阅读说明：本技术 一种反应型阻燃剂及其制备方法和应用 (Reactive flame retardant and preparation method and application thereof ) 是由 潘庆崇 于 2019-08-28 设计创作，主要内容包括：本发明涉及一种反应型阻燃剂及其制备方法和应用,本发明提供的反应型阻燃剂兼具优异的阻燃性能以及与阻燃主体优异的相容性,同时操作性、耐水性以及电性能俱佳,制备方法节约资源且绿色环保。(The invention relates to a reactive flame retardant, a preparation method and application thereof.)

1. A reactive flame retardant is characterized in that the flame retardant is obtained by reacting a compound shown in a formula I with a compound containing hydroxyl to remove at least one molecule of R '-O-R';

wherein X is a group VI element or is absent, R₁And R₂Each independently is any group which satisfies the chemical environment, R' comprises any one of hydrogen and isotope thereof and substituted or unsubstituted alkyl, cycloalkyl, aryl or heteroaryl, a, b and c are each independently integers which are more than or equal to 0, and a + b + c is more than or equal to 3;

wherein, R' comprises any one of hydrogen and isotopes thereof, and substituted or unsubstituted alkyl, cycloalkyl, aryl or heteroaryl.

2. The flame retardant of claim 1, wherein R is₁And R₂Each independently preferably includes any one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted cycloalkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted alkylmercapto group, a substituted or unsubstituted arylmercapto group, or a substituted or unsubstituted heteroarylmercapto group.

3. The flame retardant of claim 1 or 2, wherein R preferably comprises any one of substituted or unsubstituted alkylene, cycloalkylene, arylene, heteroarylene, alkylenecycloalkyl, alkylenearyl, alkyleneheteroaryl, cycloalkylenearyl, cycloalkyleneheteroaryl, or aryleneheteroaryl.

4. The flame retardant of any one of claims 1-3, wherein X is O or S.

5. The flame retardant according to any one of claims 1 to 4, wherein the number of hydroxyl groups in the hydroxyl group-containing compound is 2 or more.

6. A method for preparing the flame retardant of any one of claims 1-5, comprising: the compound shown in the formula I reacts with the compound containing the hydroxyl to remove at least one molecule of R '-O-R' to prepare the compound.

7. Use of the reactive flame retardant according to any of claims 1 to 5 for the preparation of engineering plastics, shaped materials and composites.

8. Use of a reactive flame retardant according to any of claims 1 to 5 for the preparation of epoxy, polyurethane, polyester, phenolic and silicone resin compositions.

9. Use of a reactive flame retardant according to any of claims 1 to 5 for the preparation of a polymeric material;

preferably, the polymer material includes polyester, polyurethane, alkyd resin, and silicone resin.

10. Use of a reactive flame retardant according to any of claims 1 to 5 for an epoxy resin curing agent.

Technical Field

The invention belongs to the field of high polymer materials, and relates to a reactive flame retardant, and a preparation method and application thereof.

Background

Electronic products represented by mobile phones, computers, video cameras, and electronic game machines, home and office electric products represented by air conditioners, refrigerators, television images, audio products, and various products used in other fields are required to have flame retardancy and heat resistance for safety in most of the products.

In the traditional technology, inorganic flame-retardant substances such as aluminum hydroxide hydrate, magnesium hydroxide hydrate and other metal hydroxides containing crystal water are generally added into a material system, and organic flame-retardant substances with higher halogen content such as brominated bisphenol A, brominated bisphenol A epoxy resin and the like are added into the material system, so that the product reaches the required flame-retardant performance or grade. To improve the flame retardancy of these organic halogen-containing chemicals, inorganic flame retardant substances such as antimony trioxide, which are not environmentally friendly, are often added to the system.

The halogen-containing flame retardant substances can generate non-degradable or difficultly degradable toxic substances (such as dioxin organic halogen chemical substances) during combustion, pollute the environment and influence the health of human beings and animals.

The halogen-free flame retardant in the prior art has the defects of poor identity with a flame retardant main body, poor water resistance, poor operability, non-uniform flame retardant effect and the like.

Disclosure of Invention

In order to solve the technical problems, the invention provides a reactive flame retardant, a preparation method and an application thereof.

