ANTIFOULING MATERIALS CONTAINING CATIONIC POLYSILOXANES

• US 20100204399A1
• Filed: 04/20/2010
• Published: 08/12/2010
• Est. Priority Date: 05/09/2005
• Status: Active Grant

• Current Assignee: Ndsu-Research Foundation, North Dakota State University (US Bancorp)
• Original Assignee: Ndsu-Research Foundation, North Dakota State University (US Bancorp)
• Inventors: Thomas, Johnson, Boudjouk, Philip, Chisholm, Bret Ja, Stafslien, Shane Jeremy, Christianson, David Allen
• Granted Patent: US 8,278,400 B2
• Time in Patent Office: Days
• US Class Current: 524/588
• CPC Class Codes: B63B 59/04 Preventing hull fouling anti-fouling paints C09D5/16
• CPC Class Codes: C08G 77/385 containing halogens
• CPC Class Codes: C08L 2666/44 Silicon-containing compounds
• CPC Class Codes: C09D 179/02 Polyamines
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09D 183/10 Block or graft copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00
• CPC Class Codes: C09D 183/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C09D183/10 takes precedence
• CPC Class Codes: C09D 5/1675 Polyorganosiloxane-containing compositions
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Polyamine cross-linked polysiloxanes, such as functionalized polysiloxane cross-linked with a polyalkylenepolyamine are described herein. The polyamine cross-linked polysiloxanes may be used in an antifouling composition to prevent biological fouling in marine environments.

Claims

1. A polyamine cross-linked polysiloxane which is prepared by cross linking a copolymer using a polyamine, wherein the copolymer has the formula:

wherein x is an integer from 0 to 100;

y is an integer from 0 to 100;

z is an integer from 0 to 100,

t is an integer from 0 to 100;

u is an integer from 0 to 100;

x+y+z+t+u is at least 5;

at least one of u, x and z is not zero;

n is an integer from 0 to 50;

m is an integer from 0 to 50;

p is an integer from 0 to 50;

a is an integer from 0 to 50;

b is an integer from 0 to 50;

c is an integer from 0 to 50;

d is an integer from 0 to 50;

e is an integer from 0 to 50;

f is an integer from 0 to 50;

at least one of n, m, p, a, b, c, d, e and f is not zero;

X is a halide or an end cap group;

Y is a halide or an end cap group;

Z is a halide or an end cap group;

L¹, L², and L³ are linking groups;

R¹, R², R³, and R¹⁰ are independently C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl or phenyl;

R⁴ is hydrogen, C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, or phenyl;

R⁵ is C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl, or a cross linking group;

R⁷ is hydrogen, C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl, or a cross linking group;

R⁶, R⁸, and R⁹ include independently a biocidal group that is toxic to organisms that cause fouling in an aquatic environment;

a fouling release group;

a texturizing group;

or combination thereof.

2. The polyamine cross-linked polysiloxane of claim 1 wherein the copolymer has a formula:

wherein x is an integer from 0 to 100;

y is an integer from 1 to 100;

z is an integer from 0 to 100;

x+y+z is at least 5

n is an integer from 0 to 50;

m is an integer from 0 to 50;

p is an integer from 0 to 50;

X is a halide;

L is a linking group;

R¹, R², R³ and R¹⁰ are independently C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl or phenyl;

R⁴ is hydrogen, C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl;

R⁵ is C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl, or a cross linking group;

R⁷ is hydrogen, C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl, or a cross linking group; and

R⁶, R⁸, and R⁹ are independently a biocidal group that is toxic to organisms that cause fouling in an aquatic environment;

a fouling release group;

a texturizing group;

or combination thereof.

3. The polyamine cross-linked polysiloxane of claim 2 wherein m is 0;

p is 0;

R¹, R², R³, R⁵ and R¹⁰ are methyl;

R⁴ is hydrogen or methyl;

R⁷ is hydrogen or methyl; and

R⁶ includes a group represented by the formula;

4. The polyamine cross-linked polysiloxane of claim 1 wherein the polyamine cross-linked polysiloxane further comprises one or more covalently-bound biocidal groups, which are toxic to organisms that cause fouling in an aquatic environment.

5. The polyamine cross-linked polysiloxane of claim 1 wherein the polyamine cross-linked polysiloxane comprises polyalkylenepolyamine subunits, which have an average molecular weight of at least about 500 g/mol.

6. A polymer coating comprising the polyamine cross-linked polysiloxane of claim 1.

7. A method of coating a substrate comprising:

applying a mixture, which includes a polyamine functionalized material and the copolymer having the formula shown in claim 1, to the substrate.

8. The polyamine cross-linked polysiloxane of claim 1 wherein the copolymer has a formula:

wherein x is an integer from 0 to 100;

y is an integer from 1 to 100;

z is an integer from 0 to 100;

x+y+z is at least 10;

n is an integer from 1 to 50;

a is 1, 2, or 3;

b is an integer from 1 to 15;

X is Cl and/or Br;

L is a linking group;

R¹, R², R³, and R¹⁰ independently C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl or phenyl;

R⁴ is hydrogen, C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl;

R⁵ is C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl, or a cross linking group;

R⁷ is hydrogen, C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl, or a cross linking group; and

the copolymer is a random or block copolymer.

9. A polymer coating comprising the polyamine cross-linked polysiloxane of claim 8.

10. A polyamine cross-linked polysiloxane, which is a reaction product prepared by reacting a mixture comprising a polyamine functionalized material and a copolymer having a formula:

wherein x is an integer from 2 to 100;

y is an integer from 1 to 100;

z is an integer from 0 to 100;

x+y+z is at least 5

a is 0 or 1;

b is 0 or 1;

X is a halide;

EC is an end cap group;

L⁵ and L³ are linking groups;

R¹, R², R³, R⁵, and R¹⁰ independently C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl or phenyl;

R⁶ is C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl, or a cross linking group; and

R⁷ is a C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl, phenyl, a group that includes a biocidal moiety that is toxic to organisms that cause fouling in an aquatic environment, a fouling release group, a texturizing group, or a combination thereof.

11. A polymer coating comprising the polyamine cross-linked polysiloxane of claim 10.

12. A polyamine cross-linked polysiloxane, which is a reaction product prepared by reacting a mixture comprising a polyamine functionalized material and a copolymer having a formula:

x1 is an integer from 0 to 100;

y1 is an integer from 0 to 100;

z1 is an integer from 0 to 100;

g is 0 or 1;

h is 0 or 1;

at least one of x1, y1, or z1 is not 0;

Q is a halide or an end cap group;

L⁴ and L⁵ are linking groups;

R¹¹ and R¹² independently C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl or phenyl;

R⁵ is C₁-C₁₀ alkyl, cyclopentyl, cyclohexyl, benzyl, toluoyl, xylyl or phenyl or a cross linking group;

R¹³ is an H and/or C₁-C₁₀ alkyl;

R¹¹ and R¹² include independently a biocidal group that is toxic to organisms that cause fouling in an aquatic environment;

a fouling release group;

a texturizing group;

or combination thereof.

13. A polymer coating comprising the polyamine cross-linked polysiloxane of claim 12.