Phosphorus-containing aromatic polyester and thermosetting resin composition thereof

Abstract

The invention provides phosphorus-containing aromatic polyester and a thermosetting resin composition thereof. The structural formula of the phosphorus-containing aromatic polyester is shown as a formula I. The phosphorus-containing aromatic polyester has the properties of good solubility, low dielectric, high flame retardance, low shrinkage rate during curing, low elastic modulus at high temperature and the like; and the formula I of the # imgabs0 # is shown in the specification.

Description

Technical Field

[0001] This application belongs to the field of synthetic resins for electronic materials technology, and specifically relates to a phosphorus-containing aromatic polyester, its thermosetting resin composition, and their preparation methods and applications. Background Art

[0002] The thermosetting resin composition prepared from epoxy resin and its curing agent has excellent properties such as heat resistance and insulation, and is widely used in the field of insulating materials such as printed circuit boards, semiconductor sealants, and laminated films. With the development of electronic information products towards high frequency and high speed, light, small, thin, and portable, higher requirements will be put forward for the substrate materials of printed circuit boards that carry electronic components, such as lower dielectric constant and dielectric loss, lower coefficient of thermal expansion, higher heat resistance, moisture resistance, lower water absorption rate, and the ability to achieve halogen-free flame retardancy. Compared with traditional epoxy curing agents such as amines, acid anhydrides, and phenolic resins that introduce polar hydroxyl groups during epoxy curing, the reaction between aromatic polyester and epoxy resin does not produce polar hydroxyl groups, which can meet the requirements of low dielectric and low water absorption rate of printed circuit boards. However, most aromatic polyesters do not contain flame retardant elements, and their flame retardant performance is insufficient, such as m-tris-phenol formate, m-tris-phenol acetate, phenolic polyester, etc., which limits their application in the field of high heat resistance and halogen-free flame retardant copper clad laminates.

[0003] Under high power density, the risk of local overheating of the circuit increases. If the flame retardancy of the material is insufficient, 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. At present, the by-products of the existing phosphorus-containing aromatic polyesters are often numerous and have a high content. The presence of terminal carboxyl groups and hydroxyl groups will introduce polar hydroxyl groups during the epoxy curing process, resulting in generally high dielectric constant and dielectric loss of the cured product. Moreover, the phosphorus-containing aromatic polyester contains acetyl groups, and the alkyl groups capped by acetyl groups during the epoxy curing process will transfer to the side chain of the cured structure to play a plasticizing role, resulting in a decrease in the heat resistance of the copper clad laminate. Most importantly, the above-mentioned phosphorus-containing aromatic polyesters have poor solubility and are difficult to dissolve in common organic solvents such as methyl ethyl ketone (MEK), toluene, and tetrahydrofuran at room temperature, which is not conducive to their application in the epoxy curing process. Summary of the Invention

[0004] The applicant found that the existing phosphorus-containing aromatic polyesters have poor solubility and are difficult to dissolve in common organic solvents such as methyl ethyl ketone (MEK), toluene, and tetrahydrofuran at room temperature, which is not conducive to their application in the epoxy curing process. Therefore, the development of a new type of phosphorus-containing aromatic polyester with both acetyl-free capping and good solubility has high research significance and practical value for improving the dielectric properties, moisture resistance, heat resistance, mechanical properties, flame retardancy, and processability of the epoxy curing system.

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

[0006] A phosphorus-containing aromatic polyester, the structural formula of which is shown in Formula I,

[0007]

[0008] Formula I

[0009] R2 and R4 are each independently a divalent aryl group having 6 to 12 carbon atoms;

[0010] R3 is a divalent cycloalkyl group having 6 to 18 carbon atoms, optionally further substituted by one or more divalent aryl groups having 6 to 12 carbon atoms;

[0011] R1 and R5 are each independently or

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

[0013] R6 and R7 are each independently hydrogen, a hydroxyl group or an alkyl group having 1 to 6 carbon atoms.

[0014] In some embodiments of the present application, R2 and R4 are each independently a divalent aryl group having 6 to 8 carbon atoms.

[0015] In some embodiments of the present application, R3 is selected from one of the following:

[0016] where h is 1 or 2;

[0017] R8 is a hydrogen atom,

[0018] R9 is an alkylene group having 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, 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] This application provides a method for preparing the above phosphorus-containing aromatic polyester, which includes the following steps:

[0034] Dissolve phthaloyl chloride in an organic solvent, then add a phosphorus-containing monophenol compound and a bisphenol monomer, heat the reaction and separate to obtain the phosphorus-containing aromatic polyester.

