JP4357909B2 - Production of branched polyglycerol-modified silicone - Google Patents

Description

  The present invention relates to a method for producing branched polyglycerol-modified silicones useful as cosmetics and fiber treatment agents.

  Patent Documents 1 and 2 disclose a method for producing a linear polyglycerol-modified silicone in which an organohydrogenpolysiloxane and a polyglycerol having an aliphatic unsaturated bond are reacted in the presence of a platinum catalyst.

However, these methods are methods for producing a linear polyglycerol-modified silicone, and in the above method, an addition reaction between an organohydrogenpolysiloxane and a polyglycerol having an aliphatic unsaturated bond is carried out under a platinum catalyst. In addition, a buffer agent such as potassium acetate is used for the purpose of suppressing the dehydrogenation reaction, but it is difficult to completely prevent the dehydrogenation reaction, resulting in a problem that the product takes a cross-linked structure. . Therefore, it is difficult to obtain a polyglycerol-modified silicone having an initial structure and physical properties by the above method.
JP-A-57-149290 Japanese Examined Patent Publication No. 62-34039

  An object of the present invention is to provide a method for producing a branched polyglycerol-modified silicone, particularly a method for obtaining a reproducible and highly purified product.

  The present inventors have utilized a glycerol group, which is essentially a divalent alcohol, which exhibits a very low adsorptivity when it is arranged alone or in a linear arrangement with a very high degree of freedom of movement of molecular chains. Then, by adding the following glycerol residues to both hydroxy groups, the branched structure is actively derived, and by making a multi-branched polyglycerol chain, many terminal hydroxy groups can move freely. As a result of being regulated and densely present in a narrow space region, the present inventors have found a method for producing branched polyglycerol-modified silicone that enables chelate multi-element adsorption and exhibits a remarkable adsorption promoting effect.

  That is, the present invention provides a branched polyglycerol-modified silicone, particularly a branch represented by the general formula (1), in which a branched polyglycerol having a reactive unsaturated group and an organohydrogenpolysiloxane are reacted in the presence of a platinum catalyst. A process for producing a polyglycerol-modified silicone is provided.

Wherein R ¹ , R ² , R ³ , t R ⁴ , t R ⁵ , R ⁶ , R ⁷ , R ⁸ are the same or different and are a linking group to which a branched polyglycerol chain is bonded, A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, or an aryl group having 6 to 22 carbon atoms, which may have a substituent and may be substituted with a fluorine atom Wherein at ^{least one} of R ¹ , R ² , R ³ , t R ⁴ , t R ⁵ , R ⁶ , R ⁷ , R ⁸ is a linking group to which a branched polyglycerol chain is bonded. t represents a number from 0 to 10,000.)
The present invention also provides a branched polyglycerol having a reactive unsaturated group and a branched polyglycerol chain containing a branched glycerol group represented by the following structural formula (2).

(In the formula, two oxygen atoms are the same or different, and the above structural formula (2), the following structural formula (3), (4) or (5)

The glycerol group or glycidol group represented by these is couple | bonded.
A glycerol group or a glycidol group represented by the structural formula (2), the above structural formula (3), (4) or (5) is bonded to the oxygen atom of the structural formula (3), and the structural formula (4) A glycerol group or a glycidol group represented by the structural formula (2), the structural formula (3), (4), or (5) is bonded to the oxygen atom. )

  By the production method of the present invention, branched polyglycerol-modified silicone can be obtained with high purity.

[Branched polyglycerol chain]
In the present invention, the branched polyglycerol chain contains one or more branched glycerol groups represented by the structural formula (2) (hereinafter referred to as group (2)) as branching groups. The branched polyglycerol chain has a structure represented by a group (2), b glycidol groups represented by structural formula (3) (hereinafter referred to as group (3)), and c structural formulas (4). Glycerol group (hereinafter referred to as group (4)) and d glycerol groups represented by structural formula (5) (hereinafter referred to as group (5)) as terminal groups are bonded.
In the branched polyglycerol chain, the groups (2), (3) and (4) may be bonded to each other in any sequence. As the number of groups (2) increases, the branched structure develops, and the group (5) exists at the end of each branched chain.

The branched polyglycerol having a reactive unsaturated group of the present invention contains at least one branched structure of the group (2), as described later in ¹³ C-NMR analysis, a peak specific to the group (2). You can easily prove it from what you see. Preferably, the average number of groups (2) per branched polyglycerol chain is 1 or more.

  In the present invention, the average total number of bonds (a + b + c + d) of the groups (2), (3), (4) and (5) in the branched polyglycerol chain is determined by NMR analysis described later, and is preferably 3 or more. In order for the branched polyglycerol-modified silicone to maintain appropriate silicone properties, it is more preferably 3 to 201, still more preferably 3 to 101, and particularly preferably 3 to 51. Most preferred is ~ 21.

