TW201619104A - Styrenic phosphinated phenol, epoxy thermoset and manufacturing method thereof - Google Patents

Abstract

A styrenic phosphinated phenol, an epoxy thermoset and manufacturing methods thereof are disclosed. The styrenic phosphinated phenol can be used as a hardener for manufacturing the epoxy thermoset, so that the epoxy thermoset can be featured with a high glass transition temperature and low dielectric properties.

Description

Ethylene phenylated phosphorus phenols, epoxy resin cured products and preparation method thereof

The present invention relates to a phosphorus phenol and a cured epoxy resin thereof, and a method for preparing the same, and particularly to a vinyl phenylated phosphorus phenol and an epoxy resin cured product thereof and System of law.

Epoxy resin has excellent electrical properties, dimensional stability, high temperature resistance, solvent resistance, low cost and high adhesion. It is suitable for printed circuit boards and integrated circuit packaging materials. However, epoxy resins bonded with carbon, hydrogen, and oxygen atoms are as easy to burn as normal plastic materials, which is life-threatening. Therefore, the world has strict requirements for the flame retardancy of electronic and information materials.

In the flame retardant technology, in the past, bromine atoms were mainly introduced into the epoxy resin. Brominated epoxy resins are widely used in electronic materials with flame retardant properties due to their excellent flame retardant properties. However, these bromine-containing epoxy resins release corrosive and toxic substances such as hydrogen bromide, tetrabromodibenzo-p-dioxin and tetrabromodibenzofuran during combustion.

In addition to halogen-containing compounds, organophosphorus compounds are also highly flame retardant. Phosphorus-based flame retardants will cause the polymer material to dehydrate first during combustion, so that the hydrogen of the hydrocarbon forms water with the oxygen in the air, thereby lowering the ambient temperature and making it lower than the combustion temperature to achieve a flame retardant effect. On the other hand, the phosphorus-based flame retardant decomposes under high-temperature heating to promote the carbonization of the polymer compound to form a non-combustible coke layer. In addition, phosphoric acid is further dehydrated and esterified at high temperature to form polyphosphoric acid. Polyphosphoric acid covers the surface of the combustion product to provide protection, which prevents oxygen from entering the unburned inner layer of the polymer and inhibits the release of volatile lysate. .

There are two methods for introducing phosphorus, one is to directly synthesize a phosphorus-containing epoxy resin, and the other is to harden a phosphorus-containing hardener and an epoxy resin to form a cured epoxy resin having a flame retardant effect.

Among the phosphorus-containing derivatives, the reactive 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, , DOPO) is highly regarded because it can be associated with electron-deficient compounds such as benzoquinone ^[1] , oxirane ^[2] , maleic acid ^[3] , double Malay The nucleophilic addition reaction of bismaleimide ^[4] , diaminobenzophenone ^[5-6] and terephthaldicarboxaldehyde ^[7] .

Wang et al. proposed in 2001 that the active hydrogen in DOPO can be used in an episodic manner to directly react with the epoxy group of a difunctional or polyfunctional epoxy resin to form a high glass transition temperature (Tg) and high thermal cracking. Temperature and high modulus of elasticity, and environmentally friendly flame retardant epoxy resin semi-cured ^[2] . Lin et al. also unveiled the synthesis method and application of trifunctional hardeners (dopotriol ^[8] and dopo-ta ^[9] ) in 2005, and successfully obtained flame retardant epoxy resin cured products with high glass transition temperature. However, the rosolic acid, a raw material for the synthesis of a trifunctional hardener (dopotriol) in the literature, is very expensive and is not economically viable in industrial applications, so Lin et al. followed the cheaper 4,4'-two in 2008. The reaction of 4,4'-dihydroxy benzophenone (DHBP) with DOPO and phenol/aniline successfully synthesizes phosphorus-containing flame retardants (dopotriol and dopodiolamine) ^[10] , and the epoxy resin cured by the curing thereof The material has excellent glass transition temperature, thermal stability, dimensional stability and flame retardancy. However, the aforementioned phosphorus-containing flame retardants (dopotriol and dopodiolamine) have a problem of poor solubility.

Phenolic resin is the earliest industrial synthetic resin. It is widely used in molding plastics, insulating materials, coatings, wood bonding, etc. due to the availability of raw materials, low water absorption, good processability and resin curing properties. In recent years, with the improvement of people's requirements for safety, phenolic resin with characteristics of flame retardancy, less smoke, and no toxicity has attracted people's attention, especially in public buildings such as airports, railway stations, schools, hospitals, and interior decoration of aircraft. There are more and more applications in materials and so on. It has been pointed out in the literature that bisphenol A will be cleaved by acid catalysis into phenol and unstable 4-isopropenylphonol ^[11] . Lin et al. based on this property will DOPO and polyfunctional bisphenol A. Phenolic resin (BPA novolac) synthesizes phosphorus-based polyfunctional bisphenol A phenolic resin under acid catalysis to obtain good flame retardancy.

However, the above-mentioned polyfunctional bisphenol A phenolic resin reacts with DOPO to lower its molecular weight, resulting in the synthesis of the phosphorus-based polyfunctional bisphenol A. The glass transition temperature of the phenolic resin is low, which affects its flame retardant properties. How to improve the structure of the phosphorus-based polyfunctional bisphenol A phenolic resin, so that it can be used as a hardener for a cured product having a high glass transition temperature, and is a researcher. The goal of hard work.

references:

[1] Wang, C.S. and Lin, C.H. Polymer 1999; 40; 747.

