CN110590849B - Phosphorus-nitrogen-containing DOPO derivative flame retardant and preparation method and application thereof - Google Patents

Phosphorus-nitrogen-containing DOPO derivative flame retardant and preparation method and application thereof Download PDF

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CN110590849B
CN110590849B CN201910949224.XA CN201910949224A CN110590849B CN 110590849 B CN110590849 B CN 110590849B CN 201910949224 A CN201910949224 A CN 201910949224A CN 110590849 B CN110590849 B CN 110590849B
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马超
马世聪
周峰
胡伟兆
汪碧波
宋磊
胡源
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University of Science and Technology of China USTC
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Abstract

The invention discloses a phosphorus and nitrogen containing DOPO derivative flame retardant, a preparation method and application thereof, wherein the general structural formula of the phosphorus and nitrogen containing DOPO derivative flame retardant is as follows:
Figure DDA0002225021920000011
wherein R is1、R2、R3Each independently selected from hydrogen, methyl, ethyl, propyl, butyl,
Figure DDA0002225021920000012
Figure DDA0002225021920000013
R4Selected from ethyl, propyl, butyl. The molecular structure of the flame retardant synthesized by the invention contains a ring structure with higher rigidity, the thermal stability is better, and the flame retardant contains phosphorus and nitrogen, and the flame retardant and the phosphorus and the nitrogen jointly play a flame retardant role, so that the flame retardant has better flame retardant effect.

