CN115698178A - Halogen-free very low loss resin composition - Google Patents

Halogen-free very low loss resin composition Download PDF

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CN115698178A
CN115698178A CN202080101485.7A CN202080101485A CN115698178A CN 115698178 A CN115698178 A CN 115698178A CN 202080101485 A CN202080101485 A CN 202080101485A CN 115698178 A CN115698178 A CN 115698178A
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叶思宇
E·王
E·鲍
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Blue Cube Intellectual Property Co ltd
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
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    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
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    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
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Abstract

Provided herein are halogen-free, flame retardant curable resin compositions that provide good electrical properties and good heat resistance properties sufficient to allow their use in high performance PCB systems. In particular, provided herein are novel organophosphorus olefins useful as reactive flame retardants. Surprisingly, it has been found that these reactive compounds provide good dielectric properties and heat resistance when incorporated into PCB compositions. The presence of C = C double bonds in these organophosphorus olefins allows them to react with unsaturated resins (e.g., C = C double-capped polyphenylene ethers, bismaleimides, etc.) to form a crosslinked network.

Description

Halogen-free very low loss resin composition
Background
The continual progress of computer engineering has 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-terminated polyphenylene ether (PPE) and/or cross-linkers with rich C = C double bonds.
Unfortunately, phosphorus-based flame retardants with a low enough Df to be useful in these high performance PCB systems are lacking. 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 halogen-free, flame retardant PCB materials that provide good electrical characteristics and good heat resistance characteristics sufficient to allow their use in high performance PCB systems.
Disclosure of Invention
For example, provided herein is a resin composition comprising: an organophosphorus olefin in an amount of about 10% by weight to about 65% by weight of the composition; an unsaturated resin in an amount of about 0% by weight to about 50% by weight of the composition; silica in an amount of about 20% by weight to about 80% by weight of the composition; and a free radical initiator in an amount of about 0.5% by weight to about 7.5% by weight of the composition.
In some embodiments, the resin compositions provided herein comprise an organophosphorus olefin of formula A,
Figure BDA0003966655040000021
wherein each Ar is 1 Independently is part of structure (1);
Figure BDA0003966655040000022
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;
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);
Figure BDA0003966655040000023
Figure BDA0003966655040000031
each X is independently selected from the group consisting of-CH 2 -、-C(CH 3 ) 2 -、-S-、-SO 2 -, -O-and-CO-; r is 6 And R 7 Each independently selected from the group consisting of hydrogen and alkyl, aryl, alkoxy and aryloxy groups, each of which may optionally be independently selected fromSubstituted with one or more substituents of the group consisting of methyl, ethyl, methoxy and carboxyl; and n is an integer greater than or equal to 1. For example, the organophosphorus olefins can include compounds of 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, or formula IIIf.
Also provided herein are printed circuit boards comprising the cured resin compositions, wherein the resin compositions are as provided herein.
Other objects and features will be in part apparent and in part pointed out hereinafter.
Detailed Description
Provided herein are halogen-free, flame retardant curable resin compositions that provide good electrical properties and good heat resistance properties sufficient to allow their use in high performance PCB systems.
In particular, provided herein are novel organophosphorus olefins for use as reactive flame retardants. Surprisingly, it has been found that these reactive compounds provide good electrical properties and heat resistance when incorporated into PCB compositions. The presence of the C = C double bond in these organophosphorus olefins allows them to react with unsaturated resins (e.g., C = C double-capped polyphenylene ethers, bismaleimides, etc.) to form a crosslinked network.
For example, provided herein are resin compositions comprising an organophosphorus olefin, an unsaturated resin, silica, and a free radical initiator. Each of these components is discussed in further detail below.
Organic phosphorus olefins
The resin composition may comprise one or more organophosphorus olefins as provided herein. As discussed above, it has been found that the organophosphorus olefins provided herein act as reactive flame retardants and provide surprisingly good dielectric properties and heat resistance when incorporated into PCB compositions.
