JP2013518978A5

JP2013518978A5 -

Info

Publication number: JP2013518978A5
Application number: JP2012552512A
Authority: JP
Filing date: 2011-02-09
Publication date: 2014-03-27
Anticipated expiration: 2031-02-09

Claims

An anionic polysaccharide selected from polysaccharides having a carboxyl group, wherein at least one of the hydroxyl groups is substituted by at least two hydrophobic groups (denoted as -Hy _h ), or at least one of the carboxyl groups Are substituted by at least two hydrophobic groups (denoted as -Hy _c ), which are the same or different, and the polysaccharide having the carboxyl group has a carboxyl group before being substituted by at least two hydrophobic groups. From synthetic polysaccharides selected from naturally-occurring polysaccharides or synthetic polysaccharides obtained from naturally-occurring polysaccharides, or synthetic polysaccharides obtained from neutral polysaccharides having hydroxyl groups converted to carboxyl groups Selected
The synthetic polysaccharide has the general formula VIII:

{Where,
Neutral polysaccharides are mostly bound via glycoside bonds of type (1,6) and / or (1,4) and / or (1,3) and / or (1,2) Selected from the group of polysaccharides consisting of monomers;
L is a linking group formed by coupling between the precursor of the linking arm Q and the —OH functional group of the polysaccharide, which is an ester, carbamate or ether functional group;
i represents the degree of conversion of hydroxyl group to LQ sequence per saccharide unit of the polysaccharide;
Q is the formula IX:

[Where:
1 ≦ a + b + c ≦ 6, 0 ≦ a ≦ 3, and 0 ≦ c ≦ 3,
R ₃ and R ₄ are the same or different, and are —H, a linear or branched alkyl group having 1 to 3 carbon atoms, —COOH, and general formula X:

(Where
1 ≦ d ≦ 3, and
R ′ ₃ and R ′ ₄ are the same or different and are selected from the group consisting of —H and a linear or branched alkyl group having 1 to 3 carbon atoms)
Represents}}
Selected from polysaccharides having a degree of conversion of hydroxyl groups to carboxyl groups per saccharide unit of 0.15 or more,
and,
At least one of the hydroxyl groups is substituted by at least two hydrophobic groups (denoted as -Hy _h ), or at least one of the carboxyl groups is the same or different (-Hy _c and The polysaccharide substituted by

{Where,
n _c and _{n h} _{_{_{_{is, -F c -R c - [G}}}} c -Hy c] rc and / or _-F h _-R h _- functionalization of _{[G _h} -Hy _{_h]} said by _rh polysaccharide sugar units Degree, where n _h ≧ 0 and n _c ≧ 0, and 0.01 ≦ n _h + n _c ≦ 0.5,
F _c represents an amide functional group or an ester functional group,
F _h represents a carbamate functional group,
The unfunctionalized carboxyl group of the anionic polysaccharide is in the carboxylic acid cation form, which cation is preferably an alkali metal cation such as Na ⁺ or K ⁺ ,
G _h or G _c is a reaction between an amide functional group or an ester functional group, or a reactive functional group of a hydrophobic compound (Hy _h ′ or Hy _c ′) and a precursor R _h ′ or R _c ′ of a binding arm. The carbamate functional group resulting from the coupling between the functional group and
Hy _h or Hy _c is the same or different group, and the reactive functional group of the hydrophobic compound (Hy _h ′ or Hy _c ′) and the reactive function of the precursor R _h ′ or R _c ′ of the binding arm. Resulting from the coupling between the groups, Hy _h or Hy _c may be branched and / or unsaturated, one selected from O, N and S From a carbon chain having from 4 to 50 carbon atoms, which may have one or more heteroatoms, and may have one or more saturated, unsaturated or aromatic rings or heterocycles. Consists of
R _c is branched from the reaction of a precursor R _c ′ having at least three reactive functional groups that are the same or different, selected from the group consisting of alcohol, acid and amine functional groups. And / or unsaturated, may have one or more heteroatoms selected from O, N and S, and one or more, saturated, unsaturated or aromatic A trivalent group consisting of a carbon chain having 1 to 15 carbon atoms, optionally having a group ring or a heterocycle;
R _h is a branch resulting from the reaction of a precursor R _h ′, one of which is an amine and the other having at least three reactive functional groups selected from the group consisting of alcohol, acid and amine functional groups. And / or may be unsaturated, may have one or more heteroatoms selected from O, N and / or S, and may contain one or more saturated, Represents a trivalent group consisting of a carbon chain having from 1 to 15 carbon atoms, optionally having an unsaturated or aromatic ring or heterocycle;
r _h is an integer representing the number of hydrophobic groups grafted to at least the trivalent linking arm R _h , and 2 ≦ r _h ≦ 4,
r _c is an integer representing the number of hydrophobic groups grafted to at least the trivalent linking arm R _c , and 2 ≦ r _c ≦ 4}
A polysaccharide selected from the polysaccharides represented by:

Formula II:

{Where,
n _c _is, -F _c -R _c - A represents the _{[G _c} -Hy _{_c]} degree of functionalization of the carboxyl groups of the polysaccharide by _rc sequence, a 0.5 to 0.01,
_{_{_{F c, R c, G c}}} , Hy c and _{r c} correspond to the above definition,
Wherein the polysaccharide carboxyl groups are _-F c _-R c _- If _{[G _c} -Hy _{_c]} unfunctionalized by _rc, the polysaccharide carboxyl or carboxyl Motogun is a carboxylic acid cation, said cation Is preferably an alkali metal cation such as Na ⁺ or K ⁺ and when the unfunctionalized reactive functional group of the binding arm R _c is an acid functional group, the reactive functional group is: In the chloride form, ie the carboxylic acid cation form, the cation is preferably an alkali metal cation, such as Na ⁺ or K ⁺ , and the unfunctionalized reactive function of the binding arm R _c When the group is an amine functional group, the functional group is in the form of an anion salt, and the anion is preferably a halide anion}
The polysaccharide of Claim 1 selected from the polysaccharide group represented by these.

