WO2025111137A1 - Anhydride functionalized cyclic polyorganosiloxane - Google Patents
Anhydride functionalized cyclic polyorganosiloxane Download PDFInfo
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- WO2025111137A1 WO2025111137A1 PCT/US2024/054664 US2024054664W WO2025111137A1 WO 2025111137 A1 WO2025111137 A1 WO 2025111137A1 US 2024054664 W US2024054664 W US 2024054664W WO 2025111137 A1 WO2025111137 A1 WO 2025111137A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
Definitions
- the present invention relates to a compound which is an anhydride functionalized cyclic polyorganosiloxane.
- the compound of the present invention is useful as an adhesion promoter in a composition suitable as an encapsulant for a variety of applications including automotive, electrical, electronic and medical applications.
- an adhesion promoter which includes functionalized organosiloxanes.
- US 6,887,932 B2 discloses a vast number of adhesion promoters that are functionalized polyorganosiloxanes containing Si-H groups.
- CN 103467965 A discloses adhesion promoters that are cyclic organosiloxanes containing Si-H, anhydride, and fluoroalkyl groups.
- EP 3 850 049 Bl discloses adhesion promoters that are acid anhydride functionalized polyorganosiloxanes containing Si-H groups.
- WO 2021/262830 discloses a telechelic anhydride terminated polyorganosiloxane of the following formula: where n is from 2 to 20.
- the present invention addresses a need in the art by providing a compound of Formula 1 :
- each R is a Cs-Cn-alkyl anhydride group; the sum of m and n is in the range of from 1 to 4; and -D H X - is a mono- or diradical of the compound of Formula 2:
- the compound of the present invention is useful as an adhesion promoter for polyorganosiloxane compositions. Detailed Description of the Invention
- the present invention addresses a need in the art by providing a compound of Formula 1:
- each R is a C3-Ci2-alkyl anhydride group; the sum of m and n is in the range of from
- anhydride substituents include succinic anhydride, maleic anhydride, oxalic anhydride, and phthalic anhydride groups.
- R is represented by the following fragment: where z is from 1 to 10, and where the dotted line represents the point of attachment to the D H X diyl group.
- D H X is represented by the compound of Formula 2.
- y is 1 .
- D H 4 is represented by the compound of Formula 2a:
- R 1 is phenyl, m is 1, n is 1, y is 1, and z is 1. Accordingly, a possible configuration of a compound of the present invention is represented by Formula 3:
- the R groups can be attached to any of the Si atoms of the D H X groups and that the D H X groups may be a blend of D H X groups.
- D H X may be a mixture of D H 4, D H 5, and D H 6.
- the compound of Formula 1 may comprise a blend of mono-, di-, tri-, and tetrasubstituted alkyl anhydride groups.
- the compound of Formula 1 comprises a blend of mono- and disubstituted alkyl anhydride groups; i.e., m + n is in the range of 1 to 2.
- Formula l 0 and Anh is an anhydride group.
- An example of a suitable acid catalyst is tris(pentafluorophenyl)borane (BCF).
- the compound of the present invention has been found to be suitable as an adhesion promoter in a composition used to improve the adhesion of an organopolysiloxane to a substrate such as paper, metal, plastic, or glass.
- a compound of Formula 2 (99.97 g, y is predominantly 1) then anhydrous toluene (49.97 g) were added to a N2 purged 1-L 3-neck round bottom flask equipped with a thermocouple, an overhead stirrer, and a septum. The contents of the flask were stirred, then BCF catalyst solution (0.32 g, 1% wt.% in toluene) was added. Diphenyldisilanol (56.07 g) was added in 4 portions over the course of ⁇ 1.5 h while maintaining a reaction temperature ⁇ 30 °C. The contents were stirred for an additional 1.5 h after addition was complete. A clear solution was obtained and treated with 36 pL of phenyl acetylene before volatiles were removed in vacuo at 80 °C.
- a liquid silicone rubber (LSR) formulation was prepared by first forming two master batches generally in accordance with the procedure described in US 5,679,727, column 6.
- a second master batch (MB2) was prepared by combining the fumed silica (24.8 pbw) with the vinyl-terminated polydimethylsiloxane (68.0 pbw), and contacting this blend with hexamethyldisilazane and l,l,3,3-tetramethyl-l,3-divinyldisilazane and water to give a vinyl functionalization of 0.08 mmol/g.
