CN114051502A - Phosphorus-containing resin end-capped with unsaturated group, method for producing same, and resin composition containing phosphorus-containing resin end-capped with unsaturated group - Google Patents

Phosphorus-containing resin end-capped with unsaturated group, method for producing same, and resin composition containing phosphorus-containing resin end-capped with unsaturated group Download PDF

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CN114051502A
CN114051502A CN202080048680.8A CN202080048680A CN114051502A CN 114051502 A CN114051502 A CN 114051502A CN 202080048680 A CN202080048680 A CN 202080048680A CN 114051502 A CN114051502 A CN 114051502A
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CN114051502B (en
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康圣圭
成都庆
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Kolon Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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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Abstract

The present disclosure relates to a phosphorus-containing resin whose end is terminated with an unsaturated group, a method for preparing the same, and a resin composition comprising the phosphorus-containing resin. The unsaturated group at the terminal may reduce dielectric constant and dielectric dissipation factor, and may exhibit excellent flame retardancy by including a high phosphorus content.

Description

Phosphorus-containing resin end-capped with unsaturated group, method for producing same, and resin composition containing phosphorus-containing resin end-capped with unsaturated group
Technical Field
The present disclosure relates to a phosphorus-containing resin whose end is terminated with an unsaturated group, a method for preparing the same, and a resin composition comprising the phosphorus-containing resin.
Background
In various electronic products such as computers, semiconductors, displays, and communication devices, a Printed Circuit Board (PCB) on which a predetermined electronic circuit is printed is being used. Signal lines for signal transmission, an insulating layer for preventing short circuits between wirings, switching elements, and the like may be formed on the board.
A prepreg sheet prepared by impregnating an epoxy resin in a glass cloth and semi-curing is stacked on an inner-layer circuit board on which a circuit is formed to form a printed circuit board. The printed circuit board may also be formed by a build-up (build-up) method of alternately stacking insulating layers onto a circuit pattern of an inner layer circuit board on which a circuit is formed. The overlay method has advantages in that a thin and high-density printed circuit board is obtained by increasing wiring density by forming via holes (via holes) and forming circuits using laser processing.
Recently, the trend toward small and lightweight electronic devices has led to highly integrated, high-density printed circuit boards, and thus electrical, thermal, and mechanical stability of the printed circuit boards is becoming an important factor in ensuring stability and reliability of the electronic devices.
In printed circuit boards, as electronic devices become smaller in size and thickness and higher in performance, high-density wiring by reducing a line pitch is required. For this reason, in place of other existing wire bonding methods, a flip chip bonding method is generally used to bond a semiconductor device and a wiring board using a solder ball.
In the flip chip bonding method, a solder ball is arranged between a wiring substrate and a semiconductor device, and the entire resultant structure is heated, and the wiring substrate and the semiconductor device are bonded by melting back the solder, so that an insulating material having high ignition resistance is required.
In addition, there is a tendency toward high-speed and high-frequency signals in electronic devices according to the demand for high-performance electronic devices. Transmission loss and dielectric loss factor (D) of electric signalf) Proportional to the frequency. Transmission loss increases at higher frequencies, which causes signal attenuation, ultimately reducing the reliability of signal transmission. In addition, the transmission loss is converted into heat, and thus, a problem of heat generation may be caused. Accordingly, there is a need for insulating materials having a dielectric constant and dielectric dissipation factor that are much smaller than existing insulating materials.
However, it is not easy to reduce the dielectric constant and dielectric dissipation factor of the epoxy resin composition and the cured product thereof, which are widely used as an insulating material in the prior art, due to the inherent properties of the epoxy resin.
In this regard, Korean patent registration No.10-1596992 discloses a non-halogen flame retardant polymer having excellent impregnation, adhesion, flame retardancy, and compatibility with other polymers.
In addition, korean patent laid-open publication No. 2016-.
In the proposed flame retardant polymer or active ester resin, the final cured product thereof demonstrates improved flame retardancy to some extent, but the improvement in flame retardancy is still insufficient and dielectric properties are not taken into consideration.
Disclosure of Invention
Technical problem
Accordingly, an aspect of the present disclosure provides a resin satisfying both flame retardancy and dielectric characteristics by capping the end of a phosphorus-based flame retardant resin with an unsaturated group, a method of manufacturing the same, and a resin composition including the same.
Technical scheme
One aspect of the present disclosure provides a phosphorus-containing resin end-capped with an unsaturated group, comprising a compound represented by formula 1:
[ formula 1]
Figure BDA0003448963410000021
Wherein X1And X2The same or different, and each independently is hydrogen, hydroxy or a group represented by formula 2 or formula 3,
X1and X2Is represented by formula 2 or formula 3,
Y1and Y2The same or different, and represented by one of formulas 4 to 8,
R1' is C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20Aryl radical, and
n1 is an integer from 1 to 15;
[ formula 2]
Figure BDA0003448963410000031
Wherein R is2' is hydrogen, C1To C8Alkyl, or
Figure BDA0003448963410000032
R3' is hydrogen or C1To C8An alkyl group, a carboxyl group,
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5, and
when m2 is 2 or more than 2, R3Two or more of' are the same or different;
[ formula 3]
Figure BDA0003448963410000033
[ formula 4]
Figure BDA0003448963410000034
Wherein R is1To R4Are the same or different and are hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a1 and b1 are each independently an integer from 0 to 4,
when a1 is 2 or greater than 2, R1Two or more of which are the same or different, and
when b1 is 2 or greater than 2, R2Two or more of which are the same or different;
[ formula 5]
Figure BDA0003448963410000035
Wherein R is9To R14Are the same or different and are hydrogen or C1To C3An alkyl group, a carboxyl group,
[ formula 6]
Figure BDA0003448963410000041
Wherein R is15And R16Are the same or different and are hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a2 and b2 are each independently an integer from 0 to 4,
when a2 is 2 or greater than 2, R15Two or more of which are the same or different, and
when b2 is 2 or greater than 2, R16Two or more of which are the same or different;
[ formula 7]
Figure BDA0003448963410000042
Wherein R is21And R22Are the same or different and are hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a3 and b3 are each independently an integer from 0 to 3,
when a3 is 2 or greater than 2, R21Two or more of which are the same or different, and
when b3 is 2 or greater than 2, R22Two or more of which are the same or different; and
[ formula 8]
Figure BDA0003448963410000043
Wherein R is25Is hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or greater than 2, R25Two or more of which are the same or different.
Another aspect of the present disclosure provides a method for preparing a phosphorus-containing resin end-capped with an unsaturated group, the method comprising: (S1) providing a hydroxyl terminated oligophosphonate; and (S2) reacting the hydroxyl terminated oligophosphonate with an unsaturated group to prepare a phosphorus-containing resin terminated at its end with an unsaturated group, wherein the unsaturated group is an acrylate group or a vinylbenzyl group.
