TWI408143B - Compounds with asymmetric phosphorus-containing diphenols, derivatives, and one-pot method for preparing thereof - Google Patents

Abstract

Compounds having the following formula (I) and one-pot method for preparing thereof are disclosed, wherein R1-R6 are independently selected from the group consisting of hydrogen, C1-C10 alkyl, C1-C10 alkyoxy, C1-C10 halo-alkyl, C3-C10 cyclic alkyl, -CF3, -OCF3 and halogen, and if one of R5 and R6 is hydrogen, the other one would not be hydrogen. R7 is selected from the group consisting of phenyl, C1-C10 alkyl, C3-C10 cyclic alkyl, -CF3, and halogen. The advanced epoxy derivatives of the compounds having the following formula (II) are also disclosed. The advanced epoxy derivatives of the compounds having the following formula (II) can exhibit low water-absorption property.

Description

Compound having asymmetric phosphorus bisphenol structure, epoxy resin semi-cured derivative thereof and one-pot manufacturing method thereof

The present invention relates to a phosphorus-based bisphenol compound, a derivative thereof, and a process for producing the same, and, in particular, to a process for producing a derivative of a phosphorus-based bisphenol having an asymmetric structure and an epoxy resin semi-cured product.

In recent years, organophosphorus-containing compounds have been studied to improve the flame retardant properties of high molecular polymers. When the organophosphorus reactive groups are introduced into the main structure of the polymer, the polymer is more resistant to flame retardation. Compared with halogen-containing flame retardants, organophosphorus compounds do not produce toxic gases, and have the advantages of good processability, low added amount, and low smoke generation.

For example, a phosphorus-containing compound 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) is taken as an example. It is a compound having an active hydrogen atom reactive with an electron-deficient compound. DOPO can be associated with electron-deficient compounds such as benzoquinone, oxirane, bismaleimide, maleic acid, terephthalic arbonaldehyde, and diamines. Diaminobenzophenone reaction.

Bisphenol compounds are important industrial raw materials for the synthesis of many commercial polymer precursors, such as epoxy resins, benzoxazine resins, polyether quinones. (polyether imide), polyether ketone (PEK), polysulfone, polyester, and the like.

The phosphorus-based bisphenol monomer is a polymer which uses a reactive functional group of a bisphenol compound to introduce a phosphorus-containing group into a polymer material, thereby synthesizing a polymer having flame retardancy characteristics, excellent thermal properties, and thermal stability. For example, U.S. Patent Publication No. US 2010/0016585 A1 discloses a phosphorus bisphenol compound (DMP), a derivative thereof and a process for producing the same, which have been found to have high thermal properties and excellent heat. stability.

However, the thermal and electrical properties of the compound are affected by the moisture content of the material. Excessive moisture content will reduce the thermal and electrical properties of the material. In subsequent high-temperature processes, the material will be destroyed due to the instantaneous evaporation of the water. . Therefore, how to reduce the water absorption rate of the phosphorus bisphenol compound material and maintain its original properties is also an important issue.

It is pointed out in the research literature that introduction of a fluorine-containing group or an alkyl group into a compound structure can effectively reduce water absorption. However, in actual synthesis, it has been found that the introduction of a soft segment such as an alkyl group causes a decrease in the thermal properties of the material, which in turn affects the thermal properties of the subsequent derivative.

Therefore, the present invention utilizes a phosphorus-based bisphenol compound to introduce a fluorine-containing group and an alkyl group to form a phosphorus-based bisphenol compound having an asymmetric structure, which can not only effectively reduce the water absorption rate, but also maintain the original material due to the asymmetric structure. It has thermal properties.

One aspect of the present invention provides a series of phosphorus-based bisphenol compounds having an asymmetric structure and a one-pot process thereof, using an organic cyclic phosphorus compound represented by the formula (a), b) a compound, a compound of the formula (c) and a monoacid catalyst, which synthesize a phosphorus-based bisphenol compound having an asymmetric structure as shown in the formula (I).