The resin composition can include an organophosphorus olefin, for example, in an amount of about 10% by weight to about 65% by weight, about 15% by weight to about 50% by weight, about 20% by weight to about 40% by weight, about 20% by weight to about 35% by weight, or about 25% by weight to about 35% by weight of the composition.
In a preferred embodiment, the resin composition comprises a compound of formula A,
Figure BDA0003966655040000041
wherein each Ar is 1 Independently is part of structure (1);
Figure BDA0003966655040000042
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;
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);
Figure BDA0003966655040000043
Figure BDA0003966655040000051
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.
In a preferred embodiment, R 4 And R 5 Each independently selected from the group consisting of structure (1), structure (2), and structure (3);
Figure BDA0003966655040000052
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, the 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, i.e., hydrogen 1 H (also called 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 of the present invention,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 some embodiments, each Ar is 2 Are the same. For example, each Ar 2 May 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 of compositions. 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, the resin composition may include a compound of formula I,
Figure BDA0003966655040000071
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;
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 hydrogen and alkyl, aryl, alkoxy and aryl(ii) in the group consisting of oxo, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy and carboxy;
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 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 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,
Figure BDA0003966655040000081
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 independentlyIs 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 are each selected 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 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 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.
Figure BDA0003966655040000091
The resin composition may include a compound of formula II,
Figure BDA0003966655040000092
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 be independently selected from the group consisting of methyl, ethyl, methoxy and carboxylSubstituted with one or more substituents of (a);
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.
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 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 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 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,
Figure BDA0003966655040000101
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;
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 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 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 consisting of. For example, X may be-C (CH) 3 ) 2 -。
In a preferred embodiment of the compound of formula IIa, 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 IIa-i.
Figure BDA0003966655040000111
The resin composition may comprise a compound of formula IIb,
Figure BDA0003966655040000112
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;
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 consisting of alkyl radicals and R 3 Is hydrogen.
In a preferred embodiment of the compounds of formula IIb, 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 IIb-i.
Figure BDA0003966655040000121
The resin composition may include a compound of formula IIc,
Figure BDA0003966655040000122
Figure BDA0003966655040000131
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;
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 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.
Figure BDA0003966655040000132
The resin composition may comprise a compound of formula IId,
Figure BDA0003966655040000141
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 be independently selected from the group consisting of methyl, ethyl, methoxy and carboxylSubstituted with one or more substituents;
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.
Figure BDA0003966655040000151
The resin composition may include a compound of formula IIe,
Figure BDA0003966655040000152
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;
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.
Preferred embodiments of the compounds of the formula IIeIn, 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 consisting of alkyl radicals and R 3 Is hydrogen.
In a preferred embodiment of the compound 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.
Figure BDA0003966655040000161
The resin composition may comprise a compound of formula IIf,
Figure BDA0003966655040000162
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.
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 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 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 an exemplary embodiment, 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.
Figure BDA0003966655040000171
Further provided herein are compounds of formula III,
Figure BDA0003966655040000181
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 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.
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 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 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 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 compound has formula IIIa,
Figure BDA0003966655040000191
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;
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 III.
In a preferred embodiment of the 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 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 IIIa, 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 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.
Figure BDA0003966655040000192
Figure BDA0003966655040000201
The resin composition may include a compound of formula IIIb,
Figure BDA0003966655040000202
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 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.
Figure BDA0003966655040000211
The resin composition may include a compound of formula IIIc,
Figure BDA0003966655040000212
wherein R is 1 、R 2 And R 3 Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryl(ii) oxy, each of which may be optionally independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, carboxy;
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 the compound 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 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 IIIc, 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 IIIc-i.
Figure BDA0003966655040000221
The resin composition may comprise a compound of formula IIId,
Figure BDA0003966655040000222
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;
and n is an integer greater than or equal to 1.
