WO2022045163A1 - Procédé de production de sel d'acide gras de guanidine et composition associée - Google Patents

Procédé de production de sel d'acide gras de guanidine et composition associée Download PDF

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Publication number
WO2022045163A1
WO2022045163A1 PCT/JP2021/031075 JP2021031075W WO2022045163A1 WO 2022045163 A1 WO2022045163 A1 WO 2022045163A1 JP 2021031075 W JP2021031075 W JP 2021031075W WO 2022045163 A1 WO2022045163 A1 WO 2022045163A1
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WO
WIPO (PCT)
Prior art keywords
fatty acid
guanidine
acid salt
polysiloxane
composition
Prior art date
Application number
PCT/JP2021/031075
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English (en)
Japanese (ja)
Inventor
麻耶 岡庭
和良 上等
和志 杉本
克之 村井
Original Assignee
三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to JP2022545652A priority Critical patent/JPWO2022045163A1/ja
Publication of WO2022045163A1 publication Critical patent/WO2022045163A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C279/02—Guanidine; Salts, complexes or addition compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a method for producing a guanidine fatty acid salt and a composition thereof.
  • Non-Patent Document 1 is known as a method for producing a guanidine fatty acid salt.
  • Non-Patent Document 1 after dissolving fatty acid in an alcohol solvent, guanidine carbonate is added, and the mixture is heated in a hot water bath at a predetermined temperature for 4 hours, filtered, the solvent is distilled off, the mixture is pulverized under reduced pressure, and further in a vacuum desiccator.
  • a method of synthesizing guanidine soap, which is a guanidine fatty acid salt, by drying for a long time is shown.
  • the present inventors have studied in detail a conventional method for producing a guanidine fatty acid salt as described in Non-Patent Document 1. As a result, it was found that carbon dioxide is generated by the reaction between the fatty acid and guanidine carbonate, and the carbon dioxide raises the liquid level of the reaction solution. Such an increase in the liquid level causes, for example, a decrease in yield and production efficiency, a poor liquid phase, and difficulty in controlling the production conditions in the production of the guanidine fatty acid salt.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method and composition for producing a guanidine fatty acid salt, which suppresses an increase in the liquid level due to carbon dioxide generated during the production of the guanidine fatty acid salt. ..
  • the present inventors have found that when a predetermined compound is used in the production of a guanidine fatty acid salt, the liquid level rise due to carbon dioxide generated during the production can be suppressed.
  • the invention was completed.
  • the present invention is as follows.
  • a guanidine fatty acid salt comprising a step of heating a mixture containing guanidine carbonate, a fatty acid having 6 to 22 carbon atoms, and polysiloxane to 40 ° C. or higher and 200 ° C. or lower to obtain a composition containing a guanidine fatty acid salt.
  • Manufacturing method [2] The method for producing a guanidine fatty acid salt according to [1], wherein the polysiloxane contains polydimethylsiloxane.
  • the content of the polysiloxane in the composition is 0.01 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the guanidine fatty acid salt, according to [1] or [2].
  • the present invention it is possible to provide a method and composition for producing a guanidine fatty acid salt, which suppresses an increase in the liquid level due to carbon dioxide generated during the production of the guanidine fatty acid salt.
  • the present embodiment will be described in detail, but the present invention is not limited to the following embodiments.
  • the present invention can be modified in various ways without departing from the gist thereof.
  • a mixture containing guanidine carbonate, a fatty acid having 6 to 22 carbon atoms (hereinafter, also simply referred to as “fatty acid”), and polysiloxane is mixed at 40 ° C. or higher and 200 ° C. or lower. It has a step of obtaining a composition containing a guanidine fatty acid salt (hereinafter, also referred to as a “fatty acid salt synthesis step”).
  • the production method of the present embodiment may include a step of preparing a mixture, that is, a mixture containing a fatty acid having 6 to 22 carbon atoms, polysiloxane, and guanidine carbonate prior to the above-mentioned fatty acid salt synthesis step. good.
  • the fatty acid is not particularly limited as long as it has 6 to 22 carbon atoms, and can be used from a medium-chain fatty acid having 6 carbon atoms to a long-chain fatty acid (higher fatty acid) having 22 carbon atoms. From the viewpoint of more effectively and surely exerting the action and effect according to the present invention, a fatty acid having 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms is preferably used as the fatty acid.