  In the branched polyglycerol chain, a / (a + b + c + d) is preferably 1/20 or more and less than 1/2, more preferably 1/10 or more and less than 1/2, in order to have a sufficient adsorption effect. 1/6 or more and less than 1/2 is particularly preferable.

  In the branched polyglycerol chain, the groups (2), (3), (4) and (5) may optionally be bonded.

  The number of groups (2) (that is, a) is preferably 1 to 100, more preferably 2 to 100, and still more preferably 2 to 50 in the branched polyglycerol chain. 2 to 25 are particularly preferable, and 2 to 10 are most preferable. The number of groups (5) (ie, d) is preferably 2 to 101, more preferably 3 to 101, and still more preferably 3 to 51 in the branched polyglycerol chain. 3 to 26 are particularly preferable, and 3 to 11 are most preferable. The number of groups (3) (ie, b) and the number of groups (4) (ie, c) are the same or different and are preferably 0 to 198, more preferably 0 to 196. 0 to 96 are more preferable, 0 to 46 are particularly preferable, and 0 to 16 are most preferable.

[Branched polyglycerol having a reactive unsaturated group]
The branched polyglycerol having a reactive unsaturated group of the present invention has a reactive unsaturated group and a branched polyglycerol chain, and the branched polyglycerol chain is preferred as the branched polyglycerol chain.

  Examples of the reactive unsaturated group include monovalent groups including a vinyl group, vinylene group, vinylidene group, and the like, and monovalent groups including a vinyl group are preferable.

  As the branched polyglycerol having a reactive unsaturated group, those having a structure represented by the following general formula (6) or (7) are more preferable.

_{^{X- (R 11) p -O- (}} AO) q -Y (6)
(In the formula, X represents a vinyl group, vinylene group or vinylidene group, and R ¹¹ may have a substituent, a linear or branched alkylene group having 1 to 20 carbon atoms, an alkenylene group, or An arylene group having 6 to 20 carbon atoms, AO is an alkyleneoxy group having 1 to 4 carbon atoms (also referred to as an oxyalkylene group) or an aryleneoxy group having 6 to 10 carbon atoms (also referred to as an oxyarylene group), and p is 0 or 1 , Q represents a number from 0 to 30, and q AOs may be the same or different. Y represents a branched polyglycerol chain.)
_{^{X- (R 12) p -COO- (}} AO) r -Y (7)
(In the formula, X, Y, AO and p have the same meaning as described above, and R ¹² represents a linear or branched alkylene group having 1 to 20 carbon atoms and an alkenylene group which may have a substituent. Or an arylene group having 6 to 20 carbon atoms, r represents a number of 0 to 30, and r AOs may be the same or different.
In the general formulas (6) and (7), the arylene group in R ¹¹ and R ¹² includes an alkylene arylene group, an arylene alkylene group, and an alkylene arylene alkylene group. R ¹¹ and R ¹² are preferably an alkylene group or alkenylene group having 1 to 16 carbon atoms, particularly preferably 1 to 12, and methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene. , Octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group and the like. Among these, a methylene, ethylene, propylene or trimethylene group is more preferable, and a methylene group is particularly preferable from the viewpoint of ease of synthesis.

  q and r are the same or different and are preferably 0 to 15, more preferably 0 to 8, and particularly preferably 0 to 5.

  The q AOs and the r AOs are the same or different, and may be alternating, random, block, or a periodic arrangement other than these, or may be combined in any form. AO is preferably an ethyleneoxy group, a propyleneoxy group or a phenyleneoxy group, and more preferably an ethyleneoxy group.

As substituents in R ¹¹ and R ¹² , a hydroxy group, an amino group (1 to 22 carbon atoms), an imino group (1 to 22 carbon atoms), a carboxy group, an alkoxy group (1 to 22 carbon atoms), an acyl group ( C1-C22) etc. are mentioned.

  The most preferred branched polyglycerol having a reactive unsaturated group is a compound represented by the following general formula (8).

X—CH ₂ —O—CH ₂ CH ₂ —O—Y (8)
(In the formula, X and Y have the same meaning as described above.)
[Production of branched polyglycerol having a reactive unsaturated group]
A branched polyglycerol having a reactive unsaturated group is obtained by adding glycidol (2,3-epoxy) to a compound having a reactive unsaturated group and a functional group (preferably a hydroxy group or a carboxy group) in the presence of an acidic catalyst or a basic catalyst. -1-propanol) can be added and reacted.

