TWI527825B - Phosphorus-containing benzoxazine and preparing method thereof - Google Patents

Description

Phosphorus oxynitride benzocyclohexane and preparation method thereof

The present invention relates to a series of phosphorus bisphenol derivatives and processes for their preparation, and in particular to a process for the production of a series of derivatives developed from phosphorus bisphenols.

Since ancient times, fires have always been one of the biggest accidents that endanger human life and property. Therefore, fireproof materials required for different types of sites and public buildings are also different. Conventional fire-retardant materials are mostly added with a halogen-containing compound to form a composition having high heat resistance. Although it has a considerable effect on fire suppression, it will produce corrosive and toxic substances, such as Dioxin, which may cause abnormalities in the body's metabolism and cause tension, sleep disorders, headache, eye diseases, arteriosclerosis, liver tumors, etc. The experiment was found to cause cancer.

In recent years, organophosphorus compounds have been studied for high molecular weight polymers, and have excellent flame retardant properties. Compared with halogen-containing flame retardants, organophosphorus compounds do not produce smoke or toxic gases, and have processability. Good, low added amount, low smoke, etc., especially organic phosphorus The main structure of the reactive group introduced into the polymer will make the polymer more flame retardant.

The phosphorus-containing compound DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide) is an active hydrogen atom which can react with electron-deficient compounds, and can be associated with electron-deficient compounds such as benzoquinone, oxirane, maleic acid, The derivatives of bismaleimide, diaminobenzophenone, and terephthaldicarboxaldehyde are highly regarded by the academic community and the industry.

In 1991, Smith, CD et al. synthesized DOPOBQ from DOPO and benzoquinone with the following structure:

DOPOBQ is a pioneer in phosphorus-based bisphenol monomers, but its high raw material cost, coupled with poor solubility and reactivity, limits its industrial application.

Accordingly, one aspect of the present invention is to provide a range of phosphorus bisphenols for expanding the range of applications of phosphorus containing compounds.

Another aspect of the present invention provides a method for producing a series of phosphorus bisphenol derivatives, which comprises synthesizing a series of phosphorus bisphenol derivatives having a reactive functional group at the terminal.

According to the present invention, there is proposed a phosphorus compound having the structure represented by the chemical formula (I):

Wherein R ₁ to R ₄ may be hydrogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ oxyalkyl, C ₁ -C ₁₀ haloalkyl, C ₃ -C ₁₀ cycloalkyl, -CF ₃ ,- OCF ₃ or a halogen atom; R ₅ may be a C ₁ -C ₁₀ alkyl group; A and B may be selected from -OH, -OCH ₃ , -OCH ₂ CH ₃ , -OCN, and The group of people formed. Ar ¹ and Ar ² are

According to the present invention, there is provided a process for producing a synthetic phosphorus bisphenol (DDP) derivative comprising an organic cyclic phosphorus compound represented by the formula (i), a ketone compound represented by the formula (ii), and a formula (iii) a compound and an acid catalyst, wherein a phosphorus compound in which R ₁ to R ₅ are an alkyl group or a phenyl group is synthesized:

The phosphorus-based compound can further synthesize an epoxy group-containing compound, a cyanate ester or a phosphorus-based compound having oxoazobenzocyclohexane.

According to an embodiment of the present invention, a schematic diagram of the reaction of synthesizing phosphorus nitrooxobenzocyclohexane (Benzoxazines) is as follows:

R' represented by the above formula may be hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl, biphenyl, halogen, nitro, phenoxy, C ₃ ~ C ₇ Cycloalkyl or Wherein R'" may be hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl, biphenyl, phenoxy, C ₃ -C ₇ cycloalkyl or halogen; R" is -OH, -NH ₂ , -NO ₂ , -SH, -COOH, -SO ₃ H, -COH, -NHCOCH ₃ or -OCH ₃ ; n, m may each be an integer of 0-4.

According to the above, it is understood that the phosphorus-based bisphenol of the present invention has a reactive functional group at the terminal, and can be synthesized into a material such as an epoxy resin, a cyanate ester, an oxoazobenzocyclohexane, or an epoxy resin. hardener. Therefore, the phosphorus bisphenol of the present invention can replace the more expensive DOPOBQ for industrial application.

The phosphorus-based bisphenol main structure of the present invention is reactive with an epoxy group in an epoxy resin, and the reactive functional group is located at a side chain position of the phosphorus-based compound. It can have better heat resistance than general phosphorus compounds or epoxy resins, and is suitable as a flame retardant composition without affecting processing properties.

