ZWITTERIONIC LIGNIN DERIVATIVES FOR MARINE ANTIFOULING COATINGS

• US 20130236630A1
• Filed: 03/07/2012
• Published: 09/12/2013
• Est. Priority Date: 03/07/2012
• Status: Active Grant

• Current Assignee: Empire Technology Development LLC (Allied Inventors Management, LLC)
• Original Assignee: Empire Technology Development LLC (Allied Inventors Management, LLC)
• Inventors: Brizius, Glen Leon
• Granted Patent: US 9,150,734 B2
• Time in Patent Office: Days
• US Class Current: 427/2.12
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: A01N 33/12 Quaternary ammonium compounds
• CPC Class Codes: A01N 41/10 Sulfones; Sulfoxides
• CPC Class Codes: C09D 101/02 Cellulose; Modified cellulose
• CPC Class Codes: C09D 103/02 Starch; Degradation products thereof, e.g. dextrin
• CPC Class Codes: C09D 105/14 Hemicellulose; Derivatives thereof
• CPC Class Codes: C09D 197/005 Lignin
• CPC Class Codes: C09D 197/02 Lignocellulosic material, e.g. wood, straw or bagasse
• CPC Class Codes: C09D 5/1656 characterised by the film-forming substance C09D5/1637 takes precedence

Abstract

Disclosed are antifouling compositions that can include a biopolymeric matrix which is substantially zwitterionic. The compositions may include a biopolymer matrix having positively charged functional groups, negatively charged functional groups, zwitterionic functional groups, or a combination thereof, such that the composition is substantially zwitterionic. The compositions can be used as additives and as compositions further containing a base material such as paint or lacquer. Methods of making and using such compounds and compositions are also disclosed.

Claims

1. An anti-fouling composition comprising:

at least one biopolymer matrix comprising;

a) one or more positively charged functional groups;

b) one or more negatively charged functional groups;

c) one or more zwitterionic functional groups;

or

d) combinations thereof;

such that the composition is substantially zwitterionic.

2. The anti-fouling composition of claim 1, wherein at least one biopolymer matrix comprises at least one zwitterionic biopolymer matrix, itself comprising a combination of at least one positively charged functional group and at least one negatively charged functional group.

3. The anti-fouling composition of claim 1, wherein at least one biopolymer matrix comprises at least two biopolymer matrices, wherein

at least one of the at least two biopolymer matrices has at least one positively charged functional group;

and

at least one of the at least two biopolymer matrices has at least one negatively charged functional group.

6. The anti-fouling composition of claim 1, wherein at least one biopolymer matrix comprises one or more zwitterionic functional groups.

7. The anti-fouling composition of claim 1, further comprising a base material selected from a paint, lacquer, coating, varnish, stain, or a combination thereof.

10. The anti-fouling composition of claim 1, wherein the biopolymer is selected from the group consisting of lignin, cellulose, hemicellulose, dextrin, a wood-derived biopolymer or a combination thereof.

11. The anti-fouling composition of claim 1, wherein the biopolymer comprises two or more hydroxyl groups of an alcohol, carboxylic acid or phenol substituted with the

one or more positively charged functional groups, and one or more negatively charged functional groups;

one or more zwitterionic functional groups;

or

a mixture thereof.

12. The anti-fouling composition of claim 1, wherein each of the one or more positively charged functional groups is independently selected from -L-S-Q⊕

;

wherein S is selected from, C_1-20 alkyl, C_6-18 aryl, C_1-20 arylene, C_6-20 aryl, C_3-20 cycloalkane, C_1-20 alkyloxybenzene, methoxy benzene, (2-ethoxy-ethoxy)-4-(1,1,3,3-tetramethyl-butyl)-benzene, benzene, a carbohydrate and an oligomer of ethylene glycol;

wherein Q is a positively charged moiety selected from —

N ⊕

R¹R²R³ and S⊕

R¹R²;

wherein each R¹, R², and R³ is independently selected from H, C_1-20 alkyl, C_6-20 aryl, C_3-20 cycloalkane, C_1-20 alkyl acetamide of formula C_nH_(2n+1)—

