CN105713040A - Bis(dihalidepropyl) phenylphosphonate compound and preparation method thereof - Google Patents

Bis(dihalidepropyl) phenylphosphonate compound and preparation method thereof Download PDF

Info

Publication number
CN105713040A
CN105713040A CN201610037029.6A CN201610037029A CN105713040A CN 105713040 A CN105713040 A CN 105713040A CN 201610037029 A CN201610037029 A CN 201610037029A CN 105713040 A CN105713040 A CN 105713040A
Authority
CN
China
Prior art keywords
phenyl
phosphonic acid
dihalo
propyl group
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610037029.6A
Other languages
Chinese (zh)
Other versions
CN105713040B (en
Inventor
韩志慧
俞春雷
卫唯
董荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University of Science and Technology
Original Assignee
Suzhou University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University of Science and Technology filed Critical Suzhou University of Science and Technology
Priority to CN201610037029.6A priority Critical patent/CN105713040B/en
Publication of CN105713040A publication Critical patent/CN105713040A/en
Application granted granted Critical
Publication of CN105713040B publication Critical patent/CN105713040B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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 invention relates to bis(dihalidepropyl) phenylphosphonate compound and a preparation method thereof. This compound has a structure shown as in the following formula, wherein C3H5X2 is CH2CHClCH2Cl, CH(CH2Cl)2, CH2CHBrCH2Br, CH(CH2Br)2. The preparation method comprises: subjecting diphenyl phosphate and halogenated alcohol to transesterification in the presence of a catalyst or subjecting phenyl phosphonyl dihalide and epoxy halide propane to additive etherification in an organic solvent, and purifying to obtain light yellow thick liquid, the bis(dihalidepropyl) phenylphosphonate. This compound of the invention contains two flame-retardant elements, phosphorus and halogen, is high in halogen level, has good synergic flame-retardant effect, has good plasticity and is useful as a flame-retardant plasticizer for materials such as PVC (polyvinyl chloride), polyurethane, epoxy resin, and unsaturated resin; the preparation method is simple and free of hydrogen chloride pollution, is low in equipment investment and easy for large-scale production.

