Preparation method and application of phosphorus-containing active ester compound

Abstract

The invention relates to the technical field of epoxy resin additives, and particularly provides a preparation method and application of a phosphorus-containing active ester compound. The melting preparation method of the phosphorus-containing active ester compound comprises the following steps: mixing a phosphorus-containing bisphenol monomer and an acetylation reagent, dissolving, and carrying out reflux reaction; further adding a catalyst and acid, heating, carrying out esterification reaction under a vacuum condition, and cooling to obtain a solid product; and leaching or dissolving the reaction product with an organic solvent, settling, carrying out solid-liquid separation, and carrying out vacuum drying to obtain the phosphorus-containing active ester compound. The phosphorus-containing active ester compound is prepared by a melting method or a low-temperature solution polymerization method, and a product purification post-treatment step is added in the production process, so that the product with more excellent performance and good appearance is prepared by a low-cost and efficient method.

Description

Technical Field

[0001] This application relates to the technical field of epoxy resin additives, and specifically relates to a preparation method and application of a phosphorus-containing active ester compound. 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, 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. However, in the existing rigid copper clad laminates, epoxy resin systems are generally cured by compounds such as amines, acid anhydrides, and phenolics. Due to the introduction of polar hydroxyl groups during the curing process, the dielectric constant and dielectric loss of the cured products are generally high, and they cannot meet the requirements of low dielectric and low moisture absorption properties required for the design of printed circuit boards.

[0003] The reaction between the active ester compound and epoxy resin will not produce polar hydroxyl groups, which can meet the requirements of low dielectric and low water absorption rate of printed circuit boards. However, most active ester compounds generally do not have flame retardant elements and have insufficient flame retardant performance, such as m-tris-phenol formate, m-tris-phenol acetate, phenolic active ester, etc., which limit their application in the field of high heat resistance and halogen-free flame retardant copper clad laminates. The related prior art discloses a phosphorus-containing active ester compound, mainly referring to a compound with the following structure of formula (Ι):

[0004]

[0005] Where Ac is an acetyl group. The epoxy resin composition cured by the above phosphorus-containing active ester compound exhibits characteristics such as high heat resistance, low coefficient of thermal expansion, good dielectric properties, and flame retardancy. However, the by-products of this phosphorus-containing active ester compound are relatively many, including about 3% of DOPO-HQ-monoacetate, about 3% of DOPO-HQ-acetate-terephthalate, and about 10% of DOPO-HQ-diacetate. Among them, the terminal carboxyl group and hydroxyl group in DOPO-HQ-monoacetate and DOPO-HQ-acetate-terephthalate will introduce polar hydroxyl groups during the curing process with epoxy resin, resulting in generally high dielectric constant and dielectric loss of the epoxy cured product. The capping group acetyl group is unstable and prone to hydrolysis. Even the solid resin without solvent will slowly hydrolyze during storage, and the hydrolyzed acetic acid will accelerate the hydrolysis process. Moreover, the hydrolysis (or acidolysis) produces acetic acid and phenolic hydroxyl group-containing compounds, which are not conducive to the moisture resistance, dielectric properties, and heat resistance of the cured product.

[0006] In addition, the alkyl group capped by the acetyl group during the 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. For example, the prior art discloses an active ester curing agent compound for thermosetting resins. In this study, too high a content of DOPO-HQ-diacetate that did not participate in the esterification reaction (up to about 10%) would seriously exacerbate the occurrence of the above phenomenon. Therefore, reducing by-products is crucial for improving the application properties such as the dielectric properties, heat and humidity resistance, heat resistance, and mechanical properties of the epoxy system cured by the phosphorus-containing active ester compound. Summary of the Invention

[0007] The present application provides a preparation method and application of a phosphorus-containing active ester compound. The present application prepares the phosphorus-containing active ester compound by a melting method, and adds a step of treating with an organic solvent in the product purification to prepare a product with more excellent performance and good appearance by a low-cost and efficient method. Compared with the synthesis of active esters by the solvent method, a large amount of organic solvents are used in the solvent method, polluting the environment, or most polymerization reactions use acyl chloride monomers that are easy to hydrolyze and have a relatively high price; while the present application can effectively avoid the use of a large amount of organic solvents and avoid using acyl chloride monomers through the melting transesterification method, which is easy to scale up production.

[0008] The present application relates to the following content:

[0009] In a first aspect, the present application provides a melting preparation method of a phosphorus-containing active ester compound, which comprises the following steps:

[0010] Mix and dissolve a phosphorus-containing bisphenol monomer and an acetylation reagent, and carry out a reflux reaction;

[0011] Cool the solution after the reflux reaction, add a catalyst and a dibasic acid, heat up and carry out an esterification reaction under vacuum conditions, and then cool to obtain a reaction product;

[0012] Wash the reaction product with an organic solvent or dissolve it in an organic solvent and then sediment, carry out solid-liquid separation, and dry to obtain the phosphorus-containing active ester compound;

[0013] Wherein, when the reaction product is washed with an organic solvent, the organic solvent is selected from any one or more of anhydrous methanol, anhydrous ethanol, acetone, tetrahydrofuran, 1,4-dioxane, ethylene glycol monoethyl ether, and ethyl acetate; preferably anhydrous methanol and / or anhydrous ethanol;

[0014] Wherein, dissolving the reaction product in an organic solvent and then sedimenting comprises the following steps: dissolving the reaction product in a first organic solvent and then sedimenting with a second organic solvent;

[0015] Among them, the first organic solvent is selected from any one or more of dichloromethane, chloroform, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, and methyl ethyl ketone;

[0016] Among them, the second organic solvent is selected from any one or more of aqueous acid solution, saturated brine solution, deionized water, absolute methanol, absolute ethanol, acetone, ethyl acetate, and acetonitrile; preferably absolute ethanol and absolute methanol, more preferably absolute ethanol.

[0017] Preferably, the volume of the second organic solvent is at least 1.5 times the volume of the first organic solvent.

[0018] Optionally, the phosphorus-containing bisphenol monomer is selected from any one or more of the following group: DOPO-HQ, DOPO-NQ, 2DOPO-2PhOH, or other monomers containing DOPO or phosphate ester structure;

[0019] And / or, the acetylation reagent is selected from any one or more of the following group: acetyl chloride, acetyl bromide, and acetic anhydride, preferably acetic anhydride.

[0020] Optionally, when the phosphorus-containing bisphenol monomer and the acetylation reagent are mixed and dissolved, the dissolution temperature is 120-150 °C;

[0021] And / or, the reflux reaction time is 1-5 h.

[0022] Optionally, when the solution after the reflux reaction is cooled, the temperature is reduced to 25-140 °C, preferably 80-120 °C;

[0023] And / or, in the esterification reaction under vacuum conditions after heating, the temperature is raised to 200-260 °C;

[0024] And / or, the esterification reaction time is 2-20 h.

