A phosphorus-containing aromatic polyester and a thermosetting resin composition thereof

Abstract

The application provides a phosphorus-containing aromatic polyester and a thermosetting resin composition thereof, and a structural formula of the phosphorus-containing aromatic polyester is shown as formula I. The phosphorus-containing aromatic polyester has good solubility, low dielectric, high flame retardancy, low shrinkage during curing, low elastic modulus at high temperature and other performances.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of synthetic resins for electronic material technology, and particularly relates to a phosphorus-containing aromatic polyester and a thermosetting resin composition thereof, a preparation method and application thereof. BACKGROUND

[0002] The thermosetting resin composition prepared from the epoxy resin and the curing agent has excellent heat resistance, insulation and other properties, and is widely used in the field of insulating materials such as printed circuit board, semiconductor sealant, laminated film, etc. With the development of electronic information products towards high frequency, high speed, light, small, thin and portable, higher requirements will be put forward for the substrate material of the printed circuit board carrying electronic components, such as lower dielectric constant and dielectric loss, lower thermal expansion coefficient, higher heat resistance, humidity resistance, lower water absorption, and halogen-free flame retardant, etc. Compared with the traditional epoxy curing agents such as amines, acid anhydrides and phenolic aldehydes which introduce polar hydroxyl groups in the epoxy curing process, the reaction of aromatic polyester with epoxy resin will not produce polar hydroxyl groups, which can meet the requirements of low dielectric and low water absorption of printed circuit board. However, most aromatic polyesters do not contain flame-retardant elements, and their flame-retardant performance is insufficient, such as m-triphenyl phenol formate, m-triphenyl phenol acetate, phenolic polyester, etc., which limits their application in the field of high-heat-resistant, halogen-free flame-retardant copper-clad plates.

[0003] Under high power density, the risk of local overheating of the circuit increases, and if the material has insufficient flame retardancy, it may cause combustion or even fire. The improvement of flame retardant performance can effectively reduce the safety hazards of equipment under extreme working conditions. However, the by-products of the current phosphorus-containing aromatic polyester are often more and have a high content, and the presence of carboxyl and hydroxyl groups will introduce polar hydroxyl groups in the epoxy resin curing process, making the dielectric constant and dielectric loss of the cured product generally higher. Moreover, the phosphorus-containing aromatic polyester contains acetyl groups, and the alkyl groups capped in the epoxy curing process will be transferred to the side chain of the cured structure and play a plasticizing role, which reduces the heat resistance of the copper-clad plate. Most importantly, the solubility of the above-mentioned phosphorus-containing aromatic polyester is poor, and it is difficult to dissolve in common organic solvents such as methyl ethyl ketone (MEK), toluene and tetrahydrofuran at room temperature, which is not conducive to its application in the epoxy curing process. SUMMARY

[0004] The applicant found that the solubility of the existing phosphorus-containing aromatic polyester is poor, and it is difficult to dissolve in common organic solvents such as methyl ethyl ketone (MEK), toluene and tetrahydrofuran at room temperature, which is not conducive to its application in the epoxy curing process. Therefore, the development of a new type of phosphorus-containing aromatic polyester with no acetyl end-capping and good solubility has high research significance and practical value for improving the dielectric properties, humidity resistance, heat resistance, mechanical properties, flame retardancy and processability of the epoxy curing system.

[0005] To solve the above problems, the present application provides the following:

[0006] A phosphorus-containing aromatic polyester having a structure represented by Formula I,

[0007]

[0008] Formula I

[0009] R2and R4are each independently a divalent aromatic group of 6 to 12 carbon atoms;

[0010] R3is a divalent cycloalkyl group of 6 to 18 carbon atoms, optionally further substituted by one or more divalent aromatic groups of 6 to 12 carbon atoms;

[0011] R1and R5are each independently or

[0012] n is a positive integer greater than or equal to 1;

[0013] R6and R7are each independently hydrogen, hydroxyl, or an alkyl group of 1 to 6 carbon atoms.

[0014] In some embodiments of the present application, R2and R4are each independently a divalent aromatic group of 6 to 8 carbon atoms.

[0015] In some embodiments of the present application, wherein R3is selected from one of the following:

[0016] wherein h is 1 or 2;

[0017] R8is a hydrogen atom,

[0018] R9is an alkylene group of 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group;

[0019] R 10 is a hydrogen atom, a methyl group, or an ethyl group;

[0020] R 11 is a hydrogen atom or an alkyl group;

[0021] Z is a covalent bond, -SO2-, -C(CH3)2-, -CH(CH3)-, or -CH2-;

[0022] a is a positive integer between 0 and 2; b is a positive integer between 0 and 2, and a and b cannot both be 0; preferably

[0023] .

[0024] In some embodiments of the present application, n is 1 to 10.

[0025] In some embodiments of the present application, wherein Formula I is selected from the following structures:

[0026] Formula I-1

[0027]

[0028] Formula I-2

[0029]

[0030] Formula I-3

[0031]

[0032] Formula I-4.

[0033] The present application provides a method for preparing the above phosphorus-containing aromatic polyester, which comprises the following steps:

[0034] The phthaloyl chloride is dissolved in an organic solvent, then a phosphorus-containing monophenol compound and a bisphenol monomer are added, heated to react, and separated to obtain the phosphorus-containing aromatic polyester.

[0035] In some aspects of the present application, wherein,

[0036] The phthaloyl chloride is selected from any one of the following:

[0037] Preferably, it is any one of the following:

[0038] Or,

[0039] The phosphorus-containing monophenol compound is selected from any one of the following:

[0040] ;

[0041] Preferably, it is any one of the following: Or ;

[0042] Or,

[0043] The bisphenol monomer is selected from any one of the following: Preferably, it is any one of the following: .

