WO2021237695A1

WO2021237695A1 - Reactive type phosphate and preparation process

Info

Publication number: WO2021237695A1
Application number: PCT/CN2020/093358
Authority: WO
Inventors: Simon YE; Ethan Wang; Emerson Bao
Original assignee: Blue Cube Ip Llc
Priority date: 2020-05-29
Filing date: 2020-05-29
Publication date: 2021-12-02
Also published as: TW202144372A; CN115698157A

Abstract

Provided herein are phosphorus-based flame retardant compounds that provide both good electrical characteristics and good heat resistance characteristics when incorporated into PCB compositions. In particular, provided herein are new organophosphorus-based polymers that contain C=C double bonds, which allows them react with other components (for example, C=C bond capped polyphenyl ether, unsaturated hydrocarbon resin, bismaleic imide, etc. ) to form a crosslinked network.

Description

REACTIVE TYPE PHOSPHATE AND PREPARATION PROCESS

BACKGROUND

Continuing advances in computer engineering have created an increasing demand for high speed, low loss printed circuit board ( “PCB” ) materials. As compared to previous generations of PCB materials, high speed, low loss PCB materials exhibit less change in the dielectric constant (Dk) as the transmission frequency increases, and exhibit a relatively low dielectric loss.

Recently, it has become particularly important to develop high speed, low loss PCB materials that are halogen-free and exhibit a superior low dissipation factor (Df) . Formulations known in the art are typically based on radically cured resin systems, for example, systems comprising hydrocarbon resins containing abundant C=C double bonds, acrylate capped polyphenyl ether (PPE) , and/or crosslinking agents with abundant C=C double bonds.

Unfortunately, there is an absence of phosphorus-based flame retardants having a sufficiently low Df to be useful in these high-performance PCB systems. Currently known reactive-type flame retardants do not provide the required electrical performance characteristics. While certain additive-type flame retardants, such as resorcinol bis [di (2, 6-dimethylphenyl) phosphate] , will provide the required electrical performance characteristics, these additive-type flame retardants will significantly decrease the heat resistance of the composition, including the glass transition temperature (Tg) and decomposition temperature (Td) .

Accordingly, it is desirable to develop alternatives to existing phosphorus-based flame retardants that provide both good electrical characteristics and good heat resistance characteristics. In particular, there is a need in the art for an alternative phosphorus-based flame retardant that provides electrical performance characteristics comparable to (or better than) resorcinol bis [di (2, 6-dimethylphenyl) phosphate] while also providing improved heat resistance characteristics relative to resorcinol bis [di (2, 6-dimethylphenyl) phosphate] .

SUMMARY

Provided herein is a compound of Formula A,

wherein each Ar ¹ is independently a moiety of structure (1) ;

R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

R ⁴ and R ⁵ are each independently a moiety comprising at least one C=C double bond;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-; R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl; and n is an integer greater than or equal to 1.

Also provided herein is a compound of Formula I,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

and n is an integer greater than or equal to 1.

Also provided herein is a compound of Formula II,

and n is an integer greater than or equal to 1.

Further provided herein is a compound of Formula III,

and n is an integer greater than or equal to 1.

Also provided herein is a curable unsaturated resin composition, wherein the composition comprises at least one unsaturated resin and a flame retardant compound selected from the group consisting of Formula A, Formula I, Formula Ia, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula IId, Formula IIe, Formula IIf, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IIIe, and Formula IIIf.

As used herein, the term “unsaturated resin” refers to a resin comprising at least one C=C double bond.

Also provided herein is a cured unsaturated resin composition, wherein the unsaturated resin composition comprises a flame retardant compound selected from the group consisting of Formula A, Formula I, Formula Ia, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula IId, Formula IIe, Formula IIf, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IIIe, and Formula IIIf.

Also provided herein is a printed circuit board comprising a cured unsaturated resin composition, wherein the unsaturated resin composition comprises a flame retardant compound selected from the group consisting of Formula A, Formula I, Formula Ia, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula IId, Formula IIe, Formula IIf, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IIIe, and Formula IIIf.

Other objects and features will be in part apparent and in part pointed out hereinafter.

