JP2006199749A - Siloxane compound containing phosphorylcholine group, method for producing the same and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new siloxane compound containing a phosphorylcholine group widely useful as an surfactant in chemical industrial fields and to provide a method for producing the same. <P>SOLUTION: The siloxane compound containing a phosphorylcholine group is represented by formula (1) (R<SP>1</SP>and R<SP>2</SP>are each a 1-10C saturated hydrocarbon group or a specific group containing a phosphorylcholine group; n is an integer of 0-100; R<SP>1</SP>and R<SP>2</SP>may be the same or different and at least one of R<SP>1</SP>and R<SP>2</SP>is a specific group containing a phosphorylcholine group). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a phosphorylcholine group-containing siloxane compound that can be widely used in the field of chemical industry as a surfactant or an emulsifier, a method for producing the same, and a use of the phosphorylcholine group-containing siloxane compound.

  Conventionally, various compounds classified as cationic, anionic, nonionic or zwitterionic have been proposed as compounds showing surface activity, and their detergency, dispersion power, solubilization power, wetting power, bactericidal power, Utilizing bubble force or osmotic force, it has been put to practical use in a wide range of fields for various purposes.

  Among them, synthetic surfactants having a phosphorylcholine group have attracted particular attention in recent years because they are presumed to have biocompatibility similar to phospholipids in addition to the effects of known surfactants. ing. For example, branched alkyl compounds (Patent Document 1) and perfluoroalkyl compounds (Patent Document 2) are known as alkyl compounds having a phosphorylcholine group. However, conventional alkylphosphorylcholine compounds do not have sufficient surface tension reducing ability, and perfluoroalkylphosphorylcholine compounds can also be used for hair cleansing agents such as shampoos and rinses, emulsifiers for cosmetics, etc. The feeling of use and the emulsifying ability were insufficient.

  On the other hand, a polymer having a phosphorylcholine group in the main chain of a siloxane polymer has also been reported (Patent Documents 3 and 4). However, there are many unknowns about the functions of siloxane compounds having these phosphorylcholine groups in the polymer main chain, and a new structure of phosphorylcholine groups with excellent emulsifying ability has been promoted in the development of new markets in the life chemical industry such as cosmetics. There has been a demand for the development of siloxane compounds.

  On the other hand, a phosphorylcholine group-containing siloxane compound having a phosphorylcholine group at the molecular end of a siloxane polymer has not been conventionally known.

JP 62-126192 A (2nd page) JP 2000-355594 A (2nd page) JP 63-277246 A (second page) JP 2004-175830 A (second page)

  An object of the present invention is to provide a phosphorylcholine group-containing siloxane compound, a production method thereof, and a surfactant comprising the phosphorylcholine group-containing siloxane compound, which are used in cosmetic raw materials and the like to improve the feeling of use and emulsification ability of cosmetics. And

  As a result of intensive studies to solve the above problems, the present inventor has conceived a novel siloxane compound having a biocompatible phosphorylcholine group in the molecule, and has completed the present invention.

That is, the present invention includes the following [1] to [3].
[1], formula (1)

[Wherein R ¹ and R ² are a saturated hydrocarbon group having 1 to 10 carbon atoms or a compound represented by the formula (2)

(Wherein, m is an integer of 1 to 10), and n is an integer of 0 to 100. R ¹ and R ² may be the same or different from each other, but at least one of them is a group represented by the formula (2). ] The phosphorylcholine group containing siloxane compound shown by this.