[0025] Optionally, the catalyst is selected from any one or more of the following group: sodium methoxide, zinc oxide, sodium hydroxide, p-toluenesulfonic acid, sulfuric acid, sodium acetate, and potassium acetate;

[0026] And / or, the dicarboxylic acid is selected from any one or more of the following group: terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, phthalic acid, and oxalic acid.

[0027] Optionally, the drying temperature is 50-150 °C; and / or, the drying time is 2-48 h.

[0028] In a second aspect, the present application provides a method for preparing a low-temperature solution of a phosphorus-containing active ester compound, which comprises the following steps:

[0029] Under an inert gas atmosphere, a phosphorus-containing bisphenol monomer, a third organic solvent and an acid-binding agent are mixed evenly, and then an acyl chloride monomer and a capping monomer are added. After heating the reaction until it is completed, a reaction solution is obtained;

[0030] The reaction solution and a precipitating agent are mixed to precipitate white flocculates. After solid-liquid separation and vacuum drying, the phosphorus-containing active ester compound is obtained.

[0031] Optionally, the addition of the acyl chloride monomer and the capping monomer specifically includes the following steps: adding a first mixed solution containing the acyl chloride monomer and the capping monomer, and the molar ratio of the phosphorus-containing bisphenol monomer to the acyl chloride monomer is 1.1-3:1;

[0032] Alternatively, the addition of the acyl chloride monomer and the capping monomer specifically includes the following steps: adding a second mixed solution containing the acyl chloride monomer, and after pre-reaction, filtering to obtain a pre-reaction solution;

[0033] Adding the capping monomer to the pre-reaction solution;

[0034] Wherein, the molar ratio of the phosphorus-containing bisphenol monomer to the acyl chloride monomer is 2-3:1.

[0035] Optionally, the phosphorus-containing bisphenol monomer is selected from any one or more of the following groups: DOPO-HQ, DOPO-NQ, 2DOPO-2PhOH, or other monomers containing DOPO or phosphate ester structures;

[0036] And / or, the acid-binding agent is selected from any one or more of the following groups: triethylamine, pyridine, KOH, NaOH, N,N-dimethylaniline, sodium carbonate, potassium carbonate, and calcium oxide;

[0037] And / or, the third organic solvent is selected from any one or more of the following groups: dichloromethane, chloroform, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, n-hexane, cyclohexane, n-heptane, n-decane, 1,1,2,2-tetrachloroethane, toluene, xylene, acetone, dioxane.

[0038] Optionally, the heating reaction time is 1-10 h;

[0039] And / or, the heating reaction temperature is 20-120 °C.

[0040] Optionally, the acyl chloride monomer is selected from any one or two of the following groups: isophthaloyl chloride, terephthaloyl chloride, malonyl chloride;

[0041] And / or, the mixed solution containing the acyl chloride monomer and the capping monomer contains a fourth organic solvent, and the fourth organic solvent is selected from any one or more of the following groups: dichloromethane, chloroform, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, n-hexane, cyclohexane, n-heptane, n-decane, 1,1,2,2-tetrachloroethane, toluene, xylene, acetone, dioxane;

[0042] And / or, the capping monomer is selected from any one or more of the following groups: phenol, o-cresol, m-cresol, p-cresol, α-naphthol, β-naphthol, acetyl chloride, acetyl bromide, and acetic anhydride.

[0043] Optionally, the precipitant is selected from any one or more of the following groups: ketones, alcohols, ethers, etc., preferably any one or more of acid aqueous solution, saturated brine solution, deionized water, anhydrous methanol, anhydrous ethanol, acetone, tetrahydrofuran, acetonitrile, 1,4-dioxane, ethylene glycol monoethyl ether, ethyl acetate, preferably anhydrous ethanol and anhydrous methanol, more preferably anhydrous ethanol.

[0044] Optionally, the temperature of the vacuum drying is 50-150 °C;

[0045] And / or, the time of the vacuum drying is 2-48 h.

[0046] In a third aspect, the present application provides an epoxy resin composition, which comprises an epoxy resin, and a phosphorus-containing active ester compound obtained by the melting preparation method of the above phosphorus-containing active ester compound, and / or a phosphorus-containing active ester compound obtained by the low-temperature solution preparation method of the above phosphorus-containing active ester compound.

[0047] Optionally, relative to 100 parts by weight of the epoxy resin, 10-150 parts by weight of the phosphorus-containing active ester compound is contained.

[0048] In other aspects, the present application provides an article, which comprises the above epoxy resin composition;

[0049] Preferably, the article is used in lead-free soldering and electronic devices.

[0050] Preferably, the article further comprises a copper foil.

[0051] Preferably, the article is a printed circuit board.

[0052] In other aspects, the present application provides a prepreg, which comprises the above epoxy resin composition.

[0053] In other aspects, the present application provides a laminate, which comprises the above epoxy resin composition.

[0054] In other aspects, the present application provides an adhesive sheet comprising the above epoxy resin composition.

[0055] In other aspects, the present application provides a printed wiring board comprising the above prepreg.

[0056] In other aspects, the present application provides a printed wiring board comprising the above laminate or adhesive sheet.

[0057] In other aspects, the present application provides a method for manufacturing the above laminate, which comprises the following steps:

[0058] Impregnating the epoxy resin composition into a filler to form a prepreg;

[0059] Treating the prepreg under heating to promote partial curing to the B-stage, and then laminating two or more of the prepregs under pressure and heating to form a laminate.

[0060] Advantages of the Invention

[0061] 1. The present application prepares acetyl-terminated phosphorus-containing active ester compounds with low by-product content and narrow molecular weight distribution by the melting method and the solvent method respectively.

[0062] 2. By preparing the phosphorus-containing active ester compound by the melting method, the present application avoids the use of a large amount of organic solvents in the reaction stage compared with the preparation of the phosphorus-containing active ester compound by the solvent method.

[0063] 3. When preparing the phosphorus-containing active ester compound by the melting method, the present application can remove a large amount of low-molecular-weight impurities only by treating the product with a suitable organic solvent, so as to ensure higher product purity, meet the appearance requirements, and be conducive to improving the application properties such as the mechanical properties, dielectric properties, and thermal properties of the epoxy cured product. Description of the Drawings

[0064] Figure 1 . FTIR and GPC spectra of the phosphorus-containing active ester compound provided in Comparative Example 1.

[0065] Figure 2 . FTIR and GPC spectra of the phosphorus-containing active ester compound prepared in Example 2.

[0066] Figure 3 . FTIR and GPC spectra of the phosphorus-containing active ester compound prepared in Example 15.

