# US 2021/0277218 A1 · Cross-linked thermoplastic polyvinylidene fluoride compositions

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- Number: US 2021/0277218 A1
- Document ID: US20210277218A1
- Status: Published application
- Kind: A1
- Application number: 17/261,187
- Filed: 2019-07-24
- Published: 2021-09-09
- Earliest claimed: 2018-07-25
- Assignees: Arkema Inc.
- Applicants: Arkema Inc.
- Inventors: James J. HENRY; Gregory S. O'BRIEN
- Web page: https://patentgrep.com/patent/US20210277218A1

## CPC

- B32B 5/20: foamed in situ
- C08L 27/16: Homopolymers or copolymers or vinylidene fluoride
- B32B 1/08: Tubular products
- B32B 5/18: characterised by features of a layer {of} foamed material
- B32B 5/22: characterised by the presence of two or more layers which {are next to each other and are fibrous, filamentary, formed of particles or foamed (layer formed of natural mineral fibres or particles next to a foam layer B32B19/047, next to a layer made of particles B32B19/048, or next to a fibrous or filamentary layer B32B19/06; paper layer or cardboard layer next to a paper layer or cardboard layer B32B29/005, next to a foam layer B32B29/007, next to a fibrous or filamentary layer B32B29/02, or next to a particulate layer B32B29/04)}
- B32B 5/32: {at least two} layers being foamed {and next to each other}
- B32B 27/06: as the main or only constituent of a layer, {which is} next to another layer of {the same or of} a {different material (next to a layer of a particular substance B32B9/045; next to a bituminous or tarry layer B32B11/046; next to a water setting substance layer B32B13/12; next to a metal layer B32B15/08; next to a glass layer B32B17/10; next to a layer formed of natural mineral fibres or particles B32B19/045; next to a wood layer B32B21/08; next to a cellulosic plastic layer B32B23/08; next to a natural or synthetic rubber layer B32B25/08)}
- B32B 27/08: of synthetic resin
- B32B 27/20: using fillers, pigments, thixotroping agents
- B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF}
- B32B 27/322: {comprising halogenated polyolefins, e.g. PTFE}
- C08F 214/22: Vinylidene fluoride
- C08F 259/08: on to polymers containing fluorine
- C08K 5/34924: {containing cyanurate groups; Tautomers thereof}
- C09D 127/16: Homopolymers or copolymers of vinylidene fluoride
- H01B 3/445: {from vinylfluorides or other fluoroethylenic compounds}
- B32B 2266/0235: Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
- B32B 2270/00: Resin or rubber layer containing a blend of at least two different polymers
- B32B 2307/546: Flexural strength; Flexion stiffness
- B32B 2307/558: Impact strength, toughness
- B32B 2307/712: Weather resistant
- B32B 2307/736: Shrinkable
- B32B 2457/00: Electrical equipment
- B32B 2571/00: Protective equipment
- B32B 2597/00: Tubular articles, e.g. hoses, pipes
- C08F 2800/20: as weight or mass percentages
- C08F 2810/20: leading to a crosslinking, either explicitly or inherently
- C08L 2203/202: use in electrical wires or wirecoating
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08L 2312/00: Crosslinking
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- 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})

## Abstract

The invention relates to polyvinylidene fluoride (PVDF) copolymer compositions that have improved crosslinking efficiency and performance. The PVDF copolymer contains a high level (>14 and preferably greater than 16 wt %) of a fluorinated comonomer, and has a high molecular weight as measured by the melt viscosity at 230°C. and 100 sec-1 of 18 to 40 kpoise. The composition can be effectively cross-linked with a low level radiation (high cross-linking efficiency). The cross-linked composition is useful in high-temperature applications, such as automotive wire and cable, and heat shrink tubing.

