CN105820333B - A kind of preparation method of Polyhaxemethylenguanidine Hydrochloride - Google Patents
A kind of preparation method of Polyhaxemethylenguanidine Hydrochloride Download PDFInfo
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- CN105820333B CN105820333B CN201610266257.0A CN201610266257A CN105820333B CN 105820333 B CN105820333 B CN 105820333B CN 201610266257 A CN201610266257 A CN 201610266257A CN 105820333 B CN105820333 B CN 105820333B
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Abstract
The invention discloses a kind of preparation method of Polyhaxemethylenguanidine Hydrochloride, this method comprises the following steps：(1) polycondensation reaction, first raw material guanidine hydrochloride and 1, in 6 hexamethylene diamines input reactor, stirring heating is reacted in two stages, and the first stage raises material temperature to 130~150 DEG C of 2~10h of reaction, second stage and raises material temperature and react 1~5h again to 185~195 DEG C；(2) saponification, reduces material temperature to 140~160 DEG C, adds sodium hydroxide solution tune pH to more than 12, insulation is in 90~120 DEG C of more than 1h after lye adds；(3) liquid separation, washing, reaction solution lower aqueous layer is separated, and upper strata washing, obtains polyhexamethylene guanide not soluble in water；(4) into salt, polyhexamethylene guanide is dissolved with hydrochloric acid solution, pH value of solution is adjusted, obtains Polyhaxemethylenguanidine Hydrochloride aqueous solution；(5) it is dry, the solid Polyhaxemethylenguanidine Hydrochloride product by aqueous solution drying process up to high-purity.The method reaction condition of the present invention is gentle, and preparation method is simple, and for products obtained therefrom purity more than 96%, yield is adapted to large-scale production and application up to more than 90%.
Description
Technical field
The invention belongs to high molecular polymer preparing technical field, specifically a kind of system of Polyhaxemethylenguanidine Hydrochloride
Preparation Method.
Background technology
Polyhaxemethylenguanidine Hydrochloride (PHMG) is broad-spectrum antimicrobial agent, is that a kind of environment-friendly multipurpose novel cation gathers
Compound, soluble easily in water, aqueous solution colorless and odorless, there is extremely extensive purposes in industrial or agricultural, medical and daily life.It is killed
Microbial inoculum mechanism is：Since guanidine radicals has very high activity, make polymer into electropositive, easily by usually in electronegative all kinds of thin
Bacterium, viruses adsorption, so as to inhibit the splitting function of bacterial virus, make bacterial virus lose fecundity, and polymerize organic
Multiple guanidine radicals are concentrated on and this effect are more strengthened on same molecule by guanidine；Simultaneously as be high molecular polymer, polymer shape
Into film can block the respiration channel of microorganism, microorganism is choked to death rapidly.PHMG due to its unique molecular structure,
Make it have many excellent performances, such as broad-spectrum high efficacy, concentration it is low, it is still, without the resistance to the action of a drug, biodegradable, water-soluble
Property it is good the features such as, become very promising a kind of daily chemical product and water treatment biocide.《Disinfection technology standard》(2002
Version) polyhexamethylene guanide has been classified as new guanidine disinfectant, promote the use of at home.
The method of PHMG is prepared at present mainly with guanidine hydrochloride and 1, and 6- hexamethylene diamines are raw material, using pyrocondensation polymerizing technology system
It is standby.When PHMG products are in line style and molecular weight is bigger within the specific limits, its bactericidal effect is better, and ideal product mainly passes through
Adjustment thermal polycondensation technological parameter obtains.Molecular weight product usually measures product number-average molecular weight Mn and Weight-average molecular by cohesion chromatography
Mw is measured to be characterized, Mn and Mw is close to generally indicate that line style product is more, and narrow molecular weight distribution.If molecular weight of product is too low
(＜ 400), then product is water-soluble strong, is easily lost in, and absorption film-forming antibacterial effect weakens；If molecular weight is excessive (＞ 1600),
Then cross-linked polymer is more, and the effective guanidine radicals for playing antibacterial effect is reduced, and product viscosity is big, poorly water-soluble, using limited.Therefore one
As think that molecular weight product has preferable antibacterial effect in the range of 800~1200 and has actual application value.
