CN101613374A - A kind of side group is polymeric phosphorus-containing flame retardant of DOPO and preparation method thereof - Google Patents
A kind of side group is polymeric phosphorus-containing flame retardant of DOPO and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of side group is 9, the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound and preparation method thereof, feature is with 9, the 10-dihydro-9-oxy is assorted-the aromatic base dihydric phenol of 10-phospho hetero phenanthrene-10-oxide modifying and pentaerythritol diphosphate two phosphoryl chlorides (or bromine) by the reaction mol ratio in the anhydrous acetonitrile solvent, under inert atmosphere, be heated to 80 ℃, stirring reaction to non-halogen hydrogen is emitted, be cooled to room temperature, removal of solvent under reduced pressure; Products therefrom phosphorus content height has and well expand into charcoal, good flame retardation effect; When fire retarding epoxide resin, its limiting oxygen index(LOI) has raising by a relatively large margin, and the vertical combustion grade has reached the V-0 level; Overcome existing small molecules phosphorus flame retardant heat decomposition temperature shortcoming low, poor, that easily move with the polymeric matrix consistency; The inventive method is simple, need not to use catalyzer, and last handling process is easy.
Description
Technical field
The invention belongs to the phosphonium flame retardant technical field, being specifically related to side group is 9, the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound (being called for short DOPO) and preparation method thereof.
Background technology
At present, be all respects that the goods of raw material have been widely used in life and have produced with polymkeric substance such as Resins, epoxy, unsaturated polyester and polymeric amide, but they are inflammable material mostly, easily lead to fire, and safety of life and property is caused very big threat.Therefore, polymer materials fire-retardant becomes a hot issue that needs to be resolved hurrily.Extensively adopt at present and in each base polymer, add fire retardant to improve its flame retardant properties.Advantages such as phosphorus flame retardant is efficient with it, low toxicity, environmental protection have obtained lot of domestic and foreign scholar's broad research.
The preparation method of a kind of phosphonium flame retardant that Chinese patent application publication number CN1910263A introduces, take organo phosphorous compounds DOPO and unsaturated acid or its acid anhydrides are reacted in alkylene glycol, but the prepared phosphonium flame retardant of this method is some small molecules P contained compounds, bad with the polymeric matrix consistency, there is the leaching problem.
The organic compound that contains many DOPO of Chinese patent application publication number CN1835960A report is to carry out addition reaction by DOPO with the alkynes class that has reactivity or ester group to form.This addition reaction must just can be carried out under the condition that catalyzer exists, and used catalyzer is some heavy metal salts, and toxicity is bigger.
The preparation method of a kind of polymer type phosphor-containing fire retardant that Chinese patent application publication number CN1563152A proposes, dichloro (bromine) the oxygen phosphorus that adopts the Resorcinol of DOPO modification or naphthalenediol, phenyl or naphthyl are replaced is response matrix, thereby obtains phosphorated polymer-type fire retardant.Catalyzer to be used in the preparation process of this fire retardant, a large amount of precipitation agents will be used in the sepn process, bigger to the pollution of environment.
Summary of the invention
The objective of the invention is to propose a kind of side group is 9, the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound and preparation method thereof, to overcome the above-mentioned defective of prior art.
Side group of the present invention is 9, the 10-dihydro-9-oxy is assorted-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 by the reaction mol ratio, under the protection of rare gas element, in the anhydrous acetonitrile solvent, be heated to 80 ℃, stirring reaction to non-halogen hydrogen is emitted, be 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 can be expressed as with chemical equation:
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:
Described rare gas element can be selected nitrogen, argon gas or helium for use.
Employed anhydrous acetonitrile is used after preferably heavily steaming before use again in the above-mentioned reaction.
Side group by method for preparing of the present invention 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, R be following structure (phenyl, naphthyl, 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound replace to diphenyl methyl) in one or more:
This fire retardant has following repeating unit:
Polymerization degree n=1～50 wherein, R is phenyl, naphthyl or substituted-phenyl.