According to one or more embodiments of the present invention, wherein R ₁ -R ₆ are each independently a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 haloalkyl group, a C3-C10 naphthenic ring. a group, -CF ₃ , -OCF ₃ or a halogen atom, and R ₅ and R _{6 are} not simultaneously a hydrogen atom, R ₇ is hydrogen, phenyl, C1-C10 alkyl, C3-C10 cycloalkyl, CF ₃ or halogen atom.

According to one or more embodiments of the present embodiment, a phosphorus-based bisphenol compound having an asymmetric structure is synthesized, and an acid catalyst is used in an amount of 0.1 wt% to 30 wt% of the organic phosphide raw material content represented by the formula (a). %, the acid catalyst can be protonic acid or Lewis acid.

According to one or more embodiments of the present embodiment, the phosphorus-based bisphenol compound having an asymmetric structure may be a compound represented by the following formulas (1) to (16):

Another aspect of the present invention provides a phosphorus-based epoxy resin semi-cured product derived from a compound having a structure represented by the general formula (I) and a process for producing the same.

According to one or more embodiments of the present embodiment, a method for producing a phosphorus-based epoxy resin semi-cured product includes a phosphorus-based bisphenol compound having an asymmetric structure represented by formula (I) (for example, Formula 1-16) The compound shown) is subjected to chain extension reaction with a compound having an epoxy group structure as shown in the formula (d) to obtain a phosphorus epoxy resin semi-cured epoxy resin having a low water absorption. The phosphorus-based epoxy resin semi-cured material can be further cured to form a phosphorus-based epoxy resin cured product having a low water absorption rate.

The epoxy resin semi-cured derivative synthesized according to the embodiment of the present invention has the structure of the general formula (II) shown below, and can be further cured to form a phosphorus-based epoxy resin cured product having a low water absorption ratio, and the general formula (II) Where n is an integer from 1 to 5.

According to one or more embodiments of the present embodiment, the chain extension reaction can be carried out at 100-200 ° C; the catalyst used is an imidazole compound, a tertiary phosphine, a tertiary amine, a quaternary phosphonium salt, boron trifluoride. Mismatched salt, lithium, quaternary phosphorus or quaternary amine compounds. Wherein the ratio of the number of epoxy equivalents to the phenolic equivalent is from 1:1 to 10:1; the amount of the catalyst used is from 0.1 to 5% by weight of the epoxy resin.

According to the above, the embodiments of the present invention have the following advantages:

1. The present invention provides a novel route for synthesizing a phosphorus-based bisphenol compound, successfully synthesizing a compound having an asymmetric phosphorus-based bisphenol structure by a one-pot process, and simplifying the conventional process requires at least two steps to synthesize a phosphorus double The shortcomings of phenolic compounds are suitable for industrial mass production.

2. A phosphorus-based bisphenol compound having an asymmetric structure synthesized by the embodiment of the present invention, which can improve the phosphorus double by hindering molecular stacking by an asymmetric structure The problem of poor solubility of the phenolic compound, in addition to the difficulty of rotating the molecular chain having an asymmetric structure with a more symmetrical structure, can also increase the glass transition temperature.

3. The phosphorus-based bisphenol compound having an asymmetric structure synthesized in the embodiment of the present invention, wherein a halogen-containing group or an alkyl group is introduced into the structure, can effectively reduce the water absorption of the material.

4. The phosphorus-based bisphenol compound having an asymmetric structure synthesized in the embodiment of the present invention can be semi-cured with an epoxy resin to synthesize a phosphorus-based epoxy resin semi-cured product having low water absorption characteristics, and the synthesis step is simple and has Convenient for processing and mass production.

5. A phosphorus-based epoxy resin semi-cured product according to an embodiment of the present invention, which has a high glass transition temperature and has excellent properties of low water absorption, good flame retardancy and thermal stability.

Embodiments of the present invention include: (a) a series of phosphorus-based bisphenol compounds having an asymmetric structure and a one-pot synthesis method thereof; (b) a phosphorus-based bisphenol compound having an asymmetric structure Epoxy resin semi-cured product derivative and its synthesis method.

The "one-pot synthesis method" as used herein refers to a plurality of reaction steps carried out in the same reaction vessel without separation and purification.

