CN101941989A - Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof - Google Patents
Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof Download PDFInfo
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- CN101941989A CN101941989A CN 201010260355 CN201010260355A CN101941989A CN 101941989 A CN101941989 A CN 101941989A CN 201010260355 CN201010260355 CN 201010260355 CN 201010260355 A CN201010260355 A CN 201010260355A CN 101941989 A CN101941989 A CN 101941989A
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- Prior art keywords
- phosphite
- benzoquinone
- sherwood oil
- dialkyl
- acyl group
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 125000005499 phosphonyl group Chemical group 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003063 flame retardant Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007983 Tris buffer Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 230000002459 sustained effect Effects 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 33
- 238000004821 distillation Methods 0.000 claims description 29
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 9
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- KCRLWVVFAVLSAP-UHFFFAOYSA-N octyl dihydrogen phosphite Chemical compound CCCCCCCCOP(O)O KCRLWVVFAVLSAP-UHFFFAOYSA-N 0.000 claims description 2
- YRODAVZDENZNAE-UHFFFAOYSA-N pentyl dihydrogen phosphite Chemical compound CCCCCOP(O)O YRODAVZDENZNAE-UHFFFAOYSA-N 0.000 claims description 2
- PRAHMDIEZMWIRW-UHFFFAOYSA-N propyl dihydrogen phosphite Chemical compound CCCOP(O)O PRAHMDIEZMWIRW-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011152 fibreglass Substances 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 239000013078 crystal Substances 0.000 description 26
- 239000012065 filter cake Substances 0.000 description 26
- -1 phosphine compound Chemical class 0.000 description 15
- 239000003208 petroleum Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- ILFXTQPXQOZOBB-UHFFFAOYSA-N [H]C([H])([H])OP(O)(OC([H])([H])[H])C([H])([H])[H] Chemical class [H]C([H])([H])OP(O)(OC([H])([H])[H])C([H])([H])[H] ILFXTQPXQOZOBB-UHFFFAOYSA-N 0.000 description 7
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
Abstract
The invention relates to tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and a preparation method thereof. The structure of the compound is shown in the specification, wherein R is straight chain or branched chain alkyl containing 1-8 C atoms. The preparation method comprises the following steps: adding a certain molar ratio of chloranil and tris phosphite (P(OR)3) into an organic solvent under the heating condition for carrying out sustained reaction for a period of time, and then, purifying and drying the reactants to prepare the tetra-(0,0-dialkyl phosphonyl) p-benzoquinone. The tetra-(0,0-dialkyl phosphonyl) p-benzoquinone of the invention has high flame resistance, stable physical and chemical properties and good compatibility with high molecular materials, can be used as the flame retardant of polyester, polyamide, epoxy resin, glass reinforced plastic resin, paint and the like, is favorable for environment protection, has simple process, low equipment investment, low cost and high phosphorus content in products, and can realize scale production easily.
Description
Technical field
The present invention relates to a kind of organic phosphine compound and preparation method thereof, be specifically related to a kind of four (0,0-dialkyl phosphine acyl group) para benzoquinone and preparation method thereof, this compound can be used as the fire retardant of polyester, polymeric amide, Resins, epoxy, fiber glass resin, coating etc.
Background technology
At present, the whole world is very high to the non-halogen cry of fire retardant, because the organic phosphine fire retardant has low cigarette, low toxicity, the pollution-free favor that more is subjected to people, the exploitation of environment-friendly type organic phosphine fire retardant has been become a research focus in the flame-retarded technology field.Though have novel organic phosphine fire retardant to succeed in developing at present,, hindered its large-scale production and application owing to reasons such as technology and price and processing characteristicies.Require the fire retardant kind that adapts also more again owing to the macromolecular material kind is more, the organic phosphine fire retardant exists the property demanded urgently in market.This invention structural symmetry is good, belong to many phosphorus structure, phosphorus content height, good stability, the one-tenth charcoal is good, volatility is low, with good, the good processability of intermiscibility of material, have very much novelty, application and development prospect is preferably arranged.
Summary of the invention
One of purpose of the present invention is to propose a kind of four (0,0-dialkyl phosphine acyl group) para benzoquinone compound, its synthesis technique is simple, physical and chemical performance stable, nontoxic, flame-retarded efficiency is high, with the macromolecular material consistency good, can overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of four (0,0-dialkyl phosphine acyl group) para benzoquinone is characterized in that the structure of this compound is shown below:
R is the straight or branched alkyl that contains 1～8 C atom.