[2] Lin, C.H. and Wang, C.S. Polymer., 2001, 42, 1869.

[3] Wang, C.S.; Lin, C.H. and Wu, C.Y. J. Appl. Polym. Sci. 2000, 78, 228.

[4] Lin, C.H. and Wang, C.S. J. Polym. Sci. Part A: Polym. Chem. 2000, 38, 2260.

[5] Liu, Y.L. and Tsai, S.H. Polymer 2002; 43; 5757.

[6] Wu, C.S.; Liu, Y.L. and Chiu, Y.S. Polymer 2002; 43; 1773.

[7] Liu, Y.L.; Wang, C.S.; Hsu, K.Y. and Chang, T.C. J. Polym. Sci. Part A: Polym. Chem. 2002, 40, 2329.

[8] Lin, C.H.; Cai, S.X. and Lin, C.H. J. Polym. Sci. Polym. Chem. 2005, 43, 5971.

[9] Cai, S.X. and Lin, C.H. J. Polym. Sci. Polym. Chem. 2005, 43, 2862.

[10] Lin, CH; Lin, TL; Chang SL; Dai, SHA; Cheng, RJ; Hwang, KU; Tu, AP; Su, WCJ Polym. Sci. Part A: Polym. Chem. 2008, 46, 7898.

[11] Andrew J.C. and Julia L.L. J. Org. Chem. 1997, 62, 1058.

An object of the present invention is to provide a vinyl phenylated phosphorus phenol which can be used as a hardener for an epoxy resin, whereby the resulting epoxy resin cured product has a high glass transition temperature and a low dielectric. nature.

Another object of the present invention is to provide a process for producing a phosphorus phenylphosphorus phenol, whereby the ethylene phenylphosphine phenol can be used as a curing agent for an epoxy resin.

Another object of the present invention is to provide a cured epoxy resin having high glass transition temperature and low dielectric properties, which can provide excellent flame retardant properties and facilitate the production of electronic materials such as printed circuit boards and integrated bodies. Circuit packaging material.

Still another object of the present invention is to provide a method for producing a cured epoxy resin, whereby the cured epoxy resin has high glass transition temperature and low dielectric properties, and provides excellent flame retardant properties.

According to one embodiment of the present invention, there is provided a vinylphenylphosphorus phenol which comprises a structure as shown in formula (I) and/or formula (II):

Wherein each R ^{1 group} is independently H, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, F, Cl, Br or I, and each R ^{2 group} is independently H or (i) One of the structures shown: And at least one of the R ² is H, at least one of which is a structure represented by the formula (i), a is an integer of 0 to 30, and b is an integer of 1 to 30.

According to another embodiment of the present invention, there is provided a cured epoxy resin obtained by copolymerization of the aforementioned ethylene phenylphosphorus phenol and an epoxy resin.

According to an embodiment of another aspect of the present invention, there is provided a method for producing a vinylphenylphosphorus phenol, which comprises providing a polyphenol and performing a vinyl phenylation step. The polyphenols comprise a structure as shown by the formula (pre-I) and/or (pre-II):

Wherein each R ^{1 group} is independently H, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, F, Cl, Br or I, a is an integer of 0 to 30, and b is 1 to 30. The integer.

The ethylene phenylation step is carried out by reacting polyphenols with 4-chloromethylstyrene in the presence of a base catalyst to obtain the aforementioned ethylenephenylphosphorus phenols.

According to another embodiment of another aspect of the present invention, a method for preparing a cured epoxy resin, comprising performing a copolymerization step of mixing the aforementioned ethylene phenylphosphine phenols and an epoxy resin to form a vinyl phenyl group; The phosphorus phenols are copolymerized with an epoxy resin to form a cured epoxy resin.

To make the above and other objects, features, advantages and embodiments will become better understood, the accompanying drawings described as follows: ¹ H-NMR spectrum of the final product of the embodiment of FIG. 1 of the first embodiment graph; 2 The Figure ^{1 is a 1} H-NMR spectrum of the final product of Example 2; Figure 3 is a ¹ H-NMR spectrum of the final product of Example 3; and Figure 4 is a ¹ H-NMR spectrum of the final product of Example 4. FIG; Comparative Example 5 the picture shows the final spectrum of ¹ H-NMR of the product 1; Comparative Example 6 the picture shows the final spectrum of ¹ H-NMR of the product 2; the final product of Comparative Example 3 ¹ 7 Pictured H-NMR spectrum chart; Fig. 8 is a dynamic mechanical analysis (DMA) chart of the epoxy resin cured product of Comparative Example 4 and Examples 5 to 7; and Fig. 9 is a comparative example 4 and Example 5 to the example A thermogravimetric loss analysis (TGA) chart of the cured epoxy resin of 7; a DMA chart of the cured epoxy resin of Comparative Example 5 and Examples 8 to 10; and a comparative example 5 of FIG. And TGA diagrams of the cured epoxy resins of Examples 8 to 10.

