A three-proof triazine composite flame retardant and preparation method thereof

Abstract

The present invention provides a three-proof triazine composite flame retardant and a preparation method thereof, wherein the three-proof triazine composite flame retardant comprises the following raw material components in molar ratio, the three-proof composite agent: triazine flame retardant is 0.1-0.5:2; wherein the three-proof composite agent comprises the following raw material components in molar ratio, the three-proof auxiliary agent: molecular composite agent is 1:1.5-2. The three-proof triazine composite flame retardant of the present invention encapsulates the three-proof auxiliary agent in the molecular composite agent through the host-guest interaction between the molecular composite agent and the three-proof auxiliary agent, thereby avoiding the release of irritating odor during processing, and at the same time, the triazine flame retardant is combined with the surface hydroxyl group of the molecular composite agent, and the three-proof auxiliary agent is encapsulated again while imparting flame retardant properties.

Description

Technical Field

[0001] The invention belongs to the technical field of material synthesis, and in particular relates to a three-proof triazine composite flame retardant and a preparation method thereof. Background Art

[0002] As the "aorta" of information transmission, communication cables are generally composed of two parts: the inner cable core and the sheath. The sheath includes the sheath and possible outer sheath. When laying communication cables outdoors, they are usually laid overhead, directly buried, or in pipelines. However, except for underwater laying, other laying methods have caused rodents to damage the cables to varying degrees across the country, which seriously affects the safety and stability of the communication system. Ants and microorganisms may devour the outer layer of the cable, while mice may bite off the protective layer and insulation layer of the cable, exposing the wires and causing corrosion of the outer layer of the cable. The corroded outer layer may cause the wires to short-circuit and be damaged, causing immeasurable losses. Based on this, many researchers are committed to researching and developing improved outer layer cable materials to improve their three-proof safety and flame retardancy.

[0003] As a nitrogen-based flame retardant, triazine flame retardants achieve gas-phase flame retardancy by decomposing and absorbing heat and generating non-flammable gases during combustion without releasing harmful gases. They have been widely used in materials such as polyamide, polyurethane, and polyethylene. Triazine flame retardants mainly refer to melamine and its salt compounds. Melamine is prone to hydrogen bonding with other substances due to the hydrogen bonds on its triazine ring, thus forming melamine salt compounds. Therefore, a few melamine salt compounds have the problem of high reaction viscosity.

[0004] Capsaicin and its derivatives (capsaicinoid) are compounds composed of vanillin and unsaturated fatty chains containing 8-13 carbon atoms. Because they contain spicy chemicals, they have good pest repellent effects and are often used in the fields of pesticides and pest control. However, the pungent smell released by capsaicin during use will seriously affect the processing environment.

[0005] Therefore, how to develop materials with good flame retardant properties while giving them the three-proof functions of preventing rats, ants and insects from biting and avoiding the irritating effects of the three-proof additives during operation is an urgent problem that R&D personnel need to overcome. Summary of the invention

[0006] In view of this, in order to solve the above technical problems, the present invention proposes a three-proof triazine composite flame retardant and a preparation method thereof. Through the interaction between the molecular composite agent and the three-proof auxiliary agent, the three-proof auxiliary agent is encapsulated in the molecular composite agent to avoid the release of irritating odor during processing. At the same time, the triazine flame retardant is covered on the surface of the three-proof composite agent composed of the molecular composite agent and the three-proof auxiliary agent through hydrogen bonds, further encapsulating the three-proof auxiliary agent and imparting flame retardant properties.

[0007] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0008] On the one hand, the present invention provides a three-proof triazine composite flame retardant, comprising the following raw material components in molar ratio, the three-proof composite agent: triazine flame retardant is 0.1-0.5:2; wherein the three-proof molecular composite agent comprises the following raw material components in molar ratio, the molar ratio of the three-proof auxiliary agent: molecular composite agent is 1:1.5-2.

[0009] In some preferred embodiments of the three-proof triazine composite flame retardant of the present invention, the three-proof auxiliary agent is capsaicin, dihydrocapsaicin, nordihydrocapsaicin or homodihydrocapsaicin.

[0010] In some preferred embodiments of the three-proof triazine composite flame retardant of the present invention, the molecular composite agent is caprolactam, propylene glycol, polyvinyl alcohol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, sucrose, starch, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin or chitosan.

[0011] In some preferred embodiments of the three-proof triazine composite flame retardant of the present invention, the triazine flame retardant is melamine or melamine urate.

