CN113121730B

CN113121730B - Flame retardant, preparation method thereof and flame-retardant composite material containing flame retardant

Info

Publication number: CN113121730B
Application number: CN201911420081.XA
Authority: CN
Inventors: 李娟�; 李彩霞
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2019-12-31
Filing date: 2019-12-31
Publication date: 2022-09-06
Anticipated expiration: 2039-12-31
Also published as: CN113121730A

Abstract

The application discloses a flame retardant, which is an ionic liquid polymer; the ionic liquid polymer is a cross-linked structure and consists of an ionic liquid linear polymerization section and a cross-linking center; the structural general formula of the ionic liquid linear polymerization section is

The structural general formula of the ionic liquid cross-linking center is

Or

Description

Flame retardant, preparation method thereof and flame-retardant composite material containing flame retardant

Technical Field

The application relates to a flame retardant, a preparation method thereof and a flame-retardant composite material containing the flame retardant, belonging to the field of high polymer materials.

Background

Polymeric materials are now ubiquitous in human life and industrial manufacturing, and are rapidly replacing traditional materials such as metals, ceramics, wood, cotton, and natural rubber. However, the polymer material itself is flammable, and can cause fire, thereby causing casualties and property loss, compared to other materials. Therefore, most end products containing polymeric materials (e.g., cables, carpets, furniture cabinets, etc.) must have a satisfactory degree of fire resistance to ensure protection of the public from fire hazards. With the intensive research on the flame retardant technology of the high polymer material and the improvement of environmental awareness, the requirements on the flame retardant not only meet the basic requirement of flame retardance, but also meet the characteristics of environmental protection, low smoke, low toxicity, low corrosion and the like, and the performance of the material cannot be greatly sacrificed. Currently, the mainstream flame retardant is mainly halogen-free and environment-friendly, nano, bio-based, polymer type and the like are emerging development directions, and although some progress has been made, many problems still exist and need to be solved.

Ionic Liquids (ILs) are generally low temperature organic salts consisting entirely of ions, which have many excellent properties, such as excellent chemical and thermal stability, non-flammability and rich structural designability, and meet the new concept of safe halogen-free, efficient and environmentally friendly flame retardation. In recent years, ILs have been extensively studied by many researchers and applied to the field of flame retardancy of materials.

Therefore, the provision of the polyguanidine ionic liquid flame retardant is of great significance.

Disclosure of Invention

According to the first aspect of the application, the flame retardant provided by the application has the dual advantages of a polymer and an ionic liquid, namely the characteristics of good chemical stability, flame retardancy and difficult volatilization of the ionic liquid are kept, and meanwhile, the problems of insufficient water resistance, poor compatibility and easy precipitation of the small molecular ionic liquid are overcome, so that the flame retardant is more suitable for processing and application. The flame retardant is a broad-spectrum flame retardant and has good flame retardant effect in different high polymer materials.

The flame retardant is an ionic liquid polymer; the ionic liquid polymer is a cross-linked structure and consists of an ionic liquid linear polymerization section and a cross-linking center; the structural general formula of the ionic liquid linear polymerization section is

Wherein R is C ₁ ～C ₃ Alkylene or C ₆ ～C ₁₈ One of the arylene groups of (a); r ₁ 、R ₂ 、R ₃ And R ₄ Each independently selected from H-, -CH ₃ 、

One of (1); anion M ^- Is one of phosphate radical or substituted phosphate radical; the structural general formula of the crosslinking center is

One of (1); wherein D and E are each independently

One of (1); m and n are each 1 to 300.

Optionally, the substituted phosphate comprises at least one of pyrophosphate and phytate.

Optionally, cationic to

At least one of which is a core.

According to a second aspect of the present application, there is provided a process for the preparation of a flame retardant provided by the first aspect of the present application, comprising: 1) polymerizing a monomer containing guanidine salt ionic liquid in the presence of an initiator, and crosslinking by using a crosslinking agent to obtain a product I; 2) and carrying out ion exchange reaction on the product I and phosphoric acid or substituted phosphoric acid to obtain the flame retardant.

Optionally, step 1) comprises: and (2) carrying out polymerization reaction on mixed liquid of a monomer containing guanidine salt ionic liquid and an initiator, and then adding a cross-linking agent to carry out cross-linking reaction to obtain the product I.

Optionally, in the step 1), the molar ratio of the guanidine salt ionic liquid to the crosslinking agent to the initiator is 1: 0.25-1: 0.01-0.04.

Optionally, the initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxybenzoate; the crosslinking agent is at least one selected from divinylbenzene, triallylisocyanurate, N-methylenebisacrylamide and diallyl phthalate.

Optionally, the preparation method of the guanidine salt ionic liquid comprises the following steps: and (2) carrying out a reaction I on a mixed solution containing a guanidyl raw material and halogenated olefin to obtain the guanidinium ionic liquid.

Optionally, the molar ratio of the guanidyl-containing raw material to the halogenated olefin is 1: 1-2.

Optionally, the guanidine-containing raw material is selected from at least one of 1,1,3, 3-tetramethylguanidine, diphenylguanidine, 1, 3-di-o-tolylguanidine, sulfaguanidine and 1- (o-tolyl) biguanide; the halogenated olefin is selected from at least one of 4-vinylbenzyl chloride, 4-vinylbenzyl bromide, 3-vinylbenzyl chloride, 3-vinylbenzyl bromide, chloropropene and bromopropylene; the solvent in the mixed liquid containing the guanidyl raw material and the halogenated olefin is selected from at least one of acetonitrile, methanol, ethanol and trichloromethane.

Optionally, the reaction I is a microwave reaction; the power of the microwave reaction is 30-200 w; the temperature of the microwave reaction is 25-50 ℃; the microwave reaction time is 1-4 h.

Optionally, the reaction I is carried out under the protection of inert gas; the inert gas is at least one of nitrogen, helium, neon, argon, krypton and xenon.

Optionally, the preparation method of the guanidine salt ionic liquid further comprises the steps of adding a precipitator into the reaction system after the reaction I is finished, separating and drying; wherein the precipitant is at least one selected from ethyl acetate, tetrahydrofuran, acetone, n-hexane and petroleum ether.

Optionally, the drying temperature of the drying is 60-100 ℃; the drying time is 8-20 h.

Optionally, the solvent in the mixed solution of the monomer containing the guanidine salt ionic liquid and the initiator is at least one selected from methanol, ethanol, toluene, xylene, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.

Optionally, in step 1): the reaction time of the polymerization reaction is 4-10 h; the reaction time of the crosslinking reaction is 1-2 h.

Optionally, the polymerization reaction and/or the crosslinking reaction is a microwave reaction; the power of the microwave reaction is 50-200 w; the temperature of the microwave reaction is 50-120 ℃.

Optionally, the polymerization reaction and/or the crosslinking reaction is carried out under the protection of inert gas; the inert gas is at least one of nitrogen, helium, neon, argon, krypton and xenon.

Optionally, in step 2), the substituted phosphate is at least one selected from pyrophosphoric acid and phytic acid.

Optionally, the molar ratio of the guanidine salt ionic liquid to the phosphoric acid or the substituted phosphoric acid is 1: 1-2.

Alternatively, the ion exchange reaction is an anion exchange reaction.

Optionally, the ion exchange reaction is a microwave reaction; the power of the microwave reaction is 50-150 w; the temperature of the microwave reaction is 25-80 ℃; the microwave reaction time is 2-5 h.

Optionally, the ion exchange reaction is carried out under the protection of inert gas; the inert gas is at least one of nitrogen, helium, neon, argon, krypton and xenon.

Optionally, the preparation method further comprises the steps of separating and drying after the ion exchange reaction; the drying temperature of the drying is 50-110 ℃; the drying time is 8-20 h.