[2], formula (3)

[Wherein, R ³ and R ⁴ are each a saturated hydrocarbon group having 1 to 10 carbon atoms or —CH ₂ (CH ₂ CH ₂ O) _m H (where m is an integer of 1 to 10). N is an integer of 0 to 100. R ³ and R ⁴ may be the same or different, but at least one of them is a group represented by —CH ₂ (CH ₂ CH ₂ O) _m H. Is reacted with 2-chloro-2-oxo-1,3,2-dioxaphosphorane in an aprotic solvent in the presence of a hydrogen chloride trapping agent. 4)

[Wherein, R ⁵ and R ⁶ are each a saturated hydrocarbon group having 1 to 10 carbon atoms or a compound represented by the formula (5)

(Wherein, m is an integer of 1 to 10), and n is an integer of 0 to 100. R ⁵ and R ⁶ may be the same or different, but at least one of them is a group represented by the formula (5). The method for producing a phosphorylcholine group-containing siloxane compound according to the above item [1], wherein a ring-opening addition reaction is performed with trimethylamine after obtaining a dioxaphosphorane phosphate group-containing siloxane compound represented by the formula:

[3] A surfactant comprising the phosphorylcholine group-containing siloxane compound according to [1].

  The present invention provides a phosphorylcholine group-containing siloxane compound having a novel structure and a method for producing the same. The phosphorylcholine group-containing siloxane compound of the present invention has a structure similar to natural phospholipid and is useful as a surfactant. The phosphorylcholine group-containing siloxane compound provided by the production method of the present invention has high efficiency and high purity, and has excellent industrial value.

  The phosphorylcholine group-containing siloxane compound of the present invention has the formula (1)

It is represented by
In the formula (1), R ¹ and R ² are each a saturated hydrocarbon group having 1 to 10 carbon atoms or the formula (2)

R ¹ and R ² may be the same or different from each other, but at least one of them is a group represented by the formula (2), and n is an easily synthesized compound. Any integer from 0 to 100 may be used from the viewpoint of availability of raw materials, but an integer from 5 to 80 is preferable, and an integer from 8 to 60 is most preferable.

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms in the formula (1) include groups such as an ethyl group, a propyl group, and a group represented by C ₄ H _9. Preferably, the compound is synthesized. It is a group represented by C ₄ H ₉ for reasons of ease. In the formula (2), m may be any integer from 1 to 10 from the viewpoints of ease of synthesis of the compound, availability of raw materials, etc., but preferably an integer from 2 to 5. Good, most preferably 2. From the viewpoint of ease of synthesis, R ¹ and R ² are preferably both groups represented by the formula (2), but only one of them is a group represented by the formula (2). . Preferable specific examples of the phosphorylcholine group-containing siloxane compound of the formula (1) include those of the following formulas [a] to [c].

  In the method for producing a phosphorylcholine group-containing siloxane compound represented by the formula (1) of the present invention, the formula (3)

A siloxane compound having a hydroxyl group represented by formula (6)

Is reacted with a 2-chloro-2-oxo-1,3,2-dioxaphosphorane represented by the formula (4) in the presence of a hydrogen chloride trapping agent in an aprotic solvent. A phosphorylcholine group-containing siloxane compound represented by the formula (1) can be obtained by obtaining a phosphate ester group-containing siloxane compound and subjecting it to a ring-opening addition reaction with trimethylamine.

In the formula (3), R ³ and R ⁴ are each a saturated hydrocarbon group having 1 to 10 carbon atoms or —CH ₂ (CH ₂ CH ₂ O) _m H (where m is the ease of synthesis of the compound, Any number may be used as long as it is an integer of 1 to 10 from the viewpoint of availability of raw materials, but it is preferably an integer of 2 to 5, most preferably 2.), and n May be any integer from 0 to 100 in terms of the ease of synthesis of the compound and the availability of raw materials, but is preferably an integer from 5 to 80, most preferably from 8 to 60. Is an integer. R ³ and R ⁴ may be the same or different, but at least one of them is a group represented by —CH ₂ (CH ₂ CH ₂ O) _m H.

  As the siloxane compound having a hydroxyl group represented by the formula (3) used in the production method of the present invention, a compound synthesized from a known raw material by using a known synthesis method may be used, but a commercially available product is used. You can also. Preferable specific examples of such a siloxane compound having a hydroxyl group include those represented by the following formulas [A] and [B].

