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Block copolymer comprising catechol ,segment and inorganic nanoparticles coated by said block copolymer, as well as method for producing block copolymer comprising catechol, segment and method for producing inorganic nanoparticles coated by said block copolymer meetings

Foreign code F190009717
File No. K10504WO
Posted date Feb 7, 2019
Country United States of America
Application number 201515121097
Gazette No. 20170008993
Date of filing Feb 27, 2015
Gazette Date Jan 12, 2017
International application number JP2015055769
International publication number WO2015129846
Date of international filing Feb 27, 2015
Date of international publication Sep 3, 2015
Priority data
  • P2014-039963 (Feb 28, 2014) JP
  • 2015JP55769 (Feb 27, 2015) WO
Title Block copolymer comprising catechol ,segment and inorganic nanoparticles coated by said block copolymer, as well as method for producing block copolymer comprising catechol, segment and method for producing inorganic nanoparticles coated by said block copolymer meetings
Abstract Provided is a block copolymer that makes it possible to produce inorganic nanoparticles that can be dispersed in an organic solvent, the inorganic nanoparticles being of uniform size and a reducing agent not having to be used.
A block copolymer including a catechol segment represented by formula (1).
<chemistry id="CHEM-US-00001" num="00001"> </chemistry>
Outline of related art and contending technology BACKGROUND
Nanoparticles are known to exhibit different physical and chemical properties from the bulk material due to the quantum size effect, increase in specific surface area, and the like among the high precision, high density, small size, and light weight required in science and technology in recent years. Examples include a significant reduction in the melting temperature and firing temperature, fluorescence emission, and higher efficiency and novel reactions of catalysts. Nanoparticles are therefore expected to find application in materials for secondary batteries and fuel cells, fluorescent materials, electronic component materials, magnetic recording materials, magnetic fluids, nanostructure modifiers for ceramics, thin film synthesis, coating materials, sensors, abrasive materials, pigments, cosmetic materials, drug delivery, novel contrast agents, fluorescent labels, prosthetic bone, and other such technical fields.
However, inorganic fine particles of metals, semiconductors, or oxides, and the like are known to tend to agglomerate as their size enters the nanodomain. Inorganic nanoparticles are also known to be difficult to disperse in organic solvents because they are fundamentally hydrophilic. The dispersion of inorganic nanoparticles in an organic solvent therefore poses a problem for the application of inorganic nanoparticles in the above technical fields.
The production of metal nanoparticles coated with poly(styrene-block-2-vinylpyridine), by forming a reverse micelle by adding poly(styrene-block-2-vinylpyridine) (poly(styrene-b-2-vinylpyridine)) to toluene, then reducing the metal ion by adding chlorauric acid (HAuCl4), followed by hydrazine (N2H4), is known as a technique for dispersing inorganic nanoparticles in an organic solvent (Non-patent Document 1).
The production of metal nanoparticles coated by thiol-terminated polystyrene by adding chlorauric acid (HAuCl4) to a solvent of thiol-terminated polystyrene, then reducing the metal ion by adding sodium borohydride (NaBH4), is also known (Non-patent Document 2).
The dispersion of magnetic nanoparticles using a dispersant having a catechol backbone capable of coordination bonding with magnetic nanoparticles is also known (Patent Document 1).
Incidentally, catechol groups are known to reduce metal ions without using a reducing agent and to be capable of granulation (Non-patent Document 3). For example, a resin obtained by random copolymerization of a 3,4-hydroxystyrene monomer and a styrene monomer is known as a resin capable of reducing metal ions by utilizing the reductive capacity of catechol groups (Patent Document 2).