As a specific embodiment, a preparation method of a polyguanidine ionic liquid flame retardant at least comprises the following steps:

1) synthesis of guanidine salt ionic liquid intermediate: at room temperature, adding a guanidino monomer 1, a halogenated olefin monomer 2 and a solvent A into a round-bottom flask, heating to 25-50 ℃ in a microwave reactor under the protection of nitrogen, and reacting for 1-4 hours under the condition that the output power of the microwave reactor is 30-200 w; wherein the molar ratio of the guanidyl monomer 1 to the halogenated olefin monomer 2 is 1: 1-1: 2. After the reaction is finished, using 200-500 mL of solvent B as a precipitator to precipitate a product, performing suction filtration and washing for 3 times, and drying at 60-100 ℃ for 8-20 hours to obtain the intermediate guanidine salt ionic liquid.

2) And (3) synthesis of a product: adding a guanidine salt ionic liquid intermediate, an initiator and a solvent C into a round-bottom flask at room temperature, heating to 50-120 ℃ in a microwave reactor under the protection of nitrogen, reacting for 4-10 h under the condition that the output power of the microwave reactor is 50-200 w, adding a cross-linking agent, and continuing to react for 1-2 h; wherein the molar ratio of the intermediate, the crosslinking agent and the initiator is 1: 0.25-1: 0.01-0.04. After the reaction is finished, adding phosphoric acid or substituted phosphoric acid into the system, and reacting for 2-5 hours under the protection of nitrogen, at the temperature of 25-80 ℃ in a microwave reactor and at the output power of 50-150 w in the microwave reactor; wherein the molar ratio of the intermediate to the phosphoric acid or the substituted phosphoric acid is 1: 1-1: 2. After the reaction is finished, carrying out suction filtration, washing for 3 times by using 200-500 mL of deionized water, and drying for 8-20 h at 50-110 ℃ to obtain the target product.

According to a third aspect of the present application, there is provided a compounded flame retardant comprising a first component and a second component; the first component is selected from at least one of a flame retardant as described in the first aspect of the present application, a flame retardant prepared according to the method as described in the second aspect of the present application; the second component is pentaerythritol.

Optionally, the mass ratio of the first component to the second component in the compound flame retardant is 2-4: 1.

According to a fourth aspect of the present application, there is provided a flame retardant composite comprising at least one of the flame retardant of the first aspect of the present application, the flame retardant prepared according to the method of the second aspect of the present application, the formulated flame retardant of the third aspect of the present application.

According to a fifth aspect of the present application, there is provided a flame retardant polymer material, comprising at least one of the flame retardant according to the first aspect of the present application, the flame retardant prepared according to the second aspect of the present application, and the compounded flame retardant according to the third aspect of the present application.

Optionally, the polymer material is selected from at least one of polylactic acid, nylon 6, epoxy resin, polypropylene, and polyethylene vinyl acetate.

Optionally, the mass content of the flame retardant in the flame-retardant polymer material is 3% to 25%.

The beneficial effect that this application can produce includes:

1) the novel poly guanidine ionic liquid flame retardant with the cross-linking structure is prepared by adopting guanidine and halogenated olefin to react to form small molecular guanidine salt ionic liquid, polymerizing the small molecular guanidine salt ionic liquid with a cross-linking agent and then carrying out anion exchange with phosphoric acid or substituted phosphoric acid.

2) In the application, the preparation method that the intermediate guanidine salt ionic liquid is prepared firstly, then the initiator is added for reaction for a period of time, and then the cross-linking agent is added is adopted, so that the composition of molecular chain segments in a target product can be changed, the finally prepared polyguanidine ionic liquid is mainly self-polymerized and is assisted by cross-linking, and therefore the polyguanidine ionic liquid has better thermal stability and stronger water resistance, and can show more excellent compatibility characteristics in a high polymer material matrix.

3) The application provides a polyguanidine ionic liquid flame retardant has polymer and ionic liquid's dual advantage simultaneously concurrently, has kept ionic liquid chemical stability good promptly, and difficult fire, the difficult volatile characteristics have overcome the not enough, the not good and easy problem of appearing of compatibility of micromolecular ionic liquid water resistance again simultaneously, more are applicable to processing and apply.

4) The polyguanidine ionic liquid flame retardant provided by the application is a broad-spectrum flame retardant, has good compatibility with high polymer materials on the basis of overcoming the defect of insufficient water resistance of small molecular ionic liquid, and has good flame retardant effect in different high polymer materials; the flame retardant can be independently used in polylactic acid (PLA), nylon 6(PA6) and epoxy resin (EP), can also be compounded with Pentaerythritol (PER) and used in polypropylene (PP) and polyethylene vinyl acetate (EVA), has the characteristics of low addition amount and high flame retardant efficiency, does not contain halogen, is green and environment-friendly, is suitable for various high polymer materials, and is a flame retardant with excellent comprehensive performance.

5) In the application, the microwave reaction is adopted, so that the reaction speed can be increased, and the yield and the purity of a target reaction product are improved.

Drawings

Fig. 1 is a nuclear magnetic resonance hydrogen spectrum of an intermediate represented by formula (1) according to example 1 of the present application.

FIG. 2 is an infrared spectrum of an intermediate represented by formula (1), divinylbenzene, and a target product represented by formula (19) according to example 1 of the present application.

FIG. 3 is a graph showing the thermogravimetric curves of the objective product represented by formula (19) according to example 1 of the present application under a nitrogen atmosphere.

Fig. 4 is a nuclear magnetic resonance hydrogen spectrum of an intermediate represented by formula (2) according to example 2 of the present application.

FIG. 5 is an infrared spectrum of an intermediate represented by formula (2), divinylbenzene, and a target product represented by formula (20) according to example 2 of the present application.

FIG. 6 is a thermogravimetric plot of the target product of formula (20) according to example 2 of the present application under nitrogen atmosphere.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially.

In the examples, the IR spectroscopy was performed on a Thermo-Fisher Nicolet 6700 Fourier IR spectrometer, which was a 400cm scan range of 4000 plus 400cm by drying the sample and potassium bromide (KBr) powder, mixing the powder uniformly in a mortar and tabletting ^-1 。

In the examples, NMR spectra ¹ HNMR were tested on a 400 AVANCE III 400M NMR spectrometer from Bruker using CDCl ₃ As solvent, 16 scans were performed.

In the examples, the weight loss on heating is determined on the company Mettler Toledo, Switzerland (TGA/DSC 1).

In the embodiment, x, y, z, m and n are natural numbers more than or equal to 1, and x, y, z, m and n are less than or equal to 300.

Example 1

Synthesis of intermediate formula (1): 0.1mol of 1,1,3, 3-tetramethylguanidine, 0.1mol of 4-vinylbenzyl chloride and 40mL of acetonitrile are added into a 100mL round-bottom flask at room temperature, heated to 40 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1h under the condition that the output power of the microwave reactor is 50 w. After the reaction is finished, using 200mL ethyl acetate as a precipitator to separate out a product, after suction filtration, washing with ethyl acetate for 3 times, and drying in a vacuum oven at 80 ℃ for 12h to obtain the intermediate shown in the formula (1).

Synthesis of the product formula (19): at room temperature, 0.05mol of intermediate compound formula (1), 200mL of methanol and 0.0005mol of azobisisobutyronitrile are added into a 500mL round-bottom flask, heated to 65 ℃ in a microwave reactor under the protection of nitrogen, reacted for 4h under the condition that the output power of the microwave reactor is 100w, then 0.0125mol of divinylbenzene is added, and the reaction is continued for 1 h. After the reaction is finished, cooling the system to room temperature, slowly dripping 0.06mol of phytic acid into the round bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor of 30 ℃ and the output power of the microwave reactor of 80w, and completely dripping within 0.5 h. The reaction was continued for 2h after the end of the dropping. After the reaction is finished, the target product shown in the formula (19) is obtained after the reaction product is filtered, washed for 3 times by 200mL of deionized water and dried for 12 hours in a vacuum oven at 105 ℃.

Example 2

Synthesis of intermediate formula (2): 0.2mol of 1,1,3, 3-tetramethylguanidine, 0.2mol of 4-vinylbenzyl bromide and 80mL of methanol are added into a 100mL round-bottom flask at room temperature, heated to 50 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1h under the condition that the output power of the microwave reactor is 80 w. After the reaction is finished, 200mL of tetrahydrofuran is used as a precipitator to separate out a product, the product is filtered, washed for 3 times by the tetrahydrofuran, and dried for 12 hours in a vacuum oven at 80 ℃ to obtain the intermediate shown in the formula (2).