[0044] The present application provides an epoxy resin composition comprising the phosphorus-containing aromatic polyester described above or the phosphorus-containing aromatic polyester prepared by the method described above, a thermosetting resin, and a curing agent.

[0045] In some embodiments of the present application, the thermosetting resin is an epoxy resin.

[0046] In some embodiments of the present application, the thermosetting resin is one or two or more of a halogen-free epoxy, a phosphorus-free epoxy, and a phosphorus-containing epoxy.

[0047] In some embodiments of the present application, the phosphorus-containing aromatic polyester is 10 to 150 parts by weight with respect to 100 parts by weight of the epoxy resin.

[0048] In some embodiments of the present application, it is used in any one of a coating formulation, an encapsulant, a composite material, an adhesive, a molded article, a bonding sheet, or a laminate.

[0049] The present application provides an article comprising the composition described above.

[0050] In some embodiments of the present application, the article is used in lead-free soldering or electronic devices.

[0051] In some embodiments of the present application, the article is a copper foil.

[0052] In some embodiments of the present application, the article is a printed circuit board.

[0053] The present application provides a prepreg comprising the composition described above.

[0054] The present application provides a laminate or a bonding sheet comprising the composition described above.

[0055] The present application provides a printed wiring board comprising the prepreg described above.

[0056] The present application provides a printed wiring board comprising the laminate described above.

[0057] The present application provides a process of manufacturing the laminate described above, which comprises impregnating the composition into a filler material to form a prepreg, then treating the prepreg at an elevated temperature to promote partial curing to a B-stage, and then laminating two or more of the prepregs at an elevated pressure and temperature to form a laminate.

[0058] The present application provides a printed circuit board, which is manufactured by the process described above.

[0059] The present application has the following advantages compared to the prior art:

[0060] The present application aims to overcome the above-mentioned deficiencies in the prior art and provides a phosphorus-containing aromatic polyester and a thermosetting resin composition thereof, which have good solubility, low dielectric, high flame retardancy, low shrinkage during curing, low elastic modulus at high temperature, and other properties.

[0061] The present application designs and synthesizes a new type of phosphorus-containing monophenol compound to replace the end-capping compound, naphthol, in the phosphorus-containing aromatic polyester described in CN109476822A of DIC Corporation. Therefore, the compound described in the present application has the following characteristics: it can simultaneously (combinatorially) act as a flame retardant and an active ester curing agent for thermosetting resins such as epoxy resins, and endows the cured system with higher heat resistance and thermal stability, high mechanical strength, low water absorption, good processability, low dielectric loss tangent, and simultaneously sufficiently low dielectric constant. In addition, the phosphorus-containing aromatic polyester of the present application is soluble in common industrial organic solvents such as MEK and tetrahydrofuran at room temperature.

[0062] The solvent (A) described in the present application can be an organic solvent commonly used in the manufacture of thermosetting formulations or epoxy laminates, such as in printed wiring boards, and can be selected from methyl ethyl ketone, acetone, 1-methoxy-2-propanol, tetrahydrofuran, toluene, xylene, propylene glycol methyl ether and its acetate, and combinations thereof.

[0063] The use of the phosphorus-containing aromatic polyester (Formula (I)) of the present application as a curing agent can reduce the formation of polar hydroxyl groups during the epoxy curing reaction. In addition, based on the fact that the phosphorus-containing aromatic polyester acts as a reactive ester group per molecule, the use of the multifunctional curing agent of the present application significantly increases the crosslinking density of the epoxy resin cured product. Therefore, the glass transition temperature and mechanical strength of the epoxy cured product are higher and the material can be better used as an electrical insulating material. In addition, the phosphorus-containing aromatic polyester of the present application can be easily used on reinforcing agents such as glass fibers using varnish solutions.

[0064] The present application further provides an epoxy resin composition comprising the phosphorus-containing flame-retardant multifunctional phosphorus-containing aromatic polyester (Formula (I)), which exhibits excellent flame-retardant, heat-resistant, mechanical, and dielectric properties. BRIEF DESCRIPTION OF DRAWINGS

[0065] Figure 1 NMR spectra of the phosphorus-containing aromatic polyester of Example 1 are shown;

[0066] Figure 2 FTIR spectra of the phosphorus-containing aromatic polyester of Example 1 are shown;

[0067] Figure 3 A and B in the figure show the GPC spectra of the phosphorus-containing aromatic polyester of Example 1, respectively. DETAILED DESCRIPTION

[0068] The application will be further described below with reference to the examples. It should be understood that the examples are only used to further illustrate and explain the application, and are not used to limit the application.

[0069] Unless otherwise defined, all technical and scientific terms used in the present disclosure have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, methods and materials are described below. In case of conflict, the present specification, including that set forth in the preceding section, controls. In the following detailed description of the application, numerous specific details are set forth in order to provide a thorough understanding of the application. However, the application can be practiced without some or all of these specific details. In other instances, well known methods have not been described in detail, in order not to unnecessarily obscure the application.

[0070] Although the present application has been disclosed in the context of certain implementations, it will be understood by those skilled in the art that the application extends beyond the specifically disclosed implementations, and it will therefore be appreciated that changes might be made in the form, details, and / or combinations of the technology disclosed herein without departing from the spirit or essential characteristics of the application. The scope of the application should, therefore, be determined only by the broadest interpretation of the appended claims to be supported by this disclosure.

[0071] "Alkyl" when used as a group or part of a group refers to a straight or branched chain saturated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. 20 straight or branched chain aliphatic hydrocarbon group. Preferably, the alkyl group has 1 to 6 carbon atoms. 10 alkyl, more preferably C1-C6 alkyl. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, s-butyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-ethyl-2-methylpropyl, 1,1,2-trimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl, and the like. The alkyl group can be substituted or unsubstituted.