<Ethylene Phenyl Phosphate Phenols>

The vinylphenylphosphorus phenols include a structure as shown in formula (I) and/or formula (II):

Wherein each R ^{1 group} is independently H, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, F, Cl, Br or I, and each R ^{2 group} is independently H or (i) One of the structures shown:

And at least one of the R ² is H, at least one of which is a structure represented by the formula (i), a is an integer of 0 to 30, and b is an integer of 1 to 30.

<Preparation method of ethylene phenylphosphorus phenols>

A method for producing a vinyl phenylphosphorus phenol, which comprises providing a polyphenol and performing a vinyl phenylation step.

The polyphenols comprise a structure as shown by the formula (pre-I) and/or (pre-II):

A vinyl phenylation step is carried out by reacting polyphenols with 4-chloromethylstyrene in the presence of a base catalyst to obtain the aforementioned ethylene phenylated phosphorus phenols.

The polyphenols may have a phosphorus content of from 3 to 8 weight percent based on the aforementioned preparation method of the ethylene phenylphosphorus phenol. When the phosphorus content is low At 3 wt%, there is a lack of flame retardancy, and when the phosphorus content is more than 8 wt%, there is a lack of thermal properties such as poor thermal stability or poor heat resistance.

According to the above preparation method of the ethylene phenylphosphorus phenol, the equivalent number of 4-chloromethylstyrene may be 10% to 80% of the total equivalent amount of the phenol group of the polyphenol. When the equivalent number of 4-chloromethylstyrene is less than 10%, when the ethylene phenylated phosphorus phenol is used to prepare a cured epoxy resin, the water absorption of the cured epoxy resin is too high, when 4- The equivalent number of chloromethyl styrene is higher than 80%, and the solubility of ethylene phenylphosphine phenols is drastically lowered. Preferably, the number of equivalents of 4-chloromethylstyrene may range from 30% to 80% of the total number of equivalents of the phenolic group of the polyphenol.

According to the preparation method of the aforementioned ethylene phenylphosphorus phenols, the alkali catalyst may be potassium carbonate (K ₂ CO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydroxide (KOH), sodium hydroxide (NaOH). Or sodium bicarbonate (NaHCO ₃ ). The molar ratio of 4-chloromethylstyrene to base catalyst can be from 1 to 0.8 to 1 to 1.2. When the content of the alkali catalyst is low, there is a possibility that the reaction is incomplete and the hydrochloric acid remains. When the content of the alkali catalyst is high, there is a possibility that the alkali catalyst remains and the unmodified phenol group is salinized. .

According to the above preparation method of the ethylene phenylphosphorus phenol, the ethylene phenylation step can be carried out using a solvent or without using a solvent. If carried out in a solvent, the solvent used may be N,N-dimethylacetamide (DMAC), ethoxyethanol, methoxyethanol, 1-methoxy- 2-propoxy-2-propanol, monomethyl ether propylene glycol Monomethyl ether, DOW PM), dioxane or a cosolvent consisting of the above solvents. The reaction time of the vinyl phenylation step may be from 12 hours to 48 hours. The reaction temperature of the vinyl phenylation step may be from 80 ° C to 160 ° C.

Polyphenols can be prepared by providing a compound of the formula (ii) and formula (iii) in the presence of an acid catalyst to obtain polyphenols:

In formula (III), R ¹ s each line is independently H, C 1 alkyl group, a cycloalkyl group having a carbon number of 3-6, F, Cl, Br or I 6, n is an integer from 1 to 60.

In the above reaction, the compound of the formula (ii) can be reacted with the isopropylidiene at the terminal position and/or the intermediate position of the compound of the formula (iii), and thus the structure of the product polyphenol contains the formula (pre-I) and/or Or the structure shown by the formula (pre-II).

In the preparation method of the above polyphenols, the acid catalyst may be acetic acid, p-toluenesulfonic acid (PTSA), methanesulfonic acid, fluorosulfonic acid, trifluoromethanesulfonate. Trifluoromethanesulfonic acid, sulfuric acid, orthanilic acid, 3-pyridinesulfonic acid, 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 ) or a combination of the foregoing various acids. The acid catalyst may be used in an amount of from 0.1% by weight to 10% by weight, based on the compound of the formula (iii), preferably from 1% by weight to 5% by weight. The reaction time may be from 6 hours to 24 hours, preferably from 12 hours to 20 hours. The reaction temperature can be from 60 ° C to 150 ° C. The preparation method of the above polyphenols can be carried out with or without a solvent. If it is carried out using a solvent, the solvent used may be the same as that used in the aforementioned vinyl phenylation step.

<Epoxy resin cured product>

The epoxy resin cured product is obtained by copolymerization of the above-mentioned ethylene phenylphosphorus phenols and an epoxy resin.

The epoxy resin may be a diglycidyl ether of bisphenol A (DGEBA) or a dicyclopentadiene type novolac epoxy resin according to the aforementioned epoxy resin cured product.

According to the cured epoxy resin, the equivalent ratio of the ethylene phenylphosphorus phenol to the epoxy resin is 1 to 1, and when the number of equivalents of the ethylene phenylphosphine phenol is less than the equivalent number of the epoxy resin, the residue remains. When the number of equivalents of the ethylene phenylated phosphorus phenols is larger than the equivalent number of the epoxy resin, the unreacted epoxy group improves the material brittleness of the epoxy resin cured product.

