CN101560226B - Novel phosphorous compound, its production method and use - Google Patents

Abstract

The invention provides a phosphorus compound as shown in a general formula (1),

wherein R is₁～R₁₀、A、B、D、X、Y、R₁₁～R₁₂And the substituents are defined in the specification. The invention provides a method for preparing a compound shown as a formula (1). The invention also provides a hardener. The invention also provides a flame-retardant epoxy resin and a preparation method thereof.

Description

Novel phosphorous compound, its production method and use

technical field

The invention discloses a phosphorus-containing compound, which can be used as an epoxy resin hardener and used for preparing flame-retardant epoxy resin hardened products.

Background technique

Epoxy resin has the advantages of excellent electrical properties, shape stability, high temperature resistance, solvent resistance, low cost and high adhesion, and is most suitable for printed circuit boards and integrated circuit packaging materials. However, epoxy resin is as easy to burn as general plastic materials and endangers life. Therefore, there are strict requirements for the flame retardancy of electronic and information materials used all over the world. Epoxy resins containing bromine atoms are especially suitable for circuit boards with flame retardant properties. However, these bromine-containing epoxy resins release corrosive and toxic substances such as tetrabromodibenzo-p-dioxin and tetrabromodibenzofuran during combustion. In addition to halogen-containing compounds, another flame-retardant method is to coat the plastic with a non-flammable outer layer. Among these flame retardant compounds, organophosphorus compounds are highly flame retardant. Phosphorous flame retardants will promote the dehydration of polymer materials when they burn, so that the hydrogen of hydrocarbons and oxygen in the air will form water, thereby reducing the temperature of the surrounding environment. The temperature is lower than the combustion temperature to achieve the flame retardant effect; on the other hand, under high temperature heating, phosphoric acid will be decomposed to promote the carbonization of polymer compounds, forming a non-combustible coke layer. In addition, phosphoric acid will be further dehydrated and esterified at high temperature to form polyphosphoric acid to cover the surface of the burning material to form a protective effect, preventing oxygen from entering the unburned inner layer of the polymer and inhibiting the release of volatile lysates. There are two ways to introduce phosphorus, one is to synthesize phosphorus-containing epoxy resin, and the other is to synthesize phosphorus-containing hardener. The invention uses the method of synthesizing a novel phosphorus-containing curing agent to harden the epoxy resin to achieve the effect of flame retardancy.

Among phosphorus-containing reactants, reactive 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, DOPO) has attracted much attention because it can interact with electron-deficient compounds such as benzoquinone, oxirane, maleic acid, bismaleimide, diaminodi Benzophenone (diaminobenzophenone) and terephthaldicarboxaldehyde (terephthaldicarboxaldehyde) etc. undergo nucleophilic addition reaction. In 2005, Lin et al. disclosed the synthesis method and application of the trifunctional hardeners dopotriol[1] and dopo-ta[2], and successfully obtained a flame-retardant epoxy resin with a high glass transition temperature. However, rosolic acid, the raw material for synthesizing dopotriol in the literature, is very expensive, and it is not economical for industrial applications. The present invention utilizes the synthetic compound A (dopotriol) that successfully reacts with cheaper 4,4'-dihydroxybenzophenone (4,4'-dihydroxybenzophenone, DHBP), DOPO and phenol, in addition, and more Further expose DHBP, 4,4'-diaminobenzophenone (4,4'-diaminobenzophenone, DABP) and 4-amino-4'-hydroxybenzophenone (4-amino-4'-hydroxy The synthetic method of benzophenone, AHBP) derivative.

references:

[1] C.H.Lin, S.X.Cai, and C.H.Lin, "Flame-retardant epoxy resins with high glass transition temperature. II. Using a novel hexafunctional curing agent: 9,10-dihydro-9-oxa-10- Phosphaphenanthrene 10-yl-tri(4-aminophenyl)methane (Flame-Retardant Epoxy Resins with High Glass-Transition Temperatures.II.Using a Novel Hexafunctional Curing Agent: 9,10-Dihydro-9-oxa-10-phosphaphenanthrene10- yl-tris(4-aminophenyl)methane,)" Polymer Science Journal of Polymer Chemistry (J.Polym.Sci.Polym.Chem.), 2005, 43, 5971.

[2] S.X.Cai and C.H.Lin, "Flame-Retardant Epoxy Resins With High Tg from a Novel Tri-functional Curing Agent: Dopotriol" from a Novel Tri-functional Curing Agent: Dopotriol," Polymer Journal of Scientific Polymer Chemistry, 2005, 43, 2862.

Contents of the invention

The object of the present invention is to provide a novel phosphorus compound, which can be used as a hardener for epoxy resin, and can also be further used to prepare epoxy resin with flame retardant properties.

The present invention discloses phosphorus compounds having the following chemical formula:

in

R ₁ to R ₁₀ are each independently selected from a hydrogen atom, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ to C ₁₀ haloalkyl, C ₃ A group consisting of ~C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and halogen atoms;

A is -OH or -NH ₂ ;

B is -OH or -NH ₂ ;

所组成的群组；D is selected from -OH, -NH ₂ , C ₁ ~C ₆ alkyl, C ₁ ~C ₆ alkoxy, C ₁ ~C ₁₀ haloalkyl, C ₃ ~C ₇ cycloalkyl, -CF ₃ , - OCF ₃ , halogen atom, -NHR ₁ , -NH(C=O)-R ₁ , -NH(O=CO)-R ₁ , -NH(O=C-NH)-R ₁ ,

the group formed;

X is an oxygen atom or -NH;

