Giant macromolecules: copolydendrimers containing heteroatoms

Abstract

A synthesis method includes synthesising copolydendrimers containing heteroatoms from at least two dendrimers as starting precursors.

Claims

1. A method comprising manufacturing nanospherical copolydendrimers forming a three-dimensional network by combining together two or more different dendrimers, wherein the two or more different dendrimers used during co-condensation include at least one heteroatom containing dendrimer that comprises terminal amine functions on a surface thereof and wherein the two or more different dendrimers include at least one heteroatom containing dendrimer that contains a photo-active molecule of viologen, spiropyran, or anthraquinone type.

2. The method according to claim 1, wherein the two or more different dendrimers used during co-condensation include a second heteroatom containing dendrimer that comprises reactive functions on a surface thereof, the reactive function being aldehyde, carboxylic acid, methyl ester, anhydride, or acid chloride functions.

3. The method according to claim 1, wherein the two or more different dendrimers include heteroatom containing amine, aldehyde and acid terminated dendrimers and the heteroatom containing amine, aldehyde and acid terminated dendrimers used during polycondensation are of generation 0 to 10.

4. The method according to claim 1, comprising a polymeric co-condensation of different heteroatom containing dendrimers that is carried out in the absence of catalyst, in the presence of a metal catalyst, a thermal, photochemical or radical initiator.

5. The method according to claim 1, wherein a core of at least one heteroatom containing dendrimer is of cyclotriphosphazene, cyclotetraphosphazene, thiophosphine type.

6. The method according to claim 1, wherein the copolydendrimers obtained are used as additives in photochromic, electrochromic and thermochromic glasses, in paints, in photovoltaic cells, in fuel cells and in nanocomposite nanotechnologies.

Description

(1) By distinction with conventional polymers (FIG. 1a), the design of copolymers (also called block polymers) developed until now has shown that the cohabitation of several segments in the same polymeric backbone confers on the final polymer the initial properties of each block (FIG. 1b). If in addition the starting blocks are complex, their combination in the final material should lead to a holistic accumulation of properties. In other words, the final polymer will not only inherit the properties of the starting elements but will also generate properties that will be specific thereto. For example, these polymers may have intuitively the reactivity of the starting entities but have in addition hierarchical porosity, preferential orientation, hydrophobicity and enhanced stability. All these elements are of great interest in the technology of polymers, their formulation and the synthesis of new materials and nanocomposites.

(2) For example, to increase the macromolecular complexity of an edifice, dendrimers have been grafted onto the side chains of linear polymers (FIG. 1c). Hyperbranched dendrimers have also been synthesised by cross-linking. However, these works only disclose an extension to already known macromolecules. Indeed, no work has concerned the synthesis of three-dimensional structures by polymerisation of two or more dendritic globules containing heteroatoms (FIG. 1d).

(3) The inventors have developed a method for synthesising poly-structured macromolecules and also a new class of giant macromolecules by polymerisation of entities having great molecular complexity, in this particular instance dendrimers. The polymers that result therefrom are called copolydendrimers.

DESCRIPTION OF THE INVENTION

(4) A first aspect of the invention consists in the preparation of new dendritic copolymers combined together by a new synthesis method.

(5) According to a second aspect of the invention, the preparation of copolydendrimers by radical polymerisation or by polymeric co-condensation of two or more different dendrimers containing heteroatoms is reported.

(6) According to a third aspect of the invention, the copolymerisation of at least two different dendrimers containing heteroatoms is reported, said copolymerisation taking place in the absence of metal as catalyst.

(7) A fourth aspect of the invention relates to the polymeric co-condensation of at least two different dendrimers containing heteroatoms and having respectively aldehyde groups and amine groups.

(8) According to a fifth aspect of the invention, the polymeric co-condensation of at least two different dendrimers containing heteroatoms and having respectively carboxylic acid groups and amine groups is described.

(9) According to a sixth aspect of the invention, the polymeric co-condensation by radical process of at least two different dendrimers containing heteroatoms is provided.

(10) According to a seventh aspect of the invention, the use of different generations of dendrimers in the polymeric co-condensation of several heteroatom containing dendrimers is provided.

(11) According to an eighth aspect of the invention, the use of dendrimers with phosphorous, nitrogen, and sulphur groups is provided.

