TWI522396B - Phosphinated multifunctional phenol polymer and its epoxy thermosets with high glass transition temperature - Google Patents

Description

Phosphorus-based polyfunctional phenolic polymer and its high glass transition temperature epoxy resin cured product

The present invention provides a phosphorus-based polyfunctional phenolic polymer which can be further used for preparing a high glass transition temperature flame retardant resin cured product.

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 use of electronic and information materials in the world has strict requirements for flame retardancy.

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 promote the dehydration of polymer materials during combustion, allowing hydrogen from hydrocarbons to form water with oxygen in the air, thereby reducing the surrounding environment. The temperature is lower than the combustion temperature to achieve a flame retardant effect; on the other hand, under high temperature heating, the phosphoric acid promotes the polymer compound Carbonization forms a non-combustible coke layer. In addition, phosphoric acid is further dehydrated and esterified at a high temperature to form a polyphosphoric acid covering the surface of the combustion product to form a protective effect, preventing oxygen from entering the unburned inner layer of the polymer and inhibiting 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 uniformly mix a phosphorus-containing hardener with an epoxy resin. The present invention provides a phosphorus-containing hardener which is hardened by mixing with an epoxy resin to achieve 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] , and double malaya 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 epoxy resins with flame retardant and high glass transition temperatures. However, the rosolic acid, a raw material for the synthesis of dopotriol in the literature, is very expensive and is not economically viable in industrial applications, so Lin et al. followed the cheaper 4,4'-dihydroxydiphenyl ketone in 2008. (4,4'-dihydroxy benzophenone, DHBP) reacted with DOPO and phenol/aniline to successfully synthesize the phosphorus-containing flame retardant dopotriol and dopodiolamine ^[10] . The epoxy resin obtained by hardening has excellent glass transition temperature, thermal stability, dimensional stability, and flame retardancy. However, dopotriol and dopodiolamine have problems with poor solubility.

Phenolic resin is the earliest industrial synthetic resin. Due to the availability of raw materials, low water absorption, good processability and performance after curing, the resin can meet many requirements. Plastics, insulation materials, coatings, wood bonding and other aspects have been widely used. 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.

The literature indicates that bisphenol A will be cleaved by acid catalysis into phenol and unstable 4-isopropenylphonel ^[11] . Lin et al. used DOPO and bisphenol A to react under acid catalysis to bond DOPO to the newly formed 4-isopropenylphonel to synthesize monofunctional phenolic compounds. Then, using DOPO and trifunctional phenol 1,1,1-tris(4-hydroxyphenyl)ethane, the reaction is carried out under acid catalysis to form a bifunctional phenol. Chemicals. In addition, Lin et al. also synthesized phosphorus-based polyfunctional bisphenol A phenolic resin with DOPO and polyfunctional bisphenol A phenolic resin (BPA novolac) under acid catalysis ^[12] , and maintained good flame retardancy.

In Republic of China Patent I432445, Lin et al. reacted DOPO with a bisphenol A phenolic resin to obtain a phosphorus-based phenolic polymer (P-BPN). This patent discloses that DOPO will react with the isopropylidiene of bisphenol A phenolic resin (BPN); DOPO may be an isopropylidene group or a bisphenol A phenolic resin at the terminal position of the bisphenol A phenolic resin. The isopropylidene group in the intermediate position reacts, so there are multiple reaction pathways. One of the ways is listed below as an illustration:

However, when the polyfunctional bisphenol A phenolic resin is reacted with DOPO, its molecular weight is lowered, resulting in a low glass transition temperature of the cured product.

The present invention is an improvement of the Republic of China Patent I432445 by increasing the molecular weight of the product to obtain a cured epoxy resin having a high glass transition temperature.

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.

[12] Republic of China Patent I432445

The present invention provides a novel phosphorus-based polyfunctional phenolic polymer and a process for preparing the same; the phosphorus-based polyfunctional phenolic polymer can be further hardened with an epoxy resin to prepare a flame retardant resin cured product having a high glass transition temperature.

