CN105713040B - Phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof - Google Patents

Phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof Download PDF

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CN105713040B
CN105713040B CN201610037029.6A CN201610037029A CN105713040B CN 105713040 B CN105713040 B CN 105713040B CN 201610037029 A CN201610037029 A CN 201610037029A CN 105713040 B CN105713040 B CN 105713040B
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phenyl
phosphonic acid
propyl
ester
dihalo
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CN105713040A (en
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韩志慧
俞春雷
卫唯
董荣
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Suzhou University of Science and Technology
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Suzhou University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40Esters thereof
    • C07F9/4003Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4021Esters of aromatic acids (P-C aromatic linkage)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/53Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333Esters of phosphonic acids
    • C08K5/5337Esters of phosphonic acids containing also halogens
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Abstract

The present invention relates to a kind of phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof, and the structure of the compound is shown below:Wherein C3H5X2For CH2CHClCH2Cl、CH(CH2Cl)2、CH2CHBrCH2Br、CH(CH2Br)2.Preparation method is:Phenyl-phosphonic acid diester occurs ester exchange reaction or phenyl phosphonic dihalo- with halohydrin and addition esterification occurs in organic solvent with epoxyhalopropane in the presence of a catalyst, after purified processing, faint yellow thick liquid phenyl-phosphonic acid two (dihalo- propyl) ester is obtained.The compounds of this invention contains two kinds of phosphorus, halogen ignition-proof elements, and halogen amount is high, and cooperative flame retardant effect is good, also preferable plasticity, is suitable as the flame-retardant plasticizer of the materials such as PVC, polyurethane, epoxy resin, unsaturated-resin;Preparation method is simple for process, does not have chlorination hydrogen contamination, and equipment investment is few, is easy to large-scale production.

Description

Phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof
Technical field
The present invention relates to a kind of phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof, which contains Two kinds of phosphorus, halogen ignition-proof elements, cooperative flame retardant effect is good, is suitable as the materials such as PVC, polyurethane, epoxy resin, unsaturated-resin Flame-retardant plasticizer.
Background technology
With the fast development of China's synthesis Macromolecular materials industry, high molecular material is in building materials, electronic apparatus, traffic fortune The every field such as defeated, space flight and aviation, household furniture, interior decoration and clothing, food, lodging and transportion -- basic necessities of life are widely used.Due to it mostly With inflammability, often cause fire, seriously endanger to people's safety of life and property, thus promote fire retardant research and The application of fire proofing.The production of China's fire retardant is mainly halogen system product with consumption, but sends out RoHS from European Union in 1986 and refer to After order, polybrominated diphenyl ethers has been first subjected to query, then all produces negative effect to the application of broad sense halogenated flame retardant, together When propose higher requirement to halogenated flame retardant, exploitation high-efficiency low-toxicity halogenated flame retardant is had become as important research topic, In to improve flame-retarded efficiency by the compoundings of a variety of fire retardants be effective method, and designing multielement collaboration by intramolecular is also Obtain the approach of efficient flame-retarding agent.
The invention discloses a kind of phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof, which contains Two kinds of phosphorus, halogen ignition-proof elements, cooperative flame retardant effect is good, and aromatic ring in molecule and polyester structure can increase it is compatible with base material Property, plasticity is good, and halogen amount is high, is a kind of excellent flame-retardant plasticizer of comprehensive cost performance, and simple for process, easy to operate, if Standby small investment, it is environmental-friendly, there is preferable application and development prospect.
Invention content
It is an object of the present invention to proposing a kind of phenyl-phosphonic acid two (dihalo- propyl) ester compounds, which contains Two kinds of phosphorus, halogen ignition-proof elements, cooperative flame retardant efficiency is high, can effectively overcome the shortcomings of in existing flame-retarded technology.
For achieving the above object, present invention employs following technical solutions:
A kind of phenyl-phosphonic acid two (dihalo- propyl) ester compounds, which is characterized in that the structure of the compound is shown below:
Wherein C3H5X2For CH2CHClCH2Cl、CH(CH2Cl)2、CH2CHBrCH2Br、CH(CH2Br)2
Another object of the present invention is to propose a kind of preparation method of phenyl-phosphonic acid two (dihalo- propyl) ester, technique letter List is easy to large-scale production, and this method is:
In the reactor equipped with fractionating device, the air in kettle is displaced with nitrogen, adds in phenyl-phosphonic acid diester, catalysis Agent, the halohydrin of certain mol proportion are warming up to 110-150 DEG C, and fractionation reaction 6-8h, control fractionation column top temperature is in separated alcohol Boiling temperature, until the alcohol that fractionates out is up to theoretical amount, stop reaction, vacuum distillation removes excessive halohydrin (recycling uses) And a small amount of low boilers, purified processing, obtain faint yellow thick liquid phenyl-phosphonic acid two (dihalo- propyl) ester.