  As the compound having a reactive unsaturated group and a functional group (hydroxy group or carboxy group), a compound represented by the following general formula (9) or (10) is preferable.

_{^{X- (R 11) p -O- (}} AO) q -H (9)
(In the formula, X, R ¹¹ , AO, p and q have the same meaning as described above.)
_{^{X- (R 12) p -COO- (}} AO) r -H (10)
(In the formula, X, R ¹² , AO, p and r have the same meaning as described above.)
Examples of the acidic catalyst include Lewis acids such as BF ₃ · OEt ₂ , HPF ₆ · OEt ₂ , TiCl ₄ , SnCl ₄ , sulfuric acid, PhCOSbF ₆ , perchloric acid, fluorosulfuric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid. (Here Et represents an ethyl group and Ph represents a phenyl group). Examples of the basic catalyst include metal hydroxides such as LiOH, NaOH, KOH, and CsOH, alkali metal simple substances such as Li, Na, K, and Cs, or mercury amalgams thereof, general formula ROM ¹ (R: alkyl group, preferably A metal alcoholate represented by an alkyl group having 1 to 4 carbon atoms, M ¹ : alkali metal), a metal hydride of an alkali metal or an alkaline earth metal, n-butyllithium, t-butyllithium, pentadienylpotassium, naphthalenepotassium And organometallic compounds such as Grignard reagents. Among these, alkali metals alone, metal hydroxides, metal alcoholates and organometallic compounds are preferable because of their high activity. Among them, K, KOH, CsOH, potassium hydride, potassium methoxide, potassium isopropoxide, potassium butoxide However, it is particularly preferable as a catalyst species having both convenience and high activity. The catalyst amount is preferably 0.01 to 2 molar equivalents, more preferably 0.03 to 1.0 molar equivalents, and particularly preferably 0.05 to 0.8 molar equivalents with respect to 1 molar equivalent of the functional group.

  What is necessary is just to select the usage-amount of glycidol suitably according to the introduction amount of the target branched polyglycerol chain | strand. It is possible to adjust the average number of glycerol groups per branched polyglycerol chain by the number of moles of glycidol used, and for each mole of the compound having a reactive unsaturated group and a functional group, glycidol is 0.1 molar equivalent. Above, preferably 3 molar equivalents or more, more preferably 3 to 200 molar equivalents, further preferably 3 to 100 molar equivalents, particularly preferably 3 to 50 molar equivalents, 3 to 20 Most preferred is a molar equivalent.

  The solvent may or may not be used. However, if the reaction system becomes a highly viscous or solid or heterogeneous slurry mixture depending on the catalyst type, the amount of catalyst, and the amount of glycidol added, an appropriate solvent is used. In which polymerization can be carried out.

The polymerization temperature may be appropriately determined depending on the polymerization activity of the catalyst to be used, the concentration of the functional group, and the like, but -78 to 220 ° C and -30 to 150 ° C are more preferable.
In order to add glycidol, it is preferable to add it with stirring, and it is important not to add the total amount at once, but to add it dropwise or intermittently in divided portions.

  The dropping rate depends on the reaction temperature and the amount of the catalyst, but generally glycidol is added in an amount of 0.1 to 1.5 mol / hour in terms of the branched structure with respect to 1 mol of the compound having a reactive unsaturated group and a functional group. It is preferable to drop at a rate, and a dropping rate of 0.1 to 1.0 mol / hour is more preferable. By slowing the dropping rate, a branched polyglycerol having a reactive unsaturated group having a high degree of branching can be produced.

[Linking group]
In the branched polyglycerol-modified silicone, the linking group that bonds the silicon atom of the silicone and the branched polyglycerol chain is preferably a divalent group having an ether group or an ester group.

The divalent group having an ether group is preferably a group represented by the general formula (11) (hereinafter referred to as a linking group (11)). In the linking group (11), the R ¹³ side is bonded to the silicon atom of the silicone chain, and the (AO) _q side is bonded to the branched polyglycerol chain.

—R ¹³ —O— (AO) _q − (11)
(Wherein R ¹³ may have a substituent, a linear or branched alkylene group having 2 to 22 carbon atoms, an alkenylene group or an arylene group having 8 to 22 carbon atoms, AO and q are And q AOs may be the same or different.)
The divalent group having an ester group is preferably a group represented by the general formula (12) (hereinafter referred to as a linking group (12)). In the linking group (12), the R ¹⁴ side is bonded to the silicon atom of the silicone chain, and the (AO) _r side is bonded to the branched polyglycerol chain.

