CN102250140A - Polyphosphinate monomer, polyphosphinate and preparation method of polyphosphinate - Google Patents
Polyphosphinate monomer, polyphosphinate and preparation method of polyphosphinate Download PDFInfo
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Abstract
The invention provides a polyphosphinate monomer, polyphosphinate and a preparation method of polyphosphinate. The polyphosphinate has a structural formula (II) as shown in a formula (II), wherein n is larger than or equal to 1 and less than or equal to 100; R1 can be one selected from C1-C2 alkyl, carbalkoxy, aryl and arakyl; R2 can be one selected from C1-C8 alkyl, aryl and arakyl; and R3 is selected from hydromethyl, diazomethyl and C1-C8 alcoxylmethyl. The polyphosphinate synthesized by the method is a novel organic polymer material, has good thermalstability and fire resistance as well as strong organic solvent corrosion resistance, and can be used for preparing inflaming retarding materials and corrosion resistant materials. The preparation method is simple and practicable, and raw materials are economic and available.
Description
Technical field
The invention belongs to chemical field, relate in particular to poly-phosphinate monomer, poly-phosphinate and preparation method thereof.
Background technology
Along with the enhancing of human health environmental consciousness, exploitation environmental protection, low toxicity, efficient, multi-functional fire retardant have become the future trend of fire retardant industry.Phosphorus flame retardant receives much concern in fire-retardant scientific domain with the characteristics of himself, has wide development potentiality.But because some defectives that existing phosphorus flame retardant self exists, as: some fire retardant consistencies are poor, poor heat stability, the amount of being fuming is big, volatility is big, water absorbability is big etc., has limited its application.Therefore, good, the hypotoxicity of big, the Heat stability is good of exploitation phosphorus content height, molecular weight, consistency, low phosphorus series compound of giving birth to the cigarette amount are a trend of organic phosphorus flame retardant development.
Summary of the invention
The technical problem of the present invention's existing demand for the performance that solves current material can not satisfy provides a class to have Heat stability is good, contains phosphine amount height, organic solvent-resistant burn into flame retardant properties excellence, and can have the poly-phosphinate polymkeric substance of extensive use.
First purpose of the present invention provides a kind of synthetic poly-phosphinate monomer methods, has the structure shown in formula I
Formula (I)
Wherein, R
1Can be selected from C
1-C
12Alkyl, carbalkoxy, aryl and aralkyl in a kind of; R
2Can be selected from C
1-C
8Alkyl, aryl and aralkyl in a kind of.Phosphonyl chloride among the present invention can buy or prepares through the document reported method by commercial sources, as dialkyl alkylphosphonate being dissolved in the alcoholic acid NaOH solution, reflux 2-12 hour, acidizing extraction, phosphonate monoester; Phosphonate monoester is slowly added in the thionyl chloride, under the protection of inert gas reflux 3-12 hour, be cooled to room temperature, thionyl chloride is removed in distillation, phosphonyl chloride; Polymerization generation polymkeric substance can take place with the poly-phosphinate monomer of diazomethane reaction preparation.
Second purpose of the present invention provides a kind of new poly-phosphinate polymkeric substance with excellent properties such as thermostability and organic solvent-resistant dissolvings, has the structure shown in formula II
Formula II
Wherein, the scope of n is 1≤n≤100; R
1Can be selected from C
1-C
12Alkyl, carbalkoxy, aryl and aralkyl in a kind of; R
2Can be selected from C
1-C
8Alkyl, aryl and aralkyl in a kind of; R
3Be selected from methylol, dizaomethyl and C
1-C
8A kind of in the alkoxyl-methyl.
The present inventor finds that the poly-phosphinate of above-mentioned synthetic has special structure, be new organic polymer material, the temperature of initial decomposition of the poly-phosphinate of the new organic polymer material that test prepares is substantially at 250-275 ℃, the poly-phosphinate of new organic polymer material becomes the carbon amount at 20-40%wt in the time of 1000 ℃, heat release is less in thermogravimetric and differential thermal analysis (TG-DTA) process simultaneously, most of the time all is in the heat absorption state, and material has good thermostability and flame retardant resistance.Find that through test the poly-phosphinate of the new organic polymer material make is in common organic solvents as all insoluble in the common solvents such as alcohol, ether, ester, carboxylic acid, acid amides, anti-organic-dissolvable performance is obvious, be that organic solvent-resistant corrodibility is strong, make it have application market widely.Polymkeric substance has the higher phosphine amount that contains simultaneously, has flame retardant properties preferably, can adapt to the high speed development of prior art, can be advantageously used in special materials such as fire-retardant, corrosion-resistant, is with a wide range of applications, and potential application market is extensive.