This method can also be:
It is being connected in the reactor of drying tube equipped with blender, thermometer, high performance reflux condenser and condenser pipe is suitable for reading, Nitrogen displaces air, adds in phenyl phosphonic dihalo-, organic solvent, and under stirring, the epoxy halogen of certain mol proportion is added dropwise under liquid level Propane is no more than 70 DEG C with rate of addition controlling reaction temperature, after dripping off, after being warming up to 80-100 DEG C of insulation reaction 4-5h, subtracts Organic solvent (recycling uses), excessive epoxyhalopropane (recycling uses) and a small amount of low boilers are distilled off in pressure, purified Processing, obtains faint yellow thick liquid phenyl-phosphonic acid two (dihalo- propyl) ester.
Phenyl-phosphonic acid diester as described above is phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethylester or phenyl-phosphonic acid diisopropyl Ester.
The halohydrin of certain mol proportion as described above is 1,3-, bis- chloro- 2- propyl alcohol, 2,3- dichlorohydrins, 1,3- bis- are bromo- 2- propyl alcohol, 2,3- dibromo-propanols, molar ratio are phenyl-phosphonic acid dimethyl ester: halohydrin=1: 2-1: 3.
Catalyst as described above is calcium chloride, zinc chloride, aluminium chloride or magnesium chloride, and dosage is phenyl-phosphonic acid dimethyl ester The 1%-2% of quality.
Phenyl phosphonic dihalo- as described above is phenyl phosphonyl chloride or phenyl phosphonic dibromo.
Epoxyhalopropane as described above is epoxychloropropane or epoxy bromopropane.
Organic solvent as described above is dichloroethanes or dioxane, and dosage volume milliliter number is theoretical product quality 2-4 times of grams.
The epoxyhalopropane of certain mol proportion as described above is phenyl phosphonic dihalo-: epoxyhalopropane=1: 2-1: 2.5.
Purification process as described above is to add in the water of 2-3 times of product Theoretical Mass, molten with 5% sodium carbonate under stirring Liquid is adjusted to neutrality, stratification, separates lower floor's feed liquid, is evaporated under reduced pressure out water micro in material.
Phenyl-phosphonic acid two (dihalo- propyl) ester of the present invention is faint yellow thick liquid, yield 88.1%-95.4%, The flame-retardant plasticizer for being suitable as the materials such as PVC, polyurethane, epoxy resin, unsaturated-resin is used.
The preparation process principle of phenyl-phosphonic acid two (dihalo- propyl) ester is shown below:
Wherein X is Cl or Br.
Compared with prior art, innovation of the invention is:
1. the structure of phenyl-phosphonic acid two (dihalo- propyl) ester of the present invention has preferable symmetric characteristics, physical chemistry It can stablize, the aromatic ring and ester structure in molecule can increase the compatibility of product and base material, and plasticity is good, can substitute part increasing It moulds agent to use, processing performance is good, and product is phosphorous, two kinds of ignition-proof elements of halogen, and halogen amount is high, and flame retardant property is good.
2. preparation method yield of the present invention is high, there is no chlorination hydrogen contamination, corrosivity is not generated to equipment.
3. preparation method phenyl phosphonic dihalo- of the present invention and epoxyhalopropane opening, contract without any small molecule It goes, atom utilization 100%, belongs to green chemistry process.
4. preparation method of the present invention is simple for process, raw material is cheap and easy to get, and equipment investment is few, is easy to large-scale production.
Description of the drawings
Drawings described below is provided in order to further illustrate the structure and performance spy of product.