DETAILED DESCRIPTION

Provided herein are phosphorus-based flame retardant compounds that provide both good electrical characteristics and good heat resistance characteristics.

In particular, provided herein are new organophosphorus-based polymers that contain C=C double bonds, which allows them react with other components (for example, C=C double capped polyphenyl ether, unsaturated hydrocarbon resin, bismaleic imide, etc. ) to form a crosslinked network. Surprisingly, it has been discovered that these reactive-type compounds provide good dielectric performance and heat resistance when incorporated into PCB compositions.

For example, provided herein is a compound of Formula A,

wherein each Ar ¹ is independently a moiety of structure (1) ;

and n is an integer greater than or equal to 1.

In preferred embodiments, R ⁴ and R ⁵ are each independently selected from the group consisting of structure (1) , structure (2) , and structure (3) ;

As used herein, the term “alkyl” refers to a straight or branched chain moiety comprising up to 10 carbon atoms. Non-limiting examples of suitable alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. The alkyl group may be a straight-chain alkyl group or a branched alkyl group (e.g., isopropyl) . In some embodiments, the alkyl group is optionally independently substituted with one or more substituents selected from the group consisting of methoxyl, carboxyl, .

As used herein, the term “aryl” refers to an aromatic moiety comprising from 6 to 14 carbon atoms. In some embodiments, the aryl group is optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl. Non-limiting examples of suitable aryl groups include phenyl, naphthyl, benzyl, tolyl, and xylyl.

As used herein, the term “alkoxyl” refers to a group of the form -OR′, wherein R′ is alkyl as defined herein. For example, the group -OCH ₃ may be referred to herein as “methoxyl. ” The group -OCH ₂CH ₃ may be referred to herein as “ethoxyl. ”

As used herein, the term “aryloxyl” refers to a group of the form -OR′, wherein R′ is aryl as defined herein. For example, the group -O (C ₆H ₆) may be referred to herein as “phenoxyl. ”

As used herein, the term “hydrogen” includes both stable isotopes of hydrogen, namely ¹H (also known as protium) and ²H (also known as deuterium) .

As used herein, the term “carboxyl” refers to a group of the form -C (O) OH.

In preferred embodiments, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In some embodiments, each Ar ² is the same. For example, each Ar ² may be a moiety of structure (4) wherein each X is the same. In other embodiments, each Ar ² is a moiety of structure (5) .

In preferred embodiments, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments, n is an integer of from 1 to 10. For example, n may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In one exemplary embodiment, n is 1.

For example, provided herein is a compound of Formula I,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, ;

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, Ar ², X, and n may be selected as described above with respect to Formula A.

In preferred embodiments of the compound of Formula I, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula I, Ar ² is selected from the group consisting of structure (4) and structure (5) , and each Ar ² is the same.

In exemplary embodiments of the compound of Formula I, Ar ² is a moiety of structure (4) , and X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula I, n is 1.

For example, when Ar ² is a moiety of structure (4) , the compound is of Formula Ia,

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, X, and n may be selected as described above with respect to Formula A and/or Formula I.

In preferred embodiments of the compound of Formula Ia, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula Ia, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula Ia, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula Ia-i.

Further provided herein is a compound of Formula II,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula II, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula II, Ar ² is selected from the group consisting of structure (4) and structure (5) , and each Ar ² is the same.

In exemplary embodiments of the compound of Formula II, Ar ² is a moiety of structure (4) , and X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula II, n is 1.

For example, when Ar ² is a moiety of structure (4) , the compound is of Formula IIa,

X is selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, X, and n may be selected as described above with respect to Formula A and/or Formula II.

In preferred embodiments of the compound of Formula IIa, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIa, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula IIa, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula IIa-i.

Also provided herein is a compound of Formula IIb,

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, and n may be selected as described above with respect to Formula A and/or Formula II.

In preferred embodiments of the compound of Formula IIb, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIb, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIb-i.

Also provided herein is a compound of Formula IIc,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IIc, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIc, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIc-i.

Also provided herein is a compound of Formula IId,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IId, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IId, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IId-i.

Also provided herein is a compound of Formula IIe,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IIe, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIe, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIe-i.