[0072] "Alkenyl" refers to an alkyl group as defined above containing at least two carbon atoms and at least one carbon-carbon double bond. Representative examples include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl, 1-, 2-, or 3-butenyl, and the like. The alkenyl group can be optionally substituted or unsubstituted.

[0073] "Alkynyl" refers to an aliphatic hydrocarbon group containing one carbon-carbon triple bond and which can be straight or branched. Preferably, the alkynyl group has 2 to 6 carbon atoms. 10"Alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond. The alkynyl group can be substituted or unsubstituted. Alkynyl groups have from one to twelve carbon atoms in straight chain or branched chain configuration. More preferably, the alkynyl group has from one to six carbon atoms in straight chain or branched chain configuration. Most preferably, the alkynyl group has from one to four carbon atoms in straight chain or branched chain configuration. Examples of alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-, 2-, or 3-butynyl, and the like. The alkynyl group can be substituted or unsubstituted.

[0074] "Cycloalkyl" refers to saturated or partially saturated carbocyclic rings which are monocyclic, fused, bridged, and spiro. Preferably, cycloalkyl is C3-C8cycloalkyl, most preferably C3-C6cycloalkyl. Examples of monocyclic cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptatrienyl, cyclooctyl, and the like, preferably cyclopropyl, cyclohexenyl. The cycloalkyl group can be optionally substituted or unsubstituted. 12 Cycloalkyl, more preferably C3-C8cycloalkyl, most preferably C3-C6cycloalkyl. Examples of monocyclic cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptatrienyl, cyclooctyl, and the like, preferably cyclopropyl, cyclohexenyl. The cycloalkyl group can be optionally substituted or unsubstituted.

[0075] "Heterocyclyl," "heterocycloalkyl," "heterocycle," or "heterocyclic" are used interchangeably herein and refer to non-aromatic heterocyclic groups in which one or more of the atoms in the ring is a heteroatom, such as boron, oxygen, nitrogen, sulfur, and the like, including mono-, bi-, poly-, fused, bridged, and spiro rings. Preferably, the heterocyclyl group is a 5- to 7-membered monocyclic ring or a 7- to 10-membered bicyclic or tricyclic ring which can contain 1, 2, or 3 atoms selected from nitrogen, oxygen, and / or sulfur. Examples of "heterocyclyl" groups include, but are not limited to, morpholinyl, oxetanyl, thiomorpholinyl, tetrahydrofuranyl, tetrahydropyranyl, 1,1-dioxo-thiomorpholinyl, piperidinyl, 2-oxo-piperidinyl, pyrrolidinyl, 2-oxo-pyrrolidinyl, piperazin-2-one, 8-oxa-3-aza-bicyclo[3.2.1]octyl, piperazinyl, hexahydropyrimidine. The heterocyclyl group can be substituted or unsubstituted.

[0076] "Aryl" or "aromatic" refers to a carbocyclic aromatic ring system containing one or two rings, wherein the rings can be fused together. The term "aryl" includes mono- or bicyclic aromatic groups such as the aromatic groups of benzene, naphthalene, tetrahydronaphthalene. Preferably, aryl is C6-Ci2aryl, more preferably C6-Ci0aryl, most preferably C6-C8aryl. The aryl group can be substituted or unsubstituted. 10 Aryl, more preferably aryl is phenyl and naphthyl, most preferably phenyl. The aryl group can be substituted or unsubstituted.

[0077] "Heteroaryl" means an aromatic 5- to 6-membered monocyclic ring or 8- to 10-membered bicyclic ring, which can contain 1 to 4 atoms selected from nitrogen, oxygen, and / or sulfur. Examples of "heteroaryl" groups include, but are not limited to, furanyl, pyridinyl, 2-oxo-l,2-dihydropyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, isoxazolyl, oxazolyl, oxadiazolyl, imidazolyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, isothiazolyl, 1,2,3-thiadiazolyl, benzodioxolyl, benzothienyl, benzoimidazolyl, indolyl, isoindolyl, 1,3-dioxo-isoindolyl, quinolinyl, indazolyl, benzoisothiazolyl, benzoxazolyl, benzoisoxazolyl. The heteroaryl group can be substituted or unsubstituted.

[0078] "Alkoxy" means a group of the formula (alkyl-O-), wherein alkyl is as defined herein. C1-C6alkoxy is preferred. Examples include, but are not limited to, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, t-butyloxy, and the like.

[0079] "Fused ring" means a polycyclic group in which two or more cyclic structures share a pair of atoms, one or more rings can contain one or more double bonds, but at least one ring does not have an aromatic system with fully conjugated π electrons, while at least one ring has an aromatic system with fully conjugated π electrons, wherein 0, one or more of the ring atoms are heteroatoms selected from nitrogen, oxygen or S, and the remaining ring atoms are carbon. Fused rings preferably include bicyclic or tricyclic fused rings, wherein bicyclic fused rings are preferably fused rings of aryl or heteroaryl with monocyclic heterocyclyl or monocyclic cycloalkyl. Preferably 7- to 14-membered, more preferably 8- to 10-membered.

[0080] "Epoxide" means a compound characterized by the presence of at least one cyclic ether group, i.e., a compound in which an ether oxygen atom is attached to two adjacent carbon atoms to form a ring structure. The term is intended to include mono-epoxide compounds, poly-epoxide compounds (having two or more epoxide groups), and epoxy-terminated prepolymers. "Hydroxyl" means an -OH group.

[0081] "Halogen" means fluorine, chlorine, bromine, and iodine.