C(O)—

N(CH₂)₂, C_1-20 alkyloxybenzene, methoxy benzene, (2-ethoxy-ethoxy)-4-(1,1,3,3-tetramethyl-butyl)-benzene, N-phenyl-acetamide, and oligomers of ethylene glycol

or wherein any two of R¹, R², and R³ may be joined together with the nitrogen to which they are attached to form a C_5-7 heterocycle; and

L is a linker selected from —

O—

, —

C—

O—

C(O)—

N—

, —

OC(O)O—

or —

O—

C(O)—

.

13. The anti-fouling composition of claim 1, wherein the one or more positively charged functional group is selected from the group consisting of benzalkonium, benzethonium, methylbenzethonium, cetalkonium, cetylpyridinium, cetrimonium, cetrimide, dofanium, tetraethylammonium, didecyldimethylammonium, domiphen, and combinations thereof.

15. The anti-fouling composition of claim 1, wherein the negatively charged functional group is selected from:

-L²-R⁴—

Z⊖

,

wherein Z⊖

is a negatively charged moiety selected from —

SO₃⊖ and

—

COO⊖

; and

wherein R⁴ is selected from C_1-20 alkyl, C_6-18 aryl, C_1-20 arylene, C_6-20 aryl, C_3-20 cycloalkane, C_1-20 alkyloxybenzene, methoxy benzene, (2-ethoxy-ethoxy)-4-(1,1,3,3-tetramethyl-butyl)-benzene, benzene, a carbohydrate and an oligomer of ethylene glycol of formula-O—

(CH₂)_nOH; and

L² is a linker selected from —

O—

, C—

O—

C(O)—

N—

, —

OC(O)O—

, and —

O—

C(O)—

.

16. The anti-fouling composition of claim 1, wherein the negatively charged functional group comprises a sulfonate anion.

20. The anti-fouling composition of claim 1, wherein the one or more zwitterionic functional groups are selected from (⊖

NR¹R²R³)—

(CR⁵R⁶)_n—

(R⁷⊕

), and (⊖

NR¹R²)—

(CR⁵R⁶)_n—

(R⁷⊖

);

wherein each R¹, R², and R³ is independently C_1-20 alkyl of formula, C_6-20 aryl, C_3-20 cycloalkane, C_1-20 alkyl acetamide of formula C_nH_(2n+1)—

C(O)—

N(CH₂)₂, C_1-20 alkyloxybenzene, methoxy benzene, (2-ethoxy-ethoxy)-4-(1,1,3,3-tetramethyl-butyl)-benzene, N-phenyl-acetamide;

wherein any two of R¹, R², and R³ may be joined together with the nitrogen to which they are attached to form a C_5-7 heterocycle;

wherein each R⁵ and R⁶ is independently H, OH, or C_1-20 alkyl or an oligomer of ethylene glycol;

wherein at least one R⁵ or R⁶ is a linker selected from —

O—

, C—

O—

C(O)—

N—

, —

OC(O)O—

or —

C(O)O—

by which the zwitterion is attached to the biopolymer matrix;

wherein R⁷ is —

COO⁻

or —

SO₂O⁻

; and

wherein n is an integer from 1 to 20.

21. The anti-fouling composition of claim 1, wherein the zwitterionic functional groups are selected from the group consisting of sulfobetaine acrylates, sulfobetaine acrylamides, sulfobetaine vinyl compounds, sulfobetaine epoxides, sulfobetaine methacrylate, carboxybetaine acrylates, carboxybetaine acrylamides, carboxybetaine vinyl compounds, carboxybetaine epoxides, carboxybetaine methacrylate, and mixtures thereof.

