Actinic radiation curable polymeric mixtures, cured polymeric mixtures and related processes

1. A process for producing a cured polymeric product, 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 an actinic radiation curable polymeric mixture to the interior tank, wherein the actinic radiation curable polymeric mixture comprises

(a) a polyfunctionalized diene monomer-containing polymer having a formula as follows:

[P][F] n where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F is selected from the group consisting of cyanoacrylate, epoxide, aziridine, thiopeoxide, and combinations thereof;

(b) optionally a chain extender based upon F or reactive with F;

(c) at least one actinic radiation sensitive photoinitiator;

(d) optionally, a photosensitizer; and

(e) a polyfunctional crosslinker reactive with F,

wherein the polyfunctionalized diene monomer-containing polymer (a) is present in an amount of 1-100 parts, the chain extender (b) is present in an amount of 0-99 parts, and the at least one actinic radiation sensitive photoinitiator (c) is present in an amount of about 1 part to about 10 parts (per 100 total parts of (a) and (b)),

repeatedly forming upon a support structure a layer from the actinic radiation curable polymeric mixture, and

using actinic radiation to cure each layer,

thereby producing the cured polymeric product.

2. The process of claim 1 , wherein the actinic radiation curable polymeric mixture is curable by UV-VIS light.

3. The process of claim 1 , wherein

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)).

4. The process of claim 1 , wherein at least one of the following is met:

(i) each F comprises epoxide, or thioepoxide.

5. The process of claim 1 , wherein F comprises cyanoacrylate.

6. The process of claim 1 , wherein at least one of the following is met:

(i) the diene polymer chain comprises monomers selected from at least one of: acyclic and cyclic dienes having 3 to about 15 carbon atoms;

(ii) the polyfunctionalized diene monomer-containing polymer has a Tg of about −105 to about −10° C.;

(iii) the diene polymer chain comprises 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; or

(iv) in addition to (ii) above the diene polymer chain further comprises at least one vinyl aromatic monomer.

7. The process of claim 1 , wherein at least one of the following is met:

a. the polyfunctional crosslinker (e) is selected from 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; or

b. the polyfunctional crosslinker (e) is selected from at least one of: Trimethylolpropane tri(meth)acrylate, Pentaerythritol tetraacrylate, Pentaerythritol triacrylate, Trimethylolpropane ethoxylate triacrylate, Acrylated epoxidized soybean oil, Ditrimethylol Propane Tetraacrylate, Di-pentaerythritol Polyacrylate, Di-pentaerythritol Polymethacrylate, Di-pentaerythritol triacrylate, Di-pentaerythritol trimethacrylate, Di-pentaerythritol tetracrylate, Di-pentaerythritol tetramethacrylate, Di-pentaerythritol pent(meth)acrylate, Di-pentaerythritol hexa(meth)acrylate, Pentaerythritol Poly(meth)acrylate, Pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Pentaerythritol penta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, Ethoxylated glycerine triacrylate, F-Caprolactone ethoxylated isocyanuric acid triacrylate and Ethoxylated isocyanuric acid triacrylate, Tris(2-acryloxyethyl) Isocyanulate, Propoxylated glyceryl Triacrylate, ethyleneglycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol di(meth)acrylate, ethyleneglycol dimethacrylate (EDMA), polyethyleneglycol di(meth)acrylates, polypropyleneglycol di(meth)acrylates, polybutyleneglycol di(meth)acrylates, 2,2-bis(4-(meth)acryloxyethoxyphenyl) propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl) propane, di(trimethylolpropane) tetra(meth)acrylate, and combinations thereof.

8. The process of claim 1 , wherein at least one of the following is met when the chain extender (b) is present:

(i) the chain extender (b) comprises an (meth)acrylate monomer selected from C2 to about C18 alkyl functionalized (meth)acrylates;

(ii) the chain extender has a Tg of about −65 to about 10° C.; or

(iii) the chain extender (b) has a Mw of about 72.06 to about 135,000 grams/mole.

9. The process of claim 1 , wherein the photosensitizer (d) comprises at least one of a ketocoumarin, a xanthone, a thioxanthone, a polycyclic aromatic hydrocarbon, and an oximester derived from aromatic ketone.

10. The process of claim 1 , wherein at least one of the following is met:

a. the actinic radiation sensitive photoinitiator (c) comprises at least one 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;

b. the actinic radiation sensitive photoinitiator (c) is selected from benzophenone, benzildimethylketal, 1-hydroxy-cyclohexyl-phenyl-ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, (4-methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, (4-morpholinobenzoyl)-1-(4-methylbenzyl)-1-dimethylaminopropane, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl-indan-5-yl}-2-methyl-propan-1-one, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzyloxime), oligo[2-hydroxy-2-methyl-1-[4-methylvinyl]phenyl]propanone, 2-hydroxy-2-methyl-1-phenyl propan-1-one, and combinations thereof; or

c. the actinic radiation sensitive photoinitiator (c) comprises at least one of: a benzoin, an aryl ketone, an alpha-amino ketone, a mono- or bis(acyl)phosphine oxide, a benzoin alkyl ether, a benzil ketal, a phenylglyoxalic ester or derivatives thereof, an oxime ester, a per-ester, a ketosulfone, a phenylglyoxylate, a borate, and a metallocene.

11. The process of claim 1 , wherein the actinic radiation curable polymeric mixture further comprises at least one filler.

12. The process of claim 11 , wherein at least one of the following is met:

a. the at least one filler is present in an amount of up to about ⅔ of the total volume of the actinic radiation curable polymeric mixture; or

b. the at least one filler is present in an amount of about 40 to about 80 parts (based upon 100 total parts of (a) and (b)).

13. The process of claim 1 , wherein the actinic radiation curable polymeric mixture has a viscosity at 25° C. of about 1 to about 10,000 cps, preferably about 100 to about 5,000 cps.

14. The process of claim 1 , wherein the polyfunctionalized diene monomer-containing polymer has a Mn of about 500 to about 150,000 grams/mole based upon a polystyrene standard.

15. The process of claim 1 , wherein (a) and (b) are present in a total amount of 100 parts and (c) is present in a total amount of at least about 0.1 parts (based upon 100 parts of (a) and (b)).

16. The process of claim 1 wherein at least one of the following is met:

(i) each layer has a thickness of about 0.01 mm to about 1 mm;

(ii) the forming comprises solidifying each layer by using the actinic radiation to trace a pattern in the liquid material;

(iii) the forming comprises dispensing the mixture from a printing head having a set of nozzles;

(iv) the forming comprises using the actinic radiation to provide at least one pattern on the liquid material;

(v) the forming comprises using the actinic radiation to project at least one image on the liquid material;

(iv) the interior tank is capable of receiving a liquid mixture from at least one cartridge;

(v) the liquid mixture is provided in at least one cartridge; or

(vi) at least two cartridges are utilized with one cartridge comprising (a) and (b) and a second cartridge comprising (b) in combination with (c).

17. The process of claim 1 , wherein F comprises aziridine.

18. The process of claim 1 , wherein the diene polymer chain further comprises at least one vinyl aromatic monomer.

19. The process of claim 1 , wherein the cured polymeric product is a tire component.