TW202248303A - Phosphobenzene bisphenol polymer as well as preparation method and application thereof - Google Patents

Abstract

The invention provides a phosphobenzene bisphenol polymer as well as a preparation method and application thereof, belonging to the technical field of high polymer materials. The structure of the phosphobenzene bisphenol polymer is shown as a formula I or a formula II, and the phosphobenzene bisphenol polymer is obtained by a reaction of phenylphosphonic dichloride or phenyl dichlorophosphate with a tetramethyl bisphenol compound. The phosphorus content of the phosphobenzene bisphenol polymer reaches up to 5% or above; the phosphobenzene bisphenol polymer can be easily added into a resin solvent for modulation; electronic plastics prepared from the phosphobenzene bisphenol polymer have good flame retardance and heat resistance; and plates prepared from the phosphobenzene bisphenol polymer have the advantages of high tearing strength, high glass-transition temperature, appropriate hardness of electronic plates and the like.

Description

Phosphobenzene bisphenol polymer and its preparation method and application

The invention relates to the technical field of polymer materials, in particular to a phosphobenzene bisphenol polymer and its preparation method and application.

Brominated flame retardants are commonly used in printed circuit boards. Tetrabromobisphenol A epoxy resin is a common brominated flame retardant, which has good flame retardancy. Based on the demand for environmental protection, phosphorus-based flame retardants are commonly used to replace brominated flame retardants.

In recent years, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or 10-(2,5-dihydroxyphenyl)-10-hydrogen-9- Oxa-10-phosphaphenanthrene-10-oxide (ODOPB) and other phenanthrene-type phosphorus-containing compounds and epoxy resins synthesized with phosphorus-containing epoxy resins are widely used to make halogen-free FR-4 copper-clad glass fiber laminates , the obtained halogen-free copper-clad laminate has better overall performance, but there are also problems such as high water absorption and low heat resistance of the board.

The patent application with the publication number CN1435446A discloses a halogen-free flame-retardant polycarbonate, which is formed by mixing and granulating phenylphosphonic acid chloride and bisphenol compounds. However, the material is directly kneaded, and the composition is complex and has no definite composition. It is necessary to further add alkali metal or alkaline earth metal arylsulfonic acid to increase the flame retardant effect, and it cannot be directly added or dissolved in a solvent as a printed circuit. Flame retardant in the resin of the board.

Based on this, it is necessary to address the above problems to provide a phosphobenzene bisphenol polymer with a phosphorus content as high as 5% or more, and it is easy to add to the resin solvent for preparation, and the electronic plastic produced has good flame retardancy and heat resistance. The produced board has the advantages of high tear strength, high glass transition temperature, and suitable hardness of the electronic board.

式I

式II The phosphobenzene bisphenol polymer provided by the invention has a structure as shown in formula I or formula II:

Formula I

Formula II

、

、

中的一種。 Wherein, n=2~5, R is selected from: CH ₃ CCH ₃ ,

,

,

One of.

The above-mentioned phosphobenzene bisphenol polymer has a phosphorus content as high as 5% or more, and is easy to add to the resin solvent for preparation. The electronic plastic produced has good flame retardancy and heat resistance, and the produced plate has high tear strength. It has the advantages of high transformation temperature, high dimensional stability and flatness of electronic boards.

式III

式IV The present invention also provides a preparation method of phosphobenzene bisphenol polymer, which is carried out according to the synthetic route shown in formula III or formula IV:

Formula III

Formula IV

Mix phenylphosphonyl dichloride or phenyl dichlorophosphate and tetramethyl bisphenol compound, add solvent and co-solvent, and reflux reaction to obtain the compound shown in formula I or formula II.

、

、

。 In one of the embodiments, the tetramethylbisphenol compound is selected from: tetramethylbisphenol A,

,

,

.

In one embodiment, the solvent is selected from: toluene.

In one embodiment, the co-solvent is selected from one or both of pyridine and 4-dimethylaminopyridine.

In one embodiment, the reflux reaction temperature is 120-180° C., and the reaction time is 10-20 hours.

In one embodiment, the molar ratio of the phenylphosphonyl dichloride or phenyl dichlorophosphate to the tetramethylbisphenol compound is 1: (1~2).

In one embodiment, after the reflux reaction is completed, a purification step is further included: washing the product with tetrahydrofuran or water, and distilling off the solvent to obtain a purified target product.

