CN103408596A - Phosphorus-containing spiro-compound and preparation method thereof - Google Patents
Phosphorus-containing spiro-compound and preparation method thereof Download PDFInfo
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- CN103408596A CN103408596A CN2013103043362A CN201310304336A CN103408596A CN 103408596 A CN103408596 A CN 103408596A CN 2013103043362 A CN2013103043362 A CN 2013103043362A CN 201310304336 A CN201310304336 A CN 201310304336A CN 103408596 A CN103408596 A CN 103408596A
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Abstract
Relating to a preparation method of spiro-compounds, the invention provides a phosphorus-containing spiro-compound and a preparation method thereof. The preparation method comprises the steps of: 1. reacting phosphorus-containing diol with di-n-butyltin oxide under certain conditions to generate an intermediate; 2. reacting the intermediate with carbon disulfide under certain conditions, carrying out pump filtration, washing, recrystallization and drying treatment, thus obtaining a phosphorus-containing spiro-compound product. The phosphorus-containing spiro-compound prepared in the invention can be used in epoxy resin, phenolic resin and other high polymer materials to improve the mechanical properties of polymer materials, and also can enhance the flame retardant property of the materials, thus being a multifunctional modification additive. The method adopted in the invention has the advantages of simple production process conditions, high product purity and yield, and easy aftertreatment process, etc.
Description
Technical field
The present invention relates to a kind of chemosynthesis spirocyclic compound and preparation method thereof, particularly relate to a kind of phosphorous spirocyclic compound and preparation method thereof.
Background technology
Macromolecular material, was widely used on the industries such as aviation, industry, national defence, medicine with its good performance since the later stage thirties after aspect industrial production, being applied.But the such problem of ubiquity in the macromolecular material of having developed: the performance of its practical application does not reach its theoretical performance far away.Producing this situation causes because the material internal unbalance stress produces stress concentration.The influence factor of stress concentration has a lot, and wherein topmost factor is exactly the internal stress produced due to volumetric shrinkage in polyreaction.The existence of this destructive factor, make between the inner adhesively bonded joint of polymeric matrix or resin matrix and fiber and when not being subjected to load, be subject to very large stress, thereby cause matrix strength to descend, adhesively bonded joint comes off or cracking, flexion and the size distortion etc. of material.The existence of this unrelieved stress also makes material easily produce catabiosis, thereby has affected the work-ing life of material.
During widely used epoxy resin cure, will inevitably produce certain unrelieved stress because of volumetric shrinkage, unrelieved stress in resin is a kind of potential destructive factor, it makes between resin and fiber interface or adhesively bonded joint just is subject to appreciable stress without outer year the time, thereby cause strength degradation, even can cause coming unstuck of the unstable or adhesively bonded joint of cracking, the size of matrix material etc.And the reaction of the inflated polymer of spiromonomer has the effect of eliminating unrelieved stress, namely in polymerization process, produce volumetric expansion, can obviously reduce the unrelieved stress produced due to volumetric shrinkage, thereby have a wide range of applications at the aspects such as modification of medical macromolecular materials, high strength bonding agent and polymkeric substance.
Since 1972, the people such as Bailey have developed a series of spirocyclic compounds, and in recent decades, material scholars both domestic and external have carried out research quite widely.At present, Expanding Monomer and inflated polymer reaction are for the preparation of high strength composite, high performance adhesive, biodegradated polymer materal, medical macromolecular materials, and also the modification for commodity polymer reaches synthetic oligopolymer with functional group etc.
Summary of the invention
The object of the present invention is to provide a kind of phosphorous spirocyclic compound and preparation method thereof, the present invention is with phosphorous dibasic alcohol, di-n-butyl stannic oxide and dithiocarbonic anhydride are that raw material has synthesized phosphorous spirocyclic compound, on the basis of Expanding Monomer, in its molecular structure, introduced phosphoric, make it have certain flame retardant properties, thereby realized the multifunction of product.
The objective of the invention is to be achieved through the following technical solutions:
A kind of phosphorous spirocyclic compound, described raw materials of compound comprise phosphorous dibasic alcohol A, di-n-butyl stannic oxide and dithiocarbonic anhydride, and this compound has following structure:
A kind of preparation method of phosphorous spirocyclic compound, described method comprises following preparation process: the first step generates intermediate B by phosphorous dibasic alcohol A and the reaction of di-n-butyl stannic oxide; Second step, intermediate B and dithiocarbonic anhydride reaction, through suction filtration, washing, recrystallization, drying treatment, the gained light yellow crystal is phosphorous spirocyclic compound C;
The said process chemical equation is:
The preparation method of described a kind of phosphorous spirocyclic compound, in described the first step synthetic intermediate B, phosphorous dibasic alcohol A is 1:1-1.5 with the mol ratio of reacting of di-n-butyl stannic oxide; Solvent for use can be the mixture of any one or its arbitrary proportion in benzene,toluene,xylene; Temperature of reaction is controlled at 80-150 ℃; Reaction times is 6-24 hour.
The preparation method of described a kind of phosphorous spirocyclic compound, described in second step, intermediate B and CS
2Molar ratio be 1:0.5-1; Solvent for use can be the mixture of any one or its arbitrary proportion in benzene,toluene,xylene; Temperature of reaction is 50-120 ℃; Reaction times is 6-24 hour; Recrystallization solvent is the mixture of any one or its arbitrary proportion in benzene, toluene and dimethylbenzene.
Advantage of the present invention and effect are:
String stress when 1, the phosphorous spirocyclic compound for preparing of the present invention both can be used as Expanding Monomer and is applied in the macromolecular materials such as epoxy resin, resol reduce curing reaction, improve the mechanical property of material, also can be used as the flame retardant properties of fire retardant for strongthener.
2, institute of the present invention employing method have advantages of that manufacturing condition is simple, product purity and productive rate is higher, last handling process is easy.
The accompanying drawing explanation
Fig. 1 is infrared spectra (KBr compressing tablet) figure of phosphorous spirocyclic compound.
Annotate: Fig. 1 of the present invention is the analysis schematic diagram (only for reference) of product state, the unintelligible understanding do not affected technical solution of the present invention of figure Chinese word.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
?Embodiment 1:
In the 500ml there-necked flask that water trap, reflux condensing tube, thermometer and magneton are housed, add the phosphorous dibasic alcohol of 0.1 mol and 0.1 mol di-n-butyl stannic oxide, add toluene 200ml, in 130 ℃ of reactions 8 hours.Reaction is down to room temperature after finishing, and slowly drips the CS of 0.05mol in reaction flask
2, then 100 ℃ of reactions 12 hours, the pressure reducing and steaming solvent, the bottom thick liquid repeatedly washs with normal hexane, uses the toluene recrystallization, suction filtration, drying, obtain light yellow crystal 53.5 grams, yield 75.7%.
Embodiment 2:
In the 500ml there-necked flask that water trap, reflux condensing tube, thermometer and magneton are housed, add the phosphorous dibasic alcohol of 0.1 mol and 0.1 mol di-n-butyl stannic oxide, add benzene 200ml, in 100 ℃ of reactions 12 hours.Reaction is down to room temperature after finishing, and slowly drips the CS of 0.06mol in reaction flask
2, then 80 ℃ of reactions 12 hours, the pressure reducing and steaming solvent, the bottom thick liquid repeatedly washs with normal hexane, uses the benzene recrystallization, suction filtration, drying, obtain light yellow crystal 50.3 grams, yield 71.2%.
Claims (4)
1. a phosphorous spirocyclic compound, is characterized in that, described raw materials of compound comprises phosphorous dibasic alcohol A, di-n-butyl stannic oxide and dithiocarbonic anhydride, and this compound has following structure:
2. the preparation method of a phosphorous spirocyclic compound, is characterized in that, described method comprises following preparation process: the first step generates intermediate B by phosphorous dibasic alcohol A and the reaction of di-n-butyl stannic oxide; Second step, intermediate B and dithiocarbonic anhydride reaction, through suction filtration, washing, recrystallization, drying treatment, the gained light yellow crystal is phosphorous spirocyclic compound C;
The said process chemical equation is:
。
3. the preparation method of a kind of phosphorous spirocyclic compound according to claim 2, is characterized in that, in described the first step synthetic intermediate B, phosphorous dibasic alcohol A is 1:1-1.5 with the mol ratio of reacting of di-n-butyl stannic oxide; Solvent for use can be the mixture of any one or its arbitrary proportion in benzene,toluene,xylene; Temperature of reaction is controlled at 80-150 ℃; Reaction times is 6-24 hour.
4. the preparation method of a kind of phosphorous spirocyclic compound according to claim 2, is characterized in that, described in second step, intermediate B and CS
2Molar ratio be 1:0.5-1; Solvent for use can be the mixture of any one or its arbitrary proportion in benzene,toluene,xylene; Temperature of reaction is 50-120 ℃; Reaction times is 6-24 hour; Recrystallization solvent is the mixture of any one or its arbitrary proportion in benzene, toluene and dimethylbenzene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5804061A (en) * | 1997-04-14 | 1998-09-08 | Beloit Technologies, Inc. | Multiflow pressurized deinking apparatus |
| CN101613374A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | A kind of side group is polymeric phosphorus-containing flame retardant of DOPO and preparation method thereof |
| CN102199158A (en) * | 2011-04-15 | 2011-09-28 | 沈阳化工大学 | Synthesis method for 2-decyl-2-dihydroxymethyl propylene spiro-orthocarbonate monomer |
| CN102504268A (en) * | 2011-11-11 | 2012-06-20 | 上海交通大学 | Novel flame retardant containing phosphorus and preparation method thereof |
-
2013
- 2013-07-19 CN CN201310304336.2A patent/CN103408596B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5804061A (en) * | 1997-04-14 | 1998-09-08 | Beloit Technologies, Inc. | Multiflow pressurized deinking apparatus |
| CN101613374A (en) * | 2009-07-22 | 2009-12-30 | 中国科学技术大学 | A kind of side group is polymeric phosphorus-containing flame retardant of DOPO and preparation method thereof |
| CN102199158A (en) * | 2011-04-15 | 2011-09-28 | 沈阳化工大学 | Synthesis method for 2-decyl-2-dihydroxymethyl propylene spiro-orthocarbonate monomer |
| CN102504268A (en) * | 2011-11-11 | 2012-06-20 | 上海交通大学 | Novel flame retardant containing phosphorus and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈小庆等: "一种螺环原碳酸酯膨胀单体的合成及其与环氧树脂热固化", 《南京工业大学学报》 * |
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