(1) Phosphorus bisphenol compound monomer having asymmetric structure and synthesis method thereof

According to an embodiment of the present invention, an organic cyclic phosphorus compound (DOPO) having an active hydrogen atom and an electron deficient compound such as 4-hydroxyl 4-Hydroxybenzophenone (4-HA) is reacted, and a phenol compound having different side chains can be introduced in the presence of an acid catalyst to synthesize a phosphorus-based bisphenol compound having an asymmetric structure. Further, in the reaction system, a phenol compound can be used as a solvent for the reaction.

According to one or more embodiments of the present embodiment, a phosphorus-based bisphenol compound having an asymmetric structure is synthesized, and an acid catalyst is used in an amount of from 0.1% by weight to 30% by weight based on the content of the organophosphorus compound (DOPO). The acid catalyst may be a protonic acid or a Lewis acid, for example, acetic acid, p-Toluenesulfonic acid (PTSA), methanesulfonic acid, and trifluoromethanesulfonic acid. , Fluorosulfonic acid, Calmagite, Sulfuric acid, Orthanilic acid, 3-Pyridinesulfonic acid, p-Aminobenzene Sulfanilic acid, hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), hydrogen fluoride (HF), trifluoroacetic acid (CF ₃ COOH), nitric acid (HNO ₃ ), phosphoric acid (H ₃ PO ₄ ), aluminum chloride (AlCl ₃ ), boron fluoride (BF ₃ ), iron bromide (FeBr ₃ ), ferric chloride (FeCl ₃ ), boron chloride (BCl ₃ ) or titanium chloride (TiCl _{4 )} ).

1A-1B is a diagram showing an organic cyclic phosphorus compound (formula a) and 4-hydroxybenzophenone (formula b), respectively, in combination with a phenol compound having a different substituent, in accordance with various embodiments of the present invention. Reaction, synthesis of a phosphorus-based bisphenol compound having an asymmetric structure as shown in Formula 1-16. Synthesis Example 1-4, which will be described later, will further explain the compound of Formula 1-16 shown in Figure 1A-1B. The synthetic steps.

Synthesis Example 1

In order to reduce the water absorption rate, Synthesis Example 1 is in the structure of a phosphorus bisphenol compound. The alkyl group is introduced, and the molecular stacking is hindered by synthesizing the asymmetric structure, thereby improving the solubility and making the molecular chain rotation difficult to increase the glass transition temperature.

The compounds represented by the formulae (1)-(7) are obtained by reacting DOPO, 4-hydroxybenzophenone with a series of alkyl-containing phenol compounds under acidic catalyst catalysis, and the synthesis steps are as follows: In a 0.5 liter three-neck reactor of a temperature indicating device, 13.6 g (0.1 mol) of 4-hydroxybenzophenone, 21.6 g (0.1 mol) of DOPO, 50 g of a phenol compound, and 0.86 g of a pair were added. Methylbenzenesulfonic acid, the reaction temperature was raised to 100 ° C, and the reaction system temperature was maintained at 100 ° C for 12 hours, and the precipitated product was washed in ethanol. After the cleaned product was filtered by suction, the filter cake was vacuum dried in a vacuum oven at 110 ° C to obtain a phosphorus-based bisphenol compound having an asymmetric structure. The molecular weight of the product was identified by high resolution mass spectrometry.

Using the method shown in Synthesis Example 1, a series of phosphorus-based bisphenol compounds (1) to (7) having an asymmetric structure were synthesized using different phenol compounds, and the molecular formula, molecular weight, and yield were summarized in Table 1 below:

Figure 2A is a ¹ H NMR spectrum of the product (1). The results of the spectral analysis showed that the molecular formula of the product (1) was indeed C ₂₇ H ₂₃ O ₄ P. The monomer synthesized by the method shown in Synthesis Example 1 has a relatively high purity.

Figure 2B is a ¹ H NMR spectrum of the product (2). The results of the spectral analysis showed that the molecular formula of the product (2) was indeed C ₂₈ H ₂₅ O ₄ P. The monomer synthesized by the method shown in Synthesis Example 1 has a relatively high purity.