Description

Phenyl-phosphonic acid two (dihalo-propyl group) ester compounds and preparation method thereof
Technical field
The present invention relates to a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds and preparation method thereof, this compound contains phosphorus, two kinds of ignition-proof elements of halogen, cooperative flame retardant is effective, is suitable as the flame-retardant plasticizer of the materials such as PVC, polyurethane, epoxy resin, unsaturated-resin.
Background technology
Along with China synthesizes the fast development of Macromolecular materials industry, macromolecular material is widely used in every field such as building materials, electronic apparatus, transportation, space flight and aviation, household furniture, interior decoration and clothing, food, lodging and transportion--basic necessities of life.Mostly having inflammability due to it, often cause fire, serious harm is to people's safety of life and property, thus has promoted the research of fire retardant and the application of fire proofing.The production of China's fire retardant and consumption mainly halogen system product, but after sending RoHS instruction from European Union in 1986, PBDE has been first subjected to query, subsequently the application of broad sense halogenated flame retardant is all created negative effect, halogenated flame retardant is had higher requirement simultaneously, exploitation high-efficiency low-toxicity halogenated flame retardant has become important research topic, wherein effective method by the composite raising flame-retarded efficiency of multiple fire retardant, and collaborative by design multielement in molecule be also the approach obtaining efficient flame-retarding agent.
The invention discloses a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds and preparation method thereof, this compound contains phosphorus, two kinds of ignition-proof elements of halogen, and cooperative flame retardant is effective, and aromatic ring and the many ester structures in molecule can increase the compatibility with base material, plasticity is good, halogen amount is high, is the flame-retardant plasticizer that a kind of comprehensive cost performance is excellent, and technique is simple, easy to operate, equipment investment is few, environmental friendliness, has good application and development prospect.
Summary of the invention
An object of the present invention is in that to propose a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds, and this compound contains phosphorus, two kinds of ignition-proof elements of halogen, and its cooperative flame retardant usefulness is high, can effectively overcome the deficiency in existing flame-retarded technology.
For achieving the above object, present invention employs following technical scheme:
A kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds, it is characterised in that the structure of this compound is shown below:
Wherein C3H5X2For CH2CHClCH2Cl、CH(CH2Cl)2、CH2CHBrCH2Br、CH(CH2Br)2
Another object of the present invention is to the preparation method proposing a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester, its technique is simple, be prone to large-scale production, and the method is:
Equipped with in the reactor of fractionating device, the air in still is displaced with nitrogen, add phenyl-phosphonic acid diester, catalyst, the halohydrin of certain mol proportion, it is warming up to 110-150 DEG C, fractional distillation reaction 6-8h, control the fractional distillation column top temperature boiling temperature at separated alcohol, until the alcohol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off excessive halohydrin (reclaim and use) and a small amount of low boilers, purified process, obtains faint yellow thick liquid phenyl-phosphonic acid two (dihalo-propyl group) ester.
The method can be also:
Equipped with agitator, thermometer, high performance reflux condenser in the condensing tube reactor being connected to drying tube suitable for reading, nitrogen displaces air, add phenyl phosphonic dihalo-, organic solvent, under stirring, the epoxyhalopropane of certain mol proportion is dripped under liquid level, reaction temperature is controlled less than 70 DEG C with rate of addition, after dripping off, after being warming up to 80-100 DEG C of insulation reaction 4-5h, decompression is distilled off organic solvent (reclaim and use), excessive epoxyhalopropane (reclaim and use) and a small amount of low boilers, purified process, obtain faint yellow thick liquid phenyl-phosphonic acid two (dihalo-propyl group) ester.
Phenyl-phosphonic acid diester as above is phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethylester or phenyl-phosphonic acid diisopropyl ester.