## Claims

### Claim 1

A cross-linkable polyvinylidene fluoride (PVDF) composition comprising a PVDF copolymer, and said PVDF copolymer comprises from 70 to 84 weight percent of VDF monomer units, and from 16 to 30 weight percent of one or more fluorinated comonomers, wherein the melt viscosity of the PVDF copolymer prior to crosslinking is in the range of from 22 to 29 kpoise when measured at 230° C. and 100 s-1 shear rate, kpoise, and wherein said PVDF copolymer is thermoplastic.

### Claim 2 (depends on 1)

The cross-linkable PVDF composition of claim 1, wherein said comonomer comprises hexafluoropropene.

### Claim 3 (depends on 1)

The cross-linkable PVDF composition of claim 1, wherein said copolymer has a heterogeneous morphology in the solid state.

### Claim 4 (depends on 1)

The cross-linkable PVDF composition of claim 1, wherein the copolymer has a heterogeneous morphology, and has a melting point of greater than 160° C., prior to crosslinking.

### Claim 5 (depends on 1)

The cross-linkable PVDF composition of claim 1, wherein said copolymer has a homogeneous morphology in the solid state.

### Claim 6 (depends on 1)

The cross-linkable PVDF composition of claim 1, wherein an article of the composition is clear.

### Claim 7 (depends on 1)

The cross-linkable PVDF composition of claim 1, further comprising a different PVDF polymer blended with said PVDF copolymer.

### Claim 8 (depends on 1)

The cross-linkable PVDF composition of claim 1, further comprising one or more additives selected from the group consisting of coagents, acid scavengers, fillers, fibers, colorants, carbon, silicates, antioxidants, thermal stabilizers, UV stabilizers, UV absorbers, metal oxides (and hydroxides), plasticizers, flame retardants, processing aides, lubricants, fungicides, nucleating agents, miscible polymers and immiscible polymers.

### Claim 9 (depends on 1)

The cross-linkable PVDF composition of claim 1, wherein said composition can form crosslinks as a result of e-beam, gamma or LED radiation.

### Claim 10 (depends on 9)

The cross-linkable PVDF composition of claim 9, wherein the composition can be effectively crosslinked using 6 MRad or less of radiation.

### Claim 11 (depends on 9)

The cross-linkable PVDF composition of claim 9, wherein the composition can be effectively crosslinked using 3 MRad of less of radiation.

### Claim 12 (depends on 1)

An article formed from the cross-linkable PVDF composition of claim 1, wherein said article is in the form or a wire, cable, filament or sheet.

### Claim 13 (depends on 12)

The article of claim 12, wherein said article is formed by a melt process, followed by exposure to radiation.

### Claim 14 (depends on 13)

The article of claim 13, wherein said crosslinks are formed as a result of e-beam, gamma or LED radiation.

### Claim 15 (depends on 12)

The article of claim 12 wherein the level of radiation used to form the effective crosslinking is 6 MRad or less.

### Claim 16 (depends on 12)

The article of claim 12 wherein the level of radiation used to form the effective crosslinking is 3 MRad or less.

### Claim 17 (depends on 12)

The article of claim 12, wherein the cross-linkable PVDF composition is present in the wire and cable application as the primary insulation, strength member component, fibers, jacket, sub-tube, tube, buffer or heat shrink tubing.

### Claim 18 (depends on 12)

The article of claim 12, formed by a coextrusion process, wherein the layer formed from the cross-linkable PVDF composition directly adheres to a substrate layer.

### Claim 19 (depends on 12)

A method of forming the article of claim 12, the method comprising providing a thermoplastic cross-linkable polyvinylidene fluoride (PVDF) composition comprising a polyvinylidene copolymer having 16 wt percent or more comonomer wherein the melt viscosity of the PVDF copolymer prior to crosslinking is in the range of from 22 to 29 kpoise when measured at 230° C. and 100 s-1 shear rate, melt processing the cross-linkable polyvinylidene fluoride (PVDF) composition to form a shape, exposing the formed shape to radiation.

### Claim 20 (depends on 19)

The method of claim 19, wherein said copolymer has a heterogeneous morphology in the solid state.