Post polymerization cure shape memory polymers

• US 10,494,470 B2
• Filed: 12/21/2016
• Issued: 12/03/2019
• Est. Priority Date: 05/06/2010
• Status: Active Grant

• Current Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Original Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Inventors: Wilson, Thomas S., Hearon, Michael Keith, Bearinger, Jane P.
• Primary Examiner(s): Zemel, Irina S
• Application Number:
  US15/387,256
• Publication Number:
  US 20170198080A1
• Time in Patent Office: 1,077 Days
• CPC Class Codes: B29C 45/0001 characterised by the choice of material
• CPC Class Codes: B29C 48/00 Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor extrusion blow-moulding B29C49/04
• CPC Class Codes: B29C 48/03 characterised by the shape of the extruded material at extrusion
• CPC Class Codes: B29C 51/00 Shaping by thermoforming , i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor blow moulding of tubular preforms B29C49/00, deforming of tubular or hollow preforms B29C67/0014
• CPC Class Codes: B29C 51/002 characterised by the choice of material
• CPC Class Codes: B29C 61/06 Making preforms having internal stresses, e.g. plastic memory
• CPC Class Codes: B29C 67/20 for porous or cellular articles, e.g. of foam plastics, coarse-pored chemical aspects of working up macro-molecular substances to porous or cellular articles C08J9/00
• CPC Class Codes: B29C 71/02 Thermal after-treatment B29C71/0063 and B29C71/0072 take precedence
• CPC Class Codes: B29C 71/04 by wave energy or particle radiation , e.g. for curing or vulcanising preformed articles during moulding, e.g. in a mould B29C35/08
• CPC Class Codes: B29K 2075/00 Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2105/04 cellular or porous
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/673 containing two or more acrylate or alkylacrylate ester groups
• CPC Class Codes: C08G 18/675 Low-molecular-weight compounds
• CPC Class Codes: C08G 18/722 Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 18/83 Chemically modified polymers
• CPC Class Codes: C08G 2101/00 Manufacture of cellular products
• CPC Class Codes: C08G 2280/00 Compositions for creating shape memory
• CPC Class Codes: C08G 63/52 : Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation

Abstract

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Claims

1. Articles of manufacture comprising:

a polymer composition comprising a thermoplastic polymer, having crosslinkable sites spaced along a polymer chain, which when crosslinked form a thermoset polymer having shape memory properties; and

the thermoset polymer formed by crosslinking the thermoplastic polymer;

wherein the thermoplastic polymer is at least one of a porous structure or foam fabricated by at least one of freeze drying, high inverse phase emulsion foaming, physical blowing, pore templating, solution spinning, stereolithographic patterning, extrusion, injection molding, solution casting, dip coating, thermoforming, compression molding, film blowing, ink pen printing, 3 D microdot based printing, laser machining, or combinations thereof.

2. The articles of manufacture of claim 1 wherein the crosslinkable sites are double bonds.

3. The articles of manufacture of claim 1 wherein the thermoset polymer is formed by crosslinking the thermoplastic polymer by at least one of heat, electron beam radiation, or combinations thereof.

4. The articles of manufacture of claim 1 wherein the thermoplastic and thermoset polymers are polyurethanes.

5. The articles of manufacture of claim 4 wherein monomers for the thermoplastic polymer include at least one of hexamethylene diisocyanate;

trimethylhexamethylene diisocyanate;

dicyclohexylmethane 4,4′

diisocyanate;

trans-1,4-cyclohexylene diisocyanate;

1,5-Diisocyanato-2-methylpentane;

2-butene-1,4-diol;

1,4-butanediol;

1,6-hexanediol;

1,8-octanediol;

1,10-decanediol;

1,6-hexanediylbis[oxy(2-hydroxy-3,1-propanediyl)] bisacrylate;

bisphenol A glycerolate dimethacrylate;

3,4-dihydroxy-1-butene;

7-Octene-1,2-diol;

pentaerythritol triacrylate;

diethylene glycol;

diethanolamine;

hydroquinone bis(2-hydroxyethyl) ether;

triethylene glycol, 1-(benzyloxymethyl) triethylene glycol;

2,2′

-ethyliminodiethanol, or combinations thereof.

6. The articles of manufacture of claim 1 wherein the thermoplastic polymer has a backbone comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.

7. The articles of manufacture of claim 1 wherein the thermoplastic polymer has a side chain comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.

15. The articles of manufacture of claim 2 wherein monomers for the thermoplastic polymer include at least one of hexamethylene diisocyanate;

trimethylhexamethylene diisocyanate;

dicyclohexylmethane 4,4′

diisocyanate;

trans-1,4-cyclohexylene diisocyanate;

1,5-Diisocyanato-2-methylpentane;

2-butene-1,4-diol;

1,4-butanediol;

1,6-hexanediol;

1,8-octanediol;

1, 10-decanediol;

1, 6-hexanediylbis[oxy(2-hydroxy-3, 1-propanediyl)] bisacrylate;

bisphenol A glycerolate dimethacrylate;

3,4-dihydroxy-1-butene;

7-Octene-1,2-diol;

pentaerythritol triacrylate;

diethylene glycol;

diethanolamine;

hydroquinone bis(2-hydroxyethyl) ether;

triethylene glycol, 1-(benzyloxymethyl) triethylene glycol;

2,2′

-ethyliminodiethanol, or combinations thereof.