[0035] In some embodiments of this application,

[0036] The phthaloyl chloride is selected from any one of isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride, isophthaloyl dichloride, phthaloyl dichloride, terephthaloyl dichloride, isophthaloyl dipropionyl chloride, phthaloyl dipropionyl chloride, terephthaloyl dipropionyl chloride, isophthaloyl dibutyryl chloride, phthaloyl dibutyryl chloride, terephthaloyl dibutyryl chloride, isophthaloyl dipentanoyl chloride, phthaloyl dipentanoyl chloride, terephthaloyl dipentanoyl chloride, isophthaloyl dihexanoyl chloride, phthaloyl dihexanoyl chloride, terephthaloyl dihexanoyl chloride, isophthaloyl diheptanoyl chloride, phthaloyl diheptanoyl chloride, terephthaloyl diheptanoyl chloride, isophthaloyl dioctanoyl chloride, phthaloyl dioctanoyl chloride, terephthaloyl dioctanoyl chloride, isophthaloyl dinonanoyl chloride, phthaloyl dinonanoyl chloride, terephthaloyl dinonanoyl chloride, isophthaloyl didecanoyl chloride, phthaloyl didecanoyl chloride, terephthaloyl didecanoyl chloride;

[0037] Preferably any one of isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride;

[0038] Or,

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

[0040] ;

[0041] Preferably Or ;

[0042] Or,

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

[0044] The present application provides an epoxy resin composition, which comprises the above-mentioned phosphorus-containing aromatic polyester or the phosphorus-containing aromatic polyester prepared by the above method, 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 more of a halogen-free epoxide, a phosphorus-free epoxide, and a phosphorus-containing epoxide.

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

[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, which comprises the above composition.

[0050] In some embodiments of the present application, the article is used for 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, which comprises the above composition.

[0054] The present application provides a laminate or a bonding sheet, which comprises the above composition.

[0055] The present application provides a printed wiring board, which comprises the above prepreg.

[0056] The present application provides a printed wiring board, which comprises the above laminate.

[0057] The present application provides a process for manufacturing the above laminate, 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 the 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 a printed circuit board made by the above process.

[0059] Compared with the prior art, the beneficial effects of the present application are as follows:

[0060] The present application aims to overcome the deficiencies in the above-mentioned prior art and provides a phosphorus-containing aromatic polyester and its thermosetting resin composition with properties such as good solubility, low dielectric constant, high flame retardancy, low shrinkage rate during curing, and low elastic modulus at high temperatures.

[0061] The present application designs and synthesizes a novel phosphorus-containing monophenol compound to replace the end-capping compound - naphthol in the phosphorus-containing aromatic polyester described in CN109476822A of DIC Corporation, Japan. Therefore, the characteristics of the compound described in the present application are that it can simultaneously act as a flame retardant and an active ester curing agent for thermosetting resins such as epoxy resins, endowing the curing system with higher heat resistance and thermal stability, high mechanical strength, low water absorption, good processability, and low dielectric loss tangent and a sufficiently low dielectric constant at the same time. In addition, the phosphorus-containing aromatic polyester of the present invention 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 circuit 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] Using 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 phosphorus-containing aromatic polyester acting as a multifunctional curing agent with more reactive ester groups per molecule, the use of the multifunctional curing agent in 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 invention can be easily used on a reinforcing agent such as glass fiber using a varnish solution.

[0064] The present application further provides an epoxy resin composition containing the phosphorus-containing flame-retardant multifunctional phosphorus-containing aromatic polyester (Formula (I)), which exhibits excellent flame retardancy, heat resistance, mechanical and dielectric properties. Description of the Drawings

[0065] Figure 1 Shows the NMR spectrum of the phosphorus-containing aromatic polyester of Example 1;

[0066] Figure 2 Shows the FTIR spectrum of the phosphorus-containing aromatic polyester of Example 1;

[0067] Figure 3 A and B in show the GPC spectra of the phosphorus-containing aromatic polyester of Example 1. Detailed Description

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

[0069] Unless otherwise defined, the technical and scientific terms in this specification have the same meaning as commonly understood by those skilled in the art. Although methods and materials similar or equivalent to those described herein can be used in experiments or practical applications, the materials and methods are described below. In case of conflict, the present specification, including its definitions, shall prevail. In addition, the materials, methods, and examples are for illustrative purposes only and are not restrictive. The present application will be further described below in conjunction with specific embodiments, but is not used to limit the scope of the present application.

[0070] Although this case has been disclosed above by way of embodiments, it is not intended to limit this case. Any person with ordinary knowledge in the technical field to which this case pertains may make some modifications and refinements without departing from the spirit and scope of this case. Therefore, the scope of protection of this case shall be subject to that defined by the appended patent application scope.

[0071] "Alkyl", when used as a group or part of a group, refers to a straight-chain or branched aliphatic hydrocarbon group. Preferably C1-C 20 alkyl, more preferably C1-C 10 alkyl, and even more preferably C1-C6 alkyl. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-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, etc. The alkyl can be substituted or unsubstituted.

