WO2005016994A1 - Method for preparing polyalkylenebiguanidine salt - Google Patents

Method for preparing polyalkylenebiguanidine salt Download PDF

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Publication number
WO2005016994A1
WO2005016994A1 PCT/KR2004/002048 KR2004002048W WO2005016994A1 WO 2005016994 A1 WO2005016994 A1 WO 2005016994A1 KR 2004002048 W KR2004002048 W KR 2004002048W WO 2005016994 A1 WO2005016994 A1 WO 2005016994A1
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WO
WIPO (PCT)
Prior art keywords
salt
polyalkylenebiguanidine
dihydrochloride
acid
solvent
Prior art date
Application number
PCT/KR2004/002048
Other languages
English (en)
French (fr)
Inventor
Kyung-Wook Yang
Nam-Sik Park
Jin-Man Kim
Original Assignee
Sk Chemicals Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020030056782A external-priority patent/KR20050019173A/ko
Priority claimed from KR1020030061492A external-priority patent/KR20050023927A/ko
Application filed by Sk Chemicals Co., Ltd. filed Critical Sk Chemicals Co., Ltd.
Priority to JP2006523780A priority Critical patent/JP2007502883A/ja
Publication of WO2005016994A1 publication Critical patent/WO2005016994A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C277/02—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of guanidine from cyanamide, calcium cyanamide or dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines

Definitions

  • the present invention relates to a method for preparing polyalkylenebiguanidine salt, and more specifically to a method for preparing polyalkylenebiguanidine salt, which does not require a high- viscosity reactor and a toxic solvent, and is capable of producing various polyalkylenebiguanidine salt.
  • polyhexamethylenebiguanidine salt is produced by polymerizing bisdicyandiamide and diamine or diamine salt.
  • the method has a drawback in that it requires the preliminary process for preparing bisdicyanamide. More precisely, hexamethylenebisdicyanamide, one of the reactants, should be prepared by reacting hexamethylenediamine dihydrochloride with sodium dicyanamide in the presence of butanol solvent, and the product of the preliminary process must be filtered before use.
  • U. S. pat. No. 3,428,576 provides the method for preparing polyhexamethylenebiguanidine salt which uses aqueous hydrochloride solution as a reactant and solvent.
  • sodium dicyanamide and hexamethylenediamine reacts with aqueous hydrochloride solution. The reaction is carried out while removing water.
  • the reaction product After completion of the reaction, the reaction product is dissolved with methanol to remove sodium chloride (NaCl) byproduct by precipitation. Then the reaction product is heated to remove methanol, and the final product, polyhexamethylenebiguanidine hydrochloride salt, is obtained.
  • the method has drawbacks in that the reaction time is too long, and the reactor mist be maintained in the vacuum state. Besides, in the method, sodium chloride (NaCl) byproduct, which is produced as the reaction proceeds, increases the viscosity of the reactants, which prevents the reaction mixture from being stirred in a conventional reactor. Accordingly, the reaction should be carried out in a specially designed reactor such as high- viscosity reactor.
  • the reaction requires toxic solvent, such as methanol, to remove NaCl byproduct, and additional heating process to remove methanol, and the reactor should be maintained in a vacuum state in order to improve the removal efficiency of methanol.
  • the method has other drawback in that only polyhexamethylenebiguanidine hydrochloride salt can be produced. Disclosure of Invention Technical Problem
  • the present invention provides the method for preparing polyalkylenebiguanidine salt of the following fornula 1, which comprises the steps of: polymerizing alkylenediamine dihydrochloride and dicyanamide metal salt in the presence of solvent or without solvent; neutralizing the polymerization product by adding water, and alkali metal compound or alkaline earth metal compound into the polymerization product; separating a neutralized polyalkylenebiguanidine polymer layer from an aqueous layer after inducing a phase-separation by settling the neutralized polymerization product; and adding acid into the separated polyalkylenebiguanidine polymer layer.
  • Y is independently selected from the group consisting of hydrochloride, hydrobromide, hydroiodide, nitric acid, carbonic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, dehydrogenated acetic acid, propionic acid, gluconic acid, sortie acid, fumaric acid, maleic acid and epichlorohydric acid, and n is an integer of 1 or more, preferably 2 to 100, and X represents a C3-C17 bridging group interposed between the adjacent nitrogen atoms.
  • the present invention also provides the method for preparing poly alky leneb iguanidine salt of the following formula 2, which comprises the steps of: polymerizing alkylenediamine dihydrochloride and dicyanamide metal salt in the presence of solvent; and removing solvent and byproduct from the obtained polymerization product.
  • Polyalkylenebiguanidine salt prepared according to the present invention can be represented by the following formila 1.
  • Y is independently selected from the group consisting of hydrochloride, hydrobromide, hydroiodide, nitric acid, carbonic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, dehydrogenated acetic acid, propionic acid, gluconic acid, sortie acid, fumaric acid, maleic acid and epichlorohydric acid, and n is an integer of 1 or more, preferably 2 to 100, and X represents a C3-C17 bridging group interposed between the adjacent nitrogen atoms, and optionally can be alkylene group having a heterogeneous atom such as oxygen and sulfur therebetween.
  • the reactants, alkylenediamine dihydrochloride and dicyanamide metal salt [MN(CN) , where in M is a metal] are injected into a reactor sequentially or 2 similtaneously, and then the reactants are polymerized. If desired, solvent can be added into the reactor during or before the polymerization.
  • Exemplary alkylenediamine dihydrochloride includes hexamethylenediamine dihydrochloride, de- camethylenediamine dihydrochloride, bis- ⁇ -aminopropyl ether dihydrochloride, 4,4'-diaminodicyclohexylmethane dihydrochloride, l,4-di-( ⁇ -aminopropoxy)benzene dihydrochloride, N,N'-di-isobutyl-aminohexa methylenediamine dihydrochloride, trimethylenediamine dihydrochloride, tis-(l-amino-3-propyl)-ether dihydrochloride, l,3-tis4nethylamino neopentane dihydrochloride and the mixtures thereof.
  • the preferable alkylenediamine dihydrochloride includes hexamethylenediamine dihydrochloride.
  • Exemplary metal of dicyanamide metal salt includes sodium, zinc, calcium, copper and the mixtures thereof.
  • the preferable metal includes sodium.
  • the alkylenediamine dihydrochloride and dicyanamide metal salt need not be used in equal amount(mole), and the amounts of the reactants can be varied in wide range. Fbwever, if one reactant is used excessively, there might exist excessive unreacted reactant, and the reaction efficiency might be deteriorated. [22] In case of using solvent, the solvent acts as solvent and heating medium in the polymerization reaction of alkylenediamine dihydrochloride and dicyanamide metal salt.