Synthesis of the product formula (20): at room temperature, 0.1mol of the intermediate compound (2), 200mL of methanol and 0.001mol of azobisisoheptonitrile are added into a 500mL round-bottom flask, heated to 51 ℃ in a microwave reactor under the protection of nitrogen, reacted for 5h under the condition that the output power of the microwave reactor is 150w, then 0.025mol of divinylbenzene is added, and the reaction is continued for 1 h. After the reaction is finished, when the system is cooled to room temperature, slowly dripping 0.12mol of pyrophosphoric acid into the round-bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor of 70 ℃ and the output power of the microwave reactor of 100w, and dripping off for 0.5 h. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (20) is obtained by suction filtration, washing for 3 times by 250mL of deionized water and drying for 15 hours in a vacuum oven at 110 ℃.

Example 3

Synthesis of intermediate formula (3): 0.5mol of 1,1,3, 3-tetramethylguanidine, 1mol of 3-vinylbenzyl chloride and 150mL of ethanol are added into a 250mL round-bottom flask at room temperature, heated to 40 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1.2h under the condition that the output power of the microwave reactor is 70 w. After the reaction is finished, using 500mL of n-hexane as a precipitator to separate out a product, carrying out suction filtration, washing for 3 times by using n-hexane, and drying for 20h in a vacuum oven at 70 ℃ to obtain the intermediate shown in the formula (3).

Synthesis of the product formula (21): at room temperature, 0.5mol of the intermediate (3), 200mL of ethanol and 0.005mol of dimethyl azodiisobutyrate are added into a 500mL round-bottom flask, the mixture is heated to 66 ℃ in a microwave reactor under the protection of nitrogen, the reaction is carried out for 8h under the condition that the output power of the microwave reactor is 160w, then 0.125mol of triallyl isocyanurate is added, and the reaction is continued for 1 h. After the reaction is finished, cooling the system to room temperature, slowly dripping 0.6mol of phosphoric acid into the round-bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor of 30 ℃ and the output power of the microwave reactor of 80w, and dripping out for 1 hour. The reaction was continued for 2.5h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (21) is obtained by suction filtration, washing for 3 times by 500mL of deionized water and drying for 12h in a vacuum oven at 105 ℃.

Example 4

Synthesis of intermediate formula (4): 0.2mol of 1,1,3, 3-tetramethylguanidine, 0.4mol of 3-vinylbenzyl bromide and 60mL of acetonitrile are added into a 100mL round-bottom flask at room temperature, heated to 40 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1h under the condition that the output power of the microwave reactor is 50 w. After the reaction is finished, using 200mL ethyl acetate as a precipitator to separate out a product, after suction filtration, washing with ethyl acetate for 3 times, and drying in a vacuum oven at 80 ℃ for 12h to obtain the intermediate shown in the formula (4).

Synthesis of the product formula (22): at room temperature, 0.1mol of the intermediate (4), 200mL of methanol and 0.001mol of azobisisoheptonitrile are added into a 500mL round-bottom flask, heated to 51 ℃ in a microwave reactor under the protection of nitrogen, reacted for 10h under the condition that the output power of the microwave reactor is 200w, then 0.1mol of diallyl phthalate is added, and the reaction is continued for 2 h. After the reaction is finished, cooling the system to room temperature, slowly dripping 0.2mol of pyrophosphoric acid into a round-bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor of 50 ℃ and the output power of the microwave reactor of 100w, and dripping out for 1 hour. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (22) is obtained by suction filtration, washing for 3 times by 200mL of deionized water and drying for 15 hours in a vacuum oven at 120 ℃.

Example 5

Synthesis of intermediate formula (5): at room temperature, 0.2mol of 1,1,3, 3-tetramethylguanidine, 0.2mol of chloropropene and 60mL of chloroform are added into a 250mL round-bottom flask, heated to 30 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 2h under the condition that the output power of the microwave reactor is 100 w. After the reaction is finished, 250mL of acetone is used as a precipitator to separate out a product, the product is washed for 3 times by acetone after being filtered, and the product is dried for 12 hours in a vacuum oven at 60 ℃ to obtain an intermediate shown in the formula (5).

Synthesis of the product formula (23): at room temperature, 0.05mol of intermediate compound formula (5), 10mL of dimethyl sulfoxide and 0.0005mol of tert-butyl peroxybenzoate are added into a 250mL round-bottom flask, the mixture is heated to 105 ℃ in a microwave reactor under the protection of nitrogen, the reaction is carried out for 5h under the condition that the output power of the microwave reactor is 50w, then 0.0125mol of divinylbenzene is added, and the reaction is continued for 1 h. After the reaction is finished, cooling the system to room temperature, slowly dripping 0.06mol of phytic acid into the round bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor of 30 ℃ and the output power of the microwave reactor of 50w, and completely dripping for 0.5 h. The reaction was continued for 2.5h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (23) is obtained by suction filtration, washing for 3 times by 200mL of deionized water and drying for 14h in a vacuum oven at 110 ℃.

Example 6

Synthesis of intermediate formula (6): 0.4mol of 1,1,3, 3-tetramethylguanidine, 0.8mol of bromopropene and 100mL of ethanol are added into a 250mL round-bottom flask at room temperature, heated to 30 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 2 hours under the condition that the output power of the microwave reactor is 150 w. After the reaction is finished, 250mL of ethyl acetate is used as a precipitator to separate out a product, the product is filtered, washed for 3 times by ethyl acetate, and dried for 12 hours in a vacuum oven at 80 ℃ to obtain an intermediate shown in the formula (6).

Synthesis of the product formula (24): at room temperature, 0.3mol of the intermediate (6), 200mL of N, N-dimethylacetamide and 0.003mol of benzoyl peroxide are added into a 500mL round-bottom flask, heated to 105 ℃ in a microwave reactor under the protection of nitrogen, reacted for 5 hours under the condition that the output power of the microwave reactor is 200w, and then 0.15mol of N, N-methylenebisacrylamide is added, and the reaction is continued for 1 hour. After the reaction is finished, when the system is cooled to room temperature, slowly dropwise adding 0.36mol of phosphoric acid into the round-bottom flask for 1h under the conditions of nitrogen protection, the temperature of the microwave reactor of 80 ℃ and the output power of the microwave reactor of 120 w. The reaction was continued for 2.5h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (24) is obtained by suction filtration, washing for 3 times by 300mL of deionized water and drying for 12 hours in a vacuum oven at 105 ℃.

Example 7

Synthesis of intermediate formula (7): 0.1mol of diphenylguanidine, 0.1mol of 4-vinylbenzyl chloride and 50mL of acetonitrile are added into a 100mL round-bottom flask at room temperature, heated to 40 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1.5h under the condition that the output power of the microwave reactor is 150 w. After the reaction is finished, using 200mL ethyl acetate as a precipitator to separate out a product, performing suction filtration, then washing with ethyl acetate for 3 times, and drying in a vacuum oven at 80 ℃ for 12h to obtain an intermediate shown in a formula (7).

Synthesis of the product formula (25): at room temperature, 0.05mol of the intermediate compound (7), 200mL of N, N-dimethylformamide and 0.0005mol of tert-butyl peroxybenzoate are added into a 250mL round-bottom flask, the mixture is heated to 105 ℃ in a microwave reactor under the protection of nitrogen, the reaction is carried out for 5h under the condition that the output power of the microwave reactor is 80w, then 0.0125mol of divinylbenzene is added, and the reaction is continued for 1 h. After the reaction is finished, cooling the system to room temperature, slowly dripping 0.06mol of pyrophosphoric acid into the round-bottom flask under the protection of nitrogen, at the temperature of the microwave reactor of 70 ℃ and at the output power of the microwave reactor of 120w, and dripping off for 0.5 h. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (25) is obtained by suction filtration, washing for 3 times by 200mL of deionized water and drying for 18h in a vacuum oven at 100 ℃.