The 3rd purpose of the present invention provides the preparation method of the poly-phosphinate polymkeric substance of above-mentioned special construction, step comprises: phosphonyl chloride is contacted with diazomethane, terminal be the poly-phosphinate of dizaomethyl, or with phosphonyl chloride with contact with alcohol or water after diazomethane contacts for some time the terminal poly-phosphinate that contains methylol or alkoxyl-methyl.
Preparation method of the present invention is simple, easily realizes, for its a large amount of commercial applications are laid a good foundation.
The reaction that the present invention makes the poly-phosphinate polymkeric substance of above-mentioned special construction is
This polyreaction is the Cabbeen insertion polymerization, without any need for catalyzer, it is a kind of novel polymeric mode, more traditional addition polymerization is with the obvious advantage, the present inventor finds that the material for preparing gained has special construction shown in the above-mentioned formula II, be new polymkeric substance, have the performance of special excellence, for the development of novel material is laid a good foundation.
Description of drawings
Fig. 1 is the thermogravimetric and differential thermal analysis (TG-DTA) figure of the poly-1-phenyl phosphinic acid ethyl ester that makes of the embodiment of the invention 1.
Fig. 2 is the solid state nmr carbon spectrum of the poly-1-phenyl phosphinic acid ethyl ester that makes of the embodiment of the invention 1.
Fig. 3 is the solid state nmr phosphorus spectrum of the poly-1-phenyl phosphinic acid ethyl ester that makes of the embodiment of the invention 1.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The invention provides a kind of poly-phosphinate monomer, have the structure shown in formula I
Formula I
Wherein, R
1Can be selected from C
1-C
12Alkyl, carbalkoxy, aryl and aralkyl in a kind of, more preferably methyl, ethyl, propyl group, ethoxycarbonyl, phenyl, benzyl.R
2Can be selected from C
1-C
8Alkyl, aryl and aralkyl in a kind of, more preferably methyl and ethyl.
The invention provides a kind of poly-phosphinate, have the structure shown in formula II
Formula II
Wherein, the scope of n is 1≤n≤100, and more preferably 20≤n≤80 further are preferably 25≤n≤60.R
1Can be selected from C
1-C
12Alkyl, carbalkoxy, aryl and aralkyl in a kind of, more preferably methyl, ethyl, propyl group, ethoxycarbonyl, phenyl, benzyl.R
2Can be selected from C
1-C
8Alkyl, aryl and aralkyl in a kind of, more preferably methyl and ethyl.R
3Can be selected from methylol, dizaomethyl and C
1-C
8Alkoxyl-methyl, more preferably methylol, dizaomethyl, methoxyl methyl and ethoxymethyl.Concrete material for example can be poly-1-phenyl phosphinic acid ethyl ester, poly-1-benzyl phosphinicacid ethyl ester, poly-1-ethoxycarbonyl phosphinicacid ethyl ester, poly-1-methyl phosphinicacid ethyl ester, poly-1-ethyl phosphinicacid ethyl ester, poly-1-propyl group phosphinicacid ethyl ester etc.
The phosphine amount that contains of the poly-phosphinate of preferred new organic polymer material is 14.7wt%-22.9wt%, further improves the flame retardant properties of novel material.
The weight-average molecular weight of preferred liquid poly-phosphinate is 1400-2500, and the weight-average molecular weight of preferred solid-state poly-phosphinate is 20000-50000.
The present invention provides the preparation method of above-mentioned poly-phosphinate simultaneously, and step comprises: phosphonyl chloride is contacted with diazomethane, must gather phosphinate.
The mol ratio of preferred phosphonyl chloride and diazomethane is 1:2-1:6, and is further preferred: 1:4.
Wherein, preferred temperature is-20-100 ℃, the time of contact is 1-72 hour, further optimizes reaction conditions.The present invention is not particularly limited the addition sequence of phosphonyl chloride and diazomethane, can be that diazomethane adds in the phosphonyl chloride, also can be phosphonyl chloride progressively mix afterreaction simultaneously with diazomethane makes, preferably include phosphonyl chloride is slowly added in the solution of diazomethane, the preferred speed that adds is 1-3 mL/min, all can carry out under stirring condition when slow adding and reaction, make reaction evenly, the speed of stirring can be 1-5 revolutions per second.Preferably also contain organic solvent in the solution of diazomethane, wherein, organic solvent can be ether, methylene dichloride, tetrahydrofuran (THF), dioxane and 1, and the 2-ethylene dichloride is the ether or the halohydrocarbon solution of the solution of diazomethane, further optimizes reaction.