In general, R 1 、R 2 、R 3 And n eachMay be selected as described above with respect to formula a and/or formula III.
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.
Figure BDA0003966655040000231
The resin composition may include a compound of formula IIIe,
Figure BDA0003966655040000232
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;
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 the 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 Can be independently of each otherSelected 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.
Figure BDA0003966655040000241
The resin composition may comprise a compound of formula IIIf,
Figure BDA0003966655040000242
Figure BDA0003966655040000251
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.
In general, R 1 、R 2 、R 3 、R 6 、R 7 X and n are eachSelected from those described above with respect to formula a and/or formula III.
In a preferred embodiment of 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 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 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 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 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.
Figure BDA0003966655040000252
Unsaturated resin
The resin composition may further comprise one or more unsaturated resins. As discussed above, it has been found that the presence of C = C double bonds in the organophosphorus olefins allows them to react with unsaturated resins to form a crosslinked network.
As used herein, the term "unsaturated resin" refers to a resin that includes at least one C = C double bond.
The resin composition may include one or more unsaturated resins, for example, in an amount of about 0% by weight to about 50% by weight, about 10% by weight to about 40% by weight, about 10% by weight to about 30% by weight, about 15% by weight to about 30% by weight, or about 15% by weight to about 25% by weight of the composition.
Non-limiting examples of unsaturated resins include acrylate-capped polyphenylene ethers; bismaleimides and mixtures thereof.
Acrylate-terminated polyphenylene ethers
The resin composition may include an acrylate-terminated polyphenylene ether of formula B
Figure BDA0003966655040000261
Wherein Y is an aliphatic backbone comprising 1 or more carbon atoms, and m and n are each independently greater than or equal to 1.
In some embodiments, Y is an aliphatic backbone comprising between 1 and 20 carbon atoms, e.g., between 1 and 10 carbon atoms, between 1 and 8 carbon atoms, or between 1 and 6 carbon atoms.
When the resin composition includes an acrylate-capped polyphenylene ether, the concentration of the acrylate-capped polyphenylene ether is preferably from about 20% by weight to about 80% by weight of the composition, for example, from about 40% by weight to about 70% by weight, from about 45% by weight to about 65% by weight, or from about 50% by weight to about 60% by weight.
Bismaleimide
The resin composition may include a bismaleimide of formula C
Figure BDA0003966655040000271
Wherein R is 1 Selected from the group consisting of an aliphatic backbone comprising 1 or more carbon atoms and an alicyclic backbone comprising 3 or more membered rings;
and R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen and C 1 -C 3 Alkyl groups.
In some embodiments, R 1 Is comprised between 1 and 20 carbon atoms, e.g. between 1 and 10 carbon atoms, between 1 and 8 carbon atoms or between 1 and 6 carbon atomsAn aliphatic backbone.
When the resin composition includes bismaleimide, the concentration of bismaleimide is preferably about 1% by weight to about 50% by weight of the composition, for example, about 10% by weight to about 40% by weight, about 15% by weight to about 35% by weight, or about 20% by weight to about 30% by weight.
Combinations of unsaturated resins
In some embodiments, the resin composition comprises a combination of two or more unsaturated resins. For example, the resin composition may include a combination of (1) an acrylate-capped polyphenylene ether (including but not limited to compounds of formula B), and (2) a bismaleimide (including but not limited to compounds of formula C).
By way of non-limiting example, when the composition includes both an acrylate-capped poly (phenylene ether) and a bismaleimide, the concentration of the acrylate-capped poly (phenylene ether) may range from about 1% by weight to about 30% by weight, about 2% by weight to about 25% by weight, about 5% by weight to about 20% by weight, or about 5% by weight to about 15% by weight of the composition. Similarly, the concentration of bismaleimide may range, for example, from about 1% by weight to about 30% by weight, from about 2% by weight to about 25% by weight, from about 5% by weight to about 20% by weight, or from about 5% by weight to about 15% by weight of the composition.