Fig. 1 is the infrared spectrogram of phenyl-phosphonic acid two (two chloropropyls) ester;Fig. 1 shows:695.0cm-1Locate as C-Cl keys Stretching vibration peak;1056.3cm-1Locate the stretching vibration peak for P-O keys;1096.8cm-1Locate the stretching vibration peak for C-O keys; 1132.2cm-1Locate the stretching vibration peak for P=O keys;1440.0cm-1Locate the skeleton stretching vibration peak for phenyl ring;2966.8cm-1 Locate as CH2The stretching vibration peak of upper c h bond;3062.2cm-1Locate the stretching vibration peak for c h bond on phenyl ring.
Fig. 2 is the nuclear magnetic spectrum figure of phenyl-phosphonic acid two (two chloropropyls) ester;Fig. 2 shows:With CDCl3For solvent, δ3:7.79- 7.92 (q, 2H);δ1:7.59-7.66 (t, 1H);δ2:7.46-7.55 (q, 2H);δ4:4.81-4.90 (m, 2H);δ5:3.87- 3.98 (m, 4H);δ5:3.69-3.74 (m, 4H).
Specific embodiment
Technical scheme of the present invention is described further below in conjunction with specific embodiment.
Embodiment 1 displaces the air in kettle with nitrogen in the 100mL four-hole boiling flasks equipped with fractionating device, adds in 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous magnesium chlorides, bis- chloro- 2- propyl alcohol of 12.9g (0.1mol) 1,3-, heating To 150 DEG C, fractionation reaction 6h, not higher than 65 DEG C, the methanol until fractionating out stops anti-control fractionation column top temperature up to theoretical amount Should, vacuum distillation removes a small amount of low boilers, adds in the water of 45mL, under stirring, is adjusted with 5% sodium carbonate liquor to neutrality, Stratification separates lower floor's feed liquid, is evaporated under reduced pressure out water micro in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (1, Bis- chloro- 2- propyl of 3-) ester, yield 88.1%, decomposition temperature:278 ± 5 DEG C, index of refraction:nD 20=1.6659, density (20 ℃):1.420±0.005g/cm3
Embodiment 2 displaces the air in kettle with nitrogen in the 100mL four-hole boiling flasks equipped with fractionating device, adds in 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous magnesium chlorides, bis- chloro- 2- propyl alcohol of 19.35g (0.15mol) 1,3- rise Temperature is to 140 DEG C, fractionation reaction 6h, and not higher than 65 DEG C, the methanol until fractionating out stops control fractionation column top temperature up to theoretical amount Reaction, vacuum distillation remove excessive 1,3-, bis- chloro- 2- propyl alcohol (recycling uses) and a small amount of low boilers, add in the water of 45mL, It under stirring, is adjusted with 5% sodium carbonate liquor to neutrality, stratification, separates lower floor's feed liquid, be evaporated under reduced pressure out micro in material Water, obtain faint yellow thick liquid phenyl-phosphonic acid two (1,3- bis- chloro- 2- propyl) ester, yield 94.1%, decomposition temperature:278 ± 5 DEG C, index of refraction:nD 20=1.6659, density (20 DEG C):1.420±0.005g/cm3
Embodiment 3 displaces the air in kettle with nitrogen in the 100mL four-hole boiling flasks equipped with fractionating device, adds in 10.7g (0.05mol) phenyl-phosphonic acid diethylester, 0.1g anhydrous magnesium chlorides, bis- chloro- 2- propyl alcohol of 12.9g (0.1mol) 1,3-, heating To 150 DEG C, fractionation reaction 6h, not higher than 78.5 DEG C, the methanol until fractionating out stops control fractionation column top temperature up to theoretical amount Reaction, vacuum distillation remove a small amount of low boilers, add in the water of 45mL, under stirring, adjusted with 5% sodium carbonate liquor into Property, stratification separate lower floor's feed liquid, are evaporated under reduced pressure out water micro in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (1,3- bis- chloro- 2- propyl) ester, yield 88.1%, decomposition temperature:278 ± 5 DEG C, index of refraction:nD 20=1.6659, density (20 ℃):1.420±0.005g/cm3
Embodiment 4 displaces the air in kettle with nitrogen in the 100mL four-hole boiling flasks equipped with fractionating device, adds in 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous zinc chlorides, 15.48g (0.12mol) 2,3- dichlorohydrins are warming up to 110 DEG C, fractionation reaction 8h, not higher than 65 DEG C, the methanol until fractionating out stops anti-control fractionation column top temperature up to theoretical amount Should, vacuum distillation removes excessive 2,3- dichlorohydrins (recycling uses) and a small amount of low boilers, adds in the water of 45mL, stirring Under, it is adjusted with 5% sodium carbonate liquor to neutrality, stratification, separates lower floor's feed liquid, be evaporated under reduced pressure out micro in material Water obtains faint yellow thick liquid phenyl-phosphonic acid two (2,3- bis- chloropropyl) ester, yield 90.4%, decomposition temperature:287 ± 5 DEG C, Index of refraction:nD 20=1.6675, density (20 DEG C):1.424±0.005g/cm3
