CN106832963A - A kind of phosphorous network structure fire retardant - Google Patents

Abstract

The invention relates to a network structure flame retardant. In view of the shortcomings of the existing small molecule flame retardants, which are easy to volatilize and move out, and there are few types of polymer flame retardants, and the application fields are limited, a phosphorus-containing macromolecular network structure flame retardant was developed. First prepare linear prepolymers, and obtain linear prepolymers with different degrees of polymerization by changing the reaction conditions; then add trifunctional cross-linking components to obtain macromolecule flame retardants with different network structures; finally, end-block with functional groups , to obtain the final product. This product not only improves the volatilization and migration of small molecule flame retardants, but also can adjust the thermal decomposition behavior of flame retardants by changing the structure and degree of reaction, so that products suitable for different polymer matrices can be obtained. The raw materials used in the invention have wide sources, low price, mild polymerization process conditions, easy production, and controllable structure of the flame retardant. It can be used alone as an intumescent flame retardant or as a carbon forming agent in combination with other flame retardants.

Description

A phosphorus-containing network structure flame retardant

technical field

The invention relates to a network structure flame retardant, in particular to a phosphorus element-containing network structure flame retardant.

Background technique

Due to their own structure, many polymer materials are flammable. When they are used in many fields such as construction, transportation, automobiles, toys, electrical appliances, etc., they will cause great harm due to exposure to heat sources such as light, electricity, and fire. security risks. Therefore, the flame retardancy of polymer materials is of great significance to its safe use, and it is also a globally accepted safety measure. At present, there are many varieties of commercial flame retardants, which are applied to different polymers. Among them, phosphorus-based flame retardants are currently the most mainstream halogen-free flame retardants, including various phosphates, phosphates, etc. With the improvement of environmental protection requirements in the world, it is not only expected that the flame retardant has a good flame retardant effect, but also hopes that the flame retardant should preferably be of a macromolecular type. Because macromolecular flame retardants have excellent flame retardant effects on the one hand, and good stability on the other hand, they can improve the shortcomings of small molecule phosphate flame retardants that are easy to volatilize and move out, so they have more advantages.

In order to obtain polymer-based phosphorus flame retardants, people have tried many methods, and a series of flame retardants related to linear macromolecules have been developed. In recent years, in addition to linear polymer flame retardants, people have also begun to pay attention to branched flame retardants, such as Deng et al. (European Polymer Journal40, 2004, 1137-1143) using phosphorus oxychloride and resorcinol reaction to obtain a hyperbranched polymer, which improves the flame retardancy of the epoxy resin. Chen et al. (Journal of Polymer Research, 2011, 2229-2237) developed a hyperbranched flame retardant using bisphenol A, methanol, and phosphorus oxychloride. However, each flame retardant has its disadvantages, which cannot meet the requirements of the growing new technology for flame retardant materials. Therefore, the present invention combines the advantages of polymer linear structure and hyperbranched structure to construct a novel phosphorus-containing network structure flame retardant. By changing the reaction time of the linear prepolymer, linear segments with different degrees of polymerization are obtained, and then cross-linking groups are added. group, forming a network structure, and finally introducing a silane coupling agent to adjust the surface properties, thereby obtaining a phosphorus-containing network structure flame retardant. The flame retardant is a polymer-based flame retardant. The decomposition temperature of the flame retardant is regulated through the network structure, and the compatibility with the polymer is adjusted through the surface capping, thereby adjusting the applicability of the flame retardant in different polymer matrices.

Contents of the invention

The object of the present invention is to synthesize a phosphorus-containing network structure flame retardant by a one-pot method (three steps). First, a linear prepolymer with a certain degree of polymerization is prepared by reacting phosphorus-containing compound A (dibasic phosphorus oxychloride, dichlorophosphate or phosphorous chlorine) with compound B (diamine, dihydric alcohol or dihydric phenol) AB, control the degree of polymerization by adjusting the reaction conditions; then use trifunctional POCl ₃ , PCl ₃ or cyanuric chloride as cross-linking groups to form a macromolecular flame retardant with a network structure; finally introduce specific functional groups The silane coupling agent is capped to adjust its surface properties. Compared with small molecule or linear polymer flame retardants, phosphorus-containing network structure flame retardants can regulate the decomposition behavior of flame retardants and the compatibility with polymers, so that they are suitable for different polymer matrices; and phosphorus-containing The raw materials used in the network structure flame retardant have a wide range of sources, the preparation process is mild and controllable, and the production is easy to realize.

