CN103319533A - Environment-friendly preparation method of phosphorus flame retardant, namely 2-(diphenylphosphinoyl)-1, 4-benzenediol - Google Patents
Environment-friendly preparation method of phosphorus flame retardant, namely 2-(diphenylphosphinoyl)-1, 4-benzenediol Download PDFInfo
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- CN103319533A CN103319533A CN2013102707578A CN201310270757A CN103319533A CN 103319533 A CN103319533 A CN 103319533A CN 2013102707578 A CN2013102707578 A CN 2013102707578A CN 201310270757 A CN201310270757 A CN 201310270757A CN 103319533 A CN103319533 A CN 103319533A
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Abstract
The invention discloses an environment-friendly preparation method of a phosphorus flame retardant, namely 2-(diphenylphosphinoyl)-1, 4-benzenediol. Chlorodiphenylphosphine is taken as a reaction raw material, a one-pot method is adopted for skipping the purification process of the chlorodiphenylphosphine and further directly synthesizing the 2-(diphenylphosphinoyl)-1, 4-benzenediol, and a solvent and a purification solvent, which are used by the environment-friendly preparation method are alcohols, so that the environment-friendly preparation method has the advantages of low toxicity, high yield of above 90%, capability of greatly reducing production cost and effect of meeting environment-friendly and high-efficient requirements.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of phosphorus flame retardant preparation method of environment-friendly high-efficiency.
Background technology
9,10-dihydro-9-oxy-10-phospho hetero phenanthrene-10-oxide compound (DOPO) class reactive flame retardant is a kind of important fire retardant, can obtain the epoxy resin cured product of certain flame retardant rating with epoxy prepolymer generation curing reaction, (the Synthesis and properties of epoxy resins containing2-(6-oxid-6H-dibenz(c such as Wang, e) (1,2) oxaphosphorin-6-yl) 1,4-benzenediol[J], Polym, 1998,39 (23): 5819 – 5826.) with the curing of DOPO para benzoquinone addition reaction for bisphenol A type epoxy resin, when the phosphorus massfraction was 2.1%, epoxy resin cured product UL94 test reached the V-0 rank.But because the DOPO price is high, so high add-on has limited its practical application, and addition is large, can cause that also epoxy resin cured product resistance toheat and mechanical property descend.
And the novel reaction type fire retardant 2-(phenylbenzene phosphono)-1 that synthesizes take diphenyl phosphine oxide (DPO) as reaction raw materials that reported in recent years, the 4-dihydroxy-benzene has phosphorus content and the thermal stability higher than ODOPB, and production cost is lower, have the commercial value higher than ODOPB, probably substitute the efficient flame-retarding agent that ODOPB becomes Resins, epoxy.(Flame Retardant Epoxy Resins Based on Diglycidyl Ether of (2 such as M.Sponto etc., 5-Dihydroxyphenyl) diphenyl Phosphine Oxide[J], Polym, 2007,45:2142 – 2151.) prepared 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene (HPO) also is applied in the Resins, epoxy, and when phosphorus content reached 1%, limiting oxygen index(LOI) just can reach 31.But raw material diphenyl phosphine oxide preparation technology system is comparatively loaded down with trivial details, and the synthesis yield about HPO of reporting at present is not high, only has 80%, and solvent for use is aromatics, and toxicity is larger, and purifying technique is comparatively complicated in addition, causes product yield not high.