(12) According to a ninth aspect of the invention, the use in these polymeric co-condensations, of phosphorous, nitrogen and sulphur dendrimers, containing a molecule of viologen is provided.

BRIEF DESCRIPTION OF THE FIGURES

(13) FIG. 1. Illustration of different existing polymeric structures (a-c) and the structure forming the subject matter of the present invention (d).

(14) Table 1. Table describing the combinations having made it possible to access the copolydendrimers and specifying the number of phosphorous atoms contained in the final polymer.

(15) FIG. 2. Representative diagram of amine terminated, aldehyde terminated or carboxylic acid terminated dendrimers.

(16) FIG. 3. Description of the copolymerisation of the aforementioned entities.

(17) FIG. 4. Charter of units used for the synthesis of copolydendrimers.

NON-LIMITING EXAMPLE OF PREPARATION OF COPOLYDENDRIMERS

(18) TABLE-US-00001 TALBE 1 Number of NMR NMR Dendrimer Dendrimer phosphorus .sup.31P .sup.31P Polydendrimer 1 2 units core P = S P1 1-.sub.NNH2 1-.sub.CHO 2 9.33 17.31 P2 2-.sub.NNH2 2-.sub.CHO 6 8.35 56.47 P3 2-.sub.NNH2 3-.sub.CHO 7 8.52 57.14 P4 3-.sub.NNH2 Vio-.sub.CHO 6 10.63 57.67 P5 1-.sub.NNH2 1-.sub.COOH 3 9.13 60.73 27.79 P6 1-.sub.NNH2 2-.sub.COOH 4 9.14 61.78 27.27

(19) P.sub.1: To a solution of the dendrimer 1-.sub.NNH2 (20 mg, 4.94 10.sup.−5 mol) in 3 mL of THF is added a solution of the dendrimer 1-.sub.CHO (42.5 mg, 4.93 10.sup.−5 mol) in 5 mL of THF. The mixture is left under stirring at ambient temperature for 48 hours. After filtration, the solid is washed with THF then ethanol and finally with acetone. The polydendrimer P.sub.1 is obtained in the form of a white powder. .sup.13C NMR (100 MHz) δ 31.18 (N-Me), 121.15 (C.sub.6H.sub.4), 127.70 (C.sub.6H.sub.4), 128.63 (C.sub.6H.sub.4), 133.50 (CH═N and (C.sub.6H.sub.4)), 150.05 (C.sub.6H.sub.4), 154.71 (C.sub.6H.sub.4); .sup.31P NMR (162 MHz) δ 9.33 (N.sub.3P.sub.3—O), 17.31 (N.sub.3P.sub.3—N).

(20) P.sub.2: To a solution of the dendrimer 2-.sub.NNH2 (40 mg, 5.94 10.sup.−6 mol) in 4 mL of THF is added a solution of the dendrimer 2-.sub.CHO (34 mg, 1.19 10.sup.−5 mol) in 6 mL of THF. The reaction mixture is left under stirring at ambient temperature for 48 hours. After filtration, the solid is washed with THF, ethanol then acetone. The polydendrimer P.sub.2 is obtained in the form of a white powder. .sup.13C NMR (100 MHz) δ 32.35 (N-Me), 121.32 (C.sub.6H.sub.4), 128.05 (C.sub.6H.sub.4 and C.sub.6H.sub.5), 132.89 (CH═N, C.sub.6H.sub.5 and C.sub.6H.sub.4), 151.17(C.sub.6H.sub.4); .sup.31P NMR (162 MHz) δ 8.35 (N.sub.3P.sub.3 and PPh.sub.2), 56.47 (P═S).

(21) P.sub.3: To a solution of the dendrimer 2-.sub.NNH2 (40 mg, 5.94 10.sup.−6 mol) in 4 mL of THF is added a solution of the dendrimer 3-.sub.CHO (40.5 mg, 5.91 10.sup.−6 mol) in 4 mL of THF. The reaction mixture is left under stirring at ambient temperature for 48 hours. After filtration, the precipitate is washed with THF, ethanol then with acetone. The polydendrimer P.sub.3 is obtained in the form of a white powder. .sup.13C NMR (100 MHz) δ 32.13 (N-Me), 121.42 (C.sub.6H.sub.4), 128.17 (C.sub.6H.sub.4, C.sub.6H.sub.5), 132.49 (CH═N, C.sub.6H.sub.5 and C.sub.6H.sub.4), 151.14 (C.sub.6H.sub.4); .sup.31P NMR (162 MHz) δ 8.52 (N.sub.3P.sub.3, PPh.sub.2), 57.14 (P═S).