Wherein, phosphonyl chloride is for well known to a person skilled in the art various phosphonyl chlorides, and the preferred phosphonyl chloride of the present invention is selected from a kind of in the material shown in the formula (III).
Formula III
Wherein, R
1Can be selected from C
1-C
12Alkyl, carbalkoxy, aryl and aralkyl in a kind of, more preferably methyl, ethyl, propyl group, ethoxycarbonyl, phenyl, benzyl.R
2Can be selected from C
1-C
8Alkyl, aryl and aralkyl in a kind of, more preferably methyl and ethyl.Concrete material for example can be ethoxyethyl group phosphonyl chloride, ethoxycarbonyl propyl phosphonyl chloride, oxyethyl group butyl phosphine acyl chlorides, oxyethyl group ethoxy carbonyl methylphosphine acyl chlorides, ethoxy benzyl phosphonyl chloride, phenetole ethyl phosphonyl chloride etc.
Phosphonyl chloride can be commercially available phosphonyl chloride, also can be own synthetic phosphonyl chloride.The synthetic of phosphonyl chloride can be adopted different synthetic methods according to concrete material, for example can synthesize phosphonate monoester by dialkyl alkylphosphonate, phosphonate monoester contacted under protection of inert gas with thionyl chloride to make again.Wherein can comprise the dialkyl alkylphosphonate back acidizing extraction that in alcoholic acid NaOH solution, refluxes by the synthetic phosphonate monoester of dialkyl alkylphosphonate, must phosphonate monoester.
The preparation method of further preferred above-mentioned poly-phosphinate, concrete steps can comprise:
Dialkyl alkylphosphonate is dissolved in the ethanolic soln of NaOH, reflux 4-12 hour, extract after the acidifying, get phosphonate monoester.Wherein, acidifying can be to well known to a person skilled in the art various acidifyings, and for example hcl acidifying makes its solution be acid; The temperature of reflux can be 70-90 ℃; Can remove a part of solvent by modes such as distillations earlier before the extraction, also can directly use dichloromethane extraction, take off a layer organic phase distillation removal solvent and get phosphonate monoester;
Phosphonate monoester is slowly added in the thionyl chloride, under the protection of inert gas reflux 3-12 hour, be cooled to room temperature, thionyl chloride is removed in distillation, phosphonyl chloride.Wherein, rare gas element is for well known to a person skilled in the art various rare gas elementes, for example nitrogen, argon gas etc., and the temperature of reflux can be 70-90 ℃, distillation can be straight run distillation, also can be underpressure distillation;
Phosphonyl chloride is slowly joined under-5-10 ℃ in the ethereal solution of diazomethane and stirred 24-48 hour, returned to stirring at room 12-24 hour, solid, solid is washed through ethyl acetate, dryly must gather phosphinate.
When made product is that its reaction process is as follows when gathering phosphinicacid ethyl ester:
The structure of the poly-phosphinate of gained is special, is novel material
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
1. the preparation of benzylphosphonic acid mono ethyl ester
With benzylphosphonic acid diethyl ester 2.28 g(10 mol) be dissolved in and add 0.8 g(20 mol behind the 50 mL ethanol, 2eq) NaOH, reflux 4 hours, it is orange-yellow that solution is.Add 1.2 g(30 mol again, 3 eq) NaOH, 4.5 hours postcooling of reflux are to room temperature, add 3 mol/L hydrochloric acid to solution and be acid, screw out partial solvent also with 3 * 25 mL dichloromethane extractions, take off and use methylene dichloride after layer liquid is spin-dried for solvent: ether: sherwood oil=1:2:49 (V/V) recrystallization gets clear crystal benzylphosphonic acid mono ethyl ester 1.537 g, productive rate 76.9%, mp. 68-69 ℃ (Lit. 63-64 ℃).
2. the preparation of ethoxy benzyl phosphonyl chloride
With benzylphosphonic acid mono ethyl ester 0.5g(2.5 mmol) be dissolved in 0.60 g(5 mmol, 2eq) SOCl
2, reflux is 12 hours under nitrogen protection, and excessive SOCl is removed in underpressure distillation
2, the gained phosphonyl chloride is directly used in next step reaction.