<Preparation method of epoxy resin cured product>

A method for preparing an epoxy resin cured product, comprising performing a copolymerization step of mixing the above-mentioned ethylene phenylphosphine phenols and an epoxy resin to copolymerize ethylene phenylphosphine phenols with an epoxy resin to form an epoxy resin; Resin cured product.

According to the preparation method of the epoxy resin cured product, the epoxy resin may be a bisphenol A epoxy resin or a dicyclopentadiene type novolac epoxy resin.

According to the method for producing a cured epoxy resin, the equivalent ratio of the phosphorus phenylphosphorus phenol to the epoxy resin may be 1 to 1.

According to the preparation method of the foregoing epoxy resin cured product, the copolymerization step may further comprise adding a hardening accelerator and a radical initiator. The hardening accelerator may be a nitrogen-based accelerator and a phosphorus-based accelerator such as imidazole. The free radical initiator can be azobisisobutyronitrile (AIBN) or a peroxide such as t-butyl cumyl peroxide (TBCP). The hardening accelerator may be added in an amount of 0.2% by weight to 0.5% by weight of the epoxy resin. When the amount of the hardening accelerator added is lower than the lower limit, there is a possibility that the reaction may be incomplete, and when the amount of the hardening accelerator added is higher than the upper limit, There is a possibility that the hardening accelerator remains and the material properties of the cured epoxy resin are lowered. The content of the radical initiator may be from 0.2% by weight to 0.5% by weight of the ethylene phenylphosphine phenol. When the amount of the radical initiator is less than the lower limit, there is a possibility that the reaction is incomplete, and when the amount of the radical initiator added is higher than the upper limit, the material having the radical initiator remains and causing the cured epoxy resin The possibility of a decrease in nature.

According to the preparation method of the foregoing epoxy resin cured product, the copolymerization step The reaction time can be from 2 hours to 8 hours. The reaction temperature of the copolymerization step may be from 180 ° C to 220 ° C.

According to the above embodiment, the specific embodiments will be described in detail below.

Example 1. Synthesis of polyphenols (P3)

The polyphenol (P3) having a phosphorus content of 3 wt% is obtained by reacting a compound of the formula (iii-1) with the compound of the above formula (ii) under acid catalysis, and the compound of the formula (iii-1) is as follows:

The synthesis steps of the polyphenols (P3) are as follows: 50 g of the compound of the formula (iii-1), 13.227 g of the compound of the formula (ii) and 2 g are added to a 0.5 liter three-necked reactor equipped with a temperature indicating device. The p-toluenesulfonic acid, wherein the amount of p-toluenesulfonic acid is 4 wt% of the compound of the formula (iii-1), the reaction system temperature is maintained at 140 ° C, and after 12 hours of reaction, a dope is obtained, and the adsorbent is washed away with the aqueous methanol solution. The residual p-toluenesulfonic acid was subjected to suction filtration, and the filter cake was taken. The filter cake was vacuum dried at 100 ° C in a vacuum oven, and the final product was obtained after drying. Referring to Fig. 1, which is a ¹ H-NMR spectrum of the final product of Example 1, it can be confirmed from Fig. 1 that the final product of Example 1 is a polyphenol (P3) having a phosphorus content of 3 wt%.

Example 2: Synthesis of ethylene phenylated phosphorus phenols (P3-S1)

10% ethylene phenylphosphine phenol (P3-S1) is a polyphenol (P3) having a phosphorus content of 3% by weight (from Example 1) reacted with 4-chloromethylstyrene under base catalysis. The synthesis procedure is as follows: 30 g of polyphenols (P3), 3.61 g of 4-chloromethylstyrene, 2.942 g of carbonic acid are added to a 0.5 liter three-neck reactor equipped with a temperature indicating device. Potassium and 300 ml of N,N-dimethylacetamide as a solvent, the reaction system temperature was maintained at 110 ° C, and the reaction was carried out for 24 hours. After the reaction was completed, the reaction solution was deionized with water to precipitate the product, and subjected to suction filtration. The filter cake was taken and the filter cake was vacuum dried at 50 ° C in a vacuum oven to obtain the final product of the brown powder. Please refer to Fig. 2, which is a ¹ H-NMR spectrum of the final product of Example 2. From Fig. 2, it can be confirmed that the final product of Example 2 is 10% ethylene phenylated phosphorus phenol (P3-S1). Nothing wrong. "10%" of 10% ethylene phenylphosphorus phenol (P3-S1) represents the modification ratio, that is, the equivalent number of 4-chloromethylstyrene is the total equivalent of the phenol group of polyphenols (P3). 10 percent of the number.

Example 3: Synthesis of ethylene phenylated phosphorus phenols (P3-S3)

30% ethylene phenylphosphine phenol (P3-S3) is a polyphenol (P3) having a phosphorus content of 3 wt% (from Example 1) reacted with 4-chloromethylstyrene under base catalysis. The synthesis procedure is as follows: 30 g of polyphenols (P3), 10.83 g of 4-chloromethylstyrene, 8.83 g of carbonic acid are added to a 0.5 liter three-neck reactor equipped with a temperature indicating device. Potassium and 300 ml of N,N-dimethylacetamide as a solvent, the reaction system temperature was maintained at 110 ° C, and the reaction was carried out for 24 hours. After the reaction was completed, the reaction solution was deionized with water to precipitate the product, and subjected to suction filtration. The filter cake was taken and the filter cake was vacuum dried at 50 ° C in a vacuum oven to obtain the final product of the brown powder. Please refer to Fig. 3, which is the ¹ H-NMR spectrum of the final product of Example 3. From Fig. 3, it can be confirmed that the final product of Example 3 is 30% ethylene phenylated phosphorus phenol (P3-S3). Nothing wrong. "30%" of 30% ethylene phenylphosphorus phenol (P3-S3) represents the modification ratio, that is, the equivalent number of 4-chloromethylstyrene is the total equivalent of the phenol group of polyphenols (P3). 30 percent of the number.