The present invention also provides an epoxy resin composition comprising the above-mentioned phosphobenzene bisphenol polymer.

In one of the embodiments, the epoxy resin composition includes the following raw materials in parts by weight: 90-110 parts of novolak epoxy resin, 40-60 parts of phosphobenzene bisphenol polymer, 25-35 parts of hardener, 25-35 parts of hardener, Accelerator 0.05~0.2 parts, organic solvent 140~160 parts.

The present invention also provides an application of the above-mentioned phosphobenzene bisphenol polymer or epoxy resin composition in the preparation of laminated boards.

Compared with the prior art, the present invention has the following beneficial effects:

The phosphorus benzene bisphenol polymer of the present invention has a phosphorus content as high as 5% or more, and is easy to be added to a resin solvent for preparation. The electronic plastic produced has good flame retardancy and heat resistance, and the produced plate has high tear strength. , high glass transition temperature, high dimensional stability and flatness of electronic sheet.

In order to facilitate the understanding of the present invention, preferred embodiments will be given below to describe the present invention more fully. However, the present invention can be embodied in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the invention. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the following examples and comparative examples, unless otherwise specified, the raw materials are all commercially available or prepared by conventional methods.

Example 1

(1) A phosphobenzene bisphenol polymer A1, prepared by the following method:

式V Set up a reaction bottle, install a thermometer and a reflux tube, condense with 0 °C water, add 2.84 g of tetramethylbisphenol A, 10 ml of toluene and 10 ml of pyridine into the bottle, first stir to dissolve, and then add in batches 0.49 g of phenylphosphonic acid dichloride, fed with nitrogen, heated and stirred at 140 ° C for reaction, after 16 hours of reaction, stopped the reaction and added THF (tetrahydrofuran) to wash the crude product, and then distilled under reduced pressure to obtain a structure such as formula V The product A1 shown has a yield of more than 80%. The molecular mass detected by MASS is 2316.7, n=5, and the phosphorus content is 6.68%. The results of proton nuclear magnetic resonance spectrum (NMR spectrometer of Varian Company, model Mercury-VX200 MHz) are shown in Fig. 1 .

Formula V

(2) Prepare an epoxy resin composition using A1 as a raw material, which is specifically prepared by the following method:

Weigh each raw material according to the ratio of raw materials in Table 2, put each raw material in a stirrer, stir at room temperature, mix evenly, and obtain resin composition C1.

(3) The resin composition C1 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

Coat resin composition C1 on 7628 glass fiber cloth with a roll coater, the impregnation amount of resin and glass fiber cloth is 43%, then place it in a dryer, heat and dry at 180 °C for 2~5 min, and make The semi-hardened prepreg is produced, and then eight pieces of prepreg are laminated, and a 1 oz copper foil is laminated on each of the outermost layers on both sides. This was then hot-pressed to obtain a copper foil-coated laminate D1. Among them, the hot pressing conditions are: heating up to 200 °C at a heating rate of 2.0 °C/min, and hot pressing at 200 °C with a total pressure of 25 kg/cm2 (initial pressure of 12 kg/cm2) for 90 min.

Example 2

(1) A phosphobenzene bisphenol polymer A2, prepared by the following method:

The preparation method of the phosphobenzene bisphenol polymer in Example 1 is basically the same, the difference is that the reflux reaction time is 6 hours, and the product A2 is obtained. The yield was 88.1%, the molecular mass detected by MASS was 1942, n=4, and the phosphorus content was 6.92%.

(2) Prepare an epoxy resin composition using A2 as a raw material, which is specifically prepared by the following method:

Weigh each raw material according to the ratio of raw materials in Table 2, put each raw material in a stirrer, stir at room temperature, mix evenly, and obtain resin composition C2.

(3) The resin composition C2 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

The resin composition was replaced by resin composition C2, and the others were the same as in Example 1 to obtain a laminate D2.

Example 3

(1) A phosphobenzene bisphenol polymer A3, prepared by the following method:

，得到結構如式VI所示的產物A3，產率為86%，MASS檢測分子質量為1405，n=3，含磷量為5.33%。

式VI It is basically the same as the preparation method of phosphobenzene bisphenol polymer in Example 1, the difference is that 2.84 g tetramethylbisphenol A is replaced by 3.24 g

, the product A3 with the structure shown in formula VI was obtained, the yield rate was 86%, the molecular mass detected by MASS was 1405, n=3, and the phosphorus content was 5.33%.