Y is selected from hydrogen atom, -NO ₂ , -OH, -NH ₂ , -COOH, C ₁ ~C ₆ alkyl, C ₁ ~C ₆ alkoxy, C ₃ ~C ₇ cycloalkyl, -CF ₃ , - the group formed by OCF ₃ and a halogen atom;

R ₁₁ to R ₁₂ are each independently selected from a hydrogen atom, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ to C ₁₀ haloalkyl, C ₃ A group consisting of ~C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and halogen atoms;

Its constraints are:

(1) When D is -OH, and A and B are both -NH ₂ ,

At least one of R ₁ to R ₁₀ is phenyl, nitro or phenoxy; or

(2) When A, B and D are -OH at the same time,

(i) At least one of R ₁ to R ₁₀ is C ₁ to C ₁₀ haloalkyl, -CF ₃ or -OCF ₃ ; or

(ii) At least one of the five groups of substituent combinations (R ₁ , R ₂ ), (R ₃ , R ₄ ), (R ₅ , R ₆ ), (R7, R8), (R9, R10) is combined with other groups different combinations; or

(3) When D is selected from C ₁ ~C ₆ alkyl, C ₁ ~C ₆ alkoxy, C ₁ ~C ₁₀ haloalkyl, C ₃ ~C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and A group composed of halogen atoms, and when A and B are -NH ₂ at the same time,

At least one of R ₁ to R ₁₀ is phenyl, nitro or phenoxy; or

(4) When A, B and D are -NH ₂ at the same time,

(i) At least one of R ₁ to R ₁₀ is phenyl, nitro or phenoxy, and (R ₁ , R ₂ ), (R ₃ , R ₄ ), (R ₅ , R ₆ ), (R ₇ , R ₈ ), (R ₉ , R ₁₀ ) at least one of the five substituent combinations is different from the other combinations; or

(ii) At least one of R ₁ to R ₁₀ is phenyl, nitro or phenoxy, and at least one of R ₁ to R ₁₀ is C ₁ to C ₁₀ haloalkyl, -CF ₃ , -OCF ₃ .

When A, B and D of the above-mentioned compound of formula (1) are -OH at the same time, each of R ₁ to R ₉ is a hydrogen atom, and R ₁₀ is -CH ₃ , the structural formula of the compound of formula (1) can be

An aspect of one specific embodiment is that R ₁₀ is attached to the carbon at position 3 of the benzene ring.

When A, B and D of the above-mentioned compound of formula (1) are -OH at the same time, R ₁ to R ₈ are each a hydrogen atom, and R ₉ and R ₁₀ are -CH ₃ , the structural formula of the compound of formula (1) can be

An aspect of one specific embodiment is that R ₉ and R ₁₀ are attached to carbons at positions 3 and 5 of the benzene ring.

When A and B of the above-mentioned compound of formula (1) are -OH at the same time, D is -NH ₂ , R ₁ to R ₁₀ are each a hydrogen atom, the structural formula of a specific embodiment of the compound of formula (1) can be

(D) .

When A and B of the above-mentioned compound of formula (1) are -OH at the same time, D is -NH ₂ , R ₁ to R ₉ are hydrogen atoms, and R ₁₀ is -CH ₃ , the structural formula of the compound of formula (1) can be

An aspect of one specific embodiment is that R ₁₀ is attached to the carbon at position 3 of the benzene ring.

When A and B of the above compound of formula (1) are -OH at the same time, D is -NH ₂ , R ₁ to R ₈ are hydrogen atoms, R ₉ and R ₁₀ are -CH ₃ , the compound of formula (1) The structural formula can be

An aspect of one specific embodiment is that R ₉ and R ₁₀ are attached to carbons at positions 3 and 5 of the benzene ring.

The present invention proposes a method for preparing compounds of formula (1), comprising reacting organophosphide compounds of formula (2), compounds of formula (3), and compounds of formula (4) with acid catalysts to generate compounds of formula (1) A compound, wherein R ₁ to R ₁₀ , A, B and D are as defined above;

According to the above method, in the specific embodiment of this case, when A, B and D are -OH at the same time, R ₁ ~ R ₁₀ are hydrogen atoms, the formula (2) 9,10-dihydro-9-oxa -10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-dihydroxybenzophenone (DHBP), formula (4) phenol react with acid catalyst to generate formula (A ) compound

According to the above method, in the specific embodiment of this case, when A, B and D are -OH at the same time, R ₁ ~ R ₉ are hydrogen atoms, R ₁₀ is -CH ₃ , the formula (2)9,10- Dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-dihydroxybenzophenone (DHBP), formula (4) 2-cresol and The acid catalyst is reacted to form the compound of formula (B).

According to the above method, in the specific embodiment of this case, when A, B and D are -OH at the same time, R ₁ ~ R ₈ are hydrogen atoms, R ₉ and R ₁₀ are -CH ₃ , the formula (2)9 , 10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-dihydroxybenzophenone (DHBP), formula (4) 2, 6-Dimethylphenol is reacted with an acid catalyst to produce a compound of formula (C).

According to the above method, in the specific embodiment of this case, when A and B are -OH at the same time, and D is -NH ₂ , R ₁ ~ R ₁₀ are hydrogen atoms, the formula (2) 9,10-dihydro- 9-oxa-10-phosphophenanthrene-10-oxide compound (DOPO), formula (3) 4,4'-dihydroxybenzophenone (DHBP), formula (4) aniline and acid catalyst are reacted, with A compound of formula (D) is produced.

According to the above method, in the specific embodiment of this case, when A and B are ~OH at the same time, and D is -NH ₂ , R ₁ ~R ₉ are hydrogen atoms, R ₁₀ is -CH ₃ , the formula (2) 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-dihydroxybenzophenone (DHBP), formula (4) o - Toluidine is reacted with an acid catalyst to form a compound of formula (E).

