# US 11,999,852 B2 · Use of aryl group containing organopolysiloxane gums as additives to increase rheological behavior

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- Number: US 11,999,852 B2
- Document ID: US11999852B2
- Status: Granted
- Kind: B2
- Application number: 18/190,392
- Filed: 2023-03-27
- Published: 2023-08-10
- Granted: 2024-06-04
- Earliest claimed: 2020-04-15
- Assignees: Elkem Silicones USA Corp.
- Applicants: Elkem Silicones USA Corp.
- Inventors: Remi Thiria; Daniel Hess
- Web page: https://patentgrep.com/patent/US11999852B2

## CPC

- C08L 83/04: Polysiloxanes
- B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C 64/118: using filamentary material being melted, e.g. fused deposition modelling [FDM]
- B33Y 70/00: Materials specially adapted for additive manufacturing
- B29C 64/112: using individual droplets, e.g. from jetting heads
- B29K 2083/00: Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
- B33Y 10/00: Processes of additive manufacturing
- C08G 77/12: containing silicon bound to hydrogen
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/80: {Siloxanes having aromatic substituents, e.g. phenyl side groups}
- 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 2205/035: containing four or more polymers in a blend
- 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)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- 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
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

Curable silicone compositions comprising an aryl group-containing organopolysiloxane gum having a consistency of 200 to 900 as a rheological modifier are provided. Use of the curable silicone compositions comprising an aryl group-containing organopolysiloxane gum having a consistency of 200 to 900 in methods for additive manufacturing a three-dimensional silicone elastomer article are further provided.

## Claims

### Claim 1

An addition-curable liquid silicone composition X for additive manufacturing a silicone elastomer article, wherein said addition-curable liquid silicone composition X comprises:
(A) at least one organopolysiloxane A having at least two silicon-bonded C2 to C20 alkenyl groups per molecule,
(B) at least one organosilicon crosslinker B containing at least two silicon-bonded hydrogen atoms per molecule,
(C) at least one organopolysiloxane gum C having a consistency of between 200 and 900 at 25° C. and containing at least one silicon-bonded C2 to C20 alkenyl group per molecule and at least one silicon-bonded C6 to C12 aryl groups per molecule,
(D) at least one addition reaction catalyst D,
(E) at least one filler E,
(F) optionally, at least one diorganohydrogensiloxy-terminated diorganopolysiloxane chain extender F,
(G) optionally, at least one cure rate modifier G,
(H) optionally, at least one silicone resin H, and
(I) optionally, at least one additive I.

### Claim 2 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein said at least one organopolysiloxane A having at least two silicon-bonded C2 to C20 alkenyl groups per molecule is of the following formula (1):
wherein:
n is an integer ranging from 1 to 1000,
R is independently selected from a C1 to C20 alkyl group a C6 to C12 aryl group or a C2 to C20 alkenyl group,
R′ is independently selected from a C2 to C20 alkenyl group, and
R″ is independently selected from a C1 to C20 alkyl group or a C6 to C12 aryl group.

### Claim 3 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein said at least one organopolysiloxane A having at least two silicon-bonded C2 to C20 alkenyl groups per molecule is of the following formula (1):
wherein:
n is an integer ranging from 1 to 1000,
R is a methyl group,
R′ is a vinyl group, and
R″ is a methyl group.

### Claim 4 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein the at least one organosilicon crosslinker B containing at least two silicon-bonded hydrogen atoms per molecule comprises:
(i) at least two siloxy units of formula (XL-1) which may be identical or different:
(H)(Z)eSiO(3-e)/2 (XL-1)
wherein:
the symbol H represents a hydrogen atom,
the symbol Z represents an alkyl having from 1 to 8 carbon atoms, and
the symbol e is equal to 0, 1 or 2; and
(ii) at least one, and optionally from 1 to 550 of siloxy unit(s) of formula (XL-2):
(Z)q SiO(4-g)/2 (XL-2)
wherein:
the symbol Z represents an alkyl having from 1 to 8 carbon atoms, or a C6-C12 aryl group, and
the symbol g is equal to 0, 1, 2 or 3;
wherein Z in XL-1 and XL-2 can be the same or different.

### Claim 5 (depends on 4)

The addition-curable liquid silicone composition X according to claim 4, wherein the at least one organosilicon crosslinker B comprises from 3 to 60 siloxy units of formula (XL-1) and from 1 to 250 siloxy unit(s) of formula (XL-2).

### Claim 6 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein the at least one organopolysiloxane gum C containing at least one silicon-bonded C2 to C20 alkenyl groups per molecule and at least one silicon-bonded C6 to C12 aryl groups per molecule comprises:
at least one siloxy unit of formula (A-3):
(Alk)(R)hSiO(3-h)/2 (A-3)
wherein the symbol “Alk” represents a C2 to C20 alkenyl group, and the symbol R represents a C1 to C20 alkyl group, or a C6-C12 aryl group in which each instance of “Alk” and R can be the same or different, and
wherein h=1 or 2, and
at least one siloxy unit of formula (A-4):
(Ar)k(R′)hSiO(4-h-k)/2 (A-4)
wherein the symbol “Ar” represents a C6-C12 aryl group optionally substituted by a C2-C20 alkylene group, or a C1-C20 aralkyl optionally substituted by a C2-C20 alkylene group, or a naphthyl group optionally substituted by a C1-C20 alkyl group and/or a C2-C20 alkylene group, or an anthracenyl group optionally substituted by a C1-C20 alkyl group and/or a C2-C20 alkylene group, and the symbol R1 represents a C1 to C20 alkyl group, or a C2 to 20 alkenyl group, in which each instance of “Ar” and R1 can be the same or different, and
wherein h=0, 1, or 2,
wherein k=1 or 2, and wherein h+k=1, 2, or 3;
other siloxy units of formula (A-2):
(L)g SiO(4-g)/2 (A-2)
in which the symbol L represents a C1 to C20 alkyl group, and the symbol g is equal to 0, 1, 2, or 3, in which each instance of L can be the same or different.

