Transparent polymers and methods for making the same

Patent metadata

Field	Value
Publication number	US-10414870-B2
Application number	US-201514807243-A
Country	US
Kind code	B2
Filing date	Jul 23, 2015
Priority date	Jul 23, 2015
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

A novel copolymer is made from a thiol terminated hydrocarbon monomer and at least one additional monomer chosen from the compounds of i) a terminally unsaturated hydrocarbon monomer, ii) an isocyanate functionalized hydrocarbon monomer and iii) a silane monomer substituted with two or more C 2 to C 8 terminally unsaturated alkenyl groups or C 2 to C 8 terminally unsaturated alkynyl groups, wherein the copolymer is a linear polymer, branched polymer or crosslinked polymer network, with the following provisos: if the at least one additional monomer is either a) a terminally unsaturated hydrocarbon monomer that is not a polymer having 12 carbon atoms or more, or b) a silane monomer, then the thiol terminated hydrocarbon monomer includes a saturated hydrocarbon ring with two or more terminal thiol groups attached to the hydrocarbon ring; if the terminally unsaturated hydrocarbon monomer is polybutadiene, the polybutadiene contains from about 0 mol % to about 30 mol % of polymer units in the cis-1,4-butadiene form; and if the at least one additional monomer is an isocyanate functionalized hydrocarbon monomer, then a ratio of the molecular mass of the thiol terminated hydrocarbon monomer to the number of sulfur atoms in the thiol terminated hydrocarbon monomer ranges from 65 to 500.

First claim

What is claimed is:

1. A copolymer made from a thiol terminated hydrocarbon monomer and a terminally unsaturated hydrocarbon monomer, the terminally unsaturated hydrocarbon monomer being a polymer having 12 carbon atoms or more and comprising a plurality of unsaturated groups and the thiol terminated hydrocarbon monomer being a substituted or unsubstituted, linear, branched or cyclic C 3 to C 36 saturated hydrocarbon having two or more terminal thiol groups, wherein the copolymer is a linear polymer, branched polymer or crosslinked polymer network and is transparent to radiation in the visual spectrum and the infrared (“IR”) wavelength range of about 4 microns to about 12 microns,
wherein the thiol terminated hydrocarbon monomer and the terminally unsaturated hydrocarbon monomer react to form A′ x B y , where A′ is the polymer units formed from the thiol terminated hydrocarbon monomer, B′ is the polymer units formed from the terminally unsaturated hydrocarbon monomer and x and y each range from 0.3 to 0.7, where x+y=1; and
with the proviso that if the terminally unsaturated hydrocarbon monomer is polybutadiene, the polybutadiene is a compound of formula 6:

where:
m ranges from about 70 mol % to about 90 mol %; and
n and o each range from 0 mol % to about 30 mol %, where n+o ranges from about 10 mol % to about 30 mol %.

2. The copolymer of claim 1 , wherein the thiol terminated hydrocarbon monomer is chosen from compounds of formulas 1 and 2:

where:
R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently chosen from hydrogen, —SH and —R′SH, where R′ is a C 1 to C 10 hydrocarbon bridge and at least two of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are not hydrogen; and
R 7 is a C 2 to C 10 hydrocarbon bridge.

3. The copolymer of claim 1 , wherein the terminally unsaturated hydrocarbon monomer is the compound of formula 6.

4. The copolymer of claim 3 , wherein the thiol terminated hydrocarbon monomer is a compound of formula 2:
HS—R 7 —SH   2,

where R 7 is a C 2 to C 10 hydrocarbon bridge.