Description

Phosphorus-nitrogen-containing DOPO derivative flame retardant and preparation method and application thereof
Technical Field
The invention belongs to the technical field of flame retardant preparation, and particularly relates to a phosphorus-nitrogen-containing DOPO derivative flame retardant, and a preparation method and application thereof.
Background
The polyurethane flexible foam is widely applied to cushions of vehicles, furniture and the like, interior decoration materials and the like, and the materials used in the occasions have higher flame retardant requirements. However, in practice, conventional polyurethane flexible foams are flammable and difficult to extinguish in time once ignited. How to improve the flame retardancy of polyurethane flexible foams has been a major research topic in this field. Currently used flame retardants for polyurethane foams can be divided into two broad categories: the additive flame retardant mainly comprises triethyl phosphate, dimethyl methyl phosphate (DMMP), tris (2-chloroisopropyl) phosphate (TCPP), trichloroethyl phosphate (TCEP), melamine, expandable graphite, aluminum hydroxide and the like. And the other is a reactive flame retardant, which introduces flame retardant elements such as phosphorus, nitrogen, halogen and the like into polyol or isocyanate through chemical bonds, so that the polyurethane foam material has permanent flame retardance.
The nitrogen flame retardant has the characteristics of low toxicity, low environmental pollution, low corrosivity, high thermal decomposition temperature and the like, so that the nitrogen flame retardant is widely applied to the flame retardant field. The flame retardant mechanism is briefly described as follows: after the nitrogen flame retardant is decomposed by heating, non-combustible gases such as ammonia gas, nitrogen oxide and the like are easily released, and most heat can be taken away by the generation of the non-combustible gases and the decomposition and heat absorption of the flame retardant to reduce the surface temperature of the polymer. Meanwhile, the incombustible gas not only plays a role in diluting oxygen in the air and combustible gas generated by thermal decomposition of the high polymer, but also can react with the oxygen in the air to generate substances such as nitrogen, water and the like, so that the flame retardant effect is obtained. The commonly used nitrogen flame retardant mainly comprises melamine, dicyandiamide, guanidine salt and the like, but the nitrogen flame retardant needs to be added in a large amount when being added independently, so that the mechanical property of a substrate is greatly influenced. Therefore, the phosphorus-nitrogen flame retardant is commonly used together with a phosphorus flame retardant, and the flame retardant with excellent performance is prepared by utilizing the synergistic effect of phosphorus and nitrogen.
DOPO is a novel phosphorus-containing flame retardant discovered by scientists in recent years, and the molecular structure of DOPO and derivatives thereof containsThe biphenyl ring structure and the phenanthrene ring structure with larger performance, particularly the phosphorus-containing group on the side is grafted in a mode of a cyclic O ═ P-O bond, and the thermal stability and the chemical stability are higher than those of common micromolecule phosphonate or acyclic organic phosphonate. The flame retardant mechanism is briefly described as follows: when the DOPO-based flame retardant is burnt in the high polymer material, polyphosphoric acid, phosphorous acid and phosphoric acid can be formed to dehydrate the surface of the material to form a carbon layer, so that oxygen and heat generated by burning are prevented from being transferred to the interior of the material, and condensed phase flame retardance is realized; meanwhile, free radicals such as P & PO & generated during combustion can quench high-activity H & HO & free radicals in the flame, and chain reaction of combustion is interrupted, so that gas-phase flame retardance is realized. The P-H bond in DOPO is oxidized to become P-OH, and the P-OH bond can react with amino to generate P-O-·NH3 +-. By this reaction, DOPO-derived salts can be synthesized.
Disclosure of Invention
The invention aims to provide a phosphorus-nitrogen-containing DOPO derivative flame retardant, a preparation method and application thereof, raw materials for preparing the flame retardant are cheap and easy to obtain, most of the raw materials are low in toxicity or nontoxic, water (and alcohol) is used as a solvent in the reaction process, and no by-product is generated or pollutants are discharged, so that the phosphorus-nitrogen-containing DOPO derivative flame retardant has a good industrial application prospect. The molecular structure of the flame retardant synthesized by the invention contains a ring structure with higher rigidity, so that the flame retardant has better thermal stability, and simultaneously contains phosphorus and nitrogen, thereby having better flame retardant effect.
The flame retardant containing the phosphorus-nitrogen DOPO derivative has the structural general formula as follows:
Figure BDA0002225021900000021
wherein R is1、R2、R3Each independently selected from hydrogen, methyl, ethyl, propyl, butyl,
Figure BDA0002225021900000022
Figure BDA0002225021900000023
R4Selected from ethyl, propyl, butyl.
The preparation method of the phosphorus-nitrogen-containing DOPO derivative flame retardant comprises the following steps:
step 1: dropwise adding a hydrogen peroxide solution into DOPO, keeping the temperature at 60-80 ℃ after dropwise adding, reacting for 6-8 hours, filtering after the reaction is finished, and washing the product for 3-5 times by using acetone to obtain DOPO-OH;
step 2: dispersing DOPO-OH in a solvent, adding an amine-containing substance into the dispersion liquid in batches at room temperature after ultrasonic treatment, heating to 60-80 ℃ after the addition is finished, carrying out heat preservation reaction for 4-6 hours, evaporating the solution after the reaction is finished, washing the obtained pasty product with deionized water for 3-5 times, and drying to obtain the DOPO derivative containing phosphorus and nitrogen.
In step 1, H in the hydrogen peroxide solution2O2Molar ratio to phosphorus atom in DOPO 2: 1 to 5: 1.
in step 2, the solvent is selected from water or a mixed solution of water and alcohol. The alcohol is selected from one or more of methanol, ethanol, propanol, butanol, pentanol and the like, and the volume ratio of the water to the alcohol is 1: 1 to 5: 1.
in the step 2, the ultrasonic treatment time is 1-3 hours.
In step 2, the amine-containing substance is selected from one or more of ammonia (ammonia), methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, methylethylamine, dipropylamine, dibutylamine, ethylenediamine, methylethylenediamine, ethylethylenediamine, dimethylethylenediamine, diethylethylenediamine, propylenediamine, methylpropylenediamine, ethylpropylenediamine, dimethylpropylenediamine, diethylpropylenediamine, butylenediamine, methylbutylenediamine, ethylbutylenediamine, dimethylbutylenediamine, diethylbutylenediamine, urea, dicyanodiamine, melamine, and the like; the molar ratio of DOPO-OH to amine-containing species is 1: 1 to 1: 3.
the reaction process of the invention is as follows:
the first step is as follows: the P-H bond in DOPO is oxidized to a P-OH bond by hydrogen peroxide.
Figure BDA0002225021900000031
The second step is that: the P-OH in the oxidized DOPO reacts with the amino group.
Figure BDA0002225021900000032
Wherein R is1、R2、R3Each independently selected from hydrogen, methyl, ethyl, propyl, butyl,
Figure BDA0002225021900000033
Figure BDA0002225021900000034
R4Selected from ethyl, propyl, butyl.
The application of the phosphorus-nitrogen-containing DOPO derivative flame retardant is to replace or partially replace the conventional general flame retardant with the phosphorus-nitrogen-containing DOPO derivative for preparing the flame retardant polymer.
The polymers include polyurethane, polyethylene, polypropylene, and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. the adopted raw materials are cheap and easy to obtain, the reaction steps are simple, and the utilization rate of the raw materials is high. The reaction condition is mild, nontoxic solvent water (and alcohol) is adopted, and no by-product is generated and no pollutant is discharged in the reaction process, so that the method has good industrial application prospect.
2. The molecular structure of the flame retardant synthesized by the invention contains a ring structure with higher rigidity, the thermal stability is better, and the flame retardant contains phosphorus and nitrogen, and the flame retardant and the phosphorus and the nitrogen jointly play a flame retardant role, so that the flame retardant has better flame retardant effect.
Drawings
FIG. 1 shows nuclear magnetic spectra (H spectrum and P spectrum) of the objective product obtained in example 1.
FIG. 2 shows nuclear magnetic spectra (H spectrum and P spectrum) of the objective product obtained in example 3.
FIG. 3 shows nuclear magnetic spectra (H spectrum and P spectrum) of the objective product obtained in example 5.
Detailed Description
The following examples are provided to further illustrate the materials used in the present invention.
Example 1:
1. adding 108g DOPO into a three-neck flask connected with nitrogen and a reflux condenser pipe, then heating to 60 ℃, slowly dripping 100mL of 30% hydrogen peroxide solution into the three-neck flask, heating to 80 ℃ after finishing dripping within half an hour, continuing to react for 8 hours, then removing nitrogen, and washing a product with acetone for 3 times to obtain DOPO-OH.
2. Adding 23.2g DOPO-OH and 200mL (the volume ratio of water to ethanol is 1: 1) solution into a three-neck flask connected with nitrogen and a reflux condenser tube, adding 9.0g dicyanodiamide in batches in half an hour, reacting for half an hour at room temperature, heating to 60 ℃, keeping the temperature at 60 ℃ for reacting for 8 hours, then removing nitrogen, evaporating the solvent to dryness, wherein the structural formula of a target product is as follows:
Figure BDA0002225021900000041
example 2:
firstly, 20 parts by mass of the phosphorus-nitrogen-containing DOPO derivative in example 1, 100 parts by mass of polyether polyol 330, 1.0 part by mass of silicone oil, 0.18 part by mass of dibutyltin dilaurate, 0.25 part by mass of A33 and 3.0 parts by mass of water are uniformly mixed, 41 parts by mass of TDI is added, the mixture is stirred at a high speed and poured into a mold, and the mold is placed into an oven at 60 ℃ for curing for 24 hours after foaming, so that the flame-retardant polyurethane flexible foam is obtained. The test shows that the oxygen index of the flame-retardant polyurethane soft foam is 25.0 percent. 20 parts by mass of a conventional flame retardant dimethyl methylphosphonate (DMMP) is added, and the oxygen index of the flame-retardant polyurethane flexible foam is 22.0 percent. 10 parts of the DOPO derivative containing phosphorus and nitrogen in example 1 and 10 parts of DMMP were added, and the oxygen index of the flame-retardant polyurethane flexible foam was 24.0%.
Example 3:
1. synthesis of DOPO-OH the procedure of example 1 was followed.
2. Adding 23.2g DOPO-OH and 200mL (the volume ratio of water to ethanol is 1: 1) solution into a three-neck flask connected with nitrogen and a reflux condenser pipe, adding 6.5g carbamide (urea) in batches in half an hour, reacting for half an hour at room temperature, heating to 80 ℃, and preserving heat for reaction for 5 hours under the reflux state; then removing the nitrogen, evaporating the solvent to dryness, wherein the structural formula of the target product is as follows:
Figure BDA0002225021900000051
example 4:
firstly, 20 parts by mass of the phosphorus-nitrogen-containing DOPO derivative in example 3, 100 parts by mass of polyether polyol 330, 1.0 part by mass of silicone oil, 0.23 part by mass of dibutyltin dilaurate, 0.34 part by mass of A33 and 3.0 parts by mass of water are uniformly mixed, 41 parts by mass of TDI is added, the mixture is stirred at a high speed and poured into a mold, and the mold is placed into an oven at 60 ℃ for curing for 24 hours after foaming, so that the flame-retardant polyurethane flexible foam is obtained. The test shows that the oxygen index of the flame-retardant polyurethane soft foam is 24.5 percent. 10 parts of the DOPO derivative containing phosphorus and nitrogen in example 3 and 10 parts of DMMP were added, and the oxygen index of the flame-retardant polyurethane flexible foam was 23.5%.
Example 5:
1. synthesis of DOPO-OH the procedure of example 1 was followed.
2. Adding 23.2g DOPO-OH and 200mL (the volume ratio of water to ethanol is 1: 1) solution into a three-neck flask connected with nitrogen and a reflux condenser pipe, adding 13.0g melamine in batches in half an hour, reacting for half an hour at room temperature, heating to 80 ℃, and carrying out heat preservation reaction for 5 hours in a reflux state; then removing the nitrogen, evaporating the solvent to dryness, wherein the structural formula of the target product is as follows:
Figure BDA0002225021900000061
example 6:
firstly, 20 parts by mass of the phosphorus-nitrogen-containing DOPO derivative in example 5, 100 parts by mass of polyether polyol 330, 1.0 part by mass of silicone oil, 0.18 part by mass of dibutyltin dilaurate, 0.25 part by mass of A33 and 3.0 parts by mass of water are uniformly mixed, 41 parts by mass of TDI is added, the mixture is stirred at a high speed and poured into a mold, and the mold is placed into an oven at 60 ℃ for curing for 24 hours after foaming, so that the flame-retardant polyurethane flexible foam is obtained. The test shows that the oxygen index of the flame-retardant polyurethane soft foam is 24.0 percent. 10 parts of the DOPO derivative containing phosphorus and nitrogen in example 5 and 10 parts of DMMP were added, and the oxygen index of the flame-retardant polyurethane flexible foam was 23.0%.