  The 2-chloro-2-oxo-1,3,2-dioxaphosphorane represented by the above formula (6) used in the production method of the present invention is R.I. S. Edmundson. , Chem. Ind. , (London), 1962, 1828 (1962) or the like may be synthesized by a known method, but commercially available products may also be used. The amount of 2-chloro-2-oxo-1,3,2-dioxaphospholane represented by the formula (6) is used in a molar ratio with respect to the siloxane compound having a hydroxyl group represented by the formula (3). The amount is 0.5 to 2 times, preferably 1 to 1.1 times.

  The aprotic solvent used in the production method of the present invention is not particularly limited as long as it is a solvent generally known as aprotic, and preferred examples include tetrahydrofuran, diethyl ether, ethyl acetate, methylene chloride, acetonitrile and the like. From the viewpoint of the solubility of the compound, tetrahydrofuran is most preferred. The amount of the aprotic solvent used is 1 to 20 times by weight, preferably 4 to 10 times by weight with respect to the siloxane compound having a hydroxyl group represented by the formula (3).

  As the hydrogen chloride trapping agent used in the production method of the present invention, triethylamine, pyridine, 4-dimethylaminopyridine, diisopropylamine, dicyclohexylamine and the like are used, and triethylamine and diisopropylamine are more preferably used. The hydrogen chloride trapping agent is dissolved in a reaction solvent and used in the reaction system. The hydrogen chloride trapping agent is used in an amount of 1 to 10 times in molar ratio to the 2-chloro-2-oxo-1,3,2-dioxaphosphorane represented by the formula (6). Yes, preferably 1 to 2 times the amount. At this time, if the amount of the hydrogen chloride trapping agent used is less than 1 time in molar ratio with respect to 2-chloro-2-oxo-1,3,2-dioxaphospholane represented by the formula (6), Even when hydrogen cannot be trapped sufficiently and the molar ratio is more than 10 times, the improvement of trap efficiency is slowed for hydrogen chloride traps.

  The reaction temperature in the production method of the present invention is usually in the range of −50 to 50 ° C., preferably −30 to 30 ° C., and most preferably −20 to 20 ° C. On the other hand, the reaction time varies depending on the conditions such as reaction temperature and concentration, but is usually preferably about 1 to 12 hours.

  By the above reaction, a dioxaphosphorane phosphate siloxane compound represented by the formula (4) can be obtained. The dioxaphosphorane phosphate siloxane compound represented by the formula (4) can be isolated or purified by a method such as distillation, recrystallization, reprecipitation, column treatment, ion exchange, gel filtration, or the like, without purification. And you may use for the manufacturing method of this invention. In the above reaction, a hydrogen halide salt, which is an organic base, is generated in the reaction system as a by-product of the reaction, but this may be removed by filtration or extraction operation.

  The dioxaphosphorane phosphate group-containing siloxane compound has the formula (4)

It is represented by
In said formula (4), R < ⁵ >, R < ⁶ > is a C1-C10 saturated hydrocarbon group or Formula (5).

R ⁵ and R ⁶ may be the same or different, but at least one of them is a group represented by the formula (5). In the formula (4), n may be any integer from 0 to 100 from the viewpoint of easiness of compound synthesis, availability of raw materials, etc., but preferably an integer from 5 to 80. Most preferably, it is an integer of 8 to 60.

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms in the formula (4) include groups such as an ethyl group, a propyl group, and a group represented by C ₄ H _9. Preferably, the compound is synthesized. It is a group represented by C ₄ H ₉ for reasons of ease.
In the formula (5), m may be any integer from 1 to 10 from the standpoint of ease of synthesis of the compound, availability of raw materials, etc., but preferably an integer from 2 to 5. Good, most preferably 2.
Preferable specific examples of the dioxaphosphorane phosphate group-containing siloxane compound of the formula (4) include, for example, those of the following formulas [d] to [f].