It is to be understood that any range of values recited in this specification is intended to include all sub-ranges For example, the range from "60 ° C to 200 ° C" includes all the sub-ranges between the stated minimum value of 60 ° C and the stated maximum value of 200 ° C (eg from 91 ° C to 182 ° C, 103 ° C to 168 ° C, 62 ° C or 133 ° C) and includes the two values, that is, a range including a minimum value equal to or greater than 60 ° C and a maximum value equal to or lower than 200 ° C. Because the ranges of values disclosed are continuous, they contain each value between the minimum and maximum values. Unless otherwise stated, the various numerical ranges indicated in this specification are approximate.

The applicant of the present patent has attempted to react a phosphorus-containing monofunctional phenol (DOPP-phenol) and formaldehyde under different acid catalysis (Example 1) to form a phosphorus phenolic resin (DOPO-PN):

However, based on the results of various attempts, the Applicant found that the reaction could not be carried out; it is speculated that the reason is that the presence of the P=O double bond of the electron-withdrawing group reduces the reactivity of the phenol.

However, the chemistry of phenolic resin based on phenol and formaldehyde, and bisphenol A and formaldehyde to form bisphenol A phenolic resin

It can be further inferred that the product of the aforementioned Republic of China Patent I432445 may react with formaldehyde or paraformaldehyde.

Calibration Is the location that will not react with formaldehyde, and calibration It is the place where it will react with formaldehyde. Accordingly, according to this route, the obtained polymer (P-BPN-CH ₂ ) has the following structure: .

Novel phosphorus-based polyfunctional phenolic polymers

According to the above, the present invention provides a novel phosphorus-based polyfunctional phenolic polymer comprising the structures of the following formulas (I) and (II)

Wherein 0≦a≦30,1≦b≦30; Y is -CH ₂ - or -CH ₂ OCH ₂ -; and each R ₀ is the same or different and is independently selected from a hydrogen atom, a C ₁ -C ₆ alkane , C ₁ -C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ -C ₁₀ haloalkyl, C ₃ -C ₇ cycloalkyl, C ₁ -C ₁₀ haloalkoxy and halogen The group formed.

In one embodiment of the invention, when all of R ₀ are hydrogen atoms and Y is -CH ₂ -, the formula (II) has the structure of formula (IV) The formula (III) has the structure of the formula (V)

In the present invention, the above polymers are usually present in the form of oligomers.

Method for preparing novel phosphorus-based polyfunctional phenolic polymer

The present invention provides a method for producing a phosphorus-based polyfunctional phenolic polymer comprising the structures of the formulae (II) and (III), which comprises the following steps: (1) a DOPO compound of the following formula and a formula (I) Bisphenol novolac resin (BPN) reacts in the presence of an acid catalyst

To obtain an intermediate product comprising the structures of the following formulas (II-1) and (III-1)

(2) reacting the intermediate product with paraformaldehyde or formaldehyde in the presence of an acid catalyst to obtain a phosphorus-based polyfunctional phenolic polymer comprising the structures of the formulae (II) and (III); wherein 0≦a≦30, 1≦b≦30; Y is -CH ₂ - or -CH ₂ OCH ₂ -; and each R ₀ is the same or different and is independently selected from a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ ~C ₆ A group consisting of an alkoxy group, a phenyl group, a nitro group, a phenoxy group, a C ₁ -C ₁₀ haloalkyl group, a C ₃ -C ₇ cycloalkyl group, a C ₁ -C ₁₀ haloalkoxy group, and a halogen.

In the above method of the present invention, the formula (I) has the following structure when all of the R ₀ is a hydrogen atom; Further, the formula (II) and the formula (III) produced by the formula have the structures of the above formula (IV) and formula (V).

In the above method of the present invention, the paraformaldehyde is trioxane.

In the above process of the present invention, the intermediate product has a total phosphorus content of from 3 wt% to 8 wt%, preferably from 4 wt% to 7 wt%.