Another aspect of the present disclosure provides a phosphorus-containing resin composition end-capped with an unsaturated group, comprising a compound represented by formula 1:
[ formula 1]
Figure BDA0003448963410000051
Wherein X1And X2The same or different, and each independently is hydrogen, hydroxy or a compound represented by formula 2 or formula 3,
X1and X2Is represented by formula 2 or formula 3,
Y1and Y2The same or different, and represented by one of formulas 4 to 8,
R1' is C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20Aryl radical, and
n1 is an integer from 1 to 15,
[ formula 2]
Figure BDA0003448963410000052
Wherein R is2' is hydrogen, C1To C8Alkyl or
Figure BDA0003448963410000053
R3' is hydrogen or C1To C8An alkyl group, a carboxyl group,
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5, and
when m2 is 2 or more than 2, R3Two or more ofThe same or different, and the same or different,
[ formula 3]
Figure BDA0003448963410000054
[ formula 4]
Figure BDA0003448963410000061
Wherein R is1To R4Are the same or different and are hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a1 and b1 are each independently an integer from 0 to 4,
when a1 is 2 or greater than 2, R1Two or more of which are the same or different, and
when b1 is 2 or greater than 2, R2Two or more of which are the same or different,
[ formula 5]
Figure BDA0003448963410000062
Wherein R is9To R14Are the same or different and are hydrogen or C1To C3An alkyl group, a carboxyl group,
[ formula 6]
Figure BDA0003448963410000063
Wherein R is15And R16Are the same or different and are hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a2 and b2 are each independently an integer from 0 to 4,
when a2 is 2 or greater than 2, R15Two or more of which are the same or different, and
when b2 is 2 or greater than 2, R16Two or more of which are the same or different,
[ formula 7]
Figure BDA0003448963410000064
Wherein R is21And R22Are the same or different and are hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a3 and b3 are each independently an integer from 0 to 3,
when a3 is 2 or greater than 2, R21Two or more of which are the same or different, and
when b3 is 2 or greater than 2, R22Two or more of which are the same or different,
[ formula 8]
Figure BDA0003448963410000071
Wherein R is25Is hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or greater than 2, R25Two or more of which are the same or different.
Another aspect of the present disclosure provides a copper clad laminate manufactured using a phosphorus-containing resin composition whose end is terminated with an unsaturated group.
Advantageous effects
The phosphorus-containing resin whose terminal is terminated with an unsaturated group according to the present disclosure may have a reduced dielectric constant and dielectric dissipation factor by having an unsaturated group at the terminal, and may exhibit excellent flame retardancy by including a high content of phosphorus.
Drawings
FIG. 1 is a graph showing GPC measurement results of a phosphorus-containing resin whose end is terminated with an unsaturated group; and
FIG. 2 is a graph showing the NMR results of a phosphorus-containing resin whose terminal is terminated with an unsaturated group.
Detailed Description
Various aspects and embodiments of the disclosure are described in more detail below.
The terms or words used in the present specification and claims should not be construed restrictively as a general or dictionary meaning, but should be construed as a meaning and concept consistent with the technical idea of the present invention based on the principle that an inventor can properly define the concept of the terms to describe his/her invention in the best way.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the inventive concepts. Unless the context has a significantly different meaning, the use of the singular forms covers the plural forms of expressions. As used herein, it is to be understood that terms such as "comprising," "having," and "including" are intended to indicate the presence of the features, numbers, steps, actions, components, parts, ingredients, materials, or combinations thereof disclosed in this specification, but do not preclude the possibility that one or more other features, numbers, steps, actions, components, parts, ingredients, materials, or combinations thereof may be present or added.
As used herein, the terms "flame retardant property", "flame retardancy" or "ignition resistance" refer to the property of a difficult-to-burn material intermediate between flammable and non-flammable properties, and have the same meaning as ignition resistance, flame resistance, smoke resistance, and the like.
As used herein, the term "alkyl" refers to a straight or branched chain saturated monovalent hydrocarbon radical of 1 to 20, preferably 1 to 10, and more preferably 1 to 8 carbon atoms. Alkyl may refer collectively to both unsubstituted groups and groups further substituted with one or more of the given substituents that will be described below. Examples of the alkyl group may include methyl, ethyl, 2-propyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, iodomethyl, bromomethyl, and the like.
As used herein, the term "alkenyl" refers to a straight or branched chain monovalent hydrocarbon group of 2 to 20, preferably 2 to 10, and more preferably 2 to 6 carbon atoms having one or more carbon-carbon double bonds. An alkenyl group may be bonded through a carbon atom having one or more carbon-carbon double bonds or a saturated carbon atom. Alkenyl may collectively refer to both unsubstituted groups and groups further substituted with one or more given substituents as will be described later. Examples of the alkenyl group may include vinyl, 1-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl, dodecenyl and the like.
As used herein, the term "alkynyl" refers to a straight or branched chain monovalent hydrocarbon radical of 2 to 20, preferably 2 to 10, and more preferably 2 to 6 carbon atoms having one or more carbon-carbon triple bonds. The alkynyl group may be bonded through a carbon atom having one or more carbon-carbon triple bonds or a saturated carbon atom. Alkynyl may collectively refer to a residue further substituted with one or more of the given substituents described later. Examples of the alkynyl group may include ethynyl, propynyl and the like.
As used herein, the term "cycloalkyl" refers to a saturated or unsaturated monovalent monocyclic, bicyclic or tricyclic non-aromatic hydrocarbon group of 3 to 20, preferably 3 to 12, cyclic carbons, and may collectively refer to a residue further substituted with one or more given substituents as will be described later. Examples of the cycloalkyl group may include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptenyl, cyclooctyl, decahydronaphthyl, adamantyl, norbornenyl (i.e., bicyclo [2,2,1] -5-heptenyl), and the like.
As used herein, the term "aryl" refers to a monovalent monocyclic, bicyclic, or tricyclic aromatic hydrocarbon group of 6 to 40, and preferably 6 to 20 ring atoms, and may collectively refer to a residue further substituted with one or more given substituents as will be described later. Examples of the aryl group may include phenyl, biphenyl, or fluorenyl.
Unless otherwise specified, all compounds or substituents described herein may be substituted or unsubstituted. The term "substituted" as used herein means that a hydrogen atom is substituted with any one selected from the group consisting of a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group, an alkoxy group, a nitrile group, an aldehyde group, an epoxy group, an ether group, an ester group, a carbonyl group, an acetal group, a ketone group, an alkyl group, a perfluoroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an allyl group, a benzyl group, an aryl group, a heteroaryl group, derivatives thereof, and combinations thereof.
According to a new trend of miniaturization and high performance of electronic devices and communication apparatuses, signal transmission speeds of these products have been increased, and frequency bands of signals used are moving from the MHz region to the GHz region. If the frequency of the signal becomes high, the number of lost signals increases and noise may also increase, so that it is difficult to ensure the reliability of signal transmission, and heat converted by transmission loss may cause a heat generation problem. However, since epoxy resins widely used as insulating materials of existing printed circuit boards have high dielectric constants and increased dielectric dissipation factors, epoxy resins are limited in their application to small highly integrated printed circuit patterns. Therefore, in order to comply with the technical trend for reducing halogen-based flame retardants according to the trend for high-speed and high-frequency electronic devices, an insulating material having both low dielectric properties and good flame retardancy is required.
Accordingly, the present disclosure provides a phosphorus-based flame retardant resin having excellent flame retardancy and low dielectric properties by substituting the end thereof with an unsaturated group.