[0082] "Amino" means -NH2.

[0083] "Cyano" means -CN.

[0084] "Nitro" means -NO2.

[0085] "Carboxyl" means -C(O)OH.

[0086] "Heteroaryl" means an aromatic 5- to 6-membered monocyclic ring or 8- to 10-membered bicyclic ring, which can contain 1 to 4 atoms selected from nitrogen, oxygen, and / or sulfur. Examples of "heteroaryl" groups include, but are not limited to, furanyl, pyridinyl, 2-oxo-l,2-dihydropyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, isoxazolyl, oxazolyl, oxadiazolyl, imidazolyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, isothiazolyl, 1,2,3-thiadiazolyl, benzodioxolyl, benzothienyl, benzoimidazolyl, indolyl, isoindolyl, 1,3-dioxo-isoindolyl, quinolinyl, indazolyl, benzoisothiazolyl, benzoxazolyl, benzoisoxazolyl. The heteroaryl group can be substituted or unsubstituted.

[0087] "Aminoalkyl" means an amino-substituted alkyl group.

[0088] "Haloalkyl" means an alkyl group substituted with one or more halogen atoms.

[0089] "Aminoalkyl" means an alkyl group substituted with one or more amino groups.

[0090] "Aryloxy" means an aryl group substituted with one or more hydroxyl groups.

[0091] "Substituted" means that one or more hydrogen atoms, preferably up to 5, more preferably 1 to 3, of the group are independently of each other replaced with a corresponding number of substituents. It goes without saying that substituents are only in their possible chemical positions, which can be determined (experimentally or theoretically) by the person skilled in the art without undue effort, as to whether a substitution is possible or not. For example, an amino or hydroxyl group with a free hydrogen can not be stable when bound to a carbon atom with an unsaturated (e.g. olefinic) bond.

[0092] "Substituted" or "substitution" as used in the present specification, if not specified otherwise, means that a group can be substituted with one or more substituents selected from the group consisting of alkyl, alkoxy, alkylthio, alkylamino, halogen, hydroxy, nitro, cyano, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkoxy, heterocycloalkoxy, cycloalkylthio, heterocycloalkylthio, amino, haloalkyl, hydroxyalkyl;

[0093] The present application provides a phosphorus-containing aromatic polyester having the structural formula of Formula I,

[0094]

[0095] Formula I

[0096] wherein R2, R3, R4 are each independently alkyl, aryl, cycloalkyl or alkoxy, which alkyl, aryl, cycloalkyl or alkoxy can be optionally further substituted with one or more substituents selected from the group consisting of deuterium, tritium, alkyl, haloalkyl, halogen, amino, hydroxy, cyano, formyl, acetyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or alkoxy;

[0097] R1 and R5 are each independently or

[0098] R6and R7are each independently hydrogen, halogen, aryl, phenoxy, alkyl, carboxyl, amino, hydroxyl, cyano, amido, alkoxy, alkylamino, thiol, cycloalkyl, heterocycloalkyl, heteroaryl, which aryl, phenoxy, alkyl, amido, alkoxy, alkylamino, thiol, cycloalkyl, heterocycloalkyl, heteroaryl can be optionally further substituted with one or more substituents selected from the group consisting of halogen, aryl, phenoxy, alkyl, carboxyl, amino, hydroxyl, cyano, amido, alkoxy, alkylamino, thiol, cycloalkyl, heterocycloalkyl, heteroaryl; or, which alkyl can be optionally further substituted with one or more branched alkyl groups containing at least 1 carbon atom, which alkoxy can be optionally further substituted with one or more branched alkoxy groups containing at least 1 carbon atom;

[0099] n is a positive integer greater than or equal to 1.

[0100] In some embodiments of the present application, R6and R7are each independently hydrogen, hydroxyl, or alkyl of 1 to 6 carbon atoms.

[0101] In some embodiments of the present application, R6is hydrogen.

[0102] In some embodiments of the present application, R7is hydrogen.

[0103] In some embodiments of the present application, R6is hydrogen, and R7is hydrogen.

[0104] In some embodiments of the present application, R2and R4are each independently a divalent aryl group of 6 to 12 carbon atoms, a divalent linear or branched alkylene group of 1 to 8 carbon atoms, a divalent linear or branched alkenylene group of 2 to 8 carbon atoms; which divalent aryl group of 6 to 12 carbon atoms is optionally further substituted with one or more alkyl or alkoxy groups of up to 6 carbon atoms.

[0105] In some embodiments of the present application, R2and R4are each independently a divalent aryl group of 6 to 12 carbon atoms, further preferably a divalent aryl group of 6 to 8 carbon atoms.

[0106] In some embodiments of the present application, R3is selected from one of the following: R3is a divalent cycloalkyl group of 6 to 18 carbon atoms, optionally further substituted with one or more divalent aryl groups of 6 to 12 carbon atoms.

[0107] In some embodiments of the present application, R3is selected from one of the following:

[0108] wherein h is 1 or 2;

[0109] R8is a hydrogen atom,

[0110] R9is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group;

[0111] R 10 is a hydrogen atom, a methyl group, or an ethyl group;

[0112] R 11 is a hydrogen atom or an alkyl group;

[0113] Z is a covalent bond, -SO2-, -C(CH3)2-, -CH(CH3)-, or -CH2-;

[0114] a is a positive integer between 0 and 2; b is a positive integer between 0 and 2, and a and b cannot both be 0.

[0115] In some embodiments of the present application, R3is .

[0116] In some embodiments of the present application, n is 1 to 10. For example, n is one or two or more of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0117] In some embodiments of the present application, formula I is selected from the following structures:

[0118] Formula I-1

[0119]

[0120] Formula I-2

[0121]

[0122] Formula I-3

[0123]

[0124] Formula I-4.