Patent WO99/54291 discloses a kind of synthetic method of Polyhaxemethylenguanidine Hydrochloride, and this method synthesizes production in two steps
Product, first first has guanidine carbonate and ammonium chloride synthetic hydrochloric acid guanidine, and second step reaction adds hexamethylene diamine and the poly- second two as solvent
Alcohol, temperature reaction in two stages, 150 DEG C of reaction 3h of first stage, 180 DEG C of reaction 1h of second stage, cooling is anti-after reaction
Liquid is answered, upper strata is solvent layer after reaction, and lower floor is product.Due to unreacted raw material and oligomer in polyethylene glycol it is molten
Xie Du is larger, and is substantially insoluble in product, thus certain refining effect is played to product.But the technique still has several sides
The deficiency in face, first, adding cost using solvent, has partial solvent to remain in product by the way of natural layering after cooling
In；Second, lower floor's product condenses into hard solid after cooling, blowing, stirring and dissolving are all relatively difficult.
Patent CN101245141A refer to a kind of preparation method of Polyhaxemethylenguanidine Hydrochloride solid, its principle is by salt
Sour guanidine and triethylenediamine simultaneously add initiator and polymerize at high temperature, and initial polymer uses ion isolation after making aqueous solution
Membrane separator is exchanged, Polyhaxemethylenguanidine Hydrochloride is separated from solution, then the concentrate isolated is dried to solid,
Solid is crushed again to obtain product.Although this report refer to a kind of separation method, but do not provide specific technique and operation
Parameter, while solid product its production cost is made is also quite high using the method for UF membrane.
Patent CN101289536A reports a kind of preparation method of high polymerization degree Polyhaxemethylenguanidine Hydrochloride, and this method is
Using polyethylene glycol as catalyst, with guanidine hydrochloride and 1,6- hexamethylene diamines are raw material, and the Polyhaxemethylenguanidine Hydrochloride of synthesis produces for liquid
Product, the degree of polymerization is more than 2000.But the number average molecular weight distribution situation of this report product is unknown, while product is not also referred to
Purification process, products application scope are limited.
《Using chemical industry》The 1st phase of volume 43 in 2014,《The synthesis of polyhexamethylene guanidine radicals hydrochloride》, with hexamethylene diamine and salt
Sour guanidine is raw material, has investigated influence of each technological parameter to polymer molecular weight, gained polyhexamethylene guanidine radicals hydrochloride product
Molecular weight is 500~600.Due to using an elementary reaction, the products obtained therefrom degree of polymerization is relatively low.
The product that above method obtains is water aqua type, and the phase is low-boiling point material and unhindered amina in reduction system after the reaction
Content, frequently with the mode for dragging down vacuum, but this method is very limited to the degree for improving product purity.Institute currently on the market
The Polyhaxemethylenguanidine Hydrochloride that can be bought is mainly aqueous solution type, and substance content is generally less than 40%, and product is not purified
Processing.Water aqua type product can cause the higher of cost of transportation in the transport of long range；Product is without in purification processes then product
Remain the complete raw material of unreacted, oligomer, reaction generation and the impurity such as ammonia for not escaping, applied to biological medicine,
Food, daily chemical product can be restricted when field.
Patent CN102369944A is using hydrochloric acid carbotriamine, hexamethylene diamine as primary raw material, addition polyethylene glycol, first
Benzene -4- sulfonic acid, is prepared for the solid product that a kind of effective active composition is 100%.In the technique due to polyethylene glycol, toluene-
4- sulfonic acid is not engaged in polymerisation, remains on after reaction in solid product, therefore product quality is affected.
In conclusion in the prior art to prepare based on aqueous solution Polyhaxemethylenguanidine Hydrochloride product, it is high preparing solid-state
It can also be improved on the product and raising product quality and yield of purity.
