CN107474247B - Preparation method of phosphorus-nitrogen synergistic water-soluble polymer flame retardant - Google Patents
Preparation method of phosphorus-nitrogen synergistic water-soluble polymer flame retardant Download PDFInfo
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Abstract
The invention belongs to the field of functional polymer material application, and particularly relates to a preparation method of a phosphorus-nitrogen synergistic water-soluble polymer flame retardant. The method comprises the steps of preparing a phosphorus-containing intermediate from neopentyl glycol and phosphorus oxychloride, activating the phosphorus-containing intermediate by using potassium thiocyanate, and reacting the phosphorus-containing intermediate with macromolecular nitrogen-containing polyethyleneimine to obtain a tawny powdery phosphorus-nitrogen synergistic macromolecular flame retardant. The flame retardant is soluble in water, the molecular weight can be adjusted according to requirements, the flame retardant has good compatibility with high polymer materials, and the flame retardant property of the materials can be improved. The flame retardant can effectively solve the problem that the common phosphorus-nitrogen synergistic flame retardant is insoluble in water, can be effectively dispersed when being applied to the preparation of materials such as water-blown polyurethane and the like, is not easy to migrate and separate out from the materials, and overcomes the problem of poor mechanical properties of the materials. The invention has simple and convenient production process conditions, high product purity and convenient use.
Description
Technical Field
The invention relates to a preparation method of a phosphorus-nitrogen synergistic water-soluble polymer flame retardant. Belongs to the field of functional polymer material application.
Background
With the application of polymer materials in various fields such as chemical industry, building, aviation, automobiles, electrical appliances and the like, especially the increase of the application amount of foam materials with good heat preservation, heat insulation and sound insulation functions, the problem of flammability becomes the key point of research. At present, high polymer materials such as polyurethane, polyethylene and the like are generally used, contain a large amount of combustible hydrocarbon chain segments, have low limiting oxygen index, and particularly after being prepared into foam materials, have the advantages of increased specific surface area, low density, higher air circulation, easy combustion and easy generation of a large amount of toxic smoke in the combustion process. Once a fire occurs, fire extinguishment is difficult, and serious disasters and losses are easily caused.
The flame retardant property of the high polymer material is improved by mainly adding a flame retardant into the material to form a composite system or directly introducing a flame retardant group into a high polymer chain through reaction and the like. Because the mechanical and processing properties of the material are easily changed by the reactive flame retardant, the additive flame retardant is still mainly used at present. The elements with flame retardance mainly comprise Al, N, P, Br, Cl, Si and the like, wherein the flame retardant containing Al is mostly inorganic type, and the flame retardant containing other flame retardant elements is mainly organic type. China is the largest fire retardant consuming market in the world at present, annual consumption exceeds 30 ten thousand tons, and the most used fire retardant is brominated fire retardant. Although the bromine-based flame retardant has high flame retardant efficiency, its drawbacks in terms of environmental protection and safety are increasingly manifested. Most of the bromine-based flame retardants are gas-phase flame retardant, so that a large amount of smoke, corrosive gas and toxic gas are generated when the flame retardant effect is exerted, part of the bromine-based flame retardants can release hydrogen halide gas and dioxin (polybrominated dibenzodioxin and polybrominated dibenzofuran) harmful to human bodies and the environment in the combustion process, and the bromine-based flame retardants are not easy to decompose and easy to accumulate in the environment and cause long-term harm to the environment and organisms. Therefore, the flame retardant is gradually developed in the direction of environmental protection, low toxicity, high efficiency, multi-functionalization, and the like.
Phosphorus flame retardants and nitrogen flame retardants are representative of low-smoke and low-toxicity flame retardants at present and have good environmental protection performance. Particularly, the intumescent flame retardant represented by a phosphorus and nitrogen synergistic type integrates a carbon source, an acid source and a gas source, has good environmental protection performance, can prevent combustion from different ways, and has excellent flame retardant efficiency. However, these flame retardants are mostly inorganic or organic small molecules, and when used for flame retarding of polymer materials, problems such as reduction in mechanical properties and thermal stability of the materials and bleeding tend to occur due to poor compatibility. Therefore, the existing flame retardant is also developed to be high in molecular weight so as to solve the problems that the small molecular flame retardant is poor in compatibility with a high molecular material, easy to migrate and influences the mechanical property and mechanical strength of the material. On the other hand, the high molecular intumescent flame retardant is generally difficult to dissolve in a solvent, and is easy to phase separate when added into a high molecular material, so that the flame retardant property distribution is uneven. Therefore, the development of soluble, easily added and used intumescent flame retardants is also the current direction of research.
