Granted Patent B2

US 12,516,079 · App. 18/408,396 · Granted Jan 6, 2026

Inventor: Ramanathan Ravichandran (Suffern, NY)

Assignee: Southwire Company, LLC

C07F17/02H01B3/46H01B13/322

Abstract

Claims (137)

1 . An acyl metallocene compound of formula (1):

wherein:

M is a metal ion selected from Fe(II), Mn(II), Ni(II), Co(II), Ru(II), or Os(II);

m is 1-4, where a silane acyl groups group(s) can be at any position(s) on one or both of the cyclopentadienyl rings;

p can vary from 2 to 20 carbon atoms;

R 1 and R 2 are C 1 -C 4 linear or branched alkyl, or H;

X is a C 1 -C 5 linear or branched alkyl;

Y is C 1 -C 4 acyloxy, C 1 -C 4 alkyloxy, or silyloxy; and

wherein for m=1, n is two or three, and for m=2-4, n is one, two, or three.

2 . The compound of claim 1 , wherein for formula (1): M is Fe(II).

3 . The compound of claim 2 , wherein for formula (1): M is Fe(II); m is 1-2; R1 and R2 are C1-C2 alkyl or H; X is C1-C2 alkyl; and Y is C1-C4 alkyloxy.

4 . The compound of claim 3 , wherein for formula (1): M is Fe(II); m is 1; R1 and R2 are H; X is —CH3; and Y is C1-C2 alkyloxy.

5 . The compound of claim 1 , wherein the compound is selected from the group consisting of:

6 . The compound of claim 5 , wherein the compound is 11-(dimethoxymethylsilyl)-1-oxo-undecyl-1-ferrocene (AcylFc-DMS), or 3-(dimethoxymethylsilyl)-1-oxo-propyl-1-ferrocene.

7 . A dielectric enhancement fluid, comprising:

(a) an acyl metallocene compound of formula (1):

wherein:

M is a metal ion selected from Fe(II), Mn(II), Ni(II), Co(II), Ru(II), or Os(II);

m is 1-4, where a silane acyl group(s) can be at any position(s) on one or both of the cyclopentadienyl rings;

p can vary from 2 to 20 carbon atoms;

R1 and R2 are C1-C4 linear or branched alkyl, or H;

X is a C1-C5 linear or branched alkyl;

Y is C1-C4 acyloxy, C1-C4 alkyloxy, or silyloxy; and

wherein for m=1, n is two or three, and for m=2-4, n is one, two, or three; and

(b) at least one component selected from:

(1) at least one a water-reactive material selected from:

(i) an organosilane monomer having at least two water-reactive groups,

(ii) the organosilane monomer (1) wherein at least one of the water-reactive groups is substituted with a condensable silanol group,

(iii) an oligomer of the above organosilane monomer (I), and/or

(iv) a co-oligomer of the above organosilane monomer (i) with a different organosilane monomer;

(2) a non-water-reactive organic material having a diffusion coefficient of less than about 10-9 cm2/sec and an equilibrium concentration of at least about 0.005 gm/cm3 in a polymeric insulation, the diffusion coefficient and the equilibrium concentration being determined at temperature T;

(3) metallocenes having a metal ion selected from Fe(II), Mn(II), Ni(II), Co(II), Ru(II), or Os(II), sandwiched between two cyclopentadienyl rings, and derivatives thereof;

(4) an organic compound having an equilibrium concentration in the polymeric insulation at 55° C., which is less than 2.25 times the equilibrium concentration at 22° C.;

(5) at least one silane functional additive derived from:

(i) a hindered phenolic antioxidant based on 2,6-di-tert-butyl phenol,

(ii) a hindered amine light stabilizer, based on tetramethyl piperidine, and/or

(iii) a UV absorber or energy quencher selected from benzotriazoles, triazines, benzophenones, and/or nickel chelates; and/or

(6) at least one catalyst suitable to catalyze hydrolysis and condensation of the water reactive materials of (a), (1), and (5).

8 . The dielectric enhancement fluid of claim 7 , wherein the catalyst is a strong acid, or a compound of titanium and/or tin.

9 . The dielectric enhancement fluid of claim 7 , wherein for formula (1): M is Fe(II).

10 . The dielectric enhancement fluid of claim 9 , wherein for formula (1): M is Fe(II); m is 1-2; R1 and R2 are C1-C2 alkyl or H; X is C1-C2 alkyl; and Y is C1-C4 alkyloxy.

11 . The dielectric enhancement fluid of claim 10 , wherein for formula (1): M is Fe(II); m is 1; R1 and R2 are H; X is —CH3; and Y is C1-C2 alkyloxy.

12 . The dielectric enhancement fluid of claim 11 , wherein for formula (1) the compound is selected from the group consisting of:

13 . The dielectric enhancement fluid of claim 12 , wherein the compound is 11-(dimethoxymethylsilyl)-1-oxo-undecyl-1-ferrocene (AcylFc-DMS), or 3-(dimethoxymethylsilyl)-1-oxo-propyl-1-ferrocene.