Scope of claims [claim1]
1. A block copolymer comprising a catechol segment, the block copolymer represented by formula (1),
wherein:
R1 represents a linear, branched, or cyclic C1-18 alkyl group, C2-18 alkenyl group, monovalent aromatic C6-18 hydrocarbon group, or monovalent heterocyclic group having a total of 3-18 carbon atoms and hetero atoms selected from N, S, O, Se, and Te, and hydrogens of the C1-18 alkyl group, C2-18 alkenyl group, monovalent aromatic C6-18 hydrocarbon group, and monovalent heterocyclic group having a total of 3-18 atoms of R1 may each be substituted by a carboxyl group, hydroxyl group, cyano group, or C1-20 alkyl group,
Z represents a hydrogen atom, chlorine atom, carboxyl group, cyano group, C1-20 alkyl group, monovalent aromatic C6-20 hydrocarbon group, monovalent heterocyclic group having a total number of atoms of 3-20 carbon atoms and hetero atoms selected from N, S, O, Se, and Te, ―OH, ―SR7, ―N(R7)2, ―OC(═O)R7, ―C(═O)OR7, ―C(═O)N(R7)2, ―P(═O)(OR7)2, or P(═O)(R7)2, R7 represents a C1-20 alkyl group, monovalent aliphatic C3-20 hydrocarbon group, monovalent aromatic C6-20 hydrocarbon group, monovalent heterocyclic group having a total of 3-20 carbon atoms and hetero atoms, ―OR′, ―SR′, ―N(R′)2, or monovalent group having a polymer chain, each R′ represents a C1-18 alkyl group, C2-18 alkenyl group, monovalent aromatic C6-18 hydrocarbon group, or monovalent heterocyclic group having a total of 3-18 atoms of carbon atoms and hetero atoms selected from N, S, O, Se, and Te, and hydrogens of the C1-20 alkyl group, monovalent aromatic C6-20 hydrocarbon group, monovalent heterocyclic C3-20 group, and carboxyl group of Z and R7 may each be substituted by a carboxyl group, hydroxyl group, cyano group, or C1-20 alkyl group,
n represents an integer of 3-1000, m represents an integer of 3-1000, and t represents an integer of 3-1000, but one of n and t need not be included;
R2 represents a linear, branched, or cyclic C1-20 alkyl group, C6-20 aryl group, or C7-20 aralkyl group;
X represents an amide or ester, but need not be included;
Y represents an amide or ester, but need not be included;
p represents an integer of 1-10, but need not be included;
R8 represents H or R3, R9 represents H or R4, R3 and R4 represent protecting groups, and the proportion of H of R8+R9 is 60% or higher;
R5 represents H or CH3; and
R6 represents H or CH3.
[claim2]
2. The block copolymer of claim 1, wherein R8 and R9 are H.
[claim3]
3. The block copolymer of claim 1, wherein n, m, and t are m/(n+t)≦1.
[claim4]
4. Inorganic nanoparticles coated by the block copolymer of claim 1.
[claim5]
5. A liquid composition of the inorganic nanoparticles of claim 4 dispersed in an organic solvent.
[claim6]
6. A film containing the inorganic nanoparticles of claim 4.
[claim7]
7. A method for producing a block copolymer comprising a catechol segment, the method comprising
(a) a step for living-radical-polymerizing a radical-polymerizable hydrophobic vinyl monomer represented by formula (3),
(b) a step for living-radical-polymerizing a radical-polymerizable vinyl monomer represented by formula (4), and
(c) a step for deprotecting R3 and R4 of the living polymer obtained and forming hydroxy groups
in an organic solvent comprising a compound used in reversible addition-fragmentation chain transfer (RAFT) represented by formula (2),
wherein, in formula (2):
R1 represents a linear, branched, or cyclic C1-18 alkyl group, C2-18 alkenyl group, monovalent aromatic C6-18 hydrocarbon group, or monovalent heterocyclic group having a total of 3-18 carbon atoms and hetero atoms selected from N, S, O, Se, and Te, and hydrogens of the C1-18 alkyl group, C2-18 alkenyl group, monovalent aromatic C6-18 hydrocarbon group, and monovalent heterocyclic group having a total of 3-18 atoms of R1 may each be substituted by a carboxyl group, hydroxyl group, cyano group, or C1-20 alkyl group; and