Example 4: Synthesis of ethylene phenylated phosphorus phenols (P3-S5)

50% ethylene phenylphosphine phenol (P3-S5) is a polyphenol (P3) having a phosphorus content of 3 wt% (from Example 1) reacted with 4-chloromethylstyrene under base catalysis. The synthesis procedure is as follows: 30 g of polyphenols (P3), 18.05 g of 4-chloromethylstyrene, and 14.71 g of carbonic acid are added to a 0.5 liter three-neck reactor equipped with a temperature indicating device. Potassium and 300 ml of N,N-dimethylacetamide as a solvent, the reaction system temperature was maintained at 110 ° C, and the reaction was carried out for 24 hours. After the reaction was completed, the reaction solution was deionized with water to precipitate the product, and subjected to suction filtration. The filter cake was taken and the filter cake was vacuum dried at 50 ° C in a vacuum oven to obtain the final product of the brown powder. Please refer to Fig. 4, which is a ¹ H-NMR spectrum of the final product of Example 4. From Fig. 4, it can be confirmed that the final product of Example 4 is 50% ethylene phenylphosphine phenol (P3-S5). Nothing wrong. The "50%" of 50% ethylene phenylphosphorus phenols (P3-S5) represents the modification ratio, that is, the equivalent number of 4-chloromethylstyrene is the total equivalent of the phenolic group of polyphenols (P3). 50 percent of the number.

Comparing Fig. 1 to Fig. 4, it is apparent that 1, 2', 3 of 4-chloromethylstyrene in the final products of Examples 2 to 4 as the amount of 4-chloromethylstyrene added increases. The characteristic peaks of the number are gradually increased, and the Ar-OH characteristic peak of 9.0 ppm to 9.6 ppm is gradually decreased (Ar is a phenyl group), indicating that the upgrading is successful.

Comparative Example 1. Synthesis of methyl methacrylate-based phosphorus phenols (P3-M3)

30% methyl methacrylate phosphorus phenol (P3-M3) is a polyphenol (P3) having a phosphorus content of 3% by weight (from Example 1) and methacrylic anhydride at 4 - dimethylamino pyridine (4-DMAP) catalyzed reaction, the synthesis steps are as follows: in a 0.5 liter three-neck reactor with a temperature indicating device, add 30 grams of polyphenols ( P3), 9.522 g of methacrylic anhydride, 0.381 g of 4-DMAP, and 300 ml of N,N-dimethylacetamide as a solvent, wherein 4-DMAP is added in an amount of 4 wt% of methacrylic anhydride. The reaction system temperature was maintained at 50 ° C, and the reaction was carried out for 24 hours. After the reaction was completed, the reaction solution was deionized with water to precipitate a product to obtain a gray viscous material, which was subjected to suction filtration, and the filter cake was taken. The filter cake was vacuum oven at 40 ° C. Drying in a vacuum gives the final product of the gray powder. Please refer to Fig. 5, which is a ¹ H-NMR spectrum of the final product of Comparative Example 1. "30%" of 30% methyl methacrylate phosphorus phenols (P3-M3) represents the modification ratio, that is, the equivalent number of methacrylic anhydride is the total number of phenolic groups of polyphenols (P3) 30 percent.

Comparative Example 2, Synthesis of methyl methacrylate, phosphorus phenol (P3-M5)

50% methyl methacrylate-phosphorus phenol (P3-M5) is a polyphenol (P3) having a phosphorus content of 3 wt% (from Example 1) and methacrylic anhydride under 4-DMAP catalysis The reaction was carried out in the following steps: in a 0.5 liter three-neck reactor equipped with a temperature indicating device, 30 g of polyphenols (P3), 15.87 g of methacrylic anhydride, and 0.635 g of 4-DMAP were added. And 300 ml of N,N-dimethylacetamide as a solvent, wherein 4-DMAP is added in an amount of 4 wt% of methacrylic anhydride, the reaction system temperature is maintained at 50 ° C, and the reaction is carried out for 24 hours, after the reaction is completed The reaction solution was deionized water to precipitate the product to obtain a gray viscous material, which was subjected to suction filtration, and the filter cake was taken. The filter cake was vacuum dried at 40 ° C in a vacuum oven to obtain a final product of the gray powder. Please refer to Fig. 6, which is a ¹ H-NMR spectrum of the final product of Comparative Example 2. "50%" of 50% methyl methacrylate phosphorus phenols (P3-M5) represents the modification ratio, that is, the equivalent number of methacrylic anhydride is the total number of phenolic groups of polyphenols (P3) 50 percent.