22. The anti-fouling composition of claim 1, wherein the zwitterionic functional groups comprise a cephalosporin-based antimicrobial functional group, cefepime, cephaloridine or a combination thereof.

4. (canceled)

5. (canceled)

8. (canceled)

9. (canceled)

14. (canceled)

17. (canceled)

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23. (canceled)

24. A method of synthesizing a zwitterionic biopolymer compound, the method comprising:

contacting at least one zwitterionic functional group with a biopolymer matrix

wherein the zwitterionic functional group comprises a formula;

(⊖

NR¹R²R³)—

(CR⁵R⁶)_n—

(R⁷⊖

);

wherein each R¹, R², and R³ is independently C_1-20 alkyl, C_6-20 cycloalkane, aryl, C_3-20 cycloalkane, C_1-20 alkyl acetamide of formula C_nH_(2n+1)—

C(O)—

N(CH₂)₂, C_1-20 alkyloxybenzene, methoxy benzene, (2-ethoxy-ethoxy)-4-(1,1,3,3-tetramethyl-butyl)-benzene, N-phenyl-acetamide or an oligomer of ethylene glycol;

wherein any two of R¹, R², and R³ may be joined together with the nitrogen to which they are attached to form a C_5-7 heterocycle;

wherein each R⁵ and R⁶ is independently H, OH, or C_1-20 alkyl;

wherein at least one R⁵ or R⁶ is selected from —

OH, C—

O—

C(O)—

NH₂ or —

OC(O)OH;

wherein R⁷ is —

COO⁻

or —

SO₂O⁻

;

wherein n is an integer from 1 to 20.

25. The method of claim 24, wherein the zwitterionic functional group is selected from the group consisting of sulfobetaine acrylates, sulfobetaine acrylamides, sulfobetaine vinyl compounds, sulfobetaine epoxides, sulfobetaine methacrylate, carboxybetaine acrylates, carboxybetaine acrylamides, carboxybetaine vinyl compounds, carboxybetaine epoxides, carboxybetaine methacrylate, and mixtures thereof.

26. The method of claim 24, wherein the zwitterionic functional group comprises a cephalosporin-based antimicrobial functional group, cefepime, cephaloridine, or a combination thereof.

27. The method of claim 24, wherein the biopolymer is selected from the group consisting of lignin, cellulose, hemicellulose, dextrin, or a combination thereof.

28. (canceled)

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30. (canceled)

31. (canceled)

32. A method of synthesizing a zwitterionic biopolymer compound, the method comprising:

providing at least one positively charged chloroformate;

providing at least one negatively charged chloroformate; and

contacting the at least one positively charged chloroformate and the at least one negatively charged chloroformate with a biopolymer matrix to form a biopolymer compound comprising at least one positively charge functional group and at least one negatively charged functional group.

33. The method of claim 32, wherein the at least one positively charged chloroformate is prepared by:

contacting a positively charged compound of formula;

HO—

(C_1-20)alkyl-Q⊕

with carbon monoxide, sulphur, 1,8-diazabicyclo[5.4.0]undec-7-ene, or a combination thereof followed by treatment with sulfuryl chloride to form a chloroformate of the formula;

Cl—

C(O)—

O—

(C_1-20)alkyl-Q⊖

,

wherein Q⊕

is a positively charged moiety selected from NR¹R²R³ wherein R¹, R², and R³ are independently C_1-20 alkyl, C_6-20 aryl, C_3-20 cycloalkanes, C_1-20 alkyl acetamide of formula C_nH_(2n+1)—

C(O)—

N(CH₂)₂, C_1-20alkyloxybenzene, methoxy benzene, (2-ethoxy-ethoxy)-4-(1,1,3,3-tetramethyl-butyl)-benzene, and N-phenyl-acetamide; and

wherein R¹, R², and R³ may be joined together with the nitrogen to which they are attached to form a C_5-7 heterocycle.