—R ¹⁴ —COO— (AO) _r − (12)
(Wherein R ¹⁴ may have a substituent, a linear or branched alkylene group having 2 to 22 carbon atoms, an alkenylene group or an arylene group having 8 to 22 carbon atoms, AO and r And the r AOs may be the same or different.)
In the linking groups (11) and (12), the arylene group in R ¹³ and R ¹⁴ includes an alkylene arylene group, an arylene alkylene group, and an alkylene arylene alkylene group. R ¹³ and R ¹⁴ are preferably alkylene groups or alkenylene groups having 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octane. And methylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene groups and the like. Among these, an ethylene, propylene or trimethylene group is more preferred, and a trimethylene group is particularly preferred from the viewpoint of ease of synthesis.

  q and r are the same or different and are preferably 0 to 15, more preferably 0 to 8, and particularly preferably 0 to 5.

  The q AOs and the r AOs are the same or different, and may be alternating, random, block, or a periodic arrangement other than these, or may be combined in any form. AO is preferably an ethyleneoxy group, a propyleneoxy group or a phenyleneoxy group, and more preferably an ethyleneoxy group.

  In the linking group (11) and the linking group (12), the linking group is bonded to the branched polyglycerol chain on the oxygen side of the alkyleneoxy group or aryleneoxy group of AO, and on the alkylene or arylene side of the alkyleneoxy group or aryleneoxy group. It binds to the ether group or ester group contained in

As substituents in R ¹³ and R ¹⁴ , a hydroxy group, an amino group (1 to 22 carbon atoms), an imino group (1 to 22 carbon atoms), a carboxy group, an alkoxy group (1 to 22 carbon atoms), an acyl group ( C1-C22) etc. are mentioned.

  The most preferred linking group is a linking group represented by the following general formula (13) (hereinafter referred to as linking group (13)). In the linking group (13), the trimethylene side is bonded to the silicon atom of the silicone chain, and the oxygen atom side is bonded to the branched polyglycerol chain.

—CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ —O— (13)
[Organohydrogenpolysiloxane]
The organohydrogenpolysiloxane used in the present invention is derived from a polysiloxane having two or more silicon atoms, and the shape of the silicone may be linear, branched or cyclic. Moreover, the number average molecular weight of polysiloxane becomes like this. Preferably it is 300-700,000, More preferably, it is 300-200,000, More preferably, it is 1000-20,000. The number average molecular weight can be determined by a gel permeation chromatograph (hereinafter referred to as GPC) method described later.

  As the organohydrogenpolysiloxane of the present invention, a linear silicone represented by the general formula (14) (hereinafter referred to as silicone (14)) is preferable.

(Wherein R ²¹ , R ²² , R ²³ , s R ²⁴ , s R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are the same or different and have a hydrogen atom or a substituent. Or a linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, or an aryl group having 6 to 22 carbon atoms, which may be substituted with a fluorine atom, R ²¹ , R ²² , R ²³ , s R ²⁴ , s R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are at least one hydrogen atom, and s is a number from 0 to 10,000.
In the silicone (14), R ²¹ , R ²² , R ²³ , s R ²⁴ , s R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , groups other than hydrogen atoms are the same or different and are substituted. A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, or an aryl group having 6 to 22 carbon atoms, which may have a group and may be substituted with a fluorine atom. And examples of the alkyl group having 1 to 22 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, trifluoropropyl, and the like. Examples of the 22 alkenyl group include a vinyl group and an allyl group. Examples of the alkoxy group having 1 to 22 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Hexyloxy, heptyloxy, octyloxy, phenoxy group and the like. In these, a C1-C12 linear or branched alkyl group, a vinyl group, an allyl group, or a C6-C12 aryl group is preferable, More preferably, a C1-C3 alkyl group or A phenyl group, particularly preferably a methyl group, a propyl group or a phenyl group. Among these, a methyl group is more preferable from the viewpoint of versatility and price, but a phenyl group is more preferable from the viewpoint of heat resistance.

In the silicone (14), as a substituent that R ^{21 to} R ²⁸ may have, a phenyl group, a phenol group, a hydroxy group, a carboxy group, an amino group (0 to 14 carbon atoms), an imino group, (aminoethyl) ) Amino group, (dimethylaminoethyl) amino group, polyoxyalkylene group, mercapto group, and epoxy group. When it has these substituents, a propyl group is particularly preferable as R ^{21 to} R ²⁸ .

In the silicone (14), at least one, preferably 1 to 10, more preferably R ²¹ , R ²² , R ²³ , s R ²⁴ , s R ²⁵ , R ²⁶ , R ²⁷ , R ^28. 1 to 5, particularly preferably 1 to 2 are hydrogen atoms. This hydrogen atom may be located at any of the side chain, one end and / or both ends of the silicone (14), or a mixture thereof.

