JPH05140213A - Polymer containing sugar group and its production - Google Patents

Abstract

PURPOSE:To obtain a polymer which is mild to the skin, can develop surface activity and has alkyl glycoside groups as the side chains by using specified units as the repeating units in the main chain. CONSTITUTION:A polymer containing units of formulas I, II or III as the repeating units in the main chain and having alkyl glycoside groups as the side chains. In the formulas, E is a group of formula IV, Gm is a sugar residue derived by removing all of the hydrogen atoms of the nonglycosidic hydroxyl groups and all of the hydrogen atoms of the glycosidic hydroxyl groups; A is a group of formula V, R<2> is 1-22C alkyl or the like; R<3> is 2-4C alkylene; Z is 0-20; R<1> is 2-4C alkylene; (x) is 0-10; (y) is the number of the nonglycosidic hydroxyl groups; and B is H or a group of formula VI and at least one of yXB groups is a group of formula VI provided that when B is H, then it is bonded to the O atom, while when B is a group of formula IV, then one of its terminals is bonded to the O atom and the other is bonded to the N atom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer having a sugar group in its side chain, which is useful as a high molecular type surfactant mild to the skin, and a method for producing the polymer.

[0002]

BACKGROUND OF THE INVENTION Sugars are renewable natural resources and are important materials from the viewpoint of resource saving and pollution-free. For example, obtained by substituting the hydrogen atom of the glycosidic hydroxyl group of sugar with a long-chain alkyl group, the alkyl glycoside is a nonionic surfactant that is mild to the skin and exerts excellent detergency. It is used as the main ingredient in hair and tableware cleaners. If such an alkyl glycoside can be made to have a high molecular weight, such a polymer is expected to be useful as an agent that enhances adsorptivity to hair and the like while maintaining mildness to the skin and imparts high moisturizing performance and the like. Will be
No such polymer has hitherto been available. An object of the present invention is to be mild to the skin and express a surface active function,
It is intended to provide a novel polymer having an alkyl glycoside group in a side chain.

[0003]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that
It was found that a novel polymer having an alkyl glycoside group in its side chain can be obtained by using 2,3-epoxypropylated glycoside proposed in 93432 as a raw material, and completed the present invention. That is, the present invention has (a) a unit represented by the general formula (I) and a unit represented by the general formula (II) as a repeating unit in the main chain, or (b)
The present invention provides a polymer having a sugar group in the side chain, which has a unit represented by the general formula (III), and a method for producing the same.

[0004]

[Chemical 5]

[In the formula, E is a group bonded to a nitrogen atom and represents a group represented by the formula A (Gm) [(R ¹ O) _x B] _y . Here, Gm: a reducing sugar having 5 to 6 carbon atoms or a condensate thereof (however,
m represents the degree of condensation, and represents the sugar residue remaining after removing the hydrogen atoms of all non-glycoside hydroxyl groups and the hydrogen atoms of glycoside hydroxyl groups in (1) to (10) having an average value of 1 to 10. A: The A group is bonded to the sugar residue Gm by an O-glycoside bond, and R
² (OR ³ ) _z -group is shown.

Here, R ² is a linear or branched carbon number of 1 to
22 represents an alkyl group, an alkenyl group or an alkylphenyl group, R ³ represents an alkylene group having 2 to 4 carbon atoms, and z represents a number having an average value of 0 to 20. R ¹ : an alkylene group having 2 to 4 carbon atoms, one end of which is ether-bonded to an oxygen atom derived from the non-glycoside hydroxyl group in the sugar residue Gm. x: (the total number of moles of alkylene oxide added to the non-glycosidic hydroxyl group in the reducing sugar having 5 to 6 carbon atoms or its condensate) / y is represented by a number of 0 to 10. y: Indicates the number of non-glycosidic hydroxyl groups in a reducing sugar having 5 to 6 carbon atoms or a condensate thereof. B: hydrogen atom or

[0007]

[Chemical 6]

When the B group is a hydrogen atom, the B group is bonded to the oxygen atom of (R ¹ O) _x or the oxygen atom derived from the non-glycosidic hydroxyl group in the sugar residue Gm. Also, the B group is

[0009]

[Chemical 7]

Alternatively, it is bonded to an oxygen atom derived from a non-glycoside hydroxyl group in the sugar residue Gm, and the other end is represented by the general formula (I) or (I
It bonds to the nitrogen atom to which E bonds in the unit represented by I) or (III). In the above definition of symbols, Gm is exemplified as follows.