One aspect of the present disclosure provides a phosphorus-containing resin end-capped with an unsaturated group, comprising a compound represented by formula 1:
[ formula 1]
Figure BDA0003448963410000101
Wherein X1And X2The same or different, and each independently is hydrogen, hydroxy or a group represented by formula 2 or formula 3,
X1and X2Is represented by formula 2 or formula 3,
Y1and Y2The same or different, and represented by one of formulas 4 to 8,
R1' is C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20Aryl radical, and
n1 is an integer from 1 to 15;
[ formula 2]
Figure BDA0003448963410000102
Wherein R is2' is hydrogen, C1To C8Alkyl or
Figure BDA0003448963410000103
R3' is hydrogen or C1To C8An alkyl group, a carboxyl group,
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5, and
when m2 is 2 or more than 2, R3Two or more of' are the same or different;
[ formula 3]
Figure BDA0003448963410000104
[ formula 4]
Figure BDA0003448963410000105
Wherein R is1To R4Are the same or different and are hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a1 and b1 are each independently an integer from 0 to 4,
when a1 is 2 or greater than 2, R1Two or more of which are the same or different, and
when b1 is 2 or greater than 2, R2Two or more of which are the same or different;
[ formula 5]
Figure BDA0003448963410000111
Wherein R is9To R14Are the same or different and are hydrogen or C1To C3An alkyl group;
[ formula 6]
Figure BDA0003448963410000112
Wherein R is15And R16Are the same or different and are hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a2 and b2 are each independently an integer from 0 to 4,
when a2 is 2 or greater than 2, R15Two or more of which are the same or different, and
when b2 is 2 or greater than 2, R16Two or more of which are the same or different；
[ formula 7]
Figure BDA0003448963410000113
Wherein R is21And R22Are the same or different and are hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a3 and b3 are each independently an integer from 0 to 3,
when a3 is 2 or greater than 2, R21Two or more of which are the same or different, and
when b3 is 2 or greater than 2, R22Two or more of which are the same or different; and
[ formula 8]
Figure BDA0003448963410000121
Wherein R is25Is hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or greater than 2, R25Two or more of which are the same or different.
In formulas 2 to 8, asterisks (—) indicate positions to be bonded to adjacent atoms.
In the phosphorus-containing resin whose terminal is terminated with an unsaturated group according to the present disclosure, inherent flame retardancy is exhibited by the phosphorus-containing resin, and the terminal reactive unsaturated group advantageously participates in curing the resin by a crosslinking reaction with other products added to prepare a resin composition. In addition, the acrylate group of formula 2 or the vinylbenzyl group of formula 3, which is an unsaturated group terminating the end, has a shorter chain than other unsaturated groups, and thus may be advantageous in terms of crosslinking.
In addition, although the phosphonate ester having the conventional structure only serves as an additive and thus undergoes degradation in heat resistance and dielectric properties after curing, the phosphonate ester having the structure of formula 1 according to the present disclosure can participate in crosslinking, and thus heat resistance and dielectric properties are not degraded even after curing.
In an exemplary embodiment, formula 4 may be represented by formula 4-1:
[ formula 4-1]
Figure BDA0003448963410000122
Wherein R is3To R8May be the same or different and may be hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20And (4) an aryl group.
In addition, formula 6 may be represented by formula 6-1:
[ formula 6-1]
Figure BDA0003448963410000123
Wherein R is17To R20May be the same or different and may be hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20And (4) an aryl group.
Formula 7 may be represented, for example, by formula 7-1:
[ formula 7-1]
Figure BDA0003448963410000131
Wherein R is23And R24May be the same or different and may be hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20And (4) an aryl group.
In the formula, R1' preferably C1To C6Alkyl radical, C2To C5Alkenyl radical, C2To C6Alkynyl, C3To C6Cycloalkyl or C6To C12Aryl, more preferably methyl, ethyl, methylene, ethylene, cyclohexyl, phenyl or naphthyl, and most preferably methyl or phenyl, because when R in formula 11' is a functional group as listed above, has good compatibility with other resins and solvents used in forming the composition.
In one embodiment, in formula 1, Y1And Y2May be the same or different, and may be a compound represented by one of formulae 9 to 16, respectively:
[ formula 9]
Figure BDA0003448963410000132
[ formula 10]
Figure BDA0003448963410000133
[ formula 11]
Figure BDA0003448963410000134
[ formula 12]
Figure BDA0003448963410000141
[ formula 13]
Figure BDA0003448963410000142
[ formula 14]
Figure BDA0003448963410000143
[ formula 15]
Figure BDA0003448963410000144
[ formula 16]
Figure BDA0003448963410000145
In an exemplary embodiment, in formula 1, R1' may be C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl, and n1 can be an integer from 1 to 8; in formula 2, R2' may be hydrogen or C1To C8An alkyl group; in formula 4, R1To R4May be the same or different and may be hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group; in formula 5, R9To R14May be the same or different and may be hydrogen or methyl; in formula 6, R15To R16May be the same or different and may be hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group; in formula 7, R21To R22May be the same or different and may be hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group; and in formula 8, R25Can be hydrogen or C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20And (4) an aryl group.
Specifically, n1 is preferably an integer of 1 to 8, and when n1 is more than 8, the molecular weight of the composition increases and the viscosity becomes high, so that the composition cannot have sufficient fluidity, and moldability of the cured product thereof may be impaired.
As described above, since the compound represented by formula 1 has a high content of phosphorus, it can be imparted with flame retardancy as in the existing phosphorus-based compound. However, the conventional phosphorus-based compound may not have reactivity or may have extremely low reactivity, the curing-crosslinking density may be reduced, and the physical properties of the final cured product may be greatly degraded. In addition, the unsaturated group present in the compound represented by formula 1 may provide excellent reactivity and improved heat resistance.
In addition, in formula 1, X1And X2Both are preferably compounds represented by formula 2 or formula 3. In the compound having both terminals represented by formula 2 or formula 3, the low dielectric property exhibited by the unsaturated group of the terminal may be improved, and the reactivity may also be improved, so that a commercially suitable gel time of a resin composition to be prepared later may be expected in the resin composition molding process.
The content of phosphorus contained in the compound represented by formula 1 may be 7 to 15 mass% based on the total weight of the compound. When the content of phosphorus is less than 7 mass%, flame retardancy and heat resistance may be reduced and a large amount of flame retardant additive may be required, and when the content of phosphorus is more than 15 mass%, reactivity may be reduced and compatibility and solubility with a solvent and other products may be reduced.
The weight average molecular weight of the compound represented by formula 1 may be 1000g/mol to 7000g/mol, preferably 1500g/mol to 4000 g/mol. When the weight average molecular weight is less than 1000g/mol, the heat resistance and dielectric property improving effect may be insufficient, and when the weight average molecular weight is more than 7000g/mol, the compatibility with the solvent may be reduced, thereby making it difficult to practically use the compound.
The glass transition temperature of the compound represented by formula 1 may be 170 ℃ to 210 ℃. When the glass transition temperature is within the above range, the compound represented by formula 1 has excellent heat resistance.
According to an exemplary embodiment, the phosphorus-containing resin whose terminal is terminated with an unsaturated group may be represented by formula 17-1, formula 17-2, or formula 17-3:
[ formula 17-1]
Figure BDA0003448963410000151
[ formula 17-2]
Figure BDA0003448963410000161
[ formula 17-3]
Figure BDA0003448963410000162
Wherein each R in formula 17-1, formula 17-2 or formula 17-3 is independently C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
each n2 is independently an integer from 1 to 8.
According to another exemplary embodiment, the phosphorus-containing resin whose terminal is terminated with an unsaturated group may be represented by formula 18-1, formula 18-2, or formula 18-3:
[ formula 18-1]
Figure BDA0003448963410000163
[ formula 18-2]
Figure BDA0003448963410000164
[ formula 18-3]
Figure BDA0003448963410000165
Wherein each R in formula 18-1, formula 18-2 or formula 18-3 is independently C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
each n2 is independently an integer from 1 to 8.