  S in the silicone (14) represents a number of 0 to 10,000, preferably a number of 1 to 3,000, more preferably a number of 5 to 500, and particularly preferably a number of 10 to 150. .

[Production method of branched polyglycerol-modified silicone]
The method for producing a branched polyglycerol-modified silicone of the present invention is a method in which an organohydrogenpolysiloxane and a branched polyglycerol having a reactive unsaturated group are reacted in the presence of a platinum catalyst. At this time, either a branched polyglycerol or an organohydrogenpolysiloxane having a reactive unsaturated group is used to suppress the dehydrogenation reaction, and as a result, to suppress gelation (which is considered to be a crosslinked structure). A method in which one and the platinum catalyst are mixed (step 1) and then the resulting mixture and the remaining one are reacted (step 2) is preferable.

  In step 1, either a branched polyglycerol having a reactive unsaturated group or an organohydrogenpolysiloxane is mixed with a platinum catalyst. Preferably, the branched polyglycerol having a reactive unsaturated group and the platinum catalyst are mixed. Mix.

The mixing temperature is preferably 20 to 40 ° C. Examples of the platinum catalyst include chloroplatinic acid, speier reagent (isopropyl alcohol solution of chloroplatinic acid), platinum carbon or a support such as alumina, silica, and the like, on which solid platinum is supported. Reagents are preferred. The amount of the platinum catalyst used is not particularly limited as long as it is sufficient to promote the reaction between the organohydrogenpolysiloxane and the branched polyglycerol having a reactive unsaturated group. The range of 10 ⁻⁶ to 10 ⁻¹ mol is preferable with respect to 1 mol of hydrogen atom of the reactive unsaturated group or organohydrogenpolysiloxane in the branched polyglycerol having a group, and 10 ⁻⁶ to 10 ⁻³ mol. The range is preferable from the viewpoint of reaction rate and economy. The mixing time is not particularly limited, but is preferably 0.5 to 5 hours from the viewpoint of reaction rate and dehydrogenation reaction.

  In step 2, the obtained mixture and the remaining one are reacted. The ratio of the reaction between the branched polyglycerol having a reactive unsaturated group and the organohydrogenpolysiloxane is from the viewpoint of the reaction rate, the branching having a reactive unsaturated group with respect to 1 mole of hydrogen atom of the organohydrogenpolysiloxane. The reactive unsaturated group of polyglycerol is preferably 0.1 to 1.5 mol, more preferably 0.6 to 1.5 mol. The reaction temperature is preferably 0 to 40 ° C., more preferably 20 to 40 ° C. from the viewpoint of suppressing the dehydrogenation reaction and obtaining a highly pure branched polyglycerol-modified silicone. The reaction time is not particularly limited as long as it is sufficient to promote the reaction between the organohydrogenpolysiloxane and the branched polyglycerol having a reactive unsaturated group, but is preferably 0.5 to 24 hours. The reaction may be performed by dropping the remaining one into the obtained mixture, or may be performed by mixing both together.

  In steps 1 and 2, the use of a solvent is not essential, but the reaction may be carried out in an appropriate solvent as necessary. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbon solvents such as pentane, hexane and cyclohexane; benzene solvents such as benzene, toluene and xylene; ether systems such as diethyl ether and diisopropyl ether Solvent: Alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol and the like. When an alcohol solvent is used, it is preferable to use a pH adjuster such as potassium acetate (Japanese Patent Publication No. Sho 62-34039) in order to prevent or suppress the dehydrogenation reaction.

[Branched polyglycerol-modified silicone]
The number average molecular weight of the branched polyglycerol-modified silicone obtained by the method of the present invention is preferably 500 to 500,000, more preferably 750 to 200,000, particularly preferably 1,000 to 100,000. The method for measuring the number average molecular weight is based on GPC (polystyrene or polyethylene glycol equivalent) as described later.

  The branched polyglycerol-modified silicone obtained by the production method of the present invention is a silicone represented by the general formula (1) in which the hydrogen atom in the silicone (14) is replaced by a linking group to which a branched polyglycerol chain is bonded. Is preferred.

In the general formula (1), ^one selected from the group consisting of R ^{1 to} R ³ and one selected from the group consisting of R ^{6 to} R ⁸ represent a linking group to which a branched polyglycerol chain is bonded, and the remainder R ^{1 to} R ³ and R ^{6 to} R ⁸ , t R ⁴ , and t R ⁵ represent other groups, the branched polyglycerol-modified silicone of the present invention is a branched polyglycerol having both ends substituted type. It becomes a modified silicone, which is very preferable because it can be interconnected in water or other solvents to take a higher order structure. At that time, the remaining R ^{1 to} R ³ and R ^{6 to} R ⁸ , t R ⁴ , and t R ⁵ are particularly preferably methyl groups.

