CN108864184A - A kind of synthesis N, N- bis-（2- ethoxy）The method of aminomethyl phosphonic acid diethylester - Google Patents
A kind of synthesis N, N- bis-（2- ethoxy）The method of aminomethyl phosphonic acid diethylester Download PDFInfo
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- CN108864184A CN108864184A CN201810590827.0A CN201810590827A CN108864184A CN 108864184 A CN108864184 A CN 108864184A CN 201810590827 A CN201810590827 A CN 201810590827A CN 108864184 A CN108864184 A CN 108864184A
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- UIBCDEFKKLRXHR-UHFFFAOYSA-N diethoxyphosphorylmethanamine Chemical compound CCOP(=O)(CN)OCC UIBCDEFKKLRXHR-UHFFFAOYSA-N 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 13
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- -1 1, N- bis- (2- ethoxy) aminomethyl phosphonic acid diethylester Chemical compound 0.000 claims description 7
- JNZDAFRQKAMUTN-UHFFFAOYSA-N C(C)OP(OCC)(=O)CN(OCC)OCC Chemical compound C(C)OP(OCC)(=O)CN(OCC)OCC JNZDAFRQKAMUTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 abstract description 8
- 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 7
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 238000005292 vacuum distillation Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- USPDYHQWWULKMD-UHFFFAOYSA-N N=NC=NN.N=NC=NN.P(O)(O)O Chemical compound N=NC=NN.N=NC=NN.P(O)(O)O USPDYHQWWULKMD-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- HFRIKICAVPEGGW-UHFFFAOYSA-N CCON(OCC)CP(O)(O)=O Chemical compound CCON(OCC)CP(O)(O)=O HFRIKICAVPEGGW-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- SULWMEGSVQCTSK-UHFFFAOYSA-N diethyl hydrogen phosphite Chemical group CCOP(O)OCC SULWMEGSVQCTSK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a kind of synthesis N, the method for N- bis- (2- ethoxy) aminomethyl phosphonic acid diethylester is related to technical field of flame retardant.Synthetic method of the present invention is：Diethanol amine is added in reaction flask, paraformaldehyde is slowly added to no more than 100 DEG C, after adding, is stirred to react at this temperature 1 hour, 60 DEG C are cooled to, dimethylphosphite is slowly added dropwise, is reacted 3 hours at this temperature, after completion of the reaction, it is evaporated under reduced pressure, middle fraction is product；The major advantage of the method for the present invention improves yield, while entire generation of the reaction without waste water, used solvent recovery are applied in avoiding the hydrolysis of intermediate.
Description
Technical field
The present invention relates to technical field of flame retardant, more particularly, to a kind of synthesis N, N- bis- (2- ethoxy) aminomethyl phosphonic acid
The method of diethylester.
Background technique
N, N- bis- (2- ethoxy) aminomethyl phosphonic acid diethylester can be used as preparing the resistance of flame-retardant thermoset ornament materials intumescent
The basins anti-flaming thermal-insulation liners such as flame-retardant polyurethane composite coating furniture flame retardant polyurethane cushion liquefied methane, flame-retardant plywood,
The response type or additive flame retardant of electronic circuit insulation board etc., its advantages are not influence or assign certain performances of material,
Such as heat distortion temperature, anti-hydrolytic performance and crack resistance, anti-smolderability, low temperature resistivity, electrical insulating property and moisture resistance.BHAPE
It is the good stable agent of urethane raw polyether-type or polyester polyol compound, can prevents compound from becoming viscous or generating and sink
It forms sediment.The phosphorus system such as BHAPE and oligomeric halogenated organic phosphorus, halogenated phosphonate ester, tetrabromobisphenol A or bromide fire retardant dissolve each other, and are easily prepared into
Composite flame-proof additive.Research has shown that BHAPE toxicity is lower, does not inhibit the activity of blood plasma, red blood cell or cerebral choline lipase.
The method that prevailing technology uses at present is reacted for formalin with diethanol amine, and phosphorous acid diethyl is then added dropwise
Ester, after completion of the reaction, vacuum distillation first steams water and other low-boiling-point substances, then improves vacuum degree, steam product, yield is about
85% or so.
