CN101613374B - Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof - Google Patents

Abstract

The invention discloses a polymeric phosphorus-containing flame retardant whose side group is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a preparation method thereof, which is characterized in that 9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide modified aryl dihydric phenol and pentaerythritol diphosphate diphosphoryl chloride (or bromine) are in anhydrous acetonitrile solvent according to the reaction molar ratio, Heat to 80°C under an inert atmosphere, stir the reaction until no hydrogen halide gas is released, cool to room temperature, and remove the solvent under reduced pressure; the resulting product has high phosphorus content, good expansion into charcoal, and good flame retardant effect; When burning epoxy resin, its limiting oxygen index has been greatly improved, and the vertical combustion level has reached V-0 level; it overcomes the low thermal decomposition temperature of existing small molecule phosphorus flame retardants and poor compatibility with polymer matrix , the shortcoming of easy migration; the method of the present invention is simple and easy to implement, without using a catalyst, and the post-treatment process is simple and convenient.

Description

A polymeric phosphorus-containing flame retardant whose side group is DOPO and its preparation method

technical field

The invention belongs to the technical field of phosphorus-containing flame retardants, in particular to a polymeric phosphorus-containing flame retardant whose side group is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO for short) and its preparation method.

Background technique

At present, products made of polymers such as epoxy resins, unsaturated resins and polyamides have been widely used in various aspects of life and production, but most of them are flammable materials that are easy to cause fires and are harmful to life and property. pose a great threat. Therefore, the flame retardancy of polymer materials has become a hot issue to be solved urgently. At present, it is widely used to add flame retardants to various polymers to improve their flame retardant properties. Phosphorus-based flame retardants have been extensively studied by many scholars at home and abroad for their advantages of high efficiency, low toxicity, and environmental protection.

Chinese Patent Application Publication No. CN1910263A introduces a method for preparing a phosphorus-containing flame retardant, which adopts the reaction of an organic phosphorus compound DOPO with an unsaturated acid or its anhydride in an alkylene glycol, but the phosphorus-containing flame retardant prepared by this method The additives are some small molecular phosphorus-containing compounds, which have poor compatibility with the polymer matrix and have leaching problems.

The multi-DOPO-containing organic compound reported in Chinese Patent Application Publication No. CN1835960A is formed by the addition reaction of DOPO and alkynes with reactive or ester groups. This addition reaction can only be carried out in the presence of a catalyst, and the catalyst used is some heavy metal salts, which are more toxic.

Chinese Patent Application Publication No. CN1563152A proposes a method for preparing a polymer-type phosphorus-containing flame retardant, which uses DOPO-modified hydroquinone or hydronaphthalenediol, phenyl or naphthyl-substituted dichloro (bromo) oxygen Phosphorus is used as a reactive substrate to obtain a phosphorus-containing polymer flame retardant. A catalyst is used in the preparation process of the flame retardant, and a large amount of precipitant is used in the separation process, which causes great pollution to the environment.

Contents of the invention

The purpose of the present invention is to propose a side group of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide polymeric phosphorus-containing flame retardant and its preparation method, to overcome the existing The aforementioned shortcomings of the technology.

The preparation method of the polymeric phosphorus-containing flame retardant whose side group is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is characterized in that 9,10-dihydro -9-Oxa-10-phosphaphenanthrene-10-oxide modified aryl dihydric phenol, and pentaerythritol diphosphate diphosphoryl chloride or pentaerythritol diphosphate diphosphoryl bromide are added to the reactor according to the reaction molar ratio , under the protection of an inert gas, heated to 80 ° C in anhydrous acetonitrile solvent, stirred until no hydrogen halide gas was released, cooled to room temperature, and removed the solvent under reduced pressure. The obtained pink solid product is the side group 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide polymeric phosphorus-containing flame retardant;

The above process can be expressed as a chemical reaction formula:

Wherein the degree of polymerization n is an integer ranging from 1 to 50, X is a chlorine atom or a bromine atom, and R is one or more of the following structures:

The inert gas may be nitrogen, argon or helium.

The anhydrous acetonitrile used in the above reaction is preferably re-distilled before use.