Formula VI

(2) Prepare an epoxy resin composition using A3 as a raw material, which is specifically prepared by the following method:

Weigh each raw material according to the ratio of raw materials in Table 2, put each raw material in a stirrer, stir at room temperature, mix evenly, and obtain resin composition C3.

(3) The resin composition C3 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

The resin composition was replaced by resin composition C3, and the others were the same as in Example 1 to obtain a laminate D3.

Example 4

(1) A phosphobenzene bisphenol polymer A4, prepared by the following method:

式VII The preparation method of the phosphobenzene bisphenol polymer in Example 1 is basically the same, the difference is that 0.49 g of phenylphosphonic acid dichloride is replaced by 0.53 g of phenyl dichlorophosphate to obtain the product A4 with a structure as shown in formula VII, and produce The rate was 89%, the molecular mass detected by MASS was 1357.4, n=3, and the phosphorus content was 5.8%. The results of proton nuclear magnetic resonance spectroscopy (NMR spectrometer of Varian Company, model Mercury-VX200 MHz) are shown in Fig. 2 .

Formula VII

(2) Prepare an epoxy resin composition using A4 as a raw material, which is specifically prepared by the following method:

Weigh each raw material according to the ratio of raw materials in Table 2, put each raw material in a stirrer, stir at room temperature, and mix evenly to obtain resin composition C4.

(3) The resin composition C4 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

The resin composition was replaced by resin composition C4, and the others were the same as in Example 1 to obtain a laminate D4.

Example 5

(1) A phosphobenzene bisphenol polymer A5, prepared by the following method:

，得到結構如式VIII所示的產物A5，產率為83%，MASS檢測分子質量為2058，n=3，含磷量為5.64%。

式VIII The preparation method of the phosphobenzene bisphenol polymer in Example 4 is basically the same, the difference is that 2.84 g tetramethylbisphenol A is replaced by 3.24 g

, the product A5 with the structure shown in formula VIII was obtained, the yield was 83%, the molecular mass detected by MASS was 2058, n=3, and the phosphorus content was 5.64%.

Formula VIII

(2) Prepare an epoxy resin composition using A5 as a raw material, which is specifically prepared by the following method:

Weigh each raw material according to the ratio of raw materials in Table 2, put each raw material in a stirrer, stir at room temperature, mix evenly, and obtain resin composition C5.

(3) The resin composition C5 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

The resin composition was replaced by resin composition C5, and the others were the same as in Example 1 to obtain a laminate D5.

Comparative example 1

(1) An epoxy resin composition, specifically prepared by the following method:

Weigh each raw material according to the ratio of raw materials in Table 2, put each raw material in a stirrer, stir at room temperature, mix evenly, and obtain resin composition E1.

(3) The resin composition E1 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

The resin composition was replaced by resin composition E1, and the others were the same as in Example 1 to obtain laminate F1.

Comparative example 2

(1) An epoxy resin composition, specifically prepared by the following method:

Weigh each raw material according to the ratio of raw materials in Table 2, put each raw material in a stirrer, stir at room temperature, mix well, and obtain resin composition 2.

(3) The resin composition E2 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

The resin composition was replaced by the resin composition E2, and the others were the same as in Example 1 to obtain the laminate F2.

Comparative example 3

(1) An epoxy resin composition, specifically prepared by the following method:

Each raw material was weighed according to the ratio of raw materials in Table 2, each raw material was placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E3.

(3) The resin composition E3 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

The resin composition was replaced by the resin composition E3, and the others were the same as in Example 1 to obtain a laminate F3.

Comparative example 4

(1) A phosphobenzene bisphenol polymer B2, prepared by the following method:

The preparation method of the phosphobenzene bisphenol polymer in Example 1 is basically the same, the difference is that the reflux reaction temperature is 100° C., and the reaction time is 16 hours to obtain the product B2. MASS detects that the molecular mass is less than 1000, and the reactivity decreases.

(2) Prepare an epoxy resin composition using B2 as a raw material, which is specifically prepared by the following method:

Each raw material was weighed according to the ratio of raw materials in Table 2, each raw material was placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E4.