In order to make the aforementioned and other objects of the present invention, features, advantages and embodiments can be more fully understood by reading the detailed description of the accompanying drawings as follows: ¹ H NMR spectrum of FIG. 1A A graph of the phosphorus-based compound; 1B graph of ¹³ C NMR spectrum of phosphorus compound A; FIG. 1C is a ³¹ P NMR spectrum of phosphorus compound A; FIG. 2A is a ¹ H NMR spectrum of phosphorus compound B; and FIG. 2B is a phosphorus compound B ¹³ C NMR spectrum; and FIG. 2C is a ³¹ P NMR spectrum of the phosphorus compound B.

In order to make the features, methods, objectives, and advantages of the present invention more comprehensible, the present invention is illustrated by the accompanying drawings.

The method for producing a phosphorus-based bisphenol (DDP) derivative of the present invention comprises an organic cyclic phosphorus compound represented by the formula (i), a ketone compound represented by the formula (ii), and a formula (iii). a compound and an acid catalyst to form a phosphorus bisphenol derivative as shown in the formula (I):

Wherein R ₁ to R ₄ may be hydrogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ oxyalkyl, C ₁ -C ₁₀ haloalkyl, C ₃ -C ₁₀ cycloalkyl, -CF ₃ , -OCF ₃ or a halogen atom; R ₅ may be a C ₁ -C ₁₀ alkyl group. A and B may be selected from -OH, -OCH ₃ , -OCH ₂ CH ₃ , -OCN, respectively. The group of people formed.

Ar ¹ and Ar ² are

When R ₁ to R ₄ are hydrogen, R ₅ is a methyl group, A and B are OH, and Ar ¹ and Ar ² are a phenyl group, and are represented by the general formula (i), the general formula (ii), and the general formula (iii). The phosphorus compound A synthesized by the compound and the acid catalyst has a structure represented by the chemical formula (II); and the epoxy compound A is used to synthesize the epoxy group-containing compound A-ep having the structure represented by the chemical formula (III). Phosphorus compound A can synthesize cyanate A-cy, which has the structure shown in formula (IV); phosphorus compound A can synthesize A-bz with oxoazobenzocyclohexane, having the chemical formula (V) ) The structure shown.

Synthesis Example 1: Synthesis of Compound A

According to an embodiment of the present invention, a phosphorus-based compound A in which R is a methyl group and A and B are OH is synthesized using an organic cyclic phosphorus compound DOPO, phenol, 4'-Hydroxyacetophenone and an acid catalyst. The synthesis steps are as follows.

The organic cyclic phosphorus compound DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) 10.81 g (0.05 mol), phenol 23.28 g (0.25 mol), 4'- Hydroxyacetophenone 6.81 g (0.05 mol), p-methylbenzoic acid 0.216 g (2 wt% of DOPO), placed in a 250 ml three-neck reactor.

Next, raise the reaction temperature to 130 ° C and maintain the reaction for 24 hours. Stop stirring afterwards. The reactor was cooled to room temperature, poured into ethanol and poured into hot water to precipitate, and dried by filtration to obtain product A, a yield of 85%, and a melting point of 306 °C.

Please refer to FIGS. 1A to 1C for the ¹ H NMR spectrum, the ¹³ C NMR spectrum, and the ³¹ P NMR spectrum of the phosphorus compound A, respectively.

Synthesis Example 2: Synthesis of Compound A-cy

According to an embodiment of the present invention, A-cy is synthesized using a phosphorus compound A. The synthesis steps are as follows.

Anhydrous acetone (70 g) was added to a three-necked reactor. After cooling the reactor to -15 ° C, BrCN 7.2027 g (0.068 mol) was added and stirred while the temperature was lowered to below -25 °C. Further, 8.5684 g (0.02 mol) of phosphorus compound A and Et ₃ N 6.1321 g (0.0606 mol) were thoroughly mixed and dissolved in anhydrous acetone (100 g), and then slowly dropped into the reactor with a feed funnel, and the temperature. The reaction was maintained at -30 ° C for 2 hours. When the reaction temperature returned to -30 ° C, the reaction was dropped into deionized water to wash to remove the ammonium bromide salt. After filtration, the resulting precipitate was extracted with CH ₂ Cl ₂ /H ₂ O. The organic phase was collected and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the CH ₂ Cl _{2 was} removed using a rotary evaporator at room temperature to give a cyanate ester solid.

Synthesis Example 3: Synthesis of Compound A-ep

According to an embodiment of the present invention, A-ep is synthesized from phosphorus compound A. The synthesis steps are as follows.