When the linking group to which the branched polyglycerol chain is bonded is present in three or more selected from t R ⁴ and t R ⁵ , the branched polyglycerol-modified silicone of the present invention is a side chain multi-substituted type. The branched polyglycerol-modified silicone is preferable because of increased hydrophilicity and adsorption ability.

  The branched polyglycerol-modified silicone obtained in the present invention comprises a total number of silicon atoms (Si) in the silicone and groups (2), (3), (4) and (5) in the branched polyglycerol chain (hereinafter referred to as glycerol). The ratio (G / Si) of (G) is preferably 0.001 to 50, more preferably 0.05 to 10, still more preferably 0.1 to 3, and particularly preferably 0.15 to 1. Within this range, the residual rate of adsorption to various substrates, skin, hair and fibers is high.

  In the branched polyglycerol-modified silicone obtained by the present invention, unless the silicone characteristic, the hydrophilic property and the high adsorptivity, which are the characteristics of the branched polyglycerol-modified silicone of the present invention, are significantly inhibited. In addition, a small amount of ethyleneoxy group and / or propyleneoxy group may be present in the branched polyglycerol chain. Ethyleneoxy groups and / or propyleneoxy groups may be present randomly in the branched polyglycerol chain, or a plurality of ethyleneoxy groups and / or propyleneoxy groups form a chain and block in the branched polyglycerol chain. May be present. In this case, the block composed of a plurality of ethyleneoxy groups and / or propyleneoxy groups may be present in the vicinity of the linking group of the branched polyglycerol chain, may be present at the terminal, or may be present in the middle. You may do it. When the ethyleneoxy group and / or propyleneoxy group is present, the ethyleneoxy group and / or propyleneoxy group is preferably present in an amount of 0.001 to 0.5 molar equivalents relative to 1 molar equivalent of the glycerol group. More preferably, it is present at 0.02 to 0.2 molar equivalent.

The assignment of each peak in the ¹ H-NMR spectrum of the branched polyglycerol-modified silicone obtained in the following examples is somewhat shifted depending on the solvent, but is generally as follows.

0.0-0.2 ppm: Si—C H ₃
0.6-0.7 ppm: Si—C H ₂ —CH ₂ — (4H)
_{1.5-1.7ppm: Si-CH 2 -C H} 2 - (4H)
_{2.4-2.7ppm: Si-CH 2 -CH 2} -C H 2 - (4H)
3.3-4.0 ppm: H of branched polyglycerol chain (excluding terminal hydroxy groups, 5H × number of glycerol groups)
In addition, in the ¹³ C-NMR spectrum, the assignment of the peak derived from each carbon of the groups (2) to (5) forming the branched polyglycerol chain was referred to the values described in Macromolecules, 1999, 32, 4240.

Example 1
(1) Production of branched polyglycerol having a reactive unsaturated group 45.3 g (0.45 mol) of 2-allyloxyethanol was charged into a 300-ml four-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel. Then, 0.7 g of KOH catalyst was added and heated to 70 ° C. From a dropping funnel, 160 ml (2.41 mol) of glycidol made from Japanese fat was gradually dropped over 5 hours. After the reaction product was stirred at 70 ° C. for 2 hours, volatile components were distilled off under reduced pressure at the same temperature for 1 hour. Then, 10g of Kyowa Chemical Industry Co., Ltd. Kyoward 600 and 100g of water were added and stirred at room temperature for 0.5 hour, followed by filtration to produce a reaction product as a reactive unsaturated compound represented by the following formula (15). 168.5 g of branched polyglycerol having a group (yield 75%) was obtained.

CH ₂ = CHCH ₂ OCH ₂ CH ₂ OY ¹ (15)
(Y ¹ represents a branched polyglycerol chain.)
The ¹ H-NMR spectrum (water-d ₂ solution) of the branched polyglycerol having this reactive unsaturated group is shown in FIG. 1, and the ¹³ C-NMR spectrum (water-d ₂ solution) is shown in FIG. Moreover, attribution of the peak derived from the methine carbon of the group (2) in the ¹³ C-NMR spectrum is shown below.

Analysis of the ¹³ C-NMR spectrum confirmed that it was a branched polyglycerol having a group (2). Further, from the analysis of ¹ H-NMR spectrum, the average number of glycerol groups (G) = 5.4, and from the analysis of ¹³ C-NMR spectrum and ¹ H-NMR spectrum, the branching ratio [a / (a + b + c + d)] is 1/5. .9.