According to yet another exemplary embodiment, the phosphorus-containing resin whose terminal is terminated with an unsaturated group may be represented by formula 19-1, formula 19-2, or formula 19-3:
[ formula 19-1]
Figure BDA0003448963410000171
[ formula 19-2]
Figure BDA0003448963410000172
[ formula 19-3]
Figure BDA0003448963410000173
Wherein each R in formula 19-1, formula 19-2 or formula 19-3 is independently C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
each n4 is independently an integer from 1 to 8.
According to still another exemplary embodiment, the phosphorus-containing resin whose end is terminated with an unsaturated group may be represented by formula 20-1, formula 20-2, or formula 20-3:
[ formula 20-1]
Figure BDA0003448963410000174
[ formula 20-2]
Figure BDA0003448963410000175
[ formula 20-3]
Figure BDA0003448963410000176
Wherein each R in formula 20-1, formula 20-2 or formula 20-3 is independently C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
each n5 is independently an integer from 1 to 8.
As described above, the compounds represented by formula 17 to formula 20 may have high reactivity and improved heat resistance through the unsaturated group present therein. Specifically, it was confirmed that the compounds represented by formulae 17 to 20 have excellent compatibility with other resins and solvents used in forming the composition.
The phosphorus-containing resin end-capped with an unsaturated group may have a dielectric constant (D) of less than 3.6 at 1GHzk). In addition, the phosphorus-containing resin end-capped with an unsaturated group may have a dielectric loss factor (D) of less than 0.0050 at 1GHzf)。
As described above, according to the present disclosure, the phosphorous-containing resin whose terminal is terminated with an unsaturated group can exhibit excellent low dielectric properties by the structural characteristics exhibited by introducing an acrylate group or a vinylbenzyl group into the terminal. In addition, the phosphorus-containing resin may have significantly improved flame retardancy by including a phosphorus-containing phosphonate as a repeating unit. Specifically, as described above, according to the present disclosure, the phosphorus-containing resin whose end is terminated with an unsaturated group contains a relatively high phosphorus content in the range of 7 to 15 mass%, and thus the resin composition to be subsequently prepared can satisfy the requirement of the phosphorus content therein even if a small amount of the phosphorus-containing resin is used in the resin composition as compared with other resins containing a low phosphorus content.
Another aspect of the present disclosure provides a method for preparing a phosphorus-containing resin end-capped with an unsaturated group, the method comprising: (S1) providing a hydroxyl terminated oligophosphonate; and (S2) preparing a phosphorus-containing resin end-capped with an unsaturated group by reacting the hydroxyl-terminated oligophosphonate with a reactant including an unsaturated group, wherein the unsaturated group is an acrylate unsaturated group or a vinylbenzyl unsaturated group. The method can be used for a purification process without a curing process, thereby effectively removing by-products and salts, and can be easily applied to an industrial process.
The reaction of step S2 may be performed in the presence of a catalyst, and the catalyst may be selected from 4-dimethylaminopyridine, pyridine, triethylamine, ammonia, NaOH, KOH, LiOH, K2CO3Tetramethylammonium hydroxide and AlCl3Or a mixture of two or more thereof. Specifically, when an alkali metal oxide is used, a suitable concentration thereof may be in the range of 0 to 50 mass%.
When an aqueous catalyst is used, the reaction may be carried out in the presence of a phase transfer catalyst in combination with the aqueous catalyst. Specifically, when an alkali metal hydroxide is used, the reaction may be carried out in the presence of a phase transfer catalyst. When the reaction is completed in a phase of a polar solvent such as water and a nonpolar solvent, the phase transfer catalyst serves to bring the alkali metal hydroxide from the polar solvent into the nonpolar solvent.
Specifically, when an aqueous solution of sodium hydroxide as an alkali metal hydroxide is used as a catalyst for an organic solvent such as toluene, the catalyst hardly contributes to promotion of the reaction without using a phase transfer catalyst.
The phase transfer catalyst may include, but is not particularly limited to, quaternary ammonium salts such as tetra-n-butylammonium chloride (TBAC) or tetra-n-butylammonium bromide (TBAB).
The reactant comprising an unsaturated group may be one selected from the group consisting of: one of methacryl halide (methacryl halide), methacrylic anhydride, acrylic anhydride, methacrylic acid, acrylic acid, a mixture of 4-vinylbenzyl halide (4-vinylbenzyl halide) and 2-vinylbenzyl halide (2-vinylbenzyl halide), a mixture of 4-vinylbenzyl alcohol (4-vinylbenzyl alcohol) and 2-vinylbenzyl alcohol (2-vinylbenzyl alcohol), or a mixture of two or more thereof. The methacryloyl halide may be selected from the group consisting of methacryloyl fluoride, methacryloyl chloride, methacryloyl bromide, methacryloyl iodide and combinations thereof, and the 4-vinylbenzyl halide or 2-vinylbenzyl halide may be selected from the group consisting of vinylbenzyl fluoride, vinylbenzyl chloride, vinylbenzyl bromide, vinylbenzyl iodide and combinations thereof.
The reactant containing the unsaturated group is preferably a mixture of 4-vinylbenzyl chloride and 2-vinylbenzyl chloride, which is more effective in promoting the reaction than the other reactants presented herein.
In step S2, the reactant including an unsaturated group may be added in an amount of 0.5 to 5 equivalents based on 1 hydroxyl equivalent of the oligophosphonate. When the amount of the reactant is less than the above range, the amount of the unsaturated group may be significantly reduced, and when the amount of the reactant exceeds the above range, the resin prepared from an excessive amount of unreacted material may have a reduced quality and may undesirably increase unnecessary production costs.
The reaction of step S2 may be carried out at a temperature in the range of 50 ℃ to 90 ℃. When the temperature is less than 50 ℃, the reaction rate is greatly reduced and a very long time is required to prepare the resin, and when the temperature is more than 90 ℃, the reaction rate is greatly increased and an excessive reaction may undesirably proceed.
The solvent used in the reaction of step 2 is not particularly limited as long as the reaction with the compound is not hindered by the solvent. Examples of the solvent may include one selected from the group consisting of: dimethylaniline, acetonitrile, Dimethylformamide (DMF), toluene, xylene, dichloromethane, chlorobenzene, cyclohexane, cyclohexanol, Tetrahydrofuran (THF), acetone, Methyl Ethyl Ketone (MEK), and methyl isobutyl ketone (MIBK), or a mixture of two or more thereof. In particular, a nonpolar solvent such as toluene or xylene is preferable because the use of a nonpolar solvent can improve the purification efficiency of the polymerization product.
The method may include (S3) removing unreacted materials by adding a basic compound to the phosphorus-containing resin terminated with an unsaturated group of step S2, thereby purifying the phosphorus-containing resin terminated with an unsaturated group of S2. The purification step may be performed to mainly remove the produced salt and its by-products, slightly different depending on the kinds of reactants, and, for example, an aqueous NaOH solution may be used as the basic compound.