[0067] Figure 4 . FTIR and GPC spectra of the phosphorus-containing active ester compound prepared in Comparative Example 2. Detailed Description of the Invention

[0068] It should be noted that in the specification and claims, certain terms are used to refer to specific components. Those skilled in the art should understand that technicians may use different nouns to refer to the same component. The specification and claims do not use the difference in nouns as a way to distinguish components, but rather use the difference in the functions of components as the criterion for distinction.

[0069] As used throughout the specification and claims, the terms "comprising" or "including" are open-ended terms and should be interpreted as "including but not limited to". The following description in the specification is the preferred embodiment for implementing the present application, but the description is for the purpose of the general principles of the specification and is not intended to limit the scope of the present application. The scope of protection of the present application shall be subject to what is defined by the appended claims. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

[0070] It should be understood that the embodiments of the present application described herein include embodiments of "consisting of" and / or "consisting essentially of". References herein to a "about" value or parameter include (and describe) variations that are specific to that value or parameter itself. For example, the description of "about X" includes the description of "X".

[0071] As used herein, a reference to a "not" value or parameter generally means and describes a value or parameter "except for". For example, the method is not used to treat cancer of type X, which means the method is used to treat cancers other than type X.

[0072] As used herein, the term "about X - Y" has the same meaning as "about X to about Y".

[0073] As used in this application and the appended claims, the singular forms "a / an" and "the" include plural referents unless the context clearly dictates otherwise. It should also be noted that the claims may be drafted to exclude any optional elements. Thus, this statement is intended as a basis for use in conjunction with the recitation of claim elements using exclusive terms such as "only", "solely", etc., or using a limitation of "not".

[0074] As used herein, the term "and / or" in phrases such as "A and / or B" is intended to include both A and B; A or B; A alone; and B alone. Similarly, as used herein, the term "and / or" in phrases such as "A, B and / or C" is intended to include each of the following embodiments: A, B and C; A, B or C; A or C; A or B; B or C; A and C; A and B; B and C; A alone; B alone; and C alone.

[0075] The low molecular weight components are the components with an elution time of 18 - 20 min in the gel permeation chromatography results.

[0076] ;

[0077] Compound 1, Compound 2, Compound 3

[0078] The method for determining the low molecular weight components is: gel permeation chromatography. Specifically, for example, the dry sample is dissolved in a mixed solvent of DMF and THF, where the sample concentration is 3 - 4 mg / mL, and the volume ratio of DMF to THF is about 1:4; the chromatographic column is a tandem of PLgel 5μm MIXED - D and PLgel 3μm MIXED - E, the mobile phase is a mixed solution of 5 mL / L acetic acid and THF, and the column oven temperature is 40°C.

[0079] The low molecular weight components mainly include the three compounds as shown in the figure above; among them, the content of Compound 1 is about 7 - 15 wt%, such as 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%; the content of Compound 2 is about 1 - 5 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%; the content of Compound 3 is about 1 - 5 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%.

[0080] In a first aspect, the present application provides a method for preparing a phosphorus - containing active ester compound, which comprises the following steps:

[0081] Mix and dissolve the phosphorus - containing bisphenol monomer and the acetylation reagent, and carry out a reflux reaction;

[0082] Cool the solution after the reflux reaction, add a catalyst and a dibasic acid, heat up and carry out an esterification reaction under vacuum conditions, and then cool to obtain a reaction product;

[0083] Wash the reaction product with an organic solvent or dissolve it in an organic solvent and then precipitate, carry out solid - liquid separation, and dry to obtain the phosphorus - containing active ester compound.

[0084] In some embodiments, the molar ratio of the phosphorus - containing bisphenol monomer to the dibasic acid is 1.1 - 1.8:1; for example, it can be 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1 or 1.8:1.

[0085] In some embodiments, when the reaction product is washed with an organic solvent, the organic solvent is selected from ketones, alcohols, ethers, etc., such as any one or more of anhydrous methanol, anhydrous ethanol, acetone, tetrahydrofuran, 1,4-dioxane, ethylene glycol monoethyl ether, and ethyl acetate; preferably anhydrous methanol and / or anhydrous ethanol.

[0086] In some embodiments, when the reaction product is dissolved in an organic solvent and then sedimented, it includes the following steps: dissolving the reaction product in a first organic solvent and then sedimenting with a second organic solvent.

[0087] In some embodiments, the volume of the second organic solvent is at least 1.5 times that of the first organic solvent, such as at least 1.5 times, at least 2 times, at least 2.5 times, at least 3 times, specifically it can be 1.2 times, 1.5 times, 2 times, 2.5 times, 3 times, 4 times, 5 times, 8 times, 10 times or any multiple within the range of at least 1.5 times. A product with better appearance can be obtained by this method; for example, significantly reducing or avoiding undesirable situations in terms of the color of the product, and undesirable colors such as the product turning yellow, turning brown, etc.

[0088] In some embodiments, the first organic solvent is selected from any one or more of the following groups: high-boiling solvents such as dichloromethane, chloroform, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone; in some embodiments, the first organic solvent is selected from any one or more of the following groups: low-boiling solvents such as methyl ethyl ketone, dichloromethane, chloroform, methanol, and ethyl acetate. In some embodiments, the first organic solvent is dichloromethane; in some embodiments, the first organic solvent is chloroform; in some embodiments, the first organic solvent is dimethyl sulfoxide; in some embodiments, the first organic solvent is N,N-dimethylacetamide; in some embodiments, the first organic solvent is N,N-dimethylformamide; in some embodiments, the first organic solvent is methyl ethyl ketone; in some embodiments, dichloromethane; in some embodiments, the first organic solvent is chloroform; in some embodiments, the first organic solvent is methanol; in some embodiments, the first organic solvent is ethyl acetate.

[0089] In some embodiments, the second organic solvent is selected from any one or more of the following groups: aqueous acid solution, saturated brine solution, deionized water, anhydrous methanol, anhydrous ethanol, acetone, ethyl acetate, and acetonitrile. In some preferred embodiments, the second organic solvent is selected from anhydrous ethanol and anhydrous methanol. In some more preferred embodiments, the second organic solvent is anhydrous ethanol.

[0090] In some embodiments, the phosphorus-containing bisphenol monomer is selected from any one or more of the following group: DOPO-HQ, DOPO-NQ, 2DOPO-2PhOH, or other monomers containing DOPO or phosphate ester structure. The molecular formula of DOPO-HQ is C 18 H 13 PO4, with CAS number 99208-50-1. DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) reacts with 1,4-naphthoquinone to obtain the reactive flame retardant DOPO-NQ; two DOPOs successively undergo nucleophilic addition and nucleophilic substitution reactions with the carbonyl group of 4,4'-dihydroxybenzophenone to obtain the reactive flame retardant 2DOPO-2PhOH containing double DOPO.