  • the solvent increases the stirring efficiency of alkylenediamine dihydrochloride and dicyanamide metal salt which is in the solid phase, and prevents the viscosity of the reaction mixture from increasing excessively.
  • Preferable solvent is organic solvent such as polyhydric alcohol or its derivative, which has boiling point of 150 °C or more and does not directly participate in the polymerization reaction of alkylenediamine dihydrochloride and dicyanamide metal salt.
  • the specific examples of the solvent include ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol, polyethylene glycol (Mw is 1,000 or less), 1,3-propylene glycol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol (Mw is 1,000 or less), 2-methyl- 1 J-propyleneglycol, 1 J-butyleneglycol, 1 ,4-butyleneglycol, 1,5-penthanediol, neopentylglycol, 1,6-hexanediol, trimethylolethane, trimethy- lolpropane, glycerol, alpha-methyl glucoside, 24nethyl-2,4-pentane glycol, methyl- cellulose, ethylene carbonate, propylene carbonate, propyleneoxide modified bisphenol A, dibromoneopentyl glycol and the mixtures thereof.
  • EG ethylene glycol
  • the preferable amount of the solvent is 1 to 200 weight parts, more preferably 5 to 100 weight parts with respect to the total 100 weight parts of alkylenediamine dihydrochloride and dicyanamide metal salt. If the amount of the solvent is less than 1 weight part with respect to the total 100 weight parts of alkylenediamine dihydrochloride and dicyanamide metal salt, the viscosity of the reaction mixture does not decreases sufficiently, which can deteriorate stirring efficiency and prevents homogeneous reaction from being carried out. If the amount of the solvent is more than 200 weight parts, the reaction time can be prolonged, and the reaction residue and the reaction cost may increase.
  • a conventional reactor as well as a high- viscosity reactor can be used for the method of the present invention.
  • Exemplary reactor which is suitable for the present invention, includes a stirring vessel, a kneader, an extruder, a mixer, a mill reactor, and so on. More preferable reactor includes a stirring vessel.
  • the temperature in which the reaction mixtures and the solvent is injected into the reactor is not limited to a specific range, but considering the convenience in handling of reactants, and working conditions, the preferable temperature is room temperature.
  • the preferable polymerization temperature is 100 °C to 200 °C
  • the preferable polymerization reaction time is 2 to 24 hours.
  • reaction temperature or time of the polymerization reaction is less than the above ⁇ nentioned range, the polymerization reaction can not be carried out adequately. On the contrary, if the reaction temperature or time of the polymerization reaction is more than the above-mentioned range, side reactions may occur to an excessive extent, which may increase the amount of the byproducts. As the polymerization reaction proceeds, the viscosity of the reaction mixture increases, and the state of the reaction mixture changes from mobile and sticky polymer to a paste-type solid. Accordingly the progress of the reaction can be estimated with the viscosity of the reaction mixture.
  • the neutralization of the polymerization product and the byproduct removal process are carried out.
  • the neutralization process is carried out by adding water to the polymerization product, and stirring the polymerization product to dissolve the same, and subsequently by adding alkali metal compound or alkaline earth metal compound such as sodium hydroxide and potassium hydroxide to the polymerization product and stirring the polymerization product.
  • the amount of water can be about 5 to 40 times, preferably 10 to 40 times, more preferably 15 to 30 times in mole ratio with respect to the amount of dicyanamide metal salt used in the polymerization reaction, and the amount of the alkali metal compound or alkaline earth metal compound can be about 0J to 2 times, preferably 0.5 to 1.5 times in mole ratio with respect to the amount of dicyanamide metal salt.
  • the alkali metal compound or alkaline earth metal compound can be added singly or in aqueous solution state, and stirred at the temperature of 20 °C to 80 °C , preferably 30 °C to 60 °C for 30 minutes to 3 hours, preferably 1 to 2 hours.
  • the neutralized polyalkylenebiguanidine polymer layer may not be formed adequately, and the phase separation due to the difference of the specific gravity may not occur sufficiently.
  • the amount of alkali metal compound or alkaline earth metal compound is more than the above mentioned range, unnecessary alkali metal compound or alkaline earth metal compound exist in the target compound, and it is economically unfavorable without any special advantages.
  • the amount of water or the stirring time is more than the above ⁇ nentioned range, the more preferable effect may not be obtained.
  • the neutralized polymerization product After neutralizing the polymerization product and stopping the stirring, the neutralized polymerization product is stayed at room temperature for 0.5 hours or more, preferably for 3 hours or more to induce a phase-separation into a neutralized polyalkylenebiguanidine polymer layer and an aqueous layer. Then the solvent and the byproducts, for example, metal salt such as sodium chloride (NaCl) produced during the polymerization reaction dissolve into the aqueous layer. Such phase-separation is due to the difference in solubility and specific gravity between the neutralized polyalkylenebiguanidine polymer layer and the aqueous layer in which metal salt dissolves.
  • metal salt such as sodium chloride (NaCl)
  • a pure neutralized polyalkylenebiguanidine polymer layer from which solvent and metal salt are removed, can be obtained.