The specific structure of the phosphorus-containing network structure flame retardant of the present invention is as follows:

first step:

Take compound B and dissolve it in solvent L1 at 0-200°C, and at the same time add acid-binding agent F (B: acid-binding agent=1:2-1:6) in molar ratio, stir well in a three-necked flask, pass _N2 protection, and connected to the exhaust absorption device. Take A (B:A=1.01:1-1.6:1) according to the molar ratio and dissolve it in the solvent L2, and place it in a constant pressure dropping funnel, and drop it into the B solution at a speed of 1-2 drops/s, and react 0.5-10h.

Step two:

Take trifunctional crosslinking components (POCl ₃ , PCl ₃ or cyanuric chloride) Dissolve in solvent L2, and drop into the above solution at a rate of 1-2 drops/s, keep the temperature at 30-200°C for 0.5-10 hours;

third step:

Add coupling agent C (molar amount C=0.01(B-A)~0.2(B-A)) to block the flame retardant, continue to react for 0.5~5h, filter with suction, wash with alcohol (ethanol, methanol) 3~5 times, The product is obtained after drying in a blast oven at 50-100°C.

The general formula of the diamine in B is NH ₂ -R1-NH ₂ or NH-R1-NH, preferably p-phenylenediamine, m-phenylenediamine, ethylenediamine, 1,6-hexanediamine, 1, One or more of 4-butanediamine, 4,4-diaminodiphenyl ether, 4,4-diaminodiphenylsulfone, 4,4-diaminodiphenylmethane, and piperazine;

The general formula of dihydric alcohol and phenol in B is HO-R1-OH, preferably ethylene glycol, 1,3-propanediol, 1,4-butanediol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, hydroquinone, resorcinol, catechol, bisphenol A, 2,7-bis Hydroxynaphthalene, methylhydroquinone, 4,4'-dihydroxydiphenyl ether, or 4,4'-dihydroxydiphenylsulfone.

The general formula of A is R2-POCl ₂ , phosphonic dichloride of R2-OPOCl ₂ or monosubstituted phosphorus dichloride of R1-PCl ₂ , preferably phenyl phosphonic dichloride, phenyl dichlorophosphate, phenyl One or more mixtures of phosphorus dichloride, cyclohexyl dichlorophosphine, methylphosphonophthalein dichloride, 4-methoxyphenylphosphonodichloride, cyclohexylphosphonodichloride.

The R1 and R2 are linear alkyl groups, cycloalkyl groups, aryl groups containing 1 to 30 carbon atoms, alkyl groups with benzene rings on the straight chains, aryl groups with alkyl groups between multiple benzene rings, Cycloalkylaryl, or arylcycloalkyl, or straight-chain alkyl, cycloalkyl, aryl, straight-chain alkyl with benzene rings containing S, O, N, Si or P atoms, An aryl group, a cycloalkylaryl group, or an arylcycloalkyl group with an alkyl group between multiple benzene rings. R1 and R2 may be the same or different.

The C is 3-aminopropyltrimethoxysilane (KH-540), 3-aminopropyltriethoxysilane (KH-550), 3-mercaptopropyltriethoxysilane (KH-580) , 3-Mercaptopropyltrimethoxysilane (KH-590), Anilinomethyltriethoxysilane (ND-42).

The L1 is: 1,4-dioxane, toluene, p-xylene, tetrahydrofuran, acetone, dichloromethane, chloroform, ether, N-methylpyrrolidone (NMP);

The L2 is: acetonitrile, 1,4-dioxane, toluene, tetrahydrofuran, acetone, dichloromethane, n-heptane, n-hexane, cyclohexane, NMP;

The F is one or a mixture of N,N-diisopropylethylamine, triethylamine, pyridine, N-methylimidazole and N-butylimidazole.