Therefore, the nitrogen-phosphorus synergistic high-molecular flame retardant which has good flame-retardant efficiency, good compatibility with high-molecular materials and safety and environmental protection is prepared by the reaction of the phosphorus-containing intermediate and the high-molecular nitrogen-containing intermediate, has certain water solubility and convenient use by controlling the structure of the flame retardant, adjusts the molecular weight of the flame retardant according to the requirement, and is suitable for the flame retardance of various high-molecular materials.
Disclosure of Invention
The invention aims to provide a preparation method of a phosphorus-nitrogen synergistic water-soluble polymer flame retardant.
The technical scheme of the invention is as follows: firstly, neopentyl glycol and phosphorus oxychloride are taken as raw materials, reflux reaction is carried out for 4-10 hours in a solvent I at 85 ℃, performing rotary evaporation and drying to obtain a white phosphorus-containing intermediate 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane lactam phosphate, performing reflux reaction on the 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane lactam phosphate and potassium thiocyanate in a solvent II at the temperature of 60 ℃ for 4-10 hours, filtering to remove potassium chloride to obtain 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane phosphate filtrate, adding macromolecular nitrogenous intermediate polyethyleneimine into the filtrate, reacting for 4-12 hours, and performing suction filtration, washing and drying treatment on the product to obtain brown powder, namely the phosphorus-nitrogen synergistic macromolecular flame retardant.
The invention relates to a preparation method of a phosphorus-nitrogen synergistic water-soluble polymer flame retardant, which is soluble in water, has adjustable molecular weight according to requirements, has good compatibility with polymers, and can improve the flame retardant property of materials. The flame retardant can effectively solve the problem that the common phosphorus-nitrogen synergistic flame retardant is insoluble in water, can be effectively dispersed when being applied to the preparation of materials such as water-blown polyurethane and the like, is not easy to migrate and separate out from the materials, and overcomes the problem of poor mechanical properties of the materials. The invention has simple and convenient production process conditions, high product purity and convenient use.
Specifically, the process steps and conditions of the method are as follows:
(1) neopentyl glycol (NPG) and phosphorus oxychloride (POCl) are first reacted3) Dissolving in a solvent I, carrying out reflux reaction for 4-10 hours at 85 ℃, and carrying out rotary evaporation and dryingDrying to obtain a white phosphorus-containing intermediate 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane lactam phosphate;
(2) dissolving the 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane lactam phosphate obtained in the step (1) in a solvent II containing potassium thiocyanate (KSCN), performing reflux reaction for 4-10 hours at the temperature of 60 ℃, and filtering to remove potassium chloride to obtain 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane lactam phosphate filtrate;
(3) adding macromolecular nitrogenous intermediate Polyethyleneimine (PEI) into the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinanolide phosphate filtrate obtained in the step (2), reacting for 4-12 hours, performing suction filtration, and drying to obtain a tawny powdery phosphorus-nitrogen synergistic water-soluble macromolecular flame retardant;
the chemical reaction formula is as follows:
the structural formula of the obtained phosphorus-nitrogen synergistic water-soluble polymer flame retardant is as follows:
wherein n is a positive integer greater than 0.
In the preparation method, the feeding molar ratio of the neopentyl glycol to the phosphorus oxychloride is 1: 1-1: 6, and the solvent I is any one of dichloromethane, acetone, 1, 2-dichloroethane and acetonitrile; the feeding molar ratio of the 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane phosphate to the potassium thiocyanate is 1:1, and the solvent II is any one of acetone and 1, 2-dichloroethane; the polyethyleneimine is branched, and the weight-average molecular weight of the polyethyleneimine is 600-60000 Da; the feeding molar ratio of the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane phosphate to the polyethyleneimine is 3: 1-405: 1, and the substitution degree of amino groups on the surface of the polyethyleneimine is 50% -90%.
Detailed Description
The following examples will illustrate the method of operation of the present invention in detail, but should not be construed as limiting the invention thereto.