Another object of the present invention is to propose the synthetic method of a kind of four (0,0-dialkyl phosphine acyl group) para benzoquinone, its technology is simple, be convenient to control, be easy to large-scale production, and raw material is cheap and easy to get, and facility investment is few, and is with low cost, and its technical scheme is as follows:
The preparation method of four (0,0-dialkyl phosphine acyl group) para benzoquinone as mentioned above is characterized in that this method is:
Chloranil and tris phosphite (P (OR) with certain mol proportion
3), under heating condition, sustained reaction after for some time in organic solvent, to reactant purify, drying, make four (0,0-dialkyl phosphine acyl group) para benzoquinone.Wherein certain mol proportion is 1: 4～1: 8; Tris phosphite is a trimethyl phosphite, triethyl-phosphite, tricresyl phosphite propyl ester, tributyl phosphate, tricresyl phosphite pentyl ester, own ester of tricresyl phosphite or tricresyl phosphite monooctyl ester; Temperature of reaction is 60 ℃～130 ℃; Organic solvent can be a benzene, toluene, dimethylbenzene, chlorobenzene; Reaction times is 4～8h; Method of purification is for after steaming solvent (solvent recuperation utilization) with reactant, cool off preliminary crystallization and go out portioned product, add petroleum ether extraction again and go out the byproduct of reaction dialkyl alkylphosphonate, make product sufficient crystallising, filtration, dry four (0,0-dialkyl phosphine acyl group) para benzoquinone; Above-mentioned crystallization filtrated stock distillation is reclaimed sherwood oil and is obtained dialkyl alkylphosphonate.
The synthesis technique principle of this four (0,0-dialkyl phosphine acyl group) para benzoquinone is shown below:
Compared with prior art, beneficial effect of the present invention is:
1. because symmetry constitutional features, many phosphorus constitutional features of organic phosphine fire retardant four of the present invention (0,0-dialkyl phosphine acyl group) para benzoquinone, itself and macromolecular material intermiscibility are good, and can not change the mechanical property of material, flame-retarded efficiency height;
2. four (0,0-dialkyl phosphine acyl group) of the present invention para benzoquinone is not halogen-containing, helps environmental protection, so good prospects for application is arranged;
The synthesis technique of four (0,0-dialkyl phosphine acyl group) 3. of the present invention para benzoquinone is single step reaction, and is simple and easy to control, and building-up process need not to add catalyzer, need not the special reaction condition, and equipment is simple, and is with low cost, is suitable for large-scale production.
The synthesis reaction solvent of four (0,0-dialkyl phosphine acyl group) 4. of the present invention para benzoquinone is directly recycled, and the distillation of purification solvent sherwood oil is reclaimed and used, and obtains by product organic phosphine fire retardant dialkyl alkylphosphonate simultaneously.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further.
Embodiment 1 is in being equipped with the 500ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 160ml benzene, stirring makes its dissolving, be warmed up to 60 ℃, drip the 1.0mol trimethyl phosphite in 3 hours, holding temperature reaction 7h, reaction finishes the back underpressure distillation and goes out benzene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, 0-dimethyl phosphine acyl group) para benzoquinone, its productive rate is 60%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 2 is in being equipped with the 500ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 160ml toluene, stirring makes its dissolving, be warmed up to 100 ℃, drip the 0.8mol trimethyl phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out toluene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, 0-dimethyl phosphine acyl group) para benzoquinone, its productive rate is 73%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 3 is in being equipped with the 500ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 160ml toluene, stirring makes its dissolving, elevated temperature to 100 ℃ drips the 1.6mol trimethyl phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out toluene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, 0-dimethyl phosphine acyl group) para benzoquinone, its productive rate is 88%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 4 is in being equipped with the 500ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 160ml toluene, stirring makes its dissolving, elevated temperature to 90 ℃ drips the 1.2mol trimethyl phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out toluene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, 0-dimethyl phosphine acyl group) para benzoquinone, its productive rate is 90%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 5 is in being equipped with the 500ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 160ml chlorobenzene, stirring makes its dissolving, elevated temperature to 80 ℃ drips the 1.4mol trimethyl phosphite in 3 hours, holding temperature reaction 4h, reaction finishes the back underpressure distillation and goes out chlorobenzene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, 0-dimethyl phosphine acyl group) para benzoquinone, its productive rate is 70%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 6 is in being equipped with the 500ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 160ml dimethylbenzene, stirring makes its dissolving, elevated temperature to 80 ℃ drips the 1.0mol trimethyl phosphite in 3 hours, holding temperature reaction 8h, reaction finishes the back underpressure distillation and goes out dimethylbenzene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, 0-dimethyl phosphine acyl group) para benzoquinone, its productive rate is 83%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 7 is in being equipped with the 500ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 160ml dimethylbenzene, stirring makes its dissolving, elevated temperature to 90 ℃ drips the 1.2mol trimethyl phosphite in 3 hours, holding temperature reaction 8h, reaction finishes the back underpressure distillation and goes out dimethylbenzene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, 0-dimethyl phosphine acyl group) para benzoquinone, its productive rate is 86%, and fusing point is 97 ± 1 ℃, and decomposition temperature is 237 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the methyl-phosphorous acid dimethyl esters.