The halohydrin of certain mol proportion as above is 1,3-bis-chloro-2-propanol, 2,3-dichlorohydrins, 1,3-bis-bromo-2-propanol, 2,3-dibromo-propanols, and its mol ratio is phenyl-phosphonic acid dimethyl ester: halohydrin=1: 2-1: 3.
Catalyst as above is calcium chloride, zinc chloride, aluminum chloride or magnesium chloride, and its consumption is the 1%-2% of phenyl-phosphonic acid dimethyl ester quality.
Phenyl phosphonic dihalo-as above is phenyl phosphonyl chloride or phenyl phosphonic dibromo.
Epoxyhalopropane as above is epoxychloropropane or epoxy bromopropane.
Organic solvent as above is dichloroethanes or dioxane, and its consumption volume milliliter number is 2-4 times of theoretical product quality grams.
The epoxyhalopropane of certain mol proportion as above is phenyl phosphonic dihalo-: epoxyhalopropane=1: 2-1: 2.5.
Purification process as above is add the water of product Theoretical Mass 2-3 times, under stirring, adjusts to neutrality, stratification with the sodium carbonate liquor of 5%, separates lower floor's feed liquid, and decompression distills out the water of trace in material.
Phenyl-phosphonic acid two (dihalo-propyl group) ester of the present invention is faint yellow thick liquid, and productivity is 88.1%-95.4%, and it is suitable as the use of flame-retardant plasticizer of the materials such as PVC, polyurethane, epoxy resin, unsaturated-resin.
The preparation technology principle of phenyl-phosphonic acid two (dihalo-propyl group) ester is shown below:
Wherein X is Cl or Br.
Compared with prior art, the innovation of the present invention is in that:
1. the structure of phenyl-phosphonic acid two (dihalo-propyl group) ester of the present invention has good symmetric characteristics, its physical and chemical performance is stable, aromatic ring in molecule and ester structure can increase the compatibility of product and base material, plasticity is good, can using by Substitute For Partial plasticizer, good processability, product is phosphorous, two kinds of ignition-proof elements of halogen, and halogen amount is high, fire resistance is good.
2. preparation method productivity of the present invention is high, it does not have hydrogen chloride pollutes, and equipment is not produced corrosivity.
3. preparation method phenyl phosphonic dihalo-of the present invention and epoxyhalopropane opening, it does not have the contracting of any little molecule is gone, atom utilization 100% belongs to green chemistry process.
4. preparation method technique of the present invention is simple, and cheaper starting materials is easy to get, and equipment investment is few, it is easy to large-scale production.
Accompanying drawing explanation
Structure and performance spy in order to further illustrate product are given as accompanying drawing.
Fig. 1 is the infrared spectrogram of phenyl-phosphonic acid two (two chloropropyls) ester;Fig. 1 shows: 695.0cm-1Place is the stretching vibration peak of C-Cl key;1056.3cm-1Place is the stretching vibration peak of P-O key;1096.8cm-1Place is the stretching vibration peak of C-O key;1132.2cm-1Place is the stretching vibration peak of P=O key;1440.0cm-1Place is the skeleton stretching vibration peak of phenyl ring;2966.8cm-1Place is CH2The stretching vibration peak of upper c h bond;3062.2cm-1Place is the stretching vibration peak of 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).
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 is equipped with in the 100mL four-hole boiling flask of fractionating device, the air in still is displaced with nitrogen, add 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous magnesium chloride, 12.9g (0.1mol) 1, the chloro-2-propanol of 3-bis-, it is warming up to 150 DEG C, fractional distillation reaction 6h, control fractional distillation column top temperature not higher than 65 DEG C, until the methanol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off a small amount of low boilers, add the water of 45mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (1, the chloro-2-propyl group of 3-bis-) ester, yield is 88.1%, decomposition temperature: 278 ± 5 DEG C, index of refraction: nD 20=1.6659, density (20 DEG C): 1.420 ± 0.005g/cm3
