CN107474247A - A kind of preparation method of phosphorus nitrogen synergistic water soluble polymer fire retardant - Google Patents

Abstract

The invention belongs to the application field of functional polymer materials, and in particular relates to a preparation method of a phosphorus-nitrogen synergistic water-soluble polymer flame retardant. The method uses neopentyl glycol and phosphorus oxychloride as raw materials to prepare phosphorus-containing intermediates, and then activates them with potassium thiocyanate, and then reacts with macromolecular nitrogen-containing intermediates polyethyleneimine to obtain yellowish-brown powdery phosphorus-nitrogen co- Efficient polymer flame retardant. The flame retardant is soluble in water, and its molecular weight can be adjusted according to requirements. It has good compatibility with polymer materials and can improve the flame retardant performance of materials. The flame retardant can effectively solve the insoluble problem of ordinary phosphorus-nitrogen synergistic flame retardants, and can be effectively dispersed when used in the preparation of water-foamed polyurethane and other materials, and it is not easy to migrate and precipitate from the material, which overcomes the deterioration of the mechanical properties of the material The problem. The invention has the advantages of simple and convenient production process conditions, high product purity and convenient use.

Description

A kind of preparation method of phosphorus and nitrogen synergistic water-soluble polymer flame retardant

technical field

The invention relates to a preparation method of a phosphorus-nitrogen synergistic water-soluble polymer flame retardant. It belongs to the application field of functional polymer materials.

Background technique

With the application of polymer materials in various fields such as chemical industry, construction, aviation, automobiles, electrical appliances, etc., especially the increase in the application of foam materials with good thermal insulation, heat insulation, and sound insulation functions, the problem of its flammability has become a problem for people. The focus of the research. At present, polymer materials such as polyurethane and polyethylene are widely used, which contain a large number of flammable hydrocarbon segments and have a low limiting oxygen index. Especially after being prepared as a foam material, the specific surface area is increased, the density is small, and it has high air circulation. Not only is it extremely flammable, but it is also easy to produce a large amount of toxic smoke during the combustion process. Once a fire breaks out, it will be difficult to put out the fire, which will easily cause serious disasters and losses.

Improving the flame retardant properties of polymer materials is mainly achieved by adding flame retardants to the materials to form a composite system, or by reacting and directly introducing flame retardant groups into the polymer chains. Since reactive flame retardants are easy to change the mechanical and processing properties of materials, additive flame retardants are still the main ones at present. Elements with flame retardancy mainly include Al, N, P, Br, Cl, Si, etc. Among them, flame retardants containing Al are mostly inorganic types, and flame retardants containing other flame retardant elements are mainly organic types. my country is currently the world's largest consumer market for flame retardants, with an annual consumption of more than 300,000 tons, and brominated flame retardants are the most used. Although brominated flame retardants have high flame retardant efficiency, their disadvantages in terms of environmental protection and safety are increasingly apparent. Because most of its flame retardant mechanism is gas phase flame retardant, it will produce a lot of smoke, corrosive gas and toxic gas when it exerts its flame retardant effect. Hydrogen gas and dioxins (polybrominated dibenzodioxins and polybrominated dibenzofurans), and most brominated flame retardants are not easy to decompose, easy to accumulate in the environment, and cause long-term harm to the environment and organisms. Therefore, flame retardants are gradually developing in the direction of environmental protection, low toxicity, high efficiency, and multi-function.

Phosphorus-based and nitrogen-based flame retardants are currently the representatives of low-smoke and low-toxicity flame retardants, and have good environmental performance. In particular, the intumescent flame retardant represented by the phosphorus and nitrogen synergistic type has a carbon source, an acid source and a gas source in one. It not only has good environmental protection performance, but also prevents combustion from different ways, and has excellent flame retardancy. efficiency. However, most of these flame retardants are inorganic and organic small molecules. When used in the flame retardancy of polymer materials, they are prone to poor compatibility, which will lead to a decrease in the mechanical properties and thermal stability of the material, and leakage. issues such as sex. Therefore, the current flame retardants are also developing towards polymerization to solve the problems of poor compatibility between small molecule flame retardants and polymer materials, easy migration, and affecting the mechanical properties and mechanical strength of materials. On the other hand, polymer intumescent flame retardants are generally difficult to dissolve in solvents, and are prone to phase separation when added to polymer materials, resulting in uneven distribution of flame retardant properties. Therefore, the development of soluble, easy-to-add and use intumescent flame retardants is also a current research direction.