16. The articles of manufacture of claim 15 wherein the thermoplastic polymer has a backbone comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.

17. The articles of manufacture of claim 4 wherein the thermoplastic polymer has a backbone comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.

18. The articles of manufacture of claim 5 wherein the thermoplastic polymer has a backbone comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.

19. The articles of manufacture of claim 2 wherein the thermoplastic polymer has a backbone comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.

20. The articles of manufacture of claim 2 wherein the thermoplastic and thermoset polymers are polyurethanes.

21. The articles of manufacture of claim 20 wherein monomers for the thermoplastic polymer include at least one of hexamethylene diisocyanate;

trimethylhexamethylene diisocyanate;

dicyclohexylmethane 4,4′

diisocyanate;

trans-1,4-cyclohexylene diisocyanate;

1,5-Diisocyanato-2-methylpentane;

2-butene-1,4-diol;

1,4-butanediol;

1,6-hexanediol;

1, 8-octanediol;

1, 10-decanediol;

1,6-hexanediylbis[oxy(2-hydroxy-3, 1-propanediyl)] bisacrylate;

bisphenol A glycerolate dimethacrylate;

3,4-dihydroxy-1-butene;

7-Octene-1,2-diol;

pentaerythritol triacrylate;

diethylene glycol;

diethanolamine;

hydroquinone bis(2-hydroxyethyl) ether;

triethylene glycol, 1-(benzyloxymethyl) triethylene glycol;

2,2′

-ethyliminodiethanol, or combinations thereof.

22. The articles of manufacture of claim 21 wherein the thermoplastic polymer has a backbone comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.

23. The articles of manufacture of claim 21 wherein the thermoplastic polymer has a side chain comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.

24. The articles of manufacture of claim 1 wherein the thermoplastic polymer has crosslinkable sites substantially regularly spaced along the polymer chain.

25. The articles of manufacture of claim 1 wherein the thermoset polymer has:

(a) a glass transition temperature (Tg) between 25 degrees Celsius and 80 degrees Celsius, (b) a gel fraction of at least 90%, and (c) a percent strain recovery of at least 94%.

26. The articles of manufacture of claim 1 wherein the thermoset polymer has a glass transition temperature (Tg) between 37 and 42 degrees Celsius.

8. A method of making polymeric articles having shape memory properties comprising:

forming a thermoplastic linear or branched polymer having crosslinkable sites spaced along a polymer chain,

processing the thermoplastic polymer into a shape, the processing comprising fabricating the thermoplastic polymer into a porous structure or foam having the shape by at least one of freeze drying, high inverse phase emulsion foaming, physical blowing, pore templating, solution spinning, stereolithographic patterning, extrusion, ink pen printing, 3 D microdot based printing, injection molding, extrusion, solution casting, dip coating, thermoforming, compression molding, film blowing, laser machining, or combinations thereof; and

curing or crosslinking the thermoplastic polymer so that a thermoset polymer is formed that has the device shape and form as the permanent shape and may be made to take a stable secondary shape through the application of stress or strain at a temperature above its actuation transition, then held at the secondary shape while cooled to a temperature below its transition temperature.

9. The method of claim 8 wherein the curing or crosslinking includes a curing mechanism that includes at least one of:

(a) thermally or radiatively initiated radical crosslinking of vinyl groups,

(b) peroxide or sulfur based crosslinking of vinyl groups,

(c) thiol addition to vinyl,

(d) reaction of isocyanate containing curing agents with hydroxyl, carboxylic acid, or amine on the polymer chains,

(e) condensation of ester linkages,

(f) epoxy chemistry, silane and siloxane coupling reactions, or

(g) combinations thereof.

10. The method of claim 8 wherein the thermoplastic polymer is made from monomers, the monomers including at least one of hexamethylene diisocyanate;

trimethylhexamethylene diisocyanate;

dicyclohexylmethane 4,4′

diisocyanate;

trans-1,4-cyclohexylene diisocyanate;

1,5-Diisocyanato-2-methylpentane;

2-butene-1,4-diol;

1,4-butanediol;

1,6-hexanediol;

1,8-octanediol;

1,10-decanediol;

1,6-hexanediylbis[oxy(2-hydroxy-3,1-propanediyl)] bisacrylate;

bisphenol A glycerolate dimethacrylate;

3,4-dihydroxy-1-butene;

7-Octene-1,2-diol;

pentaerythritol triacrylate;

diethylene glycol;

diethanolamine;

hydroquinone bis(2-hydroxyethyl) ether;

triethylene glycol, 1-(benzyloxymethyl) triethylene glycol;

2,2′

-ethyliminodiethanol, or combinations thereof.

11. The method of claim 8 wherein the thermoplastic polymer has a backbone or side chain comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.

12. Articles of construction made by the method of claim 8.

13. The articles of claim 12 wherein the thermoplastic and thermoset polymers are polyurethanes.

14. The articles of claim 12 wherein the thermoplastic polymer has a backbone or side chain comprising, in the following order:

an electron withdrawing group, a methylene or methyne carbon in the alpha position to the electron withdrawing group, and an unsaturated carbon-carbon double bond in the beta position to the electron withdrawing group.