Example 8

Synthesis of intermediate formula (8): at room temperature, 0.5mol of diphenylguanidine, 0.5mol of 4-vinylbenzyl bromide and 100mL of ethanol are added into a 250mL round-bottom flask, heated to 60 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1h under the condition that the output power of the microwave reactor is 120 w. After the reaction is finished, separating out a product by using 400mL of tetrahydrofuran as a precipitator, filtering, washing for 3 times by using tetrahydrofuran, and drying for 12 hours in a vacuum oven at 70 ℃ to obtain the intermediate shown in the formula (8).

Synthesis of the product formula (26): at room temperature, 0.3mol of the intermediate (8), 200mL of toluene and 0.003mol of azobisisobutyronitrile are added into a 500mL round-bottom flask, heated to 65 ℃ in a microwave reactor under the protection of nitrogen, reacted for 8 hours under the condition that the output power of the microwave reactor is 200w, then 0.075mol of N, N-methylene bisacrylamide is added, and the reaction is continued for 1 hour. After the reaction is finished, cooling the system to room temperature, slowly dripping 0.6mol of phytic acid into the round-bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor of 30 ℃ and the output power of the microwave reactor of 150w, and completely dripping for 1 hour. The reaction was continued for 2.5h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (26) is obtained by suction filtration, washing for 3 times by 500mL of deionized water and drying for 15h in a vacuum oven at 105 ℃.

Example 9

Synthesis of intermediate formula (9): 0.2mol of diphenylguanidine, 0.2mol of 3-vinylbenzyl chloride and 50mL of trichloromethane are added into a 100mL round-bottom flask at room temperature, heated to 40 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1.5h under the condition that the output power of the microwave reactor is 160 w. After the reaction is finished, 200mL of n-hexane is used as a precipitator to separate out a product, the product is filtered, washed for 3 times by the n-hexane, and dried for 12 hours in a vacuum oven at 80 ℃ to obtain an intermediate shown in the formula (9).

Synthesis of the product formula (27): at room temperature, 0.2mol of the intermediate (9), 200mL of xylene and 0.002mol of dimethyl azodiisobutyrate are added into a 500mL round bottom flask, heated to 65 ℃ in a microwave reactor under the protection of nitrogen, reacted for 8h under the condition that the output power of the microwave reactor is 100w, and then 0.05mol of N, N-methylene bisacrylamide is added, and the reaction is continued for 2 h. After the reaction is finished, when the system is cooled to room temperature, slowly dropwise adding 0.24mol of phosphoric acid into the round-bottom flask for 1h under the conditions of nitrogen protection, the temperature of the microwave reactor of 30 ℃ and the output power of the microwave reactor of 150 w. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (27) is obtained after the reaction product is filtered, washed for 3 times by 300mL of deionized water and dried for 15 hours in a vacuum oven at 105 ℃.

Example 10

Synthesis of intermediate formula (10): at room temperature, 0.1mol of diphenylguanidine, 0.1mol of 3-vinylbenzyl bromide and 50mL of acetonitrile are added into a 100mL round-bottom flask, heated to 40 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1h under the condition that the output power of the microwave reactor is 80 w. After the reaction is finished, 250mL of ethyl acetate is used as a precipitator to separate out a product, the product is filtered, washed for 3 times by ethyl acetate, and dried for 12 hours in a vacuum oven at 80 ℃ to obtain an intermediate shown in the formula (10).

Synthesis of the product formula (28): at room temperature, 0.1mol of the intermediate compound (10), 200mL of methanol and 0.001mol of azobisisobutyronitrile are added into a 500mL round-bottom flask, heated to 65 ℃ in a microwave reactor under the protection of nitrogen, reacted for 5 hours under the condition that the output power of the microwave reactor is 120w, then 0.025mol of divinylbenzene is added, and the reaction is continued for 1 hour. After the reaction is finished, when the system is cooled to room temperature, slowly dripping 0.12mol of phytic acid into the round-bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor of 30 ℃ and the output power of the microwave reactor of 80w, and completely dripping for 0.5 h. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (28) is obtained by suction filtration, washing for 3 times by 200mL of deionized water and drying for 12 hours in a vacuum oven at 105 ℃.

Example 11

Synthesis of intermediate formula (11): at room temperature, 0.4mol of diphenyl guanidine, 0.6mol of chloropropene and 100mL of methanol are added into a 250mL round-bottom flask, and the mixture is heated to 30 ℃ in a microwave reactor under the protection of nitrogen and reacted for 2h under the condition that the output power of the microwave reactor is 130 w. After the reaction is finished, taking 500mL tetrahydrofuran as a precipitator to separate out a product, performing suction filtration, washing with tetrahydrofuran for 3 times, and drying in a vacuum oven at 80 ℃ for 12h to obtain the intermediate shown in the formula (11).

Synthesis of the product formula (29): at room temperature, 0.3mol of the intermediate (11), 200mL of ethanol and 0.003mol of azobisisoheptonitrile are added into a 500mL round-bottom flask, the mixture is heated to 51 ℃ in a microwave reactor under the protection of nitrogen, the reaction is carried out for 10 hours under the condition that the output power of the microwave reactor is 100w, then 0.075mol of diallyl phthalate is added, and the reaction is continued for 2 hours. After the reaction is finished, when the system is cooled to room temperature, slowly dropwise adding 0.36mol of phosphoric acid into the round-bottom flask for 1h under the conditions of nitrogen protection, the temperature of the microwave reactor of 50 ℃ and the output power of the microwave reactor of 80 w. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (29) is obtained by suction filtration, washing for 3 times by 350mL of deionized water and drying for 10 hours in a vacuum oven at 105 ℃.

Example 12

Synthesis of intermediate formula (12): 0.5mol of diphenylguanidine, 1mol of bromopropylene and 100mL of ethanol are added into a 250mL round-bottom flask at room temperature, heated to 30 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 2 hours under the condition that the output power of the microwave reactor is 200 w. After the reaction is finished, using 500mL of acetone as a precipitator to separate out a product, performing suction filtration, then washing with acetone for 3 times, and drying in a vacuum oven at 60 ℃ for 10 hours to obtain an intermediate shown in formula (12).

Synthesis of the product formula (30): at room temperature, 0.5mol of the intermediate (12), 300mL of xylene and 0.005mol of benzoyl peroxide are added into a 500mL round-bottom flask, the mixture is heated to 105 ℃ in a microwave reactor under the protection of nitrogen, the reaction is carried out for 4 hours under the condition that the output power of the microwave reactor is 200w, then 0.125mol of triallyl isocyanurate is added, and the reaction is continued for 2 hours. After the reaction is finished, cooling the system to room temperature, slowly dripping 0.6mol of pyrophosphoric acid into a round-bottom flask under the conditions of nitrogen protection, 80 ℃ of microwave reactor temperature and 100w of microwave reactor output power, and dripping out for 1 hour. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (30) is obtained by suction filtration, washing for 3 times by 500mL of deionized water and drying for 12h in a vacuum oven at 105 ℃.

Example 13

Synthesis of intermediate formula (13): 0.1mol of 1, 3-di-o-tolylguanidine, 0.1mol of 4-vinylbenzyl chloride and 50mL of chloroform are added into a 100mL round-bottom flask at room temperature, heated to 40 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1.5h under the condition that the output power of the microwave reactor is 120 w. After the reaction is finished, 200mL of n-hexane is used as a precipitator to separate out a product, the product is filtered, washed for 3 times by the n-hexane, and dried for 12 hours in a vacuum oven at 70 ℃ to obtain an intermediate shown in a formula (13).

Synthesis of the product formula (31): at room temperature, 0.05mol of the intermediate (13), 200mL of toluene and 0.0005mol of tert-butyl peroxybenzoate are added into a 500mL round-bottom flask, the mixture is heated to 105 ℃ in a microwave reactor under the protection of nitrogen, the reaction is carried out for 4h under the condition that the output power of the microwave reactor is 200w, then 0.0125mol of divinylbenzene is added, and the reaction is continued for 2 h. After the reaction is finished, when the system is cooled to room temperature, slowly adding 0.06mol of phytic acid into the round bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor of 80 ℃ and the output power of the microwave reactor of 100w, and completely dropping for 0.5 h. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (31) is obtained by suction filtration, washing for 3 times by 200mL of deionized water and drying for 18h in a vacuum oven at 105 ℃.