Summary of the invention
There to be the defective that toxicity is large, purifying technique is complicated and product yield is not high in fire retardant 2-(phenylbenzene phosphono)-Isosorbide-5-Nitrae-dihydroxy-benzene building-up process in order overcoming, to the invention provides a kind of novel environment friendly preparation method.It is as reaction raw materials take diphenyl phosphine chloride, adopt one kettle way, skip the purification process of diphenyl phosphine oxide, directly synthetic 2-(phenylbenzene phosphono)-Isosorbide-5-Nitrae-dihydroxy-benzene, and solvent for use and purification solvent are alcohols, toxicity is little, and yield is high, can reach more than 90%, production cost reduces greatly, meets the requirement of environment-friendly high-efficiency.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of phosphorus flame retardant 2-(phenylbenzene phosphono)-1, the environment-friendly preparation method of 4-dihydroxy-benzene is characterized in that: it is to adopt one kettle way, directly prepares productive rate greater than 80% 2-(phenylbenzene phosphono)-1 with diphenyl phosphine chloride, the 4-dihydroxy-benzene, concrete preparation method is as follows:
The first step: first pass into nitrogen in the reactor and get rid of its Air, in reactor, drip diphenyl phosphine chloride at ambient temperature, then in reactor, drip water, add rear maintenance room temperature and fully react;
Second step: in the first step reaction product, slowly add the alcoholic solvent of low toxic and environment-friendly and the mixture of para benzoquinone, keep room temperature fully to react, filter and obtain the light yellow solid powder;
The 3rd step: the light yellow solid powder with purification solvent heated scrub second step obtains, then filter, the white solid powder that oven dry obtains under 120 ℃ of conditions is product; Reaction scheme is as follows:
Detailed preparation method of the present invention is as follows:
The first step: first pass into nitrogen in the reactor and get rid of its Air, in reactor, drip diphenyl phosphine chloride at ambient temperature, then the mol ratio according to the material of diphenyl phosphine chloride and water is 1:(1～2), in reactor, drip water, add rear maintenance room temperature and fully react, preferred 1 hour of reaction times;
Second step: in the first step reaction product, slowly add the mixture of alcoholic solvent and para benzoquinone, keep room temperature fully to react (preferred 1-3 of reaction times hour), filter and obtain the light yellow solid powder; The consumption that requires para benzoquinone is 1～1.2 times of diphenyl phosphine chloride molar weight, and the alcoholic solvent consumption is 1.5～3 times of diphenyl phosphine chloride quality.
Above-mentioned alcoholic solvent is the Fatty Alcohol(C12-C14 and C12-C18) of C1～C8 or the mixed solvent of one or more compositions in the aromatic alcohol
The 3rd step: use C
1-C
8Alcohols in mixed solvent heated scrub (preferred 50～200 ℃ of the Heating temperature of one or several compositions, preferred 0.5 hour of washing time) the light yellow solid powder that obtains of second step is purified, and then cools off, filters, dries the white solid powder that (preferred 120 ℃ of bake out temperature) obtain and be product.
Preparation method of the present invention compares with existing synthetic method has following advantage:
The present invention relates to the Novel synthesis technology of fire retardant 2-(phenylbenzene phosphono)-Isosorbide-5-Nitrae-dihydroxy-benzene, take diphenyl phosphine chloride as raw material, adopt one kettle way, directly synthesize 2-(phenylbenzene phosphono)-Isosorbide-5-Nitrae-dihydroxy-benzene, removed the purification process of diphenyl phosphine oxide from, and the alcohols with low toxic and environment-friendly substitutes the larger aromatics of toxicity as the solvent of reaction, meet the requirement of environmental protection, by product is few, and yield is high, purify easier, production cost reduces greatly.
Description of drawings
Fig. 1 is the infrared spectra of 2-in the embodiment of the invention 1 (phenylbenzene phosphono)-Isosorbide-5-Nitrae-dihydroxy-benzene;
Fig. 2 is the nuclear-magnetism H spectrum of 2-in the embodiment of the invention 1 (phenylbenzene phosphono)-Isosorbide-5-Nitrae-dihydroxy-benzene;
Embodiment
Embodiment 1
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2In the dry four-hole boiling flask of the 250ml of conduit, pass into the air in the drying nitrogen eliminating flask, then add 22.0g (0.1mol) diphenyl phosphate oxidation, at room temperature drip 1.8g (0.1mol) water, room temperature reaction 1 hour, then the para benzoquinone mixture that slowly adds 50g dehydrated alcohol and 10.8g (0.1mol), at room temperature reacted 2 hours, filtration obtains the light yellow solid powder, and with 50g dehydrated alcohol reflux washing 0.5 hour, cold filtration obtained the white solid powder again, be product 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene, productive rate are 81%, and the infrared spectra of product and nuclear-magnetism H spectrogram are seen respectively Fig. 1 and Fig. 2;
Embodiment 2
Embodiment 2 has changed the proportioning of diphenyl phosphine chloride and water, and concrete synthesis technique is as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2In the dry four-hole boiling flask of the 250ml of conduit, pass into the air in the drying nitrogen eliminating flask, then add 22.0g (0.1mol) diphenyl phosphate oxidation, at room temperature drip 2.7g (0.15mol) water, room temperature reaction 1 hour, then slowly add the para benzoquinone mixture that then slowly adds 50g dehydrated alcohol and 10.8g (0.1mol), at room temperature reacted 2 hours, filtration obtains the light yellow solid powder, again with 50g dehydrated alcohol reflux washing 0.5 hour, cooling, filter, oven dry obtains white solid powder, i.e. product 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene, productive rate are 94%.