35. The method of claim 33, wherein Q⊕

is selected from the group consisting of benzalkonium, benzethonium, methylbenzethonium, cetalkonium, cetylpyridinium, cetrimonium, cetrimide, dofanium, tetraethylammonium, didecyldimethylammonium, domiphen, and combinations thereof.

36. The method of claim 32, wherein the at least one negatively charged chloroformate is prepared by:

contacting a negatively charged compound of formula;

HO—

R⁴—

Z⊖

with carbon monoxide, sulphur, 1,8-diazabicyclo[5.4.0]undec-7-ene, or a combination thereof followed by treatment with sulfuryl chloride to form a chloroformate of the formula;

Cl—

C(O)—

O—

R⁴—

ZO⊖

,

wherein Z⊖

is a negatively charged moiety selected from —

SO₃⊖ and

—

COO⊖

; and

wherein R⁴ is a bond, C_1-20 alkyl or arylene.

41. The method of claim 32, wherein the biobiopolymer matrix is selected from the group consisting of lignin, cellulose, hemicellulose, dextrin, and combinations thereof.

47. The method of claim 32, wherein the positively charged functional group comprises 2-(trimethylammonium chloride) ethanol and the negatively charged functional group comprises 3-sulphopropyl.

50. The method of claim 32, wherein the biopolymer matrix is lignin.

51. The method of claim 32, wherein the biopolymer matrix is lignin and further comprising dissolving the lignin in dimethylsulfoxide, pyridine or a combination thereof prior to combining with the at least one positively charged chloroformates and the at least one negatively charged chloroformates.

34. (canceled)

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49. (canceled)

52. A method of protecting a surface from the formation of a biofilm, the method comprising:

providing a zwitterionic biopolymer matrix having at least one functional group selected from both positively charged and negatively charged functional groups, zwitterionic functional groups, polyethylene glycol functional groups or a combination thereof;

combining the zwitterionic biopolymer matrix with a base selected from paint, coating, varnish, stain, or a combination thereof;

coating the surface with the mixture; and

allowing the mixture to cure, whereby the cured mixture will reduce the formation of a biofilm on the surface.

54. The method of claim 52, wherein the surface is selected from the hull of a ship, an automotive part, an automotive body panel, an amphibious vehicle part, an amphibious vehicle body panel, an aircraft part, an aircraft body panel, a turbine, a fan, an air conditioner, an air conditioner part, a refrigeration unit, a refrigeration unit part, a humidifier, a humidifier part, a dehumidifier, a dehumidifier part, a cooling tower, a cooling tower part, a water storage tank, a water storage tank part, a water storage container, a tanker, a hose, a hose fitting, a vent, ductwork, a pipe, a tube, a plumbing part, a plumbing tool, a swimming pool, swimming pool equipment, a ceramic tile, a glass window pain, a plastic window pane, hospital equipment, culinary equipment or a textile, a spa, a shower, a bathtub, a sink, a porcelain tile, a faucet, a shower curtain, a drain, a sewer, a kitchen counter, a kitchen cabinet, a food preparation area, a surface in a hospital setting, sports and recreation equipment, food processing and handling machinery, a business machine, a consumer appliance, a general household good, a transportation interior, construction supplies, a medical device, a pair of forceps, a clamp, an occluder, a retractor, a distractor, a scalpel, a lancet, a drill bit, a rasp, a trocar, a ligature, a dilator, a specula, a suction tip, a suction tubes, a tyndaller, a drill, a dermatome, a scope, a probe, an endoscope, a tactile probe, a carrier, an applier, an ultrasound tissue disruptor, a cryotome, a laser cutting guide, a measurement device, a caliper, a stent, a catheter, a guide wire, a denture, a bridge, a crown, a pin, a rod, a screw, a plate, a prosthetic, a hip joint, a pacemaker, a cochlear implant and a drug eluting stent.

53. (canceled)

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