Filler component
The resin composition may further comprise a filler component. Without being bound by a particular theory, the presence of the filler component may improve the dimensional stability, mechanical strength, and/or thermal conductivity of the composition.
Non-limiting examples of suitable filler components include spherical silica, fused silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, boron nitride, mica, talc, and mixtures thereof. In a preferred embodiment, the filler component comprises an inorganic filler. For example, the filler component may include silica.
The resin composition may include a filler component, for example, in an amount of about 20% by weight to about 80% by weight, about 30% by weight to about 70% by weight, or about 40% by weight to about 60% by weight of the composition.
Free radical initiators
The resin composition may include one or more free radical initiators. Without being bound by a particular theory, a free radical initiator may be used to release free radicals at elevated temperatures and thereby trigger crosslinking of all components in the composition.
Non-limiting examples of free radical initiators include dicumyl peroxide, di-t-butyl peroxide, and benzoyl peroxide. For example, the free radical initiator may comprise a peroxide compound.
The resin composition may include one or more free radical initiators, for example, in an amount of about 0.5% by weight to about 7.5% by weight, about 0.5% by weight to about 5% by weight, about 0.5% by weight to about 2.5% by weight, about 1% by weight to about 2.5% by weight, or about 1.5% by weight to about 2.5% by weight of the composition.
Printed circuit board
Also provided are printed circuit boards comprising the resin compositions as provided herein.
Other objects and features will be in part apparent and in part pointed out hereinafter.
Examples
The following non-limiting examples are provided to further illustrate the present disclosure.
Experimental Material
The compositions provided herein can be formulated using typical techniques known to those skilled in the art.
Unless otherwise indicated, the materials described below are used in each of the following examples.
SA9000 is an acrylate-capped polyphenylene ether obtained from SABIC.
TAIC is triallyl isocyanurate available from Tokyo Chemical Industry co.
PX200 is resorcinol bis [ di (2, 6-dimethylphenyl) phosphate ] obtained from Daihachi Chemical Industry co.
BMI 5100 is 3,3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide available from Daiwakasei Industry co.
SC2300-SVJ is spherical silica obtained from Admatechs co.
DCP is dicumyl peroxide obtained from Sinopharm Chemical Reagent co.
SPB100 is hexaphenoxycyclotriphosphazene obtained from Otsuka Chemical co.
Abbreviations (tBuO) as used herein 2 Refers to di-tert-butyl peroxide obtained from Sinopharm Chemical Reagent Co.
Preparation of test compositions
Inventive examples 1-6 and comparative examples 1-2 were prepared as described in table 1 below.
TABLE 1
Figure BDA0003966655040000291
Figure BDA0003966655040000301
Laminate applications
Comparative and inventive examples prepared as described in table 1 were tested for laminate applications.
A varnish was prepared by combining the example formulation 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 pieces of the resulting prepreg were stacked together and half of the top and bottom surfaces were covered with 35 μm standard copper foil. The stack was then laminated in a press at 200 ℃ for 1.0 hour. The resulting laminate compositions were then tested for the characteristics shown in table 2 below.
Table 2 shows that inventive examples including organophosphorus olefins provide a desirable balance between Tg, td and Df when used in laminate applications.
TABLE 2
Figure BDA0003966655040000311
In comparative examples 1 and 2, additive flame retardants, SPB-100 and PX-200, were formulated with SA9000 and TAIC, respectively. The Tg of the laminate is much lower than 170 ℃ and cannot be considered as high Tg. Both examples show low loss performance. PX-200 can further reduce laminate Df to 0.0020 at 1GHz, better than SPB-100.
In inventive examples 1 and 2, the organophosphorus olefins of formulae Ia and IIb were formulated with SA9000 and TAIC, respectively. Both laminates have a significant improvement in Tg since the organophosphorus olefin can react with other components to increase the crosslink density. Two laminates also achieved promising low loss performance, 0.0030Df at 1GHz and 0.0028Df at 1GHz, respectively. The flame retardancy rating is V-1 level.