Embodiment 2 is equipped with in the 100mL four-hole boiling flask of fractionating device, the air in still is displaced with nitrogen, add 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous magnesium chloride, 19.35g (0.15mol) 1, the chloro-2-propanol of 3-bis-, it is warming up to 140 DEG C, fractional distillation reaction 6h, control fractional distillation column top temperature not higher than 65 DEG C, until the methanol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off excessive 1, the chloro-2-propanol of 3-bis-(reclaims and uses) and a small amount of low boilers, add the water of 45mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (1, the chloro-2-propyl group of 3-bis-) ester, yield is 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 is equipped with in the 100mL four-hole boiling flask of fractionating device, the air in still is displaced with nitrogen, add 10.7g (0.05mol) phenyl-phosphonic acid diethylester, 0.1g anhydrous magnesium chloride, 12.9g (0.1mol) 1, the chloro-2-propanol of 3-bis-, it is warming up to 150 DEG C, fractional distillation reaction 6h, control fractional distillation column top temperature not higher than 78.5 DEG C, until the methanol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off a small amount of low boilers, add the water of 45mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (1, the chloro-2-propyl group of 3-bis-) ester, yield is 88.1%, decomposition temperature: 278 ± 5 DEG C, index of refraction: nD 20=1.6659, density (20 DEG C): 1.420 ± 0.005g/cm3
Embodiment 4 is equipped with in the 100mL four-hole boiling flask of fractionating device, the air in still is displaced with nitrogen, add 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous zinc chloride, 15.48g (0.12mol) 2, 3-dichlorohydrin, it is warming up to 110 DEG C, fractional distillation reaction 8h, control fractional distillation column top temperature not higher than 65 DEG C, until the methanol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off excessive 2, 3-dichlorohydrin (reclaims and uses) and a small amount of low boilers, add the water of 45mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (2, 3-bis-chloropropyl) ester, yield is 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 is equipped with in the 100mL four-hole boiling flask of fractionating device, the air in still is displaced with nitrogen, add 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous Aluminum chloride, 16.77g (0.13mol) 2, 3-dichlorohydrin, it is warming up to 120 DEG C, fractional distillation reaction 8h, control fractional distillation column top temperature not higher than 65 DEG C, until the methanol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off excessive 2, 3-dichlorohydrin (reclaims and uses) and a small amount of low boilers, add the water of 45mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (2, 3-bis-chloropropyl) ester, yield is 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 is equipped with in the 100mL four-hole boiling flask of fractionating device, the air in still is displaced with nitrogen, add 12.1g (0.05mol) phenyl-phosphonic acid diisopropyl ester, 0.1g anhydrous zinc chloride, 15.48g (0.12mol) 2, 3-dichlorohydrin, it is warming up to 110 DEG C, fractional distillation reaction 8h, control fractional distillation column top temperature not higher than 82.5 DEG C, until the methanol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off excessive 2, 3-dichlorohydrin (reclaims and uses) and a small amount of low boilers, add the water of 45mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (2, 3-bis-chloropropyl) ester, yield is 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 is equipped with in the 100mL four-hole boiling flask of fractionating device, the air in still is displaced with nitrogen, add 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.2g anhydrous magnesium chloride, 23.98g (0.11mol) 1, the bromo-2-propanol of 3-bis-, it is warming up to 120 DEG C, fractional distillation reaction 7h, control fractional distillation column top temperature not higher than 65 DEG C, until the methanol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off excessive 1, the bromo-2-propanol of 3-bis-(reclaims and uses) and a small amount of low boilers, add the water of 60mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (1, the bromo-2-propyl group of 3-bis-) ester, yield is 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 is equipped with in the 100mL four-hole boiling flask of fractionating device, the air in still is displaced with nitrogen, add 9.3g (0.05mol) phenyl-phosphonic acid dimethyl ester, 0.1g anhydrous calcium chloride, 22.89g (0.105mol) 2, 3-dibromo-propanol, it is warming up to 130 DEG C, fractional distillation reaction 6h, control fractional distillation column top temperature not higher than 65 DEG C, until the methanol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off excessive 2, 3-dibromo-propanol (reclaims and uses) and a small amount of low boilers, add the water of 60mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (2, 3-dibromopropyl) ester, yield is 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 is equipped with agitator, thermometer, high performance reflux condenser in the condensing tube reactor being connected to drying tube suitable for reading, nitrogen displaces air, add 9.75g (0.05mol) phenyl phosphonyl chloride, 60mL dichloroethanes, under stirring, 10.64g (0.115mol) epoxychloropropane is dripped under liquid level, reaction temperature is controlled less than 70 DEG C with rate of addition, after dripping off, after being warming up to 80 DEG C of insulation reaction 5h, decompression is distilled off dichloroethanes (reclaim and use), excessive epoxychloropropane (reclaim and use) and a small amount of low boilers, add the water of 45mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (two chloropropyls) ester, yield 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.Infrared spectrogram is shown in Figure of description 1, and nuclear magnetic spectrogram is shown in Figure of description 2.