Beneficial effects of the present invention: a phosphorus-containing network structure flame retardant is synthesized by a one-pot method, and can be used alone as a flame retardant or compounded with other flame retardants by adjusting the structure and process. Moreover, when the flame retardant decomposes, no toxic gases such as hydrogen halide will be produced, and it is a green and environmentally friendly flame retardant. The flame retardant has a network structure, which is easier to form charcoal. In addition, it can also exert multi-element synergy to improve the flame retardant efficiency; adjusting the degree of polymerization of the linear segment can adjust the size of the network, so that the flame retardant has adjustable structure and performance , to expand the scope of application of flame retardants; the compatibility of flame retardants and polymers can be improved by end-capping with coupling agents, and flame-retardant materials with excellent comprehensive properties can be obtained.

The product of the invention not only improves the problem of volatilization and migration of the small molecule flame retardant, but also can adjust the thermal decomposition behavior of the flame retardant by changing the structure and reaction degree, so that products suitable for different polymer matrices can be obtained. The raw materials used in the invention have wide sources, low price, mild polymerization process conditions, easy production, controllable structure of the flame retardant, and can be used alone as an intumescent flame retardant or as a carbon forming agent combined with other flame retardants.

Description of drawings

Fig. 1 is the infrared spectrum of product under different proportions, different reaction times;

Fig. 2 is the thermogravimetric curve of the product under different proportions and different reaction times under nitrogen atmosphere.

detailed description

The present invention will be further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

As shown in Figure 1, 3427cm ^-1 is the stretching vibration of NH, 2973cm ^{-1 is the stretching vibration of CH in -CH2, 1631cm -1 is the stretching vibration of C=C in the benzene ring, and 1492cm -1 is the} characteristic of the skeleton vibration of the benzene ring The peak, 1030cm ^-1 is the absorption peak of PNC, with the prolongation of the reaction time, the absorption peaks at 1030cm ^-1 and 2973cm ^-1 are strengthened, indicating that the content of piperazine in the product increases.

Example 1

Take 2.58g (0.03mol) of piperazine and dissolve it in 20ml CH ₂ Cl ₂ at 30°C, add 6.07g (0.06mol) of acid-binding agent triethylamine at the same time, stir in a three-necked flask at a speed of 200r/min until uniform , the system is protected by N ₂ and connected to the tail gas absorption device. Take 4.87g (0.025mol) of phenylphosphonic dichloride and dissolve it in 20ml of dichloromethane and place it in a constant pressure dropping funnel, drop it into the piperazine solution at a rate of 1-2 drops/s to react for 1 hour, and a white Precipitation occurs. Then take 0.51g (0.0033mol) of POCl ₃ and dissolve it in 20ml of dichloromethane, put it in a constant pressure dropping funnel, drop the above solution, control the temperature at 40°C and continue the reaction for 1h, and finally add 0.11g (0.0005mol) of coupling agent KH550 Continue to react for 2 hours, filter with suction and fully wash with ethanol to obtain a viscous substance, dry the product in a blast oven at 60°C for 1 hour, then transfer to a vacuum oven for 2 hours at 60°C, dry and grind to obtain a light yellow powder.

This product is named as P1, the infrared spectrum is as shown in the curve a in Figure 1, and the thermogravimetric curve is as shown in the curve a in Figure 2.

Example 2

Change the reaction time of the first stage of Example 1 to 2h, and keep the other conditions unchanged, and the product P2 can be obtained. The infrared spectrum is as shown in the b curve in Figure 1, and the thermogravimetric curve is as shown in the b curve in Figure 2.