5. A method of forming a copolymer, the method comprising:
combining a thiol terminated hydrocarbon monomer and at least one additional monomer to form a mixture, the at least one additional monomer being chosen from compounds of (i) a terminally unsaturated hydrocarbon monomer and (ii) an isocyanate functionalized hydrocarbon monomer; and
reacting the thiol terminated hydrocarbon monomer and the at least one additional monomer to form the copolymer, the copolymer being transparent to radiation in at least one of the visual spectrum or the infrared (“IR”) wavelength range of about 4 microns to about 12 microns,
with the following provisos:
if the at least one additional monomer is a terminally unsaturated hydrocarbon monomer, then the thiol terminated hydrocarbon monomer is a compound of formula 1:

where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently chosen from hydrogen and R′SH, where R′ is a C 2 to C 10 hydrocarbon bridge and at least two of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are not hydrogen;

if the terminally unsaturated hydrocarbon monomer is polybutadiene, the polybutadiene contains from about 10 mol % to about 30 mol % of polymer units in a cis-1,4-butadiene form; and
if the at least one additional monomer is an isocyanate functionalized hydrocarbon monomer, then a ratio of the molecular mass of the thiol terminated hydrocarbon monomer to the number of sulfur atoms in the thiol terminated hydrocarbon monomer ranges from 65 to 500,
if the at least one additional monomer is a terminally unsaturated hydrocarbon monomer then the thiol terminated hydrocarbon monomer and the terminally unsaturated hydrocarbon monomer react to form A′ x B′ y , where A′ is the polymer units formed from the thiol terminated hydrocarbon monomer, B′ is the polymer units formed from the terminally unsaturated hydrocarbon monomer and x and y each range from 0.3 to 0.7, where x+y=1; and
if the at least one additional monomer is an isocyanate functionalized hydrocarbon monomer, then the thiol terminated hydrocarbon monomer is the compound of formula 1 above, where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently chosen from H, —SH and —R′SH, where R′ is a C 1 to C 10 hydrocarbon bridge and at least two of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are not hydrogen.

6. The method of claim 5 , wherein the at least one additional monomer is the terminally unsaturated hydrocarbon monomer, and further wherein the reacting comprises exposing the mixture to ultraviolet light.

7. The method of claim 6 , wherein the terminally unsaturated hydrocarbon monomer is a compound of formulas of 3, 4, 5, or 6:

where:
R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are independently chosen from H and alkenyl substituents having a terminal vinyl group, where at least two of R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are not hydrogen;
R′ is a C 2 to C 10 hydrocarbon bridge;
r is an integer ranging from 1 to 10;
m ranges from about 70 mol % to about 90 mol %, and
n and o each range from 0 mol % to about 30 mol %, where n+o ranges from about 10 mol % to about 30 mol %.

8. The method of claim 5 , wherein the at least one additional monomer is the isocyanate functionalized hydrocarbon monomer, and further wherein the reacting comprises adding a catalyst to the mixture.

9. The method of claim 8 , wherein the catalyst is an amine.

10. The method of claim 8 , wherein the isocyanate functionalized hydrocarbon monomer is a compound of formula 7 or 8:

where R 14 is a C 3 to C 12 n-alkyl bridge.

11. The method of claim 5 , wherein if the at least one additional monomer is an isocyanate functionalized hydrocarbon monomer, then the thiol terminated hydrocarbon monomer is the compound of formula 1 above, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently chosen from H and —R′SH, where R′ is a C 1 to C 10 hydrocarbon bridge and at least two of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are not hydrogen.

12. A copolymer made from a thiol terminated hydrocarbon monomer and at least one additional monomer chosen from compounds of i) a terminally unsaturated hydrocarbon monomer and ii) an isocyanate functionalized hydrocarbon monomer, wherein the copolymer is a crosslinked polymer network and is transparent to radiation in at least one of the visual spectrum or the infrared (“IR”) wavelength range of about 4 microns to about 12 microns,
with the following provisos:
if the at least one additional monomer is a terminally unsaturated hydrocarbon monomer, then the thiol terminated hydrocarbon monomer is a compound of formula 1:

where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently chosen from hydrogen and —R′SH, where R′ is a C 2 to C 10 hydrocarbon bridge and at least two of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are not hydrogen;

if the terminally unsaturated hydrocarbon monomer is polybutadien

Assignees

• Boeing Co

Inventors

• Nowak Andrew P
• Rodriguez April R
• Stache Erin E

Classifications

• G02B1/043

  Contact lenses · CPC title

• G02B1/04

  made of organic materials, e.g. plastics (G02B1/08 takes precedence) · CPC title

• C08G75/00

  Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule · CPC title

• C08G18/73

  acyclic · CPC title

• C08G18/722

  Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates · CPC title