- the example (LSR) formulation can be prepared as described above except for the following changes.
- the compound of Formula 3 (1.65 pbw) was added to the formulation at the last step, the amount of trimethyl-terminated polymethylhydrogen dimethylsiloxane was reduced to 0.39 pbw, and the amount of the additional vinyl-terminated polydimethylsiloxane was reduced to 5.29 pbw.
- thermoplastic Ultradur B 4300 G4 Polybutylene Terephthalate 25 -mm x 100-mm substrates with a thickness of 3 mm were cleaned with isopropanol and dried for 18 h at 120 °C.
- the thermoplastic substrates were preheated at 150 °C for 5 min prior to overmolding with the LSR.
- Substrates were overmolded with a 3-mm layer of the LSR formulation, and compression molded for 5 min at 150 °C at a pressure of 300 bar.
- Adhesion was tested in a 90° peel test using a floating roller device as described in DIN EN ISO 22631 (“Adhesives - Test method for adhesives for floor and wall coverings”). A tensile tester was used at a pulling speed of 100 mm/min. The peel strength was calculated as the average peel force, divided by the sample width (25 mm), and reported in N/mm.
- the adhesion test specimen containing the LSR that did not contain any adhesion promoter exhibited a peel strength of 0 N/mm, while the LSR containing the compound of Formula 3 exhibited a peel strength of 2.28 N/mm.
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Abstract
The present invention is a compound of Formula 1: where each R is a C3-C12-alkyl anhydride group; the sum of m and n is in the range of from 1 to 4; and -DHx- is a diradical of the compound of Formula 2: where x is from 3 to 10; and y is x - 3. The compound is useful as an adhesion promoter in a composition suitable as an encapsulant for a variety of applications including automotive, electrical, electronic and medical applications.
Description
Anhydride Functionalized Cyclic Polyorganosiloxane
Background of the Invention
The present invention relates to a compound which is an anhydride functionalized cyclic polyorganosiloxane. The compound of the present invention is useful as an adhesion promoter in a composition suitable as an encapsulant for a variety of applications including automotive, electrical, electronic and medical applications.
The adhesion of silicone-based compositions to substrates such as glass, metal, and a variety of plastics is facilitated with an adhesion promoter, which includes functionalized organosiloxanes.
For example, US 6,887,932 B2 (Azechi) discloses a vast number of adhesion promoters that are functionalized polyorganosiloxanes containing Si-H groups. CN 103467965 A (Shinetsu) discloses adhesion promoters that are cyclic organosiloxanes containing Si-H, anhydride, and fluoroalkyl groups. Similarly, EP 3 850 049 Bl (Felder) discloses adhesion promoters that are acid anhydride functionalized polyorganosiloxanes containing Si-H groups.
WO 2021/262830 (Santos) discloses a telechelic anhydride terminated polyorganosiloxane of the following formula:
where n is from 2 to 20.
There is still a need to develop alternative solutions for adhesion promoters.
Summary of the Invention
The present invention addresses a need in the art by providing a compound of Formula 1 :
Formula 1 where each R is a Cs-Cn-alkyl anhydride group; the sum of m and n is in the range of from 1 to 4; and -DH X- is a mono- or diradical of the compound of Formula 2:
Formula 2 where x is from 3 to 10, and y is x - 3.
The compound of the present invention is useful as an adhesion promoter for polyorganosiloxane compositions. Detailed Description of the Invention
The present invention addresses a need in the art by providing a compound of Formula 1:
Formula 1 where each R is a C3-Ci2-alkyl anhydride group; the sum of m and n is in the range of from
1 to 4; and -DH X- is a mono- or diradical of the compound of Formula 2:
Formula 2 where x is from 3 to 10, and y is x - 3. In another embodiment, x is from 4 to 6.
Examples of suitable anhydride substituents include succinic anhydride, maleic anhydride, oxalic anhydride, and phthalic anhydride groups. Where the anhydride group is a succinic anhydride group, R is represented by the following fragment:
where z is from 1 to 10, and where the dotted line represents the point of attachment to the DH X diyl group.