3. the preparation of poly-1-phenyl phosphinic acid ethyl ester
With 0.545 g(23 mmol) the benzyl phosphonyl chloride is added dropwise to stir in 15 mL new system diazomethane-diethyl ether solutions with the speed of 3 mL/min under 0 ℃ and returned to stirring at room 24 hours after 10 hours.The generation of adularescent solid is filtered after the ethyl acetate washing is also dry, and getting end group is the poly-1-phenyl phosphinic acid ethyl ester 0.18g of white solid state of dizaomethyl, productive rate 31%.Mother liquor and washings merge the back distillation and obtain the poly-1-phenyl phosphinic acid ethyl ester 0.20g of yellow liquid-state oligomers that end group is a dizaomethyl, productive rate 28% except that desolvating.(annotate: if in gained solid or mother liquor, add H
20 or pure, can obtain end group is the poly-1-phenyl phosphinic acid ethyl ester of methylol or alkoxyl-methyl.）
Test to such an extent that its weight-average molecular weight be 1420 through gel permeation chromatography the poly-1-phenyl phosphinic acid ethyl ester of the liquid state that makes.
With the solid of the poly-1-phenyl phosphinic acid ethyl ester product that makes through the analysis of HCT-2 type differential thermal balance, must gather the thermogravimetric and the differential thermal analysis (TG-DTA) of 1-phenyl phosphinic acid ethyl ester schemes as Fig. 1, can find out, its temperature of initial decomposition is 275 ℃, weightlessness mainly is divided into three parts, and the fs thermal weight loss is at 275-400 ℃, and this stage mainly is that polymkeric substance loses oxyethyl group in the phosphinate and the hydrogen atom on the carbon atom of phosphono ortho position, promptly losing ethanol, is unsettled P-O-C bond rupture; The subordinate phase thermal weight loss is at 400-580 ℃, and this stage mainly is that poly-phosphinate discharges water molecules under the high temperature, and the DTA curve mainly shows as endothermic process in this stage; Phase III weightlessness is at 580-1000 ℃, and this stage mainly is that the poly phosphonic acids makes organics dehydration under the high temperature.Analyze to such an extent that the polymkeric substance temperature of initial decomposition is 275 ℃, weightlessness has only 60% in the time of 1000 ℃, heat release is less in the whole process, most of the time all is in the heat absorption state, therefore polymkeric substance has good heat endurance, not only can satisfy relevant thermoplastic processes as additive flame retardant, it is 40% at 1000 ℃ of following carbon forming rates simultaneously, has the excellent fire retardant effect.
By solid state nmr poly-1-phenyl phosphinic acid ethyl ester is characterized,
13Can see in the C NMR spectrogram (Fig. 2) that chemical displacement value is two carbon in the oxyethyl group at 16.4 and 62.2 ppm places; Chemical shift is respectively the peak of phosphono a position and a ' secondary carbon in position and tertiary carbon at 37.3 and 38.5 places; and these two carbon are split by phosphorus respectively and are divided into double peak; its coupling constant is respectively 124.4 Hz and 112.5 Hz; it between 124.8-135.5 the peak of phenyl carbons; because a carbon on the phenyl can be split branch by phosphorus, so
13We can see 5 groups of peaks on the C NMR spectrogram.Owing to contain two chiral centres in the product, promptly there is a pair of cis-trans-isomer, therefore exist
31In the P NMR spectrogram (Fig. 3), can see two groups of phosphorus peaks, it is respectively 18.9 and 19.6.Compose according to this carbon spectrum and phosphorus and can illustrate well that this polymkeric substance regularity is very high, and the chemical environment of phosphorus single be that its structural unit is unique.
With solid-state poly-1-phenyl phosphinic acid ethyl ester 0.05g and 10 mL common solvent (CH
2Cl
2, CHCl
3, tetrahydrofuran (THF), ethyl acetate, ethanol, water etc.) mix, reflux 10min filters, distillation removes and desolvates, weighing find the molten solid weight of solvent institute all less than 1 mg be solubleness less than 0.1g/L, belong to material hard to tolerate, this illustrates the anti-solvent corrosion superior performance of this material.
Embodiment 2
1. the preparation of ethylphosphonic acid mono ethyl ester
With 1.7 g (10 mmol) diethyl ethylphosphate and 1.2 g(30 mmol) NaOH mixes and is dissolved in the 100 mL ethanolic solns, is heated to 100 ℃ and kept temperature 4 hours under induction stirring.Ethanol is removed in distillation after being cooled to room temperature, adds 10 mL water and 10 mL CH
2Cl
2, water,, merges organic phase and use anhydrous sodium sulfate drying with 3 * 15 mL dichloromethane extractions to pH=1 with 3 mol/L hcl acidifyings behind the separatory, distillation except that desolvate colourless liquid ethylphosphonic acid mono ethyl ester 0.4 g, productive rate 29 %.