According to the above method, in the specific embodiment of this case, when A and B are -OH at the same time, and D is -NH ₂ , R ₁ ~ R ₈ are hydrogen atoms, R ₉ and R ₁₀ are -CH ₃ , the formula (2) 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-dihydroxybenzophenone (DHBP), formula ( 4) 2,6-dimethylaniline is reacted with an acid catalyst to produce a compound of formula (F).

According to the above method, in the specific embodiment of this case, when A and B are -NH ₂ at the same time, and D is -OH, R ₁ ~ R ₁₀ are hydrogen atoms, the formula (2) 9,10-dihydro- 9-oxa-10-phosphophenanthrene-10-oxide compound (DOPO), formula (3) 4,4'-diaminobenzophenone (DABP), formula (4) phenol react with acid catalyst, with Generate the compound of formula (G)

According to the above method, in the specific embodiment of this case, when A and B are both -NH ₂ and D is -OH, R ₁ to R ₉ are hydrogen atoms, R ₁₀ is -CH ₃ , the formula (2) 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-diaminobenzophenone (DABP), formula (4) 2 -cresol is reacted with an acid catalyst to generate a compound of formula (H)

An aspect of one specific embodiment is that R ₁₀ is attached to the carbon at position 3 of the benzene ring.

According to the above method, in the specific embodiment of this case, when A and B are both -NH ₂ and D is -OH, R ₁ ~ R ₈ are hydrogen atoms, R ₉ and R ₁₀ are -CH ₃ , the formula (2) 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-diaminobenzophenone (DABP), formula ( 4) 2,6-xylenol is reacted with an acid catalyst to generate a compound of formula (I)

An aspect of one specific embodiment is that R ₉ and R ₁₀ are attached to carbons at positions 3 and 5 of the benzene ring.

According to the above method, in the specific embodiment of this case, when A, B and D are -NH ₂ at the same time, R ₁ ~ R ₁₀ are hydrogen atoms, the formula (2) 9,10-dihydro-9-oxo Hetero-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-diaminobenzophenone (DABP), formula (4) aniline and acid catalyst are reacted to generate formula ( J) compound

According to the above method, in the specific embodiment of this case, when A, B and D are -NH ₂ at the same time, R ₁ to R ₉ are hydrogen atoms, R ₁₀ is -CH ₃ , the formula (2)9,10 -Dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-diaminobenzophenone (DABP), formula (4) o-toluidine react with an acid catalyst to generate a compound of formula (K)

An aspect of one specific embodiment is that R ₁₀ is attached to the carbon at position 3 of the benzene ring.

According to the above method, in the specific embodiment of this case, when A, B and D are -NH ₂ at the same time, R ₁ to R ₈ are hydrogen atoms, R ₉ and R ₁₀ are -CH ₃ , the formula (2) 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-diaminobenzophenone (DABP), formula (4) 2 , 6-dimethylaniline is reacted with an acid catalyst to generate a compound of formula (L)

An aspect of one specific embodiment is that R ₉ and R ₁₀ are attached to carbons at positions 3 and 5 of the benzene ring.

According to the above method, in the specific embodiment of this case, when R ₁ ~ R ₁₀ are hydrogen atoms, A is -NH ₂ , and B and D are both -OH, the formula (2) 9,10-dihydro- 9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4-amino-4'-hydroxyl benzophenone (AHBP), formula (4) phenol react with acid catalyst, Can generate formula (D') compound

Since the chemical bond of the carbon atom connected to the phosphorus atom in this structure is rotated, the compound of the formula (D') can be represented by the compound of the formula (D).

According to the above method, in the specific embodiment of this case, when R ₁ ~ R ₁₀ are hydrogen atoms, A and D are both -NH ₂ , and B is -OH, the formula (2) 9,10-dihydro- 9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4-amino-4'-hydroxybenzophenone (AHBP), formula (4) aniline and acid catalyst react, Can produce formula (G') compound

For the same reason as above, since the chemical bond of the carbon atom connected to the phosphorus atom in this structure is rotated, the compound of the formula (G') can be represented by the compound of the formula (G).

The acid catalyst used in the above method is selected from the group consisting of protic acid or Lewis acid.

The acid catalyst used in the above method is selected from acetic acid, p-toluenesulfonic acid (p-Toluenesulfonic acid, PTSA), methanesulfonic acid (Methanesulfonic acid), calcium magnesium reagent (Calmagite), sulfuric acid (Sulfuric acid), 2-aminobenzenesulfonic acid (Orthanilic acid), 3-pyridinesulfonic acid (3-Pyridinesulfonic acid), p-aminobenzenesulfonic 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 ), aluminum chloride (AlCl ₃ ), boron fluoride (BF ₃ ), iron bromide ( FeBr ₃ ), ferric chloride (FeCl ₃ ), boron chloride (BCl ₃ ) and titanium chloride (TiCl ₄ ).

The amount of the acid catalyst used in the above method is 0.1wt%-30wt% of the content of the organic phosphide raw material.

The present invention discloses a curing agent, which comprises the compound of formula (1) or a mixture thereof.

The present invention also discloses a flame-retardant epoxy resin, which comprises epoxy resin and the above-mentioned hardener, wherein the epoxy resin can be bisphenol A epoxy resin (DGEBA) or phosphorous methyl novolac epoxy resin (CNE) .

The present invention also proposes a method for preparing a flame-retardant epoxy resin, which includes uniformly mixing the epoxy resin and the above-mentioned hardener in an equivalent ratio of 1:0.1 to 1:1, and then curing to obtain a hardened flame-retardant epoxy resin. epoxy resin.