Example 3

Take 3.27g (0.038mol) of piperazine and dissolve it in 25ml CH ₂ Cl ₂ at 30°C, and add 10.34g (0.08mol) of acid-binding agent N,N-diisopropylethylamine at the same time, at a speed of 300r/min Stir in a three-neck flask until uniform, protect the system with N ₂ , and connect it to a tail gas absorption device. Take 4.87g (0.024mol) of phenylphosphonic dichloride and dissolve it in 20ml of dichloromethane, place it in a constant pressure dropping funnel, add it dropwise to the piperazine solution at a rate of 1-2 drops/s, and react for 1 hour, a white precipitate appears produce. Then take 1.42g (0.0093mol) of POCl ₃ and dissolve it in 20ml of dichloromethane, put it in a constant pressure dropping funnel, drop the above solution, control the temperature at 30°C and continue the reaction for 1h, add 0.09g (0.0004mol) of coupling agent KH550 to continue React for 3 hours, filter with suction and fully wash with methanol to obtain a viscous substance, dry the product in a 70°C blast oven for 2 hours, then transfer to a vacuum oven for 3 hours at 70°C, dry and grind to obtain a light yellow powder.

This product is named as P3, the infrared spectrum is as shown in the c curve in Figure 1, and the thermogravimetric curve is as shown in the c curve in Figure 2.

Example 4

Change the reaction time of the first stage of Example 3 to 2h, and keep the rest of the conditions unchanged to obtain the product P4. The infrared spectrum is as shown in the d curve in Figure 1, and the thermogravimetric curve is as shown in the d curve in Figure 2.

Example 5

Take 3.27g (0.03mol) of p-phenylenediamine and dissolve it in 50ml of NMP at 30°C, add 6.49g (0.06mol) of acid-binding agent triethylamine at the same time, stir in a three-necked flask at a speed of 200r/min until uniform, The system is protected by N ₂ and connected to the tail gas absorption device. Take 5.27g (0.025mol) of phenyl dichlorophosphate and dissolve it in 40ml of NMP, put it in a constant pressure dropping funnel, and drop it into the p-phenylenediamine solution at a rate of 1-2 drops/s to react for 1 hour. Then take 0.48g (0.0035mol) of _PCl3 and dissolve it in 20ml of NMP, place it in a constant pressure dropping funnel and add the above solution dropwise, control the temperature at 50°C to continue the reaction for 3h, add 0.12g (0.0005mol) of coupling agent KH580 to continue the reaction 3h, filter with suction and fully wash with methanol, dry the product in a blast oven at 70°C for 2h, then transfer to a vacuum oven for 3h at 70°C, dry and grind to obtain the product.

Example 6

Take 3.00g (0.05mol) of ethylenediamine and dissolve it in 40ml of chloroform at 30°C, add 7.9g (0.10mol) of acid-binding agent pyridine at the same time, stir in a three-necked flask at a speed of 200r/min until uniform, and the system flows through N ₂ Protection, connected to the exhaust gas absorbing device. Take 9.49g (0.045mol) of phenyl dichlorophosphate and dissolve it in 50ml of dichloromethane, put it in a constant pressure dropping funnel, and drop it into the piperazine solution at a rate of 1-2 drops/s to react for 0.5h. Then take POCl ₃ 0.53g (0.0035mol) and dissolve it in 20ml of dichloromethane, put it in a constant pressure dropping funnel, drop the above solution, control the temperature at 40°C and continue the reaction for 3h, add coupling agent KH590 0.08g (0.0004mol) to continue React for 5 hours, filter with suction and fully wash with ethanol, dry the product in a blast oven at 70°C for 1 hour, then transfer to a vacuum oven for 4 hours at 70°C, dry and grind to obtain the product.

Example 7

Take 3.44g (0.04mol) of piperazine and dissolve it in 30ml CH ₂ Cl ₂ at 30°C, add 8.09g (0.08mol) of acid-binding agent triethylamine at the same time, stir in a three-necked flask at a speed of 300r/min until uniform , the system is protected by N ₂ and connected to the tail gas absorption device. Take 5.73g (0.032mol) of phenylphosphorus dichloride, dissolve it in 60ml of dichloromethane and place it in a constant pressure dropping funnel, drop it into the piperazine solution at a rate of 1-2 drops/s to react for 1 hour, and a white Precipitation occurs. Then 0.86g (0.0056mol) of POCl ₃ was dissolved in 20ml of dichloromethane and placed in a constant pressure dropping funnel to drop the above solution, the temperature was controlled at 40°C to continue the reaction for 1h, and the coupling agent ND-42 0.1g (0.0005 mol) continued to react for 5 hours, filtered with suction and fully washed with ethanol, dried the product in a blast oven at 60°C for 1 hour, then transferred to a vacuum oven for 4 hours at 60°C, dried and ground to obtain the product.