2. the preparation of ethoxyethyl group phosphonyl chloride
With ethylphosphonic acid mono ethyl ester 0.69 g(5 mmol) be added dropwise to 0.78 g(6.5 mmol) in the thionyl chloride, under the nitrogen protection reflux 8-12 hour, be cooled to room temperature, revolve to steam and remove thionyl chloride, the gained phosphonyl chloride is directly used in next step reaction.
3. the preparation of poly-1-methyl phosphinicacid ethyl ester
With 0.78 g(5 mmol) the ethoxyethyl group phosphonyl chloride is added dropwise in 20 mL new system diazomethane-diethyl ether solutions to stir after 1 hour under 0 ℃ and returned to stirring at room 24 hours.Filter the gained solid through ethyl acetate washing and dry, getting end group is the poly-1-methyl phosphinicacid ethyl ester 0.08g of white solid state of dizaomethyl, productive rate 12%.Mother liquor and washings merging back distillation obtain end group except that desolvating be the poly-1-methyl phosphinicacid ethyl ester 0.10g of dizaomethyl oligopolymer, productive rate 15%.(annotate: if in gained solid or mother liquor, add H
20 or pure, can obtain end group is the poly-1-methyl phosphinicacid ethyl ester of methylol or alkoxyl-methyl.）
It is 900 that the poly-1-methyl phosphinicacid ethyl ester liquid that makes is tested its liquid polymer weight-average molecular weight through gel permeation chromatography, with the solid of the poly-1-methyl phosphinicacid ethyl ester product that makes through the analysis of HCT-2 type differential thermal balance as can be known: its temperature of initial decomposition is 250 ℃, and 1000 ℃ of following carbon forming rates are 20%.
With solid-state poly-1-methyl phosphinicacid ethyl ester 0.05 g and 10 mL common solvent (CH
2Cl
2, CHCl
3, tetrahydrofuran (THF), ethyl acetate, ethanol, water etc.) mix, reflux 10min filters, distillation removes and desolvates, back weighing find the molten solid weight of solvent institute all less than 1 mg be solubleness less than 0.1 g/L, belong to material hard to tolerate, this illustrates the anti-solvent corrosion superior performance of this material.
Embodiment 3
1. the preparation of propyl phosphonous acid mono ethyl ester
With 2 g (11 mmol) propyl phosphonous acid diethyl ester and 1.33 g(33 mmol) NaOH mixes and is dissolved in the 100 mL ethanolic solns, is heated to 100 ℃ and kept temperature 4 hours under induction stirring.Ethanol is removed in distillation after being cooled to room temperature, adds 10 mL water and 10 mL CH
2Cl
2,Water,, merges organic phase and use anhydrous sodium sulfate drying with 3 * 15 mL dichloromethane extractions to pH=1 with 3 mol/L hcl acidifyings behind the separatory, distillation except that desolvate colourless liquid propyl phosphonous acid mono ethyl ester 0.58 g, productive rate 31 %
2. the preparation of ethoxycarbonyl propyl phosphonyl chloride
With propyl phosphonous acid mono ethyl ester 0.76 g(5 mmol) be added dropwise to 0.78 g(6.5 mmol) in the thionyl chloride, reflux is 12 hours under the nitrogen protection, is cooled to room temperature, revolves to steam to remove thionyl chloride, the gained phosphonyl chloride is directly used in next step reaction.
3. the preparation of poly-1-ethyl phosphinicacid ethyl ester
With 0.85 g(5 mmol) the ethoxycarbonyl propyl phosphonyl chloride is added dropwise in 20 mL new system diazomethane-diethyl ether solutions to stir after 1 hour under 0 ℃ and returned to stirring at room 24 hours.The gained solid is through ethyl acetate washing and dry, and getting end group is poly-1-ethyl phosphinicacid ethyl ester 0.09 g of white solid state of dizaomethyl, productive rate 12%.Mother liquor and washings merge the back distillation and obtain poly-1-ethyl phosphinicacid ethyl ester 0.12 g of yellow liquid-state oligomers that end group is a dizaomethyl, productive rate 16% except that desolvating.(annotate: if in gained solid or mother liquor, add H
20 or pure, can obtain end group is the poly-1-ethyl phosphinicacid ethyl ester of methylol or alkoxyl-methyl.）
It is 950 that the poly-1-ethyl phosphinicacid ethyl ester liquid that makes is tested its liquid polymer weight-average molecular weight through gel permeation chromatography, with the solid of the poly-1-ethyl phosphinicacid ethyl ester product that makes through the analysis of HCT-2 type differential thermal balance as can be known: its temperature of initial decomposition is 250 ℃, and 1000 ℃ of following carbon forming rates are 25%.