[0125] In some embodiments of the present application, formula I is selected from the following structures:

[0126] Formula I-1

[0127]

[0128] Formula I-2.

[0129] The present application provides a method for preparing the above-mentioned phosphorus-containing aromatic polyester, which comprises the following steps: dissolving phthaloyl chloride in an organic solvent, then adding a phosphorus-containing monophenol compound and a bisphenol monomer, heating and reacting, and separating to obtain the phosphorus-containing aromatic polyester.

[0130] In some embodiments of the application, the phthaloyl chloride is selected from any one of isophthaloyl chloride, terephthaloyl chloride, p-phthaloyl chloride, m- phthalic diethyl chloride, o-phthalic diethyl chloride, p-phthalic diethyl chloride, m- phthalic dipropionyl chloride, o-phthalic dipropionyl chloride, p-phthalic dipropionyl chloride, m-phthalic dibutyl chloride, o-phthalic dibutyl chloride, p-phthalic dibutyl chloride, m-phthalic diamyl chloride, o-phthalic diamyl chloride, p-phthalic diamyl chloride, m-phthalic dihexyl chloride, o-phthalic dihexyl chloride, p-phthalic dihexyl chloride, m-phthalic diheptyl chloride, o-phthalic diheptyl chloride, p-phthalic diheptyl chloride, m-phthalic dioctyl chloride, o-phthalic dioctyl chloride, p-phthalic dioctyl chloride, m-phthalic dinonyl chloride, o-phthalic dinonyl chloride, p-phthalic dinonyl chloride, m-phthalic didecyl chloride, o-phthalic didecyl chloride, p-phthalic didecyl chloride.

[0131] In some embodiments of the application, the phthaloyl chloride is any one of isophthaloyl chloride, terephthaloyl chloride, p-phthaloyl chloride.

[0132] In some embodiments of the application, the phosphorus-containing monophenolic compound is selected from any one of:

[0133] .

[0134] In some embodiments of the application, the phosphorus-containing monophenolic compound is or .

[0135] In some embodiments of the application, the bisphenol monomer is selected from any one of:

[0136]

[0137] In some embodiments of the application, the bisphenol monomer is preferably .

[0138] In some embodiments of the application, under nitrogen protection, a three-necked flask equipped with mechanical stirring, thermometer, condenser tube is charged with isophthaloyl chloride and toluene, and the system is subjected to nitrogen replacement under reduced pressure. After the system is completely dissolved, the phosphorus-containing monophenolic compound and the dicyclopentadiene phenolic resin are added, and the system is subjected to nitrogen replacement under reduced pressure. After complete dissolution, tetrabutylammonium bromide is added, and the temperature of the system is controlled within 60 °C. About 400 g of 20% sodium hydroxide aqueous solution is added dropwise over about 3 h. The above conditions are continued to stir for about 1.0 h. After the reaction is completed, the system is allowed to stand and separate into layers, and the water layer is removed. Deionized water is added to the toluene phase in which the reactants are dissolved, and the system is stirred for about 15 min. The system is allowed to stand and separate into layers, and the water layer is removed. The operation is repeated until the pH of the water layer is about 7.0. The water is removed by dehydration through a decanter, and a phosphorus-containing active ester / toluene solution is obtained.

[0139] The present application provides an epoxy resin composition comprising the above-mentioned phosphorus-containing aromatic polyester or the phosphorus-containing aromatic polyester prepared by the above-mentioned method, a thermosetting resin and a curing agent.

[0140] In some embodiments of the application, the thermosetting resin is an epoxy resin.

[0141] In some embodiments of the application, the thermosetting resin is one or more of a halogen-free epoxy, a phosphorous-free epoxy, and a phosphorous-containing epoxy.

[0142] In some embodiments of the application, the phosphorous-containing aromatic polyester is 10 to 150 parts by weight relative to 100 parts by weight of the epoxy resin. For example, the phosphorous-containing aromatic polyester can be 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, or any range therein, relative to 100 parts by weight of the epoxy resin.

[0143] In some embodiments of the application, it is used in any one of a coating formulation, an encapsulant, a composite material, an adhesive, a molding, a bonding sheet, or a laminate.

[0144] The present application provides an article comprising the above composition.

[0145] In some embodiments of the application, the article is used in a lead-free soldering or an electronic device.

[0146] In some embodiments of the application, the article is a copper foil.

[0147] In some embodiments of the application, the article is a printed circuit board.

[0148] The present application provides a prepreg comprising the above composition.

[0149] The present application provides a laminate or a bonding sheet comprising the above composition.

[0150] The present application provides a printed wiring board comprising the above prepreg.

[0151] The present application provides a printed wiring board comprising the above laminate.

[0152] The present application provides a process for manufacturing the above laminate, which comprises impregnating the composition into a filler material to form a prepreg, followed by treating the prepreg at an elevated temperature to promote partial curing to a B-stage and then laminating two or more of the prepregs at an elevated pressure and temperature to form a laminate.

[0153] The present application provides a printed circuit board made by the above process.