Embodiment 10 is equipped with agitator, thermometer, high performance reflux condenser in the condensing tube reactor being connected to drying tube suitable for reading, nitrogen displaces air, add 9.75g (0.05mol) phenyl phosphonyl chloride, 60mL dioxane, under stirring, 10.18g (0.11mol) epoxychloropropane is dripped under liquid level, reaction temperature is controlled less than 70 DEG C with rate of addition, after dripping off, after being warming up to 90 DEG C of insulation reaction 5h, decompression is distilled off dioxane (reclaim and use), excessive epoxychloropropane (reclaim and use) and a small amount of low boilers, add the water of 45mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (two chloropropyls) ester, yield 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 agitator, thermometer, high performance reflux condenser in the condensing tube reactor being connected to drying tube suitable for reading, nitrogen displaces air, add 14.2g (0.05mol) phenyl phosphonic dibromo, 60mL dioxane, under stirring, 16.44g (0.12mol) epoxy bromopropane is dripped under liquid level, reaction temperature is controlled less than 70 DEG C with rate of addition, after dripping off, after being warming up to 90 DEG C of insulation reaction 4h, decompression is distilled off dioxane (reclaim and use), excessive epoxy bromopropane (reclaim and use) and a small amount of low boilers, add the water of 60mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (dibromopropyl) ester, yield 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 agitator, thermometer, high performance reflux condenser in the condensing tube reactor being connected to drying tube suitable for reading, nitrogen displaces air, add 14.2g (0.05mol) phenyl phosphonic dibromo, 60mL dioxane, under stirring, 15.07g (0.11mol) epoxy bromopropane is dripped under liquid level, reaction temperature is controlled less than 70 DEG C with rate of addition, after dripping off, after being warming up to 100 DEG C of insulation reaction 4h, decompression is distilled off dioxane (reclaim and use), excessive epoxy bromopropane (reclaim and use) and a small amount of low boilers, add the water of 60mL, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separate lower floor's feed liquid, decompression distills out the water of trace in material, obtain faint yellow thick liquid phenyl-phosphonic acid two (dibromopropyl) ester, yield 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
Example main technologic parameters prepared by table 1
Owing to phenyl-phosphonic acid two (dihalo-propyl group) ester of the present invention is very close isomer, its fire resistance is essentially identical, application data is not listed one by one, chloro ester only lists the product that epoxychloropropane is prepared with phenyl phosphonyl chloride, brominated esters only lists 2, product prepared by 3-dibromo-propanol and phenyl-phosphonic acid dimethyl ester, as examples representative, has carried out the expression of application effect.
Phenyl-phosphonic acid two (dihalo-propyl group) ester of above-mentioned preparation is applied in polrvinyl chloride by inventor.The limited oxygen index of reference: GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index method " test sample product.After taking product fire retardant phenyl-phosphonic acid two (dihalo-propyl group) ester, plasticizer phthalic acid dioctyl ester, synergistic flame retardant antimony oxide and polrvinyl chloride mix homogeneously in varing proportions, extrude with extruder, make the batten that diameter is 3mm, and its fire resistance is tested, list shown in part test result such as table 2 and table 3:
Table 2 phenyl-phosphonic acid two (two chloropropyls) ester is for the fire resistance data of PVC
Table 2 shows that phenyl-phosphonic acid two (two chloropropyls) ester is for PVC, and when addition 20%, limited oxygen index, up to 29%, illustrates that it has good fire resistance.
Table 3 phenyl-phosphonic acid two (dibromopropyl) ester is for the fire resistance data of PVC
Table 3 shows that phenyl-phosphonic acid two (dibromopropyl) ester is for PVC, and when addition 20%, limited oxygen index, up to 30%, illustrates that it has good fire resistance.

Claims (10)

1. phenyl-phosphonic acid two (dihalo-propyl group) ester compounds, it is characterised in that the structure of this compound is shown below:
Wherein C3H5X2For CH2CHClCH2Cl、CH(CH2Cl)2、CH2CHBrCH2Br、CH(CH2Br)2
2. the preparation method of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds, it is characterized in that, the method is: equipped with in the reactor of fractionating device, the air in still is displaced with nitrogen, add phenyl-phosphonic acid diester, catalyst, the halohydrin of certain mol proportion, it is warming up to 110-150 DEG C, fractional distillation reaction 6-8h, control the fractional distillation column top temperature boiling temperature at distributed alcohol, until the alcohol fractionated out reaches theoretical amount, stopped reaction, decompression is distilled off excessive halohydrin and a small amount of low boilers, purified process, obtain faint yellow thick liquid phenyl-phosphonic acid two (dihalo-propyl group) ester.
3. the preparation method of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds, it is characterized in that, the method is: equipped with agitator, thermometer, high performance reflux condenser in the condensing tube reactor being connected to drying tube suitable for reading, nitrogen displaces air, add phenyl phosphonic dihalo-, organic solvent, under stirring, the epoxyhalopropane relative to phenyl phosphonic dihalo-2-2.5 times mole is dripped under liquid level, reaction temperature is controlled less than 70 DEG C with rate of addition, after dripping off, after being warming up to 80-100 DEG C of insulation reaction 4-5h, decompression is distilled off organic solvent, excessive epoxyhalopropane and a small amount of low boilers, purified process, obtain faint yellow thick liquid phenyl-phosphonic acid two (dihalo-propyl group) ester.
4. the preparation method of a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds as claimed in claim 2, it is characterised in that: described phenyl-phosphonic acid diester is phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethylester or phenyl-phosphonic acid diisopropyl ester.
5. the preparation method of a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds as claimed in claim 2, it is characterized in that: the halohydrin of described certain mol proportion is 1, the chloro-2-propanol of 3-bis-, 2,3-dichlorohydrin, 1, the bromo-2-propanol of 3-bis-, 2,3-dibromo-propanol, its mol ratio is phenyl-phosphonic acid dimethyl ester: halohydrin=1: 2-1: 3.
6. the preparation method of a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds as claimed in claim 2, it is characterized in that: described catalyst is calcium chloride, zinc chloride, aluminum chloride or magnesium chloride, its consumption is the 1%-2% of phenyl-phosphonic acid dimethyl ester quality.
7. the preparation method of a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds as claimed in claim 3, it is characterised in that: described phenyl phosphonic dihalo-is phenyl phosphonyl chloride or phenyl phosphonic dibromo.
8. the preparation method of a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds as claimed in claim 3, it is characterised in that: described epoxyhalopropane is epoxychloropropane or epoxy bromopropane.
9. the preparation method of a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds as claimed in claim 3, it is characterised in that: described organic solvent is dichloroethanes or dioxane, and its consumption volume milliliter number is 2-4 times of theoretical product quality grams.
10. the preparation method of a kind of phenyl-phosphonic acid two (dihalo-propyl group) ester compounds as described in Claims 2 or 3, it is characterized in that: described purification process is add the water of product Theoretical Mass 2-3 times, under stirring, adjust to neutrality with the sodium carbonate liquor of 5%, stratification, separating lower floor's feed liquid, decompression distills out the water of trace in material.
CN201610037029.6A 2016-01-19 2016-01-19 Phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof Active CN105713040B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610037029.6A CN105713040B (en) 2016-01-19 2016-01-19 Phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610037029.6A CN105713040B (en) 2016-01-19 2016-01-19 Phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105713040A true CN105713040A (en) 2016-06-29
CN105713040B CN105713040B (en) 2018-06-22

