Silicone polyurethane copolymers containing oxygen sensitive phosphorescent dye compounds

• US 5,155,149 A
• Filed: 10/10/1991
• Issued: 10/13/1992
• Est. Priority Date: 10/10/1991
• Status: Expired due to Fees

• Current Assignee: Becton Dickinson Critical Care Systems Pte Ltd. (Becton, Dickinson & Co)
• Original Assignee: BOC Health Care Incorporated (General Electric Company)
• Inventors: Klima, Suzanne, Atwater, Beauford W.
• Primary Examiner(s): Bleutge, John C.
• Assistant Examiner(s): Hellender, Karen A.
• Application Number:
  US07/774,769
• Time in Patent Office: 369 Days
• Field of Search: 524/588, 524/589, 524/88, 528/28, 528/38
• US Class Current: 524/88
• CPC Class Codes: C08G 18/3842 containing heterocyclic rings having at least one nitrogen atom in the ring
• CPC Class Codes: C08G 18/3897 containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 77/48 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08G77/42 takes precedence

Abstract

The present invention is directed to silicone polyurethane copolymers containing phosphorescent dye compounds wherein the copolymers are represented by the formula: ##STR1## wherein n is an integer ranging from 1 to about 30, and y, z, and w are integers ranging from 0 to about 40, wherein one of y, z, and w is at least one; and A is a diamide, B is a silicone block copolymer, D is a chain extender, and E is a phosphorescent porphyrin-type compound.

Claims

1. A silicone polyurethane copolymer containing a phosphorescent dye compound wherein the copolymer is represented by the formula:

##STR7## wherein n is an integer ranging from 1 to about 30, and y, z, and w are integers ranging from 0 to about 40, wherein one of y, z, and w is at least one; and

(a) A is a diamide group having the formula;

space="preserve" listing-type="equation">--COHN--R.sub.1 --NHCO--

wherein R₁ is selected from the group consisting of substituted and unsubstituted alkyl groups, cycloalkyl groups, and aryl groups, each R₁ group containing from 1 to about 30 carbon atoms;

(b) B is a silicone block copolymer having the formula;

space="preserve" listing-type="equation">(--XR.sub.3 O).sub.u (Si(R.sub.2).sub.2 O).sub.v (R.sub.3 X--).sub.u

wherein R₂ is selected from the group consisting of substituted and unsubstituted alkyl groups, cycloalkyl groups, and aryl groups, each R₂ group being the same or different and having from 1 to about 18 carbon atoms;

R₃ is selected from the group consisting of substituted and unsubstituted alkyl groups, cycloalkyl groups, and aryl groups, each R₃ group having from 1 to about 18 carbon atoms;

X is selected from the group consisting of oxygen and nitrogen;

u is an integer ranging from about 5 to about 15; and

v is an integer ranging from about 5 to about 50;

(c) D is a chain extender having the formula;

space="preserve" listing-type="equation">--X'"'"'--R.sub.4 --X'"'"'--

wherein R₄ is selected from the group consisting of substituted and unsubstituted alkyl groups, cycloalkyl groups, and aryl groups, each R₄ group having from 1 to about 12 carbon atoms; and

X'"'"' is selected from the group consisting of oxygen and nitrogen; and

(d) E is a phosphorescent dye compound having the formula;

##STR8## wherein R₅ is a phosphorescent compound selected from the group consisting of porphyrin and compounds selected from the group consisting of porphyrin and compounds containing the basic cyclic tetrapyrrolic ring structure of porphyrin which compound has an absorption spectrum in the region of 400-800 nm, said compound being chelated with a metal ion selected from the group consisting of platinum, palladium, rhodium, and gadolinium, and X'"'"''"'"' is selected from the group consisting of oxygen and nitrogen.

2. The silicone copolymer according to claim 1, wherein y and w are integers ranging rom 0 to about 10, z is an integer ranging from 0 to about 15, and n is an integer ranging from 1 to about 15.

3. The silicone copolymer according to claim 1, wherein R₁ is an alkyl or aryl group containing from 1 to about 20 carbon atoms.