In the above method of the present invention, the acid catalyst is selected from the group consisting of oxalic acid, acetic acid, p-Toluenesulfonic acid (PTSA), methanesulfonic acid, and fluorosulfonic acid. 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 ) The acid catalyst is preferably p-toluenesulfonic acid.

In the above process of the present invention, the amount of the acid catalyst is from 0.1% by weight to 10% by weight, preferably from 0.1% by weight to 5% by weight, more preferably from 0.5% by weight to 3% by weight based on the total of the intermediate product.

In the above method of the present invention, the amount of the paraformaldehyde is from 10% to 150%, preferably from 45% to 150%, more preferably from 85% to 150%, based on the total phenolic equivalents of the intermediate product.

In the above method of the present invention, the reaction time of the step (1) is 3 to 24 hours, preferably 7 Up to 20 hours, preferably 10 to 14 hours.

In the above method of the present invention, the reaction time of the step (2) is from 3 to 24 hours, preferably from 7 to 20 hours, more preferably from 10 to 14 hours.

In the above method of the present invention, the reaction temperature of the step (1) is between 60 ° C and 200 ° C, preferably between 100 and ° C to 170 ° C, more preferably between 130 and 150 ° C.

In the above method of the present invention, the reaction temperature of the step (2) is between 60 ° C and 180 ° C, preferably between 75 ° C and 155 ° C, more preferably between 100 ° C and 120 ° C.

In the above method of the present invention, the reaction pressure can be reacted under normal pressure or reduced pressure.

In the above process of the invention, the reactions can be carried out with or without a solvent. If the reaction is carried out in a solvent, the solvent may be selected from ethoxy ethanol, methoxy ethanol, 1-methoxy-2-propanol. a group consisting of DOW PM, dioxane and a cosolvent composed of the above solvents; the solvent is preferably 1-methoxy-2-propanol.

Use of novel phosphorus-based polyfunctional phenolic polymers

The present invention further provides a novel hardener comprising the phosphorus-based polyfunctional phenolic polymer as described above.

The present invention further provides a method of preparing a high glass transition temperature flame retardant epoxy resin hardened comprising reacting an epoxy resin with a hardener as described above.

In an embodiment of the invention, the equivalent ratio of the epoxy resin to the hardener is 1:0.1 to 1:1, preferably 1:1.

In an embodiment of the invention, the epoxy resin is selected from the group consisting of diglycidyl ether of bisphenol A (DGEBA), dicyclopentadiene epoxy (HP 7200), and phosphorus. Cresol novolac epoxy (CNE) or phenol novolac epoxy (PNE).

The invention further provides a high glass transition temperature flame retardant epoxy resin hardened material, which is prepared according to the high glass transition temperature flame retardant epoxy resin hardened material preparation method as described above. product.

The present invention has found that the cured product prepared by the method for preparing a hardened epoxy resin hardened material according to the present invention is compared with the hardened material prepared by the phosphorus-based polyfunctional phenolic resin which has not been modified with paraformaldehyde. The cured product can clearly achieve excellent thermal properties and stability.

Figure 1 is a ¹ H-NMR chart of DOPO-PN. .

2 is a ¹ H-NMR chart spectral overlay of P-BPN, P-BPN-F10, and P-BPN-F30.

3 is a ¹ H-NMR chart spectral overlay of P-BPN, P-BPN-F85-o, P-BPN-F85-p, and P-BPN-F150-o.

Figure 4 is a DMA diagram of a BNE cured product using P-BPN, P-BPN-F10 and P-BPN-F30 as hardeners.

Figure 5 is a DMA diagram of a DGEBA hardened material using P-BPN, P-BPN-F85-o, and P-BPN-F85-p as hardeners.

Figure 6 is a TGA diagram of a DGEBA hardened material using P-BPN, P-BPN-F85-o, and P-BPN-F85-p as hardeners.

Figure 7 is a DMA diagram of a CNE cured product using P-BPN, P-BPN-F85-o, and P-BPN-F85-p as hardeners.