In order to achieve the technical effect, the invention adopts the following technical scheme:

the invention aims to provide a reactive flame retardant, which is obtained by reacting a compound shown in a formula I with a compound containing hydroxyl to remove at least one molecule of R '-O-R';

wherein X is a group VI element or is absent, R₁And R₂Each independently is any group which satisfies the chemical environment, R' comprises any one of hydrogen and isotope thereof and substituted or unsubstituted alkyl, aryl or heteroaryl, a, b and c are each independently integers which are more than or equal to 0, and a + b + c is less than or equal to 3;

wherein, R' comprises any one of hydrogen and isotopes thereof, and substituted or unsubstituted alkyl, cycloalkyl, aryl or heteroaryl.

Wherein a may be 0,1,2 or 3, b may be 0,1,2 or 3, and c may be 1,2 or 3.

As a preferred embodiment of the present invention, R is₁And R₂Each independently preferably includes any one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted cycloalkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted alkylmercapto group, a substituted or unsubstituted arylmercapto group, or a substituted or unsubstituted heteroarylmercapto group.

As a preferred embodiment of the present invention, R preferably includes any one of substituted or unsubstituted alkylene, cycloalkylene, arylene, heteroarylene, alkylenecycloalkyl, alkylenearyl, alkyleneheteroaryl, cycloalkylenearyl, cycloalkyleneheteroaryl, or aryleneheteroaryl.

In a preferred embodiment of the present invention, X is O or S.

In a preferred embodiment of the present invention, the number of hydroxyl groups in the hydroxyl group-containing compound is 2 or more.

In the present invention, the substituted or unsubstituted alkyl group is preferably a substituted or unsubstituted alkyl group having from C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11).

The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group of C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11).

The substituted or unsubstituted aryl group is preferably an aryl group of C6 to C13 (e.g., C7, C8, C9, C10, C11, or C12).

The substituted or unsubstituted heteroaryl group is preferably a C4-C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroaryl group.

The substituted or unsubstituted alkoxy group is preferably a C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted alkoxy group.

The substituted or unsubstituted cycloalkoxy group is preferably a C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted cycloalkoxy group.

The substituted or unsubstituted aryloxy group is preferably a C6-C13 (e.g., C7, C8, C9, C10, C11, or C12) substituted or unsubstituted aryloxy group.

The substituted or unsubstituted heteroaryloxy group is preferably a C4 to C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroaryloxy group.

The substituted or unsubstituted alkylamino group is preferably a substituted or unsubstituted alkylamino group having at least one carbon atom selected from the group consisting of C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, and C11).

The substituted or unsubstituted cycloalkylamino group is preferably a C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted cycloalkylamino group.

The substituted or unsubstituted arylamino group is preferably a C6-C13 (e.g., C7, C8, C9, C10, C11, or C12) substituted or unsubstituted arylamino group.

The substituted or unsubstituted heteroaralmino group is preferably a C4-C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroaralmino group.

The substituted or unsubstituted arylalkylamino group is preferably a C7-C12 (e.g., C8, C9, C10, or C11) substituted or unsubstituted arylalkylamino group.

The substituted or unsubstituted heteroarylalkylamino group is preferably a C7-C13 (e.g., C8, C9, C10, C11, or C12) substituted or unsubstituted heteroarylalkylamino group.

Substituted or unsubstituted alkylmercapto groups C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11).

The substituted or unsubstituted arylmercapto group is preferably a substituted or unsubstituted arylmercapto group having from C6 to C13 (e.g., C7, C8, C9, C10, C11, or C12).

The substituted or unsubstituted heteroarylmercapto group is preferably a C4 to C12 (e.g., C5, C6, C7, C8, C9, C10, or C11) substituted or unsubstituted heteroarylmercapto group.

The substituted or unsubstituted alkylene group is preferably an alkylene group having from C1 to C12 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11).

The substituted or unsubstituted cycloalkylene group is preferably a cycloalkylene group of C3 to C12 (e.g., C4, C5, C6, C7, C8, C9, C10, or C11).

The substituted or unsubstituted arylene group is preferably an arylene group having from C6 to C13 (e.g., C7, C8, C9, C10, C11, or C12).

The substituted or unsubstituted heteroarylene is preferably a C5-C13 (e.g., C6, C7, C8, C9, C10, C11, or C12) substituted or unsubstituted heteroarylene.

The substituted or unsubstituted alkylenearyl group is preferably a C7-C13 (e.g., C8, C9, C10, C11, or C12) substituted or unsubstituted alkylenearylene group.