Also provided herein is a compound of Formula IIf,

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, R ⁶, R ⁷, X, and n may be selected as described above with respect to Formula A and/or Formula II.

In preferred embodiments of the compound of Formula IIf, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIf, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula IIf, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³, R ⁶, and R ⁷ are each hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula IIf-i.

Further provided herein is a compound of Formula III,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula III, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula III, Ar ² is selected from the group consisting of structure (4) and structure (5) , and each Ar ² is the same.

In exemplary embodiments of the compound of Formula III, Ar ² is a moiety of structure (4) , and X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula III, n is 1.

For example, when Ar ² is a moiety of structure (4) , the compound is of Formula IIIa,

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, X, and n may be selected as described above with respect to Formula A and/or Formula III.

In preferred embodiments of the compound of Formula IIIa, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIa, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula IIIa, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula IIIa-i.

Also provided herein is a compound of Formula IIIb,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, and n may be selected as described above with respect to Formula A and/or Formula III.

In preferred embodiments of the compound of Formula IIIb, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIb, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIIb-i.

Also provided herein is a compound of Formula IIIc,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IIIc, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIc, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIIc-i.

Also provided herein is a compound of Formula IIId,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula Id, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIId, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIId-i.

Also provided herein is a compound of Formula IIIe,

and n is an integer greater than or equal to 1.

In preferred embodiments of the compound of Formula IIIe, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIe, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³ is hydrogen, n is 1, and the compound is Formula IIIe-i.

Also provided herein is a compound of Formula IIIf,

and n is an integer greater than or equal to 1.

Generally, each of R ¹, R ², R ³, R ⁶, R ⁷, X, and n may be selected as described above with respect to Formula A and/or Formula III.

In preferred embodiments of the compound of Formula IIIf, R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl. For example, R ¹, R ², and R ³ can each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ and R ² are each independently selected from the group consisting of C ₁–C ₆ alkyl and R ³ is hydrogen.

In preferred embodiments of the compound of Formula IIIf, X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-. For example, X can be -C (CH ₃) ₂-.

In preferred embodiments of the compound of Formula IIIf, n is 1.

In an exemplary embodiment, R ¹ and R ² are methyl, R ³, R ⁶, and R ⁷ are each hydrogen, X is -C (CH ₃) ₂-, n is 1, and the compound is Formula IIIf-i.

Compositions and Printed Circuit Boards

Also provided herein is a curable unsaturated resin composition, wherein the composition comprises at least one unsaturated resin and a flame retardant compound selected from the group consisting of Formula A, Formula I, Formula Ia, Formula Ib, Formula Ic, Formula Id, Formula Ie, Formula If, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula IId, Formula IIe, Formula IIf, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IIIe, and Formula IIIf.

Also provided herein is a cured unsaturated resin composition, wherein the unsaturated resin composition comprises a flame retardant compound selected from the group consisting of Formula A, Formula I, Formula Ia, Formula Ib, Formula Ic, Formula Id, Formula Ie, Formula If, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula IId, Formula IIe, Formula IIf, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IIIe, and Formula IIIf.

Also provided herein is a printed circuit board comprising a cured unsaturated resin composition, wherein the unsaturated resin composition comprises a flame retardant compound selected from the group consisting of Formula A, Formula I, Formula Ia, Formula Ib, Formula Ic, Formula Id, Formula Ie, Formula If, Formula II, Formula IIa, Formula IIb, Formula IIc, Formula IId, Formula IIe, Formula IIf, Formula III, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IIIe, and Formula IIIf.

EXAMPLES

The following non-limiting examples are provided to further illustrate the present disclosure.

Example 1: Experimental Materials

The compounds provided herein can be synthesized using typical techniques that are known to those skilled in the art. Representative examples of methods that may be used to synthesize particular compounds within the scope of the present disclosure are set forth below.

Unless otherwise indicated, the materials described below were used in each of the following examples.

SA9000 (available from SABIC) is acrylate terminated polyphenyl ether.

TAIC (available from Tokyo Chemical Industry Co. ) is triallyl isocyanurate.

SPB100 (available from Otsuka Chemical Co. ) is hexaphenoxycyclotriphosphazene.