In the specific example of preparing the flame-retardant epoxy resin in this case, the epoxy resins used are bisphenol A epoxy resin (DGEBA) and phosphorus methyl novolac epoxy resin (CNE).

Description of drawings

Figure 1 is the ¹ H and ¹³ CNMR spectrum of A.

Figure 2 is the ³¹ P NMR spectrum of A.

Figure 3 is the ¹ H and ¹³ CNMR spectrum of D.

Figure 4 is the ³¹ P NMR spectrum of D.

Figure 5 is the DSC scan of DGEBA series hardened products.

Figure 6 is a DSC scan of CNE series hardened products.

Figure 7 is the DMA curve of the DGEBA series.

Figure 8 is the DMA curve of the CNE series.

Detailed ways

The following examples will further illustrate the present invention, and are not intended to limit the scope of the present invention. Any modifications and changes achieved by those skilled in the art without departing from the spirit of the present invention all belong to the scope of the present invention.

Example

The implementation of the above related inventions can be represented by flow process 1, and we will illustrate with the following specific examples.

Process 1

Example 1

Synthesis of Compound A

Compound A is obtained by reacting DHBP, DOPO and phenol under the catalysis of an acidic catalyst. The synthesis steps are as follows: in a 1-liter three-necked reactor with a temperature indicating device, add 26.75 grams (0.125 moles) of DHBP (4, 4′-dihydroxybenzophenone), 27.00 grams (0.125 moles) of DOPO (9,10-dihydro-9-oxa-10-phosphophenanthrene 10-oxide), 100 grams of phenol and 1.10 grams of Sulfuric acid, raise the reaction temperature to 130°C, maintain the temperature of the reaction system at 130°C, react for 12 hours, drop into 500 ml of hot water and stir to precipitate, which is Compound A.

After suction and filtration, the filter cake was washed with a large amount of hot water, separated by filtration, and dried in a vacuum oven at 110°C to obtain 54.50 g of Compound A with a yield of 86% and a melting point of 294°C.

^{The 1} H NMR and ¹³ CNMR spectra and ³¹ P NMR spectra of Compound A are shown in Figure 1 and Figure 2 respectively, and the results of spectral analysis show that the product is indeed Compound A.

Example 2

Synthesis of Compound B

Compound B is obtained by reacting DHBP, DOPO and 2-cresol under the catalysis of an acidic catalyst. The synthesis steps are as follows: In a 1-liter three-neck reactor with a temperature indicating device, add 21.40 grams (0.1 mole) of DHBP , 21.60 grams (0.1 moles) of DOPO, 100 grams of 2-cresol and 1.10 grams of sulfuric acid, raise the reaction temperature to 130 ° C, the temperature of the reaction system is maintained at 130 ° C, after 12 hours of reaction, drop 100 milliliters of toluene Stirring and precipitation in the medium, an orange-red sticky substance was obtained. After removing the toluene, the sticky substance was dissolved with ethanol and dropped into deionized water for precipitation.

After separation by filtration, the filter cake was vacuum-dried in a vacuum oven at 100°C to obtain 35.00 g of Compound B as an orange-red solid with a yield of 67% and a melting point of 284°C.

Example 3

Synthesis of Compound C

Compound C is obtained by reacting DHBP, DOPO and 2,6-dimethylphenol (2,6-Dimethylphenol) under the catalysis of an acidic catalyst. In, add 21.40 grams (0.1 mole) of DHBP, 21.60 grams (0.1 mole) of DOPO, 100 grams of 2,6-dimethylphenol and 1.1 grams of sulfuric acid, increase the reaction temperature to 130 ° C, the reaction system temperature Maintained at 130°C, reacted for 12 hours, dropped into 100 ml of toluene and stirred to precipitate, and obtained an orange sticky substance. After removing the toluene, the sticky substance was dissolved with ethanol and dropped into deionized water to precipitate.

After separation by filtration, the filter cake was vacuum-dried in a vacuum oven at 100°C to obtain 40.00 g of Compound C as an orange-red solid with a yield of 75% and a melting point of 291°C.

Example 4

Synthesis of Compound D

Compound D is obtained by reacting DHBP, DOPO and aniline under the catalysis of an acidic catalyst. The synthesis steps are as follows: In a 1-liter three-necked reactor with a temperature indicating device, add 21.40 grams (0.1 moles) of DHBP, 21.60 grams (0.1 mole) of DOPO, 100 grams of aniline and 4.30 grams of p-toluenesulfonic acid (p-Toluenesulfonic Acid, PTSA), raising the reaction temperature up to 130 ° C, the reaction system temperature is maintained at 130 ° C, reaction 12 After one hour, it was dropped into 100 ml of acetonitrile (acetonitrile) and stirred to precipitate to obtain a yellow solid, namely compound D.

After separation by filtration, heating and washing with acetonitrile, suction and filtration, the filter cake was vacuum-dried in a vacuum oven at 100°C to obtain 34.00 g of compound D as a white solid with a yield of 68% and a melting point of 300°C.

^{The 1} H NMR, ¹³ C NMR spectrum and ³¹ P NMR spectrum of compound D are shown in Fig. 3 and Fig. 4, respectively.

Example 5

Synthesis of Compound E

Compound E is obtained by reacting DHBP, DOPO and o-toluidine under the catalysis of an acidic catalyst. The synthesis steps are as follows: In a 1-liter three-neck reactor with a temperature indicating device, add 21.40 grams (0.1 mole) of DHBP , 21.60 grams (0.1 moles) of DOPO, 100 grams of o-toluidine and 4.30 grams of p-toluenesulfonic acid (p-Toluenesulfonic Acid, PTSA), raising the reaction temperature up to 130 ° C, the reaction system temperature is maintained After reacting at 130° C. for 12 hours, drop into 100 ml of toluene and stir to precipitate to obtain a brown sticky substance. After removing the toluene, dissolve the sticky substance with ethanol and drop into deionized water to precipitate.