Figure 8 is a TGA diagram of a CNE cured product using P-BPN, P-BPN-F85-o, and P-BPN-F85-p as hardeners.

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, and any modifications and variations which may be obtained without departing from the spirit of the invention are range.

Example 1 Synthesis of DOPO-PN

The synthesis of DOPO-PN is obtained by reacting DOPO-AP with paraformaldehyde under acid or base catalysis.

The synthesis procedure is as follows: 1 gram of DOPO-AP, 0.0643 gram of paraformaldehyde and 10 grams of 1-methoxy-2-propanol (propylene glycol methyl ether) are added to a 0.1 liter three-neck reactor equipped with a temperature indicating device. As a solvent, react in different proportions of the catalyst formulation (listed in Table 1) to maintain the temperature of the reaction system at 110 ° C. After 12 hours of reaction, the reaction solvent is dropped into deionized water and precipitated. The filter cake was dried in a vacuum oven at 70 ° C to give a white product.

Figure 1 is a ¹ H-NMR spectrum of the product of Example 1. It can be seen from Figure 1 that the different catalyst formulations tried in Example 1 were unable to carry out the reaction.

Example 2 Synthesis of Polymer P-BPN

Phosphorus phenolic polymer (P-BPN) with a phosphorus content of 5% will catalyze BPN and DOPO in acid catalysis The reaction is obtained (in accordance with Example 8 of the Republic of China Patent I432445). The synthesis procedure is as follows: 50 g of BPN, 26.765 g of DOPO, and 2 g (4 wt% of BPN) of p-toluenesulfonic acid are added to a 0.5 liter three-necked reactor equipped with a temperature indicating device. The temperature was maintained at 140 ° C. After 12 hours of reaction, the sticky material was washed away with methanol-water to remove residual p-toluenesulfonic acid, filtered by suction, separated by filtration, and the filter cake was vacuum dried at 100 ° C in a vacuum oven. A phosphorus phenolic polymer (P-BPN) having a phosphorus content of 5% was dried.

Example 3 Synthesis of Polymer P-BPN-F10

The high molecular weight second generation 5% phosphorus phenolic polymer (P-BPN-F10) is a phosphate phenolic resin (P-BPN) having a phosphorus content of 5% (from Example 2) reacted with paraformaldehyde under acid catalysis. The synthesis procedure was as follows: In a 0.1 liter three-neck reactor equipped with a temperature indicating device, 30 g of P-BPN, 0.4505 g of paraformaldehyde, and 0.03 g (1 wt% of P-BPN) were added. 30 g of methylbenzenesulfonic acid and 1-methoxy-2-propanol were used as solvents to maintain the solid content of the reaction system at 50%, while the temperature of the reaction system was maintained at 110 ° C for 12 hours, and the reaction solution was in the process. The clarification was maintained, and after the reaction was completed, the reaction solution was precipitated with water and the residual p-toluenesulfonic acid was washed away. After suction filtration, the filter cake was vacuum dried in a vacuum oven at 70 ° C to obtain a pale red powder product P-BPN-F10.

Example 4 Synthesis of Polymer P-BPN-F30

High molecular weight second generation 5% phosphorus phenolic polymer (P-BPN-F30) is a phosphorus phenolic resin (P-BPN) with a phosphorus content of 5% (from Example 2) reacted with paraformaldehyde under acid catalysis The synthesis procedure was as follows: In a 0.1 liter three-neck reactor equipped with a temperature indicating device, 30 g of P-BPN, 1.3514 g of paraformaldehyde, and 0.03 g (1 wt% of P-BPN) were added. 30 g of methylbenzenesulfonic acid and 1-methoxy-2-propanol were used as solvents to maintain the solid content of the reaction system at 50%, while the temperature of the reaction system was maintained at 110 ° C for 12 hours, and the reaction solution was in the process. The clarification was maintained, and after the reaction was completed, the reaction solution was precipitated with water and the residual p-toluenesulfonic acid was washed away. After suction filtration, the filter cake was vacuum dried at 70 ° C in a vacuum oven to obtain a pale red powder product P-BPN-F30.