PX200 (available from Daihachi Chemical Industry Co. ) is resorcinol bis [di (2, 6-dimethylphenyl) phosphate].

DCP (available from Sinopharm Chemical Reagent Co. ) is dicumyl peroxide.

As used herein, the abbreviation (tBuO) ₂ refers to di-tert-butyl peroxide (available from Sinopharm Chemical Reagent Co. ) .

Example 2: Synthesis of Compounds of Formula Ia

The compounds provided herein can be synthesized using typical techniques that are known to those skilled in the art. An exemplary synthesis for a compound of Formula Ia is provided below.

In a first step of the synthesis (Step A) , 244 grams of 2, 6-dimethylphenol (starting material) , 50 grams of xylene (solvent) , and 2 grams of anhydrous magnesium chloride (catalyst) were combined in a reactor. The temperature of the reactor was increased to 100 ℃. The reactor was slowly charged with 153 grams of phosphorus oxychloride, and maintained at 100 ℃ for 4 hours. The temperature was then increased to 160 ℃ for 4 hours, which yielded the Step A crude product.

In a second step of the synthesis (Step B) , 154.5 grams of Di-allyl bisphenol A was combined with the Step A crude product and maintained at a temperature of 160 ℃ for 4 hours, yielding the final product of Formula Ia.

Example 3: Evaluation of Compounds of Formula Ia

Two comparative formulations and two inventive formulations were prepared as described in Table 1 below.

Table 1

Example 3a: Clear Casting Application

The inventive examples prepared as described in Example 3 were tested for use in a clear casting application.

A mixed resin composition was prepared by combining a formulation prepared as described in Example 3 with methyl ethyl ketone solvent (50%of the mixed resin composition by weight) . Into an aluminum plate was poured 2–3 grams of mixed resin. The aluminum plate was then placed onto a 100℃ hot plate to remove the solvent slowly. After solvent removal, the hot plate was heated to 200℃ for post curing for 1 hour. After post curing, the cured resin was carefully peeled off the aluminum plate and tested for the properties shown in Table 2 below.

Table 2 shows that compositions containing a novel compound of Formula Ia exhibit ultra low loss performance when used in a clear casting application.

Table 2

Example 3b: Laminate Application

The comparative and inventive examples prepared as described in Example 3 were tested for use in a laminate application.

A varnish was prepared by combining a formulation prepared as described in Example 3 with methyl ethyl ketone solvent (50%of the varnish composition by weight) . Into a tray was poured about 200 grams of varnish. One piece of 7628 glass cloth (about 30 cm × 30 cm) was dipped into the varnish and then hand pulled through a gapped pair of rollers to control the thickness. One edge of the prepared glass cloth was fixed by clamps and then hung in a fume hood to allow the varnish to evenly spread and promote solvent evaporation. The glass cloth was then baked in a mini-treater (with good ventilation capability) at elevated temperature for a period of time sufficient to remove the solvent and generate a reasonable prepreg gel time, so the temperature and the time could be adjusted according to specific cases. Following the baking, the desired prepregs were obtained.

Two pieces of the resulting prepreg were stacked together, and half of the top and bottom surface was covered with a sheet of 35 um standard copper foil. The stack was then laminated in a press at 200℃ for 1.0 hours. The resulting laminate composition was then tested for the properties shown in Table 3 below.

Table 3 demonstrates that compositions comprising a compound of Formula Ia provide an ideal balance between Tg, Td, and Df when used in a laminate application.

Table 3

Example 4: Synthesis of Compounds of Formula IIb

An exemplary synthesis for a compound of Formula IIb is provided below.

Under N ₂ protection, in 2 L flask with mechanic agitation, a solution of 122 g 2, 6-dimethyl phenol, 111.1 g Et ₃N, and 122 g EtOAc was added slowly into a solution of 153.5 g POCl ₃ and 307 g EtOAc at 0℃ over 2 h. After that, the reaction mixture was agitated at room temperature for 1 h. A solution of 77 g resorcinol, 155.54 g Et ₃N, and 77 g EtOAc was added slowly at 0℃ over 1 h. After that, the reaction mixture was agitated at room temperature for 1 h. A mixture of 61.1 g diallyl amine and 66.8 g Et ₃N was added. The reaction mixture was agitated at room temperature overnight. The reaction was quenched with 400 mL water. The organic phase was washed with 150 mL diluted HCl once and 100 mL water 3 times and dried over Na ₂SO ₄. After removal of solvent, 300 g final product was obtained.