In inventive example 3, an organophosphorus olefin of formula II was formulated with SA9000. The flame retardancy rating was further increased to a V-0 level, although Df was increased a little to 0.0040 at 1 GHz.
In inventive example 4, an organophosphorus olefin of the formula IIa is formulated with SA9000. The laminate can achieve a Tg of 182 ℃ and a promising low loss, 0.0028Df at 1GHz, while the flame retardancy is impaired to a V-1 level.
In invention example 5, in order to further increase the heat resistance, BMI resin and spherical silica were included in the formulation. The Tg of the laminate increased to 205 ℃ with good low loss, 0.0025Df at 1 GHz.
In inventive example 6, SA9000 was not included. An organophosphorus olefin of formula IIa is formulated with a BMI resin. The laminate showed a Tg of 152 ℃, indicating that good crosslinking was still formed without SA9000 in the formulation. Df is not attenuated and remains below 0.003 at 1 GHz.
When introducing elements of the present disclosure or 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 (46)

1. A resin composition, comprising:
an organophosphorus olefin; and
an unsaturated resin;
wherein the organophosphorus olefin comprises a compound of formula A,
Figure FDA0003966655030000011
wherein each Ar is 1 Independently is part of structure (1);
Figure FDA0003966655030000012
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;
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);
Figure FDA0003966655030000013
Figure FDA0003966655030000021
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.
2. The composition of claim 1, wherein R 4 And R 5 Each independently selected from the group consisting of structure (1), structure (2), and structure (3):
Figure FDA0003966655030000022
3. the resin composition according to claim 1 or 2, comprising:
an organophosphorus olefin in an amount of about 10% by weight to about 65% by weight of the composition;
an unsaturated resin in an amount of about 0% by weight to about 50% by weight of the composition;
a filler component in an amount of about 20% by weight to about 80% by weight of the composition; and
a free radical initiator in an amount of about 0.5% by weight to about 7.5% by weight of the composition.
4. The composition of any one of claims 1 to 3, comprising an unsaturated resin in an amount of about 10% to about 40% by weight, about 10% to about 30% by weight, about 15% to about 30% by weight, or about 15% to about 25% by weight of the composition.
5. The composition of any one of claims 1 to 4, comprising a monomer selected from the group consisting of polyphenylene ethers capped with acrylates; bismaleimides and mixtures thereof.
6. The composition of any one of claims 1 to 5, wherein the unsaturated resin comprises an acrylate-terminated polyphenylene ether of formula B
Figure FDA0003966655030000031
Wherein Y is an aliphatic backbone comprising 1 or more carbon atoms, and m and n are each independently greater than or equal to 1.
7. The composition of claim 6, wherein Y is an aliphatic backbone comprising between 1 and 20 carbon atoms, between 1 and 10 carbon atoms, between 1 and 8 carbon atoms, or between 1 and 6 carbon atoms.
8. The composition of claim 6 or 7, wherein the concentration of acrylate-capped polyphenylene ether is about 20% by weight to about 80% by weight, about 40% by weight to about 70% by weight, about 45% by weight to about 65% by weight, or about 50% by weight to about 60% by weight of the composition.
9. The composition of any of claims 1 to 8, wherein the unsaturated resin comprises a bismaleimide of formula C
Figure FDA0003966655030000041
Wherein R is 1 Selected from the group consisting of an aliphatic backbone comprising 1 or more carbon atoms and an alicyclic backbone comprising 3 or more membered rings;
and R 2 、R 3 、R 4 And R 5 Each independently selected from hydrogen and C 1 -C 3 Alkyl groups.
10. The composition of claim 8, wherein R 1 Is an aliphatic backbone comprising between 1 and 20 carbon atoms, between 1 and 10 carbon atoms, between 1 and 8 carbon atoms, or between 1 and 6 carbon atoms.