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

[0073] "Alkynyl" refers to an aliphatic hydrocarbon group containing a carbon-carbon triple bond, which can be straight-chain or branched. Preferred is C2-C 10 alkynyl, more preferably C2-C6 alkynyl, and most preferably C2-C4 alkynyl. Examples of alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-, 2- or 3-butynyl, etc. The alkynyl can be substituted or unsubstituted.

[0074] "Cycloalkyl" refers to saturated or partially saturated monocyclic, fused-ring, bridged-ring, and spiro carbon rings. Preferably C3-C 12 cycloalkyl, more preferably C3-C8 cycloalkyl, and most preferably C3-C6 cycloalkyl. Examples of monocyclic cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptatrienyl, cyclooctyl, etc., preferably cyclopropyl and cyclohexenyl. The cycloalkyl can be optionally substituted or unsubstituted.

[0075] "Heterocyclic group", "heterocycloalkyl", "heterocycle" or "heterocyclic" are used interchangeably in this application and all refer to non-aromatic heterocyclic groups in which one or more ring-forming atoms are heteroatoms such as boron, oxygen, nitrogen, sulfur atoms, etc., including monocyclic, polycyclic, fused-ring, bridged-ring, and spiro rings. Preferably having a 5- to 7-membered monocyclic ring or a 7- to 10-membered bicyclic or tricyclic ring, which may contain 1, 2 or 3 atoms selected from nitrogen, oxygen and / or sulfur. Examples of "heterocyclic group" 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 heterocyclic group can be substituted or unsubstituted.

[0076] "Aryl" or "aromatic" refers to a carbocyclic aromatic system containing one or two rings, where the rings can be connected in a fused manner. The term "aryl" includes monocyclic or bicyclic aryl, such as phenyl, naphthyl, and aromatic groups of tetrahydronaphthyl. Preferably the aryl is C6-C 10 aryl, more preferably the aryl is phenyl and naphthyl, and most preferably phenyl. The aryl can be substituted or unsubstituted.

[0077] "Heteroaryl" refers to an aromatic 5- to 6-membered monocyclic ring or an 8- to 10-membered bicyclic ring, which may contain 1 to 4 atoms selected from nitrogen, oxygen and / or sulfur. Examples of "heteroaryl" include, but are not limited to, furyl, pyridyl, 2-oxo-1,2-dihydropyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, isoxazolyl, oxazolyl, oxadiazolyl, imidazolyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, isothiazolyl, 1,2,3-thiadiazolyl, benzodioxolyl, benzothienyl, benzimidazolyl, indolyl, isoindolyl, 1,3-dioxo-isoindolyl, quinolinyl, indazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl. The heteroaryl can be substituted or unsubstituted.

[0078] "Alkoxy" refers to the group of (alkyl-O-). Among them, the definition of alkyl can be found in this article. C1-C6 alkoxy is preferred. Examples include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.

[0079] "Fused ring" refers to a polycyclic group in which two or more cyclic structures share a pair of atoms with each other. One or more rings may contain one or more double bonds, but at least one ring does not have a fully conjugated π-electron aromatic system. At the same time, at least one ring has a fully conjugated π-electron aromatic system, in which 0, one or more of the ring atoms are heteroatoms selected from nitrogen, oxygen or S, and the remaining ring atoms are carbon. The fused ring preferably includes a bicyclic or tricyclic fused ring, and the bicyclic fused ring is preferably a fused ring of an aryl or heteroaryl and a monocyclic heterocyclic group or a monocyclic cycloalkyl group. It is preferably 7 to 14 yuan, more preferably 8 to 10 yuan.

[0080] "Epoxide" refers to a compound characterized by the presence of at least one ring ether group, that is, a compound in which an ether oxygen atom is connected to two adjacent carbon atoms to form a cyclic structure. This term is intended to include monocyclic epoxides, polycyclic epoxides (having two or more epoxy groups) and epoxy-terminated prepolymers. "Hydroxyl" refers to the -OH group.

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

[0082] "Amino" refers to -NH2.

[0083] "Cyano" refers to -CN.

[0084] "Nitro" refers to -NO2.

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

[0086] "Hydroxyalkyl" refers to an alkyl group substituted by a hydroxyl group.

[0087] "Aminoalkyl" refers to an alkyl group substituted by an amino group.

[0088] "Haloalkyl" refers to an alkyl group substituted by a halogen.

[0089] "Alkylamino" refers to an amino group substituted by an alkyl group.

[0090] "Alkoxy" refers to a hydroxyl group substituted by an alkyl group.