Formula III:

(Where
n _c , F _c and R _c correspond to the above definition,
G _c1 and G _c2 are the same or different and correspond to the definition of G _c ,
Hy _c1 and Hy _c2 are the same or different and correspond to the definition of Hy _c )
The polysaccharide of Claim 1 selected from the polysaccharide group represented by these.

Formula V:

{Where,
n _h represents the degree of functionalization of the hydroxyl group of the polysaccharide by the sequence -F _h -R _h- [G _h -Hy _h ] _rh , and is 0.01 to 0.5,
F _h , R _h , G _h , Hy _h and r _h correspond to the above definition,
The carboxyl group of the polysaccharide is in the form of a carboxylic acid cation, which cation is preferably an alkali metal cation such as Na ⁺ or K ⁺ , and an unfunctionalized reaction of the binding arm R _h When the functional group is an acid functional group, the acid functional group is in a chloride form, that is, a carboxylic acid cation form, and the cation is preferably an alkali metal cation such as Na ⁺ or K ⁺ , And when the unfunctionalized reactive functional group of the binding arm R _h is an amine functional group, the functional group is in an anionic salt form, and the anion is preferably a halide anion}
The polysaccharide of Claim 1 selected from the polysaccharide group represented by these.

Formula VI:

(Where
n _h , F _h and R _h correspond to the above definition,
G _h1 and G _h2 are the same or different and correspond to the definition of G _h ,
Hy _h1 and Hy _h2 are the same or different and correspond to the definition of Hy _h )
The polysaccharide of Claim 1 selected from the polysaccharide group represented by these.

The polysaccharide according to any one of claims 1 to 5, which is a dextran composed mainly of monomers linked via glycoside bonds of the (1,6) type .

Ru consists predominantly (1,4) type monomers bonded via a glycosidic bond, pullulan, alginate, hyaluronan, xylan, is selected from the group consisting of galacturonan and water-soluble cellulose, of claims 1 to 5 The polysaccharide of any one .

The LQ sequence is the following sequence:

(Wherein L has the above meaning)
It is selected from the group consisting of polysaccharides as claimed in any one of claims 1 to 7.

In which the —Hy _c group results from the coupling between the hydroxyl function of the hydrophobic alcohol and at least one reactive function carried by the precursor R _c ′ of the at least trivalent group R _c. From the polysaccharides represented by formulas II, III and IV, wherein the group is derived from a hydrophobic alcohol, G _c is an ester functional group or a carbamate functional group, and R _c and F _c have the above definitions The polysaccharide according to any one of claims 1 to 8 , which is selected .

The hydrophobic alcohol is a saturated or unsaturated, and divided form or unbranched branch 4 to be selected from alcohols consisting of alkyl chain having 18 carbon atoms, in claim 9 The polysaccharide described.

The hydrophobic alcohol is a saturated or unsaturated, and divided form or unbranched branches are selected from alcohols consisting of alkyl chains having eighteen more carbon atoms, to claim 9 The polysaccharide described.

In which the —Hy _c group results from the coupling between the carboxyl functionality of the hydrophobic acid and at least one reactive functionality carried by the precursor R _c ′ of the at least trivalent group R _c. From the polysaccharides represented by formulas II, III and IV, wherein the group is derived from a hydrophobic acid, G _c is an ester functional group or an amide functional group, and R _c and F _c have the above definitions The polysaccharide according to any one of claims 1 to 8 , which is selected .

The hydrophobic acid is selected from the group consisting of fatty acids consisting of alkyl chains with 6 to 50 carbon atoms, saturated or unsaturated, and branched or unbranched. Item 13. The polysaccharide according to Item 12 .

In which the —Hy _c group results from the coupling between the amine functionality of the hydrophobic amine and at least one reactive functionality carried by the precursor R _c ′ of the at least trivalent group R _c. A group of polysaccharides represented by formulas II, III and IV, wherein the group is derived from a hydrophobic amine, G _c is an amide functional group or a carbamate functional group, and R _c and F _c have the above definitions The polysaccharide according to any one of claims 1 to 8 , which is more selected.

In which the —Hy _h group results from the coupling between the amine functionality of the hydrophobic amine and at least one reactive functionality carried by the precursor R _h ′ of the at least trivalent group R _h. From the polysaccharides represented by the formulas V, VI and VII, wherein the group is derived from a hydrophobic amine, G _h is an amide functional group or carbamate functional group, and R _h and F _h have the above definitions The polysaccharide according to any one of claims 1 to 8 , which is selected .