DH X is represented by the compound of Formula 2. When x is 4, y is 1 . Thus, DH4 is represented by the compound of Formula 2a:
Formula 2a
In one embodiment, R1 is phenyl, m is 1, n is 1, y is 1, and z is 1. Accordingly, a possible configuration of a compound of the present invention is represented by Formula 3:
Formula 3
It is understood that the R groups can be attached to any of the Si atoms of the DH X groups and that the DH X groups may be a blend of DH X groups. For example, DH X may be a mixture of DH4, DH5, and DH6. It is further understood that the compound of Formula 1 may comprise a blend of mono-, di-, tri-, and tetrasubstituted alkyl anhydride groups. In one embodiment, the compound of Formula 1 comprises a blend of mono- and disubstituted alkyl anhydride groups; i.e., m + n is in the range of 1 to 2.
The compound of Formula 1 (where m is 1 and n is 1) can be prepared in 2-steps, as illustrated:
where Formula lo is represented by the following formula:
Formula l0 and Anh is an anhydride group. An example of a suitable acid catalyst is tris(pentafluorophenyl)borane (BCF).
The compound of the present invention has been found to be suitable as an adhesion promoter in a composition used to improve the adhesion of an organopolysiloxane to a substrate such as paper, metal, plastic, or glass.
Examples
Intermediate Example 1 - Preparation of Formula l0
A compound of Formula 2 (99.97 g, y is predominantly 1) then anhydrous toluene (49.97 g) were added to a N2 purged 1-L 3-neck round bottom flask equipped with a thermocouple, an overhead stirrer, and a septum. The contents of the flask were stirred, then BCF catalyst solution (0.32 g, 1% wt.% in toluene) was added. Diphenyldisilanol (56.07 g) was added in 4 portions over the course of ~1.5 h while maintaining a reaction temperature < 30 °C. The contents were stirred for an additional 1.5 h after addition was complete. A clear solution was obtained and treated with 36 pL of phenyl acetylene before volatiles were removed in vacuo at 80 °C.
Example - Preparation of a Compound of Formula 3
The compound of Formula lo (81.0 g) was charged into a three-neck round bottom flask and heated to 75 °C under N2 with stirring. Karstedt’s catalyst (5 ppm) was added, followed by the gradual addition of an allyl succinic anhydride solution (29.0 g in 7 g toluene). The addition rate was controlled so that the reaction mixture temperature did not exceed 80 °C. After completion of the addition, the reaction mixture was stirred at 75 °C under N2 for additional 1 h being allowed to cool to room temperature. 1-Ethynyl-l -cyclohexanol (0.43 g) was added to the mixture, after which time volatiles were removed in vacuo.
Preparation of Liquid Silicone Rubber Formulations
Comparative Example - Preparation of a Liquid Silicone Rubber Formulation without Adhesion Promoter
A liquid silicone rubber (LSR) formulation was prepared by first forming two master batches generally in accordance with the procedure described in US 5,679,727, column 6. A first master batch (MB1) was prepared by combining fumed silica (surface area 300 m2/g, 22.4 pbw) with a vinyl-terminated poly dimethylsiloxane (viscosity7 = 53,000 mPa s at 25°C, 70.8 pbw), and contacting the blend with hexamethyldisilazane and water. A second master batch (MB2) was prepared by combining the fumed silica (24.8 pbw) with the vinyl-terminated polydimethylsiloxane (68.0 pbw), and contacting this blend with hexamethyldisilazane and l,l,3,3-tetramethyl-l,3-divinyldisilazane and water to give a vinyl functionalization of 0.08 mmol/g.
A portion of MB1 (17.7 pbw) was blended with a portion of MB2 (70.32 pbw) along with additional vinyl-terminated polydimethylsiloxane (6.52 pbw). Then, a vinyl-terminated polydimethylsiloxane-co-methylvinylsiloxane (1.16% vinyl functionality, viscosity = 370 mPa s at 25 °C, 5.06 pbw) was blended into the mixture along with Karstedt’s catalyst (0.0025 pbw), trimethyl-terminated polymethylhydrogen dimethylsiloxane (viscosity = 30 mPa s at 25 °C, 0.80 pbw), and ethinyl-cyclohexanol (0.04 pbw). The LSR was used shortly after preparation to prevent premature curing.