Example 5: Evaluation of Compounds of Formula IIb

An inventive formulation comprising a compound of Formula IIb was prepared as described in Table 4 below.

Table 4

Inventive Example 3, shown in the table above, was tested for use in a laminate application (with 2116 glass cloth) .

A varnish was prepared by combining the formulation of Inventive Example 3 with methyl ethyl ketone solvent (50%of the varnish composition by weight) . Into a tray was poured about 200 grams of varnish. One piece of 2116 glass cloth (about 30 cm × 30 cm) was dipped into the varnish and then hand pulled through a gapped pair of rollers to control the thickness. One edge of the prepared glass cloth was fixed by clamps and then hung in a fume hood to allow the varnish to evenly spread and promote solvent evaporation. The glass cloth was then baked in a mini-treater (with good ventilation capability) at elevated temperature for a period of time sufficient to remove the solvent and generate a reasonable prepreg gel time, so the temperature and the time could be adjusted according to specific cases. Following the baking, the desired prepregs were obtained.

Six pieces of the resulting prepreg were stacked together, and half of the top and bottom surface was covered with a sheet of 35 um standard copper foil. The stack was then laminated in a press at 200℃ for 1.0 hours. The resulting laminate composition was then tested for the properties shown in Table 5 below.

Table 5 shows the results of the laminate performance evaluation (with 2116 glass cloth) on the formulation of Inventive Example 3. This formulation achieved a relatively high Tg of 178 ℃ and a relatively low Df of 0.0054 at 10 GHz.

Table 5

Laminate, 6 ply @2116

Inventive example 3 (3.3%P)

Tg (℃, DSC)	178
Td (℃, 5%wt loss in N ₂)	373
UL94 ranking	Poorer than V-1
Dk (1 GHz)	3.48
Df (1 GHz)	0.0028
Dk (10 GHz)	3.98
Df (10 GHz)	0.0055

With 3.3%total phosphorus content in the formulation of Inventive Example 3, the UL94 flame retardancy ranking of the laminate was poorer than V-1. It is believed that the flame retardancy can be improved by increasing the filler loading in the formulation. With the same 3.3%phosphorus content and increased filler loading, as shown in Inventive Example 4, the laminate achieved V-1 flame retardancy ranking. Specifically, with a high filler loading and the total phosphorus content increased to 6.0%, the flame retardancy achieved V-0 ranking.

Table 6

Example 6: Synthesis of Compounds of Formula IIa

An exemplary synthesis for a compound of Formula IIa is provided below.

Under N ₂ protection, in 2 L flask with mechanic agitation, a solution of 122 g 2, 6-dimethyl phenol, 111.1 g Et ₃N, and 122 g EtOAc was added slowly into a solution of 153.5 g POCl ₃ and 307 g EtOAc at 0 ℃ over 2 h. After that, the reaction mixture was agitated at room temperature for 1 h. A solution of 215.90 g diallyl bisphenol A, 155.54 g Et ₃N, and 216 g EtOAc was added slowly at room temperature over 2 h. After that, the reaction mixture was heated at 70 ℃ for 1 h. A mixture of 61.1 g diallyl amine and 66.8 g Et ₃N was added. The reaction mixture was agitated at room temperature overnight. The reaction was quenched with 400 mL water. The organic phase was washed with 150 mL diluted HCl once and 100 mL water 3 times and dried over Na ₂SO ₄. After removal of solvent, 400 g final product was obtained.

Example 7: Evaluation of Compounds of Formula IIa

An inventive formulation comprising a compound of Formula IIa was prepared as described in Table 7 below.

Table 7

Recipe	Inventive Example 7 (3.3%P)
SA9000 (PPO)	80.0
TAIC	--
Compound of Formula IIa	70.0
Dicumyl peroxide/Di-tert-butyl peroxide	4.5
Filler	--

Inventive Example 7, shown in the table above, was tested for use in a laminate application (with 2116 glass cloth) .

