Porous solid with outer surface grafted with a polymer

Patent metadata

Field	Value
Publication number	US-2016101192-A1
Application number	US-201514878421-A
Country	US
Kind code	A1
Filing date	Oct 8, 2015
Priority date	Oct 8, 2014
Publication date	Apr 14, 2016
Grant date	—

Abstract

A process for preparing a porous solid with an outer surface modified by at least one polymer; the polymer being simultaneously synthetized in solution and grafted on the outer surface of the solid, includes contacting:
a porous solid; and a polymer-precursor solution comprising an adhesion primer, and at least one polymerizable monomer;

under conditions enabling the formation of radical entities.

First claim

1 . Process for preparing a porous solid with an outer surface modified by at least one polymer; said polymer being simultaneously synthetized in solution and grafted on the outer surface of said solid, comprising contacting:
a porous solid, wherein the porous solid is a particular solid, preferably selected from the group comprising alumina, hydroxyapatite, B-TCP, silica, zirconia, titania and/or a MOF solid; and a polymer-precursor solution comprising an adhesion primer, and at least one polymerizable monomer;
under conditions enabling the formation of radical entities.

2 . Process according to claim 1 , wherein the porous solid is a MOF solid comprising a three-dimensional succession of units of formula (I)
M m O k X l L p
wherein
M is a metal ion selected from the group comprising Fe 2+ , Fe 3+ , Zn 2+ , Zn 4+ , Ti 4+ , Zr 4+ , Ca 2+ , Cu 2+ , Gd 3+ , Mn 2+ , Mn 3+ , Mg 2+ , Ag + , Si 4+ and Al 3+ ;
m, k, l and p are numbers ≧0 chosen so as to respect the charge neutrality of the unit; preferably, m, k, l and p are independently 0 to 4, for example m and p are independently 1, 2 or 3 and/or k and l are independently 0 or 1;
X is a ligand selected from the group comprising OH − , Cl − , F − , I − , Br − , SO 4 2− , NO 3 − , ClO 4 − , R 1 —(COO) n − , R 1 —(SO 3 ) n − , R 1 —(PO 3 ) n − , in which R 1 is a hydrogen atom, a linear or branched C1 to C8 alkyl, n=1 to 6; and
L is a polyfunctionnalized spacer ligand comprising a radical R 0 bearing q groups A, wherein
q is a integer ranging from 2 to 6;
each occurrence of A is independently:
(i) a carboxylate

(ii) a phosphonate

(iii) an imidazolate

wherein R A1 is a hydrogen atom or a C1-C6 alkyl group;
wherein * denotes the point of attachment of the group A to the radical R 0 ;
wherein # denotes the possible points of attachment of the group A to the metal ion M;
R 0 represents
(i) a C1-12 alkyl, C2-12 alkene or C2-12 alkyne radical;
(ii) a fused or non-fused monocyclic or polycyclic aryl radical, comprising 6 to 50 carbon atoms;
(iii) a fused or non-fused monocyclic or polycyclic heteroaryl, comprising 4 to 50 carbon atoms;

the R 0 radical being optionally substituted by one or more groups independently chosen in the group comprising OH, NH 2 , NO 2 or a C1-C6 alkyl radical.
with a polymer-precursor solution comprising an adhesion primer, and at least one polymerizable monomer;

under conditions enabling the formation of radical entities.

3 . Process according to claim 1 , wherein the conditions enabling the formation of radical entities comprise the use of a reducing agent, preferably iron powder.

4 . Process according to claim 1 , wherein the solvent of the polymer-precursor solution is water, deionized water, distilled water, acidified or not, acetic acids, hydroxylated solvents such as ethanol, low-molecular-weight liquid glycols such as ethyleneglycol and mixtures thereof.

5 . Process according to claim 1 , wherein the adhesion primer is selected from clivable aryl diazonium salts, aryl ammonium salts, aryl phosphonium salts and aryl sulfonium salts, preferably the adhesion primer is a 4-nitrobenzene diazonium salt.

6 . Process according to claim 1 , wherein said adhesion primer is a clivable diazonium salts of Formula (II)
R—N 2 +′ A −

wherein,
A − represents a monovalent anion,
R represents an aryl group,

preferably, the adhesion primer is a 4-nitrobenzene diazonium salt.