Synthesis Example 2

In order to effectively hinder molecular stacking, Synthesis Example 2 introduces an alkyl group having a large steric hindrance into a structure of a phosphorus-based bisphenol compound, thereby making it difficult to rotate the molecular chain and thereby increasing the glass transition temperature.

In Synthesis Example 2, a phenol compound having a large steric hindrance as shown in Table 2 below was used, and the reaction system temperature was maintained at 100 to 130 ° C depending on the selected phenol compound in substantially the same manner as in the synthesis example 1. The finished product is washed with methanol to give a compound of the formula 8-10.

The products (8)-(10) synthesized by using different phenol compounds were synthesized by the method shown in Synthesis Example 2, and the results of the molecular formula, molecular weight and yield were summarized in Table 2 below:

Figure 2C is a ¹ H NMR spectrum of the product (8). The results of the spectral analysis showed that the molecular formula of the product (8) was indeed C ₃₀ H ₂₉ O ₄ P. The monomer synthesized by the method shown in Synthesis Example 2 has a relatively high purity.

Figure 2D is a ¹ H NMR spectrum of the product (10). The results of the spectral analysis showed that the molecular formula of the product (10) was indeed C ₃₄ H ₃₇ O ₄ P. The monomer synthesized by the method shown in Synthesis Example 2 has a relatively high purity.

Synthesis Example 3

Since the introduction of an alkyl group into the structure can effectively reduce the water absorption rate, Synthesis Example 3 utilizes a phenol compound containing a longer carbon chain to react with DOPO and 4-hydroxybenzophenone under acidic catalyst catalysis, and has a low water absorption rate. An asymmetric phosphorus bisphenol compound.

The procedure of Synthesis Example 3 was substantially the same as that of Synthesis Example 1, except that the product after completion of the reaction was dissolved in ethanol and then dropped into water to precipitate.

The products (11) and (12) synthesized by using different phenol compounds were synthesized by the method shown in Synthesis Example 3. The molecular formula, molecular weight and yield were summarized in Table 3 below:

Synthesis Example 4

Since the introduction of the fluorine-containing group into the structure can effectively reduce the water absorption, the synthesis example 4 utilizes a fluorine-containing phenol compound, reacts with DOPO and 4-hydroxybenzophenone under acidic catalyst catalysis, and can be synthesized to have low water absorption. The rate of asymmetric phosphorus bisphenol compounds.

The procedure of Synthesis Example 4 was substantially the same as that of Synthesis Example 1, except that the product after the completion of the reaction was dissolved in ethanol and then dropped into water to precipitate.

Using the method shown in Synthesis Example 4, the products (13)-(16) synthesized using different phenol compounds, the molecular formula, molecular weight and yield were summarized in Table 4 below:

(2) Epoxy resin semi-cured derivative of phosphorus-based bisphenol compound having asymmetric structure and synthesis method thereof

According to one or more embodiments of the present embodiment, the phosphorus-based bisphenol compounds (1) to (16) having an asymmetric structure synthesized in the above Synthesis Examples 1-4 may further have a ring in the presence of a catalyst. The compound having an oxy structure is subjected to a chain extension reaction to synthesize a low water-absorbent phosphorus-based epoxy resin semi-cured product.

According to one or more embodiments of the present embodiment, the compound having an epoxy group structure may be any suitable epoxy resin, including but not limited to diglycidyl ether of bisphenol A (DGEBA), bisphenol F. A difunctional epoxy compound such as diglycidyl ether of bisphenol F (DGEBF), diglycidyl ether of bisphenol S (DGEBS), or diglycidyl ether of biphenol. The ratio of the number of equivalents of epoxy groups to the number of equivalents of phenol groups is from 1:1 to 10:1.

The chain extension reaction can be carried out at 100-200 ° C, and the amount of the catalyst is 0.1-5 wt% of the epoxy resin content; the catalyst used may be an imidazole compound, a tertiary phosphine, a tertiary amine, a quaternary phosphonium salt, Boron trifluoride complex salt, lithium compound, quaternary phosphorus or quaternary amine compound. Wherein the imidazole compound can be, for example, 2-phenylimidazole (2-phenylimidazole), 2-methylimidazole (2MI); the tertiary phosphine may be, for example, triphenylphosphine (TPP); the quaternary phosphorus compound may be, for example, ethyltriphenylphosphonate (ethyltriphenyl) Phosphonium acetate) or ethyltriphenyl phosphonium halides; the quaternary amine compound may be, for example, benzyltrimethyl ammonium chloride or benzyltriethyl ammonium chloride Or tetrabutyl ammonium chloride.