Example 1
(1) Firstly, dissolving 10.4g of neopentyl glycol and 9.3mL of phosphorus oxychloride in 1, 2-dichloroethane, carrying out reflux reaction for 10 hours at 85 ℃, carrying out rotary evaporation and drying to obtain a white phosphorus-containing intermediate 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinanephthaloyl phosphate;
(2) then dissolving 18.5g of 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane lactam phosphate obtained in the step (1) in an acetone solution containing 9.7g of potassium thiocyanate, carrying out reflux reaction for 4 hours at the temperature of 60 ℃, filtering and removing potassium chloride to obtain 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane lactam phosphate filtrate;
(3) and (3) adding 10g of macromolecular nitrogenous intermediate polyethyleneimine with the molecular weight of 600Da into the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinanolide phosphate filtrate obtained in the step (2), reacting for 6 hours, performing suction filtration and drying to obtain a yellow brown powdery phosphorus-nitrogen synergistic water-soluble macromolecular flame retardant with the surface amino substitution degree of 90%.
Example 2
(1) Firstly, dissolving 10.4g of neopentyl glycol and 18.6mL of phosphorus oxychloride in dichloromethane, carrying out reflux reaction for 8 hours at 85 ℃, carrying out rotary evaporation and drying to obtain a white phosphorus-containing intermediate 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphocaprolactam phosphate;
(2) then 18.5g of 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane phosphate obtained in the step (1) is dissolved in 1, 2-dichloroethane solution containing 9.7g of potassium thiocyanate, reflux reaction is carried out for 6 hours at the temperature of 60 ℃, and potassium chloride is removed by filtration to obtain 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane phosphate filtrate;
(3) and (3) adding 15g of macromolecular nitrogenous intermediate polyethyleneimine with the molecular weight of 1800Da into the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinanolide phosphate filtrate obtained in the step (2), reacting for 10 hours, performing suction filtration and drying to obtain a yellow brown powdery phosphorus-nitrogen synergistic water-soluble macromolecular flame retardant with the surface amino substitution degree of 75%.
Example 3
(1) Firstly, dissolving 10.4g of neopentyl glycol and 37.2mL of phosphorus oxychloride in acetone, carrying out reflux reaction for 6 hours at 85 ℃, carrying out rotary evaporation and drying to obtain a white phosphorus-containing intermediate 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphocaprolacto phosphate;
(2) then 18.5g of 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane phosphate obtained in the step (1) is dissolved in 1, 2-dichloroethane solution containing 9.7g of potassium thiocyanate, reflux reaction is carried out for 8 hours at the temperature of 60 ℃, and potassium chloride is removed by filtration to obtain 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane phosphate filtrate;
(3) and (3) adding 18g of macromolecular nitrogenous intermediate polyethyleneimine with the molecular weight of 25000Da into the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinanolide phosphate filtrate obtained in the step (2), reacting for 12 hours, performing suction filtration and drying to obtain a yellow brown powdery phosphorus-nitrogen synergistic water-soluble macromolecular flame retardant with the surface amino substitution degree of 70%.
Example 4
(1) Firstly, dissolving 10.4g of neopentyl glycol and 55.8mL of phosphorus oxychloride in 1, 2-dichloroethane, carrying out reflux reaction for 4 hours at 85 ℃, carrying out rotary evaporation and drying to obtain a white phosphorus-containing intermediate 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinanephthaloyl phosphate;
(2) then dissolving 18.5g of 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane lactam phosphate obtained in the step (1) in an acetone solution containing 9.7g of potassium thiocyanate, carrying out reflux reaction for 10 hours at the temperature of 60 ℃, filtering and removing potassium chloride to obtain 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane lactam phosphate filtrate;
(3) and (3) adding 26.5g of macromolecular nitrogenous intermediate polyethyleneimine with the molecular weight of 60000Da into the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinanolide phosphate filtrate obtained in the step (2), reacting for 8 hours, performing suction filtration and drying to obtain a yellow brown powdery phosphorus-nitrogen synergistic water-soluble macromolecular flame retardant with the surface amino substitution degree of 50%.