(2) Production of branched polyglycerol-modified silicone In a 100 ml two-necked flask equipped with a stirrer, 14.3 g (29.0 mmol) of branched polyglycerol having a reactive unsaturated group obtained in (1) and chloroplatinic acid were added. A 2% isopropyl alcohol solution (0.4 g, 0.015 mmol) was mixed and stirred at 20 ° C. for 1 hour. In a four-necked flask with an internal volume of 500 ml equipped with a stirrer and thermometer, the following formula (16)

(In the formula, Me represents a methyl group.)
38.5 g of the above-mentioned organohydrogenpolysiloxane [hydroxyl equivalent = 1210, number average molecular weight (Mn) = 4840 (GPC conditions are columns: G4000HXL + G2000HXL, THF solution (50 mmol / L acetic acid added), 40 ° C.)] 14.7 g of a branched polyglycerol-chloroplatinic acid mixture having a reactive unsaturated group, 0.4 g (0.4 mmol) of a 10% potassium acetate solution in ethanol and 100 ml of isopropyl alcohol are allowed to react at 20 ° C. for 12 hours, and finally unreacted In order to make the organohydrogenpolysiloxane react, 12.8 g (150 mmol) of 1-hexene was added and stirred at 30 ° C. for 5 hours. After distilling off the solvent 1-hexene, the reaction product was dissolved in 30 ml of isopropyl alcohol and filtered to obtain 35.4 g (yield 67%) of a slightly yellow viscous liquid.

A ¹ H-NMR spectrum (methanol-d ₄ solution) of the obtained branched polyglycerol-modified silicone is shown in FIG. 3, and a ¹³ C-NMR spectrum (methanol-d ₄ solution) is shown in FIG. By measurement of ¹³ C-NMR spectrum, it was confirmed to be a branched polyglycerol silicone having a group (2). The average number of glycerol groups (G) and average number of silicon (Si) determined from the measurement of ¹ H-NMR spectrum were G = 18.4 and Si = 64 (G / Si = 0.29), respectively. From GPC analysis [column: G4000HXL + G2000HXL, THF solution (50 mmol / L acetic acid added), 40 ° C.], Mn = 4900 and weight average molecular weight (Mw) = 12,900.

Example 2
(1) Production of branched polyglycerol having a reactive unsaturated group Into the same 4-necked flask as used in (1) of Example 1, 21.5 g (0.21 mol) of 2-allyloxyethanol was charged, and a KOH catalyst was added. 0.3 g was added and heated to 70 ° C. From a dropping funnel, 275 ml (4.14 mol) of glycidol made from NOF was gradually added dropwise over 5 hours. The reaction product was stirred at 70 ° C. for 2 hours, and then volatiles were distilled off under reduced pressure at the same temperature for 1 hour. Thereafter, 10 g of Kyoward 600 manufactured by Kyowa Chemical Industry Co., Ltd. and 100 g of water were added and stirred at room temperature for 0.5 hour, followed by filtration to obtain 286.5 g of a reaction product (yield 88%). From the ¹ H-NMR spectrum and the ¹³ C-NMR spectrum, the obtained product was confirmed to be a branched polyglycerol having a reactive unsaturated group represented by the following formula (17).

CH ₂ = CHCH ₂ OCH ₂ CH ₂ OY ² (17)
(Y ² represents a branched polyglycerol chain.)
Analysis of the ¹³ C-NMR spectrum confirmed that it was a branched polyglycerol having a group (2). Further, from the analysis of ¹ H-NMR spectrum, the average number of glycerol groups (G) = 19.7, and from the analysis of ¹³ C-NMR spectrum and ¹ H-NMR spectrum, the branching ratio [a / (a + b + c + d)] is 1 / 5.2.

(2) Production of branched polyglycerol-modified silicone In a 100 ml two-necked flask equipped with a stirrer, 58.3 g (40 mmol) of branched polyglycerol having a reactive unsaturated group obtained in (1) and 2 of chloroplatinic acid were added. % Isopropyl alcohol solution 0.4 g (0.015 mmol) was mixed and stirred at 20 ° C. for 1 hour. Chisso organohydrogenpolysiloxane with hydrogen atoms at both ends in a 500 ml four-necked flask equipped with a stirrer and thermometer [Model number: IC-8461-1F20-BL, hydroxyl group equivalent = 3000, Mn = 6000 ( GPC conditions are as follows: Column: G4000HXL + G2000HXL, THF solution (50 mmol / L acetic acid added, 40 ° C.)] 30 g, 58.7 g of the branched polyglycerol-chloroplatinic acid mixture having the above reactive unsaturated groups, 10% ethanol solution of potassium acetate 0.4 g (0.4 mmol) and 100 ml of isopropyl alcohol were added and reacted at 20 ° C. for 12 hours. Further, 20.5 g (240 mmol) of 1-hexene was added and stirred at 30 ° C. for 5 hours. After distilling off the solvent 1-hexene, the reaction product was dissolved in 30 ml of isopropyl alcohol and filtered to obtain 24.5 g (yield 74%) of a slightly yellow viscous liquid. Similar to Example 1, it is a branched polyglycerol-modified silicone in which G = 9.0, Si = 78, Mn = 5600, Mw = 11500 by measuring ¹³ C-NMR spectrum, ¹ H-NMR spectrum, and GPC. It was confirmed.