[0011]

[Chemical 8]

[M represents the degree of sugar bond and the average value is a number from 1 to 10] The polymer having a sugar group in the side chain provided by the present invention is obtained by the following production methods 1 and 2. be able to. Production Method 1 The repeating unit in the main chain is represented by the general formula (I)
Units represented and units represented by the general formula (II)
For producing polymer having poly ( ethyleneimine)

[0013]

[Chemical 9]

A polymer having units] and the general formula (IV) A (Gm) [(R ¹ O) _x Q] _y (IV) [wherein A, Gm, R ¹ , x and y are as defined above] Show the meaning. Q is a hydrogen atom or

[0015]

[Chemical 10]

It can be obtained by reacting a 2,3-epoxypropylated glycoside represented by the formula (1) in the presence of an alkali catalyst. This reaction can be represented by a formula as follows, for example.

[0017]

[Chemical 11]

[In the series of formulas, E has the above-mentioned meaning. p,
q represents a positive number, and p + q = 10 to 10,000 is preferable. Also,

[0019]

[Chemical 12]

Random bonds in the polymer. ] As 2,3-epoxypropylated glycoside (IV), 2,3-
The reaction formula when 3-epoxypropylated lauryl glucoside (IV-1) is selected is shown below.

[0021]

[Chemical 13]

[In the series of formulas, p and q have the above-mentioned meanings. Manufacturing method 2 As a repeating unit in the main chain,
Method for producing polymer having units represented by poly.3 -amino-1-propylene

[0023]

[Chemical 14]

And 2,3 represented by the general formula (IV)
-Epoxypropylated glycoside is obtained by reacting in the presence of an alkali catalyst. This reaction can be represented by a formula as follows, for example.

[0025]

[Chemical 15]

[In the series of formulas, E has the above-mentioned meaning. r
Represents a positive number, preferably in the range of 10 to 10,000. ] As 2,3-epoxypropylated glycoside (IV), 2,3-
The reaction formula when 3-epoxypropylated lauryl glucoside (IV-1) is selected is shown below.

[0027]

[Chemical 16]

[In the series of formulas, r has the above-mentioned meaning. ] 2,3-epoxypropylated groups used in the present invention
Lycoside (IV) The 2,3-epoxypropylated glycoside (IV) used in the present invention is obtained by, for example, reacting a starting glycoside represented by the general formula (V) with epihalohydrin in the presence of an acidic catalyst. It is obtained by reacting the product with an alkaline substance (see Japanese Patent Application No. 2-93432).

A (Gm) [(R ¹ O) _x H] _y (V) [In the formula, A, Gm, R ¹ , x and y have the above-mentioned meanings. In this case, the starting glycoside (V) used as the starting material for synthesis is a known method (Japanese Patent Publication No. 47-24532, USP).
No. 3839318, EP 092355, JP-A-59-139397, JP-A-58-189195, etc.), in which a saccharide and a higher alcohol are directly reacted in the presence of an acid catalyst. Method, or sugars in advance with methanol, ethanol,
It can be obtained by any method of reacting with a lower alcohol such as propanol or butanol and then reacting with a higher alcohol. Further, the glycoside compound thus obtained, to which an alkylene oxide having 2 to 4 carbon atoms is added, can be used as a synthetic raw material in the present invention.

Monosaccharides, oligosaccharides or polysaccharides are used as the saccharides used in the synthesis of the starting glycoside (V). Specific examples of the monosaccharide include aldoses such as allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribose, arabinose, xylose, lyxose and fructose which are ketose. Specific examples of oligosaccharides include maltose, lactose, sucrose, maltotriose and the like. Specific examples of the polysaccharides include hemicellulose, inulin, dextrin, dextoslan, xylan, starch, hydrolyzed starch and the like.

The higher alcohol used as a raw material for synthesizing the glycoside (V) is a linear or branched alkanol having 6 to 22 carbon atoms, an alkenol, an alkylphenol or the like, and examples of the alkanol include hexanol, Heptanol, octanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, methylpentanol, methylhexanol, methylheptanol, methyloctanol, methyldecanol, Methylundecanol, methyltridecanol, methylheptadecanol, ethylhexanol, ethyloctanol, ethyldecanol, ethyldodecanol, 2-heptanol, 2-nonanol, 2-unde Nord, 2-tridecanol, 2
-Pentadecanol, 2-heptadecanol, 2-butyloctanol, 2-hexyloctanol, 2-octyloctanol, 2-hexyldecanol, 2-octadecanol, etc. are mentioned, and examples of alkenol include hexenol, heptenol, Octenol, Nonenone, Decenol, Undecenol, Dodecenol,
Examples thereof include tridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, and examples of alkylphenols include octylphenol and nonylphenol. Furthermore, the above-mentioned alkylene oxide adducts having 2 to 4 carbon atoms of alkanol, alkenol or alkylphenol are also used.