After separation by filtration, heating and washing with acetonitrile, suction and filtration, the filter cake was vacuum-dried in a vacuum oven at 100°C to obtain 37.00 g of Compound E as a pinkish-purple solid with a yield of 72% and a melting point of 283°C.

Example 6

Synthesis of Compound F

Compound F is obtained by reacting DHBP, DOPO and 2,6-dimethylaniline (2,6-Dimethylaniline) under the catalysis of an acidic catalyst. The synthesis steps are as follows: in a 1-liter three-neck reactor with a temperature indicating device In, add 21.40 grams (0.1 moles) of DHBP, 21.60 grams (0.1 moles) of DOPO, 100 grams of 2,6-dimethylaniline and 4.30 grams of p-toluenesulfonic acid (p-Toluenesulfonic Acid, PTSA ), raise the reaction temperature to 130°C, and maintain the temperature of the reaction system at 130°C. After 12 hours of reaction, drop into 100 ml of toluene and stir to precipitate to obtain a brown sticky substance. After removing the toluene, use ethanol to dissolve the sticky After the substance was dissolved, it was dropped into deionized water to precipitate.

After separation by filtration, heating and washing with acetonitrile, suction and filtration, the filter cake was vacuum-dried in a vacuum oven at 100°C to obtain 27.00 g of Compound F as a pale yellow solid with a yield of 50% and a melting point of 292°C.

Example 7

Synthesis of Compound G

Compound G is obtained by reacting DABP, DOPO and phenol under the catalysis of an acidic catalyst. The synthesis steps are as follows: In a 1-liter three-neck reactor with a temperature indicating device, add 26.53 grams (0.125 moles) of DABP, 27.00 grams (0.125 moles) of DOPO, 25.00 grams of phenol and 1.10 grams of sulfuric acid, raise the reaction temperature to 130°C, maintain the temperature of the reaction system at 130°C, and react for 12 hours. Drop into 500 ml of hot water and stir to precipitate an orange solid, which is compound G.

After filtration and separation, the filter cake was washed with a large amount of hot water, and after suction and filtration, the filter cake was vacuum-dried in a vacuum oven at 110°C to obtain 45.40 g of compound G with a yield of 72% and a melting point of 298°C.

Example 8

Synthesis of Compound H

Compound H is obtained by reacting DABP, DOPO and 2-cresol under the catalysis of an acidic catalyst. The synthesis steps are as follows: In a 1-liter three-neck reactor with a temperature indicating device, add 26.53 grams (0.125 moles) of DABP , 27.00 grams (0.125 moles) of DOPO, 100 grams of 2-cresol and 1.10 grams of sulfuric acid, raising the reaction temperature to 130 ° C, the temperature of the reaction system is maintained at 130 ° C, after 12 hours of reaction, drop 100 milliliters of toluene Stirring and precipitation in medium, a brown sticky substance was obtained. After removing the toluene, the sticky substance was dissolved with ethanol and dropped into deionized water to precipitate.

After separation by filtration, the filter cake was vacuum-dried in a vacuum oven at 100°C to obtain 3.70 g of compound H3 as a pink solid with a yield of 65% and a melting point of 287°C.

Example 9

Synthesis of Compound I

Compound I is obtained by reacting DABP, DOPO and 2,6-dimethylphenol (2,6-Dimethylphenol) under the catalysis of an acidic catalyst. In, add 26.53 grams (0.125 moles) of DABP, 27.00 grams (0.125 moles) of DOPO, 100 grams of 2,6-dimethylphenol and 1.10 grams of sulfuric acid, raise the reaction temperature to 130 ° C, the reaction system temperature Maintained at 130°C, reacted for 12 hours, dropped into 100 ml of toluene and stirred to precipitate to obtain a brown sticky substance. After removing the toluene, the sticky substance was dissolved with ethanol and dropped into deionized water to precipitate.

After separation by filtration, the filter cake was vacuum-dried in a vacuum oven at 100°C to obtain 40.40 g of Compound I as a purple solid with a yield of 76% and a melting point of 293°C.

Example 10

Synthesis of Compound J

Compound J is obtained by reacting DABP, DOPO and aniline under the catalysis of an acidic catalyst. The synthesis steps are as follows: In a 1-liter three-neck reactor with a temperature indicating device, add 26.53 grams (0.125 moles) of DABP, 27.00 grams (0.125 moles) of DOPO, 100.00 grams of aniline and 4.30 grams of PTSA, raising the reaction temperature to 130°C, maintaining the temperature of the reaction system at 130°C, and reacting for 12 hours, dropping it into 100 milliliters of acetonitrile and stirring to precipitate to obtain powder The purple solid is compound J.

After separation by filtration, heating and washing with acetonitrile, suction and filtration, drying in a vacuum oven at 100°C to obtain 29.00 g of Compound J with a yield of 57% and a melting point of 330°C.

Example 11

Synthesis of Compound K

Compound K is obtained by reacting DABP, DOPO and o-toluidine under the catalysis of an acidic catalyst. The synthesis steps are as follows: In a 1-liter three-neck reactor with a temperature indicating device, add 26.53 grams (0.125 moles) of DABP , 27.00 grams (0.125 moles) of DOPO, 100.00 grams of o-toluidine and 4.30 grams of PTSA, raising the reaction temperature to 130 ° C, the temperature of the reaction system was maintained at 130 ° C, after 12 hours of reaction, drop 100 milliliters of toluene Stirring and precipitation in medium, a brown sticky substance was obtained. After removing the toluene, the sticky substance was dissolved with ethanol and dropped into deionized water to precipitate.

