Inorganic siloxane ladder composites and methods of their preparation

Patent metadata

Field	Value
Publication number	US-9994597-B2
Application number	US-201415306471-A
Country	US
Kind code	B2
Filing date	Apr 24, 2014
Priority date	Apr 24, 2014
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

Inorganic siloxane ladder polymers with metal-aza/thio crown complexes, and methods of making and using such siloxane ladder polymers are disclosed. The polymers described herein may exhibit self-healing properties, a low dielectric constant, and a low refractive index. These siloxane ladder polymers are anchored to transparent, high-refractive index (RI) metal nanoparticles, such as ZrO 2 , via aza/thio crown macromolecules. The siloxane ladder polymers may be considered as “living polymer network” since the polymer active chain ends may further undergo anionic polymerization.

First claim

What is claimed is:

1. A compound of formula I:

wherein
q is an integer from 1 to 3;
r is an integer from 1 to 10000;
each A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 independently is, —CH 3 , substituted —CH 3 , —CH 2 —C(═O)—H, substituted —CH 2 —C(═O)—H, —C 6 H 5 , substituted —C 6 H 5 , —CH═CH 2 , substituted —CH═CH 2 , —CH 2 —CH═CH 2 , substituted —CH 2 —CH═CH 2 , a metal-aza crown complex, a metal-thio crown complex, or a metal-acrylic acid complex, and wherein at least one of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 is a metal-aza crown complex or a metal thio crown complex, wherein the metal-aza crown complex of the metal-thio crown complex comprises a metallic nanoparticle selected from a ZrO 2 nanoparticle, a TiO 2 nanoparticle, a ZnS nanoparticle, a ZnO nanoparticle, or any combination thereof complex; and
each A 13 , A 14 , A 15 , and A 16 independently is, —CH 2 — or —CF 2 —.

2. The compound of claim 1 , wherein when any one of A 1 to A 12 is the metal-aza crown complex, the metal-aza crown complex comprises the metallic nanoparticle in contact with an aza crown molecule, and the aza crown molecule is selected from formula IIa or IIb:

wherein
s is an integer from 3 to 12;
each R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and
each R 1 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, —NH 2 , a bivalent —O— linked to the siloxane polymer of formula I, a bivalent —CF 2 — linked to the siloxane polymer of formula I, or a bivalent —NH— linked to the siloxane polymer of formula I.

3. The compound of claim 1 , wherein when any one of A 1 to A 12 is the metal-thio crown complex, the metal-thio crown complex comprises a metallic nanoparticle in contact with a thio-crown molecule, and the thio-crown molecule is selected from formula IIIa or IIIb:

wherein:
t is an integer from 3 to 12;
each R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and
each R 1 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, —NH 2 , a bivalent —O— linked to the siloxane polymer of formula I, a bivalent —CF 2 — linked to the siloxane polymer of formula I, or a bivalent —NH— linked to the siloxane polymer of formula I.

4. The compound of claim 1 , wherein the metal-aza crown complex is selected from:

wherein:
M is ZrO 2 nanoparticle, TiO 2 nanoparticle, ZnS nanoparticle, or ZnO nanoparticle;
R is —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and
each R 1 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, —NH 2 , a bivalent —O— linked to the siloxane polymer of formula I, a bivalent —CF 2 — linked to the siloxane polymer of formula I, or a bivalent —NH— linked to the siloxane polymer of formula I.

5. The compound of claim 1 , wherein the metal-thio crown complex is selected from:

wherein:
M is ZrO 2 nanoparticle, TiO 2 nanoparticle, ZnS nanoparticle, or ZnO nanoparticle;
R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and
each R 1 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, —NH 2 , a bivalent —O— linked to the siloxane polymer of formula I, a bivalent —CF 2 — linked to the siloxane polymer of formula I, or a bivalent —NH— linked to the siloxane polymer of formula I.

6. A compound of formula IV:

wherein:
n is an integer from 1 to 100;
A 17 is a metal-aza crown complex or a metal-thio crown complex;
A 18 is a metal-aza crown complex or a metal-thio crown complex;
A 19 is a metal-aza crown complex or a metal-thio crown complex; and
A 20 is a metal-aza crown complex or a metal-thio crown complex.

7. The compound of claim 6 , wherein when any one of A 17 , A 18 , A 19 , or A 20 is the metal-aza crown complex, the metal-aza crown complex comprises a metallic nanoparticle in contact with an aza crown molecule, and the aza crown molecule is selected from formula IIc or IId:

wherein
s is an integer from 3 to 12;
each R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and
each R 2 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, or —NH 2 .

8. The compound of claim 6 , wherein when any one of A 17 , A 18 , A 19 , or A 20 is the metal-thio crown complex, the metal-thio crown complex comprises a metallic nanoparticle in contact with a thio-crown molecule, and the thio-crown molecule is selected from formula IIIc or IIId:

wherein:
t is an integer from 3 to 12;
each R is independently, —O—, —CF 2 —, —C(═O)—O—, —C(═O)—NH—, or —NH—; and
each R 2 is independently, —H, —F, —CF 3 , —OH, —CF 2 Cl, or —NH 2 .

9. The compound of claim 7 , wherein the metallic nanoparticle is a ZrO 2 nanoparticle, a TiO 2 nanoparticle, a ZnS nanoparticle, a ZnO nanoparticle, or any combination thereof.

10. An optical waveguide structure comprising:
a light transmitting core material having a first refractive index; and
a cladding material partially contacting or entirely surrounding the light transmitting core material, wherein the cladding material has a second refractive index lower than the first refractive index of the light transmitting core material, and wherein the light transmitting core material comprises one or more compounds of formula I

wherein:
q is an integer from 1 to 3;
r is an integer from 1 to 10000;
each A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 independently is, —CH 3 , substituted —CH 3 , —CH 2 —C(═O)—H, substituted —CH 2 —C(═O)—H, —C 6 H 5 , substituted —C 6 H 5 , —CH═CH 2 , substituted —CH═CH 2 , —CH 2 —CH═CH 2 , substituted —CH 2 —CH═CH 2 , a metal-aza crown complex, a metal-thio crown complex, or a metal-acrylic acid complex, and wherein at least one of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 , and A 12 is a metal-aza crown complex or a metal-thio crown complex; and
each A 13 , A 14 , A 15 , and A 16 independently is —CH 2 — or —CF 2 —.

11. A method to make a siloxane compound of formula I, the method comprising:
contacting a metal-crown complex with trifluorochloromethane and a silicon metal to form a dichlorosilane-trifluoromethyl-metal-crown complex;
hydrolyzing the dichlorosilane-trifluoromethyl-metal-crown complex to form a fluorinated siloxane polymer compound of formula IV

wherein:
n is an integer from 1 to 100,
A 17 is a metal-aza crown complex or a metal-thio crown complex,
A 18 is a metal-aza crown complex or a metal-thio crown complex,
A 19 is a metal-aza crown complex or a metal-thio crown compl

Assignees

• Empire Technology Dev Llc

Inventors

• Sjong Angele
• Adam Georgius Abidal

Classifications

• G02B6/122

  Basic optical elements, e.g. light-guiding paths · CPC title

• G02B2006/12038

  Glass (SiO2 based materials) · CPC title

• G02B2006/1219

  Polymerisation · CPC title

• C08G83/001

  Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica · CPC title

• C07F7/0838 Primary

  Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21) · CPC title