Comparative Example 3, Synthesis of methyl methacrylate-based phosphorus phenols (P3-M7)

70% methyl methacrylate-phosphorus phenol (P3-M7) is a polyphenol (P3) having a phosphorus content of 3 wt% (from Example 1) and methacrylic anhydride under 4-DMAP catalysis The reaction was carried out in the following steps: in a 0.5 liter three-neck reactor equipped with a temperature indicating device, 30 g of polyphenols (P3), 22.218 g of methacrylic anhydride, and 0.889 g of 4-DMAP were added. And 300 ml of N,N-dimethylacetamide as a solvent, wherein 4-DMAP is added in an amount of 4 wt% of methacrylic anhydride, the reaction system temperature is maintained at 50 ° C, and the reaction is carried out for 24 hours, after the reaction is completed The reaction solution was deionized water to precipitate the product to obtain a gray viscous material, which was subjected to suction filtration, and the filter cake was taken. The filter cake was vacuum dried at 40 ° C in a vacuum oven to obtain a final product of the gray powder. Please refer to Fig. 7, which is a ¹ H-NMR spectrum of the final product of Comparative Example 3. "70%" of 70% methyl methacrylate phosphorus phenols (P3-M7) represents the modification ratio, that is, the equivalent number of methacrylic anhydride is the total number of phenolic groups of polyphenols (P3) 70 percent.

Comparing Fig. 1 and Fig. 5 to Fig. 7, in which the final product of Comparative Example 1 has a reaction solvent (marked at *), the reaction solvent may not be washed away smoothly due to high viscosity, and Comparative Example 2 and Comparative Example 3 The final product showed a failure to respond. From the results of Comparative Example 1 to Comparative Example 3, it was found that it was difficult to successfully reform the polyphenols (P3) by methacrylic anhydride.

Example 5, synthetic epoxy resin cured product (P3-S1/DGEBA)

Using the ethylene phenylphosphorus phenol (P3-S1) of Example 2 as a hardener, the ethylene phenylphosphine phenol (P3-S1) and DGEBA were placed in a mold at an equivalent ratio of 1:1. Uniformly mixed, and added with imidazole (addition amount of DGEBA 0.2wt%) as the hardening accelerator for the reaction and t-butyl cumene peroxide (addition amount of ethylene phenylated phosphorus phenols (P3-S1) 0.2 wt%) was used as a radical initiator, and each was reacted at 180 ° C, 200 ° C, and 220 ° C for 2 hours to obtain a cured epoxy resin (P3-S1/DGEBA).

Example 6. Synthetic epoxy resin cured product (P3-S3/DGEBA)

The hardener ethylene phosphine phenol (P3-S1) in Example 5 The ethylene phenylphosphorus phenol (P3-S3) of Example 3 was changed, and the other reaction conditions and procedures were the same to obtain a cured epoxy resin (P3-S3/DGEBA).

Example 7, Synthetic Epoxy Resin (P3-S5/DGEBA)

The hardener vinylphenylphosphonate phenol (P3-S1) in Example 5 was changed to the ethylene phenylphosphine phenol (P3-S5) of Example 4, and the other reaction conditions and procedures were the same. A cured epoxy resin (P3-S5/DGEBA) was obtained.

Comparative Example 4, synthetic epoxy resin cured product (P3/DGEBA)

The hardener vinylphenylphosphorus phenol (P3-S1) in Example 5 was changed to the polyphenol (P3) of Example 1, and the other reaction conditions and procedures were the same to obtain a cured epoxy resin ( P3/DGEBA).

Please refer to FIG. 8 , which is a DMA diagram of the cured epoxy resin of Comparative Example 4 and Examples 5 to 7. It shows that the higher the modification ratio of the curing agent, the higher the glass transition temperature of the cured epoxy resin. High, when using unmodified polyphenols (P3) as a hardener, the epoxy resin cured product of Comparative Example 4 (P3/DGEBA) has a glass transition temperature of about 132 ° C when using modified ethylene benzene. The phosphorus-based phenol (P3-S5) is used as a hardener, and the glass transition temperature of the epoxy resin cured product (P3-S5/DGEBA) of Example 7 is greatly increased to about 202 ° C, and is increased by about 70 ° C. When the ethylene phenylphosphine phenol of the invention is used as a curing agent for an epoxy resin, the cured epoxy resin can have a high glass transition temperature.

Please refer to FIG. 9 , which is a TGA diagram of the cured epoxy resin of Comparative Example 4 and Examples 5 to 7, showing that the modified ratio of the hardener is higher. High, the coke residual ratio of the epoxy resin cured product is also higher, when the unmodified polyphenol (P3) is used as the hardener, the coke residual ratio of the cured epoxy resin (P3/DGEBA) of Comparative Example 4 About 17%, when the modified ethylene phenylphosphorus phenol (P3-S5) is used as a hardener, the coke residual ratio of the cured epoxy resin (P3-S5/DGEBA) of Example 7 is about increased. When the use of the ethylene phenylphosphine phenol of the present invention as a curing agent for an epoxy resin is shown to be 45%, the cured epoxy resin can have excellent thermal stability.

Please refer to Table 1, which is the water absorption test results of the cured epoxy resin of Comparative Example 4 and Examples 5 to 7. The test method is as follows: epoxy resin of Comparative Example 4 and Examples 5 to 7 The cured product was cut into 1 x 1 x 0.3 cm, and the weight was weighed and placed in boiling water. At intervals, the cured epoxy resin was taken out and wiped and weighed.