[0091] "Substituted" means that one or more, preferably up to 5, more preferably 1 to 3 hydrogen atoms in a group are independently replaced by the corresponding number of substituents. It goes without saying that the substituents are only at their possible chemical positions, and those skilled in the art can determine (by experiment or theory) what substitutions are possible or impossible without much effort. For example, an amino or hydroxyl group with a free hydrogen may be unstable when combined with a carbon atom having an unsaturated (such as olefinic) bond.

[0092] As used in this specification, "substituted" or "substitution", unless otherwise specified, means that a group can be substituted by one or more substituents selected from the following: alkyl, alkoxy, alkylthio, alkylamino, halogen, mercapto, hydroxyl, nitro, cyano, cycloalkyl, heterocyclic group, aryl, heteroaryl, cycloalkoxy, heterocycloalkoxy, cycloalkylthio, heterocycloalkylthio, amino, haloalkyl, hydroxyalkyl;

[0093] This application provides a phosphorus-containing aromatic polyester, the structural formula of which is shown in Formula I,

[0094]

[0095] Formula I

[0096] wherein R2, R3, and R4 are each independently alkyl, aryl, cycloalkyl, or alkoxy, and the alkyl, aryl, cycloalkyl, or alkoxy may optionally be further substituted by one or more substituents selected from deuterium, tritium, alkyl, haloalkyl, halogen, amino, hydroxyl, cyano, formyl, acetyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or alkoxy;

[0097] R1 and R5 are each independently or

[0098] R6 and R7 are each independently hydrogen, halogen, aryl, phenoxy, alkyl, carboxyl, amino, hydroxyl, cyano, amido, alkoxy, alkylamino, mercapto, cycloalkyl, heterocycloalkyl, heteroaryl, and the aryl, phenoxy, alkyl, amido, alkoxy, alkylamino, mercapto, cycloalkyl, heterocycloalkyl, heteroaryl may optionally be further substituted by one or more substituents selected from halogen, aryl, phenoxy, alkyl, carboxyl, amino, hydroxyl, cyano, amido, alkoxy, alkylamino, mercapto, cycloalkyl, heterocycloalkyl, heteroaryl; or, the alkyl may optionally be further substituted by one or more branched alkyls containing at least 1 carbon atom, and the alkoxy may optionally be further substituted by one or more branched alkoxys 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, R6 and R7 are each independently hydrogen, a hydroxyl group, or an alkyl group having 1 to 6 carbon atoms.

[0101] In some embodiments of the present application, R6 is hydrogen.

[0102] In some embodiments of the present application, R7 is hydrogen.

[0103] In some embodiments of the present application, R6 is hydrogen and R7 is hydrogen.

[0104] In some embodiments of the present application, R2 and R4 are each independently a divalent aryl group having 6 to 12 carbon atoms, a divalent linear or branched alkylene group having 1 to 8 carbon atoms, or a divalent linear or branched alkenylene group having 2 to 8 carbon atoms; the divalent aryl group having 6 to 12 carbon atoms is optionally further substituted by one or more alkyl or alkoxy groups having at most 6 carbon atoms.

[0105] In some embodiments of the present application, R2 and R4 are each independently a divalent aryl group having 6 to 12 carbon atoms, more preferably a divalent aryl group having 6 to 8 carbon atoms.

[0106] In some embodiments of the present application, R3 is selected from one of the following: R3 is a divalent cycloalkyl group having 6 to 18 carbon atoms, optionally further substituted by one or more divalent aryl groups having 6 to 12 carbon atoms.

[0107] In some embodiments of the present application, R3 is selected from one of the following:

[0108] where h is 1 or 2;

[0109] R8 is a hydrogen atom,

[0110] R9 is 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, R3 is .

[0116] In some embodiments of the present application, n is from 1 to 10. For example, n is one 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 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 for reaction and separating to obtain the phosphorus-containing aromatic polyester.

[0130] In some embodiments of the present application, the phthaloyl chloride is any one of isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride, isophthalic diacetyl chloride, phthalic diacetyl chloride, terephthalic diacetyl chloride, isophthalic dipropionyl chloride, phthalic dipropionyl chloride, terephthalic dipropionyl chloride, isophthalic dibutyryl chloride, phthalic dibutyryl chloride, terephthalic dibutyryl chloride, isophthalic dipentanoyl chloride, phthalic dipentanoyl chloride, terephthalic dipentanoyl chloride, isophthalic dihexanoyl chloride, phthalic dihexanoyl chloride, terephthalic dihexanoyl chloride, isophthalic diheptanoyl chloride, phthalic diheptanoyl chloride, terephthalic diheptanoyl chloride, isophthalic dioctanoyl chloride, phthalic dioctanoyl chloride, terephthalic dioctanoyl chloride, isophthalic dinonanoyl chloride, phthalic dinonanoyl chloride, terephthalic dinonanoyl chloride, isophthalic didecanoyl chloride, phthalic didecanoyl chloride, terephthalic didecanoyl chloride.