Example 14

Synthesis of intermediate formula (14): 0.2mol of 1, 3-di-o-tolylguanidine, 0.4mol of chloropropene and 100mL of methanol are added into a 250mL round-bottom flask at room temperature, heated to 30 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 2h under the condition that the output power of the microwave reactor is 100 w. After the reaction is finished, using 200mL of petroleum ether as a precipitator to separate out a product, performing suction filtration, washing for 3 times by using the petroleum ether, and drying for 15 hours in a vacuum oven at 80 ℃ to obtain an intermediate shown in the formula (14).

Synthesis of the product formula (32): at room temperature, adding 0.1mol of intermediate compound (14), 200mL of dimethyl sulfoxide and 0.001mol of azobisisobutyronitrile into a 500mL round-bottom flask, heating to 65 ℃ in a microwave reactor under the protection of nitrogen, reacting for 10 hours under the condition that the output power of the microwave reactor is 200w, then adding 0.05mol of N, N-methylene bisacrylamide, and continuing to react for 2 hours. After the reaction is finished, when the system is cooled to room temperature, slowly dripping 0.12mol of pyrophosphoric acid into a round-bottom flask for 1h under the conditions of nitrogen protection, the temperature of the microwave reactor of 70 ℃ and the output power of the microwave reactor of 100 w. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (32) is obtained by suction filtration, washing for 3 times by 250mL of deionized water and drying for 12 hours in a vacuum oven at 105 ℃.

Example 15

Synthesis of intermediate formula (15): at room temperature, 0.1mol of sulfaguanidine, 0.1mol of 4-vinylbenzyl bromide and 50mL of ethanol are added into a 100mL round-bottom flask, and the mixture is heated to 40 ℃ in a microwave reactor under the protection of nitrogen and reacted for 2 hours under the condition that the output power of the microwave reactor is 100 w. After the reaction is finished, 200mL of ethyl acetate is used as a precipitator to separate out a product, after suction filtration, tetrahydrofuran is used for washing for 3 times, and the product is dried for 12 hours in a vacuum oven at 80 ℃ to obtain an intermediate shown in the formula (15).

Synthesis of the product formula (33): at room temperature, 0.05mol of the intermediate compound (15), 200mL of methanol and 0.0005mol of azobisisoheptonitrile are added into a 500mL round-bottom flask, the mixture is heated to 51 ℃ in a microwave reactor under the protection of nitrogen, the reaction is carried out for 5h under the condition that the output power of the microwave reactor is 150w, then 0.0125mol of triallyl isocyanurate is added, and the reaction is continued for 1 h. After the reaction is finished, when the system is cooled to room temperature, slowly adding 0.06mol of phytic acid into the round bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor at 50 ℃ and the output power of the microwave reactor at 100w, and completely dropping for 0.5 h. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (33) is obtained after the reaction product is filtered, washed for 3 times by 250mL of deionized water and dried for 12 hours in a vacuum oven at 105 ℃.

Example 16

Synthesis of intermediate formula (16): 0.3mol of sulfaguanidine, 0.3mol of 4-vinylbenzyl chloride and 50mL of acetonitrile are added into a 250mL round bottom flask at room temperature, heated to 40 ℃ in a microwave reactor under the protection of nitrogen, and reacted for 1.5h under the condition that the output power of the microwave reactor is 90 w. After the reaction is finished, 350mL of tetrahydrofuran is used as a precipitator to separate out a product, after suction filtration, tetrahydrofuran is used for washing for 3 times, and the intermediate shown in the formula (16) is obtained after drying for 12 hours in a vacuum oven at 80 ℃.

Synthesis of the product formula (34): at room temperature, 0.3mol of the intermediate (16), 200mL of N, N-dimethylacetamide and 0.003mol of benzoyl peroxide are added into a 500mL round-bottom flask, heated to 105 ℃ in a microwave reactor under the protection of nitrogen, reacted for 5 hours under the condition that the output power of the microwave reactor is 150w, then 0.15mol of divinylbenzene is added, and the reaction is continued for 1 hour. After the reaction is finished, when the system is cooled to room temperature, slowly dripping 0.6mol of phytic acid into the round-bottom flask under the conditions of nitrogen protection, the temperature of the microwave reactor of 30 ℃ and the output power of the microwave reactor of 150w, and completely dripping for 1 hour. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (34) is obtained by suction filtration, washing for 3 times by 450mL of deionized water and drying for 15h in a vacuum oven at 105 ℃.

Example 17

Synthesis of intermediate formula (17): 0.3mol of 1- (o-tolyl) biguanide, 0.6mol of 4-vinylbenzyl chloride and 150mL of acetonitrile were added to a 250mL round-bottom flask at room temperature, heated to 40 ℃ in a microwave reactor under nitrogen protection, and reacted for 1.5h at a microwave reactor output of 100 w. After the reaction is finished, 400mL of petroleum ether is used as a precipitator to separate out a product, after suction filtration, the product is washed by petroleum ether for 3 times, and is dried for 12 hours in a vacuum oven at 80 ℃ to obtain an intermediate shown in a formula (17).

Synthesis of the product formula (35): at room temperature, 0.2mol of the intermediate (17), 200mL of toluene and 0.002mol of dimethyl azodiisobutyrate are added into a 500mL round-bottom flask, heated to 66 ℃ in a microwave reactor under the protection of nitrogen, reacted for 7h under the condition that the output power of the microwave reactor is 200w, then 0.1mol of divinylbenzene is added, and the reaction is continued for 2 h. After the reaction is finished, cooling the system to room temperature, slowly dripping 0.24mol of pyrophosphoric acid into a round-bottom flask under the conditions of nitrogen protection, 80 ℃ of microwave reactor temperature and 80w of microwave reactor output power, and dripping off for 1 hour. The reaction was continued for 4h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (35) is obtained by suction filtration, washing for 3 times by 400mL of deionized water and drying for 15h in a vacuum oven at 105 ℃.

Example 18

Synthesis of intermediate formula (18): 0.4mol of 1- (o-tolyl) biguanide, 0.8mol of bromopropene and 100mL of ethanol were added to a 250mL round-bottomed flask at room temperature, heated to 30 ℃ under nitrogen protection in a microwave reactor and reacted for 2h at a microwave reactor output of 150 w. After the reaction is finished, using 500mL ethyl acetate as a precipitator to separate out a product, after suction filtration, washing the product for 3 times by using ethyl acetate, and drying the product for 12 hours in a vacuum oven at 80 ℃ to obtain an intermediate shown in the formula (18).

Synthesis of the product formula (36): at room temperature, 0.3mol of the intermediate (18), 200mL of N, N-dimethylformamide and 0.003mol of tert-butyl peroxybenzoate are added into a 500mL round-bottom flask, the mixture is heated to 105 ℃ in a microwave reactor under the protection of nitrogen, the reaction is carried out for 5h under the condition that the output power of the microwave reactor is 180w, then 0.15mol of N, N-methylene bisacrylamide is added, and the reaction is continued for 2 h. After the reaction is finished, when the system is cooled to room temperature, slowly dripping 0.3mol of pyrophosphoric acid into a round-bottom flask for 1h under the conditions of nitrogen protection, the temperature of the microwave reactor of 80 ℃ and the output power of the microwave reactor of 120 w. The reaction was continued for 2.5h after the completion of the dropwise addition. After the reaction is finished, the target product shown in the formula (36) is obtained after the reaction product is filtered, washed for 3 times by 400mL of deionized water and dried for 12 hours in a vacuum oven at 105 ℃.

