# US 10,319,492 B2 · Halogen free flame retardant thermoplastic elastomer compositions having improved insulation resistance

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- Number: US 10,319,492 B2
- Document ID: US10319492B2
- Status: Granted
- Kind: B2
- Application number: 15/911,209
- Filed: 2018-03-05
- Published: 2018-07-12
- Granted: 2019-06-11
- Earliest claimed: 2012-06-06
- Assignees: E.I. du Pont de Nemours and Company
- Applicants: E I Du Pont De Nemours and Company
- Inventors: Eleni Karayianni; Judith Alison Peacock
- Web page: https://patentgrep.com/patent/US10319492B2

## CPC

- H01B 3/422: {Linear saturated polyesters derived from dicarboxylic acids and dihydroxy compounds}
- C08K 5/523: with hydroxyaryl compounds
- C08K 5/5313: Phosphinic compounds, e.g. R2=P(:O)OR'
- C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L 67/025: {containing polyether sequences}
- H01B 7/295: using material resistant to flame
- H01B 3/427: {Polyethers}
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Halogen-free flame retardant compositions comprising copolyetherester thermoplastic elastomers, melamine cyanurate and epoxy-containing compounds and cables and wires made from such flame retardant polymer composition provide good electrical insulation resistance during use.

## Claims

### Claim 1

A wire or cable comprising a coating made of a flame retardant polymer composition, wherein the flame retardant polymer composition comprises:
a) one or more copolyetherester thermoplastic elastomers;
b) melamine cyanurate;
c) at least one epoxy-containing compound; and
d) optionally at least one compound selected from the group consisting of phosphites and aromatic phosphate ester flame retardants and mixtures thereof;
with the proviso that i) when the flame retardant polymer composition comprises an aromatic phosphate ester flame retardant and a phosphite, the amount of epoxy-containing compound present is such that the total epoxy functional group equivalent weight is at least about 32 milliequivalents per kg of the combined weight of the one or more copolyetherester thermoplastic elastomers and the aromatic phosphate ester flame retardant and ii) when the flame retardant polymer composition comprises an aromatic phosphate ester flame retardant in the absence of phosphite, the amount of epoxy-containing compound present is such that the total epoxy functional group equivalent weight is at least about 56 milliequivalents per kg of the combined weight of the one or more copolyetherester thermoplastic elastomers and the aromatic phosphate ester flame retardant,
wherein the amount of melamine cyanurate b) is from at or about 10 to 30 weight percent based on the total weight of the flame retardant polymer composition.

### Claim 2 (depends on 1)

The wire or cable according to claim 1, wherein the one or more copolyetherester thermoplastic elastomers are copolyetherester elastomers having a multiplicity of recurring long-chain ester units and short-chain ester units joined head-to-tail through ester linkages, said long-chain ester units being represented by formula (A):
and said short-chain ester units being represented by formula (B):
wherein:
G is a divalent radical remaining after the removal of terminal hydroxyl groups from poly(alkylene oxide)glycols having a number average molecular weight of between about 400 and about 6000;
R is a divalent radical remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than about 300; and
D is a divalent radical remaining after removal of hydroxyl groups from a diol having a molecular weight less than about 250.

### Claim 3 (depends on 1)

The wire or cable according to claim 1, wherein the one or more copolyetherester thermoplastic elastomers are copolyetherester elastomers prepared from monomers comprising (1) poly(tetramethylene oxide) glycol or poly(trimethylene oxide) glycol and mixtures thereof; (2) a dicarboxylic acid selected from the group consisting of isophthalic acid, terephthalic acid and mixtures thereof; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol and mixtures thereof.

### Claim 4 (depends on 1)

The wire or cable according to claim 1, wherein the at least one copolyetherester thermoplastic elastomers are copolyetherester elastomers prepared from monomers comprising (1) poly(tetramethylene oxide) glycol; (2) a dicarboxylic acid selected from the group consisting of terephthalic acid; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol and mixtures thereof and wherein the level of poly(tetramethylene oxide) glycol is less than about 25 weight percent based on the total weight of the copolyetherester elastomers.

### Claim 5 (depends on 4)

The wire or cable according to claim 4, further comprising at least one copolyetherester thermoplastic elastomer prepared from monomers comprising (1) poly(tetramethylene oxide) glycol; (2) a dicarboxylic acid selected from the group consisting of mixtures of isophthalic acid and terephthalic acid; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol and mixtures thereof and wherein the level of said copolyetherester elastomer is from about 5 to about 50 weight percent based on the total weight of the copolyetherester elastomers.

### Claim 6 (depends on 1)

The wire or cable according to claim 1, wherein the amount of phosphite is from at or about 0.1 to 1 weight percent based on the total weight of the flame retardant polymer composition.

### Claim 7 (depends on 1)

The wire or cable according to claim 1, wherein the amount of aromatic phosphate ester is from at or about 2 to 12 weight percent based on the total weight of the flame retardant polymer composition.

### Claim 8 (depends on 1)

The wire or cable according to claim 1, wherein the epoxy-containing compound c) is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane-epichlorohydrin copolymer and tetraglycidyl ether of tetraphenol ethane and combinations thereof.

### Claim 9 (depends on 1)

The wire or cable according to claim 1, wherein the phosphite is a pentaerythritol diphosphite.

