# US 9,752,031 B2 · Tube made of hydrophilized silicone

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- Number: US 9,752,031 B2
- Document ID: US9752031B2
- Status: Granted
- Kind: B2
- Application number: 14/508,624
- Filed: 2014-10-07
- Published: 2015-04-09
- Granted: 2017-09-05
- Earliest claimed: 2013-10-07
- Assignees: Saint-Gobain Performance Plastics France
- Applicants: Saint-Gobain Performance Plastics France
- Inventors: Alban Letailleur; Boris Jaffrennou; Christophe Le Baron
- Web page: https://patentgrep.com/patent/US9752031B2

## CPC

- C08L 83/04: Polysiloxanes
- B29C 48/0022: {combined with cutting}
- B29C 48/09: Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C 48/10: flexible, e.g. blown foils
- B29C 48/91: Heating, e.g. for cross linking
- B29C 48/9105: {of hollow articles}
- B29C 48/92: Measuring, controlling or regulating
- B29C 48/022: {characterised by the choice of material}
- B29C 2948/92704: Temperature
- B29K 2083/00: Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
- B29K 2105/0088: {Blends of polymers}
- B29L 2023/005: {Hoses, i.e. flexible}
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/46: containing polyether sequences
- C08L 2205/02: containing two or more polymers of the same C08L -group
- F16L 11/04: made of rubber or flexible plastics
- Y10T 428/139: Open-ended, self-supporting conduit, cylinder, or tube-type article
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29L: INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- F16L: PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The invention relates to a process for the production of a piece made of silicone including: (a) the blending of 100 parts by weight of an HCR silicone base having a viscosity of greater than 106 mPa·s with from 0.3 to 7 parts by weight, such as from 0.5 to 5 parts by weight, of an amphiphilic copolymer including hydrophobic polydiorganosiloxane blocks and hydrophilic poly(ethylene oxide), poly(propylene oxide) or ethylene oxide and propylene oxide copolymer blocks, until a homogeneous blend of HCR base and amphiphilic copolymer is obtained, (b) the shaping of the homogeneous blend obtained, and (c) the curing of the shaped blend by heating or irradiation. It also relates to a piece, in particular a tube, manufactured according to this process and to a device comprising such a tube.

## Claims

### Claim 1

A process for the production of a piece made of silicone comprising:
(a) blending of 100 parts by weight of an HCR silicone base having a viscosity of greater than 106 mPa·s with from 0.3 to 7 parts by weight of an amphiphilic copolymer comprising hydrophobic polydiorganosiloxane blocks and hydrophilic poly(ethylene oxide), poly(propylene oxide) or ethylene oxide and propylene oxide copolymer blocks, characterized in that the amphiphilic copolymer comprises, in its polydiorganosiloxane part, reactive groups capable of reacting with the HCR silicone base, wherein the reactive groups comprise vinyl, silanol, alkoxysilyl, hydrosilyl groups, or combination thereof, until a homogeneous blend of HCR base and amphiphilic copolymer is obtained,
(b) shaping of the homogeneous blend obtained, and
(c) curing of the shaped blend.

### Claim 2 (depends on 1)

The process according to claim 1, characterized in that the curing is carried out by heating at a temperature of between 120° C. and 225° C. by irradiation with an appropriate electromagnetic radiation, or combination thereof.

### Claim 3 (depends on 1)

The process according to claim 1, characterized in that the HCR silicone base is:
a two-component base comprising a polydimethylsiloxane having vinyl groups (VMQ), a crosslinking agent having hydrosilyl groups and platinum as catalyst.

### Claim 4 (depends on 1)

The process according to claim 1, characterized in that stage (b) is a stage of extrusion or comprises a stage of extrusion of a profiled element, wherein the profiled element comprises a tube.

### Claim 5 (depends on 1)

The process according to claim 1, characterized in that the amphiphilic copolymer is chosen from the group formed by triblock copolymers of A-B-A structure where each A represents a poly(ethylene oxide) block and B represents a PDMS block, grafted copolymers comprising a single PDMS block to which several poly(ethylene oxide) blocks are grafted, and copolymers formed of a PDMS block comprising from 3 to 8 dimethylsiloxane units to which a single poly(ethylene oxide) block is grafted.