Example 19

Example 19 was prepared substantially similarly to example 1, except that: in the synthesis process of the intermediate body formula (1), the microwave reaction temperature is 25 ℃, the microwave reaction power is 30w, the reaction time is 4h, the drying temperature is 100 ℃, and the drying time is 8 h. The reaction temperature of the product formula (19) is 120 ℃ in the polymerization reaction process in the presence of a cross-linking agent and an initiator; in the ion exchange reaction with phytic acid, the reaction temperature was 25 ℃, the drying temperature after the reaction was 50 ℃ and the drying time was 8 hours, and the other reaction conditions were the same as in example 1, and the target product represented by formula (19) was obtained in the same manner.

And (3) product analysis:

the intermediates prepared in examples 1-19 and the target products were analyzed, typically as shown in fig. 1-6.

FIG. 1 shows an intermediate represented by the formula (1) in example 1 ¹ HNMR spectrogram successfully proves the successful preparation of the intermediate shown in the formula (1). An absorption peak with a chemical shift of 2.8-2.9 ppm is attributed to twelve hydrogens of four methyl groups on a guanidino group, an absorption peak with a chemical shift of 4.0-4.3 ppm is attributed to two hydrogens on a methylene group connected with a nitrogen atom of the guanidino group, an absorption peak with a chemical shift of 5.3-6.8 ppm is attributed to three hydrogens on a double bond, an absorption peak with a chemical shift of 7.2-7.5 ppm is four hydrogens on a benzene ring, and an absorption peak with a chemical shift of 8.1ppm is attributed to one hydrogen with a guanidino group connected with nitrogen. The absorption peaks at the chemical shifts are consistent with the theoretical absorption peaks, and the peak area ratios of the absorption peaks in each group are consistent with the theoretical absorption peaks, which shows that the intermediate shown in the formula (1) is successfully prepared.

FIG. 2 is an IR spectrum of an intermediate represented by the formula (1), divinylbenzene, and a target product represented by the formula (19) in example 1; a represents an infrared spectrum of an intermediate shown in a formula (1); b represents an infrared spectrum of divinylbenzene; c represents an infrared spectrum of the target product represented by formula (19). FIG. 2 successfully demonstrates the successful preparation of the target product, formula (19). 1550cm ^-1 The absorption peak is the vibration of the skeleton of the benzene ring, and the peak isThe strength is obviously enhanced compared with the intermediate formula (1), which indicates that the divinylbenzene crosslinking polymerization is successful. 1176cm ^-1 The absorption peak is P ═ O, 1017cm ^-1 The absorption peak is (P) -O-C, 993cm ^-1 The absorption peak is P-O- (C), which indicates that the phytate anion successfully replaces the chloride ion, and indicates that the target product shown in the formula (19) is successfully prepared.

FIG. 3 is a thermogravimetric plot of the target product of formula (19) according to example 1 of the present application under nitrogen atmosphere. As can be seen from fig. 3: the temperature at which the weight of the target product, formula (19), was reduced by 5 wt% under a nitrogen atmosphere was 238 c, indicating that the flame retardant has good thermal stability and can meet the processing temperatures of various polymeric materials described in the present invention.

FIG. 4 shows a process for preparing an intermediate represented by the formula (2) in example 2 ¹ HNMR spectrogram successfully proves the successful preparation of the intermediate shown in the formula (2). An absorption peak with a chemical shift of 2.8-2.9 ppm is attributed to twelve hydrogens of four methyl groups on a guanidino group, an absorption peak with a chemical shift of 4.0-4.3 ppm is attributed to two hydrogens on a methylene group connected with a nitrogen atom of the guanidino group, an absorption peak with a chemical shift of 5.2-6.8 ppm is attributed to three hydrogens on a double bond, an absorption peak with a chemical shift of 7.2-7.5 ppm is four hydrogens on a benzene ring, and an absorption peak with a chemical shift of 8.0ppm is attributed to one hydrogen with a guanidino group connected with nitrogen. The absorption peaks at the chemical shifts are consistent with the theoretical absorption peaks, and the peak area ratios of the absorption peaks in each group are consistent with the theoretical absorption peaks, which shows that the intermediate shown in the formula (2) is successfully prepared.

FIG. 5 is an IR spectrum of an intermediate represented by the formula (2), divinylbenzene, and a target product represented by the formula (20) in example 2; a represents an infrared spectrum of an intermediate shown in a formula (2); b represents an infrared spectrum of divinylbenzene; c represents an infrared spectrum of the target product represented by the formula (20). FIG. 5 successfully demonstrates the successful preparation of the target product of formula (20). 1550cm ^-1 The absorption peak is the skeleton vibration of a benzene ring, and the peak intensity is obviously enhanced compared with that of the intermediate formula (1), which indicates that the divinylbenzene is successfully crosslinked and polymerized. 1227cm ^-1 The absorption peak is P ═ O, 997cm ^-1 The absorption peak at (A) is P-O-P, indicating that pyrophosphate anion successfully replaced bromide ion.

FIG. 6 is a graph showing the thermogravimetric curves of the objective product expressed by formula (20) according to example 2 of the present application under a nitrogen atmosphere. As can be seen from fig. 6: under the nitrogen atmosphere, the temperature of the target product formula (20) when the weight is reduced by 5 wt% is 245 ℃, which shows that the flame retardant has good thermal stability and can meet the processing temperature of various high polymer materials in the invention.

Example 20

Polylactic acid (PLA) and the polyguanidine ionic liquid flame retardant formula (19) prepared in example 1 were vacuum oven dried at 80 ℃ for 4h, melt blended at a weight ratio of 96:4 at 180 ℃ in a high speed blender, and then flame retardant composite specimens were prepared using a press vulcanizer and a sample cutter according to various test standards.

Example 21

Polylactic acid (PLA) and the polyguanidine ionic liquid flame retardant prepared in example 2, formula (20), were vacuum oven dried at 80 ℃ for 4h, melt blended at a weight ratio of 95:5 in a high speed blender at 180 ℃ and then flame retardant composite specimens were prepared using a flat press and a sample cutter according to various test standards.

Example 22

Polylactic acid (PLA) and the polyguanidine ionic liquid flame retardant prepared in example 9, formula (27), were vacuum oven dried at 80 ℃ for 4h, melt blended at a weight ratio of 97:3 at 180 ℃ in a high speed blender, and then flame retardant composite specimens were prepared using a flat press and a sample cutter according to various test standards.

Example 23

Polylactic acid (PLA) and the polyguanidine ionic liquid flame retardant prepared in example 12, formula (30), were vacuum oven dried at 80 ℃ for 4h, melt blended at a weight ratio of 96:4 at 180 ℃ in a high speed blender, and then flame retardant composite bars were prepared using a flat press and a sample cutter according to various test standards.

Example 24

Nylon 6(PA6) and the polyguanidine ionic liquid flame retardant formula (20) prepared in example 2 were vacuum oven dried at 110 ℃ for 3h, melt blended at a weight ratio of 95:5 at 240 ℃ in a high speed blender, and then flame retardant composite bars were prepared using a press vulcanizer and a sample cutter according to various test standards.

Example 25

Nylon 6(PA6) and the polyguanidine ionic liquid flame retardant of formula (21) prepared in example 3 were vacuum oven dried at 110 ℃ for 3h, melt blended at a weight ratio of 93:7 at 240 ℃ in a high speed blender, and then flame retardant composite bars were prepared using a press vulcanizer and a sample cutter according to various test standards.

Example 26

Nylon 6(PA6) and the polyguanidine ionic liquid flame retardant of formula (31) prepared in example 13 were vacuum oven dried at 110 ℃ for 3h, melt blended at a weight ratio of 94:6 in a high speed blender at 240 ℃ and then flame retardant composite specimens were prepared using a press and a cutter according to various test standards.

Example 27

Nylon 6(PA6) and the polyguanidine ionic liquid flame retardant of formula (32) prepared in example 14 were vacuum oven dried at 110 ℃ for 3h, melt blended at a weight ratio of 94:6 at 240 ℃ in a high speed blender, and then flame retardant composite bars were prepared using a press vulcanizer and a sample cutter according to various test standards.

Example 28

Polypropylene (PP), the polyguanidine ionic liquid flame retardant of formula (25) prepared in example 7 and Pentaerythritol (PER) were vacuum oven dried at 80 ℃ for 4h, melt blended at 200 ℃ in a high speed blender in a weight ratio of 80:15:5, and then flame retardant composite bars were prepared with a flat press and a sample cutter according to various test standards.