Because the present invention takes 9, the 10-dihydro-9-oxy is assorted-and the aromatic base dihydric phenol of 10-phospho hetero phenanthrene-10-oxide modifying and pentaerythritol diphosphate two phosphoryl chlorides or pentaerythritol diphosphate two phosphoryl bromides carry out polyreaction, this preparation method is simple, need not to use catalyzer, last handling process is very easy.
The side group that adopts the inventive method to prepare is 9, the 10-dihydro-9-oxy is assorted-and the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound compares with existing small molecules phosphorus flame retardant, overcome low, poor with the polymeric matrix consistency, the easy shortcoming of migration of small molecules phosphorus flame retardant heat decomposition temperature; And its phosphorus content height has and well expand into charcoal, good flame retardation effect; When fire retarding epoxide resin, its limiting oxygen index(LOI) (LOI) has raising by a relatively large margin, and the vertical combustion grade has reached the V-0 level.
Embodiment
Further describing side group of the present invention by the following examples 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 and the mensuration of oxygen index, vertical combustion and thermogravimetric analysis thereof.
Embodiment 1:
Mechanical stirrer is being housed, is having in the 500ml there-necked flask of nitrogen inlet and prolong and add 29.7g (0.10mol) pentaerythritol diphosphate two phosphoryl chlorides, 150ml anhydrous acetonitrile and 32.4g (0.10mol) 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound-Resorcinol, be warming up to 80 ℃, do not emit to there being HCl gas in the following reaction that continues to stir, be cooled to room temperature, removal of solvent under reduced pressure obtains peach solid product.Productive rate reaches 95%, and fusing point is 220 ℃.
Products therefrom is carried out infrared analysis, 583-541cm in pentaerythritol diphosphate two phosphoryl chlorides
-1The characteristic peak of the P-Cl of place key disappears, and 929,1189cm
-1The P-O-Ph of place characteristic peak, 1442cm
-1The P-Ph characteristic peak occurs.Hence one can see that, and the present embodiment product is that side group is 9, and the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound.
The side group of getting above-mentioned preparation is 9, the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant 6.6 grams of 10-phospho hetero phenanthrene-10-oxide compound, Resins, epoxy (E-44) 40.0 grams, stir 30min at 120 ℃, add 20.0 gram low molecular polyamides (model: 651), be cast to after mixing in the mould of the long 10cm that makes by tetrafluoroethylene, wide 10mm, thick 3mm, then 60 ℃ of curing 1 hour, naturally cool to room temperature, the demoulding.
Solidified sample is surveyed its oxygen index with oxygen index instrument, and oxygen index is up to 30.5; Surveying its burning rank with the vertical combustion instrument is the V-0 level.Solidified sample is tested as can be known through thermogravimetric analyzer, the initial heat decomposition temperature of Resins, epoxy after fire-retardant reaches 291 ℃, and the maximum heat decomposition temperature is 350 ℃, residual massfraction 20.8% in the time of 700 ℃.
Embodiment 2:
Mechanical stirrer is being housed, is having in the 500ml there-necked flask of nitrogen inlet and prolong and add 29.7g (0.10mol) pentaerythritol diphosphate two phosphoryl chlorides, 150ml anhydrous acetonitrile and 39.8g (0.10mol) 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound-to naphthalenediol, be warming up to 80 ℃, under lasting the stirring, react and do not emit to there being HCl gas, be cooled to room temperature, removal of solvent under reduced pressure obtains peach solid product.Productive rate is 92%, and fusing point is 235 ℃.
Products therefrom is carried out infrared analysis, 583-541cm in pentaerythritol diphosphate two phosphoryl chlorides
-1The characteristic peak of the P-Cl of place key disappears, and 929,1189cm
-1The P-O-Ph of place characteristic peak, 1442cm
-1The P-Ph characteristic peak occurs.As can be known, the present embodiment product is that side group is 9, the 10-dihydro-9-oxy is assorted-and the polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound.
