CN114051502B - Phosphorus-containing resin terminated at end with unsaturated group, process for producing the same, and resin composition containing phosphorus-containing resin terminated at end with unsaturated group - Google Patents
Phosphorus-containing resin terminated at end with unsaturated group, process for producing the same, and resin composition containing phosphorus-containing resin terminated at end with unsaturated group Download PDFInfo
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- CN114051502B CN114051502B CN202080048680.8A CN202080048680A CN114051502B CN 114051502 B CN114051502 B CN 114051502B CN 202080048680 A CN202080048680 A CN 202080048680A CN 114051502 B CN114051502 B CN 114051502B
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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
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- 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
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- 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
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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
- 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
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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
- 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
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- 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
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- 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
Abstract
The present disclosure relates to a phosphorus-containing resin terminated at the end with an unsaturated group, a method for preparing the same, and a resin composition comprising the same. The unsaturated group at the end can lower the dielectric constant and dielectric dissipation factor, and can exhibit excellent flame retardancy by containing a high phosphorus content.
Description
Technical Field
The present disclosure relates to a phosphorus-containing resin terminated at the end with an unsaturated group, a method for preparing the same, and a resin composition comprising the same.
Background
In various electronic products such as computers, semiconductors, displays, and communication devices, a Printed Circuit Board (PCB) having predetermined electronic circuits printed thereon is being used. On the board, a signal line for signal transmission, an insulating layer for preventing short-circuiting between wirings, a switching element, and the like may be formed.
The printed circuit board is formed by stacking prepreg sheets prepared by impregnating an epoxy resin in a glass cloth and semi-curing onto an inner layer circuit board on which a circuit is formed. The printed circuit board may also be formed by a build-up (build-up) method of alternately stacking insulating layers onto circuit patterns of an inner layer circuit board on which circuits are formed. The superposition method has an advantage in that a thin and high-density printed circuit board is obtained by increasing the wiring density by forming via holes (via holes) and forming circuits using laser processing.
Recently, a trend toward small and lightweight electronic devices has resulted in a highly integrated, high-density printed circuit board, and thus the electrical, thermal, and mechanical stability of the printed circuit board is becoming an important factor for ensuring the stability and reliability of the electronic devices.
In a printed circuit board, as the size and thickness of electronic devices become smaller and the performance becomes higher, it is required to realize high-density wiring by shrinking the line pitch. For this reason, flip chip bonding methods are generally used to bond a semiconductor device and a wiring board using solder balls instead of other existing wire bonding methods.
In the flip chip bonding method, a solder ball is disposed 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 reflow of solder, so that an insulating material having high ignition resistance is required.
In addition, there is a trend toward high-speed and high-frequency signals in electronic devices according to demands for high-performance electronic devices. Transmission loss of electric signal and dielectric loss factor (D f ) Proportional to the frequency. At higher frequencies the transmission loss increases, which causes signal attenuation, eventually reducing the reliability of the signal transmission. In addition, the transmission loss is converted into heat, and thus may cause a problem of heat generation. 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, due to the inherent properties of epoxy resins, it is not easy to reduce the dielectric constant and dielectric dissipation factor of epoxy resin compositions widely used as insulating materials in the prior art and cured products thereof.
In this regard, korean patent registration No.10-1596992 discloses a non-halogen flame retardant polymer having excellent impregnation degree, adhesion, flame retardancy and compatibility with other polymers.
In addition, korean patent laid-open No.2016-0018507 discloses an active ester resin containing a phosphorus atom, which is used in an epoxy resin composition to provide improved flame retardancy, heat resistance and dielectric properties.
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 of 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 terminal of a phosphorus-based flame retardant resin with an unsaturated group, a method of manufacturing the same, and a resin composition including the resin.
Technical proposal
One aspect of the present disclosure provides a phosphorus-containing resin terminated at the end by an unsaturated group, comprising a compound represented by formula 1:
[ 1]
Wherein X is 1 And X 2 Identical or different and are each independently hydrogen, hydroxyl or a group represented by formula 2 or formula 3,
X 1 and X 2 At least one of which is represented by formula 2 or formula 3,
Y 1 and Y 2 Identical or different, and is represented by one of formulas 4 to 8,
R 1 ' C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl group, and
n1 is an integer from 1 to 15;
[ 2]
Wherein R is 2 ' is hydrogen, C 1 To C 8 Alkyl, or
R 3 ' is hydrogen or C 1 To C 8 An alkyl group, a hydroxyl 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, R 3 Two or more of' same or different;
[ 3]
[ 4]
Wherein R is 1 To R 4 Identical or different and is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a1 and b1 are each independently integers from 0 to 4,
when a1 is 2 or more than 2, R 1 Two or more of them being the same or different, and
when b1 is 2 or more than 2, R 2 The two or more of which are the same or different;
[ 5]
Wherein R is 9 To R 14 Identical or different and is hydrogen or C 1 To C 3 An alkyl group, a hydroxyl group,
[ 6]
Wherein R is 15 And R is 16 Identical or different and is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a2 and b2 are each independently integers from 0 to 4,
when a2 is 2 or more than 2, R 15 Two or more of them being the same or different, and
when b2 is 2 or greater than 2, R 16 The two or more of which are the same or different;
[ 7]
Wherein R is 21 And R is 22 Identical or different and is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a3 and b3 are each independently integers from 0 to 3,
when a3 is 2 or more than 2, R 21 Two or more of them being the same or different, and
when b3 is 2 or more than 2, R 22 Two or more of which are identicalOr different; and
[ 8]
Wherein R is 25 Is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or more than 2, R 25 The two or more of which are the same or different.