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

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

[0133] 。

[0134] In some embodiments of the present application, the phosphorus-containing monophenol compound is or 。

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

[0136]

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

[0138] In some embodiments of the present application, under nitrogen protection, in a three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, isophthaloyl chloride and toluene are added, and nitrogen displacement is carried out under reduced pressure. After the system is completely dissolved, a phosphorus-containing monophenol compound and dicyclopentadiene phenolic resin are added, and nitrogen displacement is carried out under reduced pressure. After complete dissolution, tetrabutylammonium bromide is added, and the system temperature is controlled within 60 °C. About 400 g of 20% aqueous sodium hydroxide solution is added dropwise over about 3 h; stirring is continued for 1.0 h under the above conditions. After the reaction is completed, the mixture is allowed to stand for liquid separation to remove the aqueous layer; deionized water is added to the toluene phase in which the reactants are dissolved, and stirring is carried out for about 15 min, followed by standing for liquid separation to remove the aqueous layer; this operation is repeated until the pH of the aqueous layer is about 7.0, and the water is removed by decantation to obtain a phosphorus-containing active ester / toluene solution.

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

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

[0141] In some embodiments of the present application, the thermosetting resin is one or more of an epoxy compound without halogen, an epoxy compound without phosphorus, and an epoxy compound with phosphorus.

[0142] In some embodiments of the present application, relative to 100 parts by weight of the epoxy resin, the phosphorus-containing aromatic polyester is 10 to 150 parts by weight. For example, relative to 100 parts by weight of the epoxy resin, the phosphorus-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 therebetween.

[0143] In some embodiments of the present application, it is used in any one of coating formulations, encapsulants, composite materials, adhesives, moldings, adhesive sheets or laminates.

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

[0145] In some embodiments of the present application, the article is used for lead-free soldering or electronic devices.

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

[0147] In some embodiments of the present 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 adhesive 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, then treating the prepreg at an elevated temperature to promote partial curing to the 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 which is a printed circuit board made by the above process.

[0154] Examples

[0155] Example 1

[0156] Under nitrogen protection, in a three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, add isophthaloyl chloride (203 g, 1.0 mol, the number of moles of acyl chloride group is 2.0) and 1338 g of toluene. Conduct nitrogen replacement under reduced pressure. After the system is completely dissolved, add a phosphorus-containing monophenol compound (207 g, 0.67 mol), 220 g of dicyclopentadiene phenolic resin (the number of moles of phenolic hydroxyl group is 1.33). Conduct nitrogen replacement under reduced pressure. After complete dissolution, add 1.12 g of tetrabutylammonium bromide. Control the system temperature within 60 °C and slowly add 400 g of 20% sodium hydroxide aqueous solution dropwise over about 3 h; continue stirring under the above conditions for 1.0 h. After the reaction is completed, let it stand and separate the liquid, removing the aqueous layer; add deionized water to the toluene phase in which the reactants are dissolved, stir for about 15 min, let it stand and separate the liquid, and remove the aqueous layer; repeat this operation until the pH of the aqueous layer is about 7.0, and dehydrate and remove the water through a decanter to 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 as shown in Formula 1.

[0158]

[0159] Formula 1

[0160] The reaction process is as follows:

[0161]

[0162] Example 2

[0163] Under nitrogen protection, in a three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, add isophthaloyl chloride (203 g, 1.0 mol, the number of moles of acyl chloride group is 2.0) and 1338 g of toluene. Conduct nitrogen replacement under reduced pressure. After the system is completely dissolved, add a phosphorus-containing monophenol compound (308 g, 1.0 mol), 165 g of dicyclopentadiene phenolic resin (the number of moles of phenolic hydroxyl group is 1.0). Conduct nitrogen replacement under reduced pressure. After complete dissolution, add 0.1 g of tetrabutylammonium bromide. Control the system temperature within 60 °C and slowly add 400 g of 20% sodium hydroxide aqueous solution dropwise over about 3 h; continue stirring under the above conditions for 1.0 h. After the reaction is completed, let it stand and separate the liquid, removing the aqueous layer; add deionized water to the toluene phase in which the reactants are dissolved, stir for about 15 min, let it stand and separate the liquid, and remove the aqueous layer; repeat this operation until the pH of the aqueous layer is about 7.0, and dehydrate and remove the water through a decanter to obtain a phosphorus-containing active ester / toluene solution with a solid content of about 65%.

[0164] The structural formula of the phosphorus-containing monophenol compound is as shown in Formula 1.