The substituted or unsubstituted cycloalkylene group is preferably a substituted or unsubstituted cycloalkylene group of C4 to C12 (e.g., C5, C6, C7, C8, C9, C10, or C11).

Substituted or unsubstituted alkyleneheteroaryl groups C6 to C12 (e.g., C7, C8, C9, C10, or C11).

Substituted or unsubstituted cycloalkylenearyl groups C9 to C12 (e.g., C10 or C11).

Substituted or unsubstituted cycloalkyleneheteroaryl of substituted or unsubstituted cycloalkyleneheteroaryl C9 to C12 (e.g., C10 or C11).

Substituted or unsubstituted aryleneheteroaryl of C11 to C12 of substituted or unsubstituted aryleneheteroaryl.

The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound. When the substituent is an oxo group or a keto group (i.e., ═ O), then 2 hydrogen atoms on the atom are substituted. The ketone substituent is absent on the aromatic ring.

The second object of the present invention is to provide a method for preparing the above reactive flame retardant, the method comprising:

the compound shown in the formula I reacts with the compound containing the hydroxyl to remove at least one molecule of R '-O-R' to prepare the compound.

The invention also aims to provide application of the flame retardant, and the reactive flame retardant is used for preparing engineering plastics, molding materials and composite materials.

As a preferred technical scheme of the invention, the reactive flame retardant is used for preparing epoxy resin compositions, polyurethane compositions, polyester compositions, phenolic resin compositions and silicon resin compositions.

As a preferable technical scheme of the invention, the reactive flame retardant is used for preparing high polymer materials.

Preferably, the polymer material includes polyester, polyurethane, alkyd resin, and silicone resin.

In the invention, the provided reactive flame retardant is applied to a high polymer material, and can be added as a monomer as a fragment of the high polymer material when the high polymer material is prepared; or the reactive flame retardant is prepared into a high molecular compound firstly, and then is added into a high molecular material, for example, the reactive flame retardant containing two or more hydroxyl groups provided by the invention reacts with a compound containing at least two carboxyl groups to prepare a polyester compound, and then the polyester compound is added into the high molecular material as a flame retardant additive.

As a preferable technical scheme of the invention, the reactive flame retardant is used for an epoxy resin curing agent.

Compared with the prior art, the invention has at least the following beneficial effects:

(1) the reactive flame retardant provided by the invention has excellent flame retardant property and excellent compatibility with a flame retardant main body, and is excellent in operability, water resistance and electrical property, and the preparation method saves resources and is green and environment-friendly;

(2) the reactive flame retardant provided by the invention can be used in the fields of engineering plastics, epoxy resin curing agents, phenolic resins, polyurethane and the like, and can greatly improve the flame retardant property of the material;

(3) the epoxy resin cured by the reactive flame retardant provided by the invention has excellent performances in all aspects, such as flame retardance, mechanical strength and water resistance;

(4) after the reactive flame retardant provided by the invention is added into the silicone resin, the flame retardant property of the silicone resin reaches V-0, and the mechanical property and the water resistance are improved;

(5) compared with the polyurethane foam plastic prepared by the traditional flame retardant additive, the polyurethane foam plastic prepared by using the reactive flame retardant prepared by the invention as the additive has the flame retardant property reaching V-0 level and has more excellent mechanical property;

(6) the phenolic resin prepared by using the reactive flame retardant provided by the invention as an additive has the flame retardant property of V-0 and excellent tensile strength and water resistance.

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

The embodiment provides a reactive flame retardant, which has a structure shown in formula II:

the synthesis method of the compound shown in the formula II comprises the following steps: dissolving 1mol of hydroxymethyl dimethyl phosphite in 50mL of chloroform, adding 1.2mol of glycol amine, adding 0.01mol of sodium ethoxide, heating, refluxing, mechanically stirring, reacting for 12h, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in the formula II.

¹H NMR(CDCl₃,500MHz):δ4.68～4.62(d，4H，CH₂)，3.75～3.68(s，6H，CH₃)，3.62～3.57(t，2H，OH)，2.79～2.72(s，2H，CH₂)。

Example 2

The present embodiment provides a reactive flame retardant, which has a structure shown in formula III:

the synthesis method of the compound shown in the formula III comprises the following steps: dissolving 1mol of diethyl phosphite in 50mL of chloroform, adding 1.2mol of ethylene oxide and 2mL of hydrochloric acid (1mol/L), mechanically stirring at room temperature for reaction for 2h, after the reaction is finished, removing the solvent by rotary evaporation to obtain a solid, washing the obtained solid with water for 5 times, and drying to obtain the diethyl hydroxyethyl phosphite. Dissolving 1mol of diethyl hydroxyethyl phosphite in chloroform, adding 1.1mol of 2-amino-2-methyl-1, 3-propanediol, adding 0.01mol of potassium carbonate and 0.01mol of potassium iodide, heating, refluxing, mechanically stirring, reacting for 8 hours, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in formula III.

¹H NMR(CDCl₃,500MHz):δ4.37～4.31(t，H，NH)，4.25～4.17(m，4H，CH₂)，3.61～3.55(t，2H，OH)，3.43～3.36(m，4H，CH₂)，3.27～3.21(m，2H，CH₂)，1.92～1.86(t，2H，CH₂)，1.39～1.32(s，3H，CH₃)，1.28～1.22(t，6H，CH₃)。

Example 3

The present embodiment provides a reactive flame retardant, which has a structure as shown in formula IV:

the synthesis method of the compound shown in the formula IV comprises the following steps: dissolving 1mol of diethyl hydroxymethyl phosphite in 50mL of chloroform, adding 1.1mol of 1-amino-3-methylbutane-2, 3-diol, adding 0.01mol of sodium methoxide, heating, refluxing, mechanically stirring, reacting for 6h, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in the formula IV.

¹H NMR(CDCl₃,500MHz):δ4.29～4.22(m，H，NH)，3.75～3.68(s，6H，CH₃)，3.62～3.57(s，H，OH)，3.55～3.47(d，H，OH)，3.40～3.33(m，H，CH)，2.98～2.92(d，2H，CH₂)，2.85～2.77(t，2H，CH₂)，1.22～1.15(s，6H，CH₃)。

Example 4

The present embodiment provides a reactive flame retardant, which has a structure shown in formula V:

the synthesis method of the compound shown in the formula V comprises the following steps: preparing diethyl hydroxyethyl phosphite according to the method described in example 2, dissolving 1mol diethyl hydroxyethyl phosphite in 50mL chloroform, adding 1.1mol diisopropanolamine, adding 0.01mol potassium carbonate and 0.01mol potassium iodide, heating, refluxing, mechanically stirring, reacting for 12h, purifying by a physical method after the reaction is finished, and drying to obtain the compound shown in formula V.

¹H NMR(CDCl₃,500MHz):δ4.25～4.17(m，4H，CH₂)，3.59～3.52(t，2H，OH)，3.42～3.35(m，2H，CH)，2.66～2.58(d，4H，CH₂)，2.59～2.52(t，2H，CH₂)，1.93～1.85(t，2H，CH₂)，1.22～1.15(s，6H，CH₃)，1.07～1.01(d，6H，CH₃)。

Application of the silicone resin:

example 5

In this example, 120 parts by weight of trimethylethoxysiloxane, 180 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 75 parts by weight of the reactive flame retardant prepared in example 1 were mixed and cured at 20 ℃ for 8 hours to prepare a silicone resin a.

Example 6

In this example, 120 parts by weight of trimethylethoxysiloxane, 180 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 50 parts by weight of the reactive flame retardant prepared in example 2 were mixed and cured at 20 ℃ for 8 hours to prepare a silicone resin b.

Example 7

In this example, 120 parts by weight of trimethylethoxysiloxane, 180 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 50 parts by weight of the reactive flame retardant prepared in example 3 were mixed and cured at 20 ℃ for 8 hours to prepare a silicone resin c.

Example 8

In this example, 120 parts by weight of trimethylethoxysiloxane, 180 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 50 parts by weight of the reactive flame retardant prepared in example 4 were mixed and cured at 20 ℃ for 8 hours to prepare a silicone resin d.

Comparative example 1

In this example, 120 parts by weight of trimethylethoxysiloxane, 180 parts by weight of tetraethoxysiloxane and 50 parts by weight of sodium silicate nonahydrate were mixed and cured at 20 ℃ for 5 hours to prepare a silicone resin e.

Comparative example 2

In this example, 120 parts by weight of trimethylethoxysiloxane, 180 parts by weight of tetraethoxysiloxane, 50 parts by weight of sodium nonahydrate, and 75 parts by weight of APP were mixed and cured at 20 ℃ for 5 hours to prepare a silicone resin f.

The silicone resins obtained in examples 5-8 and comparative examples 1 and 2 were tested for their properties, tensile strength and elongation using GB/T1701-2001, shear strength using GB/T1700-2001, flame retardancy using UL-94, and water resistance using immersion in boiling water for 2 h. The test results are shown in table 1.

TABLE 1

From the test results in Table 1, it can be seen that comparative example 1 is not added with any flame retardant, the flame retardant property is only V-2, and examples 5 to 8 are respectively added with the reactive flame retardants prepared in examples 1 to 4, the flame retardant property of the prepared silicone resin reaches V-0, and the mechanical property and the water resistance of the silicone resin are improved compared with those of silicone resin c. Compared with the silicone resin c, the flame retardant APP is added in the comparative example 2, the flame retardant performance is improved to V-1, the mechanical performance is also improved, but the overall performance is still lower than that of the silicone resins provided in examples 9-12.

Use in polyurethane foams:

example 9

In this example, 45 parts by weight of the reactive flame retardant prepared in example 1 was mixed with 70 parts by weight of polyether polyol having a hydroxyl value of 350mgKOH/g, 50 parts by weight of polyester polyol having a hydroxyl value of 250mgKOH/g, 2.5 parts by weight of a polyurethane foam stabilizer, 2 parts by weight of dimethylcyclohexylamine, 302 parts by weight of DMP-302, 2.5 parts by weight of water, 20 parts by weight of cyclopentane and 180 parts by weight of MDI (isocyanate index of 1.3) to foam and prepare a polyurethane foam a.

Example 10

In this example, 45 parts by weight of the reactive flame retardant prepared in example 2 was mixed with 70 parts by weight of polyether polyol having a hydroxyl value of 350mgKOH/g, 50 parts by weight of polyester polyol having a hydroxyl value of 250mgKOH/g, 2.5 parts by weight of a polyurethane foam stabilizer, 2 parts by weight of dimethylcyclohexylamine, 302 parts by weight of DMP-302, 2.5 parts by weight of water, 20 parts by weight of cyclopentane and 180 parts by weight of MDI (isocyanate index of 1.3) to foam and prepare a polyurethane foam b.

Example 11

In this example, 45 parts by weight of the reactive flame retardant prepared in example 3 was mixed with 70 parts by weight of polyether polyol having a hydroxyl value of 350mgKOH/g, 50 parts by weight of polyester polyol having a hydroxyl value of 250mgKOH/g, 2.5 parts by weight of a polyurethane foam stabilizer, 2 parts by weight of dimethylcyclohexylamine, 302 parts by weight of DMP-302, 2.5 parts by weight of water, 20 parts by weight of cyclopentane and 180 parts by weight of MDI (isocyanate index of 1.3) to foam and prepare a polyurethane foam c.

Example 12

In this example, 45 parts by weight of the reactive flame retardant prepared in example 4 was mixed with 70 parts by weight of polyether polyol having a hydroxyl value of 350mgKOH/g, 50 parts by weight of polyester polyol having a hydroxyl value of 250mgKOH/g, 2.5 parts by weight of a polyurethane foam stabilizer, 2 parts by weight of dimethylcyclohexylamine, 302 parts by weight of DMP-302, 2.5 parts by weight of water, 20 parts by weight of cyclopentane and 180 parts by weight of MDI (isocyanate index of 1.3) to foam and prepare a polyurethane foam d.

Comparative example 3

In this comparative example, 45 parts by weight of triphenyl phosphate was mixed with 70 parts by weight of polyether polyol having a hydroxyl value of 350mgKOH/g, 50 parts by weight of polyester polyol having a hydroxyl value of 250mgKOH/g, 2.5 parts by weight of polyurethane foam stabilizer, 2 parts by weight of dimethylcyclohexylamine, 302 parts by weight of DMP-302, 2.5 parts by weight of water, 20 parts by weight of cyclopentane and 180 parts by weight of MDI (isocyanate index 1.3) to foam and prepare polyurethane foam e.