With solid-state poly-1-ethyl phosphinicacid ethyl ester 0.05 g and 10 mL common solvent (CH
2Cl
2, CHCl
3, tetrahydrofuran (THF), ethyl acetate, ethanol, water etc.) mix, reflux 10 min filter, distillation removes and desolvates, back weighing find the molten solid weight of solvent institute all less than 1 mg be solubleness less than 0.1 g/L, belong to material hard to tolerate, this illustrates the anti-solvent corrosion superior performance of this material.
Embodiment 4
1. the preparation of butyl phosphonic acids mono ethyl ester
With 6 g (30 mmol) butyl phosphine diethyl phthalate and 3.6 g(90 mmol) NaOH mixes and is dissolved in the 120 mL ethanolic solns, is heated to 100 ℃ and kept temperature 4 hours under induction stirring.Ethanol is removed in distillation after being cooled to room temperature, adds 15 mL water and 15 mL CH
2Cl
2, water,, merges organic phase and use anhydrous sodium sulfate drying with 3 * 15 mL dichloromethane extractions to pH=1 with 3 mol/L hcl acidifyings behind the separatory, distillation except that desolvate colourless liquid butyl phosphonic acids mono ethyl ester 2.9 g, productive rate 59 %
2. the preparation of oxyethyl group butyl phosphine acyl chlorides
With butyl phosphonic acids mono ethyl ester 0.42(2.5 mmol) be added dropwise to 0.39 g(3.3 mmol) in the thionyl chloride, reflux is 12 hours under the nitrogen protection, is cooled to room temperature, revolves to steam to remove thionyl chloride, the gained phosphonyl chloride is directly used in next step reaction.
3. the preparation of poly-1-propyl group phosphinicacid ethyl ester
With 0.46 g(5 mmol) oxyethyl group butyl phosphine acyl chlorides is added dropwise in 20 mL new system diazomethane-diethyl ether solutions to stir after 1 hour under 0 ℃ and returned to stirring at room 24 hours.The gained solid is through ethyl acetate washing and dry, and getting end group is poly-1-propyl group phosphinicacid ethyl ester 0.05 g of white solid state of dizaomethyl, productive rate 13%.Mother liquor and washings merging back distillation obtain end group except that desolvating be poly-1-propyl group phosphinicacid ethyl ester 0.069 g of dizaomethyl oligopolymer, productive rate 18%.(annotate: if in gained solid or mother liquor, add H
20 or pure, can obtain end group is the poly-1-propyl group phosphinicacid ethyl ester of methylol or alkoxyl-methyl.）
It is 1020 that the poly-1-propyl group phosphinicacid ethyl ester liquid that makes is tested its liquid polymer weight-average molecular weight through gel permeation chromatography, with the solid of the poly-1-propyl group phosphinicacid ethyl ester product that makes through the analysis of HCT-2 type differential thermal balance as can be known: its temperature of initial decomposition is 250 ℃, and 1000 ℃ of following carbon forming rates are 28%.
With solid-state poly-1-propyl group phosphinicacid ethyl ester 0.05 g and 10 mL common solvent (CH
2Cl
2, CHCl
3, tetrahydrofuran (THF), ethyl acetate, ethanol, water etc.) mix, reflux 10 min filter, distillation removes and desolvates, back weighing find the molten solid weight of solvent institute all less than 1 mg be solubleness less than 0.1 g/L, belong to material hard to tolerate, this illustrates the anti-solvent corrosion superior performance of this material.
Embodiment 5
1. the preparation of styroyl phosphonic acids mono ethyl ester
With 2.42 g (10 mmol) styroyl diethyl phosphonate and 1.2 g(30 mmol) NaOH mixes and is dissolved in the 100 mL ethanolic solns, is heated to 100 ℃ and kept temperature 4 hours under induction stirring.Ethanol is removed in distillation after being cooled to room temperature, adds 15 mL water and 15 mL CH
2Cl
2,Water,, merges organic phase and use anhydrous sodium sulfate drying with 3 * 15 mL dichloromethane extractions to pH=1 with 3 mol/L hcl acidifyings behind the separatory, distillation except that desolvate colourless liquid styroyl phosphonic acids mono ethyl ester 1.03 g, productive rate 48 %
2. the preparation of phenetole ethyl phosphonyl chloride
With phenetole ethylphosphonic acid mono ethyl ester 1 g(5 mmol) be added dropwise to 0.78 g(6.5 mmol) in the thionyl chloride, reflux is 12 hours under the nitrogen protection, is cooled to room temperature, revolves to steam to remove thionyl chloride, the gained phosphonyl chloride is directly used in next step reaction.