A varnish was prepared by combining the formulation of Inventive Example 7 with methyl ethyl ketone solvent (50%of the varnish composition by weight) . Into a tray was poured about 400 grams of varnish. One piece of 2116 glass cloth (about 30 cm × 30 cm) was dipped into the varnish and then hand pulled through a gapped pair of rollers to control the thickness. One edge of the prepared glass cloth was fixed by clamps and then hung in a fume hood to allow the varnish to evenly spread and promote solvent evaporation. The glass cloth was then baked in a mini-treater (with good ventilation capability) at elevated temperature for a period of time sufficient to remove the solvent and generate a reasonable prepreg gel time, so the temperature and the time could be adjusted according to specific cases. Following the baking, the desired prepregs were obtained.

Six pieces of the resulting prepreg were stacked together, and half of the top and bottom surface was covered with a sheet of 35 um standard copper foil. The stack was then laminated in a press at 200℃ for 1.0 hours. The resulting laminate composition was then tested for the properties shown in Table 8 below

This formulation achieved high Tg of 182 ℃ and low Df of 0.0054 at 10 GHz. However, the flame retardancy was poorer than V-1 ranking.

Table 8

Laminate, 6 ply @2116	Inventive example 7 (3.3%P)
Tg (℃, DSC)	182
Td (℃, 5%wt loss in N ₂)	380
UL94 ranking	Poorer than V-1
Dk (1 GHz)	3.53
Df (1 GHz)	0.0028
Dk (10 GHz)	3.49
Df (10 GHz)	0.0054

Example 8: Synthesis of Compounds of Formula II

An exemplary synthesis for a compound of Formula II is provided below.

Under N ₂ protection, in 1 L flask with mechanic agitation, a solution of 24.43 g 2, 6-dimethyl phenol, 22.24 g Et ₃N, and 100 mL EtOAc was added slowly into a solution of 30.67 g POCl ₃ and 50 mL EtOAc at 0 ℃ over 40 min. After that, the reaction mixture was agitated at room temperature for another 40 min. A solution of 30.99 g diallyl bisphenol A, 22.25 g Et ₃N, and 50 mL EtOAc was added slowly at room temperature over 50 min. After that, the reaction mixture was heated at 70 ℃ for 1 h. A hot solution of 19.45 g DOPHQ, 13.33 g Et ₃N, and 100 mL NMP was added over 30 min. After that, the reaction mixture continued to be heated at 70 ℃ for 1.5 h. A mixture of 8.02 g diallyl amine and 9.03 g Et ₃N was added. The reaction mixture was agitated at room temperature overnight. The reaction was quenched with 200 mL water and extracted with 300 mL EtOAc twice. The combined organic phase was washed with 150 mL diluted HCl once and 150 mL water 3 times and dried over Na ₂SO ₄. After removal of solvent, 83.74 g final product was obtained.

Example 9: Evaluation of Compounds of Formula II

An inventive formulation comprising a compound of Formula II was prepared as described in Table 9 below.

Table 9

Recipe	Inventive Example 8 (3.5%P)
SA9000 (PPO)	60.4
TAIC	--
Compound of Formula II	39.6
Dicumyl peroxide/Di-tert-butyl peroxide	3.0
Filler	--

Inventive Example 8, shown in the table above, was tested for use in a laminate application (with 2116 glass cloth) .

A varnish was prepared by combining the formulation of Inventive Example 8 with methyl ethyl ketone solvent (50%of the varnish composition by weight) . Into a tray was poured about 200 grams of varnish. One piece of 2116 glass cloth (about 30 cm × 30 cm) was dipped into the varnish and then hand pulled through a gapped pair of rollers to control the thickness. One edge of the prepared glass cloth was fixed by clamps and then hung in a fume hood to allow the varnish to evenly spread and promote solvent evaporation. The glass cloth was then baked in a mini-treater (with good ventilation capability) at elevated temperature for a period of time sufficient to remove the solvent and generate a reasonable prepreg gel time, so the temperature and the time could be adjusted according to specific cases. Following the baking, the desired prepregs were obtained.