Example 8

In Example 5, p-phenylenediamine was replaced by m-phenylenediamine, and the remaining conditions were unchanged to obtain the product.

Example 9

Take 3.44g (0.035mol) of 1,6-hexanediamine and dissolve it in 40ml of NMP at 70°C, add 8.09g (0.08mol) of acid-binding agent triethylamine at the same time, and stir in a three-necked flask at a speed of 300r/min To uniformity, the system is protected by _N2 , and connected to the tail gas absorption device. Take 5.85g (0.03mol) of phenylphosphonic dichloride and dissolve it in 60ml of NMP, place it in a constant pressure dropping funnel, add it dropwise to the 1,6-hexanediamine solution at a rate of 1-2 drops/s, and react for 1 hour. Then take POCl ₃ 0.54g (0.0035mol) and dissolve it in 20ml NMP and place it in a constant pressure dropping funnel to drop the above solution, control the temperature at 80°C to continue the reaction for 3h, add 0.18g (0.001mol) of coupling agent KH54 to continue the reaction After 2 hours, filter with suction and fully wash with ethanol, dry the product in a blast oven at 60°C for 1 hour, then transfer to a vacuum oven for 4 hours at 60°C, dry and grind to obtain the product.

Example 10

In Example 9, 1,6-hexanediamine was replaced with 1,4-butanediamine, and the other conditions remained unchanged to obtain the product.

Example 11

Take 4.00g (0.02mol) of 4,4-diaminodiphenyl ether and dissolve it in 60ml NMP at 70°C, add 3.16g (0.04mol) of acid-binding agent pyridine at the same time, and stir in a three-necked flask at a speed of 200r/min To uniformity, the system is protected by _N2 , and connected to the tail gas absorption device. Take 2.92g (0.015mol) of phenylphosphonic dichloride and dissolve it in 30ml NMP, place it in a constant pressure dropping funnel, and add it dropwise to the 4,4-diaminodiphenyl ether solution at a rate of 1-2 drops/s to react 1h, then take 0.48g (0.0035mol) of PCl ₃ and dissolve it in 20ml of NMP and place it in a constant pressure dropping funnel to drop the above solution, control the temperature at 80°C and continue the reaction for 3h, add 0.07g (0.0003mol) of coupling agent KH580 Continue to react for 2 hours, filter with suction and fully wash with ethanol, dry the product in a blast oven at 60°C for 1 hour, then transfer to a vacuum oven for 4 hours at 60°C, dry and grind to obtain the product.

Example 12

In Example 11, 4,4-diaminodiphenyl ether was replaced with 4,4-diaminodiphenylsulfone, the acid-binding agent was changed to triethylamine, and the rest of the conditions remained unchanged to obtain the product.

Example 13

In Example 11, 4,4-diaminodiphenyl ether was replaced with 4,4-diaminodiphenylmethane, and the other conditions remained unchanged to obtain the product.

Example 14

Take 2.58g (0.03mol) of piperazine and dissolve it in 20ml of dioxane at 30°C, add 6.07g (0.06mol) of acid-binding agent triethylamine at the same time, and stir in a three-necked flask at a speed of 200r/min until uniform , the system is protected by N ₂ and connected to the tail gas absorption device. Take 4.87g (0.025mol) of phenylphosphonic dichloride and dissolve it in 20ml of dioxane, put it in a constant pressure dropping funnel, and drop it into the piperazine solution at a rate of 1-2 drops/s to react for 1 hour, and a white Precipitation occurs. Control the temperature at 95°C, then take 0.64g (0.0035mol) of cyanuric chloride and dissolve it in 20ml of dioxane, put it in a constant pressure dropping funnel, drop the above solution, continue the reaction for 1h, and finally add 0.09g of coupling agent KH580 (0.0004mol) to continue the reaction for 2 hours, filter with suction and wash thoroughly with ethanol, place the product in a blast oven at 60°C for 1 hour, then transfer to a vacuum oven for 2 hours at 60°C, dry and grind to obtain the product.

