Preparation method of phosphorus-containing compound-modified imide-based epoxy resin and resin composition

Abstract

The present invention provides a preparation method of a phosphorus-containing compound modified imido epoxy resin, comprising the following steps: step 1: reacting phenolphthalein and p-aminophenol to obtain an imido-containing polyphenol compound; step 2: reacting the imido-containing polyphenol compound and epichlorohydrin to obtain an imido-containing multifunctional epoxy resin; step 3: reacting the imido-containing multifunctional epoxy resin with a phosphorus-containing compound to obtain a phosphorus-containing compound modified imido epoxy resin. Imide groups and epoxy groups are gradually introduced into the phosphorus-containing compound, and the generated phosphorus-containing compound modified imido epoxy resin contains more benzene rings and imide structures, thereby improving the heat resistance of the epoxy resin. The N element in the imide group and the P element in the phosphorus-containing compound utilize the N-P synergistic effect to enhance flame retardancy while reducing phosphorus content, thereby reducing the water absorption rate of the resin.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic materials, and in particular to a preparation method of a phosphorus-containing compound-modified imide-based epoxy resin and a resin composition. Background Art

[0002] Traditional copper-clad laminates for printed circuits are primarily categorized as halogen-containing and halogen-free, depending on whether they contain halogens. These two types differ significantly in how they achieve flame retardancy. Halogen-containing copper-clad laminates utilize brominated epoxy resins or bromine-containing flame retardants such as tetrabromobisphenol A (TBBPA) to achieve flame retardancy. However, the combustion of waste electronic and electrical equipment containing halogens such as bromine and chlorine can release carcinogens such as dioxins and dibenzofurans, as well as highly toxic hydrogen halides.

[0003] After the EU officially implemented the Waste Electrical and Electronic Equipment (WEEE) and the Restriction of Hazardous Substances in Electrical and Electronic Equipment (RoHS) directives in 2006, the market for halogen-free flame-retardant copper-clad laminates (CCLs) has rapidly grown. Currently, most manufacturers have introduced CCLs with halogen-free flame-retardant properties, and the market continues to grow rapidly. Some companies have chosen phosphorus-containing epoxy and phenolic resins as flame-retardant resins, but these resins have unsatisfactory heat resistance, reliability, and dielectric properties. Summary of the Invention

[0004] The object of the present invention is to provide a preparation method and resin composition of a phosphorus-containing compound-modified imido epoxy resin. The above preparation method gradually introduces an imide group, an epoxy group and a phosphorus-containing compound into the final generated resin. The resulting phosphorus-containing compound-modified imido epoxy resin has good heat resistance.

[0005] In order to achieve one of the above-mentioned objects of the invention, one embodiment of the present invention provides a method for preparing a phosphorus-containing compound-modified imide-based epoxy resin, comprising the following steps:

[0006] Step 1: reacting phenolphthalein with p-aminophenol to obtain an imide-containing polyphenol compound;

[0007] Step 2: reacting the imido-containing polyphenol compound with epichlorohydrin to obtain an imido-containing multifunctional epoxy resin;

[0008] Step 3: reacting the imide-containing multifunctional epoxy resin with a phosphorus-containing compound to obtain a phosphorus-containing compound-modified imide-based epoxy resin.

[0009] As a further improvement of one embodiment of the present invention, in step three, the mass ratio of the imide group-containing multifunctional epoxy resin to the phosphorus-containing compound is 100:(10-70).

[0010] As a further improvement of one embodiment of the present invention, in step three, the mass ratio of the imide group-containing multifunctional epoxy resin to the phosphorus-containing compound is 100:(20-50).

[0011] As a further improvement of one embodiment of the present invention, in step 1, 0.001 to 5 parts by weight of an acidic catalyst is added, and the acidic catalyst is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, tetrafluorophosphoric acid, hexafluorophosphoric acid, tetrafluoroborate ferric chloride, cupric chloride, phosphoric acid, polyphosphoric acid, and trifluoroacetic acid.

