultaneously
Working substance, improves product yield, and yield, up to more than 90%, is that current all of prior art is not up to.
Detailed description of the invention:
Below in conjunction with embodiment, the invention will be further described, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1:
By raw material 1,6-hexamethylene diamine and guanidine hydrochloride put in there-necked flask, and wherein 1, the mol ratio of 6-hexamethylene diamine and guanidine hydrochloride is 1.05: 1, rises material temperature extremely
It is warming up to 190 DEG C after 140 DEG C of reaction 6h and reacts 2h again.Cooling material, fall material temperature, to 150 DEG C, adds and 1,6-hexamethylene diamine equimolar ratio
15% sodium hydroxide solution, is incubated 2h at 100 DEG C.Separating lower aqueous solution, polyhexamethylene guanidine deionized water in upper strata rinses 2 times.With 15%
Polyhexamethylene guanidine after dissolving with hydrochloric acid rinsing, regulation Polyhaxemethylenguanidine Hydrochloride pH value of solution is to 6.5, and 120 DEG C of vacuum drying solution obtain solid salt
Acid polyhexamethylene guanidine product.Product purity 96.7%, yield 92.3%, Mn=1105.9, Mw=1198.3.
Embodiment 2:
By raw material 1,6-hexamethylene diamine and guanidine hydrochloride put in there-necked flask, and wherein 1, the mol ratio of 6-hexamethylene diamine and guanidine hydrochloride is 1.05: 1, rises material temperature extremely
It is warming up to 185 DEG C after 150 DEG C of reaction 5h and reacts 3h again.Cooling material, fall material temperature, to 150 DEG C, adds and 1,6-hexamethylene diamine equimolar ratio
15% sodium hydroxide solution, is incubated 2h at 105 DEG C.Separating lower aqueous solution, polyhexamethylene guanidine deionized water in upper strata rinses 2 times.With 15%
Polyhexamethylene guanidine after dissolving with hydrochloric acid rinsing, regulation Polyhaxemethylenguanidine Hydrochloride pH value of solution is to 6.5, and 120 DEG C of vacuum drying solution obtain solid salt
Acid polyhexamethylene guanidine product.Product purity 97.2%, yield 93.5%, Mn=1015.4, Mw=1156.7.
Embodiment 3:
By raw material 1,6-hexamethylene diamine and guanidine hydrochloride put in there-necked flask, and wherein 1, the mol ratio of 6-hexamethylene diamine and guanidine hydrochloride is 1.10: 1, rises material temperature extremely
It is warming up to 185 DEG C after 140 DEG C of reaction 8h and reacts 3h again.Cooling material, fall material temperature, to 150 DEG C, adds and 1,6-hexamethylene diamine equimolar ratio
10% sodium hydroxide solution, is incubated 2h at 100 DEG C.Separating lower aqueous solution, polyhexamethylene guanidine deionized water in upper strata rinses 2 times.With 15%
Polyhexamethylene guanidine after dissolving with hydrochloric acid rinsing, regulation Polyhaxemethylenguanidine Hydrochloride pH value of solution is to 6.5, and 120 DEG C of vacuum drying solution obtain solid salt
Acid polyhexamethylene guanidine product.Product purity 97.4%, yield 91.8%, Mn=997.3, Mw=1147.2.
Embodiment 4:
By raw material 1,6-hexamethylene diamine and guanidine hydrochloride put in there-necked flask, and wherein 1, the mol ratio of 6-hexamethylene diamine and guanidine hydrochloride is 1.10: 1, rises material temperature extremely
It is warming up to 190 DEG C after 150 DEG C of reaction 5h and reacts 2h again.Cooling material, fall material temperature, to 150 DEG C, adds and 1,6-hexamethylene diamine equimolar ratio
15% sodium hydroxide solution, is incubated 1.5h at 110 DEG C.Separating lower aqueous solution, polyhexamethylene guanidine deionized water in upper strata rinses 2 times.With 15%
Polyhexamethylene guanidine after dissolving with hydrochloric acid rinsing, regulation Polyhaxemethylenguanidine Hydrochloride pH value of solution is to 7.0, and 120 DEG C of vacuum drying solution obtain solid salt
Acid polyhexamethylene guanidine product.Product purity 96.2%, yield 94.7%, Mn=1028.5, Mw=1179.6.