  • the fatty acid may be a synthesized fatty acid or a fatty acid derived from natural animals and plants.
  • the fatty acid may be a straight chain or a branched chain, and may be a saturated fatty acid or an unsaturated fatty acid.
  • Examples of fatty acids include caproic acid, enanthic acid, capric acid, nonanoic acid, caproic acid, lauric acid, myristic acid, pentadecic acid, palmitic acid, palmitreic acid, margaric acid, stearic acid, oleic acid, bacenoic acid and linoleic acid.
  • Linolenic acid isostearic acid, arachidic acid, behenic acid, ricinoleic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, and docosahexaenoic acid.
  • fatty acids derived from natural animal and vegetable oils include perilla oil fatty acid, dehydrated perilla oil fatty acid, macadamia nut oil fatty acid, palm oil fatty acid, peanut oil fatty acid, fish oil fatty acid, rapeseed oil fatty acid (canola oil fatty acid), and hybrid sunflower oil fatty acid.
  • Sunflower oil fatty acid sunflower seed oil fatty acid, palm oil fatty acid, cottonseed oil fatty acid, soybean oil fatty acid, safflower oil fatty acid, wheat germ oil fatty acid, rice bran oil fatty acid, sesame oil fatty acid, corn oil fatty acid, evening primrose seed oil fatty acid, lanolin fatty acid, Non-hydroxylanolin fatty acid, hydroxylanolin fatty acid, milk fat fatty acid, linseed oil fatty acid, rapeseed oil fatty acid, and olive oil fatty acid, which have 6 to 22 carbon atoms.
  • the fatty acid of the present embodiment may be a fatty acid derived from natural animals and plants to which hydrogen is further added. These fatty acids may be used alone or in combination of two or more. Among these, lauric acid, stearic acid and coconut oil are preferable from the viewpoint of more effectively and surely exerting the action and effect according to the present invention.
  • the polysiloxane preferably has a structure represented by the following formula (1), has a terminal bonded to an oxygen atom of -SiR 1 R 2 R 3 , and a terminal bonded to a silicon atom of -OSiR. It may be 1 R 2 R 3 , and both ends may be directly bonded to form a ring.
  • R 1 , R 2 and R 3 are independently synonymous with R 1 and R 2 in the following formula (1).
  • m may be a number having a weight average molecular weight described later.
  • R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-heptyl group and an n-hexyl group. Can be mentioned. From the viewpoint of more effectively and surely exerting the action and effect according to the present invention, the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 3, and 1 or. 2 is particularly preferable.
  • one polysiloxane is used alone or in combination of two or more.
  • the polysiloxane can be obtained by a known method, and can be produced, for example, by the method described in JP-A-2020-11165.
  • a commercially available product may be obtained.
  • the commercially available product may be a commercially available product containing polysiloxane in the solvent.
  • BYK registered trademark
  • -061, 063, 065, 066N, 067A, 070, 072 manufactured by BYK Co., Ltd. may be used.
  • polysiloxane preferably contains polydimethylsiloxane.
  • the polydimethylsiloxane is represented by the following formula (2).
  • n may be a number having a weight average molecular weight described later.
  • Polydimethylsiloxane can be obtained by a known method, and can be produced, for example, by the method described in JP-A-7-109354. In addition, a commercially available product may be obtained.
  • the use of polysiloxane makes it possible to suppress an increase in the liquid level when preparing a guanidine fatty acid salt.
  • the present inventors have found that the effect of polysiloxane on suppressing the rise in liquid level is significantly superior to that of a conventionally known defoaming agent.
  • the present inventors also confirmed that there is no direct correlation between the defoaming ability of a substance generally used as a defoaming agent and the effect of suppressing the rise in liquid level in the present embodiment.
  • the rise in the liquid level is thought to be mainly due to the generation of carbon dioxide, but when polysiloxane is used, the viscosity of the molecular film due to the guanidine fatty acid salt surrounding the bubbles of carbon dioxide is lowered, and the stability of the bubbles is further lowered. It is presumed that the rise in liquid level can be suppressed. However, the factors are not limited to this.
  • the weight average molecular weight of the polysiloxane is preferably 1000 or more and 100,000 or less, more preferably 1500 or more and 80,000 or less, and 2000 or more and 65,000 or less, from the viewpoint of more effectively and surely exerting the action and effect of the present invention. It is even more preferably 2000 or more and 60,000 or less, and particularly preferably 3000 or more and 30,000 or less.
  • the weight average molecular weight corresponds to the sum of the amounts obtained by multiplying the molecular weight of the corresponding component by the weight fraction thereof, and is measured by the gel permeation chromatography (GPC) method using polystyrene as a standard material. ..