The content of the invention
The technical problem to be solved in the present invention is：For present Polyhaxemethylenguanidine Hydrochloride mainly based on aqua, exist
The problem of content is low, impurity component is more, have developed the preparation of a kind of high-purity and solid Polyhaxemethylenguanidine Hydrochloride in high yield
Method.
A kind of preparation method of Polyhaxemethylenguanidine Hydrochloride, comprises the following steps：(1) polycondensation reaction, first raw material hydrochloric acid
In guanidine and 1,6- hexamethylene diamine input reactor, stirring heating is reacted in two stages, and the first stage raises material temperature to 130~150 DEG C
2~10h is reacted, second stage raises material temperature and reacts 1~5h again to 185~195 DEG C,；(2) saponification, reduces material temperature to 140
~160 DEG C, sodium hydroxide solution tune pH to more than 12 is added, insulation is in 90~120 DEG C of more than 1h after lye adds；(3) liquid separation,
Washing, reaction solution lower aqueous layer is separated, and upper strata washing, obtains polyhexamethylene guanide not soluble in water；(4) into salt, by poly- six
Methylene guanidine is dissolved with hydrochloric acid solution, is adjusted pH value of solution, is obtained Polyhaxemethylenguanidine Hydrochloride aqueous solution；(5) it is dry, aqueous solution is done
The dry solid Polyhaxemethylenguanidine Hydrochloride product handled up to high-purity.
Molar ratio=1.0~1.2 of 1,6- hexamethylene diamines and guanidine hydrochloride in step (1): 1.
The lye that step (2) adds includes sodium hydroxide, potassium hydroxide, sodium carbonate, one kind in solution of potassium carbonate or several
Kind.
The lye that step (2) adds is sodium hydroxide solution.
Step (4) is dissolved with hydrochloric acid solution, adjusts pH value of solution to 6.0~7.5.
Step (5) is using spray drying or vacuum drying mode.
The detailed step of the present invention is as follows：
1st, polycondensation reaction
With guanidine hydrochloride and 1,6- hexamethylene diamines are raw material, n (1,6- hexamethylene diamine): n (guanidine hydrochloride)=1~1.2: 1, raw material is thrown
Enter stirring heating in reactor to react in two stages, the first stage raises material temperature to 130~150 DEG C of 2~10h of reaction, second-order
Duan Shenggao material temperatures react 1~5h to 185~195 DEG C again.Reaction equation is as follows：
NH2-(CH2)6-NH2+NH2- C (=NHHCl)-NH2→H-[HN-(CH2)6- NH-C (=NHHCl)-NH]n-H
+NH32nd, saponification reduces material temperature to 140~160 DEG C, adds sodium hydroxide solution, the high hydrochloric polyhexamethylene of the degree of polymerization
Guanidine reacts with lye, generates the polyhexamethylene guanide of thick white shape not soluble in water.After lye adds insulation 90~
120 DEG C of more than 1h.Be conducive to low polymer under alkaline condition further to polymerize, improve the product degree of polymerization.Unreacted is complete
Raw material and a small amount of oligomer component it is soluble in water.
System pH is adjusted to more than 12 by the lye added in this step, the lye of addition is sodium hydroxide, potassium hydroxide,
One or more of aqueous solutions in the raw materials such as sodium carbonate, potassium carbonate.It is preferred that sodium hydroxide.
3rd, liquid separation, washing
The solution that step 2 is obtained is filtered, and washing, obtained white paste not soluble in water is poly- six methylene
Base guanidine.
4th, into salt
Polyhexamethylene guanide is dissolved with aqueous hydrochloric acid solution, adjusts aqueous solution pH to 6.0~7.5, it is sub- up to hydrochloric acid poly- six
Methylguanidine aqueous solution.
5th, it is dry
The aqueous solution that step 4 is obtained is spray-dried or is dried in vacuo poly- six methylene of solid hydrochloric acid up to high-purity
Base guanidine product, product can be powdered or block.
The preparation method of the present invention has the following advantages：
1st, product of the invention is solid, has the advantages that transport, stores, is easy to use.Product purity up to 96% with
On, have a wide range of application.