(22) P.sub.4: To a solution of the dendrimer 3-.sub.NNH2 (40 mg, 2.74 10.sup.−6 mol) in 5 mL of acetone is added a solution of Vio-.sub.CHO (45 mg, 6.58 10.sup.−5 mol) in 6 mL of acetone. The mixture is left under stirring at ambient temperature for 72 hours then filtered and the precipitate is washed with acetone. The polydendrimer P.sub.4 is obtained in the form of an orange powder. .sup.13C NMR (100 MHz,) δ 32.06 (N-Me), 64.43 (N—CH.sub.2), 122.38 (C.sub.6H.sub.4, NC.sub.5H.sub.4), 129.00 (C.sub.6H.sub.5, C.sub.6H.sub.4, NC.sub.5H.sub.4), 130.11 (C.sub.6H.sub.4, NC.sub.5H.sub.4), 132.07 (C.sub.6H.sub.4, NC.sub.5H.sub.4), 137.75 (CH═N, C.sub.6H.sub.5 and (C.sub.6H.sub.4), 145.48 (NC.sub.5H.sub.4), 151.39 (C.sub.6H.sub.4, NC.sub.5H.sub.4), 153.69 (C.sub.6H.sub.4, NC.sub.5H.sub.4); .sup.31P NMR (162 MHz,) δ-143.96 (hept, J═702.6 Hz, PF.sub.6), 10.70 (N.sub.3P.sub.3, PPh.sub.2), 57.23 (P═S).

(23) P.sub.5: To a mixture of 1-.sub.COOH (20 mg, 5.95 10.sup.−6 mol), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (15 mg, 7.85 10.sup.−5 mol) and dimethylaminopyridine (9 mg, 7.4 10.sup.−5 mol) in 10 mL of THF is added a solution of the dendrimer 1-.sub.NNH2 (4.8 mg, 1.19 10.sup.−5 mol). The mixture is left under stirring at ambient temperature for 120 hours. After filtration, the residue is washed with THF and CH.sub.2Cl.sub.2. The polydendrimer P.sub.5 is obtained in the form of a white powder. .sup.13C NMR (100 MHz) δ 35.52 (N—CH.sub.3), 39.73 (N-Me), 121.03 (C.sub.6H.sub.4), 122.04 (C.sub.6H.sub.4), 132.03 (C.sub.6H.sub.4), 138.75 (CH═N and (C.sub.6H.sub.4), 140.41 (C.sub.6H.sub.4), 151.24 (C.sub.6H.sub.4), 167.10 (C.sub.6H.sub.4); .sup.31P NMR (162 MHz) δ 9.13 (N.sub.3P.sub.3—O), 27.79 (N.sub.3P.sub.3—N), 60.73 (P═S).

(24) P.sub.6: To a mixture of the dendrimer 2-.sub.COOH (60 mg, 7.63 10.sup.−6 mol), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (38 mg, 2.10 10.sup.−4 mol) and dimethylaminopyridine (22 mg, 1.83 10.sup.−5 mol) in 20 mL of THF is added a solution of the dendrimer 1-.sub.NNH2 (12 mg, 2.96 10.sup.−5 mol). The reaction mixture is left under stirring for 120 hours at ambient temperature. After filtration, the residue is washed with THF and CH.sub.2Cl.sub.2. The polydendrimer P.sub.6 is obtained in the form of a white powder. .sup.13C NMR (100 MHz) δ 40.76 (N-Me), 122.39 (C.sub.6H.sub.4), 131.99 (C.sub.6H.sub.4), 139.99 (C.sub.6H.sub.4), 151.19 (C.sub.6H.sub.4), 168.22 (CON); Solid state .sup.31P NMR (162 MHz) δ 5 9.14 (N.sub.3P.sub.3—O), 27.27 (N.sub.3P.sub.3—N), 61.78 (P═S).