[0012] As a further improvement of one embodiment of the present invention, in step three, 0.001 to 5 parts by weight of an amine catalyst is added, and the amine catalyst is selected from at least one of triethylenediamine, bis(dimethylaminoethyl) ether or its derivatives, N,N-dimethylcyclohexylamine, tetramethylalkylenediamine, triethylamine, N,N-dimethylbenzylamine, tributylamine, solid amine, N-ethylmorpholine, diethylpiperazine, N,N'-lutidine, tertiary amine, and quaternary ammonium salt.

[0013] As a further improvement of one embodiment of the present invention, in step one, the reaction temperature is controlled at 100-200°C, and the reaction time is controlled at 1-10 hours; in step two, the reaction temperature is controlled at 30-100°C, and the reaction time is controlled at 1-5 hours; in step three, the reaction temperature is controlled at 100-180°C, and the reaction time is controlled at 2-8 hours.

[0014] As a further improvement of one embodiment of the present invention, the phosphorus-containing compound is at least one of the following structures (1) to (3):

[0015] Structure (1);

[0016] structure (2);

[0017] Structure (3).

[0018] One embodiment of the present invention further provides a resin composition comprising the following components by weight:

[0019] (a) phosphorus-containing compound-modified imide-based epoxy resin: 100 parts by weight;

[0020] (b) curing agent: 1 to 60 parts by weight;

[0021] The phosphorus-containing compound modified imido epoxy resin is prepared by the aforementioned method for preparing the phosphorus-containing compound modified imido epoxy resin.

[0022] As a further improvement of one embodiment of the present invention, the curing agent is at least one of active ester compounds, phenolic compounds, acid anhydride compounds, amine compounds, benzoxazine compounds, cyanate compounds, and polyphenylene ether compounds.

[0023] As a further improvement of one embodiment of the present invention, the amine compound is selected from diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, dicarboxyphthalimide, dicyandiamide or imidazole;

[0024] The acid anhydride compound is selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride or styrene-maleic anhydride;

[0025] The phenolic compound is selected from bisphenol A phenolic resin, phenol phenolic resin, naphthalene phenolic resin, biphenyl phenolic resin, biphenyl phenol naphthol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin;

[0026] The active ester compound is selected from the compound represented by the following structural formula (5): Structural (4),

[0027] Wherein, X is an aromatic group; j is 0 or 1; k is 0 or 1; and n represents a repeating unit and is 0.25 to 1.25.

[0028] As a further improvement of one embodiment of the present invention, a filler is further included. The filler content is 30 to 300 parts by weight based on 100 parts by weight of the resin composition. The filler is surface-modified using a silane coupling agent having the following structure:

[0029] Structural formula (5);

[0030] Structural formula (6);

[0031] Structural formula (7).

[0032] One or more technical solutions provided by the present invention have at least the following technical effects or advantages:

[0033] The preparation method of the phosphorus-containing compound-modified imido epoxy resin provided by the present invention gradually introduces imido groups and epoxy groups into the phosphorus-containing compound. The resulting phosphorus-containing compound-modified imido epoxy resin contains a large number of benzene rings and imido structures, thereby improving the heat resistance of the epoxy resin. The N element in the imido group and the P element in the phosphorus-containing compound utilize the NP synergistic effect to enhance the flame retardant properties while reducing the phosphorus content, thereby reducing the water absorption rate of the resin. DETAILED DESCRIPTION

[0034] The present invention will be described in detail below with reference to specific embodiments, but these embodiments do not limit the present invention. Changes in reaction conditions, reactants, or raw material amounts made by ordinary technicians in this field according to these embodiments are all included in the scope of protection of the present invention.

[0035] An embodiment of the present invention provides a method for preparing a phosphorus-containing compound-modified imide-based epoxy resin, comprising the following steps:

[0036] Step 1: reacting phenolphthalein with p-aminophenol to obtain an imide-containing polyphenol compound;

[0037] Step 2: reacting the imido-containing polyphenol compound with epichlorohydrin to obtain an imido-containing multifunctional epoxy resin;

[0038] Step 3: reacting the imide-containing multifunctional epoxy resin with a phosphorus-containing compound to obtain a phosphorus-containing compound-modified imide-based epoxy resin.