  In the production method of the present invention, in the ring-opening addition reaction of trimethylamine to the dioxaphosphorane phosphate group-containing siloxane compound of formula (4), the ring-opening addition reaction may be performed in an aprotic solvent. Acetonitrile is most preferred as the solvent from the viewpoint of using a highly polar solvent for the ring-opening addition reaction. The amount of the solvent used in the ring-opening addition reaction is 1 to 20 times by weight, preferably 4 to 10 times by weight with respect to the dioxaphosphorane phosphate group-containing siloxane.

  The trimethylamine used in the production method of the present invention is usually known as N, N-dimethylmethanamine, and commercially available trimethylamine can be preferably used. The amount of trimethylamine used is 1 to 10 times, preferably 2 to 5 times the molar ratio of the dioxaphosphorane phosphate group-containing siloxane of formula (4).

  In the production method of the present invention, the reaction temperature of the ring-opening addition reaction is usually in the range of 0 to 100 ° C, preferably 40 to 80 ° C, and most preferably 60 to 80 ° C. On the other hand, although reaction time changes with conditions, such as reaction temperature and the usage-amount of a trimethylamine, about 1 to 24 hours are preferable normally.

  As described above, the phosphorylcholine group-containing siloxane compound represented by the formula (1) of the present invention can be obtained by the production method of the present invention. The obtained phosphorylcholine group-containing siloxane compound represented by the formula (1) is isolated, purified by treatment such as drying under reduced pressure, reprecipitation, recrystallization, column, ion exchange, gel filtration, etc., and then solid, powder, liquid And can be used for surfactants, hair cleansing agents, emulsifiers, fiber treatment agents, etc., and preferably used as a surfactant in cosmetics.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
In a 500 mL four-necked flask, the following average composition formula [C]

50 g (0.05 mol), triethylamine 5.06 g (0.05 mol) and 200 mL of tetrahydrofuran were added and cooled to 0 ° C. with stirring. . 7.14 g (0.05 mol) of 2-chloro-2-oxo-1,3,2-dioxaphosphorane was dissolved in 30 mL of tetrahydrofuran, and the obtained solution was added dropwise to the flask using a dropping funnel. After completion of the dropwise addition, the reaction mixture was heated and the reaction was continued at room temperature for 2 hours. Triethylamine hydrochloride precipitated as a by-product was filtered off. Furthermore, 200 mL of diethyl ether was added and cooled to precipitate dissolved amine hydrochloride in the solution. Thereafter, filtration under reduced pressure and evaporation were repeated to obtain the following average composition formula [D]

As a result, 53.4 g of a dioxaphosphorane phosphate siloxane compound represented by the formula: The yield was 93.5%. Analytical values are shown below.

¹ H NMR (CD ₃ OD): 0.079 (s, 72H, —SiCH ₃ ), 0.55 (m, 4H, —SiCH ₂ —), 0.89 (t, 3H, —CH ₃ ), 1 .30 (m, 4H, —CH ₂ —), 3.52 (b, 4H, —CH ₂ OCH ₂ —), 3.80-4.68 (m, 4H, —CH ₂ OP)
³¹ P NMR (CD ₃ OD, external standard H ₃ PO ₄ ): 19.6 (m)
IR (KBr): 2924, 2854, 1468 cm ⁻¹ (C—H), 1260 cm ⁻¹ (Si—CH ₃ ), 1230 cm ⁻¹ (P═O), 1089 cm ⁻¹ (C—O—P), 1060 cm ^{− 1} (Si-O-Si)

  After dissolving 200 mL of acetonitrile in 53.4 g of the dioxaphosphorane phosphate ester siloxane compound represented by the average composition formula [D] thus obtained, the solution was transferred to a pressure bottle, and trimethylamine was obtained. 11.8 g (0.2 mol) was added and sealed, and reacted at 70 ° C. overnight to complete the reaction. After distilling off excess trimethylamine, the supernatant solvent was removed by decantation, and then acetone was added for washing, followed by separation with a separatory funnel. The product liquid was transferred to an evaporator and the solvent was distilled off, followed by further vacuum drying to obtain the desired product. The yield was 51.4%.