Therefore, it is planned to prepare a nitrogen-phosphorus synergistic polymer flame retardant with good flame retardant efficiency, good compatibility with polymer materials, and safety and environmental protection through the reaction of phosphorus-containing intermediates and polymer nitrogen-containing intermediates. , by controlling the structure of the flame retardant, it has a certain water solubility, which is convenient to use, and its molecular weight can be adjusted according to the demand, which is suitable for flame retardancy of various polymer materials.

Contents of the invention

The object of the present invention is to provide a method for preparing a phosphorus-nitrogen synergistic water-soluble polymer flame retardant.

The technical scheme of the present invention is as follows: first, neopentyl glycol and phosphorus oxychloride are used as raw materials, reflux reaction in solvent I at 85°C for 4 to 10 hours, rotary steaming and drying to obtain the white phosphorus-containing intermediate 5,5-di Methyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate followed by 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl Phosphate ester and potassium thiocyanate were reacted at reflux at 60°C for 4 to 10 hours in solvent II, and potassium chloride was removed by filtration to obtain 5,5-dimethyl-2-isothiocyanato-1,3,2-di Oxyphosphacaprolactoyl phosphate filtrate, and then add macromolecular nitrogen-containing intermediate polyethyleneimine to the filtrate, react for 4 to 12 hours, and the product is subjected to suction filtration, washing, and drying to obtain a yellow-brown powder, namely It is a phosphorus-nitrogen synergistic polymer flame retardant.

The invention relates to a preparation method of a phosphorus-nitrogen synergistic water-soluble polymer flame retardant. The flame retardant is soluble in water, the molecular weight can be adjusted according to requirements, and has good compatibility with polymers, which can improve the flame retardancy of materials. performance. The flame retardant can effectively solve the insoluble problem of ordinary phosphorus-nitrogen synergistic flame retardants, and can be effectively dispersed when used in the preparation of water-foamed polyurethane and other materials, and it is not easy to migrate and precipitate from the material, which overcomes the deterioration of the mechanical properties of the material The problem. The invention has the advantages of simple and convenient production process conditions, high product purity and convenient use.

Specifically, the processing steps and conditions of the method are as follows:

(1) First, neopentyl glycol (NPG) and phosphorus oxychloride (POCl ₃ ) were dissolved in solvent I, refluxed at 85°C for 4-10 hours, rotary evaporated and dried to obtain white phosphorus-containing intermediate 5, 5-Dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate;

(2) Dissolve the 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate obtained in step (1) in potassium thiocyanate (KSCN) In solvent II, reflux reaction at 60°C for 4 to 10 hours, and remove potassium chloride by filtration to obtain 5,5-dimethyl-2-isothiocyanato-1,3,2-dioxaphosphacaprolactoyl phosphate ester filtrate;

(3) Add macromolecular nitrogen-containing intermediate in the 5,5-dimethyl-2-isothiocyanate-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate obtained in step (2) Polyethyleneimine (PEI), after reacting for 4 to 12 hours, suction-filtered and dried to obtain a yellow-brown powdery phosphorus-nitrogen synergistic water-soluble polymer flame retardant;

The above chemical reaction formula is:

The structural formula of the obtained phosphorus-nitrogen synergistic water-soluble polymer flame retardant is:

In the formula, n is a positive integer greater than 0.

In the above preparation method, the molar ratio of neopentyl glycol to phosphorus oxychloride is 1:1 to 1:6, and the solvent I is any one of dichloromethane, acetone, 1,2-dichloroethane, and acetonitrile ; The molar ratio of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate and potassium thiocyanate is 1:1, solvent II is acetone, 1,2 -Any one of dichloroethane; the polyethyleneimine used is a branched chain type with a weight-average molecular weight of 600-60000Da; 5,5-dimethyl-2-isothiocyanato-1,3 , The molar ratio of 2-dioxaphosphacaprolactoyl phosphate to polyethyleneimine is 3:1-405:1, and the degree of substitution of amino groups on the surface of polyethyleneimine is 50%-90%.

detailed description

The following example will specifically illustrate the operation method of the present invention, but can not be used as the limitation of the present invention.