After separation by filtration, heating and washing with acetonitrile, suction and filtration, drying in a vacuum oven at 100°C to obtain 32.00 g of Compound K with a yield of 62% and a melting point of 323°C.

Example 12

Synthesis of Compound L

Compound L is obtained by reacting DABP, DOPO and 2,6-dimethylaniline under the catalysis of an acidic catalyst. The synthesis steps are as follows: in a 1-liter three-neck reactor with a temperature indicating device, add 26.53 grams (0.1 moles) of DABP, 21.60 grams (0.1 moles) of DOPO, 100.00 grams of 2,6-dimethylaniline and 4.30 grams of PTSA, raising the reaction temperature to 130°C, maintaining the temperature of the reaction system at 130°C, and reacting 12 Hours later, it was dropped into 100 ml of toluene and stirred to precipitate to obtain a brown sticky substance. After removing the toluene, the sticky substance was dissolved with ethanol and dropped into deionized water to precipitate.

After separation by filtration, heating and washing with acetonitrile, suction and filtration, drying in a vacuum oven at 100°C to obtain 27.60 g of compound L with a yield of 52% and a melting point of 329°C.

Example 13

Synthesis of Compound D

Compound D can also be obtained by reacting AHBP, DOPO and phenol under the catalysis of an acidic catalyst. The synthesis steps are as follows: In a 1-liter three-neck reactor with a temperature indicating device, add 21.30 grams (0.1 mole) of AHBP, 21.60 grams (0.1 mole) of DOPO, 100.00 g of phenol and 0.86 g of sulfuric acid were added to a 1-liter reactor, and the reaction temperature was increased to 130° C., and the temperature of the reaction system was maintained at 130° C. After 12 hours of reaction, 100 ml of Stir and precipitate in acetonitrile to precipitate a yellow solid, which is compound D.

After suction and filtration, the filter cake was heated and washed with acetonitrile. After filtration and separation, the filter cake was vacuum-dried in a vacuum oven at 100°C to obtain 30.00 g of compound D as a white solid with a yield of 60% and a melting point of 300°C.

The ¹ H and ¹³ CNMR spectra of the product in DMSO-D6 solution are completely consistent with those shown in Figure 1, showing that the structure of compound D is correct.

Example 14

Synthesis of Compound G

Compound G can also be obtained by reacting AHBP, DOPO and aniline under the catalysis of an acidic catalyst. The synthesis steps are as follows: In a 1-liter three-neck reactor with a temperature indicating device, add 21.30 g (0.1 mole) of AHBP, 21.60 g (0.1 mol) of DOPO, 25.00 g of aniline and 4.32 g of H ₂ SO ₄ were added to a 1-liter reactor, and the reaction temperature was increased to 130° C., and the temperature of the reaction system was maintained at 130° C. After 12 hours of reaction, dropwise Stir in 500 ml of hot water to precipitate an orange solid, which is compound G.

After filtration and separation, the filter cake was washed with a large amount of hot water, and after suction and filtration, the filter cake was vacuum-dried in a vacuum oven at 110°C to obtain 41.62 g of compound G with a yield of 66% and a melting point of 298°C.

Example 15

Preparation and Analysis of Flame Retardant Epoxy Resin

With compound A, compound B and compound E of above-mentioned synthesis example, as the curing agent of epoxy resin bisphenol A diglycidyl ether (DGEBA) and phosphorus methyl novolak epoxy resin (CNE), with equivalent ratio 1: 1 Mix evenly and cure to obtain a hardened flame retardant resin, and compare its effects through the following analysis tests. Sample codes are shown in Table 1:

Table 1: Hardened product code

Hardened product code epoxy resin hardener Catalyst A-DGEBA DGEBA A none A-DGEBA(I) DGEBA A 0.2wt% imidazole B-DGEBA DGEBA D none B-DGEBA(I) DGEBA D 0.2wt% imidazole E-DGEBA DGEBA J none E-DGEBA(I) DGEBA J 0.2wt% imidazole B-CNE CNE D none B-CNE(I) CNE D 0.2wt% imidazole E-CNE CNE J none E-CNE(I) CNE J 0.2wt% imidazole

Thermal Properties Analysis

Figure 5 is the overlay of the glass transition temperature of DGEBA after uniform mixing and hardening with different hardeners, and Figure 6 is the overlay of glass transition temperature after uniform mixing and hardening of CNE and different hardeners, Table 2 and Table 3 are the above-mentioned rings The glass transition temperature of the epoxy resin mixture was measured by DSC at different curing temperatures. We can find that the glass transition temperature of cured epoxy resin is compared in order: B-DGEBA>J-DGEBA>D-DGEBA(I)>J-DGEBA(I)>A-DGEBA(I), the result It shows that the addition of hardening accelerator (imidazole) has little effect on the glass transition temperature of cured epoxy resin. In addition, the cured epoxy resin using Compound D and Compound J as hardeners has a higher glass transition temperature, which is because Compound D and Compound J provide more crosslinking points, which can increase the crosslinking density, making it Has a higher glass transition temperature.

In addition, the glass transition temperature of the cured epoxy resin is compared in order: D-CNE>D-CNE(I)>J-CNE>J-CNE(I). The analysis results show that whether the addition of hardening accelerator has little effect. The glass transition temperature of D series epoxy resin cured products is higher than that of J series epoxy resin cured products. This is because compound J will be affected by steric barriers during the crosslinking process, which hinders the extension of the crosslinked structure and makes the glass transition temperature higher. Low. The results in Table 2 show that the A and J series have the highest glass transition temperature at a hardening temperature of 220°C, and a slight cracking phenomenon will occur at a hardening temperature of 240°C to lower the glass transition temperature. D-DGEBA has the highest glass transition temperature at a hardening temperature of 180°C, and D-DGEBA(I) can reach the highest glass transition temperature at a hardening temperature of 140°C due to the addition of a hardening accelerator. The analysis results show that the hardening speed of the D series is faster than that of the A and J series, and the highest glass transition temperature can be reached at a lower hardening temperature. Table 3 also reveals that except for D-CNE (I) which can achieve the highest glass transition temperature at the hardening temperature of 220° C., all others have the highest glass transition temperature at the hardening temperature of 240° C.