The polymeric phosphorus-containing flame retardant prepared by the above method of the present invention is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which is characterized in that it has the following general structure Formula containing pentaerythritol diphosphate diphosphoryl chloride or pentaerythritol diphosphate diphosphoryl bromide (1) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide substituted aromatic binary Polymers with phenolic (2) structure:

Wherein, X is a chlorine atom or a bromine atom, and R is the following structure (phenyl, naphthyl, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide substituted p-diphenylmethane one or more of:

This flame retardant has the following repeating units:

Wherein the degree of polymerization n=1-50, R is phenyl, naphthyl or substituted phenyl.

Since the present invention adopts 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide modified aryl dihydric phenol and pentaerythritol diphosphate diphosphoryl chloride or pentaerythritol diphosphate diphosphorus Acyl bromide is polymerized, the preparation method is simple and easy, no catalyst is needed, and the post-treatment process is very simple.

The polymerization type phosphorus-containing flame retardant prepared by the method of the present invention is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the existing small molecule phosphorus flame retardant Compared with other additives, it overcomes the disadvantages of low thermal decomposition temperature, poor compatibility with polymer matrix, and easy migration of small molecule phosphorus-based flame retardants; and its high phosphorus content has good expansion into charcoal and flame retardant effects. Good; when flame-retardant epoxy resin is used, its limiting oxygen index (LOI) has been greatly improved, and the vertical combustion level has reached V-0 level.

Detailed ways

The preparation method of the polymeric phosphorus-containing flame retardant whose side group is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide of the present invention and its oxygen index will be further described in detail below through the examples , Determination of vertical combustion and thermogravimetric analysis.

Example 1:

Add 29.7g (0.10mol) of pentaerythritol diphosphate diphosphoryl chloride, 150ml of anhydrous acetonitrile and 32.4g (0.10mol) of 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide-hydroquinone, heat up to 80°C, react under continuous stirring until no HCl gas is released, cool to room temperature, remove the solvent under reduced pressure, and obtain pink Colored solid product. The yield is 95%, and the melting point is 220°C.

The resulting product was analyzed by infrared, and the characteristic peak of the P-Cl bond at 583-541cm ^-1 in pentaerythritol diphosphate diphosphoryl chloride disappeared, and the characteristic peak of PO-Ph at 929, 1189cm- ¹ , and the characteristic peak of P-Ph at 1442cm ^-1 Appear. It can be seen that the product of this example is a polymeric phosphorus-containing flame retardant with side groups of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Take 6.6 grams of the polymeric phosphorus-containing flame retardant whose side group is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide prepared above, and 40.0 grams of epoxy resin (E-44) , stirred at 120°C for 30min, then added 20.0g of low molecular weight polyamide (type: 651), mixed evenly and poured into a mold made of polytetrafluoroethylene with a length of 10cm, a width of 10mm, and a thickness of 3mm, and cured at 60°C 1 hour, naturally cooled to room temperature, and demolded.

The oxygen index of the cured sample is measured by an oxygen index meter, and the oxygen index is as high as 30.5; the combustion level is V-0 by a vertical combustion meter. The cured sample was tested by a thermogravimetric analyzer. It can be seen that the initial thermal decomposition temperature of the flame-retardant epoxy resin reached 291°C, the maximum thermal decomposition temperature was 350°C, and the residual mass fraction was 20.8% at 700°C.

Example 2:

Add 29.7g (0.10mol) of pentaerythritol diphosphate diphosphoryl chloride, 150ml of anhydrous acetonitrile and 39.8g (0.10mol) of 9,10-dihydro -9-Oxa-10-phosphaphenanthrene-10-oxide-p-naphthalenediol, heated to 80°C, reacted under continuous stirring until no HCl gas was released, cooled to room temperature, and removed the solvent under reduced pressure to obtain a pink solid product. The yield was 92%, and the melting point was 235°C.

The resulting product was analyzed by infrared, and the characteristic peak of the P-Cl bond at 583-541cm ^-1 in pentaerythritol diphosphate diphosphoryl chloride disappeared, and the characteristic peak of PO-Ph at 929, 1189cm- ¹ , and the characteristic peak of P-Ph at 1442cm ^-1 Appear. It can be seen that the product of this example is a polymeric phosphorus-containing flame retardant with side groups of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Take 6.6 grams of the polymeric phosphorus-containing flame retardant prepared in this example with side groups of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, epoxy resin (E-44 ) 40.0 g, stirred at 120°C for 30 min, then added 20.0 g of low molecular weight polyamide (model: 651), mixed evenly and cast into a mold made of polytetrafluoroethylene with a length of 10 cm, a width of 10 mm, and a thickness of 3 mm , cured at 60°C for 1 hour, cooled naturally to room temperature, and demolded.