### Claim 6 (depends on 1)

The process according to claim 1, characterized in that stage (b) is a stage of coextrusion of the homogeneous blend obtained with at least one other composition of a thermoplastic or thermosetting organic polymer.

### Claim 7 (depends on 6)

The process according to claim 6, characterized in that the coextruded organic polymer is an elastomer, wherein the elastomer comprises a heat-curable silicone base (HCR) devoid of amphiphilic copolymer.

### Claim 8

A piece made of cured silicone comprising:
100 parts by weight of an HCR silicone base having a viscosity of greater than 106 mPa·s;
0.3 to 7 parts by weight of an amphiphilic copolymer comprising hydrophobic polydiorganosiloxane blocks and hydrophilic poly(ethylene oxide), poly(propylene oxide) or ethylene oxide and propylene oxide copolymer blocks to provide a homogeneous blend of the HCR base and the amphiphilic copolymer, characterized in that the amphiphilic copolymer comprises, in its polydiorganosiloxane part, reactive groups capable of reacting with the HCR silicone base, wherein the reactive groups comprise vinyl, silanol, alkoxysilyl, hydrosilyl groups, or combination thereof.

### Claim 9 (depends on 8)

The piece made of silicone according to claim 8, characterized in that it is a tube.

### Claim 10 (depends on 8)

The piece made of silicone according to claim 8, characterized in that the HCR silicone base is:
a two-component base comprising a polydimethylsiloxane having vinyl groups (VMQ), a crosslinking agent having hydrosilyl groups and platinum as catalyst.

### Claim 11 (depends on 8)

The piece made of silicone according to claim 8, characterized in that the amphiphilic copolymer is chosen from the group formed by triblock copolymers of A-B-A structure where each A represents a poly(ethylene oxide) block and B represents a PDMS block, grafted copolymers comprising a single PDMS block to which several poly(ethylene oxide) blocks are grafted, and copolymers formed of a PDMS block comprising from 3 to 8 dimethylsiloxane units to which a single poly(ethylene oxide) block is grafted.

### Claim 12 (depends on 8)

The piece made of silicone according to claim 8, having reduced protein adsorption of more that 70% compared to an identical material devoid of the amphiphilic copolymer.

### Claim 13

A device comprising at least one piece made of silicone comprising:
100 parts by weight of an HCR silicone base having a viscosity of greater than 106 mPa·s;
0.3 to 7 parts by weight of an amphiphilic copolymer comprising hydrophobic polydiorganosiloxane blocks and hydrophilic poly(ethylene oxide), poly(propylene oxide) or ethylene oxide and propylene oxide copolymer blocks to provide a homogeneous blend of the HCR base and the amphiphilic copolymer, characterized in that the amphiphilic copolymer comprises, in its polydiorganosiloxane part, reactive groups capable of reacting with the HCR silicone base, wherein the reactive groups comprise vinyl, silanol, alkoxysilyl, hydrosilyl groups, or combination thereof;
wherein the at least one piece made of silicone is designed so that, during operation of the device, the surface of the said piece made of silicone comes into contact with aqueous liquids comprising proteins, microorganisms or substances which promote the growth of microorganisms.

### Claim 14 (depends on 13)

The device according to claim 13, characterized in that the HCR silicone base is:
a two-component base comprising a polydimethylsiloxane having vinyl groups (VMQ), a crosslinking agent having hydrosilyl groups and platinum as catalyst.

### Claim 15 (depends on 13)

The device according to claim 13, characterized in that the amphiphilic copolymer is chosen from the group formed by triblock copolymers of A-B-A structure where each A represents a poly(ethylene oxide) block and B represents a PDMS block, grafted copolymers comprising a single PDMS block to which several poly(ethylene oxide) blocks are grafted, and copolymers formed of a PDMS block comprising from 3 to 8 dimethylsiloxane units to which a single poly(ethylene oxide) block is grafted.

### Claim 16 (depends on 13)

The device according to claim 13, characterized in that the device is an electrical device for sampling, pumping, conveying and/or dispensing liquids, designed so that, during operation of the device, the surface of the said piece made of silicone comes into contact with aqueous liquids comprising proteins, microorganisms or substances which promote the growth of microorganisms.

### Claim 17 (depends on 13)

The device according to claim 13, characterized in that the device is a beverage dispensing machine and in that the piece made of silicone is liable to come into contact with an aqueous liquid comprising proteins.