Another aspect of the present disclosure provides a method for preparing a phosphorus-containing resin terminated at a terminal by an unsaturated group, the method comprising: (S1) providing a hydroxy-terminated oligophosphonate; and (S2) reacting the hydroxyl-terminated oligophosphonate with an unsaturated group to produce a phosphorus-containing resin terminated at the end with the 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 terminated at the end by an unsaturated group, comprising a compound represented by formula 1, a curing agent, and a curing accelerator:
[ 1]
Wherein X is 1 And X 2 Identical or different and are each independently hydrogen, hydroxyl or a compound represented by formula 2 or formula 3,
X 1 and X 2 At least one of which is represented by formula 2 or formula 3,
Y 1 and Y 2 Identical or different, and is represented by one of formulas 4 to 8,
R 1 ' C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl group, and
n1 is an integer of 1 to 15,
[ 2]
Wherein R is 2 ' is hydrogen, C 1 To C 8 Alkyl or
R 3 ' is hydrogen or C 1 To C 8 An alkyl group, a hydroxyl 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, R 3 Two or more of the' are the same or different,
[ 3]
[ 4]
Wherein R is 1 To R 4 Identical or different and is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a1 and b1 are each independently integers from 0 to 4,
when a1 is 2 or more than 2, R 1 Two or more of them being the same or different, and
when b1 is 2 or more than 2, R 2 Two or more of which are the same or differentIn the same way as described above,
[ 5]
Wherein R is 9 To R 14 Identical or different and is hydrogen or C 1 To C 3 An alkyl group, a hydroxyl group,
[ 6]
Wherein R is 15 And R is 16 Identical or different and is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a2 and b2 are each independently integers from 0 to 4,
when a2 is 2 or more than 2, R 15 Two or more of them being the same or different, and
when b2 is 2 or greater than 2, R 16 Is the same or different,
[ 7]
Wherein R is 21 And R is 22 Identical or different and is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a3 and b3 are each independently integers from 0 to 3,
when a3 is 2 or more than 2, R 21 Two or more of them being the same or different, and
when b3 is 2 or more than 2, R 22 Is the same or different,
[ 8]
Wherein R is 25 Is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or more than 2, R 25 The two 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 terminated at the end with an unsaturated group.
Advantageous effects
The phosphorus-containing resin having the terminal end capped with an unsaturated group according to the present disclosure may have a reduced dielectric constant and dielectric dissipation factor by the unsaturated group contained at the terminal end, and may exhibit excellent flame retardancy by containing a high content of phosphorus.
Drawings
FIG. 1 is a graph showing GPC measurement results of a phosphorus-containing resin terminated at the end with an unsaturated group; and
FIG. 2 is a graph showing NMR results of a phosphorus-containing resin terminated at the end with an unsaturated group.
Detailed Description
Hereinafter, various aspects and embodiments of the present disclosure will be described in more detail.
The terms or words used in the present specification and claims should not be interpreted restrictively as general or dictionary meanings, but interpreted as meanings and concepts consistent with the technical idea of the present invention based on the principle that the inventor can properly define the concepts of the terms in order to describe his/her invention in the best manner.
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 clearly differs, the use of an expression in the singular encompasses the plural. As used herein, it is understood that terms such as "comprises," "comprising," "includes," and "including" are intended to indicate the presence of features, numbers, steps, acts, components, elements, materials, or combinations thereof disclosed in the specification, but do not preclude the possibility that one or more other features, numbers, steps, acts, components, elements, materials, or combinations thereof may be present or added.
As used herein, the terms "flame retardant property", "flame retardant" or "ignition resistance" refer to properties of materials that are difficult to burn, between flammable and nonflammable 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 given substituents as will be described below. Examples of alkyl groups may include methyl, ethyl, 2-propyl, n-butyl, isobutyl, t-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 radical of 2 to 20, preferably 2 to 10, and more preferably 2 to 6 carbon atoms having one or more carbon-carbon double bonds. Alkenyl groups may be bonded through a carbon atom or saturated carbon atom having one or more carbon-carbon double bonds. Alkenyl may refer collectively to both unsubstituted groups and groups further substituted with one or more given substituents as will be described later. Examples of alkenyl groups 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. Alkynyl groups may be bonded through carbon atoms having one or more carbon-carbon triple bonds or saturated carbon atoms. Alkynyl may refer generically to a residue that is further substituted with one or more given substituents as will be described later. Examples of alkynyl groups 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 residues further substituted with one or more given substituents as will be described later. Examples of cycloalkyl groups may include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptenyl, cyclooctyl, decalinyl, 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 that is further substituted with one or more given substituents as will be described later. Examples of aryl groups 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 the hydrogen atom is substituted with any one selected from the group consisting of halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, amino groups, thio groups, methylthio groups, alkoxy groups, nitrile groups, aldehyde groups, epoxy groups, ether groups, ester groups, carbonyl groups, acetal groups, ketone groups, alkyl groups, perfluoroalkyl groups, cycloalkyl groups, heterocycloalkyl groups, allyl groups, benzyl groups, aryl groups, heteroaryl groups, derivatives thereof, and combinations thereof.
According to the new trend of miniaturization and high performance of electronic devices and communication apparatuses, the signal transmission speed of these products has been increased, and the frequency band of the used signals is moving from the MHz region to the GHz region. If the frequency of the signal becomes high, the number of lost signals may increase and noise may also increase, so that it is difficult to ensure the reliability of signal transmission, and the 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 a high dielectric constant and an increased dielectric loss factor, the epoxy resins are limited in application to smaller highly integrated printed circuit patterns. Accordingly, 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 an unsaturated group for the terminal thereof.
One aspect of the present disclosure provides a phosphorus-containing resin terminated at the end by an unsaturated group, comprising a compound represented by formula 1:
[ 1]
Wherein X is 1 And X 2 Identical or different and are each independently hydrogen, hydroxyl or a group represented by formula 2 or formula 3,
X 1 and X 2 At least one of which is represented by formula 2 or formula 3,
Y 1 and Y 2 Identical or different, and is represented by one of formulas 4 to 8,
R 1 ' C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl group, and
n1 is an integer from 1 to 15;
[ 2]
Wherein R is 2 ' is hydrogen, C 1 To C 8 Alkyl or
R 3 ' is hydrogen or C 1 To C 8 An alkyl group, a hydroxyl 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, R 3 Two or more of' same or different;
[ 3]
[ 4]
Wherein R is 1 To R 4 Identical or different and is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a1 and b1 are each independently integers from 0 to 4,
when a1 is 2 or more than 2, R 1 Two or more of them being the same or different, and
when b1 is 2 or more than 2, R 2 The two or more of which are the same or different;
[ 5]
Wherein R is 9 To R 14 Identical or different and is hydrogen or C 1 To C 3 An alkyl group;
[ 6]
Wherein R is 15 And R is 16 Identical or different and is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a2 and b2 are each independently integers from 0 to 4,
when a2 is 2 or more than 2, R 15 Two or more of them being the same or different, and
when b2 is 2 or greater than 2, R 16 The two or more of which are the same or different;
[ 7]
Wherein R is 21 And R is 22 Identical or different and is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a3 and b3 are each independently integers from 0 to 3,
when a3 is 2 or more than 2, R 21 Two or more of them being the same or different, and
when b3 is 2 or more than 2, R 22 The two or more of which are the same or different; and
[ 8]
Wherein R is 25 Is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or more than 2, R 25 The two or more of which are the same or different.