[0039] Specifically: In step 1, phenolphthalein and p-aminophenol react at a temperature of 100-200° C. under the catalysis of a catalyst for 1-10 hours to obtain a polyimide-containing polyphenol compound. The reaction mechanism is as follows:

[0040]

[0041] In step 2, the imide-containing polyphenol compound and epichlorohydrin are reacted at a temperature of 30 to 100°C for 1 to 5 hours to reduce the content of epichlorohydrin in the By replacing the H in the phenolic hydroxyl group, a multifunctional epoxy resin containing an imide group is obtained.

[0042] In step three, the imide-containing multifunctional epoxy resin and the phosphorus-containing compound in a mass ratio of 100:(10-70) are reacted at a temperature of 100-180° C. for 2-8 hours under the catalysis of an amine catalyst to obtain a phosphorus-containing compound-modified imide-based epoxy resin.

[0043] Preferably, the mass ratio of the imide group-containing multifunctional epoxy resin to the phosphorus-containing compound is 100:

[0044] (20~50).

[0045] Furthermore, the catalyst in step 1 is an acidic catalyst and the addition amount is 0.001 to 5 parts by weight.

[0046] Preferably, the acidic catalyst is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, tetrafluorophosphoric acid, hexafluorophosphoric acid, ferric chloride tetrafluoroborate, cupric chloride, phosphoric acid, polyphosphoric acid, and trifluoroacetic acid.

[0047] Furthermore, in step three, 0.001 to 5 parts by weight of an amine catalyst is added, and the amine catalyst is selected from at least one of triethylenediamine, bis(dimethylaminoethyl) ether or its derivatives, N,N-dimethylcyclohexylamine, tetramethylalkylenediamine, triethylamine, N,N-dimethylbenzylamine, tributylamine, solid amine, N-ethylmorpholine, diethylpiperazine, N,N'-lutidine, tertiary amine, and quaternary ammonium salt.

[0048] Furthermore, the phosphorus-containing compound is at least one of the following structures (1) to (3):

[0049] Structure (1);

[0050] structure (2);

[0051] Structure (3).

[0052] The present invention also provides a resin composition comprising the following components by weight:

[0053] (a) phosphorus-containing compound-modified imide-based epoxy resin: 100 parts by weight;

[0054] (b) curing agent: 1 to 60 parts by weight;

[0055] The phosphorus-containing compound-modified imido epoxy resin is prepared by the aforementioned method for preparing the phosphorus-containing compound-modified imido epoxy resin.

[0056] Furthermore, the curing agent is at least one of active ester compounds, phenol compounds, acid anhydride compounds, amine compounds, benzoxazine compounds, cyanate compounds, and polyphenylene ether compounds.

[0057] Wherein, the amine compound is selected from diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, dicarboxylphthalimide, dicyandiamide or imidazole.

[0058] The acid anhydride compound is selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride or styrene-maleic anhydride.

[0059] The phenolic compound is selected from bisphenol A novolac resin, phenol novolac resin, naphthalene-type novolac resin, biphenyl-phenol-type novolac resin, biphenyl-phenol-type naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin.

[0060] The active ester compound is selected from the compound shown in the following structural formula (4):

[0061] Structure (4), wherein X is an aromatic group; j is 0 or 1; k is 0 or 1; and n represents a repeating unit and is 0.25 to 1.25.

[0062] Preferably, X is at least one of phenyl, substituted phenyl, naphthyl or substituted naphthyl.

[0063] More preferably, the active ester compound is an active ester compound with the brand name HPC-8000 or EXB-8150 produced by DIC Corporation.

[0064] Preferably, the phenolic compound is selected from at least one of the following structures:

[0065] Structural formula (8), R 11 is a methyl group, and n is an integer from 1 to 10;

[0066] Structural formula (9), kz is an integer from 1 to 10;

[0067] Structural formula (10), n is an integer from 1 to 10;

[0068] Structural formula (11), p is an integer from 1 to 10, R 3 and R 4 It is a C1~C5 alkyl group.