Example 15

Take 3.10g (0.05mol) of ethylene glycol and dissolve it in 40ml of chloroform at 30°C, add 12.31g (0.15mol) of acid-binding agent N-methylimidazole at the same time, and stir in a three-necked flask at a speed of 200r/min until uniform , the system is protected by N ₂ and connected to the tail gas absorption device. Take 9.04g (0.045mol) of cyclohexylphosphonic dichloride and dissolve it in 40ml of dichloromethane, place it in a constant pressure dropping funnel, and drop it into the ethylene glycol solution at a rate of 1-2 drops/s to react for 1h. Then take 0.48g (0.0035mol) of PCl ₃ and dissolve it in 20ml of dichloromethane, put it in a constant pressure dropping funnel, drop the above solution, control the temperature at 60°C and continue the reaction for 1h, add 0.06g (0.0003mol) of coupling agent KH590 to continue React for 4 hours, filter with suction and fully wash with ethanol, dry the product in a 60°C blast oven for 1 hour, then transfer to a vacuum oven for 3 hours at 60°C, dry and grind to obtain the product.

Example 16

Take 3.03g (0.03mol) of hydroquinone and dissolve it in 50ml NMP at 90°C, add 8.69g (0.07mol) of acid-binding agent N-butylimidazole at the same time, and stir in a three-necked flask at a speed of 300r/min until Evenly, the system is protected by _N2 , and connected to the exhaust gas absorption device. Dissolve 4.62g (0.025mol) of cyclohexyldichlorophosphine in 40ml NMP and place it in a constant pressure dropping funnel, drop it into the hydroquinone solution at a rate of 1-2 drops/s to react for 1h, then take _PCl3 0.46g (0.0034mol) was dissolved in 20ml NMP and placed in a constant pressure dropping funnel to drop the above solution, the temperature was controlled at 90°C and the reaction was continued for 2h, and 0.09g (0.0004mol) of coupling agent KH550 was added to continue the reaction for 2h, and suction filtered And fully washed with ethanol, the product was dried in a blast oven at 60°C for 2 hours, then transferred to a vacuum oven for 5 hours at 60°C, dried and ground to obtain the product.

Example 17

Take 4.65g (0.04mol) of 1,4-cyclohexanediol and dissolve it in 60ml NMP at 90°C, add 7.12g (0.09mol) of acid-binding agent pyridine at the same time, and stir in a three-necked flask at a speed of 300r/min until Evenly, the system is protected by _N2 , and connected to the exhaust gas absorption device. Take 3.99g (0.03mol) of methylphosphinephthalein dichloride and dissolve it in 30ml of dioxane, place it in a constant pressure dropping funnel, and add it dropwise to the 1,4-cyclohexanediol solution at a rate of 1-2 drops/s React for 0.5h in the middle, then take 0.96g (0.007mol) of PCl ₃ and dissolve it in 40ml of dioxane and put it into the constant pressure dropping funnel to drop the above solution, control the temperature at 95°C and continue the reaction for 2h, add the coupling agent KH590 0.1g (0.0005mol) continued to react for 4h, suction filtered and fully washed with ethanol, the product was dried in a blast oven at 70°C for 2h, then transferred to a vacuum oven at 60°C for 6h, dried and ground to obtain the product.

