CN105481704A - Method for synthesis and purification of bonding agent N-propargyl diethanol amine - Google Patents
Method for synthesis and purification of bonding agent N-propargyl diethanol amine Download PDFInfo
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- CN105481704A CN105481704A CN201610019028.9A CN201610019028A CN105481704A CN 105481704 A CN105481704 A CN 105481704A CN 201610019028 A CN201610019028 A CN 201610019028A CN 105481704 A CN105481704 A CN 105481704A
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- propargyl
- diethanolamine
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- linking agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesis and purification of the bonding agent N-propargyl diethanol amine. The structure of the compound is shown in the description. The bonding agent N-propargyl diethanol amine is expected to be applied to energetic binder type propellants. The method comprises the steps of adding 3-propargyl bromide to a diethanol amine tetrahydrofuran solution dropwise with triethylamine as the acid-binding agent under the ice-bath condition, conducting filtration after three hours of reaction, conducting filtrate concentration and reduced pressure distillation in sequence, and collecting the product. The method has the advantages of being high in yield and environmentally friendly.
Description
Technical field
The present invention relates to a kind of synthesis and method of purification of linking agent N-propargyl diethanolamine, belong to organic synthesis field.
Background technology
Composite solidpropellant is a class take macromolecule prepolymer as tackiness agent, and solid particulate is the composite high-molecular material of filler.The factor affecting its mechanical property is a lot, wherein, ensures that the effective adhesive that has at the interface of solid particulate and tackiness agent is the prerequisite that composite solidpropellant obtains excellent mechanical property.In order to improve the cohesive strength between oxygenant in solid propellant and adhesive interface, in propellant formulation of being everlasting, add ten thousand/several linking agent to some thousandths of consumption.These linking agent molecules have following three essential characteristics: (1) can be gathered in the solid particles surface of filling in propelling agent; (2) can with solidifying agent generation crosslinking reaction, thus form a hard and shell for toughness at the surface of the particles; (3) can enough functional groups be left, to form main chemical bond, make tackiness agent network and above-mentioned crust layer bonding.
Conventional linking agent mainly contains: aziridine and derivative, alkanolamine and derivative thereof, polyamines and derivative, organosilicon alkanes, organic titanate class, glycolylurea small molecules class, ferrocene-containing compound class, NPBA, evil beautiful jade class etc.
N-propargyl diethanolamine is the derivative of alkanol amine, is to be expected to be applied in the linking agent in energetic binder class propelling agent.The people such as WANGBing are referred to the preparation (WangB, ZhaoJZ.RafamycinAnalogsandMethodsforMakingSame.WO2014/08 2286) of this compound in patent disclosed in 2014, and its synthetic route is as follows:
The method is the unique method of the preparation N-propargyl diethanolamine announced at present, and take salt of wormwood as acid binding agent, react after 4 hours and adopt the method for column chromatography to be separated, productive rate is 44%.Aforesaid method reaction is for nonhomogeneous system, and productive rate is low, and the column chromatography speed that separation and purification adopts is slow, complex process, not environmentally.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides that a kind of productive rate is high, purifying process is simple, the linking agent N-propargyl diethanolamine synthesis of environmental protection and method of purification.
The reaction formula of linking agent N-propargyl diethanolamine of the present invention is as follows:
The synthesis of linking agent N-propargyl diethanolamine of the present invention and method of purification, the structure of linking agent N-propargyl diethanolamine Ru shown in Shi ﹙ Ⅰ ﹚,
Comprise the following steps:
(1) each raw material by mass, adds in reaction flask by the diethanolamine of 1 part, the triethylamine of 1 ~ 2 part and 2 ~ 4 parts of solvents; Described solvent is the mixture of a kind of in methyl alcohol, ethanol, ethyl acetate, methyl acetate, tetrahydrofuran (THF) or any two kinds;
(2) reaction flask is placed in cooling tank and is cooled to-10 ~ 10 DEG C;
(3) 1 ~ 2 part of propargyl bromide is slowly added drop-wise in reaction solution;
(4) dropwise, naturally rise to 20 ~ 25 DEG C, react 1 ~ 3 hour;
(5) cross the salt filtering precipitation, steam except unreacted raw material and solvent;
(6) underpressure distillation, collects product, obtains linking agent N-propargyl diethanolamine; The temperature of underpressure distillation is 100 ~ 200 DEG C, and the vacuum tightness of underpressure distillation is 0.5 ~ 10mmHg.