11. The composition according to claim 9 or 10, wherein the concentration of bismaleimide is about 1% by weight to about 50% by weight of the composition, for example, about 10% by weight to about 40% by weight, about 15% by weight to about 35% by weight, or about 20% by weight to about 30% by weight.
12. The composition of any one of claims 1 to 11, wherein the unsaturated resin comprises a mixture of:
(1) An acrylate-terminated polyphenylene ether; and
(2) Bismaleimide.
13. The composition of claim 12, wherein:
the concentration of the acrylate-capped polyphenylene ether is about 1% by weight to about 30% by weight, about 2% by weight to about 25% by weight, about 5% by weight to about 20% by weight, or about 5% by weight to about 15% by weight of the composition; and
the concentration of bismaleimide is about 1% by weight to about 30% by weight, about 2% by weight to about 25% by weight, about 5% by weight to about 20% by weight, or about 5% by weight to about 15% by weight of the composition.
14. The composition of any of claims 1 to 12, comprising a filler component in an amount of about 20% by weight to about 80% by weight, about 30% by weight to about 70% by weight, or about 40% by weight to about 60% by weight of the composition.
15. The composition of claim 14, wherein the filler component comprises silica.
16. The composition according to any one of claims 1 to 15 comprising a free radical initiator selected from the group consisting of dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide and mixtures thereof.
17. The composition of any one of claims 1 to 16, comprising a free radical initiator in an amount of about 0.5% by weight to about 7.5% by weight, about 0.5% by weight to about 5% by weight, about 0.5% by weight to about 2.5% by weight, about 1% by weight to about 2.5% by weight, or about 1.5% by weight to about 2.5% by weight of the composition.
18. The composition of any one of claims 1 to 17, wherein organophosphorus olefin comprises a compound of formula I,
Figure FDA0003966655030000051
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;
each Ar 2 Independently selected from the group consisting of structure (4), structure (5), structure (6), structure (7), structure (8), and structure (9);
Figure FDA0003966655030000061
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.
19. The composition of claim 18, wherein the organophosphorus olefin comprises a compound of formula Ia,
Figure FDA0003966655030000071
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 be independently substituted with one or more substituents selected from the group consisting of methyl, ethyl, methoxy, carboxyGeneration;
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.
20. The composition of claim 19, wherein X is selected from the group consisting of-CH 2 -and-C (CH) 3 ) 2 -in the group of compositions.
21. The composition of any one of claims 1 to 20, wherein organophosphorus olefin comprises a compound of formula II,
Figure FDA0003966655030000072
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;
each Ar 2 Independently selected from the group consisting of structure (4), structure (5), structure (6), structure (7), structure (8), and structure (9);
Figure FDA0003966655030000081
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, carboxyl;
and n is an integer greater than or equal to 1.
22. The composition of claim 21, wherein the organophosphorus olefin comprises a compound of formula IIa,
Figure FDA0003966655030000091
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;
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.
23. The composition of claim 22, wherein X is selected from the group consisting of-CH 2 -and-C (CH) 3 ) 2 -in the group of compositions.
24. The composition of claim 21, wherein the organophosphorus olefin comprises a compound of formula IIb,
Figure FDA0003966655030000092
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.
25. The composition of claim 21, wherein the organophosphorus olefin comprises a compound of formula IIc,
Figure FDA0003966655030000101
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.
26. The composition of claim 21, wherein the organophosphorus olefin comprises a compound of formula IId,
Figure FDA0003966655030000102
Figure FDA0003966655030000111
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.
27. The composition of claim 21, wherein the organophosphorus olefin comprises a compound of formula IIe,
Figure FDA0003966655030000112
wherein R is 1 、R 2 And R 3 Each independently selected from hydrogen, alkylAryl, 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.