(3) The resin composition E2 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

The resin composition was replaced by resin composition E4, and the other was the same as in Example 1 to obtain laminate F4.

Comparative example 5

(1) A phosphobenzene bisphenol polymer B3, prepared by the following method:

The preparation method of the phosphobenzene bisphenol polymer in Example 1 is basically the same, the difference is that the reflux reaction temperature is 200° C., and the reaction time is 16 hours to obtain the product B3. The composition of the product detected by MASS is complex, n>8, and the phosphorus content is less than 1%.

(2) Prepare an epoxy resin composition using B3 as a raw material, which is specifically prepared by the following method:

Each raw material was weighed according to the ratio of raw materials in Table 2, each raw material was placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E5.

(3) The resin composition E3 is used as a raw material to prepare a laminate, which is specifically prepared by the following method:

The resin composition was replaced by the resin composition E5, and the others were the same as in Example 1 to obtain a laminate F5.

Comparative example 6

A phosphobenzene bisphenol polymer B1, prepared by the following method:

The preparation method of the phosphobenzene bisphenol polymer in Example 1 is basically the same, the difference is that no co-solvent pyridine is added. The product B1 is obtained. MASS detects that the molecular mass is less than 1000, and the reactivity decreases.

The phosphobenzene bisphenol polymer raw material, productive rate, phosphorus content and solubility etc. in embodiment and comparative example are as shown in table 1. [Table 1] Raw materials, reaction conditions, yield and solubility of phosphobenzene bisphenol polymers in Examples and Comparative Examples A1 A2 A3 A4 A5 B1 B2 B3 Tetramethylbisphenol A 2.84g 2.84g / 2.84g / 2.84g 2.84g 2.84g Tetramethylbisphenolcyclohexane / / 3.24g / 3.24g / / / Phenylphosphonyl dichloride 0.49g 0.49g 0.49g / / 0.49g 0.49g 0.49g Phenyl dichlorophosphate / / / 0.53g 0.53g / / / toluene 10 ml 10 ml 10 ml 10 ml 10 ml 20ml 10 ml 10 ml pyridine 10 ml 10 ml 10 ml 10 ml 10 ml 0 10 ml 10 ml Reflux reaction conditions 140°C, 16 hours 140°C, 6 hours 140°C, 16 hours 140°C, 16 hours 140°C, 16 hours 140°C, 16 hours 100°C, 16 hours 200°C, 16 hours Yield ≥80% 88.1% 86% 89% 83% <10% <10% <10%, high degree of polymerization no 5 4 3 3 3 <2 <2 >8 Phosphorus content 6.68% 6.92% 5.33% 5.8% 5.64% Unable to check out Unable to check out <1% Exterior light gray powder light gray powder light gray powder White powder light yellow powder light gray powder light gray powder dark brown powder Solubility Good solubility for benzene, ketone, amide, pyridine, etc. Good solubility for benzene, ketone, amide, pyridine, etc. Good solubility for benzene, ketone, amide, pyridine, etc. Good solubility for benzene, ketone, amide, pyridine, etc. Good solubility for benzene, ketone, amide, pyridine, etc. Good solubility for benzene, ketone, amide, pyridine, etc. Good solubility for benzene, ketone, amide, pyridine, etc. Good solubility for benzene, ketone, amide, pyridine, etc.

It can be seen from the above table that the phosphobenzene bisphenol polymers A1-A5 of the embodiments of the present invention have stable components and high solvent compatibility, and can be conveniently formulated and mixed with other plastics or substrates for application.

The ratio of raw materials of the resin composition in Examples and Comparative Examples is shown in Table 2. [Table 2] Raw material ratio (parts by weight) of the resin composition in the embodiment and the comparative example Novolak epoxy resin Phosphobenzene bisphenol polymer hardener 2-Methylimidazole toluene A1 A2 A3 A4 A5 BDP B2 B3 C1 100 50 / / / / / / / 30 0.1 150 C2 100 / 50 / / / / / / 30 0.1 150 C3 100 / / 50 / / / / / 30 0.1 150 C4 100 / / / 50 / / / / 30 0.1 150 C5 100 / / / / 50 / / / 30 0.1 150 E1 100 / / / / / 50 / / 30 0.1 150 E2 100 10 / / / / / / / 30 0.1 150 E3 100 80 / / / / / / / 30 0.1 150 E4 100 / / / / / / 50 30 0.1 150 E5 100 / / / / / / 50 30 0.1 150

Among them, novolac epoxy resin is KEP-1138 (KOLON, South Korea), BDP is bisphenol A-bis(diphenyl phosphate) (CAS No.: 5945-33-5, Taiwan Liuhe Chemical), hardener (curing agent ) using EPICLON HPC-8000-65T.