Advantage of the present invention: the acid binding agent that the inventive method uses is triethylamine, therefore system is homogeneous phase, and reaction times 3h yield reaches 83.9%, and the method 4h yield of documents is 44%, and on the basis decreasing the reaction times, yield improves twice nearly; Aftertreatment adopts the method for underpressure distillation to instead of the method for the column chromatography in documents, and technique is simple, environmental protection more.
Embodiment:
Below in conjunction with embodiment, the invention will be further elaborated.
Embodiment 1
There-necked flask equipment mechanical stirring, thermometer and constant pressure funnel, additional cryosel bath cooling.First add diethanolamine 105g, triethylamine 120g, tetrahydrofuran (THF) 200g, after being cooled to 0 DEG C, slowly drip 3-propargyl bromide 126g.Exothermic heat of reaction, controls dropping temperature and makes reacting liquid temperature be no more than 25 DEG C, add rear continuation nature stirring reaction 3 hours.
After stopped reaction, suction filtration reaction solution, except the salt that dereaction generates.Filtrate is transferred to Rotary Evaporators, is 50 DEG C in temperature, steams except tetrahydrofuran (THF) and unreacted 3-propargyl bromide, triethylamine under the condition of vacuum tightness 10mmHg.Then crude product is transferred to vacuum distillation apparatus, temperature be 160 DEG C, rectifying under the condition of vacuum tightness 1 ~ 2mmHg, receive the colourless liquid 120.0g altogether that boiling point is 130 ~ 133 DEG C (vacuum tightness 1 ~ 2mmHg), yield 83.9%.
The structural characterization of N-propargyl diethanolamine
1H-NMR(MeOD/TMS)σ:3.64(t,4H,J＝5.7Hz),3.51(d,2H,J＝2.3Hz),2.73(t,4H,J＝5.7Hz),2.60(t,1H,J＝2.3Hz)。
13C-NMR(MeOD/TMS)σ:77.8,73.2,59.0,55.4,41.9。
IR (KBr coating method, ν) shows: 3290,2947,2883,2835,2103,1765,1639,1434,1330,1041.
Ultimate analysis (%): C7H13NO2
Calculated value: C, 58.72; H, 9.15; N, 9.87;
Measured value: C, 57.08; H, 9.36; N, 9.24.
Said structure characterization data illustrates that the compound of synthesis is N-propargyl diethanolamine.
Embodiment 2
There-necked flask equipment mechanical stirring, thermometer and constant pressure funnel, additional cryosel bath cooling.First add diethanolamine 105g, triethylamine 101g, tetrahydrofuran (THF) 200g, after being cooled to 0 DEG C, slowly drip 3-propargyl bromide 119g.Exothermic heat of reaction, controls dropping temperature and makes reacting liquid temperature be no more than 25 DEG C, add rear continuation nature stirring reaction 3 hours.
After stopped reaction, suction filtration reaction solution, except the salt that dereaction generates.Filtrate is transferred to Rotary Evaporators, is 50 DEG C in temperature, steams except tetrahydrofuran (THF) and unreacted 3-propargyl bromide, triethylamine under the condition of vacuum tightness 10mmHg.Then crude product is transferred to vacuum distillation apparatus, temperature be 160 DEG C, rectifying under the condition of vacuum tightness 1 ~ 2mmHg, receive the colourless liquid 113.0g altogether that boiling point is 130 ~ 133 DEG C (vacuum tightness 1 ~ 2mmHg), yield 79.0%.
Embodiment 3
There-necked flask equipment mechanical stirring, thermometer and constant pressure funnel, additional cryosel bath cooling.First add diethanolamine 105g, triethylamine 101g, tetrahydrofuran (THF) 200g, after being cooled to 0 DEG C, slowly drip 3-propargyl bromide 119g.Exothermic heat of reaction, controls dropping temperature and makes reacting liquid temperature be no more than 25 DEG C, add rear continuation nature stirring reaction 2.5 hours.