The hydroxyl terminated oligophosphonate is represented by formula 21:
[ formula 21]
Figure BDA0003448963410000201
Wherein Y is1And Y2The same or different, and is a compound represented by one of formula 4 to formula 8,
R4' is C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20Aryl radical, and
n6 is an integer from 1 to 15;
[ formula 4]
Figure BDA0003448963410000202
Wherein R is1To R4Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a1 and b1 are each independently an integer from 0 to 4,
when a1 is 2 or greater than 2, R1Two or more of which are the same or different, and
when b1 is 2 or greater than 2, R2Two or more of which are the same or different;
[ formula 5]
Figure BDA0003448963410000203
Wherein R is9To R14Are identical or different and are each hydrogen or C1To C3An alkyl group;
[ formula 6]
Figure BDA0003448963410000211
Wherein R is15And R16Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a2 and b2 are each independently an integer from 0 to 4,
when a2 is 2 or greater than 2, R15Two or more of which are the same or different, and
when b2 is 2 or greater than 2, R16Two or more of which are the same or different;
[ formula 7]
Figure BDA0003448963410000212
Wherein R is21And R22Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a3 and b3 are each independently an integer from 0 to 3,
when a3 is 2 or greater than 2, R21Two or more of which are the same or different, and
when b3 is 2 or greater than 2, R22Two or more of which are the same or different; and
[ formula 8]
Figure BDA0003448963410000213
Wherein R is25Is hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or greater than 2, R25Two or more of which are the same or different.
In formula 21, Y1And Y2May be the same or different, and each is a compound represented by one of formula 4 to formula 8.
[ formula 9]
Figure BDA0003448963410000221
[ formula 10]
Figure BDA0003448963410000222
[ formula 11]
Figure BDA0003448963410000223
[ formula 12]
Figure BDA0003448963410000224
[ formula 13]
Figure BDA0003448963410000225
[ formula 14]
Figure BDA0003448963410000226
[ formula 15]
Figure BDA0003448963410000227
[ formula 16]
Figure BDA0003448963410000231
Still another aspect of the present disclosure provides a phosphorus-containing resin composition end-capped with an unsaturated group, comprising a compound represented by formula 1, a curing agent, and a curing accelerator.
In an exemplary embodiment, in formula 1, R1' may be C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl, and n1 can be an integer from 1 to 8; in formula 2, R2' may be hydrogen or C1To C8An alkyl group; in formula 4, R1To R4May be the same or different and may each be hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group; in formula 5, R9To R14May be the same or different and may each be hydrogen or methyl; in formula 6, R15To R16May be the same or different and may each be hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group; in formula 7, R21To R22May be the same or different and may each be hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group; and in formula 8, R25Can be hydrogen or C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20And (4) an aryl group.
The phosphorus-containing resin composition may include 0.1 to 50 parts by weight of a curing agent and 0.0001 to 0.05 parts by weight of a curing accelerator, based on 100 parts by weight of the compound represented by formula 1.
When the amount of the curing agent is within the above range, an appropriate curing speed can be advantageously obtained. When the amount of the curing accelerator is less than 0.0001 parts by weight, the curing reaction may not be properly performed, and when the amount of the curing accelerator is more than 0.05 parts by weight, an excessive curing reaction may be undesirably performed.
As the curing agent, any curing agent generally used in the art to which the present disclosure pertains may be used, and examples thereof may include triallyl isocyanurate (TAIC), bismaleimide, and the like. Triallyl isocyanurate is preferred because it contains two or more unsaturated groups in its structure, whereby an effective crosslinking reaction can be carried out by introducing a plurality of functional groups into the reaction.
In addition, any curing accelerator commonly used in the art to which the present disclosure pertains may be used as the curing accelerator, and examples thereof may include peroxides such as dicumyl peroxide (DCP) or benzoyl peroxide and general radical initiators such as azobisisobutyronitrile.
The phosphorus-containing resin composition may further include a modified polyphenylene oxide (PPO) resin. Examples of modified PPO resins may include SA-9000 (available from SABIC) modified from polyphenylene ether known to have excellent dielectric constant or other dielectric properties even in the ultra-high frequency region. When included in a phosphorus-containing resin, the modified PPO may assist the crosslinking reaction and may improve dielectric properties and heat resistance.
Still another aspect of the present disclosure provides a copper-clad laminate manufactured using a phosphorus-containing resin whose end is terminated with an unsaturated group.
Hereinafter, the present disclosure may be described in further detail by examples. These examples are provided only for describing the present disclosure in more detail, and it is apparent to those skilled in the art that the scope of the present disclosure is not limited by these examples.
Examples
Example 1: preparation of phosphorus-containing resin terminated with methacryloyl group (having 4,4' - (1-methylethylidene) bis [ benzene ] Phenol and its salts]P-methylphosphonic acid diphenyl ester polymer)
500g (0.66mol) of a diphenyl p-methylphosphonate polymer having 4,4' - (1-methylethylidene) bis [ phenol ] and 1300.5g of toluene were added to a 3L three-necked flask purged with nitrogen, followed by addition of 10g of 4-Dimethylaminopyridine (DMAP) thereto, followed by raising the temperature to 75 ℃.
Subsequently, 128.48g of methacrylic anhydride (MAAH) were added slowly over a period of 4 hours. After the addition was complete, the reaction was carried out at 75 ℃ for 20 hours, and then the resulting solution was cooled. After cooling, in order to remove unreacted materials, a purification reaction was performed by adding 1938.98g of water and 107.42g of 50% NaOH and stirring the reaction solution at 75 ℃ for 1 hour.
After the stirring was completed, the obtained product was left undisturbed and liquid separation was performed. The water in the lower layer was removed, and then 517g of water was added thereto, followed by stirring. After stirring, phosphoric acid was added to set the pH level to 5 to 6. After the neutralized and washed layer was removed, the toluene solvent was degassed under vacuum reduced pressure to remove it. The reaction solvent was removed by degassing the reaction solvent at 70 ℃ under a vacuum of 200 to 300 torr, and then 214g of Methyl Ethyl Ketone (MEK) was added as a solvent.
In the resulting phosphorus-containing resin whose terminal was terminated with a methacryloyl group, the phosphorus content was 8.5% by mass, the molecular weight was 2878g/mol as measured by GPC, and the structure was identified by a Nuclear Magnetic Resonance (NMR) analysis method. Fig. 1 shows GPC measurement results of the phosphorus-containing resin of example 1, and fig. 2 shows NMR results thereof.
Example 2: preparation of a phosphorus-containing resin terminated with a vinylbenzyl group (having 4,4' - (1-methylethylidene) bis [ benzene ] Phenol and its salts]P-methylphosphonic acid diphenyl ester polymer)
500g (0.66mol) of a p-methylphosphonic acid diphenyl ester polymer with 4,4' - (1-methylethylidene) bis [ phenol ] and 1300.5g of toluene were added to a 3L three-necked flask purged with nitrogen, and 2.5g of tetra-n-butylammonium bromide (TBAB) and 111g of a vinylbenzyl chloride mixture containing 2-vinylbenzyl chloride and 4-vinylbenzyl chloride mixed at a mixing ratio of 2:8 were added thereto, followed by raising the temperature to 75 ℃.
Subsequently, 69g of aqueous NaOH solution were slowly added over 1 hour. After the addition was complete, the reaction was carried out at 75 ℃ for 20 hours, and then the resulting solution was cooled. After cooling, in order to remove unreacted materials, a purification reaction was performed by adding 1938.98g of water and 107.42g of 50% NaOH and stirring the reaction solution at 75 ℃ for 1 hour.
After the stirring was completed, the obtained product was left undisturbed and liquid separation was performed. The water in the lower layer was removed, and then 517g of water was added thereto, followed by stirring. After stirring, phosphoric acid was added to set the pH level to 5 to 6. After removing the neutralized and washed layer, the toluene solvent was degassed under reduced pressure in vacuum to remove it. The reaction solvent was removed by degassing the reaction solvent at 70 ℃ under a vacuum degree of 200 to 300 torr, and then 214g of toluene was added as a solvent.