[0091] In some embodiments, the acetylation reagent is selected from any one or more of the following group: acetyl chloride, acetyl bromide, and acetic anhydride. In some preferred embodiments, the acetylation reagent is acetic anhydride.

[0092] In some embodiments, when the phosphorus-containing bisphenol monomer and the acetylation reagent are mixed and dissolved, the dissolution temperature is 120 - 150 °C; for example, 120 °C, 123 °C, 127 °C, 130 °C, 132 °C, 134 °C, 137 °C, 140 °C, 144 °C, 147 °C, 150 °C, or any temperature within the range of 120 - 150 °C.

[0093] In some embodiments, after the phosphorus-containing bisphenol monomer and the acetylation reagent are mixed and dissolved, the reflux reaction time is 1 - 5 h; for example, 1 h, 1.3 h, 1.5 h, 1.8 h, 2 h, 2.2 h, 2.5 h, 2.7 h, 3 h, 3.4 h, 3.7 h, 4 h, 4.2 h, 4.5 h, 4.8 h, 5 h, or any time within the range of 1 - 5 h.

[0094] In some embodiments, when the solution after the reflux reaction is cooled, the temperature is reduced to 25 - 140 °C, preferably 80 - 120 °C; for example, 25 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 83 °C, 87 °C, 90 °C, 92 °C, 94 °C, 97 °C, 100 °C, 104 °C, 107 °C, 110 °C, 115 °C, 118 °C, 120 °C, 130 °C, 140 °C, or any temperature within the range of 80 - 120 °C.

[0095] In some embodiments, when the esterification reaction is carried out under vacuum conditions after heating, the temperature is raised to 200 - 260 °C; for example, 200 °C, 205 °C, 210 °C, 215 °C, 220 °C, 225 °C, 230 °C, 235 °C, 240 °C, 245 °C, 250 °C, 255 °C, 260 °C, or any temperature within the range of 200 - 260 °C.

[0096] In some embodiments, the time of the esterification reaction is 2 - 20 h; for example, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 19 h, 20 h, or any time within the range of 2 - 20 h.

[0097] In some embodiments, the catalyst is selected from any one or more of the following group: sodium methoxide, zinc oxide, sodium hydroxide, p - toluenesulfonic acid, sulfuric acid, sodium acetate, potassium acetate.

[0098] In some embodiments, the dibasic acid is selected from any one or more of the following group: terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, phthalic acid, oxalic acid.

[0099] In some embodiments, the drying temperature is 50 - 150 °C; for example, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 150 °C, or any temperature within the range of 50 - 150 °C.

[0100] In some embodiments, the drying time is 2 - 48 h; for example, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h, 43 h, 47 h, 48 h, or any time within the range of 2 - 48 h.

[0101] In a second aspect, the present application provides a method for preparing a low - temperature solvent of a phosphorus - containing active ester compound, which comprises the following steps:

[0102] Under an inert gas atmosphere, after uniformly mixing a phosphorus - containing bisphenol monomer, a third organic solvent, and an acid - binding agent, an acyl chloride monomer and a capping monomer are added, and the mixture is heated and reacted until the reaction is completed to obtain a reaction solution;

[0103] The reaction solution and a precipitant are mixed to precipitate white flocculates, followed by solid - liquid separation and vacuum drying to obtain the phosphorus - containing active ester compound.

[0104] In some embodiments, the addition of the acyl chloride monomer and the end-capping monomer specifically includes the following steps: adding a first mixed solution containing the acyl chloride monomer and the end-capping monomer, and the molar ratio of the phosphorus-containing bisphenol monomer to the acyl chloride monomer is 1.1 - 3:1. In some embodiments, the molar ratio of the phosphorus-containing bisphenol monomer to the acyl chloride monomer can be, for example, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, or 3:1.

[0105] In some embodiments, the addition of the acyl chloride monomer and the end-capping monomer specifically includes the following steps: adding a second mixed solution containing the acyl chloride monomer, after pre-reaction, filtering to obtain a pre-reaction solution;

[0106] adding the end-capping monomer to the pre-reaction solution;

[0107] wherein, the molar ratio of the phosphorus-containing bisphenol monomer to the acyl chloride monomer is 2 - 3:1; for example, it can be 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, or 3:1. In some embodiments, the time of the pre-reaction is 20 - 60 min; for example, it can be 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, or any time within the range of 20 - 60 min.

[0108] In some embodiments, the heating reaction time until the reaction is completed is 1 - 10 h, preferably 2 - 4 h; for example, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, or any time within the range of 1 - 10 h. In some embodiments, the temperature of the heating reaction is 20 - 120 °C; for example, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, or any temperature within the range of 20 - 120 °C.

[0109] In some embodiments, the phosphorus-containing bisphenol monomer is selected from any one or more of the following groups: DOPO-HQ, DOPO-NQ, 2DOPO-2PhOH, or other monomers containing DOPO or phosphate ester structures.

[0110] In some embodiments, the acid-binding agent is selected from any one or more of the following group: triethylamine, pyridine, KOH, NaOH, N,N-dimethylaniline, sodium carbonate, potassium carbonate, and calcium oxide.

[0111] In some embodiments, the third organic solvent is selected from any one or more of the following group: dichloromethane, chloroform, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, n-hexane, cyclohexane, n-heptane, n-decane, 1,1,2,2-tetrachloroethane, toluene, xylene, acetone, dioxane.

[0112] In some embodiments, the acyl chloride monomer is selected from any one or two of the following group: isophthaloyl chloride, terephthaloyl chloride, malonyl chloride.

[0113] In some embodiments, the mixed solution containing the acyl chloride monomer and the capping monomer contains a fourth organic solvent, and the fourth organic solvent is selected from any one or more of the following group: dichloromethane, chloroform, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, n-hexane, cyclohexane, n-heptane, n-decane, 1,1,2,2-tetrachloroethane, toluene, xylene, acetone, dioxane.

[0114] In some embodiments, the capping monomer is selected from any one or more of the following group: phenol, o-cresol, m-cresol, p-cresol, α-naphthol, β-naphthol, acetyl chloride, acetyl bromide, and acetic anhydride.

[0115] In some embodiments, the precipitant is selected from any one or more of the following group: ketones, alcohols, ethers, etc., preferably any one or more of acid aqueous solution, saturated brine solution, deionized water, absolute methanol, absolute ethanol, acetone, tetrahydrofuran, acetonitrile, 1,4-dioxane, ethylene glycol monoethyl ether, ethyl acetate. In some preferred embodiments, the precipitant is selected from absolute ethanol and absolute methanol; in some more preferred embodiments, the precipitant is absolute ethanol.

[0116] In some embodiments, the temperature of the vacuum drying is 50-150 °C; for example, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 150 °C or any temperature within the range of 50-150 °C.

