CN115698157A

CN115698157A - Reactive phosphate and preparation process thereof

Info

Publication number: CN115698157A
Application number: CN202080101474.9A
Authority: CN
Inventors: 叶思宇; E·王; E·鲍
Original assignee: Blue Cube Intellectual Property Co ltd
Current assignee: Blue Cube Intellectual Property Co ltd
Priority date: 2020-05-29
Filing date: 2020-05-29
Publication date: 2023-02-03
Also published as: WO2021237695A1; TW202144372A

Abstract

Provided herein are phosphorus-based flame retardant compounds that provide good electrical properties and good heat resistance properties when incorporated into PCB compositions. In particular, provided herein are novel organophosphorus based polymers containing C = C double bonds that allow them to react with other components (e.g., C = C bond terminated polyphenylene ethers, unsaturated hydrocarbon resins, bismaleimides, etc.) to form a crosslinked network.

Description

Reactive phosphate and preparation process thereof

Background

Continued advances in computer engineering have created an increased demand for high speed, low loss printed circuit board ("PCB") materials. High-speed, low-loss PCB materials exhibit a smaller variation in dielectric constant (Dk) with increasing transmission frequency and exhibit relatively low dielectric loss, as compared to previous generations of PCB materials.

Recently, it has become particularly important to develop a high-speed, low-loss PCB material which is halogen-free and exhibits an excellent low dissipation factor (Df). Formulations known in the art are typically based on thoroughly cured resin systems, for example, systems comprising hydrocarbon resins rich in C = C double bonds, acrylate-capped polyphenylene ethers (PPEs) and/or crosslinkers rich in C = C double bonds.

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

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

Disclosure of Invention

There is provided herein a compound of formula a,

wherein each Ar is ¹ Independently is part of structure (1);

R ¹ 、R ² and R ³ Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxy, each of which may optionally beIndependently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy and carboxyl;

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

each Ar ² 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 Each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxy, and aryloxy groups, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, and carboxyl; and n is an integer greater than or equal to 1.

Also provided herein are compounds of formula I,

wherein R is ¹ 、R ² And R ³ Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxy, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, 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 Each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxy, and aryloxy groups, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, and carboxyl;

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

Also provided herein are compounds of formula II,

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

Further provided herein are compounds of formula III,

wherein R is ¹ 、R ² And R ³ Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxyEach of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy and carboxyl;

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

Also provided herein are curable unsaturated resin compositions, 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 that includes at least one C = C double bond.

Also provided herein are cured unsaturated resin compositions, 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 are printed circuit boards 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 good electrical properties and good heat resistance properties.

In particular, provided herein are novel organophosphorus-based polymers containing C = C double bonds that allow them to react with other components (e.g., C = C double-capped polyphenylene ethers, unsaturated hydrocarbon resins, bismaleimides, etc.) to form a crosslinked network. Surprisingly, it has been found that these reactive compounds provide good dielectric properties and heat resistance when incorporated into PCB compositions.

For example, provided herein are compounds of formula A,

wherein each Ar is ¹ Independently is part of structure (1);

R ¹ 、R ² and R ³ Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxy, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, and carboxyl;

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

In a preferred embodiment, R ⁴ And R ⁵ 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 (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 group). In some embodiments, the alkyl is optionally independently substituted with one or more substituents selected from the group consisting of methoxy, carboxy.

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

As used herein, the term "alkoxy" refers to a group that forms-OR ', wherein R' is an alkyl group as defined herein. For example, the group-OCH ₃ May be referred to herein as "methoxy". radical-OCH ₂ CH ₃ May be referred to herein as "ethoxy".

As used herein, the term "aryloxy" refers to a group that forms-OR ', wherein R' is aryl as defined herein. For example, the group-O (C) ₆ H ₆ ) May be referred to herein as "phenoxy".

As used herein, the term "hydrogen" includes two stable isotopes of hydrogen, namely 1H (also referred to as protium) and ² h (also known as deuterium).

As used herein, the term "carboxy" refers to a group that forms a-C (O) OH.

In a preferred embodiment, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from the group consisting of C ₁ -C ₆ In the group of alkyl radicals and R ³ Is hydrogen.