14 . The dielectric enhancement fluid of claim 7 , wherein for (5), the at least one silane functional additive is selected from:

(i) a hindered phenolic antioxidant of formula (XIX) or (XIXa):

wherein:

S1 and S2 can be equal or different C1-C10 branched alkyl;

m is zero or one;

T is oxygen or sulfur;

A is a C1-C10 linear or branched alkylene, or

wherein S3, S4, and S5 are C3-C10 linear or branched alkylene;

X is a C1-C5 linear or branched alkyl;

Y is hydrogen, halogen, C1-C4 acyloxy, C1-C4 alkyloxy, amino, amino-oxy, or silyloxy; and

n is one, two, or three;

(ii) a hindered amine light stabilizer of formula (XI):

wherein:

m+n is a number from 1 to 40, n varies from zero to 50% of the sum m+n;

A is —O—;

T1 and T4 which can be identical or different are methyl, methoxy, ethoxy, or OH;

T2 is trimethylene or is also a direct bond if A is —O— and T1 and T4 are methyl;

T3 is methyl, C7-C9 alkyl, or cyclohexyl;

T5 is C1-C12 alkyl;

X1 is as defined for T1 or is a group (CH3)3 SiO—; and

X2 is hydrogen, methyl, ethyl, a group (CH3)3 Si— or, if n is zero and T1 and X1 are methyl, X2 is also a group of the formula (XIII)

and, if m+n is a number from 3 to 10, X1 and X2 together can also be a direct bond; and/or

(iii) a UV absorber or energy quencher of formula (IA) or (IIA):

wherein:

G1 and G6 are hydrogen;

G2 and G7 are independently H, cyano, CF3-, fluoro, —CO-G3, or E3SO2-;

G3 is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms;

E1 is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl groups of 1 to 4 carbon atoms each;

E2 and E9 are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; or E2 is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE11, —OE4, —NCO, —NH2, —NHCOE11, —NHE4, or —N(E4)2, or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more —O—, —NH—, or —NE4- groups or mixtures thereof and which can be unsubstituted or substituted by one or more —OH, —OE4, or —NH2 groups or mixtures thereof;

E11 is hydrogen, straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 14 carbon atoms, or phenylalkyl of 7 to 15 carbon atoms;

E3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms, or said aryl substituted by one or two alkyls of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to 16 carbon atoms;

L is methylene; and

with the proviso that at least one of E1, E2, and E9 contains a group -T1-Si(OR2)n(R1)3-n, -T1-X—CO—X-T2-Si(OR2)n(R1)3-n, -T1-CO—X-T2-Si(OR2)n(R1)3-n, —X-T1-Si(OR2)n(R1)3-n, or —X-T1-X—CO—X-T2-Si(OR2)n(R1)3-n;

where, for E1, E2, and E9, T1 and T2 are independently alkylene of 2 or 3 carbon atoms, R1 and R2 are independently alkyl of 1 to 6 carbon atoms or phenyl, n is 1, 2, or 3, and X is —O—, —NE4—, or —NH—.

15 . A hydrosilylation gel, comprising:

(A) an acyl metallocene compound of formula (1):

M is a metal ion selected from Fe(II), Mn(II), Ni(II), Co(II), Ru(II), or Os(II);

m is 1-4, where a silane acyl group(s) can be at any position(s) on one or both of the cyclopentadienyl rings;

p can vary from 2 to 20 carbon atoms;

R1 and R2 are C1-C4 linear or branched alkyl, or H;

X is a C1-C5 linear or branched alkyl;

Y is C1-C4 acyloxy, C1-C4 alkyloxy, or silyloxy; and

wherein for m=1, n is two or three, and for m=2-4, n is one, two, or three; and

(B) at least one component selected from:

(a) an Si—H endblocked polydiorganosiloxane fluid with the formula H(R2SiO)x(R2Si)H, wherein R is independently selected from alkyl radicals having from 1 to 6 carbon atoms or the phenyl radical and the average value of x is 1 to 40, and having a viscosity of 0.5 to about 100 centistokes at 25° C.,

(b) a polydiorganosiloxane fluid endblocked with groups containing unsaturated carbon-carbon functionality and having a viscosity of 0.5 to about 100 centistokes at 25° C.,

(c) a hydrosilylation catalyst suitable to cure the mixture of parts (a) and (b), and

(d) at least one organoalkoxysilane functional additive selected from the group consisting of:

(i) a hindered phenolic antioxidant based on 2,6-di-tert-butyl phenol,

(ii) a hindered amine light stabilizer, based on tetramethyl piperidine, and/or

(iii) a UV absorber or energy quencher selected from benzotriazoles, triazines, benzophenones, and/or nickel chelates.

16 . The hydrosilylation gel of claim 15 , wherein for formula (1): M is Fe(II).

17 . The hydrosilylation gel of claim 16 , wherein for formula (1): M is Fe(II); m is 1-2; R1 and R2 are C1-C2 alkyl or H; X is C1-C2 alkyl; and Y is C1-C4 alkyloxy.