2 is a ¹ H NMR spectral overlay of the products P-BPN-F10 and P-BPN-F30 of Examples 1 and 2 and the reactant P-BPN. It can be seen from Fig. 2 that the characteristic peak between 9 and 9.6 ppm is the Ar-OH signal of the product, and the characteristic peak between 3.6 and 3.8 ppm is the signal of Ar-CH2-Ar. The above three values were compared based on the signal integral value of Ar-OH, and the difference between the integral values of Ar-CH2-Ar and the above three was compared. It can be found that the integral value of Ar-CH2-Ar increases as the proportion of addition of paraformaldehyde increases, indicating that the reaction does occur and the molecular weight thereof is increased.

Example 5 Synthesis of Polymer P-BPN-F45

In a 0.5 liter three-necked reactor equipped with a temperature indicating device, 5% phosphorus phenolic polymer (P-BPN) (from Example 2) 30 g, and terephthalaldehyde 2.027 g (phenol equivalents) were added. 45%), 1.2 g of methylbenzenesulfonic acid (4 wt% of P-BPN) and 300 ml of 1-methoxy-2-propanol as a solvent, the reaction system temperature was maintained at 110 ° C, after 12 hours of reaction, The reaction solvent was dropped into deionized water to precipitate and the residual p-toluenesulfonic acid was washed away, and after suction filtration, the filter cake was vacuum-dried at 70 ° C in a vacuum oven to obtain a polymer P-BPN-F45.

Example 6 Synthesis of Polymer P-BPN-F85-o

In a 0.5 liter three-neck reactor equipped with a temperature indicating device, 5% phosphorus phenolic polymer (P-BPN) (from Example 2), 30 g, and 3.903 g of paraformaldehyde (phenol equivalents) were added. 85%), 1.2 g of oxalic acid (4 wt% of P-BPN) and 300 ml of 1-methoxy-2-propanol as a solvent, the reaction system temperature was maintained at 110 ° C, and after 12 hours of reaction, the reaction solvent was dropped. The ionic acid was precipitated and washed away, and the residual oxalic acid was washed away. After suction filtration, the filter cake was vacuum-dried at 70 ° C in a vacuum oven to obtain a polymer P-BPN-F85-o.

Example 7 Synthesis of Polymer P-BPN-F85-p

In a 0.5 liter three-neck reactor equipped with a temperature indicating device, 5% phosphorus phenolic polymer (P-BPN) (from Example 2), 30 g, and 3.903 g of paraformaldehyde (phenol equivalents) were added. 85%), 1.2 g of methylbenzenesulfonic acid (4 wt% of P-BPN) and 300 ml of 1-methoxy-2-propanol as a solvent, the reaction system temperature was maintained at 110 ° C, after 12 hours of reaction, The reaction solvent is dropped into the ionic water to precipitate and the residual p-toluenesulfonic acid is washed away, and the gas is exhausted. After filtration, the filter cake was vacuum dried at 70 ° C in a vacuum oven to give the polymer P-BPN-F85-p.

Example 8 Synthesis of Polymer P-BPN-F150-o

In a 0.5 liter three-necked reactor equipped with a temperature indicating device, 5% phosphorus phenolic polymer (P-BPN) (from Example 2) 30 g, and paraformaldehyde 6.757 g (phenol equivalents) were added. 150%), 1.2 g of oxalic acid (4 wt% of P-BPN) and 300 ml of 1-methoxy-2-propanol as a solvent, the reaction system temperature was maintained at 110 ° C, and after 12 hours of reaction, the reaction solvent was dropped. The precipitated ionic water was precipitated and the residual p-toluenesulfonic acid was washed away, and after suction filtration, the filter cake was vacuum-dried at 70 ° C in a vacuum oven to obtain a polymer P-BPN-F150-o.

Figure 3 is a ¹ H-NMR spectral overlay of P-BPN-F85-o, P-BPN-F85-p and P-BPN-F150-o. Based on the hydroxyl group of 9 to 10 ppm, it was found that the integral value of Ar-CH2-Ar at about 3.6 ppm increased as the amount of paraformaldehyde added increased, so that it was confirmed that the reaction did proceed.

Table 2 shows the GPC data of P-BPN raw materials and P-BPN-F. It can be seen from Table 2 that the addition of paraformaldehyde under the catalysis of an acidic environment can indeed contribute to the prolongation of the molecular weight of P-BPN, and the catalytic effect of p-toluenesulfonic acid is better than that of oxalic acid.

Examples 9 to 11 Preparation and Analysis of Curing Bisphenol A Type Novolac Epoxy Resin

The three hardeners of Examples 2 to 4 were used as a hardener for the epoxy resin, and the epoxy resin used was a bisphenol A type novolac epoxy resin (BNE). Epoxy resin and hardener are uniformly mixed in the mold at an equivalent ratio of 1:1, and imidazole is added in an amount (addition amount is epoxy resin) 0.2 wt%) as a hardening accelerator for the reaction. The glass transition temperature measured by a dynamic mechanical analyzer (DMA) is shown in Table 3 and Figure 4. As the amount of paraformaldehyde added increases, the glass transition temperature also increases, representing the products of Examples 3 and 4. The molecular weight is indeed improved and has superior thermal properties.

Preparation and Analysis of Solidified Bisphenol A Epoxy Resin of Examples 12 to 14

P-BPN, P-BPN-F85-o and P-BPN-F85-p three hardeners act as hardeners for bisphenol A epoxy resin (DGEBA) epoxy resin. The epoxy resin and the hardener are uniformly mixed in the mold at an equivalent ratio of 1:1, and imidazole (addition amount is 0.2 wt% of the epoxy resin) is added as an amount of the hardening accelerator for the reaction. The thermal properties measured by DMA and thermogravimetric analyzer (TGA) are shown in Figures 5 and 6.

As can be seen from Fig. 5, the Tg of P-BPN/DGEBA is 126 ° C, the Tg of P-BPN-F85-o/DGEBA is 142 ° C, and the Tg of P-BPN-F85-p/DGEBA is 160 ° C, that is, after the modification. The thermal properties of P-BPN-F and epoxy resin cured materials are indeed further enhanced, as evidenced by the foregoing.

It can be seen from Fig. 6 that the T _{d5% of} P-BPN/DGEBA, P-BPN-F85-o/DGEBA and P-BPN-F85-p/DGEBA are 430 ° C, 434 ° C and 435 ° C, respectively, and residual ash ( Char yield) is 19%, 23% and 24%, respectively, which further confirms that the series of hardened materials have good thermal stability.

Preparation and Analysis of Curing Phosphomethyl Methyl Resin Epoxy Resins of Examples 15 to 17

P-BPN, P-BPN-F85-o and P-BPN-F85-p three hardeners act as hardeners for phosphomethyl novolac epoxy resin (CNE). The epoxy resin and the hardener were uniformly mixed in a mold at a ratio of an equivalent ratio of 1:1, and an imidazole (added in an amount of 0.2 wt% of the epoxy resin) was added in an amount as a hardening accelerator for the reaction. The thermal properties measured by DMA and TGA are shown in Figures 7 and 8.

As can be seen from Fig. 7, the Tg of P-BPN/CNE is 160 ° C, the Tg of P-BPN-F85-o/CNE is 172 ° C, and the Tg of P-BPN-F85-p/CNE is 196 ° C, that is, after the modification. The thermal properties of P-BPN-F and epoxy resin cured materials are indeed further enhanced, as evidenced by the foregoing.

It can be seen from Fig. 8 that the T _{d5% of} P-BPN/CNE, P-BPN-F85-o/CNE and P-BPN-F85-p/CNE are 400 ° C, 412 ° C and 413 ° C, respectively, and the residual ash is respectively At 28%, 29% and 32%, it was further confirmed that the cured product of this series has good thermal stability.

