CN104892451A - End ester base end ethyoxyl GAP(glycidyl azide polymer) oligomer and preparation method thereof - Google Patents
End ester base end ethyoxyl GAP(glycidyl azide polymer) oligomer and preparation method thereof Download PDFInfo
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- CN104892451A CN104892451A CN201510351023.1A CN201510351023A CN104892451A CN 104892451 A CN104892451 A CN 104892451A CN 201510351023 A CN201510351023 A CN 201510351023A CN 104892451 A CN104892451 A CN 104892451A
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Abstract
The invention discloses end ester base end ethyoxyl GAP (glycidyl azide polymer) oligomer and a preparation method thereof. A structural formula of the end ester base end ethyoxyl GAP oligomer is shown as below, wherein n=5. The end ester base end ethyoxyl GAP oligomer is mainly used for energetic plasticizer of solid propellant, gun propellant and PBX compound explosive.
Description
Technical field
The present invention relates to a kind of end ester group end oxyethyl group GAP oligopolymer, be applicable to the energetic plasticiser of solid propellant, gun propellant and PBX pyrotechnic composition.
Background technology
Oligopolymer refers in particular to the low-molecular weight polymer that the polymerization degree is less than 10.
The explosive wastewater mechanical property taking azido binder as base is undesirable, and the compatibility difference between tackiness agent and Conventional plasticizers is an important reason, and based on " similar mix " principle, scientist considers to adopt azide compounds plasticising azido binder.Such as, the scientist Flanagan of Rockwell company of the U.S. is with 1,4-butyleneglycol and epoxy chloropropane are that first raw material obtains penton dibasic alcohol by cation ring-opening polymerization, then through azide and esterification two-step reaction, prepare a kind of end ester group GAP oligopolymer (see United States Patent (USP) 4938812) with following structure:
The method provided according to document carries out the study on the synthesis of above-mentioned end ester group GAP oligopolymer, find in test that above-mentioned end ester group GAP oligopolymer also exists two defects: one is energy shortage, for example (,) molecular weight be 578 end ester group GAP oligopolymer only have 29.07% nitrogen content; Two is that esterification aftertreatment technology difficulty is large, and the demand of diacetyl oxide is large, and system acidity is too strong, and not only make triazo-compound easily decompose under strongly acidic conditions, and add washing times, even so, reaction solution process also has very large difficulty to neutrality.
Summary of the invention
In order to solve deficiency or the defect of prior art existence, the invention provides a kind of end ester group end oxyethyl group GAP oligopolymer and preparation method thereof.
End ester group end oxyethyl group GAP oligopolymer provided by the invention, concrete structure is as follows:
Wherein, n=5.
The synthetic route of this oligopolymer is as follows:
Specifically comprise the following steps:
1) take ethanol as initiator, boron trifluoride ethyl ether complex is catalyzer, and methylene dichloride is solvent, and epoxy chloropropane is monomer, by cation ring-opening polymerization mechanism, and synthesis terminal hydroxy group end oxyethyl group penton; The mol ratio of ethanol, boron trifluoride ethyl ether complex and epoxy chloropropane is 2:1:10, and temperature of reaction is 12 DEG C ~ 15 DEG C;
2) make terminal hydroxy group end oxyethyl group penton carry out azido reaction with sodiumazide in dimethylformamide medium, synthesize terminal hydroxy group end oxyethyl group GAP; The mol ratio of end oxyethyl group terminal hydroxy group penton and sodiumazide is 1:5.5, and temperature of reaction is 88 DEG C ~ 90 DEG C;
3) with diacetyl oxide, the hydroxyl of terminal hydroxy group end oxyethyl group GAP is carried out esterification, obtain end ester group end oxyethyl group GAP oligopolymer, the mol ratio of terminal hydroxy group end oxyethyl group GAP and diacetyl oxide is 1:1.05, and temperature of reaction is 22 DEG C ~ 25 DEG C.
Advantage of the present invention
1) energy of the present invention is higher than end ester group GAP oligopolymer, for example (,) molecular weight be the end ester group end oxyethyl group GAP nitrogen content of 583 up to 36.02%, and the end ester group GAP nitrogen content of same molecular weight only has 29.07%.In identical plasticising than in situation, end ester group end oxyethyl group GAP oligopolymer more contributes to the energy density improving formula.