Claims (6)
1. the preparation method of a Polyhaxemethylenguanidine Hydrochloride, it is characterised in that comprise the following steps: (1) polycondensation reaction, first raw material hydrochloric acid
Guanidine and 1,6-hexamethylene diamine puts in reactor, and stirring heats up and reacts in two stages, and the first stage raises material temperature and reacts 2～10h to 130～150 DEG C, the
Two-stage raises material temperature and reacts 1～5h again to 185～195 DEG C；(2) saponification, reduction material temperature, to 140～160 DEG C, adds sodium hydroxide solution and adjusts
PH to more than 12, alkali liquor is incubated after adding at 90～120 DEG C of more than 1h；(3) separatory, washing, separates reactant liquor lower aqueous layer, upper water
Wash, obtain water-fast polyhexamethylene guanidine；(4) become salt, polyhexamethylene guanidine hydrochloric acid solution is dissolved, regulates pH value of solution, obtain hydrochloric acid
Polyhexamethylene guanidine aqueous solution；(5) it is dried, aqueous solution dried is i.e. obtained highly purified solid Polyhaxemethylenguanidine Hydrochloride product.
The preparation method of Polyhaxemethylenguanidine Hydrochloride the most according to claim 1, it is characterised in that in step (1) 1,6-hexamethylene diamine and salt
Mol ratio=1.0～1.2: 1 of acid guanidine.
The preparation method of Polyhaxemethylenguanidine Hydrochloride the most according to claim 1, it is characterised in that the alkali liquor that step (2) adds includes hydrogen
One or more in sodium oxide, potassium hydroxide, sodium carbonate, solution of potassium carbonate.
The preparation method of Polyhaxemethylenguanidine Hydrochloride the most according to claim 3, it is characterised in that the alkali liquor that step (2) adds is hydrogen-oxygen
Change sodium solution.
The preparation method of Polyhaxemethylenguanidine Hydrochloride the most according to claim 1, it is characterised in that step (4) hydrochloric acid solution dissolves,
Regulation pH value of solution is to 6.0～7.5.
The preparation method of Polyhaxemethylenguanidine Hydrochloride the most according to claim 1, it is characterised in that step (5) uses and is spray-dried or true
The empty mode being dried.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106832267A (en) * | 2017-01-11 | 2017-06-13 | 北京长江脉医药科技有限责任公司 | A kind of guanidine copolymer and preparation method thereof |
| CN109503832A (en) * | 2018-10-18 | 2019-03-22 | 上海高聚生物科技有限公司 | A kind of polycyclic oxygen propyl group hexyl guanidine hydrochloride and preparation method thereof |
| CN110078913A (en) * | 2019-05-29 | 2019-08-02 | 湖南雪天精细化工股份有限公司 | A kind of preparation method of hexamethylene |
| CN111621010A (en) * | 2019-02-28 | 2020-09-04 | 深圳市盈界生物工程有限公司 | Preparation method of polyhexamethylene guanidine hydrochloride |
| RU2750869C1 (en) * | 2020-06-12 | 2021-07-05 | Акционерное общество «Институт фармацевтических технологий» (АО «ИФТ») | Method for the separation of branched oligohexamethylenguanidine salts for their use as pharmaceutical substances (variants) |
| 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 |
| CN117264551A (en) * | 2023-11-22 | 2023-12-22 | 汕头市恒顺包装材料有限公司 | Multifunctional cold transfer gold stamping film and manufacturing method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832267A (en) * | 2017-01-11 | 2017-06-13 | 北京长江脉医药科技有限责任公司 | A kind of guanidine copolymer and preparation method thereof |
| CN109503832A (en) * | 2018-10-18 | 2019-03-22 | 上海高聚生物科技有限公司 | A kind of polycyclic oxygen propyl group hexyl guanidine hydrochloride and preparation method thereof |
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| CN110078913A (en) * | 2019-05-29 | 2019-08-02 | 湖南雪天精细化工股份有限公司 | A kind of preparation method of hexamethylene |
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| RU2750869C1 (en) * | 2020-06-12 | 2021-07-05 | Акционерное общество «Институт фармацевтических технологий» (АО «ИФТ») | Method for the separation of branched oligohexamethylenguanidine salts for their use as pharmaceutical substances (variants) |
| 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 |
| CN117264551A (en) * | 2023-11-22 | 2023-12-22 | 汕头市恒顺包装材料有限公司 | Multifunctional cold transfer gold stamping film and manufacturing method thereof |
| CN117264551B (en) * | 2023-11-22 | 2024-02-06 | 汕头市恒顺包装材料有限公司 | Multifunctional cold transfer gold stamping film and manufacturing method thereof |
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