Take 214 grams of phosphorus compound A, 925 grams of epichlorohydrin plus Into a 3 liter reactor, stir at a normal pressure to form a homogeneous mixed solution, raise the reaction temperature to 70 ° C under 185 mmHg absolute pressure and add 200 g of 20% sodium hydroxide solution in batches over 4 hours, add simultaneously and The water in the reactor is azeotropically distilled off. After the reaction, the cyclochloropropane and the solvent are distilled off by vacuum distillation, the product is dissolved in methyl ethyl ketone and deionized water, the sodium chloride in the resin is washed, and the solvent is distilled off under reduced pressure to obtain a white color. A-EPOXY (A-ep) of epoxy group having an epoxy equivalent of 242.

Synthesis Example 4: Synthesis of Compound A-bz

According to an embodiment of the present invention, A-bz with Benzoxazine is synthesized with a phosphorus compound A. The synthesis steps are as follows.

3.246 g (0.04 mol) of formaldehyde was dissolved in 1.2 ml of dioxane to prepare a 5 M solution A'. Further, 1.55 g (0.02 mol) of methylamine was dissolved in dioxane (3 ml) to prepare a 10 M solution B'. The solution A' was placed in a 100 ml reaction flask, and nitrogen was passed through an ice bath. The solution B' was then dropped into the reactor in a drop of one drop per second, the temperature was controlled below 10 ° C, and the reaction was continued for 30 minutes after the completion of the dropwise addition. After 4.284 g (0.01 mol) of the phosphorus compound A was introduced into the reactor, the temperature was raised to reflux and the reaction was carried out for 10 hours. After the reaction was completed, the solvent was drained with a vacuum concentrator, and the product was dissolved in CH ₂ Cl ₂ , extracted with 0.1 M sodium hydroxide and washed three times with deionized water, and then filtered over anhydrous sodium sulfate, filtered, and dried in a vacuum oven. A pink solid was obtained in 76% yield.

According to an embodiment of the present invention, the reaction catalyst may be used in addition to the catalysts used in the above Synthesis Examples 1 to 4, and other acid catalysts may be used, including protic acids such as acetic acid, Methanesulfonic acid, Calmagite, Sulfuric acid, and Orthanilic acid. , 3-Pyridinesulfonic acid, Sulfanilic acid, HCl, HBr, HI, HF, CF ₃ COOH, HNO ₃ or H ₃ PO _{4 ,} etc.; or Lewis acid, such as AlCl ₃ , BF ₃ , FeBr ₃ , FeCl ₃ , BCl ₃ , TiCl _4, etc. The amount of the catalyst can be from 0.1% by weight to 30% by weight.

According to another embodiment of the present invention, a method for producing a phosphorus bisphenol (DDP) derivative comprises the synthesis of a compound represented by the general formula (i), the general formula (ii), the general formula (iii), and an acid catalyst. R ₁ to R ₄ are hydrogen, R ₅ is a phenyl group having no substituent, and A and B are phosphorus compound B in which OH, Ar ¹ and Ar ² are a phenyl group.

Wherein, the phosphorus-based compound B has a structure represented by the chemical formula (VI); the phosphorus-based compound B is used to synthesize the epoxy group-containing compound B-ep, which has a structure represented by the chemical formula (VII); and the phosphorus-based compound B can synthesize cyanide. The acid ester B-cy has a structure represented by the chemical formula (VIII), and the phosphorus compound B can synthesize B-bz having oxoazobenzocyclohexane and has a structure represented by the chemical formula (IX).

Synthesis Example 5: Synthesis of Compound B

According to an embodiment of the present invention, R is a benzene ring, and A and B are OH phosphorus compounds B, using an organic cyclic phosphorus compound DOPO, phenol, 4-Hydroxybenzophenone and an acid catalyst. The synthesis steps are as follows.

Organic cyclic phosphorus compound DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) 10.81 g (0.05 mol), phenol 23.28 g (0.25 mol), 4-Hydroxybenzophenone 9.91 G (0.05 mol), p-methylbenzoic acid 0.216 g (2 wt% of DOPO), placed in a 250 ml three-neck reactor.

Next, raise the reaction temperature to 130 ° C and maintain the reaction for 24 hours. Stop stirring afterwards. The reactor was cooled to room temperature, poured into ethanol and poured into hot water to precipitate, and dried by filtration to obtain product B, yield 87%, melting point 288 °C.

Please refer to FIGS. 2A to 2C for the ¹ H NMR spectrum, ¹³ C NMR spectrum and ³¹ P NMR spectrum of the phosphorus compound B, respectively.

Synthesis Example 6: Synthesis of Compound B-cy

According to an embodiment of the present invention, B-cy is synthesized from a phosphorus compound B. The synthesis steps are as follows.