Summary of the invention
The technical problem to be solved by the present invention is to：Technique, which has problems in that, at present water in reaction process, diethanol
Amine is reversible in water with formaldehyde reaction product, and diethyl phosphite easily decomposes in water at reaction conditions, diethanol amine
Nitrogen-atoms on it may also happen that ethyl substitution reaction, affects the yield of product, while also having the generation of waste water.
In order to solve the above technical problems, the technical solution adopted by the present invention is that：
A kind of method of synthesis N, N- bis- (2- ethoxy) aminomethyl phosphonic acid diethylester, it is characterised in that：By diethanol amine,
It is added in reaction flask, is slowly added to paraformaldehyde no more than 100 DEG C, after adding, is stirred to react at this temperature 1 hour, cool down
To 60 DEG C, dimethylphosphite is slowly added dropwise, reacts 3 hours, after completion of the reaction, is evaporated under reduced pressure, middle fraction is at this temperature
For product.
The method of described synthesis N, N- bis- (2- ethoxy) the aminomethyl phosphonic acid diethylester, which is characterized in that use poly first
Aldehyde replaces formalin.
The method of described synthesis N, N- bis- (2- ethoxy) the aminomethyl phosphonic acid diethylester, which is characterized in that used is more
The amount of polyformaldehyde is 1:1.05---1:Between 2.0, preferably 1:1.4
The method of described synthesis N, N- bis- (2- ethoxy) the aminomethyl phosphonic acid diethylester, which is characterized in that poly is added
Formaldehyde temperature is 80-100 DEG C.
Generated beneficial effect is by adopting the above technical scheme：
1, former reaction uses 40% formalin, since diethyl phosphite is easy hydrolysis in water, causes yield
Low, after using paraformaldehyde instead, yield is improved by original 90% to 95% or more；
2, paraformaldehyde replaces formalin, anhydrous in entire reaction process, while avoiding the generation of waste water.
Specific embodiment
The present invention will be further described in detail with reference to the specific embodiments.
Embodiment 1
150g diethanol amine is added in reaction flask, is warming up to 80 DEG C, control temperature is no more than 100 DEG C, is slowly added to
45g paraformaldehyde after adding, is stirred to react 1 hour at this temperature, is cooled to 60 DEG C, 226g phosphorous acid diformazan is slowly added dropwise
Ester reacts 3 hours at this temperature, and vacuum distillation cuts first fraction, and middle fraction is product 309.7g, content 98.1%,
Yield is 95.5%.
Embodiment 2
150g diethanol amine is added in reaction flask, is warming up to 80 DEG C, control temperature is no more than 100 DEG C, is slowly added to
51.4g paraformaldehyde after adding, is stirred to react 1 hour at this temperature, is cooled to 60 DEG C, 226g phosphorous acid two is slowly added dropwise
Methyl esters reacts 3 hours at this temperature, and vacuum distillation cuts first fraction, middle fraction is product 314.5g, yield 97%.
Embodiment 3
150g diethanol amine is added in reaction flask, is warming up to 80 DEG C, control temperature is no more than 100 DEG C, is slowly added to
55.7g paraformaldehyde after adding, is stirred to react 1 hour at this temperature, is cooled to 60 DEG C, 226g phosphorous acid two is slowly added dropwise
Methyl esters reacts 3 hours at this temperature, and vacuum distillation cuts first fraction, middle fraction is product 320g, yield 98.6%.
Embodiment 4
150g diethanol amine is added in reaction flask, is warming up to 80 DEG C, control temperature is no more than 100 DEG C, is slowly added to
60g paraformaldehyde after adding, is stirred to react 1 hour at this temperature, is cooled to 60 DEG C, 226g phosphorous acid diformazan is slowly added dropwise
Ester reacts 3 hours at this temperature, and vacuum distillation cuts first fraction, middle fraction is product 319g, yield 98.5%.
Embodiment 5
150g diethanol amine is added in reaction flask, is warming up to 80 DEG C, control temperature is no more than 100 DEG C, is slowly added to
85.7g paraformaldehyde after adding, is stirred to react 1 hour at this temperature, is cooled to 60 DEG C, 226g phosphorous acid two is slowly added dropwise
Methyl esters reacts 3 hours at this temperature, and vacuum distillation cuts first fraction, middle fraction is product 319.8g, and yield is
98.6%.