  • various polyalkylenebiguanidine salt can be obtained by adding water and various acid into the separated polyalkylenebiguanidine polymer layer.
  • Exemplary acid for preparing polyalkylenebiguanidine salt includes hydrochloride, hydrobromide, hydroiodide, nitric acid, carbonic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, dehydrogenated acetic acid, propionic acid, gluconic acid, sortie acid, fumaric acid, maleic acid and epichlorohydric acid and the mixtures thereof.
  • the amount of the acid can be about 0J to 2 times, preferably 0.5 to 1.5 times in mole ratio with respect to the amount of dicyanamide metal salt used in the reaction. If the amount of the acid is less than 0J times, the solubility and stability of the final product are deteriorated. If the amount of the acid is more than the 2 times, the pH of the final product decreases and the final product is not desirable in an economical aspect and in commercial use.
  • Polyalkylenebiguanidine salt prepared in the forms of various salt according to the present invention includes preferably 0 to 10 weight%, more preferably 0.01 to 5 weight% of residual solvent, and the weight average molecular weight thereof is preferably 300 to 20,000, m>re preferably 500 to 10,000, most preferably 700 to 5,000.
  • Polyalkylenebiguanidine hydrochloride salt of the following formula 2 can also be prepared by polymerizing alkylenediamine dihydrochloride and dicyanamide metal salt in the presence of solvent; and by removing solvent and byproduct from the obtained polymerization product.
  • the solvent and the reaction conditions of the polymerization process can be the same with those of the polymerization process of polyalkylenebiguanidine salt of the formila 1.
  • the process of removing the solvent and the byproduct is carried out by adding water to the polymerization product, and stirring the polymerization product to dissolve the same, and subsequently by settling the polymerization product at the temperature of 20 °C to 80 °C , preferably at room temperature for 0.5 hours and more, preferably for 3 hours and more.
  • the amount of water can be about 5 to 40 times, preferably 10 to 40 times, more preferably 15 to 30 times in mole ratio with respect to dicyanamide metal salt used in the polymerization reaction.
  • polyalkylenebiguanidine hydrochloride salt does not dissolve sufficiently or the separation due to the difference in specific gravity may not be performed sufficiently. If the amount of water is more than the mentioned range, it makes the process economically unfavorable without any special advantages. Such separation is carried out due to the difference in solubility and specific gravity between the polyalkylenebiguanidine hydrochloride layer and the aqueous layer in which metal salt and solvent dissolve.
  • the solvent and the byproducts for example, metal salt such as sodium chloride (NaCl) produced in the polymerization reaction dissolve into the aqueous layer.
  • a pure polyalkylenebiguanidine hydrochloride salt can be obtained.
  • the obtained polyalkylenebiguanidine hydrochloride salt includes preferably 0 to 10 weight%, more preferably 0.01 to 5 weight% of residual solvent, and the weight average molecular weight thereof is preferably 300 to 20,000, more preferably 500 to 10,000, most preferably 700 to 5,000.
  • the preferable examples are provided for better understanding of the present invention. Fbwever, the present invention is not be limited to the following examples.
  • [32] [Example 1] Preparation of polvhexamethylenetiguanidine hydrochloride salt
  • polyhexamethylenebiguanidine phosphoric acid salt was prepared in the same manner as described in Example 1. [36] [Example 3] Preparation of polyhexamethylenebiguanidine gluconic acid salt
  • polyhexamethylenebiguanidine gluconic acid salt was prepared in the same manner as described in Example 1. [38] [Example 4] Preparation of polyhexamethylenebiguanidine acetic acid salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 1. [42] [Example 6] Preparation of polyhexamethylenebiguanidine hydrochloride salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 6. [46] [Example 8] Preparation of polyhexamethylenebiguanidine hydrochloride salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 6. [48] [Example 9] Preparation of polyhexamethylenebiguanidine hydrochloride salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 6. [50] [Example 10] Preparation of polyhexamethylenebiguanidine hydrochloride salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 6. [52] [Example 11] Preparation of polyhexamethylenebiguanidine hydrochloride salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 6. [54] [Example 12] Preparation of polyhexamethylenebiguanidine hydrochloride salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 6. [56] [Example 13] Preparation of polyhexamethylenebiguanidine hydrochloride salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 6. [58] [Example 14] Preparation of polyhexamethylenebiguanidine hydrochloride salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 6.
  • [Gbmparative Example] Preparation of polyhexamethylenebiguanidine hy- drochloride salt
  • polyhexamethylenebiguanidine hydrochloride salt was prepared in the same manner as described in Example 6.
  • the present invention prevents the viscosity of the polymerization product from increasing excessively, and therefore does not require high- viscosity reactor, and obviates the mapr disadvantage of the conventional melt process.
  • the toxic solvent is not required for the present invention, and the various target salt can be easily obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
PCT/KR2004/002048 2003-08-18 2004-08-16 Method for preparing polyalkylenebiguanidine salt WO2005016994A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006523780A JP2007502883A (ja) 2003-08-18 2004-08-16 ポリアルキレンバイグアニジン塩の製造方法

