Flexible to rigid nanoporous polyurethane-acrylate (PUAC) type materials for structural and thermal insulation applications

Patent metadata

Field	Value
Publication number	US-9994516-B2
Application number	US-201615339176-A
Country	US
Kind code	B2
Filing date	Oct 31, 2016
Priority date	Mar 13, 2013
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

Novel urethane-acrylate (UAC) Star monomers and polyurethane-acrylate (PUAC) aerogel polymers derived therefrom are described herein, along with other novel, related monomers and polymers. Also described herein are processes for preparing the UAC Star monomers, the PUAC aerogel polymers, and the other related monomers and polymers. The PUAC and related polymers herein are useful in various applications including in structural and thermal insulation.

First claim

What is claimed is:

1. A norbornene-containing star monomer formed by the reaction of a norbornene-containing hydroxyl compound of the formula (IX)

with a tris(isocyanatophenyl)methane of formula (III)

wherein W is a C 1 -C 6 straight chain or branched alkyl or alkoxyalkyl group;
wherein R1, R2, and R3 are each independently hydrogen or C 1 -C 6 straight chain or branched alkyl group; and,
wherein m is an integer from 1 to 5.

2. A process for preparing the norbornene-containing star monomer of claim 1 , the process comprising the step of mixing a tris(isocyanatophenyl)methane of formula (III) with three molar equivalents of the norbornene-containing hydroxyl compound of formula (IX) in an organic solvent.

3. The process of claim 2 , further comprising the addition of a catalyst.

4. The process of claim 3 , wherein the catalyst is an organotin compound.

5. The process of claim 4 , wherein the organotin compound is dibutyltin dilaurate.

6. The process of claim 2 wherein the organic solvent is selected from the group consisting of a ketone solvent, an ester solvent, and a combination thereof.

7. The process of claim 6 , wherein the organic solvent is acetone, ethyl acetate, or a combination thereof.

8. The norbornene-containing star monomer of claim 1 , wherein, in the norbornene-containing hydroxyl compound of formula (IX), R1=R2=R3=H, W=CH 2 CH 2 , and m=1; and, wherein, in the tris(isocyanatophenyl)methane of formula (III), the nitrogen atoms of the isocyanate groups are attached to their respective aryl rings at the 4-positions of the aryl rings.

9. A polynorbornene-polyurethane polymer formed by polymerization of a norbornene-containing star monomer obtained by the reaction of a norbornene-containing hydroxyl compound of the formula (IX)

with a tris(isocyanatophenyl)methane of formula (III)

wherein W is a C 1 -C 6 straight chain or branched alkyl or alkoxyalkyl group;
wherein R1, R2, and R3 are each independently hydrogen or C 1 -C 6 straight chain or branched alkyl group; and,
wherein m is an integer from 1 to 5.

10. The polynorbornene-polyurethane polymer of claim 9 , wherein, in the compound of formula (IX), R1=R2=R3=H, W=CH 2 CH 2 , and m=1; and, wherein, in the tris(isocyanatophenyl)methane of formula (III), the nitrogen atoms of the isocyanate groups are attached to their respective aryl rings at the 4-positions of the aryl rings.

11. A polynorbornene-polyurethane polymer formed by copolymerization of a norbornene-containing star monomer with a dinorbornene-containing chain extender, wherein the norbornene-containing star monomer is obtained by the reaction of a norbornene-containing hydroxyl compound of the formula (IX)

with a tris(isocyanatophenyl)methane of formula (III)

wherein W is a C 1 -C 6 straight chain or branched alkyl or alkoxyalkyl group;
wherein R1, R2, and R3 are each independently hydrogen or C 1 -C 6 straight chain or branched alkyl group; and,
wherein m is an integer from 1 to 5.

12. The polynorbornene-polyurethane polymer of claim 11 , wherein the dinorbornene-containing chain extender is a compound of the formula (XII):

13. The polynorbornene-polyurethane polymer of claim 9 or claim 11 , wherein the polymerization is ring-opening metathesis polymerization.

14. The polynorbornene-polyurethane polymer of claim 11 , wherein, in the compound of formula (IX), R1=R2=R3=H, W=CH 2 CH 2 , and m=1; and, wherein, in the tris(isocyanatophenyl)methane of formula (III), the nitrogen atoms of the isocyanate groups are attached to their respective aryl rings at the 4-positions of the aryl rings.

15. The polynorbornene-polyurethane polymer of claim 9 or claim 11 , wherein said polymerization is carried out under ring-opening metathesis polymerization conditions.

16. The polynorbornene-polyurethane polymer of claim 9 or claim 11 , wherein the polymer is an aerogel.

Assignees

• Univ Missouri

Inventors

• Leventis Nicholas
• Sotiriou-Leventis Chariklia
• Bang Abhishek

Classifications

• C08F222/106

  Esters of polycondensation macromers · CPC title

• C07C2602/42

  the bicyclo ring system containing seven carbon atoms · CPC title

• B01J2531/42

  Tin · CPC title

• C08F122/10

  Esters · CPC title

• C08F222/10

  Esters · CPC title