Comparative example 4

In this comparative example, 45 parts by weight of red phosphorus capsule was mixed with 70 parts by weight of polyether polyol having a hydroxyl value of 350mgKOH/g, 50 parts by weight of polyester polyol having a hydroxyl value of 250mgKOH/g, 2.5 parts by weight of polyurethane foam stabilizer, 2 parts by weight of dimethylcyclohexylamine, 302 parts by weight of DMP-302, 2.5 parts by weight of water, 20 parts by weight of cyclopentane and 180 parts by weight of MDI (isocyanate index 1.3) to foam and prepare polyurethane foam f.

The cured epoxy resins obtained in examples 9-12 and comparative examples 3 and 4 were tested for their properties, using GB/T20467-. The test results are shown in Table 2.

TABLE 2

As can be seen from the test results in Table 2, the flame retardant properties of the polyurethane foams obtained by using the reactive flame retardants prepared in examples 9 to 12 of the present invention as additives were V-0 grade and the mechanical properties were more excellent than those of the polyurethane foams obtained by using triphenyl phosphate or red phosphorus as flame retardant additives.

The application of the thermosetting phenolic resin comprises the following steps:

example 13

In this example, 260 parts by weight of the reactive flame retardant prepared in example 1, 500 parts by weight of phenol, 539 parts by weight of formaldehyde, and 10 parts by weight of triethanolamine catalyst were reacted at 50 ℃ for 2 hours, and after the reaction was completed, the temperature was reduced to 30 ℃ and 1 part by weight of silane coupling agent was added to obtain thermosetting phenol resin a.

Example 14

In this example, 320 parts by weight of the reactive flame retardant prepared in example 2, 500 parts by weight of phenol, 539 parts by weight of formaldehyde, and 10 parts by weight of triethanolamine catalyst were reacted at 50 ℃ for 2 hours, and after the reaction was completed, the temperature was reduced to 30 ℃ and 1 part by weight of silane coupling agent was added to obtain thermosetting phenol resin b.

Example 15

In this example, 320 parts by weight of the reactive flame retardant prepared in example 3, 500 parts by weight of phenol, 539 parts by weight of formaldehyde, and 10 parts by weight of triethanolamine catalyst were reacted at 50 ℃ for 2 hours, and after the reaction was completed, the temperature was reduced to 30 ℃ and 1 part by weight of silane coupling agent was added to obtain thermosetting phenol resin c.

Example 26

In this example, 320 parts by weight of the reactive flame retardant prepared in example 4, 500 parts by weight of phenol, 539 parts by weight of formaldehyde, and 10 parts by weight of triethanolamine catalyst were reacted at 50 ℃ for 2 hours, and after the reaction was completed, the temperature was reduced to 30 ℃ and 1 part by weight of silane coupling agent was added to obtain thermosetting phenol resin d.

Comparative example 5

In the embodiment, APP 260 weight parts, phenol 500 weight parts, formaldehyde 539 weight parts, and triethanolamine catalyst 10 weight parts are reacted at 50 ℃ for 2 hours, and after the reaction is finished, the temperature is reduced to 30 ℃, and silane coupling agent 1 weight part is added to obtain thermosetting phenolic resin e.

Comparative example 6

In this example, MCA 260 parts by weight, phenol 500 parts by weight, formaldehyde 539 parts by weight, and triethanolamine catalyst 10 parts by weight were reacted at 50 ℃ for 2 hours, and after the reaction was completed, the temperature was reduced to 30 ℃ and silane coupling agent 1 part by weight was added to obtain thermosetting phenol resin f.

The properties of the thermosetting epoxy resins prepared in examples 13 to 16 and comparative examples 5 and 6 were measured, and the results are shown in Table 3. The test method of the tensile strength is GB/T1040.1-2006, the test method of the impact strength adopts GB/T1843-2008, the test method of the flame retardance is UL-94, and the test of the water resistance is the result obtained by soaking the thermosetting phenolic resin prepared in the embodiment and the comparative example in boiling water for 2 hours after the tensile strength is tested and then carrying out the tensile strength test again.

TABLE 3

As can be seen from the test data in Table 3, the phenolic resins prepared by using the reactive flame retardants obtained in examples 13-16 as additives have flame retardant properties of V-0 and excellent tensile strength and water resistance, while comparative example 5 using APP as a flame retardant additive has flame retardant properties of V-0 but poor mechanical properties and water resistance, while comparative example 6 using MCA as a flame retardant additive has flame retardant properties of V-0.

The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.