Embodiment 5 displaces the air in kettle with nitrogen in the 100mL four-hole boiling flasks equipped with fractionating device, adds in 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous Aluminum chlorides, 16.77g (0.13mol) 2,3- dichlorohydrins are warming up to 120 DEG C, fractionation reaction 8h, not higher than 65 DEG C, the methanol until fractionating out stops anti-control fractionation column top temperature up to theoretical amount Should, vacuum distillation removes excessive 2,3- dichlorohydrins (recycling uses) and a small amount of low boilers, adds in the water of 45mL, stirring Under, it is adjusted with 5% sodium carbonate liquor to neutrality, stratification, separates lower floor's feed liquid, be evaporated under reduced pressure out micro in material Water obtains faint yellow thick liquid phenyl-phosphonic acid two (2,3- bis- chloropropyl) ester, yield 92.4%, decomposition temperature:287 ± 5 DEG C, Index of refraction:nD 20=1.6675, density (20 DEG C):1.424±0.005g/cm3
Embodiment 6 displaces the air in kettle with nitrogen in the 100mL four-hole boiling flasks equipped with fractionating device, adds in 12.1g (0.05mol) phenyl-phosphonic acid diisopropyl ester, 0.1g anhydrous zinc chlorides, 15.48g (0.12mol) 2,3- dichlorohydrins rise Temperature is to 110 DEG C, fractionation reaction 8h, and not higher than 82.5 DEG C, the methanol until fractionating out stops control fractionation column top temperature up to theoretical amount It only reacts, vacuum distillation removes excessive 2,3- dichlorohydrins (recycling uses) and a small amount of low boilers, adds in the water of 45mL, stirs It mixes down, is adjusted with 5% sodium carbonate liquor to neutrality, stratification, separate lower floor's feed liquid, be evaporated under reduced pressure out micro in material Water obtains faint yellow thick liquid phenyl-phosphonic acid two (2,3- bis- chloropropyl) ester, yield 90.4%, decomposition temperature:287 ± 5 DEG C, Index of refraction:nD 20=1.6675, density (20 DEG C):1.424±0.005g/cm3
Embodiment 7 displaces the air in kettle with nitrogen in the 100mL four-hole boiling flasks equipped with fractionating device, adds in 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.2g anhydrous magnesium chlorides, bis- bromo- 2- propyl alcohol of 23.98g (0.11mol) 1,3- rise Temperature is to 120 DEG C, fractionation reaction 7h, and not higher than 65 DEG C, the methanol until fractionating out stops control fractionation column top temperature up to theoretical amount Reaction, vacuum distillation remove excessive 1,3-, bis- bromo- 2- propyl alcohol (recycling uses) and a small amount of low boilers, add in the water of 60mL, It under stirring, is adjusted with 5% sodium carbonate liquor to neutrality, stratification, separates lower floor's feed liquid, be evaporated under reduced pressure out micro in material Water, obtain faint yellow thick liquid phenyl-phosphonic acid two (1,3- bis- bromo- 2- propyl) ester, yield 91.8%, decomposition temperature:279 ± 5 DEG C, index of refraction:nD 20=1.5783, density (20 DEG C):2.201±0.005g/cm3
Embodiment 8 displaces the air in kettle with nitrogen in the 100mL four-hole boiling flasks equipped with fractionating device, adds in 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous calcium chlorides, 22.89g (0.105mol) 2,3- dibromo-propanols, heating To 130 DEG C, fractionation reaction 6h, not higher than 65 DEG C, the methanol until fractionating out stops anti-control fractionation column top temperature up to theoretical amount Should, vacuum distillation removes excessive 2,3- dibromo-propanols (recycling uses) and a small amount of low boilers, adds in the water of 60mL, stirring Under, it is adjusted with 5% sodium carbonate liquor to neutrality, stratification, separates lower floor's feed liquid, be evaporated under reduced pressure out micro in material Water obtains faint yellow thick liquid phenyl-phosphonic acid two (2,3- dibromopropyl) ester, yield 91.2%, decomposition temperature:286 ± 5 DEG C, Index of refraction:nD 20=1.5792, density (20 DEG C):2.208±0.005g/cm3