Anhydrous acetone (70 g) was added to a three-necked reactor. After cooling the reactor to -15 ° C, BrCN 7.2027 g (0.068 mol) was added and stirred while the temperature was lowered to below -25 °C. Further, phosphorus compound B 9.8096 g (0.02 mol) and Et ₃ N 6.1321 g (0.0606 mol) were thoroughly mixed and dissolved in 100 g of anhydrous acetone, and then slowly dropped into the reactor through a feed funnel, and the temperature was maintained at - The reaction was maintained at 30 ° C for 2 hours. When the reaction temperature returned to -30 ° C, the reaction was dropped into deionized water to wash to remove the ammonium bromide salt. After filtration, the resulting precipitate was extracted with CH ₂ Cl ₂ /H ₂ O. The organic phase was collected and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the CH ₂ Cl _{2 was} removed using a rotary evaporator at room temperature to give a cyanate ester solid.

Synthesis Example 7: Synthesis of Compound B-ep

According to an embodiment of the present invention, B-ep is synthesized from a phosphorus-based compound B. The synthesis steps are as follows.

Take 245 grams of phosphorus compound B, 925 grams of epichlorohydrin plus Into a 3 liter reactor, stir at a normal pressure to form a homogeneous mixed solution, raise the reaction temperature to 70 ° C under 185 mmHg absolute pressure and add 200 g of 20% sodium hydroxide solution in batches over 4 hours, add simultaneously and The water in the reactor is azeotropically distilled off. After the reaction, the cyclochloropropane and the solvent are distilled off by vacuum distillation, the product is dissolved in methyl ethyl ketone and deionized water, the sodium chloride in the resin is washed, and the solvent is distilled off under reduced pressure to obtain a pale yellow color. Epoxy-containing B-EPOXY (B-ep) having an epoxy equivalent of 286.

Synthesis Example 8: Synthesis of Polymer B-bz

According to an embodiment of the present invention, B-bz with Benzoxazines is synthesized from a phosphorus compound B. The synthesis steps are as follows.

3.246 g (0.04 mol) of formaldehyde was dissolved in 1.2 ml of dioxane to prepare a 5 M solution A'. Further, 1.55 g (0.02 mol) of methylamine was dissolved in dioxane (3 ml) to prepare a 10 M solution B'. The solution A' was placed in a 100 ml reaction flask, and nitrogen was passed through an ice bath. The solution B' was then dropped into the reactor in a drop of one drop per second, the temperature was controlled below 10 ° C, and the reaction was continued for 30 minutes after the completion of the dropwise addition. After 4.094 g (0.01 mol) of the phosphorus-based compound B was placed in the reactor, the temperature was raised to reflux and the reaction was carried out for 10 hours. After the reaction was completed, the solvent was drained with a vacuum concentrator, and the product was dissolved in CH ₂ Cl ₂ , extracted with 0.1 M sodium hydroxide and washed three times with deionized water, and then filtered over anhydrous sodium sulfate, filtered, and dried in a vacuum oven. A pale yellow solid was obtained in a yield of 80%.

According to an embodiment of the present invention, in addition to the catalyst used in the above Synthesis Examples 4 to 8, the reaction catalyst may also use other acid catalysts, including protic acids such as acetic acid, Methanesulfonic acid, Calmagite, Sulfuric acid, and Orthanilic. Acid, 3-Pyridinesulfonic acid, Sulfanilic acid, H ₂ SO ₄ , HCl, HBr, HI, HF, CF ₃ COOH, HNO ₃ or H ₃ PO 4 , etc.; or Lewis acid, such as AlCl ₃ , BF ₃ , FeBr ₃ , FeCl ₃ , BCl ₃ , TiCl ₄ and the like. The amount of the catalyst can be from 0.1% by weight to 30% by weight.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention, and it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

Claims (2)

A phosphorus-based oxoazobenzocyclohexane having the structure represented by the chemical formula (1): Wherein R ₅ is C ₁ -C ₁₀ alkyl, R' is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl, biphenyl, halogen, nitro, phenoxy, C ₃ ~C ₇ cycloalkyl or Wherein R'" is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, phenyl, biphenyl, phenoxy, C ₃ -C ₇ cycloalkyl or halogen, R" is - OH, -NH ₂ , -NO ₂ , -SH, -COOH, -SO ₃ H, -COH, -NHCOCH ₃ or -OCH ₃ ; n, m are each an integer of 0-4. A method for preparing a phosphorus-based oxoazobenzocyclohexane, comprising: providing a compound of the formula (a), the formula (b), and the formula (c) to react to form the phosphorus-based oxygen according to claim 1 Alkalobenzocyclohexane (1) wherein the structures of the compounds of formula (a), formula (b), and formula (c) are as follows: