Degradable composite materials and uses

Patent metadata

Field	Value
Publication number	US-9617462-B2
Application number	US-201214369115-A
Country	US
Kind code	B2
Filing date	Dec 21, 2012
Priority date	Dec 28, 2011
Publication date	Apr 11, 2017
Grant date	Apr 11, 2017

Abstract

In general, the current application relates to degradable composite and blend materials that have accelerated degradation in water in low temperature conditions, and their various industrial, medical and consumer product uses. In some embodiments, the degradable composite composition comprises a degradable polymer mixed with discrete particles of a filler that acts to accelerate the degradation of the degradable polymer. Such materials degrade in 60 C water in less than 30 days, <14 days, and even <7 days. Various materials are provided that can degrade equally fast at lower temperatures, such as 50 C, or even 40 C.

First claim

What is claimed is:

1. A degradable composite composition comprising a degradable polymer mixed with discrete particles of a water soluble filler, a wax filler, or a reactive filler, said degradable composite degrading in 60° C. water in less than 30 days
wherein the composition further comprises a metal salt of a long chain fatty acid.

2. The degradable composite composition of claim 1 , wherein the discrete particles have a mean average size of from 10 nm to 5 micron.

3. The degradable composite composition of claim 1 , wherein the discrete particles have a protective coating.

4. The degradable composite composition of claim 1 , wherein the degradable polymer comprise aliphatic polyesters, poly(lactic acid) (PLA), poly(ε-caprolactone), poly(glycolic acid), poly(lactic-co-glycolic acid), poly(hydroxyl ester ether), polyhydroxyalkanoate (PHA), poly(hydroxybutyrate), poly(anhydride), polycarbonate, poly(amino acid), poly(ethylene oxide), poly(phosphazene), polyether ester, polyester amide, polyamides, sulfonated polyesters, poly(ethylene adipate), polyhydroxyalkanoate, poly(ethylene terephtalate), poly(butylene terephthalate), poly(trimethylene terephthalate), Poly(ethylene naphthalate) and copolymers, blends, derivatives or combination of any of these degradable polymers.

5. The degradable composite composition of claim 1 , wherein the degradable polymer comprises PLA.

6. The degradable composite composition of claim 1 wherein,
a. said water soluble filler comprises salt (NaCl), ZnCl 2 , CaCl 2 , MgCl 2 , NaCO 3 , KCO 3 , potassium phosphate (KH 2 PO 4 , K 2 HPO 4 , K 3 PO 4 ), and sulfonate salts such as sodium benzenesulfonate (NaBS), sodium dodecylbenzenesulfonate (NaDBS), water soluble/hydrophilic polymers, poly(ethylene-co-vinyl alcohol) and poly(vinyl alcohols) (PVOH), and the mixture of these fillers;
b. said wax comprises candelilla wax, carnauba wax, ceresin wax, Japan wax, microcrystalline wax, montan wax, ouricury wax, ozocerite, paraffin wax, rice bran wax, sugarcane wax, Silicon wax, Fischer-Tropsch wax, and
c. said reactive filler comprises a metal oxide, metal hydroxide, metal carbonate, Ca(OH) 2 , Mg(OH) 2 , CaCO 3 , Borax, MgO, CaO, ZnO, NiO, CuO, Al 2 O 3 , a base or a base precursor.

7. The degradable composite composition of claim 1 , wherein the long chain fatty acid comprises Zn octonoate, Zn stearate, Sn octonoate, Ca stearate, Li stearate, Ca octonoate, Sr octonoate, Co octonoate, Ni octonoate, Li octonoate or K octonoate.

8. A degradable composite composition, comprising a metal salt of a long chain fatty acid and a PLA mixed with discrete particles of either i) a water soluble material, ii) a wax filler, iii) a reactive filler, or iv) combinations thereof, said degradable composite degrading in 60° C. water in less than 14 days.

9. The composition of claim 8 , wherein the discrete particles being have a mean average size of from 10 nm to 5000 nm.

10. The composition of claim 8 , wherein the discrete particles comprise:
a. NaCl, ZnCl 2 , CaCl 2 , MgCl 2 , NaCO 3 , KCO 3 , KH 2 PO 4 , K 2 HPO 4 , K 3 PO 4 , NaBS, NaDBS, PEVOH PVOH and combinations thereof,
b. candelilla wax, carnauba wax, ceresin wax, Japan wax, microcrystalline wax, montan wax, ouricury wax, ozocerite, paraffin wax, rice bran wax, sugarcane wax, Silicon wax, Fischer-Tropsch wax, or
c. Ca(OH) 2 , Mg(OH) 2 , CaCO 3 , Borax, MgO, CaO, ZnO, NiO, CuO, Al 2 O 3 , a base or a base precursor.

11. A composition, comprising:
a. a matrix comprising a plurality of voids, said matrix comprising polylactic acid (PLA), polycarprolacton, polyglycolic acid (PGA), polylactic-co-polyglcolic acid (PLGA), or a mixture thereof;
b. a filler that fills in at least a portion of the plurality of the voids of said matrix;
c. wherein the filler comprises NaCl, ZnCl 2 , CaCl 2 , MgCl 2 , NaCO 3 , KCO 3 , KH 2 PO 4 , K 2 HPO 4 , K 3 PO 4 , NaBS, NaDBS, PEVOH, PVOH, candelilla wax, carnauba wax, ceresin wax, Japan wax, microcrystalline wax, montan wax, ouricury wax, ozocerite, paraffin wax, rice bran wax, sugarcane wax, Silicon wax, Fischer-Tropsch wax, Ca(OH) 2 , Mg(OH) 2 , CaCO 3 , Borax, MgO, CaO, ZnO, NiO, CuO, or Al 2 O 3 ; and
d. wherein the composition degrades in water at a temperature of below 60° C. in less than 2 weeks;
e. wherein the composition further comprises a metal salt of a long chain fatty acid.

12. The composition of claim 11 , wherein said filler is coated with a protective coating.

13. A method of using a degradable composite composition, comprising injecting a fluid comprising water, a metal salt of a long chain fatty acid and a degradable composite comprising a degradable polymer mixed with discrete particles of a water soluble filler, a wax filler, or a reactive filler, said degradable composite degrading in 60° C. water in less than 30 days into a subterranean reservoir; degrading said composition, and producing a hydrocarbon from said subterranean reservoir.

14. The method of claim 13 , wherein the discrete particles have a mean average size of from 10 nm to 5 micron.

15. The method of claim 13 , wherein the discrete particles have a protective coating.

16. The method of claim 13 , wherein the degradable polymer comprises PLA.

17. The method of claim 13 , wherein the discrete particles have a mean average size of from 30 nm-300 nm.

18. The method of claim 13 , wherein the degradable composite degrades in 60° C. water in less than 7 days.

Assignees

• Schlumberger Technology Corp

Inventors

• Tashiro Hitoshi
• Zhu S Sherry
• Tu Huilin
• Maheshwari Sudeep

Classifications

• C09K8/516 Primary

  characterised by their form or by the form of their components, e.g. encapsulated material · CPC title

• C09K8/50 Primary

  Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls (compositions for consolidating loose sand or the like around wells C09K8/56) · CPC title

• C08K3/22

  of metals · CPC title

• C08K2003/2296

  of zinc · CPC title

• C08K3/26

  Carbonates; Bicarbonates · CPC title