In the resulting phosphorus-containing resin terminated with a vinylbenzyl group, the phosphorus content was 8.0 mass%, and the molecular weight was 3100g/mol as measured by GPC. The structure of the resulting resin was identified by Nuclear Magnetic Resonance (NMR) analysis and FT-IR.
Example 3: preparation of a phosphorus-containing resin terminated with methacryloyl groups (Poly (m-phenylene methylphosphonate))
500g (0.66mol) of poly (m-phenylene methylphosphonate) and 1300.5g of toluene were added to a 3L three-necked flask purged with nitrogen, to which was then added 10g of 4-Dimethylaminopyridine (DMAP), followed by raising the temperature to 75 ℃.
Subsequently, 113.48g of methacrylic anhydride (MAAH) were added slowly over a period of 2 hours. After the addition was complete, the reaction was carried out at 75 ℃ for 20 hours, and then the resulting solution was cooled. After cooling, in order to remove unreacted materials, a purification reaction was performed by adding 1938.98g of water and 107.42g of 50% NaOH and stirring the reaction solution at 75 ℃ for 1 hour.
After the stirring was completed, the obtained product was left undisturbed and liquid separation was performed. The water in the lower layer was removed, and then 517g of water was added thereto, followed by stirring. After stirring, phosphoric acid was added to set the pH level to 5 to 6. After removing the neutralized and washed layer, the toluene solvent was degassed under reduced pressure in vacuum to remove it. The reaction solvent was removed by degassing the reaction solvent at 70 ℃ under a vacuum of 200 to 300 torr, and then 214g of MEK was added as a solvent.
In the resulting phosphorus-containing resin whose end was terminated with a methacryloyl group, the phosphorus content was 10.5% by mass, the molecular weight was 2127g/mol as measured by GPC, and the structure of the resulting resin was identified by NMR as well as FT-IR.
Example 4: preparation of a phosphorus-containing resin terminated with a vinylbenzyl group (Poly (m-phenylene methylphosphonate))
500g (0.66mol) of poly (m-phenylene methylphosphonate) and 1300.5g of toluene were added to a 3L three-necked flask purged with nitrogen, and then 2.5g of tetra-n-butylammonium bromide (TBAB) and 111g of a vinylbenzyl chloride mixture comprising 2-vinylbenzyl chloride and 4-vinylbenzyl chloride mixed at a mixing ratio of 2:8 were added thereto, followed by raising the temperature to 75 ℃.
Subsequently, 69g of 50% aqueous NaOH solution were slowly added over 1 hour. After the addition was complete, the reaction was carried out at 75 ℃ for 20 hours, and then the resulting solution was cooled. After cooling, to remove unreacted materials, a purification reaction was performed by adding 1938.98g of water and 107.42g of 50% NaOH and stirring the reaction solution at 75 ℃ for 1 hour.
After the stirring was completed, the obtained product was left undisturbed and liquid separation was performed. The water in the lower layer was removed, and then 517g of water was added thereto, followed by stirring. After stirring, phosphoric acid was added to set the pH level to 5 to 6. After removing the neutralized and washed layer, the toluene solvent was degassed under reduced pressure in vacuum to remove it. The reaction solvent was removed by degassing the reaction solvent at 70 ℃ under a vacuum degree of 200 to 300 torr, and then 214g of toluene was added as a solvent.
In the resulting phosphorus-containing resin whose terminal was terminated with a vinylbenzyl group, the phosphorus content was 9.5% by mass, and the molecular weight was 2442g/mol as measured by GPC. The structure of the resulting resin was identified by Nuclear Magnetic Resonance (NMR) analysis and FT-IR.
Comparative example 1: use of commercially available phosphorus-containing resins
SPV-100 (manufactured by Otsuka Chemical) was used as a commercially available phosphorus-containing resin.
Preparation of a phosphorus-containing resin composition end-capped with an unsaturated group
Phosphorus-containing resin compositions (varnishes) whose terminals were capped with unsaturated groups according to examples 1 to 4 were respectively prepared by mixing the respective components at mixing ratios listed in the following table 1 while adjusting the content of phosphorus in the compositions to 2.5 mass%.
The preparation of the varnish is specified below.
Polyfunctional triallyl isocyanurate (TAIC) groups were used as a curing agent, SA-9000 (available from SABIC) known to have an excellent dielectric constant or other dielectric properties was used as a polyphenylene ether resin known to have an excellent dielectric constant and dielectric properties, and the weight of SA-9000 used was controlled to adjust the content of phosphorus in each varnish. Dicumyl peroxide (DCP) was used as a curing accelerator, and the amount of dicumyl peroxide was 5000ppm with respect to the amount of SA-9000. To adjust the solid content of the varnish to 60 wt%, Methyl Ethyl Ketone (MEK) was additionally added.
Preparation of commercially available phosphorus-containing resin composition
A commercially available phosphorus-containing resin composition was prepared in the same manner as in examples 1 to 4, except that the commercially available phosphorus-containing resin prepared in comparative example 1 was used, instead of the phosphorus-containing resin composition whose terminal was terminated with an unsaturated group, which was prepared in examples 1 to 4, respectively. Table 1 shows the mixing ratio of the resin compositions of examples 1 to 4 and comparative example 1.
[ TABLE 1]
Figure BDA0003448963410000271
Experimental example: evaluation of physical Properties
(1) Measurement of weight average molecular weight (Mw)
The weight average molecular weight (Mw) according to polystyrene was obtained by Gel Permeation Chromatography (GPC) (Waters: Waters 707). The polymer to be measured was dissolved in tetrahydrofuran so that the concentration was 4000ppm, and the resulting solution was injected into GPC in an amount of 100 μ l. Tetrahydrofuran was used as the mobile phase of GPC and was added at a flow rate of 1.0mL/min and analyzed at 35 ℃. The columns of Waters HR-05, 1, 2 and 4E were connected in series. RI and PAD detectors were used as detectors for measurements at 35 ℃.
(2) Measurement of phosphorus content
The content of phosphorus contained in the resin was determined by acid digestion detection and by ICP-OES, and was detected by intercec Testing Services Korea ltd, reference US EPA 3052. The content of phosphorus contained in the varnish was calculated based on the content of the resin contained in the varnish.
(3) NMR analysis
An Avance 500 instrument (manufactured by Brucker) was used for NMR analysis.
(4) Manufacture of prepreg
A glass cloth was immersed in the varnish, and then naturally dried at room temperature for 1 hour, followed by drying in an oven at 155 ℃, thereby manufacturing a prepreg.
(5) Production of copper-clad laminate
Six prepared prepregs were stacked and the front and back sides of the resulting stack were covered with 1 ounce copper, followed by 40kgf/cm at 195 deg.C2And pressed for 120 minutes under pressure, thereby manufacturing a copper-clad laminate.
(6) Measurement of dielectric constant
The manufactured copper clad laminate was cut into a size of 1cm × 1cm, the copper foil was peeled off, and the dielectric constant (Dk) and the dielectric dissipation factor (Df) were measured under a condition of 1GHz using an impedance/material analyzer (AgilentE4991A RF). The measurement conditions are specified below.
Measuring frequency: 1GHz
Measuring the temperature: 25 ℃ to 27 DEG C
Measuring humidity: 45 to 55 percent
Measuring the thickness of the sample: 1.5mm
(7) Measurement of glass transition temperature (Tg)
The copper clad laminates prepared in examples 1 to 4 and comparative example 1 were subjected to DSC measurement using a TA instrument DSC Q2000 while heating from 30 ℃ to 350 ℃ at a heating rate of 20 ℃/min.