[0117] In some embodiments, the time for vacuum drying is 2 - 48 h; for example, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h, 43 h, 47 h, 48 h, or any time within the range of 2 - 48 h.

[0118] In a third aspect, the present application provides an epoxy resin composition, which comprises an epoxy resin and a phosphorus-containing active ester compound obtained by the melting preparation method or the low-temperature solvent preparation method of the above-mentioned phosphorus-containing active ester compound.

[0119] In some embodiments, the epoxy resin is selected from any one or more of the following groups: halogen-free epoxides, phosphorus-free epoxides, and phosphorus-containing epoxides.

[0120] In some embodiments, relative to 100 parts by weight of the epoxy resin, 10 - 150 parts by weight of the phosphorus-containing active ester compound is contained; for example, relative to 100 parts by weight of the epoxy resin, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150 parts by weight of the phosphorus-containing active ester compound is contained.

[0121] In other aspects, the present application provides an article, which comprises the above-mentioned epoxy resin composition.

[0122] In some embodiments, the article is used in lead-free soldering and electronic devices.

[0123] In some embodiments, the article further comprises a copper foil.

[0124] In some embodiments, the article is a printed circuit board.

[0125] In other aspects, the present application further provides a prepreg, which comprises the above-mentioned epoxy resin composition.

[0126] In other aspects, the present application further provides a laminate or a bonding sheet, which comprises the above-mentioned epoxy resin composition.

[0127] In other aspects, the present application further provides a printed wiring board, which comprises the above-mentioned prepreg.

[0128] In other aspects, the present application further provides a printed wiring board, which comprises the above-mentioned laminate or bonding sheet.

[0129] In other aspects, the present application further provides a method for manufacturing the above-mentioned laminate, which comprises the following steps:

[0130] Impregnating the epoxy resin composition into a filler to form a prepreg;

[0131] The prepreg is treated under heating to promote partial curing to the B-stage, and then two or more of the prepregs are laminated under pressure and heating to form a laminate.

[0132] In other aspects, the present application also provides a printed circuit board prepared by the above method.

[0133] Specific embodiments of the present application will be described in more detail below with reference to the accompanying drawings. Although specific embodiments of the present application are shown in the drawings, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided so that the present application can be more thoroughly understood and the scope of the present application can be fully conveyed to those skilled in the art.

[0134] In the following, Examples 1-14 and Comparative Example 1 prepare phosphorus-containing active ester compounds in a molten system. Examples 15-19 and Comparative Examples 2-3 prepare phosphorus-containing active ester compounds in a solvent system.

[0135] Examples of the molten system

[0136] Example 1.

[0137] Preparation method of phosphorus-containing active ester compound: 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, the system is completely dissolved, reflux for 2 h, and the solution changes from purple to light yellow; cool down to 100 °C, add 0.029 g of potassium acetate and isophthalic acid (70 g, 0.42 mol); when heating up to 240 °C, the system reaches a completely dissolved state, after stabilizing for 1 h, slowly adjust the vacuum degree to -0.096 to -0.098 MPa to remove excess acetic anhydride and by-product acetic acid; after reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly; the resin is further rinsed with anhydrous methanol to obtain a light yellow blocky product, ground and dried in a vacuum oven at 80 °C, and the yield is about 96%. Calculated and measured according to the feeding ratio, the ester group equivalent of the active ester provided in this example is 219.4 g / eq., and the phosphorus content is 7.06%. The reaction formula of this reaction is as follows:

[0138] 。

[0139] Example 2.

[0140] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 400 mL of dichloromethane and further sediment it in absolute ethanol. The amount of absolute ethanol used is 1.5 times the volume of dichloromethane (600 mL). Filter to obtain a white solid powder, which remains a white solid powder after drying in a vacuum oven at 80 °C, and the yield is about 93%. The reaction formula of this reaction is as in Example 1.

[0141] Example 3.

[0142] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 400 mL of dichloromethane and further sediment it in ethyl acetate. The amount of ethyl acetate used is 1.5 times the volume of dichloromethane (600 mL). Filter to obtain a light yellow solid powder, which remains a light brown solid powder after drying in a vacuum oven at 80 °C, and the yield is about 93%. The reaction formula of this reaction is as in Example 1.

[0143] Example 4.

[0144] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 400 mL of dichloromethane and further sediment it in acetone. The amount of acetone used is 1.5 times the volume of dichloromethane (600 mL). Filter to obtain a white solid powder, which remains a white solid powder after drying in a vacuum oven at 80 °C, and the yield is about 92%. The reaction formula of this reaction is as in Example 1.

[0145] Example 5.

[0146] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 400 mL of dichloromethane and further sediment it in acetonitrile. The amount of acetonitrile used is 1.5 times the volume of dichloromethane (600 mL). Filter to obtain a white solid powder, which remains a white solid powder after drying in a vacuum oven at 80 °C, and the yield is about 94%. The reaction formula of this reaction is as in Example 1.

[0147] Example 6.

[0148] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 400 mL of dichloromethane, and further sediment it in an equal volume of absolute ethanol. Filter to obtain a light yellow powder, which is still a light yellow powder after drying in a vacuum oven at 80 °C, and the yield is about 94%. The reaction formula of this reaction is as in Example 1.

[0149] Example 7.

[0150] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 400 mL of dichloromethane, and further sediment it in absolute ethanol. The amount of absolute ethanol used is twice the volume of dichloromethane (800 mL). Filter to obtain a white solid powder, which is still a white solid powder after drying in a vacuum oven at 80 °C, and the yield is about 93%. The reaction formula of this reaction is as in Example 1.

[0151] Example 8.

[0152] Preparation method of phosphorus-containing active ester compound: 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 0.029 g of potassium acetate and isophthalic acid (70 g, 0.42 mol). When the temperature is raised to 240 °C, the system reaches a completely dissolved state. After stabilizing for 1 h, slowly adjust the vacuum degree to -0.096 to -0.098 MPa to remove excess acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 400 mL of dichloromethane, and further precipitate it in absolute ethanol. The amount of absolute ethanol used is 3 times the volume of dichloromethane (800 mL). Filter to obtain a white solid powder, which remains a white solid powder after drying in a vacuum oven at 80 °C, and the yield is about 92%. The reaction formula of this reaction is as in Example 1.

[0153] Example 9.

[0154] Preparation method of phosphorus-containing active ester compound: 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 0.029 g of potassium acetate and isophthalic acid (70 g, 0.42 mol). When the temperature is raised to 240 °C, the system reaches a completely dissolved state. After stabilizing for 1 h, slowly adjust the vacuum degree to -0.096 to -0.098 MPa to remove excess acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 200 mL of N,N-dimethylacetamide, and further precipitate it in excess absolute ethanol. The amount of absolute ethanol used is 1.5 times the volume of N,N-dimethylacetamide (300 mL). Filter to obtain a light yellow solid powder, which remains a light yellow solid powder after drying in a vacuum oven at 80 °C, and the yield is about 93%. The reaction formula of this reaction is as in Example 1.