In some embodiments, each Ar is ² Are the same. For example, each Ar ² Can be part of structure (4) wherein each X is the same. In other embodiments, each Ar ² Is part of the structure (5).

In a preferred embodiment, X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group consisting of. For example, X may be-C (CH) ₃ ) ₂ -。

In a preferred embodiment, n is an integer 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 are compounds of formula I,

wherein R is ¹ 、R ² And R ³ Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxy, each of which is optionally independently selected from the group consisting of methylEthyl, methoxy;

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

In general, each R ¹ 、R ² 、R ³ 、Ar ² X and n may be selected as described above with respect to formula a.

In a preferred embodiment of the compounds of formula I, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May be each independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from the group consisting of C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compounds of formula I, ar ² Selected from the group consisting of Structure (4) and Structure (5), and each Ar ² Are the same.

In exemplary embodiments of the compounds 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 -in the group of compositions. For example, X may be-C (CH) ₃ ) ₂ -。

In a preferred embodiment of the compounds of formula I, n is 1.

For example, when Ar ² Is part of structure (4), the compound has formula Ia,

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

In general, R ¹ 、R ² 、R ³ X and n are each as described above with respect to formula a and/or formula I.

In a preferred embodiment of the compound of formula Ia, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula Ia, X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group consisting of. For example, X may be-C (CH) ₃ ) ₂ -。

In a preferred embodiment of the compound of formula Ia, n is 1.

In an exemplary embodiment, R ¹ And R ² Is methyl, R ³ Is hydrogen, X is-C (CH) ₃ ) ₂ N is 1 and the compound is of formula Ia-i.

Further provided herein are compounds of formula II,

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

In general, R ¹ 、R ² 、R ³ 、Ar ² X and n may each be selected as described above with respect to formula a.

In a preferred embodiment of the compounds of formula II, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May be each independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from the group consisting of C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula II, ar ² Selected from the group consisting of structure (4) and structure (5), and each Ar ² Are the same。

In exemplary embodiments of the compounds 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 -in the group of compositions. For example, X may be-C (CH) ₃ ) ₂ -。

In a preferred embodiment of the compound of formula II, n is 1.

For example, when Ar ² When part of structure (4), the compound has 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.

In general, R ¹ 、R ² 、R ³ X and n can each be selected as described above with respect to formula a and/or formula II.

In a preferred embodiment of the compounds of formula IIa, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from the group consisting of C ₁ -C ₆ In the group of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula IIa, X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group of compositions. For example, X may be-C (CH) ₃ ) ₂ -。

In a preferred embodiment of the compound of formula IIa, n is 1.

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

Also provided herein are compounds of formula IIb,

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

In general, R ¹ 、R ² 、R ³ And n can each be selected as described above with respect to formula a and/or formula II.

In a preferred embodiment of the compounds of formula IIb, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compounds of formula IIb, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ Is hydrogen, n is 1, and the compound is of formula IIb-i.

Also provided herein are compounds of formula IIc,

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

In a preferred embodiment of compounds of formula IIc, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compounds of formula IIc, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ Is hydrogen, n is 1, and the compound is of formula IIc-i.

Also provided herein are compounds of formula IId,

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

In general, R ¹ 、R ² 、R ³ And n can each be selected as described above for formula a and/or formula II.

In a preferred embodiment of the compounds of formula IId, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compounds of formula IId, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ Is hydrogen, n is 1, and the compound is of formula IId-i.

Also provided herein are compounds of formula IIe,

wherein R is ¹ 、R ² And R ³ Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxy, each of which may be optionally independently substituted with one or more selected from the group consisting of methyl, ethyl, methoxy, and carboxylSubstituted by radicals;

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

In preferred embodiments of compounds of formula IIe, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compounds of formula IIe, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ Is hydrogen, n is 1, and the compound is of formula IIe-i.

Also provided herein are compounds of formula IIf,

R ⁶ and R ⁷ Each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxy and aryloxy groups, each of which may beOptionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy and carboxyl;

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

In general, R ¹ 、R ² 、R ³ 、R ⁶ 、R ⁷ X and n can each be selected as described above with respect to formula a and/or formula II.