After stopped reaction, suction filtration reaction solution, except the salt that dereaction generates.Filtrate is transferred to Rotary Evaporators, is 50 DEG C in temperature, steams except tetrahydrofuran (THF) and unreacted 3-propargyl bromide, triethylamine under the condition of vacuum tightness 10mmHg.Then crude product is transferred to vacuum distillation apparatus, temperature be 160 DEG C, rectifying under the condition of vacuum tightness 1 ~ 2mmHg, receive the colourless liquid 111.0g altogether that boiling point is 130 ~ 133 DEG C (vacuum tightness 1 ~ 2mmHg), yield 77.6%.
Claims (1)
1. the synthesis of linking agent N-propargyl diethanolamine and a method of purification, the structure of linking agent N-propargyl diethanolamine as shown in formula ﹙ I ﹚,
It is characterized in that comprising the following steps:
(1) each raw material by mass, adds in reaction flask by the diethanolamine of 1 part, the triethylamine of 1 ~ 2 part and 2 ~ 4 parts of solvents; Described solvent is the mixture of a kind of in methyl alcohol, ethanol, ethyl acetate, methyl acetate, tetrahydrofuran (THF) or any two kinds;
(2) reaction flask is placed in cooling tank and is cooled to-10 ~ 10 DEG C;
(3) 1 ~ 2 part of propargyl bromide is slowly added drop-wise in reaction solution;
(4) dropwise, naturally rise to 20 ~ 25 DEG C, react 1 ~ 3 hour;
(5) cross the salt filtering precipitation, steam except unreacted raw material and solvent;
(6) underpressure distillation, collects product, obtains linking agent N-propargyl diethanolamine; The temperature of underpressure distillation is 100 ~ 200 DEG C, and the vacuum tightness of underpressure distillation is 0.5 ~ 10mmHg.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610019028.9A CN105481704A (en) | 2016-01-12 | 2016-01-12 | Method for synthesis and purification of bonding agent N-propargyl diethanol amine |
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| CN201610019028.9A CN105481704A (en) | 2016-01-12 | 2016-01-12 | Method for synthesis and purification of bonding agent N-propargyl diethanol amine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053342A (en) * | 2018-03-12 | 2018-12-21 | 西安航天化学动力有限公司 | A kind of preparation method for the medicine slurry that no bonding agent is precipitated |
| CN110423184A (en) * | 2019-08-01 | 2019-11-08 | 上海航天化工应用研究所 | A kind of solid propellant rocket propellant and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014082286A1 (en) * | 2012-11-30 | 2014-06-05 | Hangzhou Zylox Pharma Co., Ltd. | Rafamycin analogs and methods for making same |
-
2016
- 2016-01-12 CN CN201610019028.9A patent/CN105481704A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014082286A1 (en) * | 2012-11-30 | 2014-06-05 | Hangzhou Zylox Pharma Co., Ltd. | Rafamycin analogs and methods for making same |
Non-Patent Citations (4)
| Title |
|---|
| KULIS, JAKOV 等: "One-Pot Synthesis of Mikto Three-Arm AB2 Stars Constructed from Linear and Macrocyclic Polymer Chains", 《MACROMOLECULES》 * |
| LONSDALE, DARIA E 等: "Synthesis and self-assembly of amphiphilic macrocyclic block copolymer topologies", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 * |
| PENG, YUN 等: "Macrocycle-Terminated Core-Cross-Linked Star Polymers: Synthesis and Characterization", 《MACROMOLECULES》 * |
| 宣云遐 等: "N-炔丙基胺类化合物的合成", 《化学研究与应用》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053342A (en) * | 2018-03-12 | 2018-12-21 | 西安航天化学动力有限公司 | A kind of preparation method for the medicine slurry that no bonding agent is precipitated |
| CN109053342B (en) * | 2018-03-12 | 2021-09-07 | 西安航天化学动力有限公司 | Preparation method of medicinal slurry without bonding agent precipitation |
| CN110423184A (en) * | 2019-08-01 | 2019-11-08 | 上海航天化工应用研究所 | A kind of solid propellant rocket propellant and preparation method thereof |
| CN110423184B (en) * | 2019-08-01 | 2021-07-13 | 上海航天化工应用研究所 | Propellant for solid rocket engine and preparation method thereof |
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Application publication date: 20160413 |