### Claim 7 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein at least one organopolysiloxane gum C containing at least one silicon-bonded C2 to C2 alkenyl groups per molecule and at least one silicon-bonded C6 to C12 aryl groups per molecule comprises:
at least one siloxy unit of formula (A-3):
(Alk)(R)hSiO(3-h)/2 (A-3)
wherein the symbol “Alk” represents a vinyl group, and the symbol R represents a C1 to C20 alkyl group, or a C6-C12 aryl group in which each instance of “Alk” and R can be the same or different, and
wherein h=1 or 2, and
at least one siloxy unit of formula (A-4):
(Ar)k(R1)hSiO(4-h-k)2 (A-4)
wherein the symbol “Ar” represents a phenyl group, and the symbol R1 represents a C1 to C20 alkyl group, or a C2 to C20 alkenyl group, in which each instance of “Ar” and R1 can be the same or different, and
wherein h=0 or 1,
wherein k=2, and
other siloxy units of formula (A-2):
(L)g SiO(4-g)/2 (A-2)
in which the symbol L represents a C1 to C20 alkyl group, and the symbol g is equal to 0, 1, 2, or 3, in which each instance of L can be the same or different.

### Claim 8 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein the at least one organopolysiloxane gum C containing at least one silicon-bonded C2 to C20 alkenyl groups per molecule and at least one silicon-bonded C6 to C12 aryl groups per molecule is a diphenylsiloxane-dimethylsiloxane-vinylmethylsiloxane copolymer gum.

### Claim 9 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein the at least one organopolysiloxane gum C containing at least one silicon-bonded C2 to C20 alkenyl groups per molecule and at least one silicon-bonded C6 to C12 aryl groups per molecule is vinyl-terminated.

### Claim 10 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein the at least one organopolysiloxane gum C containing at least one silicon-bonded C2 to C20 alkenyl groups per molecule and at least one silicon-bonded C6 to C12 aryl groups per molecule comprises less than 30 mole % of aryl groups.

### Claim 11 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein the at least one organopolysiloxane gum C containing at least one silicon-bonded C2 to C20 alkenyl groups per molecule and at least one silicon-bonded C6 to C12 aryl groups per molecule comprises from about 10 mole % to about 20 mole % of aryl groups.

### Claim 12 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein the catalyst D is a platinum group metal-containing catalyst.

### Claim 13 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1, wherein the at least one filler E is fumed silica treated using at least one compatibilization agent in the presence of at least one portion of the at least one alkenyl group-containing organopolysiloxane A.

### Claim 14 (depends on 1)

The addition-curable liquid silicone composition X according to claim 1 for use with a 3D printer.

### Claim 15 (depends on 14)

The addition-curable liquid silicone composition X according to claim 14, wherein the 3D printer is selected from an extrusion 3D printer or a material jetting 3D printer.

### Claim 16 (depends on 2)

The addition-curable liquid silicone composition X according to claim 2, wherein
R is a C1-C20 alkyl group selected from the group consisting of a methyl, ethyl, and propyl group; a C6 to C12 aryl group selected from the group consisting of a xylyl, tolyl, and phenyl group; or a C2 to C20 alkenyl selected from the group consisting of a vinyl, allyl, hexenyl, decenyl, and tetradecenyl group;
R′ is a C2 to C20 alkenyl group selected from the group consisting of a vinyl, allyl, hexenyl, decenyl, and tetradecenyl group; and
R″ is a C1-C20 alkyl group selected from the group consisting of a methyl, ethyl, and propyl group; or a C6 to C12 aryl group selected from the group consisting of a xylyl, tolyl, and phenyl group.

### Claim 17 (depends on 4)

The addition-curable liquid silicone composition X according to claim 4, wherein the C6-C12 aryl group is selected from the group consisting of a xylyl, tolyl, and phenyl group.

### Claim 18 (depends on 6)

The addition-curable liquid silicone composition X according to claim 6, wherein “Alk” represents a C2 to C20 alkenyl group selected from the group consisting of a vinyl, allyl, hexenyl, decenyl, and tetradecenyl group;
the symbol R represents a C1 to C20 alkyl group selected from the group consisting of a methyl, ethyl, and propyl group, or or a C6-C12 aryl group selected from the group consisting of a xylyl, tolyl, and phenyl group;
the symbol “Ar” represents a C6-C12 aryl group optionally substituted by a C2-C20 alkylene group selected from the grup consisting of a xylyl, tolyl, xylene, and phenyl group;
the symbol R1 represents a C1 to C20 alkyl group selected from the group consisting of a methyl, ethyl, and propyl group, or a a C2 to 20 alkenyl group selected from the group consisting of a vinyl, allyl, hexenyl, decenyl, and tetradecenyl group; and
the symbol “L” represents a C1 to C20 alkyl group selected from the group consisting of a methyl, ethyl, and propyl group.

### Claim 19 (depends on 7)

The addition-curable liquid silicone composition X according to claim 7, wherein the symbol R represents a C1 to C20 alkyl group selected from the group consisting of methyl, ethyl, and propyl group, or a C6-C12 aryl group selected from the group consisting of xylyl, tolyl, and phenyl group;
and the symbol R1 represents a C1 to C20 alkyl group selected from the group consisting of a methyl, ethyl, and propyl group, or a C2 to C20 alkenyl group selected from the group consisting of a vinyl, allyl, hexenyl, decenyl, and tetradecenyl group; and
the symbol L represents a C1 to C20 alkyl group selected from the group consisting of a methyl, ethyl, and propyl group.