Hybrid materials and process for production thereof

1. A process for producing an inorganic/organic hybrid material comprising a polymeric component formed by ring opening polymerisation of cyclic monomer containing at least one ring heteroatom, the process comprising:

(i) forming a reaction mixture comprising cyclic monomer, optionally in the presence of solvent, and an epoxide compound comprising an epoxide ring and an inorganic component wherein the epoxide compound is an organosilicon epoxide;

(ii) adding catalyst to the reaction mixture to activate the epoxide compound and initiate cationic ring-opening polymerisation of the cyclic monomer; and

(iii) hydrolysis and condensation of the reaction mixture formed in step (ii) to produce an inorganic/organic hybrid material, wherein the material comprises covalent bonds between at least one component of the epoxide compound and the polymeric component;

wherein the cyclic monomer is tetrahydrofuran (THF), tetrahydropyran, tetrahydrothiophene, ε-caprolactone, β-propiolactone, γ-butyrolactone, p-dioxanone, N-methyl-2-pyrrolidone, 2-pyrrolidone (2-Pyrr), 3,6-Dimethyl-1,4-dioxane-2,5-dione, γ-thiobutyrolactone, ε-caprolactame, 2-methyl-2-oxazoline, 3-benzyl-1,3-oxazolidine-2-thione (BOT), 3-benzyl tetrahydro-1,3-oxazolidine-2-thione (BTOT), a cyclic siloxane, or a mixture thereof.

2. The process of claim 1 , wherein hydrolysis and condensation is achieved by addition of an acid and water to the reaction mixture formed in step (ii).

3. The process of claim 1 , wherein the process further comprises addition of an additional silica source to the reaction mixture.

4. The process of claim 3 , wherein the additional silica source is an alkylalkoxy silane, a tetraalkoxysilane, or a mixture thereof.

5. The process of claim 4 , comprising hydrolysis of the additional silica source prior to addition to the reaction mixture.

6. The process of claim 3 , wherein the monomer is tetrahydrofuran (THF), the epoxide is (3-glycidyloxypropyl)trimethoxysilane (GPTMS), no carboxylic acid is added to the reaction mixture and an additional silica source is added to the reaction mixture.

7. The process of claim 6 , wherein the process comprises the additional step of hydrolysis and condensation of the reaction mixture formed in step (ii) to produce an inorganic/organic hybrid material, wherein the hybrid material has an inorganic content of 2 to 70 wt %.

8. The process of claim 1 , wherein the epoxide is an (epoxyalkyl)alkoxysilane.

9. The process of claim 8 , wherein the (epoxyalkyl)alkoxysilane is (3-glycidyloxy-propyl)trimethoxysilane (GPTMS); (3-glycidyloxypropyl)triethoxysilane (GPTES); 3-(glycidoxy-propyl)ethyldiethoxysilane (GPMDES); 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (TRIMO); (3-glycidoxypropyl)-dimethylethoxysilane (GPMES); beta-(3,4-epoxycyclohexyl)ethyltriethoxysilane (EEES); beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (EEMS); or a mixture thereof.

10. The process of claim 1 , wherein the catalyst is selected from Brønsted Acids, Lewis Acids, carbenium ions, onium ions, or a mixture thereof.

11. The process of claim 1 , wherein the catalyst is selected from boron trifluoride (BF 3 ); boron trifluoride diethyletherate (BF 3 .OEt 2 ); a boron trifluoride complex; Iron(III) chloride (FeCl 3 ); Tin(IV) Chloride (SnCl 4 ); Antimony Pentafluoride (SbF 5 ); Fluorosulphuric acid (FSO 3 H); Trifluorosulfonic acid (CF 3 SO 3 H); Tetrafluoroborate (HBF 4 ); Scandium Triflate (Sc(OTf) 3 ); Ytterbium Triflate (Yt(OTf) 3 ); Trimethylsilyl trifluoromethanesulphonate (TMSOTf); Stannous octoate (Sn(Oct) 2 ); Sulphuric Acid (H 2 SO 4 ); Aluminium chloride (AlCl 3 ); and mixtures thereof.

12. The process of claim 1 , wherein the process comprises addition of a carboxylic acid to the reaction mixture prior to addition of catalyst and wherein the material further comprises an organic component formed by the carboxylic acid.

13. The process of claim 12 , wherein the carboxylic acid is selected from the group consisting of PCL-diCOOH of formula:

wherein each n is any integer value of 1 or greater, and X is

hexadecanedioic acid, hexanedioic acid, benzene-1,2-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, propionic acid, poly(ethylene glycol) bis(carboxymethyl) ether, polyglutamic acid, and a mixture thereof.

14. The process of claim 1 , wherein the process further comprises addition of one or more oxides, or oxide precursors, to the reaction mixture.

15. The process of claim 1 , wherein the monomer is tetrahydrofuran (THF), the epoxide is (3-glycidyloxypropyl)trimethoxysilane (GPTMS), a carboxylic acid is added to the reaction mixture and an additional silica source is added to the reaction mixture.

16. The process of claim 15 , wherein the carboxylic acid is PCL-diCOOH;

wherein X is

and each n is any integer value of 1 or greater, and the additional silica source is tetraethoxysilane (TEOS), and wherein the proportion of TEOS with respect to PCL-diCOOH is from 0 to 95% w/w.

17. The process of claim 1 , wherein the process further comprises 3D-printing of the material.

18. The process of claim 17 , wherein the process further comprises storing the material at a temperature below −40° C.