In a preferred embodiment of the compounds of formula IIf, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May be each independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group of alkyl radicals and R ³ Is hydrogen.

In preferred embodiments of compounds of formula IIf, X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group of compositions. For example, X may be-C (CH) ₃ ) ₂ -。

In a preferred embodiment of the compounds of formula IIf, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ 、R ⁶ And R ⁷ Each is hydrogen, X is-C (CH) ₃ ) ₂ N is 1 and the compound is of formula IIf-i,

further provided herein are compounds of formula III,

wherein R is ¹ 、R ² And R ³ Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxy, each of which may optionally beIndependently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, and carboxyl;

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

In general, R ¹ 、R ² 、R ³ 、Ar ² X and n can each be selected as described above with respect to formula a.

In a preferred embodiment of the compound of formula III, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula III, ar ² Selected from the group consisting of structure (4) and structure (5), and each Ar ² Are the same.

In exemplary embodiments of the compounds 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 -in the group consisting of. For example, X may be-C (CH) ₃ ) ₂ -。

In a preferred embodiment of the compound of formula III, n is 1.

For example, when Ar ² Is part of structure (4)The compounds have the formula IIIa,

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

In general, R ¹ 、R ² 、R ³ X and n may each be selected as described above with respect to formula a and/or formula III.

In a preferred embodiment of compounds of formula IIIa, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May be each independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from the group consisting of C ₁ -C ₆ In the group of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula IIIa, X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group consisting of. For example, X may be-C (CH) ₃ ) ₂ -。

In a preferred embodiment of the compound of formula IIIa, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ Is hydrogen, X is-C (CH) ₃ ) ₂ N is 1 and the compound is of formula IIIa-i.

Also provided herein are compounds of formula IIIb,

wherein R is ¹ 、R ² And R ³ Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxy, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, carboxyl;

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

In general, R ¹ 、R ² 、R ³ And n can each be selected as described above with respect to formula a and/or formula III.

In a preferred embodiment of compounds of formula IIIb, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May be each independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from the group consisting of C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula IIIb, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ Is hydrogen, n is 1, and the compound is of formula IIIb-i.

Also provided herein are compounds of formula IIIc,

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

In a preferred embodiment of compounds of formula IIIc, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May be each independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from the group consisting of C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula IIIc, n is 1.

In an exemplary embodiment, R ¹ And R ² Is methyl, R ³ Is hydrogen, n is 1, and the compound is of formula IIIc-i.

Also provided herein are compounds of formula IIId,

wherein R is ¹ 、R ² And R ³ Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxy, each of which may optionally beIndependently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy and carboxyl;

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

In a preferred embodiment of the compound of formula Id, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula IIId, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ Is hydrogen, n is 1, and the compound is of formula IIId-i.

Also provided herein are compounds of formula IIIe,

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

In a preferred embodiment of compounds of formula IIIe, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula IIIe, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ Is hydrogen, n is 1, and the compound is of formula IIIe-i.

Also provided herein are compounds of formula IIIf,

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

In general terms, the term "water-soluble" is used to describe a mixture of water-soluble polymers and water-soluble polymers，R ¹ 、R ² 、R ³ 、R ⁶ 、R ⁷ X and n can each be selected as described above with respect to formula a and/or formula III.

In a preferred embodiment of the compounds of formula IIIf, R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups. For example, R ¹ 、R ² And R ³ May each be independently selected from the group consisting of hydrogen and methyl. In a preferred embodiment, R ¹ And R ² Each independently selected from C ₁ -C ₆ In the group consisting of alkyl radicals and R ³ Is hydrogen.

In a preferred embodiment of the compound of formula IIIf, X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group consisting of. For example, X may be-C (CH) ₃ ) ₂ -。

In a preferred embodiment of the compound of formula IIIf, n is 1.

In exemplary embodiments, R ¹ And R ² Is methyl, R ³ 、R ⁶ And R ⁷ Each is hydrogen, X is-C (CH) ₃ ) ₂ N is 1 and the compound is of formula IIIf-i.

