Polycyanates of cyclododecane polyphenols and thermosets thereof

Patent metadata

Field	Value
Publication number	US-9487615-B2
Application number	US-201314375335-A
Country	US
Kind code	B2
Filing date	Feb 22, 2013
Priority date	Feb 24, 2012
Publication date	Nov 8, 2016
Grant date	Nov 8, 2016

Abstract

Polycyanates of the formula:

where R, m, Q, p and Z are as defined herein. Methods of curing said polycyanates and methods of using said polycyanates to provide high Tg thermoset products.

First claim

What is claimed is:

1. Polycyanates of the formula:

where
each m independently has a value of zero to 3;
p has a value of one to 20;
each R is independently halogen; nitrile; nitro; C 1 -C 6 alkyl or C 1 -C 6 alkoxy; wherein the alkyl and alkoxy groups may be substituted with one or more halogen atoms, C 2 -C 6 alkenyl, or C 2 -C 6 alkenyloxy;
each Z is H or —C≡N, wherein at least 25% of the Z groups are —C≡N; and
each Q is independently hydrogen or C 1 -C 6 alkyl,
or when m is 2, two R groups may independently be a C 3 -C 4 alkylene group that optionally contains one or two double bonds and is bonded to two adjacent carbons on the ring to which they are attached; thereby producing a fused, bicyclic ring.

2. Polycyanates of claim 1 , wherein R is H.

3. Polycyanates of claim 1 , wherein Q is H or C 1 -C 2 alkyl.

4. Polycyanates of claim 1 , wherein at least 50% of the Z groups are —C≡N.

5. Polycyanates of claim 1 , wherein p is 0 or 1.

6. Polycyanates of claim 1 , wherein 80-100% of the Z groups are —C≡N.

7. Methods of making the compounds of claim 1 , comprising reacting polyphenols of the formula:

where
each m independently has a value of zero to 3;
p has a value of 1 to 20;
each R is independently halogen; nitrile; nitro; C 1 -C 6 alkyl or C 1 -C 6 alkoxy;
wherein the alkyl and alkoxy groups may be substituted with one or more halogen atoms, C 2 -C 6 alkenyl, or C 2 -C 6 alkenyloxy;
each Z is H or —C≡N, wherein at least 25% of the Z groups are —C≡N; and
each Q is independently hydrogen or C 1 -C 6 alkyl,
or when m is 2, two R groups may independently be a C 3 -C 4 alkylene group that optionally contains one or two double bonds and is bonded to two adjacent carbons on the ring to which they are attached; thereby producing a fused, bicyclic ring;
with a cyanogen halide in the presence of a base, and optionally in the presence of a catalyst, a solvent or both.

8. Methods of claim 7 , wherein the reaction is conducted in the presence of at least one solvent.

9. Methods of claim 7 , wherein at least one solvent is an aliphatic ketone, cycloaliphatic ketone, chlorinated hydrocarbon or a mixture thereof.

10. Methods of claim 7 , wherein the base is a tertiary amine.

11. Methods of claim 7 , wherein the cyanogen halide is cyanogen chloride or cyanogen bromide.

12. Methods of claim 7 , wherein the reaction temperature is −10° C. to 0° C.

13. Curable compositions comprising a polycyanate of the formula:

where
each m independently has a value of zero to 3;
p has a value of 1 to 20;
each R is independently halogen; nitrile; nitro; C 1 -C 6 alkyl or C 1 -C 6 alkoxy; wherein the alkyl and alkoxy groups may be substituted with one or more halogen atoms, C 2 -C 6 alkenyl, or C 2 -C 6 alkenyloxy;
each Z is H or —C≡N, wherein at least 25% of the Z groups are —C≡N; and
each Q is independently hydrogen or C 1 -C 6 alkyl,
or when m is 2, two R groups may independently be a C 3 -C 4 alkylene group that optionally contains one or two double bonds and is bonded to two adjacent carbons on the ring to which they are attached; thereby producing a fused, bicyclic ring; and,
optionally at least one curing catalyst and/or curing accelerator.

14. Curable compositions of claim 13 , further comprising one or more thermosettable monomers other than the polycyanate of claim 1 .

15. Curable compositions of claim 14 , wherein the thermosettable monomer further comprises one or more of 1) di- or poly(cyanate) other than the cyanate of claim 1 , 2) bis- or poly(maleimide), 3) epoxy resin, 4) di- or poly(isocyanate), 5) di or poly(cyanamide), or 6) polymerizable mono-, di-, or poly(ethylenically unsaturated) monomers.

16. Curable compositions of claim 15 further comprising optionally at least one curing catalyst and/or curing accelerator.

17. Partially oligomerized or polymerized (B-staged) products, or cured (thermoset) products prepared from the curable compositions of claim 16 .

18. Cured compositions prepared from the curable compositions of claim 17 that are structural or electrical laminate and/or composites, multilayer electronic circuitry, integrated circuit packaging (such as “IC substrates”), filament windings, moldings, encapsulations, castings, composites for aerospace applications, adhesives, functional powder coatings and other protective coatings.

19. Cured compositions of claim 18 in the form of sheets, films, fibers or other shaped articles.

Assignees

• Dow Global Technologies Llc
• Dow Global Technologies Llc

Inventors

• Hefner Jr Robert E
• Molitor Erich J

Classifications

• C08G73/0655

  from polycyanurates · CPC title

• C07C2101/20

  Chemistry & Metallurgy · mapped topic

• C07C261/02

  Cyanates · CPC title

• C08G8/28 Primary

  Chemically modified polycondensates · CPC title

• C08G8/04

  of aldehydes · CPC title