[0165]

[0166] Formula 1

[0167] The reaction process is as follows:

[0168]

[0169] Example 3

[0170] Under nitrogen protection, in a three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, isophthaloyl chloride (203 g, 1.0 mol, the number of moles of acyl chloride groups is 2.0) and 1338 g of toluene are added. The system is evacuated and replaced with nitrogen. After the system is completely dissolved, a phosphorus-containing monophenol compound (197 g, 0.67 mol) and 220 g of dicyclopentadiene phenolic resin (the number of moles of phenolic hydroxyl groups is 1.33) are added. The system is evacuated and replaced with nitrogen again. After complete dissolution, 1.12 g of tetrabutylammonium bromide is added. The temperature of the system is controlled within 60 °C, and about 400 g of 20% sodium hydroxide aqueous solution is added dropwise over about 3 h. Under the above conditions, stirring is continued for 1.0 h. After the reaction is completed, the mixture is allowed to stand and separated, and the aqueous layer is removed; deionized water is added to the toluene phase in which the reactants are dissolved, stirred for about 15 min, allowed to stand and separated, and the aqueous layer is removed; this operation is repeated until the pH of the aqueous layer is about 7.0, and the water is removed by dehydration through a decanter to obtain a phosphorus-containing active ester / toluene solution with a solid content of about 65%.

[0171] The structural formula of the phosphorus-containing monophenol compound is as shown in Formula 2.

[0172]

[0173] Formula 2

[0174] The reaction process is as follows:

[0175]

[0176] Comparative Example 1

[0177] Under nitrogen protection, in a three-necked flask equipped with a mechanical stirrer, a thermometer, and a condenser, add isophthaloyl chloride (203 g, 1.0 mol, the number of moles of acyl chloride groups is 2.0) and 1338 g of toluene. Replace the nitrogen under reduced pressure. After the system is completely dissolved, add α-naphthol (96.0 g, 0.67 mol) and 220 g of dicyclopentadiene phenolic resin (the number of moles of phenolic hydroxyl groups is 1.33). Replace the nitrogen under reduced pressure. After complete dissolution, add 1.12 g of tetrabutylammonium bromide. Control the system temperature within 60 °C and slowly add 400 g of 20% aqueous sodium hydroxide solution dropwise over about 3 h; continue stirring for 1.0 h under the above conditions. After the reaction is completed, let it stand and separate the liquid to remove the aqueous layer; add deionized water to the toluene phase in which the reactants are dissolved, stir for about 15 min, let it stand and separate the liquid to remove the aqueous layer; repeat this operation until the pH of the aqueous layer is about 7.0, and dehydrate to remove water through a decanter to obtain an active ester / toluene solution with a solid content of about 65%.

[0178]

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

[0180] Comparative Example 2

[0181] Synthesize the following structure according to the method of Example 2 in CN108350157A

[0182]

[0183] The specific synthesis method is as follows: DOPO-HQ-isophthaloyl-ester (pentamer mixture): Mix DOPO-HQ (71.9 g, 221.6 mmol) and pyridine (25 mL, 310.5 mmol) in 200 mL of chloroform. Dropwise add isophthaloyl chloride (30.0 g, 147.8 mmol) in 50 mL of chloroform. Heat the suspension to the reflux temperature and form a homogeneous solution. After 3 h, cool the solution to room temperature and wash it with 0.5 M aqueous HCl solution and saturated brine. Collect the organic layer and dry it over sodium sulfate. Remove the solvent under vacuum. The final product is a white solid.

[0184] Comparative Example 3.

[0185] Synthesize the following structure according to the method of Example 1 in CN109983055B

[0186]

[0187] The specific method is as follows: Under nitrogen protection, in a 1000 mL three-necked flask equipped with a mechanical stirrer (300 r / min), a thermometer, and a condenser, add DOPO-HQ (211.6 g, 0.65 mol) and 500 g of acetic anhydride. Heat up to 140 °C until the system is completely dissolved, and reflux for 2 h. The solution changes from purple to light yellow. Cool down to 100 °C, add 0.025 g of potassium acetate and isophthalic acid (70 g, 0.42 mol). When heated up to 240 °C, the system reaches a completely dissolved state. After stabilizing for 1 h, slowly increase the pressure to -0.096 to 0.098 MPa to remove the excess acetic anhydride and by-product acetic acid. After reacting for a certain time of 2 h, pour the product into an aluminum plate while it is still hot. The resin quickly cools to light brown, grind it and remove the residual acetic acid in a vacuum oven at 137 °C, dry it, and the yield is about 98%.

[0188] The specific process is as follows:

[0189]

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

[0191] (1) Structure characterization: Use nuclear magnetic resonance (NMR) and Fourier transform infrared spectrometer (FT-IR) to chemically characterize the provided phosphorus-containing monophenol monomer; its NMR spectrum and FTIR spectrum are shown in Figure 1 and Figure 2 .