[0154] Embodiment

[0155] Example 1

[0156] Into a three-necked flask equipped with mechanical stirring, thermometer, and condenser under nitrogen protection, add isophthaloyl chloride (203 g, 1.0 mol, 2.0 moles of acyl chloride group) and 1338 g of toluene, and perform nitrogen replacement under reduced pressure. After the system is completely dissolved, add the phosphorus-containing monophenol compound (207 g, 0.67 mol), 220 g of dicyclopentadiene phenolic resin (1.33 moles of phenolic hydroxyl group), and perform nitrogen replacement under reduced pressure. After complete dissolution, add 1.12 g of tetrabutylammonium bromide, and control the system temperature within 60 °C. Drop 400 g of 20% sodium hydroxide aqueous solution in about 3 h. Continue stirring under the above conditions for 1.0 h. After the reaction is completed, separate the liquid by standing, and remove the water layer. Add deionized water to the toluene phase dissolving the reactants, stir for about 15 min, separate the liquid by standing, and remove the water layer. Repeat the operation until the pH of the water layer is about 7.0, remove the water by dehydration through a decanter, and obtain a phosphorus-containing active ester / toluene solution with a solid content of about 65%.

[0157] The structural formula of the phosphorus-containing monophenol compound is shown as formula 1.

[0158]

[0159] Formula 1

[0160] The reaction process is as follows:

[0161]

[0162] Example 2

[0163] Into a three-necked flask equipped with mechanical stirring, thermometer, and condenser under nitrogen protection, add isophthaloyl chloride (203 g, 1.0 mol, 2.0 moles of acyl chloride group) and 1338 g of toluene, and perform nitrogen replacement under reduced pressure. After the system is completely dissolved, add the phosphorus-containing monophenol compound (207 g, 0.67 mol), 220 g of dicyclopentadiene phenolic resin (1.33 moles of phenolic hydroxyl group), and perform nitrogen replacement under reduced pressure. After complete dissolution, add 1.12 g of tetrabutylammonium bromide, and control the system temperature within 60 °C. Drop 400 g of 20% sodium hydroxide aqueous solution in about 3 h. Continue stirring under the above conditions for 1.0 h. After the reaction is completed, separate the liquid by standing, and remove the water layer. Add deionized water to the toluene phase dissolving the reactants, stir for about 15 min, separate the liquid by standing, and remove the water layer. Repeat the operation until the pH of the water layer is about 7.0, remove the water by dehydration through a decanter, and obtain a phosphorus-containing active ester / toluene solution with a solid content of about 65%.

[0164] The phosphorus-containing monophenolic compound has a structure as shown in Formula 1.

[0165]

[0166] Formula 1

[0167] The reaction process is as follows:

[0168]

[0169] Example 3

[0170] Under nitrogen protection, a three-necked flask equipped with mechanical stirring, thermometer, and condenser was charged with isophthaloyl chloride (203 g, 1.0 mol, 2.0 moles of acyl chloride group), and 1338 g of toluene, and the system was subjected to nitrogen replacement under reduced pressure. After the system was completely dissolved, a phosphorus-containing monophenolic compound (197 g, 0.67 mol) and 220 g of dicyclopentadiene phenolic resin (1.33 moles of phenolic hydroxyl group) were added, and the system was subjected to nitrogen replacement under reduced pressure. After complete dissolution, 1.12 g of tetrabutylammonium bromide was added, and the system temperature was controlled within 60 °C. About 400 g of 20% sodium hydroxide aqueous solution was added dropwise over about 3 h. The above conditions were continued to be stirred for 1.0 h. After the reaction was completed, the system was allowed to stand and separate, and the water layer was removed. Deionized water was added to the toluene phase containing the reaction product, and the system was stirred for about 15 min, allowed to stand and separate, and the water layer was removed. The above operation was repeated until the pH of the water layer was about 7.0. The water was removed by dehydration through a decanter, and a phosphorus-containing active ester / toluene solution with a solid content of about 65% was obtained.

[0171] The phosphorus-containing monophenolic compound has a structure as shown in Formula 2.

[0172]

[0173] Formula 2

[0174] The reaction process is as follows:

[0175]

[0176] Comparative Example 1

[0177] Into a three-necked flask equipped with a mechanical stirrer, thermometer, and a condenser, under nitrogen, was placed isophthaloyl dichloride (203 g, 1.0 mol, 2.0 acyl chloride moles) and 1338 g of toluene. The system was degassed under reduced pressure and nitrogen. After the system was completely dissolved, a- naphthol (96.0 g, 0.67 mol), 220 g of dicyclopentadiene phenolic resin (1.33 phenolic hydroxyl moles) were added. The system was degassed under reduced pressure and nitrogen. After the system was completely dissolved, 1.12 g of tetrabutylammonium bromide was added. The system temperature was controlled below 60 °C. About 400 g of 20% sodium hydroxide aqueous solution was added dropwise over about 3 h. The above conditions were continued to stir for 1.0 h. After the reaction was completed, the system was allowed to stand and separate. The water layer was removed. Deionized water was added to the toluene phase containing the reaction product. The system was stirred for about 15 min, allowed to stand and separate. The water layer was removed. The above operation was repeated until the water layer pH was about 7.0. The water was removed by a decanter. An active ester / toluene solution with a solid content of about 65% was obtained.

[0178]

[0179] The ester equivalent of the active ester provided in Experimental Example 1-2 and Comparative Example 1 was between 220 ~ 240 g / eq.

[0180] Comparative Example 2

[0181] The following structure was synthesized according to the method of Example 2 in CN108350157A,

[0182]

[0183] The specific synthesis method is as follows: DOPO-HQ-isophthaloyl-ester (pentamer mixture): DOPO-HQ (71.9 g, 221.6 mmol) and pyridine (25 mL, 310.5 mmol) were mixed together in 200 mL of chloroform. Isophthaloyl dichloride (30.0 g, 147.8 mmol) in 50 mL of chloroform was added dropwise. The suspension was heated to reflux temperature and a homogeneous solution was formed. After 3 h, the solution was cooled to room temperature and washed with 0.5 M aqueous HCl and saturated brine. The organic layer was collected and dried over sodium sulfate. The solvent was removed under vacuum. The final product was a white solid.