Example 5
(1) Firstly, dissolving 10.4g of neopentyl glycol and 37.2mL of phosphorus oxychloride in acetonitrile, carrying out reflux reaction for 4 hours at 85 ℃, carrying out rotary evaporation and drying to obtain a white phosphorus-containing intermediate 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphocaprolacto phosphate;
(2) then 18.5g of 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane phosphate obtained in the step (1) is dissolved in 1, 2-dichloroethane solution containing 9.7g of potassium thiocyanate, reflux reaction is carried out for 8 hours at the temperature of 60 ℃, and potassium chloride is removed by filtration to obtain 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane phosphate filtrate;
(3) and (3) adding 18g of macromolecular nitrogenous intermediate polyethyleneimine with the molecular weight of 600Da into the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinanolide phosphate filtrate obtained in the step (2), reacting for 4 hours, performing suction filtration and drying to obtain a yellow brown powdery phosphorus-nitrogen synergistic water-soluble macromolecular flame retardant with the surface amino substitution degree of 50%.
Example 6
(1) Firstly, dissolving 10.4g of neopentyl glycol and 55.8mL of phosphorus oxychloride in dichloromethane, carrying out reflux reaction for 10 hours at 85 ℃, carrying out rotary evaporation and drying to obtain a white phosphorus-containing intermediate 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphocaprolacto phosphate;
(2) then dissolving 18.5g of 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane lactam phosphate obtained in the step (1) in an acetone solution containing 9.7g of potassium thiocyanate, carrying out reflux reaction for 8 hours at the temperature of 60 ℃, filtering and removing potassium chloride to obtain 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane lactam phosphate filtrate;
(3) and (3) adding 15g of macromolecular nitrogenous intermediate polyethyleneimine with the molecular weight of 60000Da into the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinanolide phosphate filtrate obtained in the step (2), reacting for 12 hours, performing suction filtration and drying to obtain a yellow brown powdery phosphorus-nitrogen synergistic water-soluble macromolecular flame retardant, wherein the surface amino substitution degree is 90%.
Example 7
The water-soluble flame retardants obtained in examples 1 to 6 of the present invention were dissolved in water, mixed with polyether, and then reacted with isocyanate to prepare foamed polyurethane in an amount of 8 wt%, and the Limiting Oxygen Index (LOI) of the material was measured according to ASTM D2863-10, and the UL-94 vertical burning properties were measured according to ASTM D3801-10, and the results are shown in Table 1.
TABLE 1 flame retardancy test results of flame retardant foamed polyurethane
Claims (5)
1. A preparation method of a phosphorus-nitrogen synergistic water-soluble polymer flame retardant comprises the following process steps and conditions:
(1) neopentyl glycol (NPG) and phosphorus oxychloride (POCl) are first reacted3) Dissolving in a solvent I, carrying out reflux reaction for 4-10 hours at 85 ℃, carrying out rotary evaporation and drying to obtain a white phosphorus-containing intermediate 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinanyl phosphate;
(2) dissolving the 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane lactam phosphate obtained in the step (1) in a solvent II containing potassium thiocyanate (KSCN), performing reflux reaction for 4-10 hours at the temperature of 60 ℃, and filtering to remove potassium chloride to obtain 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane lactam phosphate filtrate;
(3) adding macromolecular nitrogenous intermediate Polyethyleneimine (PEI) into the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinanolide phosphate filtrate obtained in the step (2), reacting for 4-12 hours, performing suction filtration, and drying to obtain a tawny powdery phosphorus-nitrogen synergistic water-soluble macromolecular flame retardant;
the chemical reaction formula is as follows:
(1)
(2)
r is H or
The structural formula of the obtained phosphorus-nitrogen synergistic water-soluble polymer flame retardant is as follows:
r is H or
In the formula, n is a positive integer larger than 0, and R is 5, 5-dimethyl-1, 3, 2-dioxaphosphorinanyl phosphoryl-2-thioacyl, and the substitution degree is 50-90%.
2. The preparation method according to claim 1, wherein the feeding molar ratio of neopentyl glycol to phosphorus oxychloride is 1: 1-1: 6, and the solvent I is any one of dichloromethane, acetone, 1, 2-dichloroethane and acetonitrile.
3. The preparation method according to claim 1, wherein the feeding molar ratio of 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinanolide phosphate to potassium thiocyanate is 1:1, and the solvent II is any one of acetone and 1, 2-dichloroethane.
4. The process according to claim 1, wherein the polyethyleneimine is branched and has a weight-average molecular weight of 600 to 60000 Da.
5. The preparation method according to claim 1, wherein the feeding molar ratio of the 5, 5-dimethyl-2-isothiocyanato-1, 3, 2-dioxaphosphorinane phosphate to the polyethyleneimine is 3: 1-405: 1, and the substitution degree of amino groups on the surface of the polyethyleneimine is 50-90%.
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