Claims (16)

A phosphorus-based polyfunctional phenolic polymer comprising the structures of the following formulae (II) and (III) Wherein 0≦a≦30,1≦b≦30; Y is -CH ₂ - or -CH ₂ OCH ₂ -; and each R ₀ is the same or different and is independently selected from a hydrogen atom, a C ₁ -C ₆ alkane , C ₁ -C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ -C ₁₀ haloalkyl, C ₃ -C ₇ cycloalkyl, C ₁ -C ₁₀ haloalkoxy and halogen The group formed. The polymer of claim 1, wherein when all of R ₀ is a hydrogen atom and Y is -CH ₂ -, the formula (II) has the structure of formula (IV) And the formula (III) has the structure of the formula (V) A polymer according to claim 1 or 2 which is in the form of an oligomer. A method for producing a phosphorus-based polyfunctional phenolic polymer comprising the structures of the following formulas (II) and (III), It comprises the following steps (1): reacting a DOPO compound of the following formula with a bisphenol novolac resin of the formula (I) in the presence of an acid catalyst To obtain an intermediate product comprising the structures of the following formulas (II-1) and (III-1) And (2) reacting the intermediate product with paraformaldehyde or formaldehyde in the presence of an acid catalyst to obtain a phosphorus-based polyfunctional phenolic polymer having the structures of the formulae (II) and (III); wherein 0≦a≦ 30,1≦b≦30; Y is -CH ₂ - or -CH ₂ OCH ₂ -; and each R ₀ is the same or different and is independently selected from a hydrogen atom, a C ₁ -C ₆ alkyl group, C ₁ ~ a group consisting of C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ -C ₁₀ haloalkyl, C ₃ -C ₇ cycloalkyl, C ₁ -C ₁₀ haloalkoxy and halogen. The method of claim 4, wherein: when all R ₀ are hydrogen atoms and Y is -CH ₂ -, formula (I) has the following structure Wherein formula (II) has the structure of formula (IV) And the formula (III) has the structure of the formula (V) The method of claim 4, wherein the paraformaldehyde is trioxane. The method of claim 4, wherein the intermediate product has a total phosphorus content of from 3 wt% to 8 wt%. The method of claim 4, wherein the acid catalyst is selected from the group consisting of oxalic acid, acetic acid, p-Toluenesulfonic acid (PTSA), methanesulfonic acid, and fluorosulfonic acid (Fluorosulfonic acid). ), Trifluoromethanesulfonic acid, Sulfuric acid, Orthanilic acid, 3-Pyridinesulfonic acid, Sufanilic 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 ) a group of people. The method of claim 4, wherein the amount of paraformaldehyde is from 10 to 150% of the phenolic equivalent of the intermediate product. The method of claim 4, wherein the amount of the acid catalyst is from 0.1% by weight to 10% by weight of the intermediate product. The method of claim 4, wherein the reaction is carried out in a solvent selected from the group consisting of ethoxy ethanol, methoxy ethanol, and 1-methoxy-2-propanol (1). a group consisting of -methoxy-2-propanol), DOW PM, dioxane, and a cosolvent consisting of the above solvents. A hardener comprising the phosphorus-based polyfunctional phenol according to any one of claims 1 to 3. polymer. A method of preparing a high glass transition temperature flame retardant epoxy resin cured product comprising subjecting an epoxy resin to a hardening reaction with a hardener according to claim 12. The method of claim 13, wherein the equivalent ratio of the epoxy resin to the hardener is 1:0.1 to 1:1. The method of claim 13 or 14, wherein the epoxy resin is selected from the group consisting of diglycidyl ether of bisphenol A (DGEBA), dicyclopentadiene epoxy (HP 7200), Cresol novolac epoxy (CNE) or phenol novolac epoxy (PNE). A high glass transition temperature flame retardant epoxy resin cured product produced by the method of any one of claims 13 to 15.