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2In the dry four-hole boiling flask of the 250ml of conduit, pass into the air in the drying nitrogen eliminating flask, then add 22.0g (0.1mol) diphenyl phosphate oxidation, at room temperature drip 3.6g (0.2mol) water, room temperature reaction 1 hour, then slowly add the para benzoquinone mixture that then slowly adds 50g dehydrated alcohol and 10.8g (0.1mol), at room temperature reacted 2 hours, filtration obtains the light yellow solid powder, again with 50g dehydrated alcohol reflux washing 0.5 hour, cooling, filter, oven dry obtains white solid powder, i.e. product 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene, productive rate are 95%.
Embodiment 4
Embodiment 4 has changed solvent load, and concrete synthesis technique is as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2In the dry four-hole boiling flask of the 250ml of conduit, pass into the air in the drying nitrogen eliminating flask, then add 22.0g (0.1mol) diphenyl phosphate oxidation, at room temperature drip 2.7g (0.15mol) water, room temperature reaction 1 hour, then slowly add the para benzoquinone mixture that then slowly adds 40g dehydrated alcohol and 10.8g (0.1mol), at room temperature reacted 2 hours, filtration obtains the light yellow solid powder, again with 50g dehydrated alcohol reflux washing 0.5 hour, cooling, filter, oven dry obtains white solid powder, i.e. product 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene, productive rate are 86%.
Embodiment 5
Embodiment 5 has changed solvent load, and concrete synthesis technique is as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2In the dry four-hole boiling flask of the 250ml of conduit, pass into the air in the drying nitrogen eliminating flask, then add 22.0g (0.1mol) diphenyl phosphate oxidation, at room temperature drip 2.7g (0.15mol) water, room temperature reaction 1 hour, then slowly add the para benzoquinone mixture that then slowly adds 60g dehydrated alcohol and 10.8g (0.1mol), at room temperature reacted 2 hours, filtration obtains the light yellow solid powder, again with 50g dehydrated alcohol reflux washing 0.5 hour, cooling, filter, oven dry obtains white solid powder, i.e. product 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene, productive rate are 90%.
Embodiment 6
Embodiment 6 selects methyl alcohol as solvent, and concrete synthesis technique is as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2In the dry four-hole boiling flask of the 250ml of conduit, pass into the air in the drying nitrogen eliminating flask, then add 22.0g (0.1mol) diphenyl phosphate oxidation, at room temperature drip 2.7g (0.15mol) water, room temperature reaction 1 hour, then slowly add the para benzoquinone mixture that then slowly adds 50g anhydrous methanol and 10.8g (0.1mol), at room temperature reacted 2 hours, filtration obtains the light yellow solid powder, again with 50g dehydrated alcohol reflux washing 0.5 hour, cooling, filter, oven dry obtains white solid powder, i.e. product 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene, productive rate are 92%.
Embodiment 7
Embodiment 7 has changed the reaction times that adds behind the pure and mild para benzoquinone mixture, and concrete synthesis technique is as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2In the dry four-hole boiling flask of the 250ml of conduit, pass into the air in the drying nitrogen eliminating flask, then add 22.0g (0.1mol) diphenyl phosphate oxidation, at room temperature drip 2.7g (0.15mol) water, room temperature reaction 1 hour, then slowly add the para benzoquinone mixture that then slowly adds 50g dehydrated alcohol and 10.8g (0.1mol), at room temperature reacted 1 hour, filtration obtains the light yellow solid powder, again with 50g dehydrated alcohol reflux washing 0.5 hour, cooling, filter, oven dry obtains white solid powder, i.e. product 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene, productive rate are 83%.
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2In the dry four-hole boiling flask of the 250ml of conduit, pass into the air in the drying nitrogen eliminating flask, then add 22.0g (0.1mol) diphenyl phosphate oxidation, at room temperature drip 2.7g (0.15mol) water, room temperature reaction 1 hour, then slowly add the para benzoquinone mixture that then slowly adds 50g dehydrated alcohol and 10.8g (0.1mol), at room temperature reacted 3 hours, filtration obtains the light yellow solid powder, again with 50g dehydrated alcohol reflux washing 0.5 hour, cooling, filter, oven dry obtains white solid powder, i.e. product 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene, productive rate are 95%.