28. The composition of claim 21, wherein the organophosphorus olefin comprises a compound of formula IIf,
Figure FDA0003966655030000121
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;
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, carboxyl;
and n is an integer greater than or equal to 1.
29. The composition of claim 28, wherein X is selected from the group consisting of-CH 2 -and-C (CH) 3 ) 2 -in the group consisting of.
30. The composition of any one of claims 1 to 29, wherein organophosphorus olefin comprises a compound of formula III,
Figure FDA0003966655030000122
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;
each Ar 2 Independently selected from the group consisting of structure (4), structure (5), structure (6), structure (7), structure (8), and structure (9);
Figure FDA0003966655030000131
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, carboxyl;
and n is an integer greater than or equal to 1.
31. The composition of claim 30, wherein the organophosphorus olefin comprises a compound of formula IIIa,
Figure FDA0003966655030000141
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;
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.
32. The composition of claim 31, wherein X is selected from the group consisting of-CH 2 -and-C (CH) 3 ) 2 -in the group of compositions.
33. The composition of claim 30, wherein the organophosphorus olefin comprises a compound of formula IIIb,
Figure FDA0003966655030000142
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.
34. The composition of claim 30, wherein the organophosphorus olefin comprises a compound of formula IIIc,
Figure FDA0003966655030000151
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.
35. The composition of claim 30, wherein the organophosphorus olefin comprises a compound of formula IIId,
Figure FDA0003966655030000152
Figure FDA0003966655030000161
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.
36. The composition of claim 30, wherein the organophosphorus olefin comprises a compound of formula IIIe,
Figure FDA0003966655030000162
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.
37. The composition of claim 30, wherein the organophosphorus olefin comprises a compound of formula IIIf,
Figure FDA0003966655030000171
wherein R is 1 、R 2 And R 3 Each independently selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, and aryloxyOptionally 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, carboxyl;
and n is an integer greater than or equal to 1.
38. The composition of claim 37, wherein X is selected from the group consisting of-CH 2 -and-C (CH) 3 ) 2 -in the group of compositions.
39. The composition according to any one of claims 1 to 38, wherein R 1 、R 2 And R 3 Each independently selected from hydrogen and C 1 -C 6 Alkyl groups.
40. The composition according to any one of claims 1 to 38, wherein R 1 、R 2 And R 3 Each independently selected from the group consisting of hydrogen and methyl.
41. The composition according to any one of claims 1 to 40, wherein R 3 Is hydrogen.
42. The composition according to any one of claims 1 to 41, wherein n is an integer from 1 to 10.
43. The composition according to any one of claims 1 to 42, wherein n is 1.
44. The composition of any of claims 1 to 43, wherein organophosphorus olefin comprises a compound of:
formula Ia-i
Figure FDA0003966655030000181
Formula IIa-i
Figure FDA0003966655030000182
Formula IIb-i
Figure FDA0003966655030000191
Formula IIc-i
Figure FDA0003966655030000192
Formula IId-i
Figure FDA0003966655030000193
Figure FDA0003966655030000201
Formula IIe-i
Figure FDA0003966655030000202
Formula IIf-i
Figure FDA0003966655030000203
Of the formula IIIa-i
Figure FDA0003966655030000204
Figure FDA0003966655030000211
Formula IIIb-i
Figure FDA0003966655030000212
Formula IIIc-i
Figure FDA0003966655030000213
Formula IIId-i
Figure FDA0003966655030000221
Formula IIIe-I
Figure FDA0003966655030000222
And formula IIIf-I
Figure FDA0003966655030000223
45. The composition of any of claims 1 to 44, comprising an organophosphorus olefin in an amount of about 10% by weight to about 65% by weight, about 15% by weight to about 50% by weight, about 20% by weight to about 40% by weight, about 20% by weight to about 35% by weight, or about 25% by weight to about 35% by weight of the composition.
46. A printed circuit board comprising the composition of any one of claims 1 to 45.
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