[0069] Furthermore, the resin composition further contains 5 to 50 parts by weight of an elastomer, and the elastomer is at least one selected from styrene elastomers, methacrylate elastomers, and silicone elastomers.

[0070] Wherein, the styrene elastomer is selected from the styrene elastomer with the brand name H1041, H1043, H1051, H1052, H1053, H1221, P1500, P2000, M1911 or M1913 produced by Asahi Kasei Corporation of Japan; and the styrene elastomer with the brand name 8004, 8006, 8076, 8104, V9827, 2002, 2005, 2006, 2007, 2104, 7125, 4033, 4044, 4055, 4077 or 4099 produced by Kuraray Co., Ltd.

[0071] The methacrylate elastomer is selected from methacrylate elastomers with the trademarks M51, M52, M22 or D51N produced by Arkema; ​​methacrylate elastomers with the trademark LA-2330 produced by Kuraray Co., Ltd.; and methacrylate elastomers with the trademarks SG-P3 series or SG-80 series produced by Nagase Co., Ltd.

[0072] The silicone elastomers are selected from the silicone elastomers with the brands X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030 produced by Shin-etsu Chemical Co., Ltd.; AY-42-119, EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655 and the like produced by DOW.

[0073] Furthermore, the resin composition further contains 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0074] Preferably, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole and zinc octoate.

[0075] Preferably, the modified imidazole is as shown in the following structure:

[0076] Structural formula (12), wherein R3, R4, R5 and R6 are the same or different and are methyl, ethyl or tert-butyl, respectively; B is methylene, ethylene, The modified imidazole with the brand name P200F50 produced by JER Company can be used.

[0077] Structural formula (13), wherein R3, R4, R5 and R6 are the same or different and are methyl, ethyl or tert-butyl, respectively; A is methylene, ethylene, Or aromatic hydrocarbon group, can use the modified imidazole of brand G8009L produced by Dai-ichi Kogyo Co., Ltd.

[0078] Furthermore, the resin composition further comprises a filler, and the filler content is 30 to 300 parts by weight based on 100 parts by weight of the resin composition.

[0079] Fillers include inorganic fillers, organic fillers and composite fillers.

[0080] Furthermore, the filler is surface treated with a silane coupling agent, wherein the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond-containing silane coupling agent, or an epoxysilane coupling agent. Preferably, the silane coupling agent is selected from the following structures:

[0081] Structural formula (5);

[0082] Structural formula (6);

[0083] Structural formula (7).

[0084] The technical solution of the present application is further illustrated below with reference to some specific synthesis examples and comparative examples.

[0085] Synthesis Example 1: Modified Epoxy Resin A

[0086] 318 g of phenolphthalein, 119 g of p-aminophenol, an appropriate amount of hydrochloric acid and toluene were added to a reaction flask and stirred to mix uniformly. The temperature was raised to 150° C. to initiate the reaction. After reacting for 4 hours, aqueous hydrochloric acid solution was added for precipitation and filtered. The precipitate was then dissolved in an aqueous sodium hydroxide solution containing activated carbon. After stirring for about 30 minutes, the mixture was filtered to remove the activated carbon. The activated carbon treatment operation was repeated once to obtain an imide-containing polyphenol compound.

[0087] 419 g of the above-mentioned imide-containing polyphenol compound, 300 g of epichlorohydrin and 500 g of organic solvent were placed in a reaction bottle for reaction at 50° C. for 2 hours. After the reaction was completed, the excess organic solvent and epichlorohydrin were removed under reduced pressure to obtain an imide-containing multifunctional epoxy resin.

[0088] 20.2 g of DPO (Structure 1), 100 g of an imide-containing multifunctional epoxy resin, 100 g of dichloromethane, and 0.3 g of tributylamine were added to a four-necked reactor equipped with a stirring and condensing device and nitrogen. The temperature was raised to 140° C. and the reaction was carried out for 4 hours. The dichloromethane was removed by distillation under reduced pressure to obtain a modified epoxy resin A having a phosphorus content of 2.58%.