Z represents a hydrogen atom, chlorine atom, carboxyl group, cyano group, C1-20 alkyl group, monovalent aromatic C6-20 hydrocarbon group, monovalent heterocyclic group having a total number of atoms of 3-20 carbon atoms and hetero atoms selected from N, S, O, Se, and Te, ―OH, ―SR7, ―N(R7)2, ―OC(═O)R7, ―C(═O)OR7, ―C(═O)N(R7)2, ―P(═O)(OR7)2, or P(═O)(R7)2, R7 represents a C1-20 alkyl group, monovalent aliphatic C3-20 hydrocarbon group, monovalent aromatic C6-20 hydrocarbon group, monovalent heterocyclic group having a total of 3-20 carbon atoms and hetero atoms, ―OR′, ―SR′, ―N(R′)2, or monovalent group having a polymer chain, each R′ represents a C1-18 alkyl group, C2-18 alkenyl group, monovalent aromatic C6-18 hydrocarbon group, or monovalent heterocyclic group having a total of 3-18 atoms of carbon atoms and hetero atoms selected from N, S, O, Se, and Te, and hydrogens of the C1-20 alkyl group, monovalent aromatic C6-20 hydrocarbon group, monovalent heterocyclic C3-20 group, and carboxyl group of Z and R7 may each be substituted by a carboxyl group, hydroxyl group, cyano group, or C1-20 alkyl group;
wherein, in formula (3):
R2 represents a linear, branched, or cyclic C1-20 alkyl group, C6-20 aryl group, or C7-20 aralkyl group;
X represents an amide or ester, but need not be included; and
R5 represents H or CH3; and
wherein, in formula (4):
R3 and R4 represent protecting groups,
R6 represents H or CH3;
Y represents an amide or ester, but need not be included; and
p represents an integer of 1-10, but need not be included.
[claim8]
8. The method for producing a block copolymer comprising a catechol segment of claim 7 wherein step (a) is carried out again between step (b) and step (c).
[claim9]
9. The method for producing a block copolymer comprising a catechol segment of claim 7 wherein the order of step (a) and step (b) is switched.
[claim10]
10. A method for producing inorganic nanoparticles coated by a block copolymer comprising a catechol segment also including
(d) a step for adding an inorganic salt or a solution in which an inorganic salt is dissolved
after the method for producing a block copolymer comprising a catechol segment of claim 7.
[claim11]
11. The block copolymer of claim 2, wherein n, m, and t are m/(n+t)≦1.
[claim12]
12. Inorganic nanoparticles coated by the block copolymer of claim 2.
[claim13]
13. Inorganic nanoparticles coated by the block copolymer of claim 3.
[claim14]
14. Inorganic nanoparticles coated by the block copolymer of claim 11.
[claim15]
15. A liquid composition of the inorganic nanoparticles of claim 12 dispersed in an organic solvent.
[claim16]
16. A liquid composition of the inorganic nanoparticles of claim 13 dispersed in an organic solvent.
[claim17]
17. A liquid composition of the inorganic nanoparticles of claim 14 dispersed in an organic solvent.
[claim18]
18. A film containing the inorganic nanoparticles of claim 12.
[claim19]
19. A film containing the inorganic nanoparticles of claim 13.
[claim20]
20. A film containing the inorganic nanoparticles of claim 14.
[claim21]
21. A method for producing inorganic nanoparticles coated by a block copolymer comprising a catechol segment also including
(d) a step for adding an inorganic salt or a solution in which an inorganic salt is dissolved
after the method for producing a block copolymer comprising a catechol segment of claim 8.
[claim22]
22. A method for producing inorganic nanoparticles coated by a block copolymer comprising a catechol segment also including
(d) a step for adding an inorganic salt or a solution in which an inorganic salt is dissolved
after the method for producing a block copolymer comprising a catechol segment of claim 9.
  • Inventor, and Inventor/Applicant
  • YABU Hiroshi
  • SAITO Yuta
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
IPC(International Patent Classification)
Reference ( R and D project ) PRESTO Molecular technology and creation of new functions AREA
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