In formulas 2 to 8, asterisks indicate the positions to be bonded to adjacent atoms.
In the phosphorus-containing resin having the terminal end capped with an unsaturated group according to the present disclosure, inherent flame retardancy is exhibited by the phosphorus-containing resin, and the terminal unsaturated group having reactivity advantageously participates in curing of the resin by 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 as the terminal-blocked unsaturated group has a shorter chain than other unsaturated groups, and thus may be advantageous in terms of crosslinking.
In addition, although the phosphonate having the conventional structure serves as only an additive and thus undergoes degradation of heat resistance and dielectric properties after curing, the phosphonate having the structure of formula 1 according to the present disclosure is able to participate in crosslinking and thus does not degrade the heat resistance and dielectric properties even after curing.
In one exemplary embodiment, formula 4 may be represented by formula 4-1:
[ 4-1]
Wherein R is 3 To R 8 May be the same or different, and may be hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl groups.
In addition, formula 6 may be represented by formula 6-1:
[ 6-1]
Wherein R is 17 To R 20 May be the same or different, and may be hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl groups.
Formula 7 may be represented, for example, by formula 7-1:
[ 7-1]
Wherein R is 23 And R is 24 May be the same or different, and may be hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl groups.
In the formula, R 1 ' preferably C 1 To C 6 Alkyl, C 2 To C 5 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 6 Cycloalkyl or C 6 To C 12 Aryl, more preferably methyl, ethyl, methylene, ethylene, cyclohexyl, phenyl or naphthyl, and most preferably methyl or phenyl, because R in formula 1 1 ' being one of the functional groups listed above, compatibility with other resins and solvents used in forming the composition is good.
In one embodiment, in formula 1, Y 1 And Y 2 May be the same or different, and may be a compound represented by one of formulas 9 to 16, respectively:
[ 9]
[ 10]
[ 11]
[ 12]
[ 13]
[ 14]
[ 15]
[ 16]
In one exemplary embodiment, in formula 1, R 1 ' may be C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl, and n1 may be an integer from 1 to 8; in formula 2, R 2 ' may be hydrogen or C 1 To C 8 An alkyl group; in formula 4, R 1 To R 4 May be the same or different, and may be hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group; in formula 5, R 9 To R 14 May be the same or different and may be hydrogen or methyl; in formula 6, R 15 To R 16 May be the same or different, and may be hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group; in formula 7, R 21 To R 22 May be the same or different, and may be hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group; and in formula 8, R 25 Can be hydrogen or C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl groups.
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 the 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 compounds. However, the conventional phosphorus-based compound may not have reactivity or may have extremely low reactivity, the cure-crosslink density may be reduced, and 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 formula 1, X is 1 And X 2 The compounds represented by formula 2 or formula 3 are both preferable. In the compound represented by formula 2 or formula 3 at both terminals, low dielectric properties exhibited by unsaturated groups at the terminals can be improved, and reactivity can also be improved, so that a commercially suitable gel time of a resin composition to be prepared later can 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 additives may be required, and when the content of phosphorus is more than 15 mass%, reactivity may be reduced, and compatibility with solvents and other products and solubility 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 4000g/mol. When the weight average molecular weight is less than 1000g/mol, the effect of improving heat resistance and dielectric properties may be insufficient, and when the weight average molecular weight is more than 7000g/mol, the compatibility with a solvent may be lowered, thereby making the compound difficult to practically use.
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 one exemplary embodiment, the phosphorus-containing resin terminated at the end by an unsaturated group may be represented by formula 17-1, formula 17-2, or formula 17-3:
[ 17-1]
[ 17-2]
[ 17-3]
Wherein each R in formula 17-1, formula 17-2 or formula 17-3 is independently C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
each n2 is independently an integer from 1 to 8.
According to another exemplary embodiment, the phosphorus-containing resin terminated at the end by an unsaturated group may be represented by formula 18-1, formula 18-2, or formula 18-3:
[ 18-1]
[ 18-2]
[ 18-3]
Wherein each R in formula 18-1, formula 18-2 or formula 18-3 is independently C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
each n2 is independently an integer from 1 to 8.
According to yet another exemplary embodiment, the phosphorus-containing resin terminated at the end by an unsaturated group may be represented by formula 19-1, formula 19-2, or formula 19-3:
[ 19-1]
[ 19-2]
[ 19-3]
Wherein each R in formula 19-1, formula 19-2 or formula 19-3 is independently C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
each n4 is independently an integer from 1 to 8.
According to still another exemplary embodiment, the phosphorus-containing resin terminated at the end by an unsaturated group may be represented by formula 20-1, formula 20-2, or formula 20-3:
[ 20-1]
[ 20-2]
[ 20-3]
Wherein each R in formula 20-1, formula 20-2 or formula 20-3 is independently C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
each n5 is independently an integer from 1 to 8.
As described above, the compounds represented by formulas 17 to 20 may have high reactivity and improved heat resistance by the unsaturated groups present therein. Specifically, it was confirmed that the compounds represented by formulas 17 to 20 have excellent compatibility with other resins and solvents used in forming the composition.