As can be seen from Table 1, when the unmodified polyphenol (P3) was used as the hardener, the epoxy resin cured product (P3/DGEBA) of Comparative Example 4 had a water absorption rate of about 1.72% for 48 hours. The ethylene phenylphosphorus phenol (P3-S1) as a curing agent, the epoxy resin cured product of Example 5 (P3-S1/DGEBA) has a water absorption rate of 2.30% for 48 hours, and it is estimated that it should be ethylene. After phenylation, the result of the interaction between the free volume effect and the polarity of the overall structure of the cured epoxy resin is obtained, and when the modification ratio is increased, the water absorption rate is lowered, and the rings of Embodiment 6 and Example 7 are obtained. The oxygen resin cured product A) had a water absorption rate lower than that of Comparative Example 4 at 48 hours.

Example 8, synthetic epoxy resin cured product (P3-S1/HP7200)

Using the ethylene phenylphosphorus phenol (P3-S1) of Example 2 as a curing agent, the ethylene phenylated phosphorus phenol (P3-S1) and the dicyclopentadiene novolac epoxy resin (HP7200) were Evenly mixed in the mold at an equivalent ratio of 1:1, and additional imidazole (added in an amount of 0.2wt% of HP7200) as a hardening accelerator for the reaction and t-butyl cumene peroxide (addition amount of ethylene benzene) The 0.2 wt% of the phosphorylated phenols (P3-S1) was used as a radical initiator, and reacted at # ° C for # hours to obtain a cured epoxy resin (P3-S1/HP7200).

Example 9. Synthetic epoxy resin cured product (P3-S3/HP7200)

The hardener ethylenephenylphosphine phenol (P3-S1) in Example 8 was changed to the ethylene phenylphosphine phenol (P3-S3) of Example 3, and the other reaction conditions and procedures were the same. A cured epoxy resin (P3-S3/HP7200) was obtained.

Example 10, synthetic epoxy resin cured product (P3-S5/HP7200)

The hardener vinylphenylphosphonate phenol (P3-S1) in Example 8 was changed to the ethylenephenylphosphorus phenol (P3-S5) of Example 4, and the other reaction conditions and procedures were the same. A cured epoxy resin (P3-S5/HP7200) was obtained.

Comparative Example 5, synthetic epoxy resin cured product (P3/HP7200)

The hardener ethylene phenylated phosphorus phenol (P3-S1) in Example 8 was changed to the polyphenol (P3) of Example 1, and the other reaction conditions and procedures were the same to obtain a cured epoxy resin ( P3/HP7200).

Please refer to FIG. 10 , which is a DMA diagram of the cured epoxy resin of Comparative Example 5 and Examples 8 to 10, showing that the higher the modification ratio of the hardener, the higher the glass transition temperature of the cured epoxy resin. High, when using unmodified polyphenols (P3) as a hardener, the epoxy resin cured product of Comparative Example 5 (P3/HP7200) has a glass transition temperature of about 149 ° C when using modified vinyl benzene. The phosphorus-based phenol (P3-S5) is used as a curing agent, and the glass transition temperature of the epoxy resin cured product (P3-S5/HP7200) of Example 10 is greatly increased to about 200 ° C, and is increased by about 51 ° C. When the ethylene phenylphosphine phenol of the invention is used as a curing agent for an epoxy resin, the cured epoxy resin can have a high glass transition temperature.

Please refer to FIG. 11 , which is a TGA diagram of the cured epoxy resin of Comparative Example 5 and Examples 8 to 10, showing that the higher the modification ratio of the hardener, the higher the coke residual ratio of the cured epoxy resin. High, when using unmodified polyphenols (P3) as a hardener, the epoxy resin cured product of Comparative Example 5 (P3/HP7200) has a coke residual ratio of about 15% when using modified vinylbenzene. The phosphorus-based phenol (P3-S5) was used as a hardener, and the coke residual ratio of the epoxy resin cured product (P3-S5/HP7200) of Example 10 was raised to about 25%, indicating the use of the ethylene phenylation of the present invention. When the phosphorus phenol is used as a curing agent for an epoxy resin, the resulting epoxy resin cured product can have excellent thermal stability.

Please refer to Table 2, which is Comparative Example 5 and Example 8 to the embodiment. The water absorption test results of the cured epoxy resin of 10, the test method is as described above, and will not be described again.

It can be seen from Table 2 that when the unmodified polyphenol (P3) is used as the hardener, the epoxy resin cured product of Comparative Example 5 (P3/HP7200) has a water absorption rate of 1.06% for 48 hours, when the modified product is used. The ethylene phenylphosphorus phenol (P3-S1) was used as a curing agent, and the epoxy resin cured product (P3-S1/DGEBA) of Example 8 had a water absorption rate of 1.41% for 48 hours, which was supposed to be ethylene phenylation. After that, the result of the interaction between the free volume effect and the polarity of the overall structure of the cured epoxy resin is obtained, and when the modification ratio is increased, the water absorption rate is lowered, and the epoxy resins of Example 9 and Example 10 are cured. The water absorption of the material A) for 48 hours was lower than that of Comparative Example 5.