Embodiment 9
Embodiment 9 has changed the consumption of para benzoquinone, and concrete synthesis technique is as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2In the dry four-hole boiling flask of the 250ml of conduit, pass into the air in the drying nitrogen eliminating flask, then add 22.0g (0.1mol) diphenyl phosphate oxidation, at room temperature drip 2.7g (0.15mol) water, room temperature reaction 1 hour, then slowly add the para benzoquinone mixture that then slowly adds 50g dehydrated alcohol and 11.3g (0.105mol), at room temperature reacted 3 hours, filtration obtains the light yellow solid powder, again with 50g dehydrated alcohol reflux washing 0.5 hour, cooling, filter, oven dry obtains white solid powder, i.e. product 2-(phenylbenzene phosphono)-1,4-dihydroxy-benzene, productive rate are 96%.
Claims (2)
1. the environment-friendly preparation method of a phosphorus flame retardant 2-(phenylbenzene phosphono)-Isosorbide-5-Nitrae-dihydroxy-benzene is characterized in that, it is to adopt one kettle way, directly prepare productive rate greater than 80% 2-(phenylbenzene phosphono)-Isosorbide-5-Nitrae-dihydroxy-benzene with diphenyl phosphine chloride, concrete preparation method is as follows:
The first step: first pass into nitrogen in the reactor and get rid of its Air, in reactor, drip diphenyl phosphine chloride at ambient temperature, then the mol ratio according to the material of diphenyl phosphine chloride and water is 1:(1～2), in reactor, drip water, add rear maintenance room temperature and fully react;
Second step: in the first step reaction product, slowly add the mixture of alcoholic solvent and para benzoquinone, keep room temperature fully to react, filter and obtain the light yellow solid powder; The consumption that requires para benzoquinone is 1～1.2 times of diphenyl phosphine chloride molar weight, and the alcoholic solvent consumption is 1.5～3 times of diphenyl phosphine chloride quality;
Above-mentioned alcoholic solvent is the Fatty Alcohol(C12-C14 and C12-C18) of C1～C8 or the mixed solvent of one or more compositions in the aromatic alcohol;
The 3rd step: use C
1-C
8Alcohols in the light yellow solid powder that obtains of the mixed solvent heated scrub second step of one or several compositions purify, then cool off, filter, dry the white solid powder that obtains and be product; Reaction scheme is as follows:
2. environment-friendly preparation method as claimed in claim 1 is characterized in that,
In the first step, the room temperature sufficient reaction time is 1 hour;
In second step, the room temperature sufficient reaction time is 1-3 hour;
In the 3rd step, the heated scrub temperature is 50～200 ℃, and the heated scrub time is 0.5 hour, and bake out temperature is 120 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198927A (en) * | 2015-10-27 | 2015-12-30 | 青岛富斯林化工科技有限公司 | Preparation method for benzoyldiphenyl phosphine oxide derivatives |
| CN114315896A (en) * | 2021-12-09 | 2022-04-12 | 湖北大学 | 2- (diphenyl thiophosphoryl) succinate and synthesis method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194564A (en) * | 1992-06-18 | 1993-03-16 | General Electric Company | Phosphine oxide substituted polycarbonate |
| CN1099046A (en) * | 1993-04-22 | 1995-02-22 | 通用电气公司 | Two phosphine oxide monomers and with this polycarbonate for preparing |
| US20060149023A1 (en) * | 2004-12-30 | 2006-07-06 | National Cheng Kung University | Phosphorus-containing cured benzoxazine resins and preparation thereof |
-
2013
- 2013-06-28 CN CN2013102707578A patent/CN103319533A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194564A (en) * | 1992-06-18 | 1993-03-16 | General Electric Company | Phosphine oxide substituted polycarbonate |
| CN1099046A (en) * | 1993-04-22 | 1995-02-22 | 通用电气公司 | Two phosphine oxide monomers and with this polycarbonate for preparing |
| US20060149023A1 (en) * | 2004-12-30 | 2006-07-06 | National Cheng Kung University | Phosphorus-containing cured benzoxazine resins and preparation thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198927A (en) * | 2015-10-27 | 2015-12-30 | 青岛富斯林化工科技有限公司 | Preparation method for benzoyldiphenyl phosphine oxide derivatives |
| CN114315896A (en) * | 2021-12-09 | 2022-04-12 | 湖北大学 | 2- (diphenyl thiophosphoryl) succinate and synthesis method and application thereof |
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Application publication date: 20130925 |