Example 1

(1) First, 10.4 g of neopentyl glycol and 9.3 mL of phosphorus oxychloride were dissolved in 1,2-dichloroethane, refluxed at 85° C. for 10 hours, rotary evaporated, and dried to obtain white phosphorus-containing intermediate 5, 5-Dimethyl-2-chloro-1,3,2-dioxaphosphocaprolactoyl phosphate;

(2) Afterwards, 18.5g of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate obtained in step (1) was dissolved in 9.7g of potassium thiocyanate In acetone solution, reflux at 60°C for 4 hours, remove potassium chloride by filtration, and obtain 5,5-dimethyl-2-isothiocyanato-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate ;

(3) 5,5-dimethyl-2-isothiocyanate-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate that step (2) obtains adds 10 g molecular weight again and is 600Da large Molecular nitrogen-containing intermediate polyethyleneimine, reacted for 6 hours, suction filtered, and dried to obtain a yellow-brown powdery phosphorus-nitrogen synergistic water-soluble polymer flame retardant, with a surface amino substitution degree of 90%.

Example 2

(1) First, dissolve 10.4g of neopentyl glycol and 18.6mL of phosphorus oxychloride in dichloromethane, reflux at 85°C for 8 hours, rotary steam and dry to obtain the white phosphorus-containing intermediate 5,5-dimethyl -2-Chloro-1,3,2-dioxaphosphacaprolactoyl phosphate;

(2) Afterwards, 18.5g of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate obtained in step (1) was dissolved in 9.7g of potassium thiocyanate In 1,2-dichloroethane solution, reflux at 60°C for 6 hours, remove potassium chloride by filtration, and obtain 5,5-dimethyl-2-isothiocyanato-1,3,2-phosphorus dioxide Heterocaprolactoyl phosphate filtrate;

(3) 5,5-dimethyl-2-isothiocyanate-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate that step (2) obtains adds 15g molecular weight again and is 1800Da macromolecule The nitrogen-containing intermediate, polyethyleneimine, was reacted for 10 hours, suction filtered, and dried to obtain a yellowish-brown powdery phosphorus-nitrogen synergistic water-soluble polymer flame retardant with a surface amino substitution degree of 75%.

Example 3

(1) First, dissolve 10.4g of neopentyl glycol and 37.2mL of phosphorus oxychloride in acetone, reflux at 85°C for 6 hours, rotary steam and dry to obtain the white phosphorus-containing intermediate 5,5-dimethyl-2 - Chloro-1,3,2-dioxaphosphacaprolactoyl phosphate;

(2) Afterwards, 18.5g of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate obtained in step (1) was dissolved in 9.7g of potassium thiocyanate In 1,2-dichloroethane solution, reflux at 60°C for 8 hours, remove potassium chloride by filtration, and obtain 5,5-dimethyl-2-isothiocyanato-1,3,2-phosphorus dioxide Heterocaprolactoyl phosphate filtrate;

(3) 5,5-dimethyl-2-isothiocyanate-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate that step (2) obtains adds 18g molecular weight again and is 25000Da macromolecule The nitrogen-containing intermediate, polyethyleneimine, was reacted for 12 hours, suction filtered, and dried to obtain a yellow-brown powdery phosphorus-nitrogen synergistic water-soluble polymer flame retardant with a surface amino substitution degree of 70%.

Example 4

(1) Firstly, 10.4g of neopentyl glycol and 55.8mL of phosphorus oxychloride were dissolved in 1,2-dichloroethane, refluxed at 85°C for 4 hours, rotary evaporated and dried to obtain white phosphorus-containing intermediate 5, 5-Dimethyl-2-chloro-1,3,2-dioxaphosphocaprolactoyl phosphate;

(2) Afterwards, 18.5g of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate obtained in step (1) was dissolved in 9.7g of potassium thiocyanate In acetone solution, reflux at 60°C for 10 hours, remove potassium chloride by filtration, and obtain 5,5-dimethyl-2-isothiocyanato-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate ;

(3) Add 26.5 g of 26.5 g of 60,000 Da in the 5,5-dimethyl-2-isothiocyano-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate obtained in step (2). Molecular nitrogen-containing intermediate polyethyleneimine, reacted for 8 hours, suction filtered, and dried to obtain a yellow-brown powdery phosphorus-nitrogen synergistic water-soluble polymer flame retardant, with a surface amino substitution degree of 50%.

Example 5

(1) First, dissolve 10.4g of neopentyl glycol and 37.2mL of phosphorus oxychloride in acetonitrile, reflux at 85°C for 4 hours, rotary steam and dry to obtain the white phosphorus-containing intermediate 5,5-dimethyl-2 - Chloro-1,3,2-dioxaphosphacaprolactoyl phosphate;

(2) Afterwards, 18.5g of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate obtained in step (1) was dissolved in 9.7g of potassium thiocyanate In 1,2-dichloroethane solution, reflux at 60°C for 8 hours, remove potassium chloride by filtration, and obtain 5,5-dimethyl-2-isothiocyanato-1,3,2-phosphorus dioxide Heterocaprolactoyl phosphate filtrate;

(3) 5,5-dimethyl-2-isothiocyanate-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate that step (2) obtains adds 18g molecular weight again and is 600Da macromolecule The nitrogen-containing intermediate polyethyleneimine was reacted for 4 hours, filtered and dried to obtain a yellowish-brown powdery phosphorus-nitrogen synergistic water-soluble polymer flame retardant with a surface amino substitution degree of 50%.