[0184] Comparative Example 3.

[0185] The following structure was synthesized according to the method of Example 1 in CN109983055B,

[0186]

[0187] The specific method is as follows: under nitrogen protection, a 1000 mL three-necked flask equipped with mechanical stirring (300 r / min), thermometer and condenser tube is charged with DOPO-HQ (211.6 g, 0.65 mol) and 500 g acetic anhydride, and the temperature is raised to 140°C, the system is completely dissolved, and the solution is refluxed for 2 h, and the solution changes from purple to light yellow; the temperature is lowered to 100°C, 0.025 g potassium acetate and isophthalic acid (70 g, 0.42 mol) are added, the temperature is raised to 240°C, the system reaches a completely dissolved state, and after being stabilized for 1 h, the pressure is slowly raised to -0.096~0.098 MPa to remove excess acetic anhydride and by-product acetic acid; after reacting for 2 h, the product is poured into an aluminum plate while hot, the resin is rapidly cooled to obtain a light brown color, and the resin is ground and dried in a 137°C vacuum oven to remove residual acetic acid, with a yield of about 98%.

[0188] The specific process is as follows:

[0189]

[0190] Performance test of the phosphorus-containing active ester compound:

[0191] (1) Structure characterization: the chemical structure of the provided phosphorus-containing monophenol monomer is characterized by nuclear magnetic resonance (NMR) and Fourier infrared spectrometer (FT-IR); the NMR spectrum and FTIR spectrum thereof are shown in Figure 1 and Figure 2 , respectively.

[0192] (2) Molecular weight test: the weight average molecular weight (M w ) and molecular weight distribution of the phosphorus-containing active ester compound provided in Example 1 are determined by a gel permeation chromatography system, as shown in Figure 3 . The weight average molecular weight (M w ) is 1096, and the molecular weight distribution is 3.78.

[0193] (3) Solubility and stability test: the solid resin is crushed into small particles, 10 g of solid resin is taken, mixed with 100 mL of solvent, sealed in a polyethylene plastic bottle, and ultrasonically dissolved; the solvents are: butanone, toluene, tetrahydrofuran, and N,N-dimethylformamide. It is found that the phosphorus-containing active ester compound prepared in Examples 1-3 can be completely dissolved in butanone, toluene, tetrahydrofuran, and N,N-dimethylformamide. The completely dissolved liquid resin is placed in a 5°C refrigerator for 7 days, and no obvious resin particles are found to precipitate, indicating that the phosphorus-containing active ester compound has good solubility and stability in butanone, toluene, tetrahydrofuran, and N,N-dimethylformamide.

[0194] Solubility test results

[0195] Table 1

[0196]

[0197] Experimental Example 1 : Small scale epoxy curing experiments with active ester compounds of Example 1 and Example 3

[0198] Under small scale, the phosphorous containing active ester compounds synthesized in Example 1 and Example 3 were combined with epoxy resins and cured (see Table 2 for material information). The samples were cured using SQDN-302, 0.12 wt. % DMAP as catalyst; the epoxy curing system was cured at 165 ~ 195 °C for 2 h, post cured at 180 ~ 210 °C for 1 h, and the heat resistance of the samples was measured by DSC Institute. To make the samples for D k and D f For the measured varnish castings, the phosphorous containing active ester compounds were blended with SQDN-302 and catalyst DMAP (abbreviated as resin); using the sample-epoxy blend, an aluminum foil was coated on one side, the aluminum foil was air dried after coating, and then B-staged at 155 °C (3 min 50 s); the epoxy was stripped from the foil, then shaped and cured at 190 °C for 2 ~ 3 h, and post cured at 200 ~ 210 °C for 1 h. The results are listed in Table 3.

[0199] Table 2 Composition, T g and dielectric properties of small scale curing experiments

[0200]

[0201] Table 3 Composition, T g and dielectric properties of small scale curing experiments

[0202]

[0203] Example 1 and Example 3 were investigated as curing agents for epoxy resin SQDN-302 laminate applications, maintaining solids content at 58% by adding MEK solvent. Catalyst was controlled by adding small increments of DMAP solution (0.5 wt.% solids in methyl ethyl ketone) to achieve an optimal varnish gel time of 270 s at 171 °C according to IPC-TM-650 test 2.3.18. In evaluating flame retardant properties, V-0 indicates that after two 10 second flame tests, the flame is extinguished within 30 seconds and no burning material can fall. V-1 indicates that after two 10 second flame tests, the flame is extinguished within 60 seconds and no burning material can fall. Additionally, it can be seen that the Tg of the phosphorus-containing active ester compound of Example 1 is higher than the Tg of the phosphorus-containing active ester compound of Example 3. The flame retardant properties of the phosphorus-containing active ester compounds of Example 1 and Example 3 are both higher than the flame retardant properties of the compound of Comparative Example 1.

[0204] Table 4 Epoxy resin laminate formulations

[0205]

[0206] The glass fabric was continuously passed through a trough containing the varnish and through a squeeze roller to obtain a uniform coating; the coated fabric section was hung in a fume hood overnight to slowly evaporate the solvent. Prepregs were prepared by drying the resin-coated glass fabric in a 160 °C preheated air circulating oven for 4 min 30 s to obtain less than 20% resin flow; the resin content was controlled between 50 and 55% (determined by the weight difference between the glass fabric and the prepreg). The gel time of the prepreg was determined by the fusible thermoplastic resin collected by crushing the prepreg in a zip-lock bag, the collected resin was tested for gel time on a hot plate at 171 °C. The properties of the prepregs are shown in Table 5.