2) esterification process of synthesis end ester group GAP needs too by force repeatedly to wash due to acidity, and reaction solution process is to neutral difficult.And the esterification step synthesizing end ester group end oxyethyl group GAP of the present invention not only the reaction times short, and aftertreatment technology is simple.Esterification of the present invention is only the former half, and washing times obviously reduces, and reaction solution easily processes neutrality.
3) the present invention is applied widely, both can be used for thermoset energetic binder system, and as nitrine class tackiness agent, nitrate ester polyether tackiness agent, also can be used for thermoplasticity energetic binder system, as nitro-cotton, and BAMO/AMMO base energetic thermoplastic elastomers.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
1 end ester group end oxyethyl group GAP oligopolymer
The synthesis of 1.1 terminal hydroxy group end oxyethyl group pentons
16.56g (0.36mol) ethanol and 180mL methylene dichloride is added successively in the 500mL four-hole boiling flask of mechanical stirring, thermometer, dropping funnel and reflux, 22.73mL (0.18mol) boron trifluoride ethyl ether complex is added after dispersed with stirring 10min, at room temperature after stirring reaction 30min, system is cooled to 12 DEG C ~ 15 DEG C, 166.5g (1.8mol) epoxy chloropropane is dripped through dropping funnel, control polymerization temperature during dropping at 12 DEG C ~ 15 DEG C, under dropwising rear room temperature, react 8h.After having reacted, stop polyreaction with the aqueous sodium carbonate that 100mL concentration is 5%, mixture is injected into stratification in separating funnel, separate lower floor's oil phase, oil phase washes with water and is washed till neutrality, last concentration and recovery solvent, obtain light yellow transparent liquid 171.16g, productive rate 93.5%.Polyreaction equation is as follows:
Structural characterization: infrared (KBr, cm
-1): 3455 (O-H), 2960 (-CH
3), 2877 (-CH
2), 1113 (C-O-C), 768 (C-Cl).The synthesis of 1.2 terminal hydroxy group end oxyethyl group GAP
Add 132.21g (0.26mol) successively in the 500mL there-necked flask of mechanical stirring, thermometer and reflux and hold oxyethyl group terminal hydroxy group penton and 150mL dimethyl formamide, stir, be heated to 80 DEG C, then 92.95g (1.43mol) sodiumazide is added, 88 DEG C ~ 90 DEG C reaction 12h.Be cooled to room temperature, reaction solution is poured into water, with dichloromethane extraction, wash oil phase with water to neutral, with anhydrous magnesium sulfate drying, filter, steam except methylene dichloride, obtain incarnadine transparent liquid 129.41g, productive rate 92.6%.Reaction equation is as follows:
Structural characterization: infrared (KBr, cm
-1): 3456 (O-H), 2976 (-CH
3), 2876 (-CH
2), 2100 (-N
3), 1118 (C-O-C).The synthesis of 1.3 end ester group end oxyethyl group GAP oligopolymers
With mechanical stirring, thermometer, 119.02g (0.22mol) terminal hydroxy group end oxyethyl group GAP is added successively in the 500mL four-hole boiling flask of dropping funnel and reflux, 13.5g (0.015mol) N-Methylimidazole and 150mL 1, 2-ethylene dichloride, after dispersed with stirring 10min, 23.46g (0.23mol) diacetyl oxide is dripped through dropping funnel at 22 DEG C ~ 25 DEG C, control reacting liquid temperature during dropping and do not exceed 40 DEG C, 8h is reacted at dropwising latter 22 DEG C ~ 25 DEG C, with the aqueous sodium carbonate neutralization that 100mL concentration is 5%, mixture is injected into stratification in separating funnel, separate lower floor's oil phase, oil phase is washed with water to neutrality, with anhydrous magnesium sulfate drying, filter, last vacuum concentration recycling design, obtain light yellow transparent liquid 117.23g, productive rate 91.4%.Reaction equation is as follows:
Structural characterization: infrared (KBr, cm
-1): 2975 (-CH
3), 2876 (-CH
2), 2101 (-N
3), 1744 (C=O), 1118 (C-O-C).
Ultimate analysis: theoretical nitrogen content is 36.02%, actual measurement nitrogen content is 35.85%.
Theoretical value average molecular weight is 583, and actual measurement number-average molecular weight is ~ 560.
Above-mentioned analytical data confirms that the material obtained by this synthetic method is end ester group end oxyethyl group GAP oligopolymer softening agent really.