Example 18

Take 4.51g (0.05mol) of 1,4-butanediol and dissolve it in 50ml NMP at 0°C, add 23.8g (0.3mol) of acid-binding agent pyridine at the same time, and stir in a three-necked flask at a speed of 200r/min until uniform , the system is protected by N ₂ and connected to the tail gas absorption device. Take 8.58g (0.044mol) of phenylphosphonic dichloride and dissolve it in 50ml of NMP, put it in a constant pressure dropping funnel, drop it into 1,4-butanediol solution at a rate of 1-2 drops/s and react for 0.5h, Then take 0.55g (0.004mol) of PCl ₃ and dissolve it in 30ml of NMP, place it in a constant pressure dropping funnel, drop the above solution in, control the temperature at 200°C and continue the reaction for 2 hours, add 0.012g (0.00006mol) of coupling agent KH590 and continue the reaction for 4 hours , filtered with suction and fully washed with ethanol. The product was dried in a blast oven at 70°C for 2 hours, then transferred to a vacuum oven for 5 hours at 70°C, dried and ground to obtain the product.

Example 19

Take 6.85g (0.03mol) of bisphenol A and dissolve it in 80ml NMP at 30°C, add 6.33g (0.08mol) of acid-binding agent pyridine at the same time, stir in a three-necked flask at a speed of 250r/min until uniform, and the system passes through N ₂ protection, and connected to the exhaust gas absorption device. Take 4.87g (0.025mol) of phenylphosphonic dichloride and dissolve it in 40ml of dioxane, put it in a constant pressure dropping funnel, and drop it into the bisphenol A solution at a rate of 1-2 drops/s to react for 0.5h. Then take 0.48g (0.0035mol) of PCl ₃ and dissolve it in 20ml of dioxane and place it in a constant pressure dropping funnel and drop the above solution in. The temperature is controlled at 90°C to continue the reaction for 2h, and then add 0.13g (0.0006mol) of coupling agent KH5500. ) continue to react for 5 hours, filter with suction and fully wash with ethanol, place the product in a blast oven at 60°C for 2 hours, then transfer it to a vacuum oven for 4 hours at 60°C, dry and grind to obtain the product.

Example 20

All the other dihydroxy compounds react with embodiment 16,17.

The above embodiments do not limit the present invention, and the present invention is not limited to the above embodiments, as long as the requirements of the present invention are met, they all belong to the protection scope of the present invention.

Claims (10)

1. a kind of phosphorous network structure fire retardant, it is characterised in that be prepared from using following methods：

The linear performed polymer AB with certain degree of polymerization is prepared using phosphorus-containing compound A and compound B reactions, it is anti-by regulation Condition is answered to control the degree of polymerization；Then using the linked of trifunctional as crosslinked group, the macromolecular with network structure is formed Fire retardant；It is finally introducing the silane coupler with specific function group to be blocked, adjusts its surface property；

Described phosphorus-containing compound A is binary phosphoryl chloride phosphorus oxychloride, either dichlorophosphate or phosphatization chlorine；

Described compound B is diamine, dihydroxylic alcohols or dihydric phenol；

The linked of described trifunctional is POCl₃、PCl₃Or Cyanuric Chloride.

2. a kind of phosphorous network structure fire retardant as claimed in claim 1, it is characterised in that prepared using method in detail below Form：

Step (1), compound B is placed in solvent L1 is dissolved at 0~200 DEG C, be subsequently adding acid binding agent F, stirred in there-necked flask Uniformly, B solution is obtained, leads to N₂Protection, and connect device for absorbing tail gas；Phosphorus-containing compound A is dissolved in solvent L2, constant pressure is placed in In dropping funel, it is added dropwise in B solution with the speed of 1~2 drop/s, reacts 0.5~10h, obtains linear performed polymer AB；

The mol ratio of described compound B and acid binding agent F is 1:2~1:6；

The mol ratio of described compound B and phosphorus-containing compound A is 1.01:1~1.6:1；

Described phosphorus-containing compound A is binary phosphoryl chloride phosphorus oxychloride, either dichlorophosphate or phosphatization chlorine；

Described compound B is diamine, dihydroxylic alcohols or dihydric phenol；

Step (2), the linked for taking trifunctional are dissolved in solvent L2, and instill above-mentioned linear performed polymer with the speed of 1~2 drop/s In AB solution, 30~200 DEG C of 0.5~10h of reaction are maintained the temperature at, obtain the macromolecular fire retardant with network structure；

The mole of the linked of described trifunctional is

The linked of described trifunctional is POCl₃、PCl₃Or Cyanuric Chloride；

Step (3), addition coupling agent C are blocked to above-mentioned macromolecular fire retardant, continue to react 0.5~5h, and suction filtration is washed with alcohol Repeatedly, product is obtained after drying；

The mole of described coupling agent C is 0.01 (B-A)~0.2 (B-A).

3. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that binary in the compound B The formula of amine is NH₂-R1-NH₂Or NH-R1-NH, dihydroxylic alcohols, the formula of dihydric phenol are HO-R1-OH；Wherein R1 is to contain 1~30 Aryl with alkyl between the alkyl with phenyl ring, multiple phenyl ring on the straight chained alkyl of individual carbon atom, cycloalkyl, aryl, straight chain, Cycloalkylaryl or cycloalkyl aryl, or be the straight chained alkyl containing S, O, N, Si or P atom, cycloalkyl, aryl, straight chain Aryl with alkyl, cycloalkylaryl or cycloalkyl aryl between the upper alkyl with phenyl ring, multiple phenyl ring.

4. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that binary in the compound B Amine is p-phenylenediamine, m-phenylene diamine (MPD), ethylenediamine, 1,6- hexamethylene diamines, Putriscine, 4,4- diaminodiphenyl ethers, 4,4- diaminos One or more in base diphenyl sulphone (DPS), 4,4- MDAs, piperazine.

5. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that binary in the compound B Alcohol, dihydric phenol are ethylene glycol, 1,3- propane diols, 1,4- butanediols, triethylene glycol, 1,5- pentanediols, 1,6-HD, 1,4- hexamethylenes Glycol, 1,3- cyclohexanediols, hydroquinones, resorcinol, catechol, bisphenol-A, 2,7 dihydroxy naphthalene, methylnaphthohydroquinone, 4, 4 '-dihydroxy diphenyl ether or 4,4 '-dihydroxydiphenylsulisomer.

6. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that the phosphorus-containing compound A's Formula is R2-POCl₂、R2-OPOCl₂Phosphonyl dichloride or R1-PCl₂A substitution phosphorus dichloride；Wherein R1, R2 are each independent It is containing being carried between the alkyl with phenyl ring, multiple phenyl ring on 1~30 straight chained alkyl of carbon atom, cycloalkyl, aryl, straight chain The aryl of alkyl, cycloalkylaryl or cycloalkyl aryl, or be the straight chained alkyl containing S, O, N, Si or P atom, cycloalkanes Aryl, cycloalkylaryl or the aryl cycloalkanes of alkyl are carried on base, aryl, straight chain between the alkyl with phenyl ring, multiple phenyl ring Base.

7. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that the phosphorus-containing compound A is Phenyl phosphonyl chloride, dichloro-phenyl phosphate, phenyl dichloro phosphorus, hexamethylene dichloro phosphine, methylphosphine phthalein dichloro, 4- anisyl phosphonos One or more mixtures of dichloro, cyclohexyl phosphonyl dichloride.

8. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that the coupling agent C is 3- ammonia Propyl trimethoxy silicane (KH-540), 3- aminopropyl triethoxysilanes (KH-550), 3- mercaptopropyltriethoxysilanes (KH-580), 3- mercaptopropyl trimethoxysilanes (KH-590) or anilinomethyl triethoxysilane (ND-42).

9. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that the solvent L1 is Isosorbide-5-Nitrae-two The ring of oxygen six, toluene, paraxylene, tetrahydrofuran, acetone, dichloromethane, chloroform, ether, 1-METHYLPYRROLIDONE (NMP)；

The solvent L2 be acetonitrile, Isosorbide-5-Nitrae-dioxane, toluene, tetrahydrofuran, acetone, dichloromethane, normal heptane, n-hexane, Hexamethylene, NMP；

The acid binding agent F is N, one kind in N- diisopropylethylamine, triethylamine, pyridine, N- methylimidazoles, N- butyl imidazoles or Several mixtures.

10. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, can be used alone as expansion type flame retardant or work It is carbon forming agent and other fire retardant compound uses.