  • Guanidine carbonate in this embodiment is represented by the following formula (3). Guanidine carbonate may be produced by a conventional method or a commercially available product may be obtained.
  • the content of the fatty acid in the mixture according to the present embodiment is not limited, but is preferably 1.0 mol or more and 3.0 mol or less, and 1.3 mol or more and 2 mol, with respect to 1 mol of guanidine carbonate. It is more preferably 0.7 mol or less.
  • the content of fatty acid is 1.0 mol or more with respect to 1 mol of guanidine carbonate, it can react more sufficiently with guanidine carbonate, and when it is 3.0 mol or less, it is an excessive amount of carbonic acid that does not contribute to the reaction. Guanidine can be further reduced.
  • the content of polysiloxane in the mixture may be adjusted so as to be a preferable content of polysiloxane in the composition described later.
  • the total content of guanidine carbonate and fatty acid may be 50 parts by mass or more and 100 parts by mass or less, and 70 parts by mass or more, with respect to 100 parts by mass of the mixture excluding polysiloxane. It may be 100 parts by mass or less, 80 parts by mass or more and 100 parts by mass or less, or 90 parts by mass or more and 100 parts by mass or less.
  • the mixture may contain any material other than guanidine carbonate, the above fatty acid, and polysiloxane as long as it does not hinder the achievement of the object of the present invention.
  • examples of such materials include solvents such as conventionally known water and other organic solvents, surfactants, defoamers, and photocurable resins. These may be used individually by 1 type or in combination of 2 or more type. From the viewpoint of further enhancing the effect of suppressing the rise in the liquid level according to the present invention, the organic solvent is preferable, and alcohol, ketone and nitrile are more preferable.
  • the content of any material does not need to be limited as long as it does not impair the achievement of the object of the present invention.
  • the content of any material is 50 parts by mass with respect to 100 parts by mass of the mixture excluding polysiloxane. It may be less than or equal to, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.
  • each material can be put into a reaction vessel at a temperature of less than 40 ° C. at a time and sufficiently stirred to obtain a mixture.
  • the fatty acid is first put into the reaction vessel and heated to melt the fatty acid, and then polysiloxane and guanidine carbonate are further added in this order and sufficiently stirred to obtain a mixture.
  • a mixture can also be obtained by putting guanidine carbonate, polysiloxane and fatty acid in this order, or putting fatty acid, polysiloxane and guanidine carbonate in this order into the reaction vessel and stirring them sufficiently.
  • Polysiloxane and guanidine carbonate may be put into the reaction vessel alone, or may be put into the reaction vessel in a state of being dissolved or dispersed in a solvent. It should be noted that the mixture may be heated as needed when preparing the mixture, and the heating temperature may be a temperature at which the guanidine fatty acid salt is not produced, or a temperature at which the guanidine fatty acid salt is produced. .. For example, when preparing the mixture, it may be heated to the heating temperature in the fatty acid salt synthesis step. In that case, the fatty acid salt synthesis step is started at the same time as the mixture containing guanidine carbonate, the fatty acid and the polysiloxane is prepared.
  • the above mixture is heated to obtain a composition containing a guanidine fatty acid salt.
  • the heating temperature is 40 ° C. or higher from the viewpoint of sufficiently melting the fatty acids and the like in the mixture and from the viewpoint of appropriately advancing the reaction. Further, the heating temperature is 200 ° C. or lower from the viewpoint of suppressing the progress of side reactions. From the same viewpoint as above, the heating temperature is preferably 70 ° C. or higher, and preferably 160 ° C. or lower.
  • the heating time in the fatty acid salt synthesis step is not particularly limited, but is preferably 0.5 to 12 hours, preferably 1.0 to 10 hours, from the viewpoint of more sufficient reaction and less unnecessary heating. It is more preferably 1.5 to 7.5 hours.
  • the content of polysiloxane when the content of polysiloxane is 0.01 part by mass or more with respect to 100 parts by mass of the guanidine fatty acid salt, the liquid level rise can be more effectively and surely suppressed. Therefore, it is preferable.
  • the content of polysiloxane is more preferably 0.05 parts by mass or more, further preferably 0.10 parts by mass or more, and 0.40 parts by mass with respect to 100 parts by mass of the guanidine fatty acid salt. It is even more preferable that the amount is more than one part.