Family

ID=56147500

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610037029.6A Active CN105713040B (en) 2016-01-19 2016-01-19 Phenyl-phosphonic acid two (dihalo- propyl) ester compounds and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105713040B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106785042A (en) * 2017-01-03 2017-05-31 华南师范大学 A kind of high thermal stability carbonic ester electrolyte and preparation method and application
CN109400653A (en) * 2018-10-23 2019-03-01 苏州科技大学 Two silicon cage alcohol ester compounds of organic silicon-phosphorus fire retardant phenyl-phosphonic acid and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49131234A (en) * 1973-04-21 1974-12-16
US3929688A (en) * 1972-04-07 1975-12-30 Stauffer Chemical Co Bis(2,3-dibromopropyl)phosphate as a flame retardant for polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929688A (en) * 1972-04-07 1975-12-30 Stauffer Chemical Co Bis(2,3-dibromopropyl)phosphate as a flame retardant for polymers
JPS49131234A (en) * 1973-04-21 1974-12-16

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A.A.BREDIKHIN.ET AL: ""Reaction of Dichlorophosphines with Glycidol.New Date on the Transformations of Cyclic Phosphonates"", 《RUSSIAN JOURNAL OF GENERAL CHEMISTRY》 *
G.C.CORFIELD ET AL: ""Determination of Ring Size in Cyclopolymers from Divinyl Phosphonates"", 《JOURNAL OF MACROMOLECULAR SCIENCE: PART A – CHEMISTRY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106785042A (en) * 2017-01-03 2017-05-31 华南师范大学 A kind of high thermal stability carbonic ester electrolyte and preparation method and application
CN106785042B (en) * 2017-01-03 2019-05-10 华南师范大学 A kind of high thermal stability carbonic ester electrolyte and the preparation method and application thereof
CN109400653A (en) * 2018-10-23 2019-03-01 苏州科技大学 Two silicon cage alcohol ester compounds of organic silicon-phosphorus fire retardant phenyl-phosphonic acid and preparation method thereof

Also Published As

Publication number Publication date
CN105713040B (en) 2018-06-22

Similar Documents

Publication Publication Date Title
CN102731825B (en) Chloro- and bromo-containing silicate flame retardant compound and preparation method thereof
CN102898450A (en) Novel chlorine and bromine-containing bisilicate fire retardant compound and preparation method thereof
CN102140115B (en) Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof
CN105713040A (en) Bis(dihalidepropyl) phenylphosphonate compound and preparation method thereof
CN103554154B (en) Fire retardant match gram three silicic acid dichloro propyl ester compounds and preparation method thereof
CN105541912B (en) Three element cooperative flame retardant plasticizer compounds of phosphorus sulphur halogen and preparation method thereof
CN105601669B (en) Esterified compound of phenyl-phosphonic acid dihalo- and preparation method thereof
CN105541911B (en) Phenylphosphonothioic acid two (haloethyl) ester compounds and preparation method thereof
CN106478727B (en) Fire retardant Phenylmethoxy silicic acid disulfide group phospha trioxa-l-phosphabicyclo octyl methyl compound and preparation method thereof
CN105713039B (en) A kind of arylphosphonic acid ester compounds and preparation method thereof
CN104650132B (en) Fire retardant dimethyl silicic acid -2,4-PD ester compounds and preparation method thereof
CN105566387B (en) Multielement synergistic fire retardant phenylphosphonothioic acid ester compounds and preparation method thereof
CN104693228A (en) Flame retardant dibenzyl dimethylsilicate compound and preparation method thereof
CN103554149B (en) Three [2-tri-(1,3-dibromo isopropoxy) silicon trimethylammonium] isocyanurate compounds and preparation method thereof
CN102140112B (en) Halogenated organic silicate ester flame-retardant plasticizer compound and preparation method thereof
CN104004020B (en) Fire-retardant carbon forming agent trimethyl silicic acid PEPA ester compounds of caged and preparation method thereof
CN102731546B (en) Flame retardant trichloroethyltribromophenoxychloropropylsilicate ester compound and preparation method thereof
CN104744504B (en) A kind of silicon, nitrogen, the preparation method of halogen multielement cooperative flame retardant immunomodulator compounds
CN103333193B (en) Flame retardant silicic acid di-(tribromophenyl) dichlorohydrin compound and preparation method thereof
CN103554158B (en) Fire retardant two [three (the bromo-2-propoxy-of 1,3-bis-) silicon acyloxy] ethane compounds and preparation method thereof
CN103554163B (en) Fire retardant two [three (chlorine propoxy-) silicon acyloxy] ethane compounds and preparation method thereof
CN103554159B (en) Two silicic acid dibromo propyl ester compound of fire retardant second dioxy support and preparation method thereof
CN103554161B (en) Fire retardant two [three (2,3-compound) silicon acyloxy] ethane compounds and preparation method thereof
CN102731551B (en) Novel silicon-halogen synergistic fire retardant plasticizer compound and preparation method thereof
CN104710451B (en) Fire retardant dimethyl silicic acid neopentyl glycol ester compound and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 215009, CREE campus, 1 hi tech Zone, Suzhou, Jiangsu Province, Suzhou University of science and technology

Applicant after: Suzhou University of Science and Technology

Address before: 215009 Suzhou City, Jiangsu province high tech Zone CREE Road, No. 1

Applicant before: University of Science and Technology of Suzhou

GR01 Patent grant
GR01 Patent grant