Example 29

Polypropylene (PP), the polyguanidine ionic liquid flame retardant of formula (26) prepared in example 8 and Pentaerythritol (PER) were vacuum oven dried at 80 ℃ for 4h, melt blended at 200 ℃ in a high speed blender in the weight ratio of 81:14.2:4.8, and then flame retardant composite bars were prepared with a press vulcanizer and a sample cutter according to various test standards.

Example 30

Polypropylene (PP), the polyguanidine ionic liquid flame retardant of formula (29) prepared in example 11 and Pentaerythritol (PER) were vacuum oven dried at 80 ℃ for 4h, melt blended at 200 ℃ in a high speed blender in a weight ratio of 83:12.7:4.3, and then flame retardant composite bars were prepared with a press vulcanizer and a sample cutter according to various test standards.

Example 31

Polypropylene (PP), the polyguanidine ionic liquid flame retardant of formula (33) prepared in example 15, and Pentaerythritol (PER) were vacuum oven dried at 80 ℃ for 4h, melt blended at 200 ℃ in a high speed blender in a weight ratio of 79:15.7:5.3, and then flame retardant composite specimens were prepared with a flat press and a sample cutter according to various test standards.

Example 32

Polyethylene vinyl acetate (EVA), the polyguanidine ionic liquid flame retardant formula (19) prepared in example 1 and Pentaerythritol (PER) were oven dried at 60 ℃ for 4 hours in vacuum, melt blended at 140 ℃ in a high speed blender in a weight ratio of 78:16.5:5.5, and then flame retardant composite specimens were prepared with a flat press and a sample cutter according to various test standards.

Example 33

Polyethylene vinyl acetate (EVA), the polyguanidine ionic liquid flame retardant formula (24) prepared in example 6, and Pentaerythritol (PER) were oven dried at 60 ℃ for 4h in vacuum, melt blended at 140 ℃ in a high speed blender in a weight ratio of 77:17.2:5.8, and then flame retardant composite specimens were prepared with a flat press and a sample cutter according to various test standards.

Example 34

Polyethylene vinyl acetate (EVA), the polyguanidine ionic liquid flame retardant of formula (34) prepared in example 16, and Pentaerythritol (PER) were oven dried at 60 ℃ for 4h in vacuum, melt blended at 140 ℃ in a high speed blender in a weight ratio of 80:15:5, and then flame retardant composite specimens were prepared with a flat press and a sample cutter according to various test standards.

Example 35

Polyethylene vinyl acetate (EVA), the polyguanidine ionic liquid flame retardant of formula (35) prepared in example 17, and Pentaerythritol (PER) were oven dried at 60 ℃ under vacuum for 4h, melt blended at 140 ℃ in a high speed blender in a weight ratio of 76:18:6, and then flame retardant composite specimens were prepared with a flat press and a sample cutter according to various test standards.

Example 36

Bisphenol a glycidyl ether epoxy (EP-44), 4' -diaminodiphenylmethane (DDM) and the polyguanidine ionic liquid flame retardant formula (22) prepared in example 4, in a weight ratio of 76.3:16.7:7, were mixed uniformly in a beaker at 80 ℃, placed upside down in a mold for specified testing, cured at 120 ℃ for 2h, cured at 170 ℃ for 4h, and after natural cooling, a flame retardant epoxy resin was obtained.

Example 37

Bisphenol a glycidyl ether epoxy (EP-44), 4' -diaminodiphenylmethane (DDM) and the polyguanidine ionic liquid flame retardant formula (23) prepared in example 5, in a weight ratio of 75.4:16.6:8, were mixed uniformly in a beaker at 80 ℃, placed upside down in a mold for specified testing, cured at 120 ℃ for 2h, cured at 170 ℃ for 4h, and after natural cooling, a flame retardant epoxy resin was obtained.

Example 38

Bisphenol a glycidyl ether epoxy (EP-44), 4' -diaminodiphenylmethane (DDM) and the polyguanidine ionic liquid flame retardant formula (28) prepared in example 10, in a weight percentage of 77.1:16.9:6, were mixed uniformly in a beaker at 80 ℃, placed upside down in a mold for specified testing, cured at 120 ℃ for 2h, cured at 170 ℃ for 4h, and after natural cooling, a flame retardant epoxy resin was obtained.

Example 39

Bisphenol a glycidyl ether epoxy (EP-44), 4' -diaminodiphenylmethane (DDM) and the polyguanidine ionic liquid flame retardant formula (36) prepared in example 18 were mixed uniformly in a beaker at a weight ratio of 76.3:16.7:7 at 80 ℃, poured into a mold for specified testing, cured at 120 ℃ for 2 hours and at 170 ℃ for 4 hours, and naturally cooled to obtain a flame retardant epoxy resin.

Comparative example 1

Drying polylactic acid (PLA) in a vacuum oven for 4 hours at 80 ℃, carrying out melt blending in a high-speed blender at 180 ℃, and then preparing the flame-retardant composite material sample strips by using a flat vulcanizing machine and a sample cutting machine according to various test standards.

Comparative example 2

Nylon 6(PA6) was oven dried at 110 ℃ for 3 hours in vacuum, melt blended at 240 ℃ in a high speed blender, and then flame retardant composite specimens were prepared using a press vulcanizer and a sample cutter according to various test standards.

Comparative example 3

Polypropylene (PP), ammonium polyphosphate (APP) and Pentaerythritol (PER) are dried in a vacuum oven for 4 hours at 80 ℃, melt blended in a high-speed blender at 200 ℃ according to the weight percentage of 79:15.7:5.3, and then flame-retardant composite material sample bars are prepared by a flat vulcanizing machine and a sample cutting machine according to various test standards.

Comparative example 4

Drying polyethylene vinyl acetate (EVA), ammonium polyphosphate (APP) and Pentaerythritol (PER) in a vacuum oven at 60 ℃ for 4 hours, carrying out melt blending in a high-speed blender at 140 ℃ according to the weight percentage of 75:18.7:6.3, and preparing the flame-retardant composite material sample strips by using a flat vulcanizing machine and a sample cutting machine according to various test standards.

Comparative example 5

Uniformly mixing bisphenol A glycidyl ether epoxy (EP-44) and 4, 4' -diaminodiphenylmethane (DDM) in a beaker at the temperature of 80 ℃ according to the weight percentage of 82:18, pouring the mixture into a mold for specified test, curing the mixture for 2 hours at the temperature of 120 ℃ and curing the mixture for 4 hours at the temperature of 170 ℃, and naturally cooling the mixture to obtain the flame-retardant epoxy resin.

The flame-retardant composite materials obtained in examples 20 to 39 and comparative examples 1 to 5 were subjected to a flame performance test in accordance with ASTM D3801 and ASTM D2863-97, and the test results are shown in Table 1, wherein NC indicates no grade.

TABLE 1 flame retardancy Properties of flame retardants in polymers

As can be seen from the data analysis in Table 1, the polyguanidine ionic liquid flame retardant disclosed by the application has a very obvious flame retardant effect on various high polymer materials. Respectively adding flame retardants of a formula (19), a formula (20), a formula (27) and a formula (30) into polylactic acid, wherein when the adding amount is 3 wt% -5 wt%, the polylactic acid can pass a V0 grade of a vertical combustion test (UL-94), the flame retardant property of the polylactic acid is obviously improved, the adding amount required by the formula (27) is minimum, and the Limiting Oxygen Index (LOI) value of the polylactic acid can be increased to 22.8% by only adding 3 wt%; the flame retardants of formula (20), formula (21), formula (31) and formula (32) are respectively added into the nylon 6, when the addition amount is 5 wt% -7 wt%, the nylon 6 can pass the UL-94V0 grade, and the LOI value of the nylon 6 is maximally increased to 29.6%, so that the flame retardant effect is good; the flame retardants of formula (22), formula (23), formula (28) and formula (36) are respectively added into the epoxy resin, when the addition amount is 6 wt% -8 wt%, the epoxy resin can pass the UL-94V0 grade, the LOI value is also obviously improved, and the flame retardant property of the epoxy resin is improved to a certain extent. In addition, the compound of the polyguanidine ionic liquid flame retardant and Pentaerythritol (PER) is used for polypropylene and polyethylene vinyl acetate to achieve good flame retardant effect. Respectively compounding a flame retardant of a formula (25), a formula (26), a formula (29) and a formula (33) with pentaerythritol in a ratio of 3:1, and then adding the mixture into polypropylene, wherein when the total addition amount is 17-20 wt%, the polypropylene can pass the UL-94V0 grade; similarly, flame retardants of formula (19), formula (24), formula (34), and formula (35) were compounded with pentaerythritol at a ratio of 3:1 and added to polyethylene vinyl acetate, respectively, such that the polyethylene vinyl acetate passed the UL-94V0 rating when the total amount added was 20 wt% to 24 wt%; the polyguanidine ionic liquid flame retardant serves as an acid source in a compound flame retardant system, plays a role in catalyzing in the material combustion process, promotes a high polymer material to form a more compact and stable carbon layer, isolates flame and oxygen, and therefore achieves a good flame retardant effect.