Polyethyleneimine or poly-3-amino
-1-Propylene and 2,3-epoxypropylated glycosyl
Reaction with de (IV) With respect to polyethyleneimine or poly-3-amino-1-propylene, 2,3-epoxypropylated glycoside is represented by general formula (I), general formula (II) or general formula (III). Used at a ratio of 1/20 to 1 equivalent per unit represented. In this reaction, a water solvent alone or a mixed solvent of water and an organic solvent (eg, isopropanol, N, N-dimethylformamide) is used as a reaction solvent. This reaction is carried out under alkaline conditions, and the pH is about 9-13, preferably 10-12. This pH is adjusted by adding a catalyst such as NaOH, KOH, Ca (OH) ₂ or the like, and in some cases, a quaternary salt addition system such as tetramethylammonium may be added. Reaction temperature is 20
~ 120 ℃, preferably 40 ~ 80 ℃, the reaction time is 24 ~
48 hours is enough. The polymer obtained by such a method can be used as it is after removing or neutralizing the catalyst, but can also be purified by extraction / recrystallization with an organic solvent, dialysis, or purification with an ion exchange resin. ..

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 a) 4075 g (21.9 mol) of lauryl alcohol, 789 g (4.38 mol) of anhydrous glucose and 11.7 g (0.06 mol) of paratoluenesulfonic acid monohydrate were heated and stirred in a 10-liter flask. After the temperature was raised to 100 ° C, the internal pressure was set to 40 mmHg and the dehydration reaction was started. At this time, nitrogen in the reaction mixture was adjusted to 0.
The water generated by blowing at 1 Nm ³ / hr was efficiently removed. It was visually confirmed that the glucose had been consumed 7.5 hours after the start of the reaction, the pressure was released and the mixture was cooled, and then NaOH water was added to neutralize it. The by-produced polysaccharide is filtered off, then the filtrate is
Distilled under the conditions of 180 ℃ and 0.3mmHg to give lauryl glucoside.
1300 g was obtained. The average degree of sugar condensation of the obtained lauryl glucoside was 1.25.

B) 389 g (1.0 mo) of the above lauryl glucoside
l), tetrabutylammonium iodide 10g (0.027mol)
Was dissolved in 2000 g of water, 100 g (1.2 mol) of 40% NaOH aqueous solution was added, and the mixture was stirred at 50 ° C. A solution of separately mixed 110 g (1.2 mol) of epichlorohydrin and 2000 g of toluene was added dropwise thereto over 3 hours while suppressing heat generation. After completion of the dropping, the mixture was aged at 50 ° C. for 2 hours, cooled, and neutralized with concentrated sulfuric acid. The obtained reaction mixture was desalted by electrodialysis. The electric conductivity of the mixed solution during electrodialysis is from 10 ms / cm to 80
It decreased to μs / cm. The solvent is distilled off from the desalted solution,
It was dissolved in methanol. Insoluble matter was filtered off, and acetone was added to remove 2,3-epoxypropylated lauryl glucoside.
0 g was obtained. ^The degree of substitution with 2,3-epoxypropylation was 1.0 from the integrated value of ¹ H-NMR.

C) 20% of polyethyleneimine (MW70000)
100 g of the aqueous solution was heated to 50 ° C., and 35.5 g (0.08 mol) of the 2,3-epoxypropylated lauryl glucoside was added at a reaction temperature of 50.
Add over 1 hour while maintaining ~ 60 ° C. 70 after addition
The mixture was aged at 8 ° C. for 8 hours and the solvent was distilled off to obtain 55.5 g of a crude polymer. Unreacted 2,3-epoxypropylated lauryl glucoside, hydrolyzate, etc. were removed with a mixed solvent of ethanol / acetone (weight ratio 1: 1), and after drying, 2,3 on the side chain represented by the following formula: 41.3 g of polyethyleneimine with epoxypropylated lauryl glucoside groups are obtained. An increase in the molecular weight of this polymer (MW70000 → 140,000, the molecular weight was measured by the GPC method) was observed, and IR showed OH groups (3424 cm ^-1 ).
The absorption derived from long-chain alkyl groups (2964 cm ^-1 , 2854 cm ^-1 ) was measured. Also, trace amounts of 2,3-epoxypropylated lauryl glucoside and hydrolyzate were found by HPLC (reverse phase system).