[0192] (2) Molecular weight test: Use a gel permeation chromatography system to determine the weight-average molecular weight (M w ) and molecular weight distribution of the phosphorus-containing active ester compound provided in Example 1, 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: Crush the solid resin into small particles. Take 10 g of the solid resin, add 100 mL of solvent and mix, seal it in a polyethylene plastic bottle, and dissolve it by ultrasonic wave; the solvents are: methyl ethyl ketone, toluene, tetrahydrofuran, N,N-dimethylformamide. Examine whether the resin is completely dissolved under the condition of 60 wt.% solid content. It is found that the phosphorus-containing active ester compounds prepared in Examples 1-3 can be completely dissolved in methyl ethyl ketone, toluene, tetrahydrofuran, and N,N-dimethylformamide. Place the completely dissolved liquid resin in a refrigerator at 5 °C for 7 days, and it is found that there are no obvious resin particles precipitated, indicating that the phosphorus-containing active ester compound has good dissolution stability in methyl ethyl ketone, toluene, tetrahydrofuran, and N,N-dimethylformamide.

[0194] Solubility test results

[0195] Table 1

[0196]

[0197] Experimental Example 1: Small-scale epoxy curing experiment of the active ester compounds in Example 1 and Example 3

[0198] On a small scale, the phosphorus-containing active ester compounds synthesized in Example 1 and Example 3 were combined with epoxy resin and cured (material information is shown in Table 2). The samples were cured using SQDN-302 and 0.12 wt.% of DMAP as a catalyst; the epoxy curing system was cured at 165-195 °C for 2 h and post-cured at 180-210 °C for 1 h, and the heat resistance of the samples was studied by DSC. To prepare varnish castings for D k and D f measurements, the phosphorus-containing active ester compound was blended with SQDN-302 and the catalyst DMAP (abbreviated as resin); the aluminum foil was coated on one side with the sample-epoxy blend, and after coating, the aluminum foil was air-dried and then B-staged at 155 °C (3 min 50 s); the epoxy was peeled off from the foil and then formed 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 the small-scale curing experiment

[0200]

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

[0202]

[0203] In Examples 1 and 3, the phosphorus-containing active ester compound was used as a curing agent for epoxy resin SQDN-302 laminate applications. The solid content was maintained at 58% by adding MEK solvent, and the composition content is shown in Table 4. The addition of the catalyst was controlled by adding a small increment of DMAP solution (0.5 wt.% solid solution 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 the flame retardancy performance, V-0 means that after two 10-second combustion tests on the sample, the flame extinguishes within 30 seconds and no burning substances can fall off. V-1 means that after two 10-second combustion tests on the sample, the flame extinguishes within 60 seconds and no burning substances can fall off. Additionally, it can be seen that the Tg of the phosphorus-containing active ester compound in Example 1 is higher than that in Example 3. The flame retardancy of the phosphorus-containing active ester compounds in Examples 1 and 3 is higher than that of the compound in Comparative Example 1.

[0204] Table 4 Epoxy Resin Laminate Formulation

[0205]

[0206] The glass fabric was continuously passed through a trough containing the varnish and through a squeezing roller to obtain a uniform coating; the coated fabric section was hung overnight in a fume hood to slowly evaporate the solvent. Preparation method of prepreg: The resin-coated glass fabric was dried in a preheated air circulation oven at 160 °C for 4 min 30 s to obtain a resin flow of less than 20%; the resin content was controlled at 50-55% (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, and the collected resin was measured for gel time on a hot plate at 171 °C. The properties of the prepreg are shown in Table 5.

[0207] Table 5 Properties of Prepreg

[0208]

[0209] Four circular stacks of prepregs with a diameter of 25 mm were placed between disposable aluminum plates, and the rheological behavior of the B-stage prepreg was studied 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 achieve good wetting of the glass cloth. The sizing solution was formulated according to the above ratio, impregnated the fiberglass cloth, and dried at 160 °C for 5 min to make a semi-cured sheet (PP). The PP was stacked in 6 layers and copper foils were attached to both sides, and then placed in a vacuum hot press. A pressure of 20 kgf / cm 2 was applied at 200 °C for 90 min, the pressure was released, and it was naturally cooled to room temperature to obtain the laminate.

[0210] The T of the multi-layer laminate was measured by a dynamic thermomechanical analyzer at a rate of 5 °C / min in a single-cantilever beam mode. g It was 179 °C.

[0211] The specimens for autoclave testing were cut from the epoxy laminate containing the phosphorus active ester compound and placed in an autoclave at 121 °C and 15 psi for 30 min; the water absorption of the specimens was approximately 0.07 - 0.14 wt.%, and none of the three specimens showed any blistering. They were rated as condition (status) 5 according to the IPC test standard. The properties of the prepreg and the laminate are shown in Tables 6 and 7 respectively.