Experimental example 1

Carry out performance test to each laminated board in embodiment and contrast, test method is as follows:

(1) Glass transition temperature test: The glass transition temperature (Tg) was measured using a dynamic mechanical analyzer (DMA). The test specification for the glass transition temperature is the IPC-TM-650.2.4.25C and 24C detection methods of the Institute for Interconnecting and Packaging Electronic Circuits (IPC).

(2) Water absorption test: carry out the pressure cooker test (PCT) test, place the laminate in a pressure vessel, and test it under the environment of 121 ℃, saturated humidity (100% R.H.) and 1.2 atmospheric pressure for 2 hours. High humidity resistance of laminates.

(3) Thermal expansion coefficient and Z-axis direction expansion rate test: Tested with the thermal expansion analyzer model TA 2940 of TA instrument company, the test condition is 50 ° C to 260 ° C at a heating rate of 5 degrees per minute, and the test sample is 3 × 3 mm ² The coefficient of thermal expansion in the thickness direction (Z-axis direction) and the expansion rate in the z-axis direction of the laminate sample of different sizes.

(4) Thermal decomposition temperature test: use a thermogravimetric analyzer (TGA) to measure the temperature when the mass is reduced by 5% compared with the initial mass, which is the thermal decomposition temperature.

(5) Lead-free solder test: Take five copper-clad substrates with a size of 290 mm × 210 mm. After three times of lead free IR reflow, observe whether there is any cracking on the appearance of the copper-clad substrates.

(6) Tear strength test: Tear strength refers to the adhesion of copper foil to the substrate, usually the copper foil per inch (25.4 mm) width is torn vertically from the board surface, with the required force The size to express the strength of adhesion. MIL-P-55110E stipulates that the pass standard for substrates with 1 oz copper foil is 8 lb/in.

(7) Flammability test: Using UL94V, vertical combustion test method, fix the printed circuit board in a vertical position, burn it with a Bunsen burner, and compare its spontaneous extinguishment and combustion-supporting characteristics.

(8) Glue removal and delamination inspection: check the appearance of laminated boards. If there is delamination and precipitation between the components of the laminate and the filler, uneven distribution of the resin or uneven distribution of the filler, it indicates that there is debonding and delamination (judged as NG, that is, No Good); if there is no such phenomenon, it indicates that there is no delamination. Adhesive delamination phenomenon (determined as OK).

(9) Flatness test: Check the A4-sized laminate and place it flat on the granite marble platform. If the laminated board can be flatly attached to the platform, and the appearance is smooth and well-proportioned, without uneven crepes or lines or grains, the flatness is better; if the appearance is not smooth and uneven, or there are uneven crepes or lines Or the particles are raised, the flatness is poor.

The test results are shown in Table 3. [Table 3] Performance of laminated boards in Examples and Comparative Examples laminate Glass transition temperature (°C) Water absorption (%) Coefficient of thermal expansion (ppm/ ^o C) Z-axis expansion (%) Thermal decomposition temperature ( ^oC ) Lead Free Solder Test Tear Strength (1oz) (lb/in) UL94（Grade） No glue delamination flatness D1 172 0.63 36.7 1.63 375 PASS 9.0 V0 OK good D2 171 0.62 36.5 1.63 379 PASS 8.9 V0 OK good D3 175 0.62 29.4 1.52 381 PASS 8.7 V0 OK good D4 173 0.70 28.6 1.48 372 PASS 9.2 V0 OK good D5 176 0.72 25.2 1.31 375 PASS 9.1 V0 OK good F1 169 0.69 44.5 1.76 371 PASS 8.9 V0 NG inferior F2 170 0.62 29.5 1.50 372 PASS 8.9 V1 OK good F3 166 0.89 41.3 1.75 371 NG 9.2 V0 NG inferior F4 171 0.62 36.4 1.62 372 PASS 7.2 V0 OK good F5 170 0.68 38.9 1.72 369 NG 9.2 V1 NG inferior

It can be seen from Table 3 that the laminates D1 to D5 prepared by using the phosphobenzene bisphenol polymers A1 to A5 of Examples 1 to 5 of the present invention as flame retardants or epoxy resins as hardeners have excellent heat resistance, size Stability, and good flatness, no adhesive seal. However, the laminates of the control example have poor flatness, deglue delamination (such as F1, F3, F5), poor flame retardancy (such as F2, F5), or low tear strength (such as F4).