(8) Measurement of flame retardancy
Flame retardancy was measured by the UL-94 method.
The respective physical properties measured in the above manner are summarized in table 2.
[ TABLE 2]
Figure BDA0003448963410000291
As shown in table 2, the gel time of the resins prepared in examples 1 to 4 was shorter than that of the resin prepared in comparative example 1, and it is presumed that the former resin participates in curing more through a crosslinking reaction than the resin prepared in comparative example 1. It was confirmed that the resins prepared in examples 1 to 4 exhibited excellent physical properties including glass transition temperature and dielectric properties.
It is to be understood that the embodiments described herein are to be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each implementation should generally be considered other similar features or aspects that may be used in other implementations. Although one or more embodiments have been described herein with reference to the accompanying drawings, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure as defined by the following claims.
Industrial applicability
Therefore, according to the present disclosure, in the phosphorus-containing resin whose terminal is terminated with an unsaturated group, the dielectric constant and the dielectric dissipation factor can be reduced by the unsaturated group contained at the terminal, and excellent flame retardancy can be exhibited by containing a high content of phosphorus.

Claims (27)

1. A phosphorus-containing resin end-capped with an unsaturated group, comprising a compound represented by formula 1:
[ formula 1]
Figure FDA0003448963400000011
Wherein X1And X2The same or different, and each independently is hydrogen, hydroxy or a group represented by formula 2 or formula 3,
X1and X2Is represented by formula 2 or formula 3,
Y1and Y2The same or different, and each represented by one of formula 4 to formula 8,
R1' is C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20Aryl radical, and
n1 is an integer from 1 to 15;
[ formula 2]
Figure FDA0003448963400000012
Wherein R is2' is hydrogen, C1To C8Alkyl or
Figure FDA0003448963400000013
R3' is hydrogen or C1To C8An alkyl group, a carboxyl group,
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5, and
when m2 is 2 or more than 2, R3Two or more of' are the same or different;
[ formula 3]
Figure FDA0003448963400000014
[ formula 4]
Figure FDA0003448963400000021
Wherein R is1To R4Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a1 and b1 are each independently an integer from 0 to 4,
when a1 is 2 or greater than 2, R1Two or more of which are the same or different, and
when b1 is 2 or greater than 2, R2Two or more of which are the same or different;
[ formula 5]
Figure FDA0003448963400000022
Wherein R is9To R14Are identical or different and are each hydrogen or C1To C3An alkyl group;
[ formula 6]
Figure FDA0003448963400000023
Wherein R is15And R16Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a2 and b2 are each independently an integer from 0 to 4,
when a2 is 2 or greater than 2, R15Two or more of which are the same or different, and
when b2 is 2 or greater than 2, R16Two or more of which are the same or different;
[ formula 7]
Figure FDA0003448963400000031
Wherein R is21And R22Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a3 and b3 are each independently an integer from 0 to 3,
when a3 is 2 or greater than 2, R21Two or more of which are the same or different, and
when b3 is 2 or greater than 2, R22Two or more of which are the same or different; and
[ formula 8]
Figure FDA0003448963400000032
Wherein R is25Is hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or greater than 2, R25Two or more of which are the same or different.
2. The phosphorus-containing resin according to claim 1, wherein in formula 1, Y is1And Y2The same or different, and each represented by one of formulae 9 to 16:
[ formula 9]
Figure FDA0003448963400000033
[ formula 10]
Figure FDA0003448963400000034
[ formula 11]
Figure FDA0003448963400000041
[ formula 12]
Figure FDA0003448963400000042
[ formula 13]
Figure FDA0003448963400000043
[ formula 14]
Figure FDA0003448963400000044
[ formula 15]
Figure FDA0003448963400000045
[ formula 16]
Figure FDA0003448963400000046
3. The phosphorus-containing resin according to claim 1, wherein R in formula 11' is C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
n1 is an integer from 1 to 8,
in formula 2, R2' is hydrogen or C1To C8An alkyl group, a carboxyl group,
in formula 4, R1To R4Are the same or different and are each hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
in formula 5, R9To R14Identical or different and are each hydrogen or methyl,
in formula 6, R15And R16Are the same or different and are each hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
in formula 7, R21And R22Are the same or different and are each hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl, and
in formula 8, R25Is hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20And (4) an aryl group.
4. The phosphorus-containing resin of claim 1, wherein the content of phosphorus contained in the compound represented by formula 1 is 7 to 15% by weight, based on the total weight of the compound.
5. The phosphorus-containing resin of claim 1, wherein the compound represented by formula 1 has a weight average molecular weight of 1000g/mol to 7000 g/mol.
6. The phosphorus-containing resin of claim 1, wherein the compound represented by formula 1 has a glass transition temperature of 170 ℃ to 210 ℃.
7. The phosphorus-containing resin of claim 1, wherein formula 1 is represented by formula 17-1, formula 17-2, or formula 17-3:
[ formula 17-1]
Figure FDA0003448963400000061
[ formula 17-2]
Figure FDA0003448963400000062
[ formula 17-3]
Figure FDA0003448963400000063
Wherein each R in formula 17-1, formula 17-2 or formula 17-3 is independently C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
each n2 is independently an integer from 1 to 8.
8. The phosphorus-containing resin of claim 1, wherein formula 1 is represented by formula 18-1, formula 18-2, or formula 18-3:
[ formula 18-1]
Figure FDA0003448963400000064
[ formula 18-2]
Figure FDA0003448963400000065
[ formula 18-3]
Figure FDA0003448963400000066
Wherein each R in formula 18-1, formula 18-2 or formula 18-3 is independently C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
each n3 is independently an integer from 1 to 8.
9. The phosphorus-containing resin of claim 1, wherein formula 1 is represented by formula 19-1, formula 19-2, or formula 19-3:
[ formula 19-1]
Figure FDA0003448963400000071
[ formula 19-2]
Figure FDA0003448963400000072
[ formula 19-3]
Figure FDA0003448963400000073
Wherein each R in formula 19-1, formula 19-2 or formula 19-3 is independently C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
each n4 is independently an integer from 1 to 8.
10. The phosphorus-containing resin of claim 1, wherein formula 1 is represented by formula 20-1, formula 20-2, or formula 20-3:
[ formula 20-1]
Figure FDA0003448963400000074
[ formula 20-2]
Figure FDA0003448963400000081
[ formula 20-3]
Figure FDA0003448963400000082
Wherein each R in formula 20-1, formula 20-2 or formula 20-3 is independently C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
each n5 is independently an integer from 1 to 8.
11. The phosphorus-containing resin of claim 1 having a dielectric constant D of less than 3.6 at 1GHzk。
12. The phosphorus-containing resin of claim 1, having a dielectric loss factor D of less than 0.0050 at 1GHzf。
13. A method for producing a phosphorus-containing resin whose terminal is terminated with an unsaturated group, the method comprising:
s1: providing a hydroxyl terminated oligophosphonate; and
s2: preparing a phosphorus-containing resin end-capped with an unsaturated group by reacting the hydroxyl-terminated oligophosphonate with a reactant containing an unsaturated group,
wherein the unsaturated group is an acrylate unsaturated group or a vinylbenzyl unsaturated group.
14. The method of claim 13, wherein
The reaction of S2 is carried out in the presence of a catalyst, and
the catalyst is selected from 4-dimethylaminopyridine, pyridine, triethylamine, ammonia water, NaOH, KOH, LiOH and K2CO3Tetramethylammonium hydroxide and AlCl3Or a mixture of two or more thereof.