An epoxy resin semi-cured derivative of a phosphorus-based bisphenol compound having an asymmetric structure synthesized according to the present embodiment has a structure of the following formula (II):

Wherein R _{1 to} R ₆ are each independently a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 haloalkyl group, a C3-C10 cycloalkyl group, a —CF ₃ , an —OCF ₃ or a halogen atom. And R ₅ and R _{6 are} not simultaneously a hydrogen atom, R ₇ is hydrogen, phenyl, C1-C10 alkyl, C3-C10 cycloalkyl, CF ₃ or a halogen atom, and n is an integer of 1-5. In order to demonstrate the influence of the side chain of the alkyl group or the fluorine-containing group on the properties of the phosphorus-based bisphenol epoxy resin cured product, the following Synthesis Examples 5-9 are based on the formulas (1), (2), (8) and (10). Taking the monomer shown as an example, a phosphorus-based bisphenol epoxy resin semi-cured product having an asymmetric structure is synthesized, and the products are named (1-2.0), (2-2.0), (8-2.0) and ( 10-2.0), and compared with the comparative example (DMP-2.0) with a symmetrical structure, the difference in water absorption and glass transition temperature. The curing of the phosphorus-based bisphenol epoxy resin semi-cured product synthesized by different monomers is determined by hardening the hardener 4,4-aminophenyl sulfonate (DDS), including: glass transition temperature. (Tg), UL-94 flame resistance test and water absorption test, UL-94 flame test is a test of the flame resistance of plastic materials in equipment and equipment. The data is shown in Table 5 below.

In the comparative example, 20 g of bisphenol A epoxy resin was placed in a 100 ml reactor, and the temperature was raised to 150 ° C and stirred for 1 hour. After adding 7.63 g of a monomer having a symmetrical phosphorus bisphenol structure (DMP) and 0.1 g of 2-methylimidazole, the reaction was maintained at 150 ° C for 2 hours, and then the product was poured out to have a symmetrical phosphorus bisphenol structure and a phosphorus content. It is a 2.0 wt% epoxy resin semi-cured product (DMP-2.0) with the following chemical formula:

The cured product of the epoxy resin semi-cured product (DMP-2.0) of the comparative example had a glass transition temperature of 195 ° C and a UL-94 ratio of V-0 (non-combustible). In the water absorption test, the water absorption rates at 1, 24, and 48 hours were 1.44, 2.07, and 2.49 wt%, respectively.

Synthesis Example 5

Synthesis Example 5 is a synthesis of an epoxy resin semi-cured product (1-2.0). Twenty grams of bisphenol A epoxy resin was placed in a 100 ml reactor and heated to 150 ° C for 1 hour with stirring. After adding 7.98 g of the phosphorus-based bisphenol monomer (1) having an asymmetric structure and 0.1 g of 2-methylimidazole, the reaction was maintained at 150 ° C for 2 hours, and then the product was poured out to be an epoxy having a phosphorus content of 2.0 wt%. Resin semi-cured (1-2.0) with the following chemical formula:

The product had an epoxy equivalent titration of 406 g/eq and a theoretical value of 398 g/eq.

The cured product of the epoxy resin semi-cured product (1-2.0) having a glass transition temperature of 193 ° C and a UL-94 rating of V-0 (non-combustible) was obtained from Table 5 below. In the water absorption test, the water absorption rates at 1, 24, and 48 hours were 1.41, 1.82, and 2.05 wt%, respectively, and it was found that the introduction of a methyl group caused a decrease in water absorption, compared with the symmetrical phosphorus bisphenol structure of the comparative example. The cured product of DMP-2.0 has a significant decrease in water absorption, and its glass transition temperature can still maintain a certain level.