[0155] Example 10.

[0156] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 200 mL of N,N-dimethylacetamide, and further sediment it in 300 mL of deionized water, where the amount of deionized water used is 1.5 times the volume of N,N-dimethylacetamide. Filter to obtain a light yellow solid powder, which becomes a dark yellow solid block after drying in a vacuum oven at 80 °C, and the yield is about 94%. The reaction formula of this reaction is as in Example 1.

[0157] Example 11.

[0158] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product into an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 200 mL of N,N-dimethylacetamide, and further sediment it in 200 mL of absolute ethanol with the same volume as N,N-dimethylacetamide. Filter directly to obtain a white solid powder, which turns yellow after drying in a vacuum oven at 80 °C, and the yield is about 93%. The reaction formula of this reaction is as in Example 1.

[0159] Example 12.

[0160] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product onto an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 200 mL of N,N-dimethylacetamide, and further precipitate it in excessive absolute ethanol. The amount of absolute ethanol used is 2 times the volume of N,N-dimethylacetamide (400 mL). Filter to obtain a white solid powder, which remains a white solid powder after drying in a vacuum oven at 80 °C, and the yield is about 93%. The reaction formula of this reaction is as in Example 1.

[0161] Example 13.

[0162] Preparation method of phosphorus-containing active ester compound: 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 0.029 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove the excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product onto an aluminum plate while it is hot, and the resin cools rapidly. Dissolve the resin in 200 mL of N,N-dimethylacetamide, and further precipitate it in excessive absolute ethanol. The amount of absolute ethanol used is 3 times the volume of N,N-dimethylacetamide (600 mL). Filter to obtain a white solid powder, which remains a white solid powder after drying in a vacuum oven at 80 °C, and the yield is about 93%. The reaction formula of this reaction is as in Example 1.

[0163] Example 14.

[0164] Preparation method of phosphorus-containing active ester compound: 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 0.029 g of potassium acetate and terephthalic 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 adjust the vacuum degree to -0.096 to -0.098 MPa to remove excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product onto an aluminum plate while it is still hot, and the resin cools rapidly. Dissolve the resin in 200 mL of N,N-dimethylacetamide, and further precipitate it in excessive absolute ethanol. The amount of absolute ethanol used is 1.5 times the volume of N,N-dimethylacetamide (300 mL). Filter to obtain a dark yellow solid, which remains a dark yellow solid after drying in a vacuum oven at 80 °C, and the yield is about 91%.

[0165] Comparative Example 1.

[0166] Preparation method of phosphorus-containing active ester compound: 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 excessive acetic anhydride and by-product acetic acid. After reacting for 2 h, pour the product onto an aluminum plate while it is still hot, and the resin cools rapidly to obtain a light brown color. Grind it and remove the residual acetic acid in a vacuum oven at 137 °C, then dry it. The yield is about 98%. The reaction formula of this reaction is as in Example 1. Calculated and measured according to the feed ratio, the ester group equivalent of the active ester provided in this comparative example is 219.4 g / eq., and the phosphorus content is 7.06%.

[0167] Performance test of phosphorus-containing active ester compound:

[0168] 1) Structure characterization: Use a Fourier transform infrared spectrometer (FT-IR) to perform infrared test characterization on the phosphorus-containing active ester compound provided in the example. The infrared spectra of the phosphorus-containing active ester compounds provided in Comparative Example 1 and Example 2 are shown in Figure 1 and Figure 2 ;

[0169] 2) Molecular weight test: The weight-average molecular weight (Mw) and molecular weight distribution of the phosphorus-containing active ester compounds provided in the examples were determined using a gel permeation chromatography system. The GPC spectra of the phosphorus-containing active ester compounds provided in Comparative Example 1 and Example 2 are shown in Figure 1 and Figure 2 ;

[0170] 3) Methyl ethyl ketone solubility and stability test: The solid resin was crushed into small particles. 10 g of the solid resin was taken and mixed with a certain amount of methyl ethyl ketone, sealed in a 100 mL polyethylene plastic bottle, and ultrasonically dissolved to investigate whether the resin was completely dissolved under the conditions of 40% and 60 wt.% solid content.

[0171] The test results are shown in Table 1.

[0172] Table 1

[0173]

[0174]

[0175] Note: In this experiment, the components with 18 - 20 min in the GPC spectrum were defined as low molecular weight components; the components with 10 - 15 min were defined as high molecular weight components

[0176] Examples of solvent systems

[0177] Example 15.

[0178] Preparation method of phosphorus-containing active ester compound: Under the protection of room temperature and nitrogen atmosphere, in a 500 mL three-necked flask equipped with a mechanical stirrer (rotation speed 200 r / min), thermometer, and condenser, at room temperature, DOPO-HQ (5.0 g, 15.4 mol), 75 mL of dichloromethane, and 5.5 mL of triethylamine were added, and the solution was turbid. Stirring was continued for 30 min; a 50 mL dichloromethane solution dissolved with isophthaloyl chloride (1.9 g, 9.4 mmol) and 2 mL of acetic anhydride (21.3 mmol) was slowly added dropwise through a constant pressure dropping funnel. As the mixed solution was added dropwise, the system changed from a turbid state to a completely dissolved state. After the addition was completed, the temperature was quickly raised to 50 °C and the reaction was carried out for about 2 h; after the reaction was completed, the reaction solution was precipitated in a large amount of anhydrous ethanol solution, a large amount of white flocculates were precipitated, filtered, and dried in a 60 °C forced air oven to obtain the target product. The reaction formula of this reaction is as follows:

[0179] 。

[0180] Example 16.

[0181] Preparation method of phosphorus-containing active ester compound: Under the protection of room temperature and nitrogen atmosphere, in a 500 mL three-necked flask equipped with a mechanical stirrer (rotation speed 200 r / min), a thermometer, and a condenser, at room temperature, add DOPO-HQ (5.0 g, 15.4 mmol), 75 mL of dichloromethane, and 5.5 mL of triethylamine. The solution is in a turbid state, and stir continuously for 30 min; slowly add dropwise a 50 mL dichloromethane solution dissolved with isophthaloyl chloride (1.9 g, 9.4 mmol) through a constant-pressure dropping funnel. As the mixed solution is added dropwise, the turbid particles in the system gradually decrease and completely dissolve; after reacting for 30 min, add 2 mL of acetic anhydride (21.3 mmol), quickly raise the temperature to 50 °C and react for about 2 h; after the reaction is completed, precipitate the reaction solution in a large amount of ethanol, a large amount of white flocculent substances precipitate out, filter, and dry in a blast drying oven at 60 °C to obtain the target product. The reaction formula of this reaction is as in Example 15.