3. the preparation of poly-1-benzyl phosphinicacid ethyl ester
With 1.16 g(5 mmol) phenetole ethyl phosphonyl chloride is added dropwise in 20 mL new system diazomethane-diethyl ether solutions to stir after 1 hour under 0 ℃ and returned to stirring at room 24 hours.The gained solid is through ethyl acetate washing and dry, and getting end group is poly-1-benzyl phosphinicacid ethyl ester 0.17 g of white solid state of dizaomethyl, productive rate 17%.Mother liquor and washings merging back distillation obtain end group except that desolvating be poly-1-benzyl phosphinicacid ethyl ester 0.21 g of dizaomethyl oligopolymer, productive rate 21%.(annotate: if in gained solid or mother liquor, add H
20 or pure, can obtain end group is the poly-1-benzyl phosphinicacid ethyl ester of methylol or alkoxyl-methyl.）
With solid-state poly-1-benzyl phosphinicacid ethyl ester 0.05 g and 10 mL common solvent (CH
2Cl
2, CHCl
3, tetrahydrofuran (THF), ethyl acetate, ethanol, water etc.) mix, reflux 10 min filter, distillation removes and desolvates, back weighing find the molten solid weight of solvent institute all less than 1 mg be solubleness less than 0.1 g/L, belong to material hard to tolerate, this illustrates the anti-solvent corrosion superior performance of this material.
It is 1100 that the poly-1-benzyl phosphinicacid ethyl ester liquid that makes is tested its liquid polymer weight-average molecular weight through gel permeation chromatography, with the solid of the poly-1-propyl phosphonous acid ethyl ester product that makes through the analysis of HCT-2 type differential thermal balance as can be known: its temperature of initial decomposition is 250 ℃, and 1000 ℃ of following carbon forming rates are 30%.
Embodiment 6
1. the preparation of ethoxy carbonyl methyl-phosphorous acid mono ethyl ester
With 5 g (23 mmol) ethoxy carbonyl methyl-phosphorous acid diethyl ester and 0.95 g(23 mmol) LiCl mixes the back and be heated to 100 ℃ and kept temperature 1 hour under induction stirring.Add entry and each 10 mL of ethyl acetate after being cooled to room temperature, water,, merges organic phase and uses anhydrous sodium sulfate drying with 3 * 15 mL dichloromethane extractions to pH=1 with 3 mol/L hcl acidifyings behind the separatory, revolve boil off desolventize colourless liquid 1.9 g, productive rate 42 %.
2. the preparation of ethoxy carbonyl methylphosphine mono ethyl ester acyl chlorides
With ethoxy carbonyl methyl-phosphorous acid mono ethyl ester 1 g(5 mmol) be added dropwise to 0.78 g(6.5 mmol) in the thionyl chloride, reflux is 12 hours under the nitrogen protection, is cooled to room temperature, revolves to steam to remove thionyl chloride, the gained phosphonyl chloride is directly used in next step reaction.
3. the preparation of poly-1-ethoxycarbonyl phosphinicacid ethyl ester
With 1.07 g(5 mmol) ethoxy carbonyl methylphosphine mono ethyl ester acyl chlorides is added dropwise in 20 mL new system diazomethane-diethyl ether solutions to stir after 1 hour under 0 ℃ and returned to stirring at room 24 hours.The gained solid is through ethyl acetate washing and dry, and getting the white solid end group is poly-1-ethoxy carbonyl phosphinicacid ethyl ester 0.17 g of dizaomethyl, productive rate 17%.Mother liquor and washings merging back distillation obtain end group except that desolvating be poly-1-ethoxy carbonyl phosphinicacid ethyl ester 0.20 g of dizaomethyl oligopolymer, productive rate 20%.If (annotate and in gained solid or mother liquor, add H
20 or alcohol obtain the 1-ethoxy carbonyl phosphinicacid ethyl ester that end group is methylol or alkoxyl-methyl.）
Test to such an extent that its weight-average molecular weight be 1000 through gel permeation chromatography the poly-1-ethoxy carbonyl phosphinicacid ethyl ester liquid that makes, with the solid of the poly-1-ethoxy carbonyl phosphinicacid ethyl ester product that makes through the analysis of HCT-2 type differential thermal balance as can be known: its temperature of initial decomposition is 250 ℃, and 1000 ℃ of following carbon forming rates are 30%.