Composition and printed circuit board

Also provided herein are curable unsaturated resin compositions, 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 are cured unsaturated resin compositions, 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 are printed circuit boards 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 Material

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

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

SA9000 (obtained from SABIC) is an acrylate-capped polyphenylene ether.

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

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

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

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

Abbreviations (tBuO) as used herein ₂ Refers to di-tert-butyl peroxide (obtained from Sinopharm Chemical Reagent Co.).

Example 2: synthesis of Compounds of formula Ia

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

In the 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 g of phosphorus oxychloride and maintained at 100 ℃ for 4 hours. The temperature was then increased to 160 ℃ for 4 hours, which yielded the phase of step a.

In the second step of the synthesis (step B), 154.5 grams of diallyl bisphenol a was combined with the crude product of step a and held at a temperature of 160 ℃ for 4 hours to produce 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

Inventive examples prepared as described in example 3 were tested for use in transparent casting applications.

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

Table 2 shows that compositions containing the novel compounds of formula Ia exhibit ultra-low loss properties when used in clear casting applications.

TABLE 2

Example 3b: laminate applications

Comparative and inventive examples prepared as described in example 3 were tested for use in laminates.

A varnish was prepared by combining the prepared formulation described in example 3 with methyl ethyl ketone solvent (50% by weight of the varnish composition). About 200 grams of varnish was poured into the tray. A piece 7628 of glass cloth (about 30 cm. Times.30 cm) was dipped into the varnish and then pulled by hand through a pair of gapped rollers to control thickness. One edge of the prepared glass cloth was held with a clip and then hung in a fume hood to allow the varnish to spread evenly and promote solvent evaporation. The glass cloth is then baked in a small processor (with good ventilation) at elevated temperature for a period of time sufficient to remove the solvent and produce a reasonable prepreg gel time, so the temperature and time can be adjusted as appropriate. After baking, the desired prepreg was obtained.

Two of the resulting prepregs were stacked together with half of the top and bottom surfaces covered with 35um standard copper foil. The stack was then laminated in a press at 200 ℃ for 1.0 hour. The resulting laminate composition was then tested for the characteristics shown in table 3 below.

Table 3 shows that compositions comprising compounds of formula Ia provide a desirable balance between Tg, td and Df when used in laminates.

: TABLE 3

Example 4: synthesis of Compounds of formula IIb

An exemplary synthesis of the compound of formula IIb is provided below.

At N ₂ 122g of 2, 6-dimethylphenol, 111.1g of Et were reacted at 0 ℃ over 2 hours in a 2L flask with mechanical stirring under protection ₃ A solution of N and 122g EtOAc was slowly added 153.5g POCl ₃ And 307g EtOAc. After that, the reaction mixture was stirred at room temperature for 1h. 77g of resorcinol and 155.54g of Et were slowly added at 0 ℃ over 1 hour ₃ N and 77g EtOAc. After that, the reaction mixture was stirred at room temperature for 1h. 61.1g of diallylamine and 66.8g of Et are added ₃ A mixture of N. The reaction mixture was stirred at room temperature overnight. The reaction was quenched with 400mL of water. The organic phase was washed once with 150mL of diluted HCl, and 3 times with 100mL of water and over Na ₂ SO ₄ And drying. After removal of the solvent, 300g of the final product are obtained.

Example 5: evaluation of Compounds of formula IIb

Inventive formulations including compounds of formula IIb were prepared as described in table 4 below.

TABLE 4

Inventive example 3 shown in the table above was tested for use in laminate applications (with 2116 glass cloth).

A varnish was prepared by combining the formulation of invention example 3 with methyl ethyl ketone solvent (50% by weight of the varnish composition). About 200 grams of varnish was poured into the tray. A piece of 2116 glass cloth (about 30 cm. Times.30 cm) was dipped into the varnish and then pulled by hand through a pair of gapped rollers to control thickness. One edge of the prepared glass cloth was fixed with a clip and then hung in a fume hood to allow the varnish to spread uniformly and to promote solvent evaporation. The glass cloth is then baked in a small processor (with good ventilation) at elevated temperatures for a period of time sufficient to remove the solvent and produce a reasonable prepreg gel time, so the temperature and time can be adjusted as appropriate. After baking, the desired prepreg is obtained.