[0182] Example 17.

[0183] Preparation method of phosphorus-containing active ester compound: Under the protection of room temperature and nitrogen atmosphere, in a 500 mL three-necked flask equipped with a mechanical stirrer (rotation speed 200 r / min), a thermometer, and a condenser, at room temperature, add DOPO-HQ (5.0 g, 15.4 mmol), 75 mL of dichloromethane, and 5.5 mL of triethylamine. The solution is in a turbid state, and stir continuously for 30 min; slowly add dropwise a 50 mL dichloromethane solution dissolved with isophthaloyl chloride (1.2 g, 6.0 mmol) through a constant-pressure dropping funnel. As the mixed solution is added dropwise, the turbid particles in the system gradually decrease but do not completely dissolve; after reacting for 30 min, filter the unreacted particles; put the transparent solution back into the reaction flask, add 2 mL of acetic anhydride (21.3 mmol), quickly raise the temperature to 50 °C and react for about 2 h; after the reaction is completed, precipitate the reaction solution in a large amount of ethanol, a large amount of white flocculent substances precipitate out, filter, and dry in a blast drying oven at 60 °C to obtain the target product. The reaction formula of this reaction is as in Example 15.

[0184] Example 18.

[0185] Preparation method of phosphorus-containing active ester compound: Under room temperature and nitrogen atmosphere protection, in a 500 mL three-necked flask equipped with a mechanical stirrer (rotation speed 200 r / min), a thermometer, and a condenser, add DOPO-HQ (5.0 g, 15.4 mmol), 75 mL of dichloromethane, and 5.5 mL of triethylamine. The solution is in a turbid state and stir continuously for 30 min. Slowly add dropwise a 50 mL dichloromethane solution in which isophthaloyl chloride (1.2 g, 6.0 mmol) and 2 mL of acetic anhydride (21.3 mmol) are dissolved through a constant pressure dropping funnel. As the mixed solution is added dropwise, the system changes from a turbid state to a completely dissolved state. After the addition is completed, quickly raise the temperature to 50 °C and react for about 2 h. After the reaction is completed, precipitate the reaction solution in a large amount of absolute ethanol solution. A large amount of white powdery substance precipitates. Filter and dry in a blast drying oven at 60 °C to obtain the target product.

[0186] Example 19.

[0187] Preparation method of phosphorus-containing active ester compound: Under room temperature and nitrogen atmosphere protection, in a 500 mL three-necked flask equipped with a mechanical stirrer (rotation speed 200 r / min), a thermometer, and a condenser, add DOPO-HQ (71.9 g, 221.6 mmol), pyridine (25 mL, 310.5 mmol), and 200 mL of chloroform and mix them together; slowly add dropwise a 50 mL chloroform solution in which isophthaloyl chloride (30 g, 147.8 mmol) and 2 mL of acetic anhydride are dissolved; 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 HCl aqueous 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 flocculent solid. The reaction formula of this reaction is as in Example 15.

[0188] Comparative Example 2.

[0189] Preparation method of phosphorus-containing active ester compound: Under room temperature and nitrogen atmosphere protection, in a 500 mL three-necked flask equipped with a mechanical stirrer (rotation speed 200 r / min), a thermometer, and a condenser, add DOPO-HQ (71.9 g, 221.6 mmol), pyridine (25 mL, 310.5 mmol), and 200 mL of chloroform and mix them together; add dropwise isophthaloyl chloride (30 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 HCl aqueous 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 flocculent solid.

[0190] Comparative Example 3.

[0191] Preparation method of phosphorus-containing active ester compound: Under the protection of room temperature and nitrogen atmosphere, add DOPO-HQ (5.0 g, 15.4 mmol), 75 mL of dichloromethane and 5.5 mL of triethylamine into a 500 mL three-necked flask equipped with a mechanical stirrer (rotation speed: 200 r / min), a thermometer and a condenser. The solution is in a turbid state and stir continuously for 30 min. Slowly drip a 50 mL dichloromethane solution dissolved with isophthaloyl chloride (1.9 g, 9.4 mmol) through a constant pressure dropping funnel. As the mixed solution is dripped, the system changes from a turbid state to a completely dissolved state. After the dripping is completed, quickly heat up to 50 °C and react for about 2 h. After the reaction is completed, precipitate the reaction solution in a large amount of absolute ethanol solution, a large amount of white flocculates will precipitate, filter, and dry in a blast drying oven at 60 °C to obtain the target product.

[0192] Performance test of phosphorus-containing active ester compound:

[0193] 1) Structure characterization: Use a Fourier transform infrared spectrometer (FT-IR) to perform infrared test characterization on the phosphorus-containing active ester compound provided in the example. The infrared spectra of the phosphorus-containing active ester compound provided in Example 15 and the phosphorus-containing active ester compound provided in Comparative Example 2 are shown in Figure 3 and Figure 4 ;

[0194] 2) Molecular weight test: Use a gel permeation chromatography system to determine the weight average molecular weight (Mw) and molecular weight distribution of the phosphorus-containing active ester compound provided in the example. The GPC spectra of the phosphorus-containing active ester compound provided in Example 15 and the phosphorus-containing active ester compound provided in Comparative Example 2 are shown in Figure 3 and Figure 4 ;

[0195] 3) Methyl ethyl ketone solubility and stability test: Crush the solid resin into small particles, take 10 g of the solid resin, add a certain amount of methyl ethyl ketone and mix, seal in a 100 mL polyethylene plastic bottle, and dissolve by ultrasonic wave to investigate whether the resin is completely dissolved under the conditions of 40% and 60 wt.% solid content.

[0196] The test results are shown in Table 2.

[0197] Table 2

[0198]

[0199] Note: In this experiment, the components with a molecular weight of 18 - 20 min in the GPC spectrum are defined as low molecular weight components; the components with a molecular weight of 10 - 15 min are defined as high molecular weight components

[0200] As can be seen from Table 1 and Table 2, the phosphorus-containing active ester compounds prepared in Examples 1-13 and Examples 15, 17 and 18 can all be completely dissolved in methyl ethyl ketone. The completely dissolved liquid resin was refrigerated in a 5°C refrigerator for 7 days, and it was found that no obvious resin particles precipitated, indicating that the phosphorus-containing active ester compound has good dissolution stability in methyl ethyl ketone.

[0201] Application Example: Small-scale epoxy curing experiment using the phosphorus-containing active ester compound of the present application

[0202] On a small scale, the DOPO-HQ derivative sample synthesized in Example 2 was combined with epoxy resin and cured (material information is shown in Table 3). The sample was cured using a 1:1 ratio of DEN438:EPON164 and 0.2 wt.% of 2-methylimidazole as a catalyst (total P% ranges from 2.4 to 2.7%); 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 and thermal stability of the sample were studied using DSC and TGA.