  • the content of polysiloxane in the composition is 5.0 parts by mass or less with respect to 100 parts by mass of the guanidine fatty acid salt, an excess amount of polysiloxane that cannot contribute to the suppression of the liquid level rise is used. It is preferable because it can prevent.
  • the content of polysiloxane is more preferably 3.0 parts by mass or less, further preferably 2.0 parts by mass or less, and 1.0 part by mass with respect to 100 parts by mass of the guanidine fatty acid salt. It is even more preferable that the content is less than or equal to a portion.
  • composition contains a guanidine fatty acid salt and polysiloxane
  • other materials contained in the mixture may appropriately remain in the composition.
  • the composition may contain an unreacted guanidine carbonate contained in the mixture, or may contain an unreacted fatty acid having 6 to 22 carbon atoms contained in the mixture.
  • the composition may include any material contained in the mixture.
  • the composition in this embodiment tends to have a much lower viscosity than the case where a guanidine fatty acid salt is obtained without using polysiloxane. It is presumed that such a decrease in viscosity makes it easier for carbon dioxide bubbles to disappear, and as a result, the effect of suppressing the rise in liquid level in the fatty acid salt synthesis step is further enhanced.
  • the viscosity of the composition in the present embodiment is preferably 1.0 Pa ⁇ s or less, more preferably 0.8 Pa ⁇ s or less, and even more preferably 0.6 Pa ⁇ s or less at 90 ° C.
  • the production method of the present embodiment is excellent in economic efficiency and environmental friendliness because it is possible to produce a guanidine fatty acid salt without using a large amount of solvent.
  • the composition of the present embodiment can also be used as, for example, a strong basic agent, a surfactant, an emulsifier, a detergent, a detergent, a bactericide, a rubber additive, and a tire additive, and is used for other purposes. Can also be used as needed.
  • PDMS-1 is a polydimethylsiloxane having a weight average molecular weight of 9000
  • PDMS-2 is a polydimethylsiloxane having a weight average molecular weight of 63000
  • PDMS-3 is a polydimethylsiloxane having a weight average molecular weight of 4000. All of them are manufactured by Alfa Aesar.
  • Examples 1 to 10 and Comparative Examples 1 to 5 The fatty acids shown in Tables 1 and 2 were put into the reaction vessel in the amounts shown in Tables 1 and 2, and placed on an aluminum block mounted on a personal organic synthesizer (trade name "CCX-1102", manufactured by Tokyo Rika Kikai Co., Ltd.). It was set and heated to the heating temperature shown in Tables 1 and 2 to melt. Next, the polysiloxane, acrylic polymer or vinyl polymer shown in Tables 1 and 2 was added to the reaction vessel while stirring the fatty acid using a stirrer, and the mixture was further stirred.
  • CCX-1102 manufactured by Tokyo Rika Kikai Co., Ltd.
  • Examples 11 to 20 and Comparative Example 6 The fatty acids and polysiloxanes, acrylic polymers or vinyl polymers shown in Tables 3 and 4 were placed in a 500 mL separable flask in the amounts shown in Tables 3 and 4, and heated to 70 ° C. in an oil bath to melt them.
  • guanidine carbonate was further added to the separable flask to obtain a mixture.
  • Nitrogen was poured into the separable flask at 3 L / min and heated in an oil bath for the heating times shown in Tables 3 and 4 to obtain a composition.
  • the viscosity of the obtained composition was measured using a rotary viscometer and a cone having a diameter of 24 mm under the conditions of 100 rpm and a measurement temperature of 90 ° C.
  • a high shear array viscometer CAP2000 + (product name) manufactured by BROOKFIELD was used as the rotary viscometer.
  • the present invention it is possible to provide a method and composition for producing a guanidine fatty acid salt, which suppresses an increase in the liquid level due to carbon dioxide generated during the production of the guanidine fatty acid salt. Therefore, there is industrial possibility in the field of producing a guanidine fatty acid salt, the field of utilizing the obtained composition, for example, the field of chemical synthesis using a guanidine fatty acid salt as a strong base.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un procédé de production de sel d'acide gras de guanidine permettant de supprimer le phénomène d'élévation de surface de liquide provoqué par le dioxyde de carbone généré pendant la production de sel d'acide gras de guanidine. Ce procédé de production de sel d'acide gras de guanidine comprend une étape qui consiste à obtenir une composition contenant un sel d'acide gras de guanidine par chauffage, à 40-200 °C, d'un mélange contenant du carbonate de guanidine, un acide gras ayant un nombre d'atomes de carbone de 6 à 22, et un polysiloxane.
PCT/JP2021/031075 2020-08-26 2021-08-25 Procédé de production de sel d'acide gras de guanidine et composition associée WO2022045163A1 (fr)