Claims (4)
1. a kind of method of synthesis N, N- bis- (2- ethoxy) aminomethyl phosphonic acid diethylester, it is characterised in that：By diethanol amine plus
Enter in reaction flask, be slowly added to paraformaldehyde no more than 100 DEG C, after adding, is stirred to react 1 hour, is cooled at this temperature
60 DEG C, dimethylphosphite is slowly added dropwise, reacts 3 hours, after completion of the reaction, is evaporated under reduced pressure, middle fraction is at this temperature
Product.
2. the method for synthesis N according to claim 1, N- bis- (2- ethoxy) aminomethyl phosphonic acid diethylester, feature exist
In replacing formalin with paraformaldehyde.
3. the method for synthesis N according to claim 1, N- bis- (2- ethoxy) aminomethyl phosphonic acid diethylester, feature exist
In the amount of paraformaldehyde used is 1:1.05---1:Between 2.0, preferably 1:1.4.
4. the method for synthesis N according to claim 1, N- bis- (2- ethoxy) aminomethyl phosphonic acid diethylester, feature exist
In it is 80-100 DEG C that paraformaldehyde temperature, which is added,.
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|---|---|---|---|
| CN201810590827.0A CN108864184A (en) | 2018-06-09 | 2018-06-09 | A kind of synthesis N, N- bis-（2- ethoxy）The method of aminomethyl phosphonic acid diethylester |
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| CN201810590827.0A CN108864184A (en) | 2018-06-09 | 2018-06-09 | A kind of synthesis N, N- bis-（2- ethoxy）The method of aminomethyl phosphonic acid diethylester |
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| CN108864184A true CN108864184A (en) | 2018-11-23 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004364A (en) * | 2019-12-23 | 2020-04-14 | 南京晨化新材料科技有限公司 | Preparation method of reactive halogen-free nitrogen-phosphorus flame retardant |
| CN113501929A (en) * | 2021-07-27 | 2021-10-15 | 扬州工业职业技术学院 | Flame-retardant wear-resistant polyurethane resin for leather |
| CN115236953A (en) * | 2021-04-22 | 2022-10-25 | 金�雄 | Stripper composition for removing photoresist and method for stripping photoresist using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57163388A (en) * | 1981-04-01 | 1982-10-07 | Asahi Denka Kogyo Kk | Production of aminoalkylphosphonic acid derivative |
| KR20100084091A (en) * | 2009-01-15 | 2010-07-23 | 풍림유화공업(주) | Flame-retardant semiconductor encapsulating epoxy resin composition |
| CN102276645A (en) * | 2011-05-18 | 2011-12-14 | 烟台万华聚氨酯股份有限公司 | Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate |
| CN105175712A (en) * | 2015-09-09 | 2015-12-23 | 济南大学 | Preparation method and application of functional dihydric alcohol |
-
2018
- 2018-06-09 CN CN201810590827.0A patent/CN108864184A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57163388A (en) * | 1981-04-01 | 1982-10-07 | Asahi Denka Kogyo Kk | Production of aminoalkylphosphonic acid derivative |
| KR20100084091A (en) * | 2009-01-15 | 2010-07-23 | 풍림유화공업(주) | Flame-retardant semiconductor encapsulating epoxy resin composition |
| CN102276645A (en) * | 2011-05-18 | 2011-12-14 | 烟台万华聚氨酯股份有限公司 | Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate |
| CN105175712A (en) * | 2015-09-09 | 2015-12-23 | 济南大学 | Preparation method and application of functional dihydric alcohol |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004364A (en) * | 2019-12-23 | 2020-04-14 | 南京晨化新材料科技有限公司 | Preparation method of reactive halogen-free nitrogen-phosphorus flame retardant |
| CN115236953A (en) * | 2021-04-22 | 2022-10-25 | 金�雄 | Stripper composition for removing photoresist and method for stripping photoresist using the same |
| CN113501929A (en) * | 2021-07-27 | 2021-10-15 | 扬州工业职业技术学院 | Flame-retardant wear-resistant polyurethane resin for leather |
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