[0203] To prepare a varnish casting for Dk and Df measurement, the phosphorus-containing active ester compound was blended with a 1:1 ratio of DEN438:EPON164 and the catalyst 2-methylimidazole; the aluminum foil was coated on one side using the sample-epoxy blend, and after coating, the foil was air-dried and then B-staged at 165°C (3 min 50 s); the epoxy was peeled off from the foil, and then it was shaped and cured at 200°C for 2-3 h and post-cured at 210-220°C for 1 h. The reagent information involved is shown in Table 3, and the specific results are shown in Table 4.

[0204] Table 3 Composition, T g 、TGA and dielectric properties

[0205]

[0206] Table 4 Composition, T g 、TGA and dielectric properties

[0207]

[0208] In Example 2, the phosphorus-containing active ester compound was investigated as a curing agent for use in epoxy resin DEN438 and EPON164 laminate applications. The solid content was maintained at 66.67 wt.% by adding methyl ethyl ketone (MEK) / Dowanol (80 / 20) solvent, and a varnish formulation with a phosphorus content of 2.7 wt.% was prepared. The composition content is shown in Table 5. The addition of the catalyst was controlled by adding small increments of 2-methylimidazole (2-MI) solution (20 wt.% solid solution in DMF) to achieve an optimal varnish gel time of 270 s at 171 °C according to IPC-TM-650 test 2.3.18.

[0209] Table 5 Epoxy resin laminate formulation

[0210]

[0211] The glass fabric was continuously passed through a trough containing the varnish and through a squeeze roll 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 bag, and the gel time of the collected resin was measured on a hot plate at 171 °C. The properties of the prepreg are shown in Table 6.

[0212] Table 6 Properties of prepreg

[0213]

[0214] 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 a rate of 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. The sizing agent 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 45 kgf / cm 2 was applied at 200 °C, cured for 120 min, the pressure was released, and it was naturally cooled to room temperature to obtain the laminate.

[0215] The Tg of the multi-layer laminate was determined to be 192 °C by a dynamic thermomechanical analyzer at a rate of 5 °C / min in single-cantilever beam mode. The thermal decomposition temperature of the composite at 5 wt.% loss was 416 °C, which was determined by TGA in a nitrogen atmosphere at a heating rate of 10 °C / min.

[0216] The specimens used for the pressure cooker test were cut from the epoxy laminate containing the phosphorus-containing active ester compound and placed in a pressure cooker at 121 °C and 15 psi for 30 min; the water absorption of the specimens was about 0.07 - 0.14 wt.%, and none of the three specimens showed any blistering, and they were rated as condition (status) 5 according to the IPC test standard.

[0217] Among them, the properties of the prepreg are shown in Table 7, and the properties of the laminate are shown in Table 8.

[0218] Table 7 Properties of the prepreg

[0219]

[0220] Table 8 Properties of the laminate

[0221]

[0222] The description of the present disclosure has been given for purposes of illustration and description, and is not intended to be exhaustive or to limit the present disclosure to the disclosed form. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the present disclosure and its practical application, and to enable those of ordinary skill in the art to understand the present disclosure so as to design various embodiments with various modifications suitable for a particular purpose.

Claims

1. A method for the melt preparation of a phosphorus-containing activated ester compound, characterized in that, It comprises the following steps: Mix and dissolve a phosphorus-containing bisphenol monomer and an acetylation reagent, and carry out a reflux reaction; Cool the solution after the reflux reaction, add a catalyst and a dibasic acid, heat up and carry out an esterification reaction under vacuum conditions, and then cool to obtain a reaction product; Wash the reaction product with an organic solvent or dissolve it in an organic solvent and then precipitate, carry out solid-liquid separation, and dry to obtain the phosphorus-containing active ester compound; Wherein, when the reaction product is washed with an organic solvent, the organic solvent is selected from any one or more of anhydrous methanol, anhydrous ethanol, acetone, tetrahydrofuran, 1,4-dioxane, ethylene glycol monoethyl ether, and ethyl acetate; Wherein, dissolving the reaction product in an organic solvent and then precipitating comprises the following steps: dissolving the reaction product in a first organic solvent and then precipitating with a second organic solvent; Wherein, the first organic solvent is selected from any one or more of the following groups: dichloromethane, chloroform, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, and methyl ethyl ketone; Wherein, the second organic solvent is selected from any one or more of the following groups: aqueous acid solution, saturated brine solution, deionized water, anhydrous methanol, anhydrous ethanol, acetone, ethyl acetate, and acetonitrile.

2. The melting preparation method of the phosphorus-containing active ester compound according to claim 1, characterized in that, Wherein, The volume of the second organic solvent is at least 1.5 times the volume of the first organic solvent.

3. The melting preparation method of the phosphorus-containing active ester compound according to claim 1, characterized in that, Wherein, The phosphorus-containing bisphenol monomer is selected from any one or more of the following groups: DOPO-HQ, DOPO-NQ, 2DOPO-2PhOH; And / or, the acetylation reagent is selected from any one or more of the following groups: acetyl chloride, acetyl bromide, and acetic anhydride.

4. The melting preparation method of the phosphorus-containing active ester compound according to claim 1, characterized in that, Wherein, When the phosphorus-containing bisphenol monomer and the acetylation reagent are mixed and dissolved, the dissolution temperature is 120-150°C; And / or, the reflux reaction time is 1-5 h.

5. The melting preparation method of the phosphorus-containing active ester compound according to claim 1, characterized in that, Wherein, When cooling the solution after the reflux reaction, the temperature is reduced to 25-140°C; And / or, when heating up and carrying out the esterification reaction under vacuum conditions, the temperature is raised to 200-260°C; And / or, the esterification reaction time is 2-20 h.

6. The melting preparation method of the phosphorus-containing active ester compound according to claim 1, characterized in that, Wherein, The catalyst is selected from any one or more of the following groups: sodium methoxide, zinc oxide, sodium hydroxide, p-toluenesulfonic acid, sulfuric acid, sodium acetate, and potassium acetate; And / or, the dibasic acid is selected from any one or more of the following groups: terephthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, phthalic acid, and oxalic acid.

7. An epoxy resin composition, characterized in that, It comprises an epoxy resin and a phosphorus-containing active ester compound prepared by the melting preparation method of the phosphorus-containing active ester compound according to any one of claims 1-6; Wherein, relative to 100 parts by weight of the epoxy resin, 10-150 parts by weight of the phosphorus-containing active ester compound is contained.

8. Prepreg, characterized in that, It comprises the epoxy resin composition according to claim 7.

9. A laminate, characterized in that, It comprises the epoxy resin composition according to claim 7.

10. Adhesive sheet, characterized in that, It comprises the epoxy resin composition according to claim 7.

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