[0089] Synthesis Example 2: Modified Epoxy Resin B

[0090] 318 g of phenolphthalein, 119 g of p-aminophenol, an appropriate amount of hydrochloric acid and toluene were added to a reaction flask and stirred to mix uniformly. The temperature was raised to 150° C. to initiate the reaction. After reacting for 4 hours, aqueous hydrochloric acid solution was added for precipitation and filtered. The precipitate was then dissolved in an aqueous sodium hydroxide solution containing activated carbon. After stirring for about 30 minutes, the mixture was filtered to remove the activated carbon. The activated carbon treatment operation was repeated once to obtain an imide-containing polyphenol compound.

[0091] 419 g of the above-mentioned imide-containing polyphenol compound, 300 g of epichlorohydrin and 500 g of organic solvent were placed in a reaction bottle for reaction at 50° C. for 2 hours. After the reaction was completed, the excess organic solvent and epichlorohydrin were removed under reduced pressure to obtain an imide-containing multifunctional epoxy resin.

[0092] 31 g of DPO-HQ (Structure 2), 100 g of a polyfunctional epoxy resin containing an imide group, 130 g of xylene, and 0.4 g of tributylamine were added to a four-necked reactor equipped with a stirring and condensing device and nitrogen. The temperature was raised to 150° C. and the reaction was carried out for 7 hours. The xylene was then removed by distillation under reduced pressure to obtain a modified epoxy resin B having a phosphorus content of 2.37%.

[0093] Synthesis Example 3: Modified Epoxy Resin C

[0094] 318 g of phenolphthalein, 119 g of p-aminophenol, an appropriate amount of hydrochloric acid and toluene were added to a reaction flask and stirred to mix uniformly. The temperature was raised to 150° C. to initiate the reaction. After reacting for 4 hours, aqueous hydrochloric acid solution was added for precipitation and filtered. The precipitate was then dissolved in an aqueous sodium hydroxide solution containing activated carbon. After stirring for about 30 minutes, the mixture was filtered to remove the activated carbon. The activated carbon treatment operation was repeated once to obtain an imide-containing polyphenol compound.

[0095] 419 g of the above-mentioned imide-containing polyphenol compound, 300 g of epichlorohydrin and 500 g of organic solvent were placed in a reaction bottle for reaction at 50° C. for 2 hours. After the reaction was completed, the excess organic solvent and epichlorohydrin were removed under reduced pressure to obtain an imide-containing multifunctional epoxy resin.

[0096] 36 g of DPO-NQ (Structural Formula 3), 100 g of a multifunctional epoxy resin containing an imide group, 130 g of xylene, and 0.4 g of tributylamine were added to a four-necked reactor equipped with a stirring and condensing device and nitrogen. The temperature was raised to 155° C. and the reaction was carried out for 3 hours. The xylene was then removed by distillation under reduced pressure to obtain a modified epoxy resin C with a phosphorus content of 2.28%.

[0097] Comparative Synthesis Example 1: Modified Epoxy Resin D

[0098] 36 g of DPO-NQ (Structural Formula 3), 100 g of biphenyl epoxy resin (NC-3000H, Nippon Kayaku), 180 g of toluene, and 0.5 g of tributylamine were added to a four-necked reactor equipped with a stirring condenser and nitrogen. The temperature was raised to 175°C and the reaction was carried out for 6 hours. The toluene was removed by distillation under reduced pressure to obtain modified epoxy resin D with a phosphorus content of 2.28%.

[0099] Comparative Synthesis Example 2: Modified Epoxy Resin E

[0100] 36 g of DPO-NQ (Structural Formula 3), 100 g of naphthalene ring epoxy resin (NC-7300L, Nippon Kayaku), 180 g of toluene, and 0.5 g of tributylamine were added to a four-necked reactor equipped with a stirring condenser and nitrogen. The temperature was raised to 170° C. and the reaction was carried out for 4 hours. The toluene was removed by distillation under reduced pressure to obtain a modified epoxy resin E with a phosphorus content of 2.28%.