Embodiment 8 is in being equipped with the 1000ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 240ml benzene, stirring makes its dissolving, elevated temperature to 80 ℃ drips the 1.0mol triethyl-phosphite in 3 hours, holding temperature reaction 7h, reaction finishes the back underpressure distillation and goes out benzene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, the 0-diethyl phosphonyl) para benzoquinone, its productive rate is 62%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 9 is in being equipped with the 1000ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 240ml chlorobenzene, stirring makes its dissolving, elevated temperature to 130 ℃ drips the 1.4mol triethyl-phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out chlorobenzene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, the 0-diethyl phosphonyl) para benzoquinone, its productive rate is 75%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 10 is in being equipped with the 1000ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 240ml toluene, stirring makes its dissolving, elevated temperature to 100 ℃ drips the 1.2mol triethyl-phosphite in 3 hours, holding temperature reaction 8h, reaction finishes the back underpressure distillation and goes out toluene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, the 0-diethyl phosphonyl) para benzoquinone, its productive rate is 80%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 11 is in being equipped with the 1000ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 240ml toluene, stirring makes its dissolving, elevated temperature to 110 ℃ drips the 1.6mol triethyl-phosphite in 3 hours, holding temperature reaction 8h, reaction finishes the back underpressure distillation and goes out toluene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, the 0-diethyl phosphonyl) para benzoquinone, its productive rate is 86%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 12 is in being equipped with the 1000ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 240ml dimethylbenzene, stirring makes its dissolving, elevated temperature to 90 ℃ drips the 1.0mol triethyl-phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out dimethylbenzene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, the 0-diethyl phosphonyl) para benzoquinone, its productive rate is 78%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
Embodiment 13 is in being equipped with the 1000ml four-hole bottle of agitator and thermometer, add 0.2mol chloranil and 240ml dimethylbenzene, stirring makes its dissolving, elevated temperature to 110 ℃ drips the 1.2mol triethyl-phosphite in 3 hours, holding temperature reaction 6h, reaction finishes the back underpressure distillation and goes out dimethylbenzene, be cooled to 25 ℃, drip sherwood oil, slowly separate out white crystal, filter, filter cake petroleum ether, filter cake get white needle-like crystals four (0 through vacuum-drying, the 0-diethyl phosphonyl) para benzoquinone, its productive rate is 90%, and fusing point is 179 ± 1 ℃, and decomposition temperature is 242 ± 2 ℃; Above-mentioned filtrated stock distillation is reclaimed sherwood oil and is obtained the ethylphosphonic acid diethyl ester.
This case contriver is also with above-mentioned synthetic four (0; 0-dialkyl phosphine acyl group) para benzoquinone is applied in the fiber glass resin; get four (0; 0-dialkyl phosphine acyl group) after para benzoquinone and fiber glass resin mix red material that the back adds 4% white material and 2% and stir; pour into and make the thick sheet material of 3mm in the mould that is placed with one deck glass wool cloth; cut into the batten of wide 7mm, thick 3mm, long 150mm again, and its flame retardant properties is tested, test-results is as shown in the table:
This shows that above-mentioned four (0,0-dimethyl phosphine acyl group) para benzoquinone really has the excellent flame retardancy energy.
This shows that above-mentioned four (0, the 0-diethyl phosphonyl) para benzoquinone really has the excellent flame retardancy energy.