Getting the side group for preparing in the present embodiment is 9, the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant 6.6 grams of 10-phospho hetero phenanthrene-10-oxide compound, Resins, epoxy (E-44) 40.0 grams, under 120 ℃ of conditions, stir 30min, add then low molecular polyamides (model: 651) 20.0 grams, be cast to after mixing in the mould of the long 10cm that makes by tetrafluoroethylene, wide 10mm, thick 3mm, curing is 1 hour under 60 ℃ of conditions, naturally cool to room temperature, the demoulding.
Used for epoxy resin oxygen index instrument after fire-retardant is surveyed its oxygen index, and oxygen index reaches 32.5; Surveying its burning rank with the vertical combustion instrument is the V-0 level.
Embodiment 3:
Mechanical stirrer is being housed, is having in the 500ml there-necked flask of nitrogen inlet and prolong and add 29.7g (0.10mol) pentaerythritol diphosphate two phosphoryl chlorides, 150ml anhydrous acetonitrile and 39.8g (0.10mol) 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound-dihydroxyphenyl propane, be warming up to 80 ℃, under lasting the stirring, react and do not emit to there being HCl gas, be cooled to room temperature, removal of solvent under reduced pressure obtains red solid product.Productive rate is 85%, and fusing point is 240 ℃.
Products therefrom is carried out infrared analysis, 583-541cm in pentaerythritol diphosphate two phosphoryl chlorides
-1The characteristic peak of the P-Cl of place key disappears, and 929,1189cm
-1The P-O-Ph of place characteristic peak, 1442cm
-1The P-Ph characteristic peak occurs.Hence one can see that, and the present embodiment products therefrom is that side group is 9, and the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound.
Getting the side group that present embodiment makes is 9, the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant 6.6 grams of 10-phospho hetero phenanthrene-10-oxide compound, Resins, epoxy (E-44) 40.0 grams, under 120 ℃ of conditions, stir 30min, add then low molecular polyamides (model: 651) 20.0 grams, be cast to after mixing in the mould of the long 10cm that makes by tetrafluoroethylene, wide 10mm, thick 3mm, curing is 1 hour under 60 ℃ of conditions, naturally cool to room temperature, the demoulding.
Used for epoxy resin oxygen index instrument after fire-retardant is surveyed its oxygen index, and oxygen index is up to 35.0; Surveying its burning rank with the vertical combustion instrument is the V-0 level.
Embodiment 4:
Mechanical stirrer is being housed, is having in the 500ml there-necked flask of nitrogen inlet and prolong and add 38.6g (0.10mol) pentaerythritol diphosphate two phosphoryl bromides, 150ml anhydrous acetonitrile and 32.4g (0.10mol) 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound-Resorcinol, be warming up to 80 ℃, do not emit to there being HBr gas in the following reaction that continues to stir, be cooled to room temperature, removal of solvent under reduced pressure obtains peach solid product, and productive rate reaches 92%.
Products therefrom is carried out infrared analysis, 583-541cm in pentaerythritol diphosphate two phosphoryl bromides
-1The characteristic peak of the P-Br of place key disappears, and 929,1189cm
-1The P-O-Ph of place characteristic peak, 1442cm
-1The P-Ph characteristic peak occurs.Hence one can see that, and the present embodiment product is that side group is 9, and the 10-dihydro-9-oxy is assorted-polymeric phosphorus-containing flame retardant of 10-phospho hetero phenanthrene-10-oxide compound.
Claims (3)
1, a kind of side group is 9, the 10-dihydro-9-oxy is assorted-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 by the reaction mol ratio, under the protection of rare gas element, in the anhydrous acetonitrile solvent, be heated to 80 ℃, stirring reaction to non-halogen hydrogen is emitted, be 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 chemical equation:
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 described rare gas element is nitrogen, argon gas or helium.
3, the side group by the described 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, R be following structure (phenyl, naphthyl, 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound replace to diphenyl methyl) in one or more:
This fire retardant has following repeating unit:
Polymerization degree n=1～50 wherein, R is phenyl, naphthyl or substituted-phenyl.
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