[0101] The components listed in Table 1 were mixed with an appropriate amount of butanone solvent and stirred to obtain a 65% solids adhesive. This adhesive was then impregnated and coated onto E-glass fiber cloth (2116) and dried in an oven at 160°C for 5 minutes to produce a prepreg.

[0102] Preparation of sample laminates for performance evaluation:

[0103] The prepreg prepared above was placed on top and bottom with a 12 micron copper foil, and then placed in a vacuum hot press to form a laminate. The specific pressing process was to press at a pressure of 1.5 MPa and a temperature of 180-220°C for 4 hours.

[0104] Table 1 Resin composition ingredients

[0105] Component / g Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Modified epoxy resin A 100 - - 100 - - - Modified epoxy resin B - 100 - - 100 - - Modified epoxy resin C - - 100 - - - - Modified epoxy resin D - - - - - 100 - Modified epoxy resin E - - - - - - 100 Phenolic resin (Structure 8) 20 20 - - - - - Active ester - - 35 35 35 35 35 2-Ethyl-4-methylimidazole 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Elastomer (V9827) 20 20 20 20 20 20 20 Silica filler 200 180 150 220 200 200 200

[0106] The prepregs and copper-clad laminates prepared in all of Examples 1 to 5 and Comparative Examples 1 to 2 were subjected to performance tests. The performance test methods are as follows:

[0107] (1) Glass transition temperature Tg (°C): DMA tester, sample size 40 mm*3 mm*0.2 mm, temperature rise rate 10°C / min, from 30°C to 320°C.

[0108] (2) Dielectric constant (Dk) / dielectric loss (Df): The vector network analyzer method (SPDR method) is used, and the test frequency is 10 GHz.

[0109] (3) XY axis CTE (ppm / °C): TMA tester, sample size 30 mm*4 mm*0.2 mm, temperature rise rate 10°C / min, from 30°C to 300°C; α1 is the CTE of 50-130°C, and α2 is the CTE of 260-280°C above the Tg point.

[0110] (4) Water absorption (%): tested according to IPC-TM-650 2.6.2.1 method.

[0111] (5) Flame retardancy: measured using the UL94 method.

[0112] (6) Curing shrinkage: The shrinkage of the cured product before and after was tested by TMA during the temperature cycle from room temperature to 260°C and then back to room temperature.

[0113] Table 2 Performance table

[0114] performance Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Phosphorus content (%) 1.17 0.97 0.93 0.93 0.93 1.17 1.17 Tg 209 215 222 206 213 189 192 Dk(10GHz) 3.41 3.45 3.31 3.28 3.19 3.75 3.87 Df(10GHz) 0.022 0.026 0.019 0.015 0.016 0.035 0.041 X / Y CTE(α1) 9.7 10.6 11.5 8.9 9.1 13.1 12.8 X / Y CTE(α2) 5.6 6.4 6.8 6.4 5.6 7.8 7.2 Water absorption 0.12 0.12 0.13 0.11 0.14 0.17 0.16 Curing shrinkage 0.32 0.29 0.27 0.36 0.30 0.45 0.40 flame retardancy V0 V0 V0 V0 V0 V0 V0

[0115] As can be seen from the above table, compared with Example 1, Comparative Examples 1 and 2 use phosphorus-modified biphenyl epoxy resin and naphthalene epoxy resin with epoxy resin curing agent and bismaleimide resin, and it is found that their Tg, dielectric properties, X / Y CTE, modulus retention, shrinkage, and resin enrichment phenomenon are all deteriorated; while the embodiments of the present invention have the characteristics of low dielectric constant, low dielectric loss, high heat resistance, high moisture and heat resistance, low X / Y axis CTE, low water absorption, low shrinkage, and not easy to resin enrichment.