[0212] Table 6

[0213]

[0214] Table 7

[0215] 。

Claims

1. A phosphorus-containing aromatic polyester, whose structural formula is shown in Formula I, ； Formula I R2 and R4 are each independently a divalent aryl group having 6 to 12 carbon atoms; R3 is a divalent cycloalkyl group having 6 to 18 carbon atoms, optionally further substituted by one or more divalent aryl groups having 6 to 12 carbon atoms; R1 and R5 are each independently or ; n is a positive integer greater than or equal to 1; R6 and R7 are each independently hydrogen, a hydroxyl group, or an alkyl group having 1 to 6 carbon atoms.

2. The phosphorus-containing aromatic polyester according to claim 1, wherein R2 and R4 are each independently a divalent aryl group having 6 to 8 carbon atoms.

3. The phosphorus-containing aromatic polyester according to claim 1, wherein R3 is selected from one of the following: ； wherein, h is 1 or 2; R8 is a hydrogen atom, R9 is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group; R 10 is a hydrogen atom, a methyl group or an ethyl group; R 11 is a hydrogen atom or an alkyl 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.

4. The phosphorus-containing aromatic polyester according to claim 1, wherein n is 1 to 10.

5. The phosphorus-containing aromatic polyester according to claim 1, wherein Formula I is selected from the following structures: Formula I-1 Formula I-2 Formula I-3 Formula I-4.

6. The method for preparing the phosphorus-containing aromatic polyester according to any one of claims 1 to 5, which comprises the following steps: Dissolve phthaloyl chloride in an organic solvent, then add a phosphorus-containing monophenol compound and a bisphenol monomer, heat and react, and separate to obtain the phosphorus-containing aromatic polyester.

7. The preparation method according to claim 6, wherein the phthaloyl chloride is selected from any one of isophthaloyl chloride, phthaloyl chloride, terephthaloyl chloride, isophthalic diacetyl chloride, phthalic diacetyl chloride, terephthalic diacetyl chloride, isophthalic dipropionyl chloride, phthalic dipropionyl chloride, terephthalic dipropionyl chloride, isophthalic dibutyryl chloride, phthalic dibutyryl chloride, terephthalic dibutyryl chloride, isophthalic dipentanoyl chloride, phthalic dipentanoyl chloride, terephthalic dipentanoyl chloride, isophthalic dihexanoyl chloride, phthalic dihexanoyl chloride, terephthalic dihexanoyl chloride, isophthalic diheptanoyl chloride, phthalic diheptanoyl chloride, terephthalic diheptanoyl chloride, isophthalic dioctanoyl chloride, phthalic dioctanoyl chloride, terephthalic dioctanoyl chloride, isophthalic dinonanoyl chloride, phthalic dinonanoyl chloride, terephthalic dinonanoyl chloride, isophthalic didecanoyl chloride, phthalic didecanoyl chloride, terephthalic didecanoyl chloride.

8. An epoxy resin composition, which comprises the phosphorus-containing aromatic polyester according to any one of claims 1 to 5 or the phosphorus-containing aromatic polyester prepared by the method according to any one of claims 6 to 7, a thermosetting resin, and a curing agent.

9. The composition according to claim 8, wherein The thermosetting resin is an epoxy resin.

10. The composition according to claim 9, wherein, The thermosetting resin is one or more of a halogen-free epoxide, a phosphorus-free epoxide, and a phosphorus-containing epoxide.

11. The composition according to claim 9, wherein, Relative to 100 parts by weight of the epoxy resin, the phosphorus-containing aromatic polyester is 10 to 150 parts by weight.

12. The composition according to any one of claims 8 to 11 is used for any one of a coating formulation, an encapsulant, a composite material, an adhesive, a molded article, a bonding sheet, or a laminate.

13. An article, which comprises the composition according to any one of claims 8 to 12.

14. The article according to claim 13, wherein, The article is used for lead-free soldering or electronic devices.

15. The article according to claim 13, wherein The article is a copper foil.

16. The article according to claim 13, wherein, The article is a printed circuit board.

17. A prepreg, which comprises the composition according to any one of claims 10 to 11.

18. A laminate or adhesive sheet, which comprises the composition according to any one of claims 8 to 12.

19. A printed wiring board, which comprises the prepreg according to claim 17.

20. A printed wiring board, which comprises the laminate according to claim 18.

21. A process for manufacturing the laminate according to claim 18, which comprises impregnating the composition into a filler material to form a prepreg, subsequently treating the prepreg at an elevated temperature to promote partial curing to the B-stage and then laminating two or more of the prepregs at an elevated pressure and temperature to form a laminate.

22. A printed circuit board, which is a printed circuit board made by the process of claim 21.

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