Embodiment 9 equipped with blender, thermometer, high performance reflux condenser and is being connected to the anti-of drying tube condenser pipe is suitable for reading It answers in device, nitrogen displaces air, adds in 9.75g (0.05mol) phenyl phosphonyl chloride, 60mL dichloroethanes, under stirring, liquid level Lower dropwise addition 10.64g (0.115mol) epoxychloropropane is no more than 70 DEG C, after dripping off, heating with rate of addition controlling reaction temperature To 80 DEG C of insulation reaction 5h, vacuum distillation removes dichloroethanes (recycling uses), excessive epoxychloropropane (recycling uses) And a small amount of low boilers, the water of 45mL is added in, under stirring, is adjusted with 5% sodium carbonate liquor to neutrality, stratification separates Lower floor's feed liquid is evaporated under reduced pressure out water micro in material, obtains faint yellow thick liquid phenyl-phosphonic acid two (two chloropropyls) ester, yield It is 94.3%, decomposition temperature:287 ± 5 DEG C, index of refraction:nD 20=1.6675, density (20 DEG C):1.424±0.005g/cm3.It is red External spectrum figure is shown in Figure of description 1, and nuclear magnetic spectrogram is shown in Figure of description 2.
Embodiment 10 is equipped with blender, thermometer, high performance reflux condenser and in the condenser pipe drying tube suitable for reading that is connected to In reactor, nitrogen displaces air, adds in 9.75g (0.05mol) phenyl phosphonyl chloride, 60mL dioxane, under stirring, liquid 10.18g (0.11mol) epoxychloropropane is added dropwise under face, is no more than 70 DEG C, after dripping off with rate of addition controlling reaction temperature, rises After temperature to 90 DEG C of insulation reaction 5h, vacuum distillation removes dioxane (recycling uses), (recycling makes the epoxychloropropane of excess With) and a small amount of low boilers, the water of 45mL is added in, under stirring, is adjusted with 5% sodium carbonate liquor to neutrality, stratification, point Go out lower floor's feed liquid, be evaporated under reduced pressure out water micro in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (two chloropropyls) ester, receive Rate is 92.5%, decomposition temperature:287 ± 5 DEG C, index of refraction:nD 20=1.6675, density (20 DEG C):1.424±0.005g/cm3。 Infrared spectrogram is shown in Figure of description 1, and nuclear magnetic spectrogram is shown in Figure of description 2.
Embodiment 11 is equipped with blender, thermometer, high performance reflux condenser and in the condenser pipe drying tube suitable for reading that is connected to In reactor, nitrogen displaces air, adds in 14.2g (0.05mol) phenyl phosphonic dibromo, 60mL dioxane, under stirring, liquid 16.44g (0.12mol) epoxy bromopropane is added dropwise under face, is no more than 70 DEG C, after dripping off with rate of addition controlling reaction temperature, rises After temperature to 90 DEG C of insulation reaction 4h, vacuum distillation removes dioxane (recycling uses), (recycling makes the epoxy bromopropane of excess With) and a small amount of low boilers, the water of 60mL is added in, under stirring, is adjusted with 5% sodium carbonate liquor to neutrality, stratification, point Go out lower floor's feed liquid, be evaporated under reduced pressure out water micro in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (dibromopropyl) ester, receive Rate is 95.4%, decomposition temperature:284 ± 5 DEG C, index of refraction:nD 20=1.5787, density (20 DEG C):2.205±0.005g/cm3
Embodiment 12 is equipped with blender, thermometer, high performance reflux condenser and in the condenser pipe drying tube suitable for reading that is connected to In reactor, nitrogen displaces air, adds in 14.2g (0.05mol) phenyl phosphonic dibromo, 60mL dioxane, under stirring, liquid 15.07g (0.11mol) epoxy bromopropane is added dropwise under face, is no more than 70 DEG C, after dripping off with rate of addition controlling reaction temperature, rises After temperature to 100 DEG C of insulation reaction 4h, vacuum distillation removes dioxane (recycling uses), (recycling makes the epoxy bromopropane of excess With) and a small amount of low boilers, the water of 60mL is added in, under stirring, is adjusted with 5% sodium carbonate liquor to neutrality, stratification, point Go out lower floor's feed liquid, be evaporated under reduced pressure out water micro in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (dibromopropyl) ester, receive Rate is 94.1%, decomposition temperature:284 ± 5 DEG C, index of refraction:nD 20=1.5787, density (20 DEG C):2.205±0.005g/cm3
1 preparation example main technologic parameters of table
Since phenyl-phosphonic acid two of the present invention (dihalo- propyl) ester is very similar isomers, flame retardant property is essentially identical, It is not listed one by one using data, chloro ester only lists the product that epoxychloropropane is prepared with phenyl phosphonyl chloride, brominated esters The product that 2,3- dibromo-propanols are prepared with phenyl-phosphonic acid dimethyl ester is only listed, as examples representative, has carried out application effect Expression.