With solid-state poly-1-ethoxy carbonyl phosphinicacid ethyl ester 0.05 g and 10 mL common solvent (CH
2Cl
2, CHCl
3, tetrahydrofuran (THF), ethyl acetate, ethanol, water etc.) mix, reflux 10 min filter, distillation removes and desolvates, back weighing find the molten solid weight of solvent institute all less than 1 mg be solubleness less than 0.1 g/L, belong to material hard to tolerate, this illustrates the anti-solvent corrosion superior performance of this material.
The above only is embodiments of the invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a poly-phosphinate monomer is characterized in that, described poly-phosphinate monomer is the phosphono diazomethane, and described phosphono diazomethane has suc as formula the structure shown in the I
The formula I
Wherein, described R
1Be selected from C
1-C
12Alkyl, carbalkoxy, aryl and aralkyl in a kind of; Described R
2Be selected from C
1-C
8Alkyl, aryl and aralkyl in a kind of.
2. poly-phosphinate monomer as claimed in claim 1 is characterized in that described R
1Be methyl, ethyl, propyl group, ethoxycarbonyl, phenyl, benzyl; Described R
2Be methyl, ethyl.
3. a poly-phosphinate is characterized in that, described poly-phosphinate has suc as formula the structure shown in the II,
The formula II
Wherein, the scope of n is 1≤n≤100; Described R
1Be selected from C
1-C
12Alkyl, carbalkoxy, aryl and aralkyl in a kind of; Described R
2Be selected from C
1-C
8Alkyl, aryl and aralkyl in a kind of; Described R
3Be selected from methylol, dizaomethyl and C
1-C
8A kind of in the alkoxyl-methyl.
4. poly-phosphinate as claimed in claim 3 is characterized in that, the scope of described n is 1≤n≤100, more preferably 25≤n≤60; Described R
1Be methyl, ethyl, propyl group, ethoxycarbonyl, phenyl, benzyl; Described R
3Be selected from methylol, dizaomethyl, methoxyl methyl and ethoxymethyl; R
2Be methyl, ethyl.
5. the preparation method as claim 3 or 4 described poly-phosphinates is characterized in that step comprises: phosphonyl chloride is contacted with diazomethane, get the terminal poly-phosphinate that contains dizaomethyl; Or phosphonyl chloride contacted last and water or C with diazomethane
1-C
7Alcohol contact, terminal methylol or the C of containing
1-C
8The poly-phosphinate of alkoxyl-methyl.
6. preparation method as claimed in claim 5 is characterized in that, the mol ratio of described phosphonyl chloride and diazomethane is 1:2-1:6; The temperature of described reaction is-20-100 ℃, and the time of described contact is 1-72 h; Or described temperature of reaction is-20-100 ℃ that institute contacts 0.1-10h with water or alcohol behind the 1-72 h.
7. preparation method as claimed in claim 5 is characterized in that, described phosphonyl chloride is selected from shown in the formula III a kind of in the material,
Formula III
Wherein, described R
1Be selected from C
1-C
12Alkyl, carbalkoxy, aryl and aralkyl in a kind of; Described R
2Be selected from C
1-C
8Alkyl in a kind of.
8. preparation method as claimed in claim 5 is characterized in that, described phosphonyl chloride contacts with diazomethane and comprises phosphonyl chloride is slowly added in the solution of diazomethane, and the speed of described adding is 1-3 mL/min; Also contain organic solvent in the solution of described diazomethane, described organic solvent is ether, methylene dichloride, tetrahydrofuran (THF), dioxane and 1, the 2-ethylene dichloride.
9. preparation method as claimed in claim 8 is characterized in that, described preparation method's step comprises:
Phosphonyl chloride is slowly joined under-5-10 ℃ in the diethyl ether solution of diazomethane and stirred 2-48 hour, returned to stirring at room 12-24 hour, solid, solid is washed through ethyl acetate, after the drying, the terminal poly-phosphinate that contains dizaomethyl; Phosphonyl chloride is slowly joined under-5-10 ℃ in the diethyl ether solution of diazomethane and stirred 2-48 hour, returned to stirring at room 12-24 hour, solid; Add entry or alcohol, continue stirring reaction 1-10h, the solid that obtains is washed through ethyl acetate, after the drying, get the terminal poly-phosphinate that contains methylol or alkoxyl-methyl.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023054663A1 (en) * | 2021-10-01 | 2023-04-06 | 国立大学法人福井大学 | Method for producing vinylphosphonic acid monoester |
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| WO2023054663A1 (en) * | 2021-10-01 | 2023-04-06 | 国立大学法人福井大学 | Method for producing vinylphosphonic acid monoester |
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