Six of the resulting prepregs were stacked together with half of the top and bottom surfaces covered with 35um standard copper foil. The stack was then laminated in a press at 200 ℃ for 1.0 hour. 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) for the formulation of inventive example 3. The formulation achieves a relatively high Tg of 178 ℃ and a relatively low Df of 0.0054 at 10 GHz.

TABLE 5

With 3.3% total phosphorus content in the formulation of invention example 3, the UL94 fire rating of the laminate is worse than V-1. It is believed that flame retardancy can be improved by increasing the filler loading in the formulation. As shown in inventive example 4, the laminate achieved a V-1 flame rating with the same 3.3% phosphorus content and increased filler loading. Specifically, with high filler loading and a total phosphorus content increased to 6.0%, the flame retardancy achieved a V-0 rating.

TABLE 6

Example 6: synthesis of Compounds of formula IIa

An exemplary synthesis of a compound of formula IIa is provided below.

In N ₂ In a 2L flask with mechanical stirring, 122g of 2,6-dimethylphenol, 111.1g of Et were added over 2 hours at 0 ℃ under protection ₃ A solution of N and 122g EtOAc was slowly added 153.5g POCl ₃ And 307g EtOAc. After that, the reaction mixture was stirred at room temperature for 1h. 215.90g of diallyl bisphenol A and 155.54g of Et were slowly added at room temperature over 2h ₃ N and 216g EtOAc. Thereafter, the reaction mixture was heated at 70 ℃ for 1h. 61.1g of diallylamine and 66.8g of Et are added ₃ A mixture of N. The reaction mixture was stirred at room temperature overnight. The reaction was quenched with 400mL of water. The organic phase was washed once with 150mL of diluted HCl, and 100 _m Washed 3 times with L water and over Na ₂ SO ₄ And drying. After removal of the solvent, 400g of the final product were 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

Formulation of	Inventive example 7 (3.3% P)
		SA9000(PPO)	80.0
TAIC	--
		A compound of formula IIa	70.0
Dicumyl peroxide/di-tert-butyl peroxide	4.5
		Filler material	--

Inventive example 7 shown in the table above was tested for use in laminate applications (with 2116 glass cloth).

A varnish was prepared by combining the formulation of invention example 7 with methyl ethyl ketone solvent (50% by weight of the varnish composition). About 400 grams of varnish was poured into the tray. A piece of 2116 glass cloth (about 30 cm. Times.30 cm) was immersed in the varnish and then pulled by hand through a pair of gapped rollers to control the thickness. One edge of the prepared glass cloth was held with a clip and then hung in a fume hood to allow the varnish to spread evenly and to promote solvent evaporation. The glass cloth is then baked in a small processor (with good ventilation) at elevated temperature for a period of time sufficient to remove the solvent and produce a reasonable prepreg gel time, so the temperature and time can be adjusted as appropriate. After baking, the desired prepreg is obtained.

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

The formulation achieves a high Tg of 182 ℃ and a low Df of 0.0054 at 10 GHz. However, the flame retardancy is worse than the V-1 rating.

TABLE 8

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

Example 8: synthesis of Compounds of formula II

An exemplary synthesis of the compound of formula II is provided below.

In N ₂ 24.43g of 2, 6-dimethylphenol, 22.24g of Et were added over 40min at 0 ℃ in a 2L flask with mechanical stirring ₃ A solution of N and 100mL EtOAc was added slowly to 30.67g POCl ₃ And 50mL EtOAc. After that, the reaction mixture was stirred at room temperature for another 40min. Slowly add 30.99g diallyl bisphenol A and 22.25g Et over 50min at room temperature ₃ N and 50mL EtOAc. Thereafter, the reaction mixture was heated at 70 ℃ for 1h. Adding 19.45g DOPHQ and 13.33g Et within 30min ₃ N and 100mL of NMP. Thereafter, the reaction mixture was heated at 70 ℃ for a further 1.5h. 8.02g of diallylamine and 9.03g of Et were added ₃ A mixture of N. The reaction mixture was stirred at room temperature overnight. The reaction was quenched with 200mL water and extracted twice with 300mL EtOAc. The combined organic phases were washed once with 150mL of diluted HCl, and 3 times with 150mL of water and over Na ₂ SO ₄ And drying. After removal of the solvent, 83.74g of the final product are obtained.