15. The preparation method of claim 13, wherein the reactant containing an unsaturated group is one selected from the group consisting of methacryloyl halide, methacrylic anhydride, acrylic anhydride, methacrylic acid, acrylic acid, 4-vinylbenzyl halide, 4-vinylbenzyl alcohol, 2-vinylbenzyl halide, and 2-vinylbenzyl alcohol, or a mixture of two or more thereof.
16. The preparation method of claim 13, wherein the reactant including an unsaturated group is added in an amount of 0.5 to 5 equivalents based on 1 hydroxyl equivalent of the oligophosphonate in S2.
17. The preparation method of claim 13, wherein the reaction of S2 is performed at a temperature ranging from 50 ℃ to 90 ℃.
18. The production method according to claim 13, wherein the solvent used in the reaction of S2 is one selected from dimethylaniline, acetonitrile, dimethylformamide DMF, toluene, xylene, dichloromethane, chlorobenzene, cyclohexane, cyclohexanol, tetrahydrofuran THF, acetone, methyl ethyl ketone MEK, and methyl isobutyl ketone MIBK, or a mixture of two or more thereof.
19. The method of claim 13, further comprising S3: purifying the unsaturated group-terminated phosphorus-containing resin of S2 by adding a basic compound to the unsaturated group-terminated phosphorus-containing resin of S2 to remove unreacted substances.
20. The method of claim 13, wherein the hydroxyl terminated oligophosphonate is represented by formula 21:
[ formula 21]
Figure FDA0003448963400000091
Wherein, Y1And Y2The same or different, and each is a group represented by one of formula 4 to formula 8,
R4' is C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20Aryl radical, and
n6 is an integer from 1 to 15;
[ formula 4]
Figure FDA0003448963400000101
Wherein R is1To R4Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a1 and b1 are each independently an integer from 0 to 4,
when a1 is 2 or greater than 2, R1Two or more of which are the same or different, and
when b1 is 2 or greater than 2, R2Two or more of which are the same or different;
[ formula 5]
Figure FDA0003448963400000102
Wherein R is9To R14Are identical or different and are each hydrogen or C1To C3An alkyl group;
[ formula 6]
Figure FDA0003448963400000103
Wherein R is15And R16Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a2 and b2 are each independently an integer from 0 to 4,
when a2 is 2 or greater than 2, R15Two or more of which are the same or different, and
when b2 is 2 or greater than 2, R16Two or more of which are the same or different;
[ formula 7]
Figure FDA0003448963400000111
Wherein R is21And R22Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a3 and b3 are each independently an integer from 0 to 3,
when a3 is 2 or greater than 2, R21Two or more of which are the same or different, and
when b3When it is 2 or more than 2, R22Two or more of which are the same or different; and
[ formula 8]
Figure FDA0003448963400000112
Wherein R is25Is hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or greater than 2, R25Two or more of which are the same or different.
21. The method of claim 20, wherein in formula 21, Y is1And Y2The same or different, and each is a group represented by one of formula 9 to formula 16,
[ formula 9]
Figure FDA0003448963400000113
[ formula 10]
Figure FDA0003448963400000121
[ formula 11]
Figure FDA0003448963400000122
[ formula 12]
Figure FDA0003448963400000123
[ formula 13]
Figure FDA0003448963400000124
[ formula 14]
Figure FDA0003448963400000125
[ formula 15]
Figure FDA0003448963400000126
[ formula 16]
Figure FDA0003448963400000131
22. A phosphorus-containing resin composition whose terminal is terminated with an unsaturated group, comprising a compound represented by formula 1:
[ formula 1]
Figure FDA0003448963400000132
Wherein X1And X2The same or different, and each independently is hydrogen, hydroxy or a group represented by formula 2 or formula 3,
X1and X2Is represented by formula 2 or formula 3,
Y1and Y2The same or different, and each represented by one of formula 4 to formula 8,
R1' is C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20Aryl radical, and
n1 is an integer from 1 to 15;
[ formula 2]
Figure FDA0003448963400000133
Wherein R is2' is hydrogen, C1To C8Alkyl or
Figure FDA0003448963400000134
R3' is hydrogen or C1To C8An alkyl group, a carboxyl group,
m1 is an integer of 0 or 1, m2 is an integer of 0 to 5, and,
when m2 is 2 or more than 2, R3Two or more of' are the same or different;
[ formula 3]
Figure FDA0003448963400000141
[ formula 4]
Figure FDA0003448963400000142
Wherein R is1To R4Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a1 and b1 are each independently an integer from 0 to 4,
when a1 is 2 or greater than 2, R1Two or more of which are the same or different, and
when b1 is 2 or greater than 2, R2Two or more of which are the same or different;
[ formula 5]
Figure FDA0003448963400000143
Wherein R is9To R14Are identical or different and are each hydrogen or C1To C3An alkyl group;
[ formula 6]
Figure FDA0003448963400000144
Wherein R is15And R16Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a2 and b2 are each independently an integer from 0 to 4,
when a2 is 2 or greater than 2, R15Two or more of which are the same or different, and
when b2 is 2 or greater than 2, R16Two or more of which are the same or different;
[ formula 7]
Figure FDA0003448963400000151
Wherein R is21And R22Are the same or different and are each hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a3 and b3 are each independently an integer from 0 to 3,
when a3 is 2 or greater than 2, R21Two or more of which are the same or different, and
when b3 is 2 or greater than 2, R22In (1)Two or more are the same or different; and
[ formula 8]
Figure FDA0003448963400000152
Wherein R is25Is hydrogen, C1To C20Alkyl radical, C2To C20Alkenyl radical, C2To C20Alkynyl, C3To C20Cycloalkyl or C6To C20An aryl group, a heteroaryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or greater than 2, R25Two or more of which are the same or different.
23. The phosphorus-containing resin composition according to claim 22, wherein in formula 1, Y is1And Y2The same or different, and each is a group represented by one of formulae 9 to 16:
[ formula 9]
Figure FDA0003448963400000153
[ formula 10]
Figure FDA0003448963400000161
[ formula 11]
Figure FDA0003448963400000162
[ formula 12]
Figure FDA0003448963400000163
[ formula 13]
Figure FDA0003448963400000164
[ formula 14]
Figure FDA0003448963400000165
[ formula 15]
Figure FDA0003448963400000166
[ formula 16]
Figure FDA0003448963400000171
24. The phosphorus-containing resin composition according to claim 22, wherein R in formula 11' is C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20Aryl radical, and
n1 is an integer from 1 to 8;
in formula 2, R2' is hydrogen or C1To C8An alkyl group;
in formula 4, R1To R4Are the same or different and are each hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group;
in formula 5, R9To R14Identical or different and are each hydrogen or methyl;
in formula 6, R15And R16Are the same or different and are each hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group;
in formula 7, R21And R22Are the same or different and are each hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20An aryl group; and is
In formula 8, R25Is hydrogen, C1To C8Alkyl radical, C2To C6Alkenyl radical, C2To C6Alkynyl, C3To C12Cycloalkyl or C6To C20And (4) an aryl group.
25. The phosphorus-containing resin composition of claim 22, wherein the composition comprises 0.1 to 50 parts by weight of the curing agent and 0.0001 to 0.05 parts by weight of the curing accelerator, based on 100 parts by weight of the compound represented by formula 1.
26. The phosphorus-containing resin composition as claimed in claim 22, further comprising a modified polyphenylene oxide PPO resin.
27. A copper-clad laminate manufactured using the phosphorus-containing resin composition terminated with an unsaturated group at the end according to any one of claims 22 to 26.
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