7 . Process according to claim 1 , wherein the polymerizable monomer is selected from any radical polymerizable alkene comprising (meth)acrylate, styrenic, acrylamide or diene and derivatives thereof; preferably the radical polymerizable monomer is (meth)acrylate based monomer; more preferably is poly(ethyleneglycol)methyl ether acrylate or hydroxyethylmethacrylate.

8 . Process according to claim 1 , wherein the polymer-precursor solution comprises a precursor of adhesion primer, said precursor of adhesion primer allowing in situ synthesis of adhesion primer before contacting with a porous solid.

9 . Porous solid with an outer surface modified by a polymer, wherein the size of the pores is modified by at most 20%, as measured preferably by BET.

10 . Porous solid with an outer surface grafted with a polymer according to claim 9 , where the polymer was simultaneously synthetized and grafted onto said outer surface, through contact of:
a porous solid; and a polymer-precursor solution comprising an adhesion primer, and at least one polymerizable monomer;
under conditions enabling the formation of radical entities.

11 . Porous solid with an outer surface grafted with a polymer according to claim 10 , where the polymer was simultaneously synthetized and grafted onto said outer surface, through contact of a porous solid comprising a three-dimensional succession of units of formula (I)
M m O k X l L p
wherein
M is a metal ion selected from the group comprising Fe 2+ , Fe 3+ , Zn 2+ , Zn 4+ , Ti 4+ , Zr 4+ , Ca 2+ , Cu 2+ , Gd 3+ , Mn 2+ , Mn 3+ , Mg 2+ , Ag + , Si 4+ and Al 3+ ;
m, k, l and p are numbers ≧0 chosen so as to respect the charge neutrality of the unit; preferably, m, k, l and p are independently 0 to 4, for example m and p are independently 1, 2 or 3 and/or k and l are independently 0 or 1;
X is a ligand selected from the group comprising OH − , Cl − , F − , I − , Br − , SO 4 2− , NO 3 − , ClO 4 − , R 1 —(COO) n − , R 1 —(SO 3 ) n − , R 1 —(PO 3 ) n − , in which R 1 is a hydrogen atom, a linear or branched C1 to C8 alkyl, n=1 to 6; and
L is a polyfunctionnalized spacer ligand comprising a radical R 0 bearing q groups A, wherein
q is a integer ranging from 2 to 6;
each occurrence of A is independently:
(i) a carboxylate

(ii) a phosphonate

(iii) an imidazolate

wherein R A1 is a hydrogen atom or a C1-C6 alkyl group;
wherein * denotes the point of attachment of the group A to the radical R 0 ;
wherein # denotes the possible points of attachment of the group A to the metal ion M;
R 0 represents
(i) a C1-12 alkyl, C2-12 alkene or C2-12 alkyne radical;
(ii) a fused or non-fused monocyclic or polycyclic aryl radical, comprising 6 to 50 carbon atoms;
(iii) a fused or non-fused monocyclic or polycyclic heteroaryl, comprising 4 to 50 carbon atoms;

the R 0 radical being optionally substituted by one or more groups independently chosen in the group comprising OH, NH 2 , NO 2 or a C1-C6 alkyl radical;
with a polymer-precursor solution comprising an adhesion primer, and at least one polymerizable monomer;

under conditions enabling the formation of radical entities.

12 . Device comprising a porous solid with an outer surface modified by a polymer, wherein the size of the pores is modified by at most 20%, as measured preferably by BET, such as, for example, a

Assignees

• Commissariat Energie Atomique
• Centre Nat Rech Scient
• Univ Versailles Saint Quentin En Yvelines
• Univ Paris Sud 11

Inventors

• Berthelot Thomas
• Bellido Vera Elena
• Gref Ruxandra
• Horcajada Cortes Patricia
• Serre Christian
• Couvreur Patrick

Classifications

• C08F220/10 Primary

  Esters · CPC title

• A61L31/16

  Biologically active materials, e.g. therapeutic substances {(A61L31/047 takes precedence)} · CPC title

• A61K31/522

  having oxo groups directly attached to the heterocyclic ring, e.g. hypoxanthine, guanine, acyclovir · CPC title

• A61L31/048

  obtained by reactions only involving carbon-to-carbon unsaturated bonds (A61L31/041 takes precedence) · CPC title

• A61K47/48869 Primary

  Human Necessities · mapped topic