Table 2: DSC glass transition temperature for different hardening temperatures

a: Add 0.2wt% (based on epoxy resin) hardening accelerator (imidazole)

b: DSC test value under nitrogen

c: data from literature [1]

d: data from literature [2]

Table 3: DSC glass transition temperature for different hardening temperatures

a: Add 0.2wt% (based on epoxy resin) hardening accelerator (imidazole)

b: DSC test value under nitrogen

Dynamic Mechanical Analysis

Figure 7 and Figure 8 are the DMA analysis diagrams of DGEBA series and CNE series respectively, and the DMA data are organized in Table 4 and Table 5. The analysis results show that the storage modulus of DGEBA series epoxy resin cured products is compared in order: J-DGEBA(I)>D-DGEBA(I)>J-DGEBA>D-DGEBA>A-DGEBA(I); CNE series The storage modulus of cured epoxy resin is compared in order: J-CNE(I)>J-CNE>D-CNE>D-CNE(I). Except that the storage modulus of D-CNE and D-CNE(I) has little difference, other cured epoxy resins with hardening accelerators have higher storage modulus. In addition, the storage modulus of the epoxy resin cured product using compound J as the hardener is the largest, followed by the storage modulus of the epoxy resin cured product using compound D as the hardener, and the epoxy resin cured product using compound A as the hardener The storage modulus of the compound is the smallest, presumably because compound A and compound D have OH groups, which become softer ethers after cross-linking and hardening with epoxy resin, so the storage modulus of the cured epoxy resin is lower ; Analyzing the tanδ value will also get the same result, because the softer cross-linked structure is relatively easy to move between molecules, so the tanδ height value is relatively large. The glass transition temperature measured by tan δ is not much different from the value measured by DSC.

Table 4: DGEBA series dynamic mechanical analysis results

a: peak height of tanδ curve

b: tanδ value when reaching the glass transition temperature

Table 5: Dynamic Mechanical Analysis Results of CNE Series

a: peak height of tanδ curve

b: tanδ value when reaching the glass transition temperature

UL-94 test

UL-94 is a method of testing flame retardancy in which a polymer sample is subjected to two burns of 10 seconds each. After the first burn, the flame was removed and the time (t ₁ ) required for the polymer to extinguish itself was recorded. If the polymer has dripping during the test, after the sample is cooled, carry out the second combustion, and record the time (t ₂ ) and dripping required for the polymer to extinguish itself. If t ₁ + t ₂ is less than 10 seconds and there is no dripping phenomenon, it is classified as V0 according to the industrial standard for flame-retardancy. If t ₁ + t ₂ is 10 to 30 seconds, then Belongs to V1 level.

Prepare the two hardener compounds D and DDS (4,4'-diaminodiphenyl sulfone) with DGEBA and CNE respectively, with phosphorus content of 1%, 1.5% and 1.8%, melt at 150°C and stir evenly, pour into In the aluminum mold, the mold is placed in a circulating oven and the temperature is raised up to 220°C to harden, and the hardened test piece is tested for UL-94 flame retardancy. Table 6 shows the test results of UL-94. The flame retardancy of cured epoxy resin increases with the increase of phosphorus content, and the phosphorus content of 1.5% can reach the V0 level.

Table 6: UL-94 test results

a: Average value of UL-94 test results

The above claims are used to define the reasonable protection scope of the present invention. However, it should be understood that various obvious improvements achieved by the skilled person based on the disclosure of the present invention should also belong to the reasonable protection scope of the present invention.

Claims (13)

1. A phosphorus compound such as general formula (1),

in R ₁ to R ₁₀ are each independently selected from a hydrogen atom, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ to C ₁₀ haloalkyl, C ₃ A group consisting of ~C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and halogen atoms; A is -OH or -NH ₂ ; B is -OH or -NH ₂ ; D is selected from -OH, -NH ₂ , C ₁ ~C ₆ alkyl, C ₁ ~C ₆ alkoxy, C ₁ ~C ₁₀ haloalkyl, C ₃ ~C ₇ cycloalkyl, -CF ₃ , - OCF ₃ , halogen atom, -NHR ₁ , -NH(C=O)-R ₁ , -NH(O=CO)-R ₁ , -NH(O=C-NH)-R ₁ ,

the group formed; X is an oxygen atom or -NH; Y is selected from hydrogen atom, -NO ₂ , -OH, -NH ₂ , -COOH, C ₁ ~C ₆ alkyl, C ₁ ~C ₆ alkoxy, C ₃ ~C ₇ cycloalkyl, -CF ₃ , - the group formed by OCF ₃ and a halogen atom; R ₁₁ to R ₁₂ are each independently selected from a hydrogen atom, C ₁ to C ₆ alkyl, C ₁ to C ₆ alkoxy, phenyl, nitro, phenoxy, C ₁ to C ₁₀ haloalkyl, C ₃ A group consisting of ~C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and halogen atoms; Its constraints are: (1) When D is -OH, and A and B are both -NH ₂ , At least one of R ₁ to R ₁₀ is phenyl, nitro or phenoxy; or (2) A, B and D are not -OH at the same time, or (3) When D is selected from C ₁ ~C ₆ alkyl, C ₁ ~C ₆ alkoxy, C ₁ ~C ₁₀ haloalkyl, C ₃ ~C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and A group consisting of halogen atoms, and when A and B are -NH ₂ at the same time, At least one of R ₁ to R ₁₀ is phenyl, nitro or phenoxy; or (4) A, B and D are not -NH ₂ at the same time. 2. The compound of formula (1) according to claim 1, wherein (a) When A and B are -OH at the same time, D is -NH ₂ , and R ₁ to R ₁₀ are hydrogen atoms, the compound of formula (1) is formula (D); or

