Patent Application
20090023891
This invention relates to amorphous polyester copolymer compositions, as disclosed in U.S. Pat. No. 5,705,575, which surprisingly have self healing and shape memory properties. There is a need for materials with such properties, and this invention is a treatment method for imparting self healing and shape memory properties to said amorphous copolyester copolymers (hereinafter referred to as CBDO copolymer(s)) of said U.S. Pat. No. 5,705,575.
A method has been discovered for treating an amorphous CBDO copolymer as described in U.S. Pat. No. 5,705,575 incorporated by reference above which comprises heating said copolymer to a temperature above its glass transition temperature. At this temperature, dents, bends, scratches, and other deformations will disappear, and the copolymer will return to its original shape and condition.
Applicants have discovered that compositions made according to U.S. Pat. No. 5,705,575 will display self healing and shape memory properties when undergoing treatment which involves heating the CBDO polymer to a temperature above its glass transition temperature. This discovery is unexpected since the CBDO polymer is an amorphous linear polymer with no crosslinks. The article by Behl et al. that reviews the current knowledge about shape memory polymers points out two main mechanisms that lead to shape memory. These include crosslinking and crystalline domains that act like crosslinks, neither of which exist in the CBDO polymer.
The examples clearly show that the CBDO copolymers display self healing and shape memory properties when heated above their glass transition temperature (Tg).
Also, it has been discovered that the cis:trans isomer content of the CBDO copolymer product affects the resulting self healing and shape memory as well. As the examples below will show, applicants tested two materials made according to the U.S. Pat. No. 5,705,575. In one, the cis:trans isomer ratio was 46/54 percent. Another had a cis:trans isomer ratio of 18/82 percent.
The examples clearly show that the superior self healing and shape memory were only observed in the polymer containing the higher cis:trans ratio. The useful copolymers of the invention are those wherein the cis isomer is present in an amount effective to yield a high level of self healing and shape memory when treated similarly to Example 1. This amount of cis isomer is referred to as “an effective amount of cis isomer.”
A strand of CBDO copolymer was bent repeatedly at right angles to form a square coil. This coil was placed on the lab bench and gently heated with a heat gun. As the polymer reached a temperature just above its Tg it straightened and resumed its former shape.
An eighth inch thick plaque of CBDO copolymer was struck with a Garner impact tester. This left a hemispherical indention approximately 0.5 cm deep. The plaque was then heated with a heat gun until just above the copolymer's Tg at which time the indention disappeared and the plaque returned to its previous perfectly planar shape.
A plaque like the one in example 2 was scored with a stylus to leave a distinct scratch on the surface. The plaque was then heated with a heat gun to just above the Tg of the copolymer, and the scratch self healed and disappeared.
A strand of CBDO copolymer with a cis:trans isomer ratio of about 18:82 percent was treated as in Example 1. The sample, when bent at a right angle and then heated to above its Tg, recovered only 30% where higher cis containing polymer recovers 100% of its original shape.
This application claims priority pursuant to 35 U.S.C. 119 to provisional U.S. Patent Application Ser. No. 60/959,518 entitled “SELF-HEALING AND SHAPE MEMORY IN CBDO COPOLYMERS,” filed Jul. 16, 2007. Commonly assigned US Application Docket No. 3031-P002US filed on even date herewith also relates to amorphous polyester copolymers compositions. This application hereby incorporates by reference U.S. Pat. No. 5,705,575, issued Jan. 6, 1998, in its entirety. This application hereby incorporates by reference the following U.S. patents: Patent No.Issue DateTitle7,193,029Mar. 20, 2007Sulfonated CopolyetheresterCompositions from HydroxyalkanoicAcids and Shaped Articles ProducedTherefrom7,169,860Jan. 30, 2007Amorphous-crystalline BlockCopolymers6,657,044Dec. 2, 2003Process For MakingPolytrimethylene Terephthalate6,287,656Sep. 11, 2001Low Melt Viscosity AmorphousCopolyesters Having ImprovedResistance to Lipids6,242,558June 5, 2001Modified PolytrimethyleneTerephthalate6,120,889Sep. 19, 2000Low Melt Viscosity AmorphousCopolyesters With Enhanced GlassTransition Temperatures6,037,424Mar. 14, 2001Clear Blends of Polycarbonates AndPolyesters5,705,575Jan. 6, 1998Copolyester Composition5,256,758Oct. 26, 1993Thermosetting Coating Compositions This application hereby incorporates by reference the following U.S. patent Application Publications: PatentPublicationNo.DateTitle2007/Nov. 29, 2007Process For the Preparation of0276065Copolyesters Based on2,2,4,4-tetramethyl-1,3-cyclobutanediolAnd 1,4-Cyclohexanedimethanol2007/Oct. 4, 2007Certain Polyester Compositions Which0232778Comprise Cyclobutanediol,Cyclohexanedimethanol, and High Trans-cyclohexanedicarboxylic Acid2006/Dec. 28, 2006Polyester Compositions Containing0293495Cyclobutanediol Having a CertainCombination Of Inherent Viscosityand Moderate Glass TransitionTemperature And Articles Made Therefrom2006/Dec. 21, 2006Polyester Compositions Containing High0287494Amounts of Cyclobutanediol and ArticlesMade Therefrom2006/Dec. 21, 2006Thermoformed SHEET(S) Comprising0287493Polyester Compositions Which CompriseCyclobutanediol2006/Oct. 12, 2006Amorphous Copolyesters0229430 This application hereby incorporates by reference the following foreign patent applications: Publication No.Publication DateTitleWO 03008477Jan. 30, 2003Amorphous CopolyestersEP 0745628Apr. 12, 1996Copolyester Composition Publications of interest: AuthorTitle/PublicationBooth,Copolyterephthalates containing tetramethylcyclobutaneChad J. et alwith impact and ballistic properties greater thanbisphenol A polycarbonate, Polymer, Volume 47, Issue18, Aug. 23, 2006, pp. 6398-6405.Behl,Shape-memory Polymers, Materials Today, April 2007,Marc et al.Volume 10, No. 4, pp. 20-28.Beall,Physical properties of CBDO based copolyterephthalateGary W. et alnanocomposites, Applied Clay Science, Volume 37,Issues 3-4, September 2007, pp. 295-306.Londa,Nanocomposites: New Materials and New Paradigms,Dr. MichelleNanotechnology Colloquium presentation and videoconference, Jan. 22, 2007,http://www.nanotxstate.org/20070122 event.htm
The U.S. Government has a paid-up license in this invention and the right in limited circumstances to require the patent owner to license others on reasonable terms as provided for by the terms of Contract No. NAVAIR N68335-07-C-0040 awarded by the United States Naval Air Systems Command.
| Number | Date | Country | |
|---|---|---|---|
| 60959518 | Jul 2007 | US |