2nd, the direct alkaline saponification method of crude product is used in technique of the invention, simplifies production technology, while oligomer is in alkali
Working substance is further aggregated under liquid effect, improves product yield, yield is existing skills all at present up to more than 90%
What art was not up to.
Embodiment：
With reference to embodiment, the invention will be further described, but the scope of protection of present invention is not limited to reality
Apply the scope of example statement.
Embodiment 1：
By raw material 1, in 6- hexamethylene diamines and guanidine hydrochloride input there-necked flask, wherein the molar ratio of 1,6- hexamethylene diamine and guanidine hydrochloride is
1.05: 1, rise material temperature to 190 DEG C being warming up to and react 2h again after 140 DEG C of reaction 6h.Cool down material, drop material temperature to 150 DEG C, add with
1,6- hexamethylene diamine equimolar than 15% sodium hydroxide solution, 100 DEG C keep the temperature 2h.Lower aqueous solution is separated, upper strata six is sub-
Methylguanidine is rinsed 2 times with deionized water.Polyhexamethylene guanide after being rinsed with 15% dissolving with hydrochloric acid, adjusts hydrochloric polyhexamethylene
Guanidine pH value of solution to 6.5,120 DEG C of vacuum drying solution obtain solid Polyhaxemethylenguanidine Hydrochloride product.Product purity 96.7%, is received
Rate 92.3%, Mn=1105.9, Mw=1198.3.
Embodiment 2：
By raw material 1, in 6- hexamethylene diamines and guanidine hydrochloride input there-necked flask, wherein the molar ratio of 1,6- hexamethylene diamine and guanidine hydrochloride is
1.05: 1, rise material temperature to 185 DEG C being warming up to and react 3h again after 150 DEG C of reaction 5h.Cool down material, drop material temperature to 150 DEG C, add with
1,6- hexamethylene diamine equimolar than 15% sodium hydroxide solution, 105 DEG C keep the temperature 2h.Lower aqueous solution is separated, upper strata six is sub-
Methylguanidine is rinsed 2 times with deionized water.Polyhexamethylene guanide after being rinsed with 15% dissolving with hydrochloric acid, adjusts hydrochloric polyhexamethylene
Guanidine pH value of solution to 6.5,120 DEG C of vacuum drying solution obtain solid Polyhaxemethylenguanidine Hydrochloride product.Product purity 97.2%, is received
Rate 93.5%, Mn=1015.4, Mw=1156.7.
Embodiment 3：
By raw material 1, in 6- hexamethylene diamines and guanidine hydrochloride input there-necked flask, wherein the molar ratio of 1,6- hexamethylene diamine and guanidine hydrochloride is
1.10: 1, rise material temperature to 185 DEG C being warming up to and react 3h again after 140 DEG C of reaction 8h.Cool down material, drop material temperature to 150 DEG C, add with
1,6- hexamethylene diamine equimolar than 10% sodium hydroxide solution, 100 DEG C keep the temperature 2h.Lower aqueous solution is separated, upper strata six is sub-
Methylguanidine is rinsed 2 times with deionized water.Polyhexamethylene guanide after being rinsed with 15% dissolving with hydrochloric acid, adjusts hydrochloric polyhexamethylene
Guanidine pH value of solution to 6.5,120 DEG C of vacuum drying solution obtain solid Polyhaxemethylenguanidine Hydrochloride product.Product purity 97.4%, is received
Rate 91.8%, Mn=997.3, Mw=1147.2.