Example - Preparation of a Liquid Silicone Rubber Formulation with Adhesion Promoter
The example (LSR) formulation can be prepared as described above except for the following changes. The compound of Formula 3 (1.65 pbw) was added to the formulation at the last step, the amount of trimethyl-terminated polymethylhydrogen dimethylsiloxane was reduced to 0.39 pbw, and the amount of the additional vinyl-terminated polydimethylsiloxane was reduced to 5.29 pbw.
Peel Strength Testing Procedure
Two thermoplastic Ultradur B 4300 G4 Polybutylene Terephthalate 25 -mm x 100-mm substrates with a thickness of 3 mm were cleaned with isopropanol and dried for 18 h at 120 °C. The thermoplastic substrates were preheated at 150 °C for 5 min prior to overmolding with the LSR. Substrates were overmolded with a 3-mm layer of the LSR formulation, and compression molded for 5 min at 150 °C at a pressure of 300 bar.
Adhesion was tested in a 90° peel test using a floating roller device as described in DIN EN ISO 22631 (“Adhesives - Test method for adhesives for floor and wall coverings”). A tensile tester was used at a pulling speed of 100 mm/min. The peel strength was calculated as the average peel force, divided by the sample width (25 mm), and reported in N/mm. The adhesion test specimen containing the LSR that did not contain any adhesion promoter exhibited a peel strength of 0 N/mm, while the LSR containing the compound of Formula 3 exhibited a peel strength of 2.28 N/mm.
Claims
1. A compound of Formula 1 :
Formula 1 where each R is a Cs-Cn-alkyl anhydride group; the sum of m and n is in the range of from 1 to 4; and -DH X- is a mono- or diradical of the compound of Formula 2:
Formula 2 where x is from 3 to 10; and y is x - 3.
2. The compound of Claim 1 wherein x is in the range of from 4 to 6; and m + n is in the range of from 1 to 2.
3. The compound of Claim 2 where x is 4.
4. The compound of Claim 1 which is represented by the following Formula 3:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202363601812P | 2023-11-22 | 2023-11-22 | |
| US63/601,812 | 2023-11-22 |
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| Publication Number | Publication Date |
|---|---|
| WO2025111137A1 true WO2025111137A1 (en) | 2025-05-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2024/054664 Pending WO2025111137A1 (en) | 2023-11-22 | 2024-11-06 | Anhydride functionalized cyclic polyorganosiloxane |
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| WO (1) | WO2025111137A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679727A (en) | 1996-03-28 | 1997-10-21 | Dow Corning Corporation | Curable organosiloxane composition with improved hysteresis characteristics |
| US6887932B2 (en) | 2000-07-11 | 2005-05-03 | Shin-Etsu Chemical Co., Ltd. | Silicone rubber adhesive composition and integrally molded article thereof |
| CN103467965A (en) | 2012-06-05 | 2013-12-25 | 信越化学工业株式会社 | Curable composition for encapsulating optical semiconductor and optical semiconductor apparatus using the same |
| WO2021262830A1 (en) | 2020-06-24 | 2021-12-30 | Dow Silicones Corporation | Silicone elastomer compositions |
| EP3850049B1 (en) | 2018-09-13 | 2023-03-08 | Momentive Performance Materials GmbH | Functional polysiloxanes |
-
2024
- 2024-11-06 WO PCT/US2024/054664 patent/WO2025111137A1/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679727A (en) | 1996-03-28 | 1997-10-21 | Dow Corning Corporation | Curable organosiloxane composition with improved hysteresis characteristics |
| US6887932B2 (en) | 2000-07-11 | 2005-05-03 | Shin-Etsu Chemical Co., Ltd. | Silicone rubber adhesive composition and integrally molded article thereof |
| CN103467965A (en) | 2012-06-05 | 2013-12-25 | 信越化学工业株式会社 | Curable composition for encapsulating optical semiconductor and optical semiconductor apparatus using the same |
| EP3850049B1 (en) | 2018-09-13 | 2023-03-08 | Momentive Performance Materials GmbH | Functional polysiloxanes |
| WO2021262830A1 (en) | 2020-06-24 | 2021-12-30 | Dow Silicones Corporation | Silicone elastomer compositions |
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