Six pieces of the resulting prepreg were stacked together, and half of the top and bottom surface was covered with a sheet of 35 um standard copper foil. The stack was then laminated in a press at 200℃ for 1.0 hours. The resulting laminate composition was then tested for the properties shown in Table 5 below

Compared to Inventive Example 7, this formulation achieved a much better flame retardancy, almost close to V-0 (50 s) . The laminate also had a relatively high Tg of 169 ℃, but the Df of 0.0068 at 10 GHz was poorer than Inventive Example 7.

Table 10

Laminate, 6 ply @2116	Inventive example 8 (3.5%P)
Tg (℃, DSC)	169
Td (℃, 5%wt loss in N ₂)	344
UL94 ranking	V-1 (55 s)
Dk (1 GHz)	3.51
Df (1 GHz)	0.0040
Dk (10 GHz)	3.57
Df (10 GHz)	0.0068

When introducing elements of the present disclosure or the preferred embodiment (s) thereof, the articles “a” , “an” , “the” , and “said” are intended to mean that there are one or more of the elements. The terms “comprising” , “including” , and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.

In view of the above, it will be seen that the several objects of the disclosure are achieved and other advantageous results attained.

As various changes could be made in the above products and methods without departing from the scope of the disclosure, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

Claims

A compound of Formula A,

wherein each Ar ¹ is independently a moiety of structure (1) ;

R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

R ⁴ and R ⁵ are each independently a moiety comprising at least one C=C double bond;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 1 wherein R ⁴ and R ⁵ are each independently selected from the group consisting of:

structure (1) , structure (2) , and structure (3) .
A compound of Formula I,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 3 wherein the compound is of Formula Ia,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

X is selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

and n is an integer greater than or equal to 1.
The compound of claim 4 wherein X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-.
A compound of Formula II,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 6 wherein the compound is of Formula IIa,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

X is selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

and n is an integer greater than or equal to 1.
The compound of claim 7 wherein X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-.
The compound of claim 6 wherein the compound is of Formula IIb,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 6 wherein the compound is of Formula IIc,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 6 wherein the compound is of Formula IId,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 6 wherein the compound is of Formula IIe,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 6 wherein the compound is of Formula IIf,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 13 wherein X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-.
A compound of Formula III,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

each Ar ² is independently selected from the group consisting of structure (4) , structure (5) , structure (6) , structure (7) , structure (8) , and structure (9) ;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 15 wherein the compound is of Formula IIIa,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

X is selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

and n is an integer greater than or equal to 1.
The compound of claim 16 wherein X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-.
The compound of claim 15 wherein the compound is of Formula IIIb,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 15 wherein the compound is of Formula IIIc,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 15 wherein the compound is of Formula IIId,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 15 wherein the compound is of Formula IIIe,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 15 wherein the compound is of Formula IIIf,

wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, and carboxyl;

each X is independently selected from the group consisting of -CH ₂-, -C (CH ₃) ₂-, -S-, -SO ₂-, -O-, and -CO-;

R ⁶ and R ⁷ are each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxyl, and aryloxyl, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxyl, carboxyl;

and n is an integer greater than or equal to 1.
The compound of claim 22 wherein X is selected from the group consisting of -CH ₂-and -C (CH ₃) ₂-.
The compound of any one of claims 1 to 23 wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and C ₁–C ₆ alkyl.
The compound any one of claims 1 to 23 wherein R ¹, R ², and R ³ are each independently selected from the group consisting of hydrogen and methyl.
The compound of any one of claims 1 to 25 wherein R ³ is hydrogen.
The compound of any one of claims 1 to 26 wherein n is an integer of from 1 to 10.
The compound of any one of claims 1 to 27 wherein n is 1.
A compound selected from the group consisting of Formula Ia-i,

Formula IIa-i,

Formula IIb-i,

Formula IIc-i,

Formula IId-i,

Formula IIe-i,

Formula IIf-i,

Formula IIIa-i,

Formula IIIb-i,

Formula IIIc-i,

Formula IIId-i,

Formula IIIe-I,

and Formula IIIf-I
A curable unsaturated resin composition comprising a compound of any one of claims 1 to 29 and at least one unsaturated resin.
A cured unsaturated resin composition comprising a compound of any one of claims 1 to 29 and at least one cured unsaturated resin.
A printed circuit board comprising the cured unsaturated resin composition of claim 31.