Embodiment 4：
By raw material 1, in 6- hexamethylene diamines and guanidine hydrochloride input there-necked flask, wherein the molar ratio of 1,6- hexamethylene diamine and guanidine hydrochloride is
1.10: 1, rise material temperature to 190 DEG C being warming up to and react 2h again after 150 DEG C of reaction 5h.Cool down material, drop material temperature to 150 DEG C, add with
1,6- hexamethylene diamine equimolar than 15% sodium hydroxide solution, 110 DEG C keep the temperature 1.5h.Separate lower aqueous solution, upper strata six
Methylene guanidine is rinsed 2 times with deionized water.Polyhexamethylene guanide after being rinsed with 15% dissolving with hydrochloric acid, adjusts poly- six methylene of hydrochloric acid
Base guanidine pH value of solution to 7.0,120 DEG C of vacuum drying solution obtain solid Polyhaxemethylenguanidine Hydrochloride product.Product purity 96.2%,
Yield 94.7%, Mn=1028.5, Mw=1179.6.
Claims (6)
1. a kind of preparation method of Polyhaxemethylenguanidine Hydrochloride, it is characterised in that comprise the following steps：(1) polycondensation reaction, first
In raw material guanidine hydrochloride and 1,6- hexamethylene diamine input reactor, stirring heating is reacted in two stages, and the first stage raises material temperature to 130
~150 DEG C of 2~10h of reaction, second stage raise material temperature and react 1~5h again to 185~195 DEG C；(2) saponification, reduces material
Temperature adds lye pH adjustment to more than 12, insulation is in 90~120 DEG C of more than 1h after lye adds to 140~160 DEG C；(3) liquid separation,
Washing, reaction solution lower aqueous layer is separated, and upper strata washing, obtains polyhexamethylene guanide not soluble in water；(4) into salt, by poly- six
Methylene guanidine is dissolved with hydrochloric acid solution, is adjusted pH value of solution, is obtained Polyhaxemethylenguanidine Hydrochloride aqueous solution；(5) it is dry, aqueous solution is done
The dry solid Polyhaxemethylenguanidine Hydrochloride product handled up to high-purity.
2. the preparation method of Polyhaxemethylenguanidine Hydrochloride according to claim 1, it is characterised in that 1,6- in step (1)
Molar ratio=1.0~1.2 of hexamethylene diamine and guanidine hydrochloride: 1.
3. the preparation method of Polyhaxemethylenguanidine Hydrochloride according to claim 1, it is characterised in that what step (2) added
Lye includes the one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, solution of potassium carbonate.
4. the preparation method of Polyhaxemethylenguanidine Hydrochloride according to claim 3, it is characterised in that what step (2) added
Lye is sodium hydroxide solution.
5. the preparation method of Polyhaxemethylenguanidine Hydrochloride according to claim 1, it is characterised in that step (4) uses hydrochloric acid
Solution dissolves, and adjusts pH value of solution to 6.0~7.5.
6. the preparation method of Polyhaxemethylenguanidine Hydrochloride according to claim 1, it is characterised in that step (5) is using spray
Mist is dry or vacuum drying mode.
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| CN106832267B (en) * | 2017-01-11 | 2019-03-05 | 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 |
| CN111621010B (en) * | 2019-02-28 | 2023-02-10 | 深圳市盈界生物工程有限公司 | Preparation method of polyhexamethylene guanidine hydrochloride |
| CN110078913B (en) * | 2019-05-29 | 2021-08-24 | 湖南雪天精细化工股份有限公司 | Preparation method of polyhexamethylene biguanide 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 |
| 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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| CN102369944A (en) * | 2010-08-11 | 2012-03-14 | 郁锋 | Polyhexamethyleneguanidine hydrochloride for bactericide raw material, and preparation method thereof |
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| RU2422137C1 (en) * | 2009-10-08 | 2011-06-27 | Виктор Вениаминович Тец | Method of obtaining biocidal polyguanidine and biocidal polyguanidine |
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| RU2165268C1 (en) * | 2000-03-21 | 2001-04-20 | Закрытое акционерное общество "ДЕСКО" | Method of synthesis disinfecting agent |
| CN1390876A (en) * | 2002-07-26 | 2003-01-15 | 于锋 | Polyhexaethylene. guanidine as raw material of bactericide and its preparing process |
| CN102369944A (en) * | 2010-08-11 | 2012-03-14 | 郁锋 | Polyhexamethyleneguanidine hydrochloride for bactericide raw material, and preparation method thereof |
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