Thiol-ene polymerization with vinylesters and vinylcarbonate

A method for augmenting or filling a structure in a patient comprising,

• implanting the curable composition into said patient at a site of the structure;
• said curable composition comprising:
• (a) 60 wt. % to 95 wt. % of one or more vinylcarbonate monomers, wherein said one or more vinylcarbonate monomers are respectively selected from compounds of the general formula (II) below:
• wherein
• n and m independently range from 2 to 1000;
• R2 is independently selected from the group consisting of:
• (i) n-valent radicals, each of said n-valent radicals comprising a carbon chain or a carbon cycle or both,
• wherein said carbon chain and/or carbon cycle each, independently from one another, comprises from 1 to 30 carbon atoms,
• wherein said carbon chain can be straight, branched, saturated or unsaturated, and optionally containing one or more interspersed heteroatoms, said heteroatoms being selected from the group consisting of oxygen, sulfur and nitrogen, and/or
• wherein said carbon chain optionally being substituted with one or more substituents selected from the group consisting of —OH, —COOH, —CN, —CHO, and ═O,
• wherein said carbon cycle can be saturated or unsaturated, and optionally containing one or more interspersed heteroatoms, said heteroatoms being selected from the group consisting of oxygen, sulfur and nitrogen, and/or
• wherein said carbon cycle optionally being substituted with one or more substituents selected from the group consisting of —OH, —COOH, —CN, —CHO, and ═O, and
• (ii) n-valent radicals of biodegradable, biocompatible oligomers and polymers, said oligomers and polymers being selected from the group consisting of polysaccharides, polypeptides, polyamides, polyesters, polycarbonates, polyethers, and fatty acid derivatives;
• (b) 0.1 to 40 wt. % of one or more multifunctional thiols;
• and
• (c) 0 to 10 wt. % of a biocompatible polymerization initiator;
• initiating said curable composition to thereby form a resorbable, biocompatible polymer.

An biodegradable implant comprising:

• a copolymer having monomer units of:
• (a) 60 wt. % to 95 wt. % of one or more vinylcarbonate monomers, wherein said one or more vinylcarbonate monomers are respectively selected from compounds of the general formula (II) below:
• wherein
• n and m independently range from 2 to 1000;
• R2 is independently selected from the group consisting of:
• (i) n-valent radicals, each of said n-valent radicals comprising a carbon chain or a carbon cycle or both,
• wherein said carbon chain and/or carbon cycle each, independently from one another, comprises from 1 to 30 carbon atoms, from 3 to 25 carbon atoms, from 4 to 20 carbon atoms, or from 5 to 15 carbon atoms,
• wherein said carbon chain can be straight, branched, saturated or unsaturated, and optionally containing one or more interspersed heteroatoms, said heteroatoms being selected from the group consisting of oxygen, sulfur and nitrogen, and/or
• wherein said carbon chain optionally being substituted with one or more substituents selected from the group consisting of —OH, —COOH, —CN, —CHO, and ═O,
• wherein said carbon cycle can be saturated or unsaturated, and optionally containing one or more interspersed heteroatoms, said heteroatoms being selected from the group consisting of oxygen, sulfur and nitrogen, and/or
• wherein said carbon cycle optionally being substituted with one or more substituents selected from the group consisting of —OH, —COOH, —CN, —CHO, and ═O, and
• (ii) n-valent radicals of biodegradable, biocompatible oligomers and polymers, said oligomers and polymers being selected from the group consisting of polysaccharides, polypeptides, polyamides, polyesters, polycarbonates, polyethers, and fatty acid derivatives;
• and
• (b) a bioactive agent.

A method of manufacturing a three-dimensional article through an additive manufacturing process, said method comprising:

• (a) depositing a layer of a curable composition into a mold of three-dimensional article;
• said curable composition comprising:
• (i) 60 wt. % to 95 wt. % of one or more vinylcarbonate monomers, wherein said one or more vinylcarbonate monomers are respectively selected from compounds of the general formula (II) below:
• wherein
• n and m independently range from 2 to 1000;
• R2 is independently selected from the group consisting of:
• (i) n-valent radicals, each of said n-valent radicals comprising a carbon chain or a carbon cycle or both,
• wherein said carbon chain and/or carbon cycle each, independently from one another, comprises from 1 to 30 carbon atoms,
• wherein said carbon chain can be straight, branched, saturated or unsaturated, and optionally containing one or more interspersed heteroatoms, said heteroatoms being selected from the group consisting of oxygen, sulfur and nitrogen, and/or
• wherein said carbon chain optionally being substituted with one or more substituents selected from the group consisting of —OH, —COOH, —CN, —CHO, and ═O,
• wherein said carbon cycle can be saturated or unsaturated, and optionally containing one or more interspersed heteroatoms, said heteroatoms being selected from the group consisting of oxygen, sulfur and nitrogen, and/or
• wherein said carbon cycle optionally being substituted with one or more substituents selected from the group consisting of —OH, —COOH, —CN, —CHO, and ═O, and
• (ii) n-valent radicals of biodegradable, biocompatible oligomers and polymers, said oligomers and polymers being selected from the group consisting of polysaccharides, polypeptides, polyamides, polyesters, polycarbonates, polyethers, and fatty acid derivatives;
• (ii) 0.1 to 40 wt. % of one or more multifunctional thiols;
• and
• (iii) 0 to 10 wt. % of a biocompatible polymerization initiator;
• (b) directing an energy source to cause radical polymerization of the curable composition to thereby form a cross-section layer of the 3D object/article, the cross-section layer having a thickness ranging from about 0.001 mm to about 3 mm;
• and
• (c) repeating steps (a) and (b) to form the three-dimensional article in a layerwise fashion.