Claims (10)
1. one kind four (0,0-dialkyl phosphine acyl group) para benzoquinone is characterized in that the structure of this compound is shown below:
R is the straight or branched alkyl that contains 1～8 C atom.
2. the preparation method of four (0,0-dialkyl phosphine acyl group) para benzoquinone according to claim 1 is characterized in that this method is:
With the chloranil of certain mol proportion and tris phosphite under heating condition, sustained reaction after for some time in organic solvent, to reactant purify, drying treatment, make four (0,0-dialkyl phosphine acyl group) para benzoquinone.
3. certain mol proportion according to claim 2 is 1: 4～1: 8 for the mol ratio of chloranil and tris phosphite.
4. tris phosphite according to claim 2 is a trimethyl phosphite, triethyl-phosphite, tricresyl phosphite propyl ester, tributyl phosphate, tricresyl phosphite pentyl ester, the own ester of tricresyl phosphite, tricresyl phosphite monooctyl ester.
5. heating condition according to claim 2 is 60 ℃～130 ℃.
6. organic solvent according to claim 2 can be benzene,toluene,xylene, chlorobenzene.
7. the reaction times according to claim 2 is 4～8h.
8. method of purification according to claim 2 is cooled off preliminary crystallization for after reactant is steamed solvent, drips the sherwood oil sufficient crystallising, filters oven dry.
9. the solvent that steams according to claim 8 directly reclaims use.
10. dropping sherwood oil sufficient crystallising according to claim 8 filters, and sherwood oil is reclaimed in its filtrated stock distillation, obtains by product organic phosphine fire retardant dialkyl alkylphosphonate simultaneously.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102603556A CN101941989B (en) | 2010-08-24 | 2010-08-24 | Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102603556A CN101941989B (en) | 2010-08-24 | 2010-08-24 | Tetra-(0,0-dialkyl phosphonyl) p-benzoquinone and preparation method thereof |
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| CN101941989A true CN101941989A (en) | 2011-01-12 |
| CN101941989B CN101941989B (en) | 2012-07-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880624A (en) * | 2014-04-16 | 2014-06-25 | 苏州科技学院相城研究院 | Tetraallyloxy p-benzoquinone compound and preparation method for same |
| CN108948087A (en) * | 2018-07-06 | 2018-12-07 | 苏州科技大学 | More silicon phosphine 1,4-benzoquinone compounds of coloured flame-retardant carbon forming agent and preparation method thereof |
| CN109021016A (en) * | 2018-07-06 | 2018-12-18 | 苏州科技大学 | Four PEPA oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2935518A (en) * | 1958-09-12 | 1960-05-03 | Monsanto Chemicals | Reaction products of tetrahalogenated quinoid compounds and trisecondary alkyl phosphites and process of making same |
| US3159537A (en) * | 1960-12-20 | 1964-12-01 | American Cyanamid Co | Potentiation of tetracycline by phosphinic acid |
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2010
- 2010-08-24 CN CN2010102603556A patent/CN101941989B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2935518A (en) * | 1958-09-12 | 1960-05-03 | Monsanto Chemicals | Reaction products of tetrahalogenated quinoid compounds and trisecondary alkyl phosphites and process of making same |
| US3159537A (en) * | 1960-12-20 | 1964-12-01 | American Cyanamid Co | Potentiation of tetracycline by phosphinic acid |
Non-Patent Citations (1)
| Title |
|---|
| 《Chemistry Letters》 19990731 Kazuya Kobiro et.al p-Benzoquinone 2,3,5,6-Tetrakis(diisopropyl phosphonate): A Novel, Highly Bent p-Benzoquinone 633-634 1-10 , 第7期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880624A (en) * | 2014-04-16 | 2014-06-25 | 苏州科技学院相城研究院 | Tetraallyloxy p-benzoquinone compound and preparation method for same |
| CN108948087A (en) * | 2018-07-06 | 2018-12-07 | 苏州科技大学 | More silicon phosphine 1,4-benzoquinone compounds of coloured flame-retardant carbon forming agent and preparation method thereof |
| CN109021016A (en) * | 2018-07-06 | 2018-12-18 | 苏州科技大学 | Four PEPA oxygroup 1,4-benzoquinone compound of coloured flame-retardant carbon forming agent and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN101941989B (en) | 2012-07-04 |
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