Actinic Radiation Curable Polymeric Mixtures, Cured Polymeric Mixtures And Related Processes

An additive manufacturing process for producing a cured polymeric product in the form of a tire tread, comprising providing an additive manufacturing device comprising a source of actinic radiation, an exterior support structure, an interior tank capable of containing a liquid mixture, and an interior support structure,

• providing a liquid mixture comprising an actinic radiation curable polymeric mixture comprising:
• (a) a polyfunctionalized diene monomer-containing polymer
• (i) having monomers selected from at least one of:
• 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, farnescene, and substituted derivatives of each of the foregoing,
• (ii) meeting at least one of the following:
• having a Mn of about 3,000 to about 135,000 grams/mole (polystyrene standard) or a Tg of about −105 to about −10° C.,
• (iii) and having the formula:
• [P][F]n where P represents a diene polymer chain, F represents a functional group comprising cyanoacrylate, epoxide, aziridine, or thioepoxide, n is 2 to about 15, and each F can be the same or different;
• (b) optionally a chain extender based upon F or reactive with F;
• (c) at least one actinic radiation sensitive;
• (d) optionally, a photosensitizer;
• and
• (e) a polyfunctional crosslinker reactive with F
• to the interior tank,
• repeatedly forming upon a support structure a layer from the liquid mixture, and using actinic radiation to cure each layer,
• thereby producing the cured polymeric product in the form of a tire tread,
• wherein at least one of the following is met:
• (ai) the polyfunctionalized diene monomer-containing polymer (a) is present in an amount of 1-100 parts and (b) is present in an amount of 0-99 parts;
• (aii) the at least one actinic sensitive photoinitiator (c) is present in an amount of about 1 part to about 10 parts (per 100 total parts of (a) and (b));
• or
• (aiii) the photosensitizer (d) is present in an amount of about 0.1 parts to about 5 parts (per 100 total parts of (a) and (b)).

An additive manufacturing process for producing a cured polymeric product in the form of a tire tread, comprising providing an additive manufacturing device comprising a source of actinic radiation, an exterior support structure, an interior tank capable of containing a liquid mixture, and an interior support structure,

• providing a liquid mixture comprising an actinic radiation curable polymeric mixture comprising:
• (a) a polyfunctionalized diene monomer-containing polymer comprising 1,3-butadiene monomers,
• (ii) meeting at least one of the following:
• having a Mn of about 3,000 to about 135,000 grams/mole (polystyrene standard) or a Tg of about −105 to about −10° C.,
• (iii) and having the formula:
• [P][F]n where P represents a diene polymer chain, F represents a functional group comprising cyanoacrylate, epoxide, aziridine, or thioepoxide, n is 2 to about 15, and each F can be the same or different;
• (b) optionally a chain extender based upon F or reactive with F;
• (c) at least one actinic radiation sensitive photoinitiator selected from the group consisting of a benzophenone, an aromatic α-hydroxyketone, a benzilketal, an aromatic α-aminoketone, a phenylglyoxalic acid ester, a mono-acylphosphinoxide, a bis-acylphosphinoxide, and a tris-acylphosphinoxide, and combinations thereof;
• (d) optionally, a photosensitizer;
• and
• (e) a polyfunctional crosslinker reactive with F and selected from the group consisting of polyol (meth)acrylates prepared from an aliphatic diol, triol, or tetraol containing 2-100 carbon atoms;
• polyallylic compounds prepared from an aliphatic diol, triol or tetraol containing 2-100 carbon atoms;
• polyfunctional amines;
• or combinations thereof
• to the interior tank,
• repeatedly forming upon a support structure a layer from the liquid mixture, and
• using actinic radiation to cure each layer,
• thereby producing the cured polymeric product in the form of a tire tread,
• wherein at least one of the following is met:
• (ai) the polyfunctionalized diene monomer-containing polymer (a) is present in an amount of 1-100 parts and (b) is present in an amount of 0-99 parts;
• (aii) the at least one actinic sensitive photoinitiator (c) is present in an amount of about 1 part to about 10 parts (per 100 total parts of (a) and (b));
• or
• (aiii) the photosensitizer (d) is present in an amount of about 0.1 parts to about 5 parts (per 100 total parts of (a) and (b)).