Please refer to Table 3, which is the dielectric constant (Dk) and dielectric loss (Df) measurement results of the epoxy resin cured materials of Comparative Examples 4 to 5 and Examples 5 to 10. The method was as follows: The epoxy resin cured materials of Comparative Examples 4 to 5 and Examples 5 to 10 were cut into 1 x 1 x 0.3 cm, and the surface was ground and directly measured by an RF impedance/material analyzer (Model: Agilgent E4991A).

It can be seen from Table 3 that the higher the modification ratio of the hardener, the lower the dielectric constant and dielectric loss of the cured epoxy resin, and the use of the ethylene phenylphosphorus phenols of the present invention as an epoxy. When the hardener of the resin is used, the cured epoxy resin can be made to have low dielectric properties.

In summary, the ethylene phenylphosphorus phenols of the present invention can be used as an epoxy resin hardener, and the epoxy resin cured product produced therefrom has excellent thermal properties such as high glass transition temperature and excellent heat. Stability, as well as low dielectric properties. When the number of equivalents of 4-chloromethylstyrene is from 10% to 80% of the total number of phenolic groups of polyphenols, the water absorption of the epoxy resin cured product and the ethylene phenylated phosphorus phenols can be controlled. Solubility.

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

Claims (20)

A vinylphenylphosphorus phenol which comprises a structure as shown in formula (I) and/or formula (II): Wherein each of the R ¹ systems is independently H, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, F, Cl, Br or I; each of the R ² systems is independently H or a formula ( i) One of the structures shown: And at least one of the R ² is H, at least one of which is the structure represented by the formula (i); the a is an integer of 0 to 30; and the b is an integer of 1 to 30. A method for preparing an ethylene phenylphosphorus phenol, comprising: providing a polyphenol comprising a structure represented by the formula (pre-I) and/or (pre-II): And performing a vinyl phenylation step of reacting the polyphenols with 4-chloromethylstyrene in the presence of a base catalyst to obtain a phosphorus phenylation phenol according to claim 1. class. The method for producing an ethylene phenylphosphorus phenol according to claim 2, wherein the polyphenol has a phosphorus content of from 3 to 8 weight percent. The method for producing an ethylene phenylphosphorus phenol according to claim 2, wherein the number of equivalents of 4-chloromethylstyrene is from 10% to 80% of the total number of equivalents of the phenol group of the polyphenol. The method for preparing an ethylene phenylphosphorus phenol according to claim 2, wherein the alkali catalyst is potassium carbonate (K ₂ CO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydroxide (KOH), Sodium hydroxide (NaOH) or sodium bicarbonate (NaHCO ₃ ). The method for preparing an ethylene phenylphosphorus phenol according to claim 2, wherein the ethylene phenylation step is carried out in a solvent which is N,N-dimethylacetamide (DMAC). ), ethoxyethanol, methoxyethanol, 1-methoxy-2-propanol, propylene glycol monomethyl ether (DOW) PM), dioxane or a cosolvent consisting of the above solvents. The method for producing an ethylene phenylphosphorus phenol according to claim 2, wherein the molar ratio of the 4-chloromethylstyrene to the alkali catalyst is from 1 to 0.8 to 1 to 1.2. The process for producing an ethylene phenylphosphorus phenol according to claim 2, wherein the reaction time of the ethylene phenylation step is from 12 hours to 48 hours. The method for producing an ethylene phenylphosphorus phenol according to claim 2, wherein the ethylene phenylation step has a reaction temperature of from 80 ° C to 160 ° C. A cured epoxy resin obtained by copolymerization of an ethylene phenylphosphorus phenol according to claim 1 with an epoxy resin. The epoxy resin cured product according to claim 10, wherein the epoxy resin is diglycidyl ether of bisphenol A (DGEBA) or dicyclopentadiene type novolac epoxy resin. The epoxy resin cured product according to claim 10, wherein an equivalent ratio of the ethylene phenylphosphorus phenol to the epoxy resin is 1 to 1. A method for preparing an epoxy resin cured product, comprising: performing a copolymerization step of mixing the ethylene phenylation phosphorus phenols and an epoxy resin according to claim 1 to make the ethylene phenylation phosphorus phenols Copolymerization with the epoxy resin forms a cured epoxy resin. The method for preparing an epoxy resin cured product according to claim 13, The epoxy resin is bisphenol A epoxy resin or dicyclopentadiene type phenolic epoxy resin. The method for producing a cured epoxy resin according to claim 13, wherein the equivalent ratio of the ethylene phenylphosphorus phenol to the epoxy resin is 1 to 1. The method for producing a cured epoxy resin according to claim 13, wherein the copolymerizing step further comprises adding a hardening accelerator and a radical initiator. The method for producing a cured epoxy resin according to claim 16, wherein the hardening accelerator is a nitrogen-based accelerator or a phosphorus-based accelerator. The method for producing a cured epoxy resin according to claim 16, wherein the radical initiator is azobisisobutyronitrile (AIBN) or a peroxide. The method for producing a cured epoxy resin according to claim 16, wherein the hardening accelerator is added in an amount of from 0.2% by weight to 0.5% by weight based on the epoxy resin. The method for producing a cured epoxy resin according to claim 16, wherein the content of the radical initiator is from 0.2% by weight to 0.5% by weight of the ethylene phenylphosphine phenol.