2 is a ¹ H-NMR spectrum of a branched polyglycerol having a reactive unsaturated group obtained in Example 1 (1). 3 is a ¹³ C-NMR spectrum of a branched polyglycerol having a reactive unsaturated group obtained in (1) of Example 1. 2 is a ¹ H-NMR spectrum of the branched polyglycerol-modified silicone obtained in (2) of Example 1. 3 is a ¹³ C-NMR spectrum of the branched polyglycerol-modified silicone obtained in (2) of Example 1.

Claims (4)

A method for producing a branched polyglycerol-modified silicone, wherein a branched polyglycerol having a reactive unsaturated group and an organohydrogenpolysiloxane are reacted in the presence of a platinum catalyst ,
The branched polyglycerol having the reactive unsaturated group is a branched polyglycerol represented by the following general formula (6) or (7):
^{_{X- (R 11) p -O- (}} AO) q -Y (6)
(In the formula, X represents a vinyl group, vinylene group or vinylidene group, and R ¹¹ may have a substituent, a linear or branched alkylene group having 1 to 20 carbon atoms, an alkenylene group, or An arylene group having 6 to 20 carbon atoms, AO is an alkyleneoxy group having 1 to 4 carbon atoms (also referred to as an oxyalkylene group) or an aryleneoxy group having 6 to 10 carbon atoms (also referred to as an oxyarylene group), and p is 0 or 1 , Q represents a number from 0 to 30, and q AOs may be the same or different. Y represents a branched polyglycerol chain.)
^{_{X- (R 12) p -COO- (}} AO) r -Y (7)
(In the formula, X, Y, AO and p have the same meaning as described above, and R ¹² represents a linear or branched alkylene group having 1 to 20 carbon atoms and an alkenylene group which may have a substituent. Or an arylene group having 6 to 20 carbon atoms, r represents a number of 0 to 30, and r AOs may be the same or different.
The branched polyglycerol chain is a branched polyglycerol chain containing a branched glycerol group represented by the following structural formula (2), and the average total number of bonds of the groups (2), (3), (4) and (5) Is 3 to 201,

(In the formula, two oxygen atoms are the same or different, and the above structural formula (2), the following structural formula (3), (4) or (5)

The glycerol group or glycidol group represented by these is couple | bonded. )
A method for producing a branched polyglycerol-modified silicone, wherein the organohydrogenpolysiloxane is a linear silicone represented by the following general formula (14).

(Wherein R ²¹ , R ²² , R ²³ , s R ²⁴ , s R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are the same or different and have a hydrogen atom or a substituent. Or a linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, or an aryl group having 6 to 22 carbon atoms, which may be substituted with a fluorine atom, R ²¹ , R ²² , R ²³ , s R ²⁴ , s R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are at least one hydrogen atom, and s is a number from 0 to 10,000. The method for producing a branched polyglycerol-modified silicone according to claim 1, wherein the branched polyglycerol-modified silicone is a silicone represented by the general formula (1).

Wherein R ¹ , R ² , R ³ , t R ⁴ , t R ⁵ , R ⁶ , R ⁷ , R ⁸ are the same or different and are a linking group to which a branched polyglycerol chain is bonded, A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, or an aryl group having 6 to 22 carbon atoms, which may have a substituent and may be substituted with a fluorine atom Wherein at ^{least one} of R ¹ , R ² , R ³ , t R ⁴ , t R ⁵ , R ⁶ , R ⁷ , R ⁸ is a linking group to which a branched polyglycerol chain is bonded. t represents a number from 0 to 10,000.)   The branched polyglycerol according to claim 1 or 2, wherein either one of the branched polyglycerol or the organohydrogenpolysiloxane having a reactive unsaturated group is mixed with a platinum catalyst, and then the resulting mixture is reacted with the remaining one. A method for producing glycerol-modified silicone.   The manufacturing method of the branched polyglycerol modified silicone in any one of Claims 1-3 whose reaction temperature is 0-40 degreeC.

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