[0207] Table 5 Properties of the prepregs

[0208]

[0209] Four circular stacks of prepreg with a diameter of 25 mm were placed between disposable aluminum plates and the rheological behavior of the B-staged prepreg was investigated by electrically heating the resin to 200 °C at 5 °C / min in an AR2000ex rheometer. Based on the rheological curve, a curing cycle was designed to obtain good wetting of the glass cloth. A sizing solution was prepared in the proportions described above, glass fiber cloth was impregnated, and a prepreg (PP) was prepared by drying at 160 °C for 5 min. The PP was stacked in 6 layers with copper foils on both sides and placed in a vacuum hot press, 20 kgf / cm2 pressure was applied at 200 °C for 90 min, the pressure was released, and the laminate was allowed to cool to room temperature. 2 ​

[0210] The Tg of the multilayer build was determined by dynamic mechanical analysis at a rate of 5 °C / min in single-cantilever beam mode g was 179 °C.

[0211] The test specimens for pressure cooker testing were cut from the epoxy build containing the phosphorus-containing active ester compound and placed in a pressure cooker at 121 °C and 15 psi for 30 minutes; the test coupons absorbed approximately 0.07 to 0.14 wt.% water and none of the three test specimens exhibited any blistering and were rated as Condition (Status) 5 according to the IPC test standard. The properties of the prepreg and build-up layer are shown in Tables 6 and 7, respectively.

[0212] Table 6

[0213]

[0214] Table 7

[0215] .

Claims

1. A phosphorus-containing aromatic polyester having a structural formula represented by Formula I, ###0001### Formula I wherein, R1 is a divalent aromatic group having 6 to 12 carbon atoms; R2 and R4 are each independently a divalent aromatic group having 6 to 12 carbon atoms; R3 is selected from one of the following: ###0002### R5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a hydroxyl group; R6 and R7 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 6 carbon atoms; h is 1 or 2; R8 is a hydrogen atom, an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group; R9 is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group; Z is a covalent bond, -SO2-, -C(CH3)2-, -CH(CH3)-, or -CH2-; a is a positive integer between 0 and 2; b is a positive integer between 0 and 2, and a and b cannot both be 0; n is a positive integer greater than 1. Formula I; 2. The phosphorus-containing aromatic polyester according to claim 1, wherein, R2 and R4 are each independently a divalent aromatic group having 6 to 8 carbon atoms.

3. The phosphorus-containing aromatic polyester according to claim 1, wherein, n is 2 to 10. ； wherein 4. The phosphorus-containing aromatic polyester according to claim 1, wherein, Formula I is selected from the following structures: ###0003### 5. A method for producing the phosphorus-containing aromatic polyester according to any one of claims 1 to 4, comprising the steps of: dissolving terephthaloyl chloride in an organic solvent, followed by adding a phosphorus-containing monophenol compound and a bisphenol monomer, heating the reaction, and isolating the phosphorus-containing aromatic polyester.

6. The method for producing according to claim 5, wherein, the terephthaloyl chloride is selected from any one of the following: isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride, isobutyroyl chloride, phthalyoyl chloride, terephthaloyl chloride, isopropyl chloride, phthalyoyl chloride, terephthaloyl chloride, isobutyl chloride, phthalyoyl chloride, terephthaloyl chloride, isopentyl chloride, phthalyoyl chloride, terephthaloyl chloride, isohexyl chloride, phthalyoyl chloride, terephthaloyl chloride, isoheptyl chloride, phthalyoyl chloride, terephthaloyl chloride, isooctyl chloride, phthalyoyl chloride, terephthaloyl chloride, isononyl chloride, phthalyoyl chloride, terephthaloyl chloride, isodecyl chloride, phthalyoyl chloride, terephthaloyl chloride. R 10 is a hydrogen atom, a methyl group or an ethyl group; R 11 is a hydrogen atom or an alkyl group; 7. An epoxy resin composition comprising the phosphorus-containing aromatic polyester according to any one of claims 1 to 4 or the phosphorus-containing aromatic polyester produced by the method according to any one of claims 5 to 6, a thermosetting resin, and a curing agent. The thermosetting resin is an epoxy resin. R1and R5are each independently or ; The thermosetting resin is one or two or more of a halogen-free epoxy, a phosphorus-free epoxy, and a phosphorus-containing epoxy. The phosphorus-containing aromatic polyester is 10 to 150 parts by weight with respect to 100 parts by weight of the epoxy resin.

11. The composition according to any one of claims 7 to 10, for use in any one of a coating formulation, an encapsulant, an adhesive, a bonding sheet, or a laminate.

12. An article comprising the composition according to any one of claims 7 to 11. The article is for use in lead-free soldering or electronic devices. The article is a copper foil.

4. The phosphorus-containing aromatic polyester according to claim 1, wherein, The article is a printed circuit board. Formula I-1; Formula I-2; Formula I-3; Formula I-4.

16. A prepreg comprising the composition according to any one of claims 10 to 11.

17. A laminate comprising the composition according to any one of claims 7 to 11.

18. A printed wiring board comprising the prepreg according to claim 16. ​ ​ 8. The composition of claim 7, wherein, ​ 9. The composition of claim 8, wherein, ​ 10. The composition of claim 8, wherein, ​ ​ ​ 13. The article of claim 12, wherein, ​ 14. The article of claim 12, wherein, ​ 15. The article of claim 12, wherein, ​ ​ ​ ​ 19. A bonded sheet comprising the composition of any one of claims 7-11.

20. A printed wiring board comprising the laminate of claim 17.

21. A process for making the laminate of claim 17 comprising impregnating the composition into a filler material to form a prepreg, subsequently treating the prepreg at elevated temperature to promote partial cure to a B-stage and then laminating two or more of the prepregs at elevated pressure and temperature to form a laminate.

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