[0012] Another aspect of the present invention provides a method for preparing a three-proof triazine composite flame retardant, comprising the following steps:

[0013] S1. Weigh each raw material component according to the ratio;

[0014] S2, dissolving the three-proof auxiliary agent and the molecular composite agent in a molar ratio of 1:1.5-2 in distilled water, stirring at 60-90°C, extracting the transparent solution after the reaction, and freeze-drying to obtain the three-proof molecular composite agent;

[0015] S3, dissolving the three-proof molecular composite agent and the triazine flame retardant in distilled water at a molar ratio of 0.1 to 0.5:2, stirring at 90 to 110° C., cooling to room temperature after the reaction is completed, washing and drying to obtain the three-proof triazine composite flame retardant.

[0016] The three-proof auxiliary agent is any one of capsaicin, dihydrocapsaicin, nordihydrocapsaicin, and high dihydrocapsaicin; the molecular composite agent is any one of caprolactam, propylene glycol, polyvinyl alcohol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, sucrose, starch, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and chitosan; the molecular composite agent is used as the main body, and the three-proof auxiliary agent is used as the object. The structure of the molecular composite agent is hydrophilic on the outside and hydrophobic in the internal cavity. The hydrophobic three-proof auxiliary agent can be encapsulated in the internal cavity to form a main-object complex, thereby avoiding the release of irritating odor during processing; the surface of the three-proof composite agent is combined with the triazine flame retardant by hydrogen bonds, which further encapsulates the three-proof auxiliary agent and gives the three-proof composite agent flame retardant properties. At the same time, the triple-proof molecular composite, as a molecular modifier with a three-dimensional structure, can participate in the preparation process of triazine flame retardants. By destroying the hydrogen bond macromolecular network structure of the triazine flame retardant, it can solve the problem of high viscosity of some triazine flame retardant systems and improve flame retardancy. At the same time, it imparts triple-proof properties such as rodent-proof, insect-proof and ant-proof.

[0017] In some preferred embodiments of the method for preparing the three-proof triazine composite flame retardant of the present invention, in S2, the mass ratio of the three-proof auxiliary agent and the molecular composite agent dissolved in distilled water is 1:1.5-3.

[0018] In some preferred embodiments of the method for preparing the three-proof triazine composite flame retardant of the present invention, in S2, the stirring speed is 250-500 r / min, and the reaction time is 60-90 min.

[0019] In some preferred embodiments of the method for preparing the three-proof triazine composite flame retardant of the present invention, in S3, the mass ratio of the triazine flame retardant and the three-proof molecular composite dissolved in distilled water is 1:1.5-3.

[0020] In some preferred embodiments of the method for preparing a three-proof triazine composite flame retardant of the present invention, in S3, the stirring speed is 300 to 500 r / min, and the reaction time is 20 to 40 min.

[0021] In some preferred embodiments of the method for preparing a three-proof triazine composite flame retardant of the present invention, in S3, ethanol is used for multiple suction filtration and washing, and the drying temperature is controlled at 50-70°C.

[0022] Compared with the prior art, the three-proof triazine composite flame retardant and the preparation method thereof described in the present invention have the following advantages:

[0023] (1) The three-proof triazine composite flame retardant of the present invention uses a molecular composite agent as a main body and a three-proof auxiliary agent as a guest. The structure of the molecular composite agent is hydrophilic on the outside and hydrophobic on the inside. The hydrophobic three-proof auxiliary agent can be encapsulated in the internal cavity to form a main-guest complex, thereby avoiding the release of irritating odor during processing. The surface of the three-proof composite agent is combined with the triazine flame retardant by hydrogen bonds, further encapsulating the three-proof auxiliary agent and imparting flame retardant properties. At the same time, the three-proof molecular composite agent, as a molecular modifier with a three-dimensional structure, can participate in the synthesis and preparation of the triazine flame retardant, and solve the problem of high viscosity of the system by destroying the hydrogen bond macromolecular network structure of part of the triazine flame retardant.

[0024] (2) In the preparation method of the three-proof triazine composite flame retardant described in the present invention, the host-guest interaction between the molecular composite agent and the three-proof auxiliary agent is utilized to synthesize the three-proof molecular composite agent, and the triazine flame retardant is synthesized in situ under the action of water as the dispersion medium and the three-proof molecular composite agent. The triazine flame retardant with three-proof properties and good flame retardant effect is prepared in two steps, and the triazine flame retardant with no irritating odor released during the processing process is simple. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a scanning electron microscope photo of the triple defense molecule composite prepared in Example 1;

[0026] Figure 2 This is a Fourier transform infrared spectrum analysis diagram of the triple defense molecule composite prepared in Example 1;

[0027] Figure 3 The viscosity change curves of the three-proof triazine composite flame retardants prepared in Examples 1-5 and the melamine urate flame retardant prepared in Comparative Example 1 are shown. DETAILED DESCRIPTION

[0028] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.

[0029] The present invention will be described in detail below with reference to the embodiments and the accompanying drawings.