4. The silicone copolymer according to claim 1, wherein R₂ is selected from the group consisting of alkyl groups and aryl groups, each R₂ groups being the same or different and having from 1 to about 6 carbon atoms.

6. The silicone copolymer according to claim 1, wherein u is an integer ranging from about 8 to about 12 and v is an integer ranging from about 15 to about 30.

9. The silicone copolymer according to claim 1, wherein the metal ion in group R₅ is selected from the group consisting of platinum and palladium.

10. The silicone copolymer according to claim 1, wherein X and X'"'"' are oxygen and X'"'"''"'"' is nitrogen.

11. The silicone copolymer according to claim 1, wherein R₁ is 4,4'"'"'-diphenylmethane, R₂ is methyl, R₃ is 1,2-ethylene, R₄ is 1,4-butylene, R₅ is platinum tetra(p-aminophenyl)porphine, X and X'"'"' are oxygen, X'"'"''"'"' is nitrogen, u is from about 9 to about 11, v is from about 18 to about 22, y and w are from 1 to about 3, z is from about 3 to about 5, and n is from about 7 to about 9.

5. The silicone copolymer according to wherein R₃ is selected from the group consisting of alkyl groups and aryl groups, each R₃ group having from 1 to about 6 carbon atoms.

7. The silicone copolymer according to wherein R₄ is an alkyl group having from 1 to about 6 carbon atoms.

8. The silicone copolymer according to wherein R₅ is selected from the group consisting of platinum tetra(p-aminophenyl)porphine, platinum tetra(p-hydroxyphenyl)porphine, platinum tetra(p-carboxyphenyl)porphine, and mixtures thereof.

12. A method for preparing a silicone polyurethane copolymer containing a phosphorescent dye compound which comprises the steps of:

(1) providing the following ingredients;

(a) a diisocyanate having the formula;

space="preserve" listing-type="equation">OCN--R.sub.1 --NCO

wherein R₁ is selected from the group consisting of substituted and unsubstituted alkyl groups, cycloalkyl groups, and aryl groups, each R₁ group containing from 1 to about 30 carbon atoms;

(b) a silicone block copolymer having the formula;

space="preserve" listing-type="equation">(HXR.sub.3 O).sub.u (Si(R.sub.2).sub.2 O).sub.v (R.sub.3 XH).sub.u

wherein R₂ is selected from the group consisting of substituted and unsubstituted alkyl groups, cycloalkyl groups, and aryl groups, each R₂ group being the same or different and having from 1 to about 18 carbon atoms;

R₃ is selected from the group consisting of substituted and unsubstituted alkyl groups, cycloalkyl groups, and aryl groups, each R₃ groups having from 1 to about 18 carbon atoms;

X is selected from the group consisting of oxygen and nitrogen;

u is an integer ranging from about 5 to about 15; and

v is an integer ranging from about 5 to about 50;

(c) a chain extender having the formula;

space="preserve" listing-type="equation">HX'"'"'--R.sub.4 --XC'"'"'H

wherein R₄ is selected from the group consisting of substituted and unsubstituted alkyl groups, cycloalkyl groups, and aryl groups, each R₄ group having from 1 to about 12 carbon atoms; and

X'"'"' is selected from the group consisting of oxygen and nitrogen; and

(d) a phosphorescent dye compound having the formula;

##STR9## wherein R₅ is a phosphorescent compound selected from the group consisting of prophyrin and compounds containing the basic cyclic tetrapyrrolic ring structure of prophyrin which compound has an absorption spectrum, in the region of 400-800 nm, said compound being chelated with a metal ion selected from the group consisting of platinum, palladium, rhodium, and gadolinium, and X'"'"''"'"' is selected from the group consisting of oxygen and nitrogen; and

(2) admixing the silicone block copolymer, the chain extender, and the phosphorescent dye compound in a solvent;

(3) reacting the diisocyanate from step (1)(a) with the admixture from step (2) to form the silicone polyurethane copolymer containing a phosphorescent dye compound.