Example 9: evaluation of Compounds of formula II

Inventive formulations including the compound of formula II were prepared as described in table 9 below.

TABLE 9

Inventive example 8 shown in the table above was tested for use in laminate applications (with 2116 glass cloth).

A varnish was prepared by combining the formulation of invention example 8 with methyl ethyl ketone solvent (50% by weight of the varnish composition). About 200 grams of varnish was poured into the tray. A piece of 2116 glass cloth (about 30 cm. Times.30 cm) was immersed in the varnish and then pulled by hand through a pair of gapped rollers to control the thickness. One edge of the prepared glass cloth was held by a clip and then hung in a fume hood to allow the varnish to spread evenly and to promote solvent evaporation. The glass cloth is then baked in a small processor (with good ventilation) at elevated temperature for a period of time sufficient to remove the solvent and produce a reasonable prepreg gel time, so the temperature and time can be adjusted as appropriate. After baking, the desired prepreg is obtained.

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

Compared to inventive example 7, this formulation achieved better flame retardancy, almost approaching V-0 (50 s). The laminate also had a relatively high Tg of 169 deg.C, while the Df of 0.0068 at 10GHz was worse than that of inventive example 7.

Watch 10

When introducing elements of the present disclosure or the preferred embodiments 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

1. A compound of the formula A, wherein,

wherein each Ar is ¹ Independently is part of structure (1);

each X is independently 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.

2. The compound of claim 1, wherein R ⁴ And R ⁵ Each independently selected from the group consisting of structure (1), structure (2), and structure (3):

3. a compound of the formula I, wherein,

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

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

4. The compound of claim 3, wherein the compound has formula Ia,

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

5. The compound of claim 4, wherein X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group of compositions.

6. A compound of the formula (II) wherein,

R ⁶ and R ⁷ Each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxy, and aryloxy groups, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, carboxyl;

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

7. The compound of claim 6, wherein the compound is of formula IIa,

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

8. The compound of claim 7, wherein X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group of compositions.

9. The compound of claim 6, wherein the compound is of formula IIb,

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

10. The compound of claim 6, wherein the compound is of formula IIc,

wherein R is ¹ 、R ² And R ³ Each independently selected from hydrogen, alkyl, arylA group consisting of aryl, alkoxy, and aryloxy, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, carboxyl;

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

11. The compound of claim 6, wherein the compound is of formula IId,

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

12. The compound of claim 6, wherein the compound is of formula IIe,

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

13. The compound of claim 6, wherein the compound is of formula IIf,

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

14. The compound of claim 13, wherein X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group of compositions.

15. A compound of the formula (III),

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

16. The compound of claim 15, wherein the compound has formula IIIa,

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

17. The compound of claim 16, wherein X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group consisting of.

18. The compound of claim 15, wherein the compound has formula IIIb,

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

19. The compound of claim 15, wherein the compound has formula IIIc,

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

20. The compound of claim 15, wherein the compound has formula IIId,

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

21. The compound of claim 15, wherein the compound has formula IIIe,

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

22. The compound of claim 15, wherein the compound has formula IIIf,

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

23. The combination of claim 22Wherein X is selected from the group consisting of-CH ₂ -and-C (CH) ₃ ) ₂ -in the group of compositions.

24. The compound according to any one of claims 1 to 23, wherein R ¹ 、R ² And R ³ Each independently selected from hydrogen and C ₁ -C ₆ Alkyl groups.

25. The compound according to any one of claims 1 to 23, wherein R ¹ 、R ² And R ³ Each independently selected from the group consisting of hydrogen and methyl.