The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as they meet the requirements of the present invention.

Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. A flame retardant, characterized in that the flame retardant is an ionic liquid polymer; the ionic liquid polymer is a cross-linked structure and consists of an ionic liquid linear polymerization section and a cross-linking center; the structural general formula of the ionic liquid linear polymerization section is

Wherein R is C ₁ ～C ₃ Alkylene or C of ₆ ～C ₁₈ One of the arylene groups of (a);

R ₁ 、R ₂ 、R ₃ and R ₄ Each independently selected from H-, -CH ₃ 、

One of (a) and (b);

anion M ^- Is one of phosphate radical or substituted phosphate radical;

the structural general formula of the crosslinking center is

One of (a) and (b); wherein D and E are each independently

One of (1); m and n are each 1 to 300.

2. The flame retardant of claim 1, wherein the substituted phosphate comprises at least one of pyrophosphate and phytate.

3. The flame retardant of claim 1, wherein the cation is selected from the group consisting of

At least one of which is a core.

4. A method of preparing a flame retardant according to any of claims 1 to 3, comprising:

1) polymerizing a monomer containing guanidine salt ionic liquid in the presence of an initiator, and crosslinking by using a crosslinking agent to obtain a product I;

2) and carrying out ion exchange reaction on the product I and phosphoric acid or substituted phosphoric acid to obtain the flame retardant.

5. The method of preparing a flame retardant according to claim 4, wherein step 1) comprises:

and (2) carrying out polymerization reaction on mixed liquid of a monomer containing guanidine salt ionic liquid and an initiator, and then adding a cross-linking agent to carry out cross-linking reaction to obtain the product I.

6. The preparation method of the flame retardant according to claim 4, wherein in the step 1), the molar ratio of the guanidine salt ionic liquid to the crosslinking agent to the initiator is 1: 0.25-1: 0.01-0.04.

7. The method of claim 4, wherein the initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, and tert-butyl peroxybenzoate; the crosslinking agent is at least one selected from divinylbenzene, triallylisocyanurate, N-methylenebisacrylamide and diallyl phthalate.

8. The method of preparing the flame retardant of claim 4, wherein the method of preparing the guanidinium ionic liquid comprises: and (2) carrying out a reaction I on a mixed solution containing a guanidyl raw material and halogenated olefin to obtain the guanidinium ionic liquid.

9. The preparation method of the flame retardant according to claim 8, wherein the molar ratio of the guanidyl-containing raw material to the halogenated olefin is 1: 1-2.

10. The method for preparing the flame retardant according to claim 8, wherein the guanidine group-containing raw material is at least one selected from the group consisting of 1,1,3, 3-tetramethylguanidine, diphenylguanidine, 1, 3-di-o-tolylguanidine, sulfaguanidine, and 1- (o-tolyl) biguanide;

the halogenated olefin is selected from at least one of 4-vinylbenzyl chloride, 4-vinylbenzyl bromide, 3-vinylbenzyl chloride, 3-vinylbenzyl bromide, chloropropene and bromopropylene;

the solvent in the mixed liquid containing the guanidyl raw material and the halogenated olefin is selected from at least one of acetonitrile, methanol, ethanol and trichloromethane.

11. The method for preparing the flame retardant according to claim 8, wherein the reaction I is a microwave reaction;

the power of the microwave reaction is 30-200 w;

the temperature of the microwave reaction is 25-50 ℃;

the microwave reaction time is 1-4 h.

12. The method for preparing the flame retardant according to claim 8, wherein the reaction I is carried out under the protection of inert gas;

the inert gas is at least one of nitrogen, helium, neon, argon, krypton and xenon.

13. The preparation method of the flame retardant according to claim 8, wherein the preparation method of the guanidine salt ionic liquid further comprises the steps of adding a precipitator into the reaction system after the reaction I is finished, separating and drying;

wherein the precipitant is at least one selected from ethyl acetate, tetrahydrofuran, acetone, n-hexane and petroleum ether.

14. The preparation method of the flame retardant according to claim 13, wherein the drying temperature of the drying is 60-100 ℃;

the drying time is 8-20 h.

15. The method according to claim 8, wherein the solvent in the mixture of the monomer containing the guanidinium ionic liquid and the initiator is at least one selected from methanol, ethanol, toluene, xylene, acetonitrile, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide.

16. The method for preparing a flame retardant according to claim 4, wherein in step 1):

the reaction time of the polymerization reaction is 4-10 h;

the reaction time of the crosslinking reaction is 1-2 h.

17. The method of claim 4, wherein the polymerization reaction and/or the crosslinking reaction is a microwave reaction;

the power of the microwave reaction is 50-200 w;

the temperature of the microwave reaction is 50-120 ℃.

18. The method for preparing the flame retardant according to claim 4, wherein the polymerization reaction and/or the crosslinking reaction is carried out under the protection of inert gas;

19. The method for preparing the flame retardant according to claim 4, wherein the substituted phosphoric acid in the step 2) is at least one selected from pyrophosphoric acid and phytic acid.

20. The preparation method of the flame retardant according to claim 4, wherein the molar ratio of the guanidine salt ionic liquid to the phosphoric acid or the substituted phosphoric acid is 1: 1-2.

21. The method of claim 4, wherein the ion exchange reaction is an anion exchange reaction.

22. The method of claim 4, wherein the ion exchange reaction is a microwave reaction;

the power of the microwave reaction is 50-150 w;

the temperature of the microwave reaction is 25-80 ℃;

the microwave reaction time is 2-5 h.

23. The method for preparing the flame retardant according to claim 4, wherein the ion exchange reaction is carried out under the protection of inert gas;

24. The method for preparing the flame retardant according to claim 4, further comprising the steps of performing separation and drying after the ion exchange reaction;

the drying temperature of the drying is 50-110 ℃;

the drying time is 8-20 h.

25. A compound flame retardant is characterized by comprising a first component and a second component;

the first component is selected from at least one of the flame retardant of any one of claims 1 to 3, the flame retardant prepared according to the method of any one of claims 4 to 24;

the second component is pentaerythritol.

26. The compound flame retardant of claim 25, wherein the mass ratio of the first component to the second component in the compound flame retardant is 2-4: 1.

27. A flame retardant composite comprising at least one of the flame retardant of any one of claims 1 to 3, the flame retardant prepared by the method of any one of claims 4 to 24, and the compounded flame retardant of claim 25.

28. A flame retardant polymer material, characterized by comprising at least one of the flame retardant of any one of claims 1 to 3, the flame retardant prepared by the method of any one of claims 4 to 24, and the compounded flame retardant of any one of claims 25 to 26.

29. The flame retardant polymer material of claim 28, wherein the polymer material is at least one selected from the group consisting of polylactic acid, nylon 6, epoxy resin, polypropylene, and polyethylene vinyl acetate.

30. The flame retardant polymer material according to claim 28, wherein the flame retardant is contained in the flame retardant polymer material in an amount of 3 to 25% by mass.