  As a result of measuring and analyzing the nuclear magnetic resonance spectrum and infrared absorption spectrum of the obtained product, the following average composition formula [E]

It was found that a phosphorylcholine group-containing siloxane compound represented by
¹ H NMR (CD ₃ OD): 0.079 (s, 72H, —SiCH ₃ ), 0.55 (m, 4H, —SiCH ₂ —), 0.89 (t, 3H, —CH ₃ ), 1 .30 (m, 4H, —CH ₂ —), 3.12 (s, 9H, —N ⁺ (CH ₃ ) ₃ ), 3.36 (t, 2H, —CH ₂ N ⁺ ), 3.52 ( b, 4H, —CH ₂ OCH ₂ —), 3.89 (t, 2H, —CH ₂ OP), 4.18 (b, 2H, —POCH ₂ )
³¹ P NMR (CD ₃ OD, external standard H ₃ PO ₄ ): 0.60 (m)
IR (KBr): 2924, 2854, 1468 cm ⁻¹ (C—H), 1260 cm ⁻¹ (Si—CH ₃ ), 1230 cm ⁻¹ (P═O), 1089 cm ⁻¹ (C—O—P), 1060 cm ^{− 1} (Si—O—Si), 970 cm ⁻¹ (—N ⁺ (CH ₃ ) ₃ )

[Example 2]
In a 500 mL four-necked flask, the following average composition formula [F]

A siloxane compound (Shin-Etsu Chemical Co., Ltd., trade name: “X-22-170DX”) 47 g (0.01 mol), 1.01 g (0.01 mol) of triethylamine and 200 mL of tetrahydrofuran were added and stirred while adding 0. Cooled to ° C. 1.43 g (0.01 mol) of 2-chloro-2-oxo-1,3,2-dioxaphosphorane was dissolved in 10 mL of tetrahydrofuran, and the obtained solution was added dropwise to the flask using a dropping funnel. After completion of the dropwise addition, the reaction mixture was heated and the reaction was continued at room temperature for 2 hours. Triethylamine hydrochloride precipitated as a by-product was filtered off. Triethylamine hydrochloride precipitated as a by-product was filtered off. Furthermore, 200 mL of diethyl ether was added and cooled to precipitate dissolved amine hydrochloride in the solution. Thereafter, filtration under reduced pressure and evaporation were repeated to obtain the following average composition formula [G]

44.5 g of a dioxaphosphorane phosphate siloxane compound represented by the formula: The yield was 91.9%. Analytical values are shown below.

¹ H NMR (CD ₃ OD): 0.079 (s, 372H, —SiCH ₃ ), 0.55 (m, 4H, —SiCH ₂ —), 0.89 (t, 3H, —CH ₃ ), 1 .30 (m, 4H, —CH ₂ —), 3.52 (b, 4H, —CH ₂ OCH ₂ —), 3.80-4.68 (m, 4H, —CH ₂ OP)
³¹ P NMR (CD ₃ OD, external standard H ₃ PO ₄ ): 19.5 (m)
^{IR (KBr): 2924,2854,1468cm -1 (} CH), 1260cm -1 (Si-CH 3), 1230cm -1 (P = O), 1090cm -1 (C-O-P), 1060cm - ¹ (Si-O-Si)

  After dissolving 200 mL of acetonitrile in 44.5 g of the dioxaphosphorane phosphate siloxane compound represented by the average composition formula [G] thus obtained, this solution was transferred to a pressure bottle, and trimethylamine was obtained. 2.4 g (0.04 mol) was added and sealed, and allowed to react overnight at 70 ° C. to complete the reaction. After excess trimethylamine was distilled off, the supernatant solvent was removed by decantation, then acetone was added for washing and separation with a separatory funnel. The product liquid was transferred to an evaporator and the solvent was distilled off, followed by further vacuum drying to obtain the desired product. The yield was 48.7%.