[0030] Example 1

[0031] The process of preparing the three-proof triazine composite flame retardant is as follows:

[0032] 1 mol of capsaicin and 2 mol of β-cyclodextrin were added to a three-necked flask with distilled water as solvent and a material-liquid mass ratio of 1:2; mechanical stirring was performed in a 70°C oil bath at a speed of 300 r / min and a reaction time of 60 min; after the reaction, the transparent solution was extracted into a beaker and freeze-dried in a freeze dryer for 48 hours, and the obtained white powder was the triple-defense molecular complex;

[0033] 2 mol of melamine cyanurate and 0.1 mol of the three-proof molecular composite agent are placed in a three-necked flask with distilled water as solvent and a material-liquid mass ratio of 1:2. The mixture is heated to 90°C in an oil bath and mechanically stirred at a speed of 450r / min for 30 minutes. After the reaction, a white liquid is obtained, which is cooled to room temperature and washed with ethanol by suction for 3 times. The white powder is dried at 60°C, which is a three-proof triazine composite flame retardant with three-proof functions.

[0034] Example 2

[0035] On the basis of Example 1, the difference from Example 1 is that the added amount of the three-defense molecule composite agent is 0.2 mol.

[0036] Example 3

[0037] On the basis of Example 1, the difference from Example 1 is that the added amount of the triple defense molecule composite agent is 0.3 mol.

[0038] Example 4

[0039] On the basis of Example 1, the difference from Example 1 is that the added amount of the triple defense molecule composite agent is 0.4 mol.

[0040] Example 5

[0041] Based on Example 1, the difference from Example 1 is that the amount of the three-defense molecule composite agent added is 0.5 mol.

[0042] Example 6

[0043] On the basis of Example 1, the difference from Example 1 is that in the preparation process of the three-defense molecular complex, the three-defense auxiliary agent used is nordihydrocapsaicin, and the molecular complex agent is polyvinyl alcohol.

[0044] Example 7

[0045] On the basis of Example 1, the difference from Example 1 is that in the preparation process of the three-defense molecular complex, the three-defense auxiliary agent used is high dihydrocapsaicin and the molecular complex agent is glucose.

[0046] Comparative Example 1

[0047] 1 mol of melamine (ME) and 1 mol of cyanate (CA) were placed in a three-necked flask with distilled water as solvent and a material-liquid mass ratio of 1:2. The mixture was heated to 90°C in an oil bath and mechanically stirred at a speed of 450 r / min for 30 minutes. After the reaction, a white liquid was obtained, which was cooled to room temperature and washed with ethanol by suction for 3 times. The white powder melamine urate (MCA) flame retardant was obtained by drying at 60°C.

[0048] Comparative Example 2

[0049] 2 mol of melamine (ME) and 0.2 mol of β-cyclodextrin were placed in a three-necked flask with distilled water as solvent and a material-liquid mass ratio of 1:2. The mixture was heated to 90°C in an oil bath and mechanically stirred at a speed of 450 r / min for 30 minutes. After the reaction, a white liquid was obtained, which was cooled to room temperature and washed with ethanol by suction for 3 times. The white powder was dried at 60°C to obtain a modified melamine flame retardant.

[0050] Performance Testing

[0051] 1. The three-defense molecular composite prepared in Example 1 was measured by scanning electron microscopy and Fourier transform infrared spectroscopy. The results are as follows: Figure 1 and Figure 2 ;

[0052] Figure 1 In the figure, a and b are scanning electron microscopic structures of β-cyclodextrin at different magnifications; c and d are scanning electron microscopic structures of capsaicin at different magnifications; e and f are scanning electron microscopic structures of the prepared three-defense molecular complex at different magnifications; it can be seen from the figure that β-cyclodextrin is a three-dimensional bowl-shaped structure with obvious grooves, and the surface of capsaicin has many strip-shaped substances and is relatively rough; the three-defense molecular complex formed after β-cyclodextrin encapsulates capsaicin becomes smoother, and the disappearance of the β-cyclodextrin three-dimensional structure and the capsaicin strip-shaped substances effectively proves that the three-defense molecular complex has been successfully prepared;

[0053] Figure 2 The infrared spectra of β-cyclodextrin, capsaicin and inclusion compound β-CD@C (three-defense molecule complex) are shown in the figure. -1 Corresponding to the stretching vibration of OH bond, 2935cm -1 and 2823cm -1 They correspond to the antisymmetric stretching vibration of -CH3 and the symmetric stretching vibration of -CH2-, which are typical characteristic peaks of β-cyclodextrin; 1646cm -1 The peak at 1646cm is the characteristic peak of the benzene ring skeleton, which belongs to capsaicin. After capsaicin is wrapped by β-cyclodextrin, β-cyclodextrin has a peak at 1646cm -1The characteristic peak of the anti-stretching vibration of the CH bond of the benzene ring skeleton of capsaicin appeared at , proving that β-CD@C was successfully prepared, which is consistent with the results of the scanning electron microscopy photograph.