Claims (3)

1. A phosphorus-nitrogen-containing DOPO derivative flame retardant is characterized in that the structural formula is as follows:
Figure FDA0003019260880000011
2. a method for preparing a flame retardant containing phosphorus-nitrogen DOPO derivative according to claim 1, characterized by comprising the steps of:
step 1: dropwise adding a hydrogen peroxide solution into DOPO, keeping the temperature at 60-80 ℃ after dropwise adding, reacting for 6-8 hours, filtering after the reaction is finished, and washing the product for 3-5 times by using acetone to obtain DOPO-OH;
step 2: dispersing 23.2g of DOPO-OH in a solvent, adding 9.0g of dicyanodiamine into the dispersion liquid in batches at room temperature after ultrasonic treatment, heating to 60 ℃ after the addition is finished, keeping the temperature and reacting for 8 hours, evaporating the solution after the reaction is finished, washing the obtained pasty product with deionized water for 3-5 times, and drying to obtain the DOPO derivative containing phosphorus and nitrogen;
in step 1, H in the hydrogen peroxide solution2O2Molar ratio to phosphorus atom in DOPO 2: 1 to 5: 1;
in the step 2, the solvent is water and ethanol according to a volume ratio of 1: 1, and (b) a mixed solution.
3. Use of a phosphorus-nitrogen-containing DOPO derivative flame retardant according to claim 1, wherein: the phosphorus-nitrogen-containing DOPO derivative is used for replacing or partially replacing conventional general flame retardant to prepare flame-retardant polymer; the polymer comprises a polyurethane soft foam.
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