The second-order transition temperature (Tg) of end ester group end oxyethyl group GAP oligopolymer softening agent is-67.43 DEG C, and start to decompose 230.52 DEG C time, decomposing peak temperature is 255.63 DEG C.
2 application of the present invention
2.1 end ester group end oxyethyl group GAP oligopolymers are to the plasticization effect containing energy thermoplastic binder
Plasticising body is obtained after being mixed with end ester group end oxyethyl group GAP oligopolymer respectively by NC or BAMO/AMMO base ETPE.In preparation method, NC is by means of acetone and softening agent mixing, and BAMO/AMMO base ETPE directly mixes with softening agent.Two kinds of plasticising bodies all only have a Tg, and do not occur oil impregnate phenomenon, its Tg is in table 1.
Table 1 end ester group end oxyethyl group GAP oligopolymer is to the plasticization effect containing energy thermoplastic binder
| Energetic binder/energetic plasticiser | Mass ratio | Tg/℃ |
| NC/ holds ester group end oxyethyl group GAP | 1.0/1.0 | －42.9 |
| ETPE/ holds ester group end oxyethyl group GAP | 1.0/1.0 | －44.7 |
2.2 end ester group end oxyethyl group GAP oligopolymers are to the plasticization effect of other thermoset energetic binder
The present invention is applied widely, can also be used for various thermoset energetic binder system, as to nitrine class tackiness agent as the plasticising of GAP, PAMMO and ATP, nitrate ester polyether tackiness agent is as the plasticising of PNMMO, PGN.These 5 kinds of tackiness agents respectively according to softening agent/tackiness agent plasticising ratio be 1/1,2/1 mixing, discovery mixed solution is as clear as crystal, even if deposit two weeks also to remain unchanged, do not go out a phenomenon such as layering or muddiness, show that end ester group end oxyethyl group GAP oligopolymer and these reactive energetic binder have good compatibility.
Claims (5)
1. hold an ester group end oxyethyl group GAP oligopolymer, it is characterized in that structural formula is as follows:
Wherein, n=5.
2. a synthetic method for end ester group end oxyethyl group GAP oligopolymer according to claim 1, is characterized in that step is as follows:
1) take ethanol as initiator, boron trifluoride ethyl ether complex is catalyzer, and methylene dichloride is solvent, and epoxy chloropropane is monomer, by cation ring-opening polymerization mechanism, and synthesis terminal hydroxy group end oxyethyl group penton;
2) make terminal hydroxy group end oxyethyl group penton carry out azido reaction with sodiumazide in dimethylformamide medium, synthesize terminal hydroxy group end oxyethyl group GAP;
3) with diacetyl oxide, the hydroxyl of terminal hydroxy group end oxyethyl group GAP is carried out esterification, obtain end ester group end oxyethyl group GAP oligopolymer.
3. synthetic method according to claim 2, is characterized in that described step 1) in the mol ratio of ethanol, boron trifluoride ethyl ether complex and epoxy chloropropane be 2:1:10, temperature of reaction is 12 DEG C ~ 15 DEG C.
4. synthetic method according to claim 2, is characterized in that described step 2) mol ratio of middle-end oxyethyl group terminal hydroxy group penton and sodiumazide is 1:5.5, temperature of reaction is 88 DEG C ~ 90 DEG C.
5. synthetic method according to claim 2, is characterized in that described step 3) mol ratio of middle-end hydroxyl terminal oxyethyl group GAP and diacetyl oxide is 1:1.05, temperature of reaction is 22 DEG C ~ 25 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669493A (en) * | 2016-03-14 | 2016-06-15 | 西安近代化学研究所 | Azide nitric acid ester oligomer and preparing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1184943A (en) * | 1981-01-21 | 1985-04-02 | Chung I. Young | Hydroxyl-terminated poly(haloalkylene ethers) |
| US4938812A (en) * | 1989-06-12 | 1990-07-03 | Rockwell International Corporation | Glycidyl azide polymer esters |
-
2015
- 2015-06-23 CN CN201510351023.1A patent/CN104892451B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1184943A (en) * | 1981-01-21 | 1985-04-02 | Chung I. Young | Hydroxyl-terminated poly(haloalkylene ethers) |
| US4938812A (en) * | 1989-06-12 | 1990-07-03 | Rockwell International Corporation | Glycidyl azide polymer esters |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669493A (en) * | 2016-03-14 | 2016-06-15 | 西安近代化学研究所 | Azide nitric acid ester oligomer and preparing method thereof |
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