Example 6

(1) First, dissolve 10.4g of neopentyl glycol and 55.8mL of phosphorus oxychloride in dichloromethane, reflux at 85°C for 10 hours, rotary evaporate and dry to obtain the white phosphorus-containing intermediate 5,5-dimethyl -2-Chloro-1,3,2-dioxaphosphacaprolactoyl phosphate;

(2) Afterwards, 18.5g of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphacaprolactoyl phosphate obtained in step (1) was dissolved in 9.7g of potassium thiocyanate In acetone solution, reflux at 60°C for 8 hours, remove potassium chloride by filtration, and obtain 5,5-dimethyl-2-isothiocyanato-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate ;

(3) 5,5-dimethyl-2-isothiocyanate-1,3,2-dioxaphosphacaprolactoyl phosphate filtrate that step (2) obtains adds 15g molecular weight again and is 60000Da macromolecule The nitrogen-containing intermediate polyethyleneimine was reacted for 12 hours, filtered and dried to obtain a yellowish-brown powdery phosphorus-nitrogen synergistic water-soluble polymer flame retardant with a surface amino substitution degree of 90%.

Example 7

The water-soluble flame retardant prepared in Examples 1-6 of the present invention is dissolved in water, mixed with polyether, and then reacted with isocyanate to prepare foamed polyurethane. The addition amount is 8 wt%, and the limit of the material is determined according to the ASTM D2863-10 standard Oxygen index (LOI), ASTM D3801-10 standard to measure UL-94 vertical combustion performance, the results are shown in Table 1.

Table 1 Flame retardant performance test results of flame retardant foamed polyurethane

Claims (5)

1. a kind of preparation method of phosphorus nitrogen synergistic water soluble polymer fire retardant, the processing step and condition of this method are as follows：

(1) first by neopentyl glycol (NPG) and POCl3 (POCl₃) be dissolved in solvent I, it is small in 85 DEG C of back flow reactions 4~10 When, revolving, drying obtain the phosphorous intermediate 5 of white, the dioxy phosphas of 5- dimethyl -2- chloro- 1,3,2- acyl phosphate in oneself；

(2) after by the chloro- 1,3,2- dioxies phosphas of 5,5- dimethyl -2- obtained in step (1) in oneself acyl phosphate be dissolved in and containing In the solvent II of potassium rhodanide (KSCN), in 60 DEG C of back flow reactions 4~10 hours, be filtered to remove potassium chloride, obtain 5,5- dimethyl- 2- isothiocyano -1,3,2- dioxies phospha acyl phosphate filtrate in oneself；

(3) the 5,5- dimethyl -2- isothiocyano -1,3,2- dioxies phospha obtained again in step (2) acyl phosphate filtrate in oneself It is middle addition the nitrogenous intermediate polyethyleneimine (PEI) of macromolecular, reaction 4~12 hours after, filter, dry yellowish-brown is powdered Phosphorus nitrogen synergistic water soluble polymer fire retardant；

Above-mentioned chemical equation is：

(1)

(2)

The structural formula of gained phosphorus nitrogen synergistic water soluble polymer fire retardant is：

N is the positive integer more than 0 in formula.

2. preparation method according to claim 1, it is characterised in that neopentyl glycol is 1 with POCl3 molar ratio:1 ~1:6, solvent I are any of dichloromethane, acetone, 1,2- dichloroethanes, acetonitrile.

3. preparation method according to claim 1, it is characterised in that the dioxy phosphas of 5,5- dimethyl -2- chloro- 1,3,2- oneself The molar ratio of interior acyl phosphate and potassium rhodanide is 1:1, solvent II is any of acetone, 1,2- dichloroethanes.

4. preparation method according to claim 1, it is characterised in that used polyethyleneimine is branched chain type, and its is heavy Molecular weight is 600~60000Da.

5. preparation method according to claim 1, it is characterised in that 5,5- dimethyl -2- isothiocyanos -1,3,2- dioxies Oneself molar ratio of interior acyl phosphate and polyethyleneimine of phospha is 3:1~405:1, the substitution of polyethyleneimine surface amino groups Spend for 50%~90%.