[0054] In Examples 2-8, the prepared triple defense molecule composite is similar to that in Example 1 and will not be described in detail.

[0055] 2. The viscosity of the three-proof triazine composite flame retardant prepared in Examples 1-5 and the melamine urate flame retardant prepared in Comparative Example 1 was measured respectively. The results are as follows: Figure 3 As shown;

[0056] Figure 3 In the experiment, with the increase of the content of the three-proof molecule complex, the viscosity of melamine cyanurate gradually decreased. When the content of the three-proof molecule complex reached 0.3 mol or above, the viscosity dropped to 1800 mPa·s. The results showed that the addition of the three-proof molecule complex can effectively reduce the reaction viscosity of traditional MCA and improve its processing conditions. The reason is that the β-CD (β-cyclodextrin) coating Cap (capsaicin) does not affect the three-dimensional structure of β-CD, and can still destroy the supramolecular force between ME-CA reactions, thereby destroying the infinitely expanding planar network structure between ME-CA and reducing its viscosity.

[0057] 3. The three-proof triazine composite flame retardants prepared in Examples 1-5 and the specimens prepared in Comparative Example 1 were subjected to vertical combustion and limiting oxygen index related tests, and the test results are shown in Table 1;

[0058] Table 1

[0059]

[0060] The vertical combustion test was conducted according to the American national standard UL-94 (ANSI / ASTMD635-77), and the size of each sample was 125×12.5×3.2mm. In the evaluation level, V-0 means that the vertical sample stops burning within 10s, and no droplets are allowed; V-1 means that the vertical sample stops burning within 30s, and no droplets are allowed; V-2 means that the vertical sample stops burning within 30s, and dripping of burning materials is allowed.

[0061] The limiting oxygen index is measured using an oxygen index meter in accordance with the American national standard LOI (ASTM D2863-97). The size of each sample is 120×6.5×3.2mm. This project tests the minimum oxygen concentration when a material just maintains balanced combustion. For flame retardant materials, the higher the index, the better.

[0062] As can be seen from Table 1, the present invention does not affect the three-dimensional structure of β-CD by coating Cap with β-CD, and can still destroy the supramolecular force between ME-CA reactions, thereby destroying the infinitely expanding planar network structure between ME-CA, reducing its viscosity, and enabling the MCA molecules to fully exert their flame retardant properties.

[0063] In summary, the present invention uses host-guest interaction and molecular composite technology to prepare a triazine flame retardant with three-proof functions. The product solves the problem of the pungent smell of capsaicin deteriorating the processing environment, and can also solve the problem of high reaction viscosity of triazine flame retardants, and improves the flame retardant properties of triazine flame retardants.

[0064] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A three-proof triazine composite flame retardant, characterized in that: The invention is composed of the following raw material components in molar ratio, the three-proof molecular compound agent: the triazine flame retardant is 0.4:2; wherein, the three-proof molecular compound agent is composed of the following raw material components in molar ratio, the three-proof auxiliary agent: the molecular compound agent is 1:2; The three-proof auxiliary agent is capsaicin; The molecular complexing agent is β-cyclodextrin; The triazine flame retardant is melamine cyanurate; The preparation method of the three-proof triazine composite flame retardant comprises the following steps: S1. Weigh each raw material component according to the ratio; S2, dissolving the three-proof auxiliary agent and the molecular composite agent in distilled water, stirring at 60-90° C., extracting the transparent solution after the reaction, and freeze-drying to obtain the three-proof molecular composite agent; S3, dissolving the triazine flame retardant and the three-proof molecular composite agent weighed according to the ratio in distilled water, stirring at 90-110° C., cooling to room temperature after the reaction is completed, washing and drying to obtain the three-proof triazine composite flame retardant.

2. The three-proof triazine composite flame retardant according to claim 1, characterized in that: In the preparation method S2, the mass ratio of the three-proof auxiliary agent and the molecular composite agent dissolved in distilled water is 1:1.5-3.

3. The three-proof triazine composite flame retardant according to claim 1, characterized in that: In the preparation method S2, the stirring speed is 250-500 r / min and the reaction time is 60-90 min.

4. The three-proof triazine composite flame retardant according to claim 1, characterized in that: In the preparation method S3, the mass ratio of the triazine flame retardant and the three-proof molecule composite dissolved in distilled water is 1:1.5-3.

5. The three-proof triazine composite flame retardant according to claim 1, characterized in that: In the preparation method S3, the stirring speed is 300-500 r / min and the reaction time is 20-40 min.

6. The three-proof triazine composite flame retardant according to claim 1, characterized in that: In the preparation method S3, ethanol is used for multiple suction filtration and washing, and the drying temperature is controlled at 50-70°C.

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