18 . The hydrosilylation gel of claim 17 , wherein for formula (1): M is Fe(II); m is 1; R1 and R2 are H; X is —CH3; and Y is C1-C2 alkyloxy.

19 . The hydrosilylation gel of claim 18 , wherein for formula (1) the compound is selected from the group consisting of:

20 . The hydrosilylation gel of claim 19 , wherein the compound is 11-(dimethoxymethylsilyl)-1-oxo-undecyl-1-ferrocene (AcylFc-DMS), or 3-(dimethoxymethylsilyl)-1-oxo-propyl-1-ferrocene.

21 . The hydrosilylation gel of claim 15 , wherein for (d), the at least one organoalkoxysilane functional additive is selected from:

(i) a hindered phenolic antioxidant of formula (XIX) or (XIXa):

wherein:

S1 and S2 can be equal or different C1-C10 branched alkyl;

m is zero or one;

T is oxygen or sulfur;

A is a C1-C10 linear or branched alkylene, or

wherein S3, S4, and S5 are C3-C10 linear or branched alkylene;

X is a C1-C5 linear or branched alkyl;

Y is hydrogen, halogen, C1-C4 acyloxy, C1-C4 alkyloxy, amino, amino-oxy, or silyloxy; and

n is one, two or three;

(ii) a hindered amine light stabilizer of formula (XI):

wherein:

m+n is a number from 1 to 40, n varies from zero to 50% of the sum m+n;

A is —O—;

T1 and T4 which can be identical or different are methyl, methoxy, ethoxy, or OH;

T2 is trimethylene or is also a direct bond if A is —O— and T1 and T4 are methyl;

T3 is methyl, C7-C9 alkyl, or cyclohexyl;

T5 is C1-C12 alkyl;

X1 is as defined for T1 or is a group (CH3)3 SiO—; and

X2 is hydrogen, methyl, ethyl, a group (CH3)3 Si— or, if n is zero and T1 and X1 are methyl, X2 is also a group of the formula (XIII)

and, if m+n is a number from 3 to 10, X1 and X2 together can also be a direct bond; and/or

(iii) a UV absorber or energy quencher of formula (IA) or (IIA):

wherein:

G1 and G6 are hydrogen;

G2 and G7 are independently H, cyano, CF3-, fluoro, —CO-G3, or E3SO2-;

G3 is straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms;

E1 is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl groups of 1 to 4 carbon atoms each;

E2 and E9 are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; or E2 is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE11, —OE4, —NCO, —NH2, —NHCOE11, —NHE4, or —N(E4)2, or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interrupted by one or more —O—, —NH—, or —NE4- groups or mixtures thereof and which can be unsubstituted or substituted by one or more —OH, —OE4, or —NH2 groups or mixtures thereof;

E11 is hydrogen, straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 14 carbon atoms, or phenylalkyl of 7 to 15 carbon atoms;

E3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms, or said aryl substituted by one or two alkyls of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to 16 carbon atoms;

L is methylene; and

with the proviso that at least one of E1, E2, and E9 contains a group -T1-Si(OR2)n(R1)3-n, -T1-X—CO—X-T2-Si(OR2)n(R1)3-n, -T1-CO—X-T2-Si(OR2)n(R1)3-n, —X-T1-Si(OR2)n(R1)3-n, or —X-T1-X—CO—X-T2-Si(OR2)n(R1)3-n;

where, for E1, E2, and E9, T1 and T2 are independently alkylene of 2 or 3 carbon atoms, R1 and R2 are independently alkyl of 1 to 6 carbon atoms or phenyl, n is 1, 2, or 3, and X is —O—, —NE4—, or —NH—.

22 . A method for extending the useful life of an insulated cable, comprising injecting, into a cable having a stranded conductor encased in a polymeric insulation jacket, a dielectric enhancement fluid comprising an acyl metallocene compound of formula (1) according to claim 7 , or a dielectric gel formulation comprising an acyl metallocene compound of formula (1) according to claim 15 , and wherein the acyl metallocene compound of formula (1) diffuses into the polymeric insulation.

23 . A method for extending the useful life of in-service electrical cable, comprising injecting a dielectric enhancement fluid composition according to claim 7 , into at least one section of an electrical cable having a stranded conductor encased in a polymeric insulation jacket, and having an average operating temperature T, and wherein the injected composition provides for both initial permeation of the acyl metallocene compound of formula (1) into the polymeric insulation, and extended retention of subsequent condensation products of the acyl metallocene compound of formula (1) in the cable insulation.

24 . A method for extending the useful life of an insulated cable, comprising injecting, into a cable having a stranded conductor encased in a polymeric insulation jacket, a dielectric gel formulation according to claim 15 , and wherein, after injection, the mixture of parts (a) and (b) is cured into a non-flowable gel in the cable, and wherein the acyl metallocene compound of formula (1) diffuses into the polymeric insulation.

Assignments (4)

Continuity (2)

References Cited (45)