Synthesis Example 6

Synthesis Example 6 is a synthesis of an epoxy resin semi-cured product (2-2.0), and the procedure thereof is substantially the same as that of Synthesis Example 5, except that 8.34 g of a monomer (2) having an asymmetric phosphorus-based bisphenol structure is added, and An epoxy resin semi-cured product of the following chemical formula:

The epoxy equivalent titration value of the product of Synthesis Example 6 was 411 g/eq, and the theoretical value was 405 g/eq. The properties were determined by hardening the hardener 4,4-diaminobisbenzoquinone (DDS), and the data are also shown in Table 5 above.

From Table 5, a cured product of an epoxy resin semi-cured product (2-2.0) having a glass transition temperature of 196 ° C and a UL-94 ratio of V-0 (non-combustible) was obtained. In the water absorption test, the water absorption rates at 1, 24, and 48 hours were 1.36, 1.71, and 1.84 wt%, respectively. It was obvious that the introduction of the asymmetric phosphorus bisphenol structure allowed the cured product to maintain the original high Tg characteristics, and The introduction of dimethyl group makes the water absorption lower than that of DMP-2.0.

Synthesis Example 7

Synthesis Example 7 is a synthesis of an epoxy resin semi-cured product (8-2.0), and the procedure thereof is substantially the same as that of Synthesis Example 5, except that 9.08 g of a monomer (8) having an asymmetric phosphorus-based bisphenol structure is added, and An epoxy resin semi-cured product of the following chemical formula:

The epoxy equivalent titration value of the product of Synthesis Example 7 was 426 g/eq, and the theoretical value was 422 g/eq. The properties were determined by hardening the hardener 4,4-diaminobisbenzoquinone (DDS), and the data are also shown in Table 5 above.

The cured product of the epoxy resin semi-cured product (2-2.0) was found in Table 5, and its UL-94 was measured to be a V-0 (non-combustible) grade. Although the long-chain segment of the tert-butyl group was introduced to slightly lower the glass transition temperature to 191 ° C, the cured product maintained high Tg characteristics due to the asymmetric phosphorus-based bisphenol structure. In the water absorption test, the water absorption rates at 1, 24, and 48 hours were 1.17, 1.50, and 1.63 wt%, respectively, and the water absorption was significantly lower than that of DMP-2.0.

Synthesis Example 8

Synthesis Example 8 is a synthesis of an epoxy resin semi-cured product (10-2.0), the procedure of which is substantially the same as that of Synthesis Example 5, except that 10.07 g of a monomer (8) having an asymmetric phosphorus-based bisphenol structure is added, and An epoxy resin semi-cured product of the following chemical formula:

The product of Synthesis Example 8 had an epoxy equivalent titration value of 471 g/eq and a theoretical value of 460 g/eq. The properties were determined by hardening the hardener 4,4-diaminobisbenzoquinone (DDS), and the data are also shown in Table 5 above.

The cured product of the epoxy resin semi-cured product (2-2.0) was found in Table 5, and its UL-94 was measured to be a V-0 (non-combustible) grade. Although the long-chain segment of di-tert-butyl was introduced, the cured product was maintained at a high Tg characteristic due to its asymmetric phosphorus-based bisphenol structure, and its glass transition temperature was slightly up to 194 °C. In the water absorption test, the water absorption rates at 12, 24, and 48 hours were 0.98, 1.17, and 1.25 wt%, respectively, and the water absorption was significantly lower than that of DMP-2.0.

According to the product property test of Synthesis Examples 5-8, it was found that the cured epoxy resin having an asymmetric phosphorus-based bisphenol structure not only has good thermal properties but also is cured as compared with an epoxy resin having a symmetrical phosphorus-based bisphenol structure. The water absorption rate of the substance can be effectively reduced by introducing an alkyl group.

It is also known from the properties of the above Synthesis Examples 5-8 that the epoxy resin cured product having the asymmetric phosphorus bisphenol of the embodiment of the present invention is suitable for the circuit board substrate, the semiconductor packaging material and the low water absorption requirement. Other related fields.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.