(b) When A and B are -OH at the same time, D is -NH ₂ , R ₁ to R ₉ are hydrogen atoms, and R ₁₀ is -CH ₃ , the compound of formula (1) is formula (E); or

(c) When A and B are -OH at the same time, D is -NH ₂ , R ₁ to R ₈ are hydrogen atoms, R ₉ and R ₁₀ are -CH ₃ , the compound of formula (1) is formula (F) 3. A method for preparing the compound of formula (1) according to claim 1, comprising reacting organophosphide formula (2), compound of formula (3), compound of formula (4) and acid catalyst, to generate formula (1) )compound of;

wherein R ₁ to R ₁ 0, A, B and D are defined in claim 1. 4. The method of claim 3, comprising, (a) When A and B are -OH at the same time, and D is -NH ₂ , R ₁ to R ₁₀ are hydrogen atoms, the formula (2) 9,10-dihydro-9-oxa-10-phosphophenanthrene- 10-oxide (DOPO), formula (3) 4,4'-dihydroxybenzophenone (DHBP), formula (4) aniline react with an acid catalyst to generate a compound of formula (D); (b) When A and B are -OH at the same time, and D is -NH ₂ , R ₁ to R ₉ are hydrogen atoms, R ₁₀ is -CH ₃ , the formula (2) 9,10-dihydro-9-oxo Hetero-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-dihydroxybenzophenone (DHBP), formula (4) o-toluidine and acid catalyst react to Generate a compound of formula (E); (c) When A and B are -OH at the same time, and D is -NH ₂ , R ₁ to R ₈ are hydrogen atoms, R ₉ and R ₁₀ are -CH ₃ , the formula (2) 9,10-dihydro- 9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-dihydroxybenzophenone (DHBP), formula (4) 2,6-dimethylaniline Reacting with an acid catalyst to generate a compound of formula (F); (d) When A and B are both -NH ₂ and D is -OH, and R ₁ to R ₁₀ are hydrogen atoms, the formula (2) 9,10-dihydro-9-oxa-10-phosphophenanthrene- 10-oxide (DOPO), formula (3) 4,4'-diaminobenzophenone (DABP), formula (4) phenol react with acid catalyst to generate formula (G) compound;

(e) When A and B are both -NH ₂ and D is -OH, R ₁ to R ₉ are hydrogen atoms, R ₁₀ is -CH ₃ , the formula (2) 9,10-dihydro-9-oxo Hetero-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-diaminobenzophenone (DABP), formula (4) 2-cresol react with acid catalyst to Generate a compound of formula (H);

(f) When A and B are both -NH ₂ and D is -OH, R ₁ to R ₈ are hydrogen atoms, R ₉ and R ₁₀ are -CH ₃ , the formula (2) 9,10-dihydro- 9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4,4'-diaminobenzophenone (DABP), formula (4) 2,6-dimethylphenol react with an acid catalyst to generate a compound of formula (I);

5. The method according to claim 3, wherein R ₁ to R ₁₀ are hydrogen atoms comprising, (a) When A is -NH ₂ , and B and D are both -OH, formula (2) 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4-amino-4'-hydroxybenzophenone (AHBP), phenol of formula (4) react with an acid catalyst to generate a compound of formula (D); (b) When A and D are both -NH ₂ and B is -OH, formula (2) 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (DOPO), formula (3) 4-amino-4'-hydroxybenzophenone (AHBP), aniline of formula (4) are reacted with an acid catalyst to produce a compound of formula (G). 6. The method of claim 3, 4 or 5, wherein the acid catalyst is selected from the group consisting of protic acids and Lewis acids. 7. The method according to claim 3, 4 or 5, wherein the acid catalyst is selected from the group consisting of acetic acid, p-toluenesulfonic acid, methanesulfonic acid, calcium magnesium reagent, sulfuric acid, 2-aminobenzenesulfonic acid, 3-pyridinesulfonic acid, p-aminobenzenesulfonic acid, hydrogen chloride, hydrogen bromide, hydrogen iodide, hydrogen fluoride, trifluoroacetic acid, nitric acid, phosphoric acid, aluminum chloride, boron fluoride, ferric bromide, ferric chloride, chloride The group consisting of boron and titanium chloride. 8. The method according to claim 3, 4 or 5, wherein the catalyst is used in an amount of 0.1wt%-30wt% of the organic phosphide raw material content. 9. A hardener comprising the compound according to claim 1 or a mixture thereof. 10. A flame retardant epoxy resin comprising epoxy resin and the hardener according to claim 9. 11. The flame retardant epoxy resin according to claim 10, wherein the epoxy resin is bisphenol A epoxy resin or phosphorous methyl novolac epoxy resin. 12. A method for preparing the flame-retardant epoxy resin according to claim 10, comprising uniformly mixing the epoxy resin with the hardener according to claim 9 in an equivalent ratio of 1: 0.1 to 1: 1, and curing Finally, a hardened flame-retardant epoxy resin is obtained. 13. The method according to claim 12, wherein the epoxy resin is bisphenol A epoxy resin or phosphorous methyl novolac epoxy resin.

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