The phosphorus-containing resin terminated at the end with unsaturated groups can have a dielectric constant (D) of less than 3.6 at 1GHz k ). In addition, the phosphorus-containing resin terminated at the end with an unsaturated group may have a dielectric dissipation factor (D) of less than 0.0050 at 1GHz f )。
As described above, according to the present disclosure, the phosphorous-containing resin end-capped with an unsaturated group may exhibit excellent low dielectric properties by introducing an acrylate group or a vinylbenzyl group into the end-exhibited structural characteristics. 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 end-capped with an unsaturated group contains a relatively high phosphorus content in the range of 7 to 15 mass%, and thus the resin composition prepared later can meet 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 terminated at a terminal by an unsaturated group, the method comprising: (S1) providing a hydroxy-terminated oligophosphonate; and (S2) preparing a phosphorus-containing resin terminated at the end by an unsaturated group by reacting a hydroxyl-terminated oligophosphonate with a reactant comprising an unsaturated group, wherein the unsaturated group is an acrylate unsaturated group or a vinylbenzyl unsaturated group. The method can be used in a purification process without a curing process, thereby effectively removing byproducts and salts, and can be easily applied to an industrial process.
The reaction of step S2 may be carried out in the presence of a catalyst, and the catalyst may be selected from 4-dimethylaminopyridine, pyridine, triethylamine, ammonia, naOH, KOH, liOH, K 2 CO 3 Tetramethyl ammonium hydroxide and AlCl 3 One of them, or a mixture of two or more thereof. Specifically, when an alkali metal oxide is used, an appropriate 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. In particular, 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 carry the alkali metal hydroxide from the polar solvent into the nonpolar solvent.
Specifically, when an aqueous sodium hydroxide solution as an alkali metal hydroxide is used as a catalyst for an organic solvent such as toluene, the catalyst has little help in promoting 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-butyl ammonium chloride (TBAC) or tetra-n-butyl ammonium bromide (TBAB).
The reactant comprising an unsaturated group may be one selected from the group consisting of: methacryloyl halide (methacryloyl 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. The methacryloyl halide may be selected from methacryloyl fluoride, methacryloyl chloride, methacryloyl bromide, methacryloyl iodide, and combinations thereof, and the 4-vinylbenzyl halide or 2-vinylbenzyl halide may be selected from vinylbenzyl fluoride, vinylbenzyl chloride, vinylbenzyl bromide, vinylbenzyl iodide, and combinations thereof.
The reactant comprising an unsaturated group is preferably a mixture of 4-vinylbenzyl chloride and 2-vinylbenzyl chloride that is more effective in promoting the reaction than the other reactants presented herein.
In step S2, the reactant including the 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 below 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 the excessive 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 lower than 50 ℃, the reaction rate is greatly reduced and a very long time is required for preparing the resin, and when the temperature is higher than 90 ℃, the reaction rate is greatly increased and an excessive reaction may be undesirably performed.
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, methylene chloride, chlorobenzene, cyclohexane, cyclohexanol, tetrahydrofuran (THF), acetone, methyl Ethyl Ketone (MEK), and methyl isobutyl ketone (MIBK), or a mixture of two or more. 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 unsaturated group-terminated phosphorus-containing resin of step S2, thereby purifying the unsaturated group-terminated phosphorus-containing resin of S2. The purification step may be performed mainly to remove the generated salt and by-products thereof, slightly different depending on the kind of the reactant, and for example, an aqueous NaOH solution may be used as the basic compound.
The hydroxyl-terminated oligophosphonate is represented by formula 21:
[ 21]
Wherein Y is 1 And Y 2 Identical or different and is a compound represented by one of the formulae 4 to 8,
R 4 ' C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl group, and
n6 is an integer from 1 to 15;
[ 4]
Wherein R is 1 To R 4 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a1 and b1 are each independently integers from 0 to 4,
when a1 is 2 or more than 2, R 1 Two or more of them being the same or different, and
when b1 is 2 or more than 2, R 2 The two or more of which are the same or different;
[ 5]
Wherein R is 9 To R 14 Identical or different and each is hydrogen or C 1 To C 3 An alkyl group;
[ 6]
Wherein R is 15 And R is 16 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a2 and b2 are each independently integers from 0 to 4,
when a2 is 2 or more than 2, R 15 Two or more of them being the same or different, and
when b2 is 2 or greater than 2, R 16 The two or more of which are the same or different;
[ 7]
Wherein R is 21 And R is 22 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a3 and b3 are each independently integers from 0 to 3,
when a3 is 2 or more than 2, R 21 Two or more of them being the same or different, and
when b3 is 2 or more than 2, R 22 The two or more of which are the same or different; and
[ 8]
Wherein R is 25 Is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or more than 2, R 25 The two or more of which are the same or different.
In formula 21, Y 1 And Y 2 And each is a compound represented by one of formulas 4 to 8.
[ 9]
[ 10]
[ 11]
[ 12]
[ 13]
[ 14]
[ 15]
[ 16]
Yet another aspect of the present disclosure provides a phosphorus-containing resin composition terminated at the end by an unsaturated group, comprising a compound represented by formula 1, a curing agent, and a curing accelerator.
In one exemplary embodiment, in formula 1, R 1 ' may be C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl, and n1 may be an integer from 1 to 8; in formula 2, R 2 ' may be hydrogen or C 1 To C 8 An alkyl group; in formula 4, R 1 To R 4 May be the same or different, and may each be hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group; in formula 5, R 9 To R 14 May be the same or different, and may each be hydrogen or methyl; in formula 6, R 15 To R 16 May be the same or different, and may each be hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group; in formula 7, R 21 To R 22 May be the same or different, and may each be hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group; and in formula 8, R 25 Can be hydrogen or C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl groups.
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, the excessive curing reaction may be undesirably performed.
As the curing agent, any curing agent commonly 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 performed 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 comprise a modified polyphenylene oxide (PPO) resin. Examples of the modified PPO resin may include SA-9000 (available from SABIC) which is modified from polyphenylene ether known to have excellent dielectric constant or other dielectric properties even in an ultra-high frequency region. When included in the phosphorus-containing resin, the modified PPO may assist the crosslinking reaction and may improve dielectric properties and heat resistance.
Yet another aspect of the present disclosure provides a copper-clad laminate manufactured using a phosphorus-containing resin terminated at the end with an unsaturated group.
Hereinafter, the present disclosure may be described in further detail by examples. These embodiments 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 embodiments.
Examples
Example 1: preparation of methacryloyl terminated phosphorus-containing resin (with 4,4' - (1-methylethylene) bis [ benzene ]
Phenol]Diphenyl p-methylphosphonate polymer)
500g (0.66 mol) of 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) was slowly added over 4 hours. After the addition was completed, the reaction was carried out at 75 ℃ for 20 hours, and then the resulting solution was cooled. After cooling, to remove unreacted substances, the purification reaction was carried out by adding 1938.98g of water and 107.42g of 50% NaOH and stirring the reaction solution at 75℃for 1 hour.
After stirring is completed, the resulting product remains undisturbed and liquid separation is performed. The water in the lower layer was removed, and 517g of water was then added thereto, followed by stirring. After stirring, phosphoric acid was added to set the pH level to 5 to 6. After the layer subjected to neutralization and washing was removed, the toluene solvent was degassed under reduced pressure in vacuo 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 having a terminal end capped with a methacryloyl group, the phosphorus content was 8.5 mass%, the molecular weight as measured by GPC was 2878g/mol, and the structure was identified by 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 vinylbenzyl-terminated phosphorus-containing resin (with 4,4' - (1-methylethylene) bis [ benzene ]
Phenol]Diphenyl p-methylphosphonate polymer)
500g (0.66 mol) 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, and 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 aqueous NaOH solution was slowly added over 1 hour. After the addition was completed, the reaction was carried out at 75 ℃ for 20 hours, and then the resulting solution was cooled. After cooling, to remove unreacted substances, the purification reaction was carried out by adding 1938.98g of water and 107.42g of 50% NaOH and stirring the reaction solution at 75℃for 1 hour.
After stirring is completed, the resulting product remains undisturbed and liquid separation is performed. The water in the lower layer was removed, and 517g of water was then added thereto, followed by stirring. After stirring, phosphoric acid was added to set the pH level to 5 to 6. After the layer subjected to neutralization and washing was removed, the toluene solvent was degassed under reduced vacuum for removal. The reaction solvent was removed by degassing the reaction solvent at 70℃under a vacuum of 200 to 300 Torr, and then 214g of toluene was added as a solvent.
In the resulting phosphorus-containing resin terminated at the end by a vinylbenzyl group, the phosphorus content was 8.0 mass%, and the molecular weight as measured by GPC was 3100g/mol. 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 (0.66 mol) of poly (m-phenylene methylphosphonate) and 1300.5g of toluene were added to a 3L three-necked flask purged with nitrogen, then 10g of 4-Dimethylaminopyridine (DMAP) was added thereto, followed by raising the temperature to 75 ℃.
Subsequently, 113.48g of methacrylic anhydride (MAAH) was slowly added over a period of 2 hours. After the addition was completed, the reaction was carried out at 75 ℃ for 20 hours, and then the resulting solution was cooled. After cooling, to remove unreacted substances, the purification reaction was carried out by adding 1938.98g of water and 107.42g of 50% NaOH and stirring the reaction solution at 75℃for 1 hour.
After stirring is completed, the resulting product remains undisturbed and liquid separation is performed. The water in the lower layer was removed, and 517g of water was then added thereto, followed by stirring. After stirring, phosphoric acid was added to set the pH level to 5 to 6. After the layer subjected to neutralization and washing was removed, the toluene solvent was degassed under reduced vacuum for removal. 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 having a terminal end capped with a methacryloyl group, the phosphorus content was 10.5 mass%, the molecular weight was 2127g/mol as measured by GPC, and the structure of the resulting resin was identified by NMR and FT-IR.
Example 4: preparation of a phosphorus-containing resin terminated with vinylbenzyl (Poly (m-phenylene methylphosphonate))
500g (0.66 mol) of poly (m-phenylene methylphosphonate) and 1300.5g of toluene were added to a 3L three-necked flask purged with nitrogen, 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 was slowly added over 1 hour. After the addition was completed, the reaction was carried out at 75 ℃ for 20 hours, and then the resulting solution was cooled. After cooling, to remove unreacted substances, the purification reaction was carried out by adding 1938.98g of water and 107.42g of 50% NaOH and stirring the reaction solution at 75℃for 1 hour.
After stirring is completed, the resulting product remains undisturbed and liquid separation is performed. The water in the lower layer was removed, and 517g of water was then added thereto, followed by stirring. After stirring, phosphoric acid was added to set the pH level to 5 to 6. After the layer subjected to neutralization and washing was removed, the toluene solvent was degassed under reduced vacuum for removal. The reaction solvent was removed by degassing the reaction solvent at 70℃under a vacuum of 200 to 300 Torr, and then 214g of toluene was added as a solvent.
In the resulting phosphorus-containing resin terminated at the end by a vinylbenzyl group, the phosphorus content was 9.5 mass%, and the molecular weight as measured by GPC was 2442g/mol. The structure of the resulting resin was identified by Nuclear Magnetic Resonance (NMR) analysis and FT-IR.
Comparative example 1: using commercially available phosphorus-containing resins
SPV-100 (manufactured by Otsuka Chemical) was used as a commercially available phosphorus-containing resin.
Preparation of phosphorus-containing resin composition terminated at the terminal by unsaturated group
Phosphorus-containing resin compositions (varnishes) end-capped with unsaturated groups according to examples 1 to 4 were prepared respectively by mixing the various components at the mixing ratios listed in table 1 below while adjusting the content of phosphorus in the compositions to 2.5 mass%.
The preparation of the varnish is as specified below.
A polyfunctional triallyl isocyanurate (TAIC) group was used as a curing agent, SA-9000 (commercially available from SABIC) known to have excellent dielectric constant or other dielectric properties was used as a polyphenylene ether resin known to have 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 relative to the amount of SA-9000. In order 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 compositions
The commercially available phosphorus-containing resin compositions were 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 compositions each having an unsaturated group-terminated end prepared in examples 1 to 4. Table 1 shows the mixing ratio of the resin compositions of examples 1 to 4 and comparative example 1.
[ Table 1 ]
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 as to have a concentration of 4000ppm, and the resulting solution was injected into GPC in an amount of 100. Mu.l. Tetrahydrofuran was used as the mobile phase of GPC and 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 when measured at 35 ℃.
(2) Measurement of phosphorus content
The content of phosphorus contained in the resin was determined by acid digestion and by ICP-OES, and the detection of phosphorus content was performed by Intertec Testing Services Korea ltd. 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 prepregs
The glass cloth was impregnated in a varnish, and then naturally dried at room temperature for 1 hour, followed by drying in an oven at 155 deg.c, thereby manufacturing a prepreg.
(5) Manufacturing copper clad laminate
Six prepared prepregs were stacked and the front of the resulting stack was covered with 1 ounce of copperSide and back side, followed by 40kgf/cm at 195 °c 2 Is pressed for 120 minutes under the pressure of (c), thereby manufacturing a copper clad laminate.
(6) Measuring 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 dielectric dissipation factor (Df) were measured using an impedance/material analyzer (agilent e4991a RF) at 1 GHz. The measurement conditions are specified as follows.
Measuring frequency: 1GHz (1 GHz)
Measuring temperature: 25 ℃ to 27 DEG C
Measuring humidity: 45 to 55%
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 being heated 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 ]
As shown in table 2, the gel times of the resins prepared in examples 1 to 4 were shorter than those of the resins prepared in comparative example 1, and it was presumed that the former resins participated in curing more by the crosslinking reaction than the resins prepared in comparative example 1. The resins prepared in examples 1 to 4 were confirmed to exhibit excellent physical properties including glass transition temperature and dielectric properties.
It should be understood that the embodiments described herein should be considered in descriptive sense only and not for purposes of limitation. The description of features or aspects within each embodiment should generally be considered to be other similar features or aspects that may be used in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present disclosure as defined by the following claims.
Industrial applicability
Therefore, according to the present disclosure, in a phosphorus-containing resin end-capped with an unsaturated group, the dielectric constant and dielectric dissipation factor can be reduced by the unsaturated group contained at the end, and excellent flame retardancy can be exhibited by containing a high content of phosphorus.
Claims (26)
1. A phosphorus-containing resin terminated at the end by an unsaturated group, comprising a compound represented by formula 1:
[ 1]
Wherein X is 1 And X 2 Identical or different and are each independently hydrogen, hydroxyl or a group represented by formula 2 or formula 3,
X 1 and X 2 At least one of which is represented by formula 2 or formula 3,
Y 1 and Y 2 Identical or different, and each represented by one of formulas 4 to 8,
R 1 ' C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl group, and
n1 is an integer from 1 to 15;
[ 2]
Wherein R is 2 ' is hydrogen, C 1 To C 8 Alkyl or
R 3 ' is hydrogen or C 1 To C 8 An alkyl group, a hydroxyl 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, R 3 Two or more of' same or different;
[ 3]
[ 4]
Wherein R is 1 To R 4 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a1 and b1 are each independently integers from 0 to 4,
when a1 is 2 or more than 2, R 1 Two or more of them being the same or different, and
when b1 is 2 or more than 2, R 2 The two or more of which are the same or different;
[ 5]
Wherein R is 9 To R 14 Identical or different and each is hydrogen or C 1 To C 3 Alkyl group；
[ 6]
Wherein R is 15 And R is 16 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a2 and b2 are each independently integers from 0 to 4,
when a2 is 2 or more than 2, R 15 Two or more of them being the same or different, and
When b2 is 2 or greater than 2, R 16 The two or more of which are the same or different;
[ 7]
Wherein R is 21 And R is 22 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a3 and b3 are each independently integers from 0 to 3,
when a3 is 2 or more than 2, R 21 Two or more of them being the same or different, and
when b3 is 2 or more than 2, R 22 The two or more of which are the same or different; and
[ 8]
Wherein R is 25 Is hydrogen、C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or more than 2, R 25 Is the same or different,
wherein the phosphorus is contained in the compound represented by formula 1 in an amount of 7 to 15% by weight based on the total weight of the compound.
2. The phosphorus-containing resin as claimed in claim 1, wherein in formula 1, Y 1 And Y 2 Identical or different, and each represented by one of formulas 9 to 16:
[ 9]
[ 10]
[ 11]
[ 12]
[ 13]
[ 14]
[ 15]
[ 16]
3. The phosphorus-containing resin as claimed in claim 1, wherein in formula 1, R 1 ' C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
n1 is an integer of 1 to 8,
in formula 2, R 2 ' is hydrogen or C 1 To C 8 An alkyl group, a hydroxyl group,
in formula 4, R 1 To R 4 Identical or different and are each hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group,
in formula 5, R 9 To R 14 Identical or different and are each hydrogen or methyl,
in formula 6, R 15 And R is 16 Identical or different and are each hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group,
in 7，R 21 And R is 22 Identical or different and are each hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group
In formula 8, R 25 Is hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl groups.
4. The phosphorus-containing resin as claimed in claim 1, wherein the weight average molecular weight of the compound represented by formula 1 is 1000g/mol to 7000g/mol.
5. The phosphorus-containing resin of claim 1, wherein the glass transition temperature of the compound represented by formula 1 is 170 ℃ to 210 ℃.
6. The phosphorus-containing resin of claim 1, wherein formula 1 is represented by formula 17-1, formula 17-2, or formula 17-3:
[ 17-1]
[ 17-2]
[ 17-3]
Wherein each R in formula 17-1, formula 17-2 or formula 17-3 is independently C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
each n2 is independently an integer from 1 to 8.
7. The phosphorus-containing resin of claim 1, wherein formula 1 is represented by formula 18-1, formula 18-2, or formula 18-3:
[ 18-1]
[ 18-2]
[ 18-3]
Wherein each R in formula 18-1, formula 18-2 or formula 18-3 is independently C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
each n3 is independently an integer from 1 to 8.
8. The phosphorus-containing resin of claim 1, wherein formula 1 is represented by formula 19-1, formula 19-2, or formula 19-3:
[ 19-1]
[ 19-2]
[ 19-3]
Wherein each R in formula 19-1, formula 19-2 or formula 19-3 is independently C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
each n4 is independently an integer from 1 to 8.
9. The phosphorus-containing resin of claim 1, wherein formula 1 is represented by formula 20-1, formula 20-2, or formula 20-3:
[ 20-1]
[ 20-2]
[ 20-3]
Wherein each R in formula 20-1, formula 20-2 or formula 20-3 is independently C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
each n5 is independently an integer from 1 to 8.
10. The phosphorous-containing resin as recited in claim 1, having a dielectric constant D of less than 3.6 at 1GHz k 。
11. The phosphorous-containing resin as claimed in claim 1, having a dielectric dissipation factor D at 1GHz of less than 0.0050 f 。
12. A method for producing a phosphorus-containing resin terminated at the end by an unsaturated group, the phosphorus-containing resin comprising a compound represented by formula 1, the method comprising:
s1: providing a hydroxyl terminated oligophosphonate; and
s2: preparing a phosphorus-containing resin terminated at the end by unsaturated groups by reacting the hydroxyl-terminated oligophosphonate with a reactant comprising unsaturated groups,
wherein the unsaturated group is an acrylate unsaturated group or a vinylbenzyl unsaturated group,
[ 1]
Wherein X is 1 And X 2 Identical or different and are each independently hydrogen, hydroxyl or a group represented by formula 2 or formula 3,
X 1 and X 2 At least one of which is represented by formula 2 or formula 3,
Y 1 and Y 2 Identical or different, and each represented by one of formulas 4 to 8,
R 1 ' C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl group, and
n1 is an integer from 1 to 15;
[ 2]
Wherein R is 2 ' is hydrogen, C 1 To C 8 Alkyl or
R 3 ' is hydrogen or C 1 To C 8 An alkyl group, a hydroxyl 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, R 3 Two or more of' same or different;
[ 3]
[ 4]
Wherein R is 1 To R 4 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a1 and b1 are each independently integers from 0 to 4,
when a1 is 2 or more than 2, R 1 Two or more of them being the same or different, and
when b1 is 2 or more than 2, R 2 The two or more of which are the same or different;
[ 5]
Wherein R is 9 To R 14 Identical or different and each is hydrogen or C 1 To C 3 An alkyl group;
[ 6]
Wherein R is 15 And R is 16 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a2 and b2 are each independently integers from 0 to 4,
when a2 is 2 or more than 2, R 15 Two or more of them being the same or different, and
when b2 is 2 or greater than 2, R 16 The two or more of which are the same or different;
[ 7]
Wherein R is 21 And R is 22 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a3 and b3 are each independently integers from 0 to 3,
when a3 is 2 or more than 2, R 21 Two or more of them being the same or different, and
when b3 is 2 or more than 2, R 22 The two or more of which are the same or different; and
[ 8]
Wherein R is 25 Is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or more than 2, R 25 Is the same or different,
wherein the phosphorus is contained in the compound represented by formula 1 in an amount of 7 to 15% by weight based on the total weight of the compound.
13. The production method according to claim 12, 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 and NaOH, KOH, liOH, K 2 CO 3 Tetramethyl ammonium hydroxide and AlCl 3 Or a mixture of two or more thereof.
14. The production method according to claim 12, wherein the unsaturated group-containing reactant is one selected from the group consisting of methacrylic acid halide, methacrylic acid anhydride, acrylic acid 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.
15. The production process according to claim 12, wherein the unsaturated group-containing reactant is added in an amount of 0.5 to 5 equivalents based on 1 hydroxyl equivalent of the oligophosphonate in S2.
16. The preparation method of claim 12, wherein the reaction of S2 is performed at a temperature in the range of 50 ℃ to 90 ℃.
17. The production method according to claim 12, 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.
18. The preparation method of claim 12, 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.
19. The method of manufacture of claim 12, wherein the hydroxy-terminated oligophosphonate is represented by formula 21:
[ 21]
Wherein Y is 1 And Y 2 Identical or different and are each a group represented by one of formulae 4 to 8,
R 4 ' C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl group, and
n6 is an integer from 1 to 15;
[ 4]
Wherein the method comprises the steps of，R 1 To R 4 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a1 and b1 are each independently integers from 0 to 4,
when a1 is 2 or more than 2, R 1 Two or more of them being the same or different, and
when b1 is 2 or more than 2, R 2 The two or more of which are the same or different;
[ 5]
Wherein R is 9 To R 14 Identical or different and each is hydrogen or C 1 To C 3 An alkyl group;
[ 6]
Wherein R is 15 And R is 16 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a2 and b2 are each independently integers from 0 to 4,
when a2 is 2 or more than 2, R 15 Two or more of them being the same or different, and
when b2 is 2 or greater than 2, R 16 The two or more of which are the same or different;
[ 7]
Wherein R is 21 And R is 22 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a3 and b3 are each independently integers from 0 to 3,
when a3 is 2 or more than 2, R 21 Two or more of them being the same or different, and
when b3 is 2 or more than 2, R 22 The two or more of which are the same or different; and
[ 8]
Wherein R is 25 Is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or more than 2, R 25 The two or more of which are the same or different.
20. The production process according to claim 19, wherein in the formula 21, Y 1 And Y 2 Identical or different, and are each a group represented by one of formulae 9 to 16,
[ 9]
[ 10]
[ 11]
[ 12]
[ 13]
[ 14]
[ 15]
[ 16]
21. A phosphorus-containing resin composition terminated at the end by an unsaturated group, comprising a compound represented by formula 1, a curing agent, and a curing accelerator:
[ 1]
Wherein X is 1 And X 2 Identical or different and are each independently hydrogen, hydroxyl or a group represented by formula 2 or formula 3,
X 1 and X 2 At least one of which is represented by formula 2 or formula 3,
Y 1 and Y 2 Identical or different, and each represented by one of formulas 4 to 8,
R 1 ' C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 Aryl group, and
n1 is an integer from 1 to 15;
[ 2]
Wherein R is 2 ' is hydrogen, C 1 To C 8 Alkyl or
R 3 ' is hydrogen or C 1 To C 8 An alkyl group, a hydroxyl 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, R 3 Two or more of' same or different;
[ 3]
[ 4]
Wherein R is 1 To R 4 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a1 and b1 are each independently integers from 0 to 4,
when a1 is 2 or more than 2, R 1 Two or more of them being the same or different, and
when b1 is 2 or more than 2, R 2 The two or more of which are the same or different;
[ 5]
Wherein R is 9 To R 14 Identical or different and each is hydrogen or C 1 To C 3 An alkyl group;
[ 6]
Wherein R is 15 And R is 16 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a2 and b2 are each independently integers from 0 to 4,
when a2 is 2 or more than 2, R 15 Two or more of them being the same or different, and
when b2 is 2 or greater than 2, R 16 The two or more of which are the same or different;
[ 7]
Wherein R is 21 And R is 22 Identical or different and are each hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a3 and b3 are each independently integers from 0 to 3,
when a3 is 2 or more than 2, R 21 Two or more of them being the same or different, and
when b3 is 2 or more than 2, R 22 The two or more of which are the same or different; and
[ 8]
Wherein R is 25 Is hydrogen, C 1 To C 20 Alkyl, C 2 To C 20 Alkenyl, C 2 To C 20 Alkynyl, C 3 To C 20 Cycloalkyl or C 6 To C 20 An aryl group,
a4 is an integer of 0 to 4, and
when a4 is 2 or more than 2, R 25 Is the same or different,
wherein the phosphorus is contained in the compound represented by formula 1 in an amount of 7 to 15% by weight based on the total weight of the compound.
22. The phosphorus-containing resin composition as claimed in claim 21, wherein in formula 1, Y 1 And Y 2 Identical or different, and are each a group represented by one of formulae 9 to 16:
[ 9]
[ 10]
[ 11]
[ 12]
[ 13]
[ 14]
[ 15]
[ 16]
23. The phosphorus-containing resin composition as claimed in claim 21, wherein in formula 1, R 1 ' C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl group, and
n1 is an integer from 1 to 8;
in formula 2, R 2 ' is hydrogen or C 1 To C 8 An alkyl group;
in formula 4, R 1 To R 4 Identical or different and are each hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group;
in formula 5, R 9 To R 14 Identical or different and are each hydrogen or methyl;
in formula 6, R 15 And R is 16 Identical or different and are each hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group;
in formula 7, R 21 And R is 22 Identical or different and are each hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 An aryl group; and is also provided with
In formula 8, R 25 Is hydrogen, C 1 To C 8 Alkyl, C 2 To C 6 Alkenyl, C 2 To C 6 Alkynyl, C 3 To C 12 Cycloalkyl or C 6 To C 20 Aryl groups.
24. The phosphorus-containing resin composition of claim 21, 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.
25. The phosphorus-containing resin composition of claim 21, further comprising a modified polyphenylene oxide PPO resin.
26. A copper clad laminate manufactured using the phosphorus-containing resin composition terminated with an unsaturated group according to any one of claims 21 to 25.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020190115560A KR102346010B1 (en) | 2019-09-19 | 2019-09-19 | A phosphorous-containing resin whose terminal is capped with and unsaturated group, a method for preparing the same, and a resin composition comprising a phosphorus-containing resin whose terminal is capped with an unsaturated group |
| KR10-2019-0115560 | 2019-09-19 | ||
| PCT/KR2020/012636 WO2021054771A1 (en) | 2019-09-19 | 2020-09-18 | Phosphorous-containing resin endcapped with unsaturated group, preparation method therefor, and resin composition comprising phosphorous-containing resin endcapped with unsaturated group |
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| CN114051502A CN114051502A (en) | 2022-02-15 |
| CN114051502B true CN114051502B (en) | 2023-06-09 |
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| JP (1) | JP7254972B2 (en) |
| KR (1) | KR102346010B1 (en) |
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| JPS63227632A (en) * | 1987-03-17 | 1988-09-21 | Daihachi Kagaku Kogyosho:Kk | Production of flame retardant |
| JP2000336126A (en) | 1999-05-27 | 2000-12-05 | Nippon Shokubai Co Ltd | Vinyl ester and flame retardant resin composition |
| JP4353589B2 (en) * | 1999-07-09 | 2009-10-28 | 株式会社Ａｄｅｋａ | Flame retardant epoxy resin composition |
| US7427652B2 (en) | 2002-11-08 | 2008-09-23 | Supresta Llc | Composition of epoxy resin, OH-terminated phosphonate oligomer and inorganic filler |
| JP2011084697A (en) * | 2009-10-19 | 2011-04-28 | Showa Denko Kk | Polymerizable phosphorus-containing (poly)xylylene aryl ether compound, method for producing the same, flame-retardant thermocurable resin composition, cured product and laminated board |
| EP2816048B1 (en) | 2010-12-22 | 2017-03-15 | Frx Polymers, Inc. | Oligomeric phosphonates and compositions including the same |
| US9290639B2 (en) * | 2011-10-31 | 2016-03-22 | Lubrizol Advanced Materials, Inc. | Non-halogen flame retardant polymers |
| KR101469270B1 (en) | 2011-12-30 | 2014-12-08 | 제일모직주식회사 | Polyphosphonate copolymer, method for preparing thereof and flame retardant thermoplastic resin composition comprising the same |
| KR101596992B1 (en) | 2012-06-26 | 2016-02-23 | 코오롱인더스트리 주식회사 | Non Halogen Flame Retardant Polymer and Composition Containing the Same |
| JP6098876B2 (en) | 2013-04-09 | 2017-03-22 | 川崎化成工業株式会社 | 4-[(Disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound, process for producing the same, radical polymerizable composition containing them, and polymer thereof |
| WO2014199655A1 (en) | 2013-06-10 | 2014-12-18 | Dic株式会社 | Active ester resin containing phosphorus atom, epoxy resin composition and cured product thereof, prepreg, circuit board, and build-up film |
| CN105623238B (en) * | 2014-11-06 | 2018-07-27 | 江苏雅克科技股份有限公司 | Phosphorous functionalized poly (arylene ether) and prepare composition using it as raw material |
| CN107250205A (en) * | 2015-02-20 | 2017-10-13 | Frx 聚合物股份有限公司 | Anti-flammability thermoset composition |
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