Phenyl-phosphonic acid two (dihalo- propyl) ester of above-mentioned preparation is applied in polyvinyl chloride by inventor.Reference:GB/ T2406-2008《Plastics Combustion method for testing performance-oxygen index method》The limit oxygen index of sample.Take product fire retardant phenyl Phosphonic acids two (dihalo- propyl) ester, plasticizer phthalic acid dioctyl ester, synergistic flame retardant antimony oxide and polyvinyl chloride be not with In proportion after mixing, it is squeezed out with extruder, the batten of a diameter of 3mm is made, and its flame retardant property is tested, arranged Part test result is gone out as shown in table 2 and table 3:
Table 2 phenyl-phosphonic acid two (two chloropropyls) ester is used for the flame retardant property data of PVC
Table 2 shows phenyl-phosphonic acid two (two chloropropyls) ester for PVC, and when additive amount 20%, limit oxygen index is reachable 29%, illustrate that it has preferable flame retardant property.
Table 3 phenyl-phosphonic acid two (dibromopropyl) ester is used for the flame retardant property data of PVC
Table 3 shows phenyl-phosphonic acid two (dibromopropyl) ester for PVC, and when additive amount 20%, limit oxygen index is reachable 30%, illustrate that it has preferable flame retardant property.

Claims (4)

1. a kind of preparation method of phenyl-phosphonic acid two (dihalo- propyl) ester compounds, which is characterized in that this method is:Equipped with point In the reactor of distillation unit, the air in kettle is displaced with nitrogen, add in phenyl-phosphonic acid diester, catalyst, certain mol proportion Halohydrin is warming up to 110-150 DEG C, and fractionation reaction 6-8h, control is fractionated boiling temperature of the column top temperature in distributed alcohol, directly To the alcohol fractionated out up to theoretical amount, stop reaction, vacuum distillation removes excessive halohydrin and a small amount of low boilers, adds in product The water of 2-3 times of Theoretical Mass under stirring, is adjusted to neutrality, stratification with 5% sodium carbonate liquor, separates lower floor's feed liquid, subtract Pressure distills out water micro in material, obtains faint yellow thick liquid phenyl-phosphonic acid two (dihalo- propyl) ester, the structure of the compound It is shown below:
C in formula3H5X2For CH2CHClCH2Cl、CH(CH2Cl)2、CH2CHBrCH2Br、CH(CH2Br)2
2. a kind of preparation method of phenyl-phosphonic acid two (dihalo- propyl) ester compounds as described in claim 1, it is characterised in that:Institute The phenyl-phosphonic acid diester stated is phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethylester or phenyl-phosphonic acid diisopropyl ester.
3. a kind of preparation method of phenyl-phosphonic acid two (dihalo- propyl) ester compounds as described in claim 1, it is characterised in that:Institute The halohydrin for the certain mol proportion stated is 1,3-, bis- chloro- 2- propyl alcohol, 2,3- dichlorohydrins, 1,3-, bis- bromo- 2- propyl alcohol, 2,3- dibromos Propyl alcohol, molar ratio are phenyl-phosphonic acid dimethyl ester: halohydrin=1: 2-1: 3.
4. a kind of preparation method of phenyl-phosphonic acid two (dihalo- propyl) ester compounds as described in claim 1, it is characterised in that:Institute The catalyst stated is calcium chloride, zinc chloride, aluminium chloride or magnesium chloride, and dosage is the 1%-2% of phenyl-phosphonic acid dimethyl ester quality.
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