  As a result of measuring and analyzing the nuclear magnetic resonance spectrum and infrared absorption spectrum of the obtained product, the following average composition formula [H]

It was found that a phosphorylcholine group-containing siloxane compound represented by
¹ H NMR (CD ₃ OD): 0.079 (s, 372H, —SiCH ₃ ), 0.55 (m, 4H, —SiCH ₂ —), 0.89 (t, 3H, —CH ₃ ), 1 .30 (m, 4H, —CH ₂ —), 3.12 (s, 9H, —N ⁺ (CH ₃ ) ₃ ), 3.35 (t, 2H, —CH ₂ N ⁺ ), 3.52 ( _{b, 4H, -CH 2 OCH 2} -), 3.88 (t, 2H, -CH 2 OP), 4.19 (b, 2H, -POCH 2)
³¹ P NMR (CD ₃ OD, external standard H ₃ PO ₄ ): 0.61 (m)
IR (KBr): 2924, 2854, 1468 cm ⁻¹ (C—H), 1260 cm ⁻¹ (Si—CH ₃ ), 1229 cm ⁻¹ (P═O), 1088 cm ⁻¹ (C—O—P), 1061 cm ^{− 1} (Si—O—Si), 969 cm ⁻¹ (—N ⁺ (CH ₃ ) ₃ )

[Example 3]
The phosphorylcholine group-containing siloxane compounds obtained in Examples 1 and 2 were dissolved in water, and the surface tension was measured at normal temperature and pressure. A 1.0 wt% aqueous solution of the phosphorylcholine group-containing siloxane compound represented by the average composition formula [E] obtained in Example 2 was obtained in Example 4 at 22.5 dyn · cm ⁻¹ at normal temperature and pressure. The 0.1 wt% aqueous solution of the phosphorylcholine group-containing siloxane compound represented by the average composition formula [H] exhibited a low surface tension of 28.3 dyn · cm ⁻¹ at normal temperature and pressure.
Moreover, when this aqueous solution was put in a container so as to form a gap and sealed, and shaken with both hands, foaming occurred vigorously.

  From this, it was found that the phosphorylcholine group-containing siloxane compounds obtained in Examples 1 and 2 have surface activation ability and are useful as surfactants.

Claims (3)

Formula (1)
[Wherein R ¹ and R ² are a saturated hydrocarbon group having 1 to 10 carbon atoms or a compound represented by the formula (2)
(Wherein, m is an integer of 1 to 10), and n is an integer of 0 to 100. R ¹ and R ² may be the same or different from each other, but at least one of them is a group represented by the formula (2). ] The phosphorylcholine group containing siloxane compound shown by this. Formula (3)
[Wherein, R ³ and R ⁴ are each a saturated hydrocarbon group having 1 to 10 carbon atoms or —CH ₂ (CH ₂ CH ₂ O) _m H (where m is an integer of 1 to 10). N is an integer of 0 to 100. R ³ and R ⁴ may be the same or different, but at least one of them is a group represented by —CH ₂ (CH ₂ CH ₂ O) _m H. Is reacted with 2-chloro-2-oxo-1,3,2-dioxaphosphorane in an aprotic solvent in the presence of a hydrogen chloride trapping agent. 4)
[Wherein, R ⁵ and R ⁶ are each a saturated hydrocarbon group having 1 to 10 carbon atoms or a compound represented by the formula (5)
(Wherein, m is an integer of 1 to 10), and n is an integer of 0 to 100. R ⁵ and R ⁶ may be the same or different, but at least one of them is a group represented by the formula (5). The ring-opening addition reaction is performed with trimethylamine after obtaining the dioxaphosphorane phosphate group-containing siloxane compound represented by the formula: A surfactant comprising the phosphorylcholine group-containing siloxane compound according to claim 1.