Compared with laminates F4, D2, D1 and F5, the polymerization amount n is preferably 2~5, n is too low (<2), the phosphorus content of phosphobenzene bisphenol polymer is high, the tear strength is low, and n is too high (>5), the phosphorus content is low, the flame retardant effect is only V1 grade, and the thermal stability of the laminate is deteriorated, the solder resistance is deteriorated, the flatness is poor, and there will be deglue and delamination.

Compared with laminates F2, D1 and F3, the addition of phosphobenzene bisphenol polymer is too low, the tear strength of the laminate is low, and the addition of phosphobenzene bisphenol polymer is too high, the heat resistance of the laminate is not good. Poor stability, poor solder resistance test.

Comparing the laminates F1, D1 and D4, compared with the commonly used BDP, using the phosphobenzene bisphenol polymer (R is CH ₃ CCH ₃ ) of the present invention, the obtained laminates have high Tg, high heat resistance and high thermal stability , Strong tear strength, no adhesive seal, good flatness.

），所得積層板的Tg高、耐熱性高、熱穩定性高，抗撕拉強度強，無排膠封層，平整性好。 Contrast laminates F1, D3 and D5, compared to commonly used BDP, adopt the phosphobenzene bisphenol polymer of the present invention (R is

), the resulting laminates have high Tg, high heat resistance, high thermal stability, strong tear strength, no adhesive sealing layer, and good flatness.

Comparing the laminates F1, D1 and D3, compared with the commonly used BDP, the Tg, heat resistance and thermal stability of D1 and D3 are better.

Comparing the laminates F1, D4 and D5, compared with the commonly used BDP, the Tg, heat resistance and thermal stability of D4 and D5 are better.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention shall be subject to the appended claims.

Figure 1 is the hydrogen nuclear magnetic resonance spectrum of phosphobenzene bisphenol polymer A1. Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the phosphobenzene bisphenol polymer A4.

Claims (10)

A phosphobenzene bisphenol polymer, wherein its structure is as shown in formula I or formula II:

Formula I

Formula II wherein, n=2~5, R is selected from: CH ₃ CCH ₃ ,

,

,

One of. A preparation method of the phosphobenzene bisphenol polymer as described in claim 1, wherein, according to the synthetic route shown in formula III or formula IV:

Formula III

Formula IV Mix phenylphosphonic dichloride or phenyl dichlorophosphate and tetramethylbisphenol compound, add solvent and co-solvent, and reflux reaction to obtain the compound shown in formula I or formula II. The preparation method of phosphobenzene bisphenol polymer as claimed in item 2, wherein, the tetramethyl bisphenol compound is selected from: tetramethyl bisphenol A,

,

,

. The preparation method of phosphobenzene bisphenol polymer as claimed in item 2, wherein the solvent is selected from: toluene. The preparation method of phosphobenzene bisphenol polymer according to claim 2, wherein the co-solvent is selected from one or both of pyridine and 4-dimethylaminopyridine. The preparation method of phosphobenzene bisphenol polymer as described in Claim 2, wherein the reflux reaction temperature is 120-180°C, and the reaction time is 10-20 hours. The preparation method of phosphobenzene bisphenol polymer according to claim 2, wherein the molar ratio of the phenylphosphonic acid dichloride or phenyl dichlorophosphate to tetramethyl bisphenol compound is 1: (1~2) . The preparation method of phosphobenzene bisphenol polymer as described in any one of claims 2 to 6, wherein, after the reflux reaction is completed, a purification step is also included: the product is washed with tetrahydrofuran or water, and the solvent is removed by distillation to obtain purified target product. An epoxy resin composition, including the phosphobenzene bisphenol polymer as described in Claim 1. An application of the phosphobenzene bisphenol polymer as described in claim 1 or the epoxy resin composition as described in claim 9 in the preparation of laminated boards.

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