[0036]

[Chemical 17]

Example 2 100 g of a 20% aqueous solution of HCl salt of poly-3-amino-1-propylene (polyallylamine: a commercial name) (MW 10000)
Was prepared, and at 50 ° C., 2, obtained in b) of Example 1,
3-Epoxypropylated lauryl glucoside 17.8 g (0.0
4 mol) and 48% NaOH aqueous solution 18.4 g were added. 70 ° C after addition
After aging for 8 hours at room temperature, the solvent is removed and desalted to obtain the crude polymer 3.
0.6 g was obtained. Ethanol / acetone (weight ratio 1: 1)
Unreacted 2,3-epoxypropylated lauryl glucoside and a hydrolyzate are removed with a mixed solvent, and after drying, a poly-containing poly (2,3-epoxypropylated lauryl glucoside) group is contained in the side chain represented by the following formula. 3-amino-1-propylene
21.1 g was obtained. This polymer has an increased molecular weight (MW10000 →
18,000, molecular weight was measured by GPC method. ) Is recognized,
From IR, OH group (3424 cm ^-1 ), long chain alkyl group (2964 cm ^-1 , 2
The absorption derived from 854 cm ⁻¹ was measured. Also, HPLC (reverse phase system)
The trace amount of 2,3-epoxypropylated lauryl glucoside and hydrolyzate was traced.

[0038]

[Chemical 18]

[0039]

INDUSTRIAL APPLICABILITY The polymer of the present invention is an amphipathic polymer having a sugar group as a side chain, has good polymer type surface activity mild to the skin, and is preferable in terms of safety. Further, it has excellent hair conditioning effect, moisturizing property and gel property, and can be widely used in various fields.

Claims (6)

[Claims] 1. As the repeating unit in the main chain, (a)
Having a unit represented by the general formula (I) and a unit represented by the general formula (II), or (b) having a unit represented by the general formula (III), having a sugar group in a side chain Polymer. [Chemical 1] [In the formula, E is a group bonded to a nitrogen atom, and is represented by the formula A (Gm)
A group represented by [(R ¹ O) _x B] _y is shown. Here, Gm: a reducing sugar having 5 to 6 carbon atoms or a condensate thereof (however,
m represents the degree of condensation, and represents the sugar residue remaining after the hydrogen atoms of all the non-glycoside hydroxyl groups and the hydrogen atoms of the glycoside hydroxyl groups in (1) to (10) are averaged. A: The A group is bonded to the sugar residue Gm by an O-glycoside bond, and R
² (OR ³ ) _z -group is shown. Here, R ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkylphenyl group, R ³ represents an alkylene group having 2 to 4 carbon atoms, and z has an average value of 0 to 0. Indicates the number of 20. R ¹ : an alkylene group having 2 to 4 carbon atoms, one end of which is ether-bonded to the oxygen atom derived from the non-glycoside hydroxyl group in the sugar residue Gm. x: (the total number of moles of alkylene oxide added to the non-glycosidic hydroxyl group in the reducing sugar having 5 to 6 carbon atoms or its condensate) / y is represented by a number of 0 to 10. y: Indicates the number of non-glycosidic hydroxyl groups in a reducing sugar having 5 to 6 carbon atoms or a condensate thereof. B: hydrogen atom or When the B group is a hydrogen atom, the B group is bonded to the oxygen atom of (R ¹ O) _x or the oxygen atom derived from the non-glycosidic hydroxyl group in the sugar residue Gm. Also, the B group is Alternatively, the sugar residue Gm is bonded to an oxygen atom derived from a non-glycosidic hydroxyl group, and the other end is represented by the general formula (I), (II) or (III)
In the unit represented by, bond to the nitrogen atom to which E bonds. ] 2. The total number of units represented by general formula (I) and the number of units represented by general formula (II), or the number of units represented by general formula (III) is 10 to 10,000. The polymer having a sugar group in the side chain according to claim 1. 3. In the E group in the unit represented by the general formula (I), (II) or (III), the sugar residue Gm is a hydrogen atom of all non-glycosidic hydroxyl groups of the glucose or its condensate and a glycosidic group. The polymer having a sugar group in the side chain according to claim 1 or 2, which is a sugar residue remaining after removing a hydrogen atom of a hydroxyl group. 4. The E group in the unit represented by the general formula (I), (II) or (III), wherein the A group is a linear or branched alkyl group having 1 to 22 carbon atoms. The polymer having a sugar group in the side chain according to any one of 3 above. 5. A compound represented by the general formula (IV) A (Gm) [(R ¹ O) _x Q] _y (IV) [wherein A, Gm, R ¹ , x, and y have the above-mentioned meanings. Q is a hydrogen atom or The 2,3-epoxypropylated glycoside represented by the formula and polyethyleneimine are reacted with an alkaline substance as a catalyst, and the repeating unit in the main chain is a unit represented by the general formula (I) or A process for producing a polymer having a sugar group in its side chain, which has a unit represented by the general formula (II). 6. A 2,3-epoxypropylated glycoside represented by the general formula (IV) and poly-3-amino-1-
Propylene, as a repeating unit in the main chain, characterized by reacting with an alkaline substance as a catalyst,
A method for producing a polymer having a sugar group in a side chain, which has a unit represented by the general formula (III).