### Claim 10

A wire or cable comprising a coating made of a flame retardant polymer composition, wherein the flame retardant polymer composition consists of:
a. one or more copolyetherester thermoplastic elastomers;
b. an amount of melamine cyanurate that is at least 10 weight percent based on the total weight of the flame retardant polymer composition;
c. one or more epoxy-containing compounds; and optionally
d. 0 to 2 weight percent based of the total weight of the flame retardant polymer composition of phosphite,
e. 0 to 15 weight percent based on the total weight of the flame retardant polymer composition of an aromatic phosphate ester flame retardant, with the proviso that i) when the flame retardant polymer composition comprises an aromatic phosphate ester flame retardant and a phosphite, the amount of epoxy-containing compound present is such that the total epoxy functional group equivalent weight is at least about 32 milliequivalents per kg of the combined weight of the one or more copolyetherester thermoplastic elastomers and the aromatic phosphate ester flame retardant and ii) when the flame retardant polymer composition comprises an aromatic phosphate ester flame retardant in the absence of phosphite, the amount of epoxy-containing compound present is such that the total epoxy functional group equivalent weight is at least about 56 milliequivalents per kg of the combined weight of the one or more copolyetherester thermoplastic elastomers and the aromatic phosphate ester flame retardant, and
f. from 0.05 to 10 weight percent based on the total weight of the flame retardant polymer composition of additives
wherein the sum of component a) to f) amounts to 100 weight percent,
wherein the additives are selected from the group consisting of stabilizers, processing agents, metal deactivators, antioxidants, UV stabilizers, heat stabilizers, dyes and/or pigments.

### Claim 11

A wire or cable comprising a coating made of a flame retardant polymer composition, wherein the flame retardant polymer composition comprises:
a) one or more copolyetherester thermoplastic elastomers;
b) melamine cyanurate;
c) at least one epoxy-containing compound; and
d) optionally at least one compound selected from the group consisting of phosphites and aromatic phosphate ester flame retardants and mixtures thereof;
with the proviso that i) when the flame retardant polymer composition comprises an aromatic phosphate ester flame retardant and a phosphite, the amount of epoxy-containing compound present is such that the total epoxy functional group equivalent weight is at least about 32 milliequivalents per kg of the combined weight of the one or more copolyetherester thermoplastic elastomers and the aromatic phosphate ester flame retardant and ii) when the flame retardant polymer composition comprises an aromatic phosphate ester flame retardant in the absence of phosphite, the amount of epoxy-containing compound present is such that the total epoxy functional group equivalent weight is at least about 56 milliequivalents per kg of the combined weight of the one or more copolyetherester thermoplastic elastomers and the aromatic phosphate ester flame retardant,
wherein the amount of epoxy-containing compound c) is such that it provides from at or about 2.4 to about 10 milliequivalents of total epoxy functionality based on hundred grams of the total weight of the flame retardant polymer composition.

### Claim 12 (depends on 11)

The wire or cable according to claim 11, wherein the one or more copolyetherester thermoplastic elastomers are copolyetherester elastomers having a multiplicity of recurring long-chain ester units and short-chain ester units joined head-to-tail through ester linkages, said long-chain ester units being represented by formula (A):
and said short-chain ester units being represented by formula (B):
wherein:
G is a divalent radical remaining after the removal of terminal hydroxyl groups from poly(alkylene oxide)glycols having a number average molecular weight of between about 400 and about 6000;
R is a divalent radical remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than about 300; and
D is a divalent radical remaining after removal of hydroxyl groups from a diol having a molecular weight less than about 250.

### Claim 13 (depends on 11)

The wire or cable according to claim 11, wherein the one or more copolyetherester thermoplastic elastomers are copolyetherester elastomers prepared from monomers comprising (1) poly(tetramethylene oxide) glycol or poly(trimethylene oxide) glycol and mixtures thereof; (2) a dicarboxylic acid selected from the group consisting of isophthalic acid, terephthalic acid and mixtures thereof; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol and mixtures thereof.

### Claim 14 (depends on 11)

The wire or cable according to claim 11, wherein the at least one copolyetherester thermoplastic elastomers are copolyetherester elastomers prepared from monomers comprising (1) poly(tetramethylene oxide) glycol; (2) a dicarboxylic acid selected from the group consisting of terephthalic acid; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol and mixtures thereof and wherein the level of poly(tetramethylene oxide) glycol is less than about 25 weight percent based on the total weight of the copolyetherester elastomers.

### Claim 15 (depends on 14)

The wire or cable according to claim 14, further comprising at least one copolyetherester thermoplastic elastomer prepared from monomers comprising (1) poly(tetramethylene oxide) glycol; (2) a dicarboxylic acid selected from the group consisting of mixtures of isophthalic acid and terephthalic acid; and (3) a diol selected from the group consisting of 1,4-butanediol, 1,3-propanediol and mixtures thereof and wherein the level of said copolyetherester elastomer is from about 5 to about 50 weight percent based on the total weight of the copolyetherester elastomers.

### Claim 16 (depends on 11)

The wire or cable according to claim 11, wherein the amount of phosphite is from at or about 0.1 to 1 weight percent based on the total weight of the flame retardant polymer composition.

### Claim 17 (depends on 11)

The wire or cable according to claim 11, wherein the amount of aromatic phosphate ester is from at or about 2 to 12 weight percent based on the total weight of the flame retardant polymer composition.

### Claim 18 (depends on 11)

The wire or cable according to claim 11, wherein the epoxy-containing compound c) is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane-epichlorohydrin copolymer and tetraglycidyl ether of tetraphenol ethane and combinations thereof.

### Claim 19 (depends on 11)

The wire or cable according to claim 11, wherein the phosphite is a pentaerythritol diphosphite.