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JP2022545652A JPWO2022045163A1 (fr) 2020-08-26 2021-08-25

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JP2020-142513 2020-08-26

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006378A1 (fr) * 1996-08-13 1998-02-19 Pierre Fabre Dermo-Cosmetique Sels de guanidines anti-seborrheiques
JP2019131480A (ja) * 2018-01-29 2019-08-08 旭化成株式会社 経皮吸収促進剤及び経皮製剤
WO2020039788A1 (fr) * 2018-08-24 2020-02-27 三菱瓦斯化学株式会社 Composition de caoutchouc et pneu

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006378A1 (fr) * 1996-08-13 1998-02-19 Pierre Fabre Dermo-Cosmetique Sels de guanidines anti-seborrheiques
JP2019131480A (ja) * 2018-01-29 2019-08-08 旭化成株式会社 経皮吸収促進剤及び経皮製剤
WO2020039788A1 (fr) * 2018-08-24 2020-02-27 三菱瓦斯化学株式会社 Composition de caoutchouc et pneu

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
INOUE OSAMU, MIKUMO JIRO, KUSANO AKIRA: "Guanidine on the stone eyelids", THE JOURNAL OF THE SOCIETY OF CHEMICAL INDUSTRY , vol. 57, no. 4, 1 January 1954 (1954-01-01), JP , pages 330 - 332, XP009535010, ISSN: 0023-2734 *

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TW202219031A (zh) 2022-05-16

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