The oxygen index of the flame-retardant epoxy resin is measured by an oxygen index instrument, and the oxygen index reaches 32.5; the combustion level is V-0 by a vertical combustion instrument.

Example 3:

Add 29.7g (0.10mol) of pentaerythritol diphosphate diphosphoryl chloride, 150ml of anhydrous acetonitrile and 39.8g (0.10mol) of 9,10-dihydro -9-Oxa-10-phosphaphenanthrene-10-oxide-bisphenol A, heated to 80°C, reacted under continuous stirring until no HCl gas was released, cooled to room temperature, and removed the solvent under reduced pressure to obtain a red solid product. The yield was 85%, and the melting point was 240°C.

The resulting product was analyzed by infrared, and the characteristic peak of the P-Cl bond at 583-541cm ^-1 in pentaerythritol diphosphate diphosphoryl chloride disappeared, and the characteristic peak of PO-Ph at 929, 1189cm- ¹ , and the characteristic peak of P-Ph at 1442cm ^-1 Appear. It can be seen that the product obtained in this example is a polymeric phosphorus-containing flame retardant with side groups of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Get 6.6 grams of the polymeric phosphorus-containing flame retardant whose side group is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, epoxy resin (E-44 ) 40.0 g, stirred at 120°C for 30 min, then added 20.0 g of low molecular weight polyamide (type: 651), mixed evenly and cast into a mold made of polytetrafluoroethylene with a length of 10 cm, a width of 10 mm, and a thickness of 3 mm , cured at 60°C for 1 hour, cooled naturally to room temperature, and demolded.

The oxygen index of the flame-retardant epoxy resin is measured by an oxygen index instrument, and the oxygen index is as high as 35.0; the combustion level is V-0 by a vertical combustion instrument.

Example 4:

Add 38.6g (0.10mol) of pentaerythritol diphosphate diphosphoryl bromide, 150ml of anhydrous acetonitrile and 32.4g (0.10mol) of 9,10-bis Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide-hydroquinone, heated to 80°C, reacted under continuous stirring until no HBr gas was released, cooled to room temperature, and removed the solvent under reduced pressure to obtain Pink solid product in 92% yield.

The resulting product was analyzed by infrared, and the characteristic peak of the P-Br bond at 583-541cm ^-1 in pentaerythritol diphosphate diphosphoryl bromide disappeared, and the characteristic peak of PO-Ph at 929, 1189cm ^-1 , and the characteristic peak of P-Ph at 1442cm ^-1 peak appears. It can be seen that the product of this example is a polymeric phosphorus-containing flame retardant with side groups of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Claims (3)

1. a side group is 9, the 10-dihydro-9-oxy is assorted-and the preparation method of the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound, it is characterized in that 9; The 10-dihydro-9-oxy is assorted-the aromatic base dihydric phenol of 10-phospho hetero phenanthrene-10-oxide modifying; With pentaerythritol diphosphate two phosphoryl chlorides or pentaerythritol diphosphate two phosphoryl bromides, add in the reactor drum, under the protection of rare gas element by the reaction mol ratio; In the anhydrous acetonitrile solvent, be heated to 80 ℃; Stirring reaction to non-halogen hydrogen is emitted, and is cooled to room temperature, removal of solvent under reduced pressure; It is 9 that resulting pink solid product is side group, the 10-dihydro-9-oxy is assorted-and the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound;

Said process is expressed as with reaction formula:

Wherein polymerization degree n is 1～50 integer, and X is chlorine atom or bromine atoms, and R is one or more in the following structure:

2. side group as claimed in claim 1 is 9, the 10-dihydro-9-oxy is assorted-and the preparation method of the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound, be characterised in that said rare gas element is nitrogen, argon gas or helium.

3. the side group by the said method preparation of claim 1 is 9; The 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound; Be characterised in that its be have a following general structure contain pentaerythritol diphosphate two phosphoryl chlorides or pentaerythritol diphosphate two phosphoryl bromides (1) and 9, the 10-dihydro-9-oxy is assorted-polymkeric substance of 10-phospho hetero phenanthrene-10-oxide compound substituted aromatic dihydric phenol (2) structure:

Wherein, X is chlorine atom or bromine atoms, and R is one or more in the following structure:

This fire retardant has following repeating unit:

Polymerization degree n=1～50 wherein.