[0116] It should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation method can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

[0117] The series of detailed descriptions listed above are only specific descriptions of feasible implementation methods of the present invention. They are not intended to limit the scope of protection of the present invention. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a phosphorus-containing compound-modified imide-based epoxy resin, characterized in that: The steps include: Step 1: reacting phenolphthalein with p-aminophenol to obtain an imide-containing polyphenol compound; Step 2: reacting the imido-containing polyphenol compound with epichlorohydrin to obtain an imido-containing multifunctional epoxy resin; Step 3: reacting the imide-containing multifunctional epoxy resin with a phosphorus-containing compound to obtain a phosphorus-containing compound-modified imide-based epoxy resin; The phosphorus-containing compound is at least one of the following structures (1) to (3): Structure (1); Structure (2); Structure (3).

2. The method for preparing a phosphorus-containing compound-modified imide-based epoxy resin according to claim 1, wherein: In step 3, the mass ratio of the imide group-containing multifunctional epoxy resin to the phosphorus-containing compound is 100:(10-70).

3. The method for preparing a phosphorus-containing compound-modified imide-based epoxy resin according to claim 2, wherein: In step 3, the mass ratio of the imide group-containing multifunctional epoxy resin to the phosphorus-containing compound is 100:(20-50).

4. The method for preparing a phosphorus-containing compound-modified imide-based epoxy resin according to claim 3, wherein: In step 1, 0.001 to 5 parts by weight of an acidic catalyst is added, wherein the acidic catalyst is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, tetrafluorophosphoric acid, hexafluorophosphoric acid, tetrafluoroborate ferric chloride, cupric chloride, phosphoric acid, polyphosphoric acid, and trifluoroacetic acid.

5. The method for preparing a phosphorus-containing compound-modified imide epoxy resin according to claim 3, wherein: In step 3, 0.001 to 5 parts by weight of an amine catalyst is added, wherein the amine catalyst is selected from at least one of triethylenediamine, bis(dimethylaminoethyl) ether or its derivatives, N,N-dimethylcyclohexylamine, tetramethylalkylenediamine, triethylamine, N,N-dimethylbenzylamine, tributylamine, N-ethylmorpholine, diethylpiperazine, N,N'-lutidine, and a quaternary ammonium salt.

6. The method for preparing a phosphorus-containing compound-modified imide-based epoxy resin according to claim 3, wherein: In step 1, the reaction temperature is controlled at 100-200°C, and the reaction time is controlled at 1-10 hours; in step 2, the reaction temperature is controlled at 30-100°C, and the reaction time is controlled at 1-5 hours; in step 3, the reaction temperature is controlled at 100-180°C, and the reaction time is controlled at 2-8 hours.

7. A resin composition, characterized in that By weight, including: (a) phosphorus-containing compound-modified imide-based epoxy resin: 100 parts by weight; (b) curing agent: 1 to 60 parts by weight; The phosphorus-containing compound-modified imido epoxy resin is prepared by the method for preparing a phosphorus-containing compound-modified imido epoxy resin according to any one of claims 1 to 6.

8. The resin composition according to claim 7, characterized in that The curing agent is at least one of active ester compounds, phenolic compounds, acid anhydride compounds, amine compounds, benzoxazine compounds, cyanate compounds, and polyphenylene ether compounds.

9. The resin composition according to claim 8, characterized in that The amine compound is selected from diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, dicarboxyphthalimide, dicyandiamide or imidazole; The acid anhydride compound is selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride or styrene-maleic anhydride; The phenolic compound is selected from bisphenol A phenolic resin, phenol phenolic resin, naphthalene phenolic resin, biphenyl phenolic resin, biphenyl phenol naphthol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin; The active ester compound is selected from the compound represented by the following structural formula (4): Structural formula (4), wherein X is an aromatic group; j is 0 or 1; k is 0 or 1; and n represents a repeating unit and is 0.25 to 1.

25.

10. The resin composition according to claim 7, characterized in that The resin composition further comprises a filler, wherein the filler content is 30 to 300 parts by weight based on 100 parts by weight of the resin composition, and the filler is surface-modified using a silane coupling agent having the following structure: Structural formula (5); Structural formula (6); Structural formula (7).

Images