Applications Claiming Priority (4)

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KR10-2003-0056782 2003-08-18
KR1020030056782A KR20050019173A (ko) 2003-08-18 2003-08-18 폴리알킬렌바이구아니딘염의 제조 방법
KR10-2003-0061492 2003-09-03
KR1020030061492A KR20050023927A (ko) 2003-09-03 2003-09-03 중화 공정을 이용한 폴리알킬렌바이구아니딘염의 제조 방법

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018042367A3 (en) * 2016-08-31 2018-04-12 Vyome Biosciences Pvt. Ltd. Compounds, compositons and methods related to antimicrobial applications
CN110577639A (zh) * 2019-08-09 2019-12-17 上海高聚生物科技有限公司 一种聚五亚甲基胍盐及其制备方法和应用
CN114436380A (zh) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 一种木质素基絮凝剂及其制备方法
US11486049B2 (en) 2010-12-21 2022-11-01 Basf Se Composition for metal electroplating comprising leveling agent

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT516070B1 (de) * 2014-07-31 2016-08-15 Sealife Pharma Gmbh Verfahren zur Herstellung von Polyguanidinen

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US5302620A (en) * 1990-08-22 1994-04-12 Basf Aktiengesellschaft Bisguanidines and fungicides containing them
WO1999054291A1 (de) * 1998-04-22 1999-10-28 P.O.C. Oil Industry Technology Beratungsges.Mbh Verfahren zur gewinnung von polyhexamethylenguanidin
US6031119A (en) * 1996-07-08 2000-02-29 Yukong Limited Polyalkylene guanidine salts or polyalkylene biguanidine salts having a branched silane compound, method for preparing same and uses thereof
JP2000272236A (ja) * 1999-03-29 2000-10-03 Nicca Chemical Co Ltd 被記録材

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US4439208A (en) * 1981-06-22 1984-03-27 Sandoz Ltd. Method for improving the fastness of dyeings with basic dyes on cellulosic substrates
US5302620A (en) * 1990-08-22 1994-04-12 Basf Aktiengesellschaft Bisguanidines and fungicides containing them
US6031119A (en) * 1996-07-08 2000-02-29 Yukong Limited Polyalkylene guanidine salts or polyalkylene biguanidine salts having a branched silane compound, method for preparing same and uses thereof
WO1999054291A1 (de) * 1998-04-22 1999-10-28 P.O.C. Oil Industry Technology Beratungsges.Mbh Verfahren zur gewinnung von polyhexamethylenguanidin
JP2000272236A (ja) * 1999-03-29 2000-10-03 Nicca Chemical Co Ltd 被記録材

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11486049B2 (en) 2010-12-21 2022-11-01 Basf Se Composition for metal electroplating comprising leveling agent
WO2018042367A3 (en) * 2016-08-31 2018-04-12 Vyome Biosciences Pvt. Ltd. Compounds, compositons and methods related to antimicrobial applications
CN110577639A (zh) * 2019-08-09 2019-12-17 上海高聚生物科技有限公司 一种聚五亚甲基胍盐及其制备方法和应用
CN114436380A (zh) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 一种木质素基絮凝剂及其制备方法
CN114436380B (zh) * 2020-10-31 2023-07-28 中国石油化工股份有限公司 一种木质素基絮凝剂及其制备方法

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