1A is a schematic diagram showing the synthesis of compounds (1) to (8) having an asymmetric phosphorus bisphenol structure according to an embodiment of the present invention;

1A is a schematic diagram showing the synthesis of compounds (9) to (16) having an asymmetric phosphorus-based bisphenol structure according to an embodiment of the present invention;

1B is a ¹ H NMR spectrum of the phosphorus-based bisphenol compound (Ia) according to an embodiment of the present invention;

2A is a ¹ H NMR spectrum of the compound (1) according to an example of the present invention;

2B is a ¹ H NMR spectrum of the compound (2) according to an example of the present invention;

2C is a ¹ H NMR spectrum of the compound (8) according to an example of the present invention;

Fig. 2D is a ¹ H NMR spectrum of the compound (10) according to an example of the present invention.

Claims (9)

A phosphorus epoxy resin semi-cured product having the structure represented by the following formula (II): Wherein R1 to R4 are each a hydrogen atom, and R5 and R6 each independently represent a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 haloalkyl group, a C3-C10 cycloalkyl group, or a CF ₃ group. , -OCF ₃ or a halogen atom, and R 5 and R 6 are not a hydrogen atom at the same time, R 7 is a C 1 -C 10 alkyl group, a phenyl group, a C 3 -C 10 cycloalkyl group, a CF ₃ or a halogen atom, and n is an integer of 1-5. Y is selected from the group consisting of the following groups: A phosphorus-based epoxy resin semi-cured product according to claim 1, wherein each of R _{1 to} R ₅ is a hydrogen atom, R ₇ is a methyl group, and R ₆ is selected from the group consisting of methyl, ethyl, propyl and isopropyl. a group consisting of tert-butyl, tert-butyl group, second butyl group, fluorine atom, trifluoromethyl group and trifluoromethoxy group. A phosphorus-based epoxy resin semi-cured product according to claim 1, wherein each of R _{1 to} R ₄ is a hydrogen atom, and R _{5 to} R ₇ are a methyl group. The phosphorus-based epoxy resin semi-cured product of claim 1, wherein R _{1 -} R _{4 are} each a hydrogen atom, R ₇ is a methyl group, R _{5 -} R ₆ are the same group, and R _{5 -} R ₆ are selected From the group consisting of ethyl, isopropyl and tert-butyl. A method for preparing a phosphorus-based epoxy resin semi-cured product, comprising: performing a chain extension reaction by reacting a phosphorus compound with an epoxy resin in the presence of a catalyst to synthesize a phosphorus-based epoxy resin semi-cured Wherein the structure of the phosphorus compound is as shown in formula (I): The structure of the epoxy resin is as shown in formula (d): The structure of the phosphorus epoxy resin semi-cured product is as shown in the formula (II): Wherein Y is selected from the group consisting of the following groups: R1-R4 are each a hydrogen atom, R5-R6 are each independently a hydrogen atom based, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 haloalkyl, C3-C10 cycloalkyl, -CF _3, - OCF ₃ or a halogen atom, and R 5 and R 6 are not a hydrogen atom at the same time, R 7 is a C1-C10 alkyl group, a phenyl group, a C 3 -C 10 cycloalkyl group, a CF ₃ or a halogen atom, and n is an integer of 1-5. The method for producing a phosphorus-based epoxy resin semi-cured material according to claim 5, wherein the epoxy group has an epoxy group equivalent ratio of the phosphorus compound to a phenol group equivalent ratio of from 1:1 to 10:1. The method for producing a phosphorus-based epoxy resin semi-cured material according to claim 5, wherein the catalyst is used in an amount of from about 0.1% by weight to about 5% by weight based on the epoxy resin. The method for producing a phosphorus-based epoxy resin semi-cured product according to claim 5, wherein the catalyst is an imidazole compound, a tertiary phosphine, a tertiary amine, a quaternary phosphonium salt, a boron trifluoride mis-salt salt, and a lithium compound. , quaternary phosphorus or quaternary amine compounds. The method for producing a phosphorus-based epoxy resin semi-cured product according to claim 8, wherein the catalyst is 2-phenylimidazole, 2-methylimidazole, triphenylphosphine, TPP), ethyltriphenyl phosphonium acetate, ethyltriphenyl phosphonium Halides), benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride or tetrabutyl ammonium chloride.