阅读说明：本技术 一种含能端异氰酸酯基固化剂及其合成方法 (One kind terminal isocyanate group curing agent containing energy and its synthetic method ) 是由 李娜 赵凤起 杨燕京 安亭 张建侃 李辉 张明 蒋周峰 于 2019-08-28 设计创作，主要内容包括：本发明属于固体推进剂领域,具体涉及一种含能端异氰酸酯基固化剂及其合成方法,其结构式如下：<Image he="311" wi="700" file="DDA0002182482580000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,x,y,z均为2～6的正整数。本发明的固化剂和叠氮粘合剂、硝酸酯粘合剂和硝酸酯增塑剂都有着良好的相溶性,具备了调节力学性能的必要条件。(The invention belongs to solid propellant fields, and in particular to one kind terminal isocyanate group curing agent containing energy and its synthetic method, structural formula are as follows: Wherein, x, y, z are 2~6 positive integer.Curing agent and azido binder of the invention, nitric acid ester adhesive and nitrate ester plasticizer suffer from good intermiscibility, have the necessary condition for adjusting mechanical property.)

1. one kind terminal isocyanate group curing agent containing energy, which is characterized in that structural formula is as follows:

Wherein, x, y, z are 2~6 positive integer.

2. a kind of synthetic method of the terminal isocyanate group curing agent described in claim 1 containing energy, which is characterized in that specific steps It is as follows:

1) with 1,3,5- trihydroxyethyl isocyanuric ester for initiator, boron trifluoride etherate is catalyst, dichloroethanes For solvent, 3- azido-methyl -3- nitrate methy oxetane is monomer, by cation ring-opening polymerization mechanism, synthesizes end hydroxyl Base 3- azido-methyl -3- nitrate methy oxetane polyethers；

2) in ethyl acetate medium, triphenyl bismuth is catalyst, terminal hydroxy group 3- azido-methyl -3- nitric acid ester methyl oxa- ring fourth Alkane polyethers reacts to form the terminal isocyanate group curing agent containing energy with isophorone diisocyanate.

3. synthetic method according to claim 2, which is characterized in that initiator 1 in the step 1), 3,5- trihydroxyethyls The molar ratio of chlorinated isocyanurates and 3- azido-methyl -3- nitrate methy oxetane is 1:6~18, initiator 1,3,5- tri- The molar ratio of hydroxyethyl isocyanurate ester and boron trifluoride etherate is 2:1, and reaction temperature is 12 DEG C~15 DEG C.

4. synthetic method according to claim 2, which is characterized in that terminal hydroxy group 3- azido-methyl -3- in the step 2) The molar ratio of nitrate methy oxetane polyethers and isophorone diisocyanate is 1:3.1, triphenyl bismuth and terminal hydroxy group The molar ratio of 3- azido-methyl -3- nitrate methy oxetane polyethers is 1:40, and reaction temperature is 82 DEG C~85 DEG C.

Technical field

The invention belongs to solid propellant fields, and in particular to one kind terminal isocyanate group curing agent containing energy and its synthesis side Method.

Background technique

In recent years, people did not required nothing more than its energy height to solid propellant, were both also to require micro- cigarette, few cigarette and low rapid wear Property, and think that Development of Novel energetic binder system is to combine to solve one of these contradictory effective ways.Nitrine bonding Agent has the advantages that fast positive generation heat, burning, energy height, combustion gas cleaning, thermal stability are good and mechanical sensitivity is low etc., thus is generation The important goal that various countries, boundary are competitively studied.After Vandenberg in 1972 synthesizes GAP soon, azido binder agent is in rifle It is used widely in big gun propellant powder, propellant, gas generator and high explosive, due to containing energy, therefore is used to replace Traditional inert binder (such as HTPB or HTPE).Azido binder is the high molecular polymer containing terminal hydroxy group, when in use generally Isocyanate cure systems are formed with polyfunctionality isocyanate curing agent (such as IPDI, N-100), pass through terminal hydroxy group and isocyanide Perester radical reaction solidification, in order to make azide propellant that there is good mechanical property and structural intergrity, it is necessary to selection or synthesis The azido binder and curing agent of suitable construction, the two have a major impact the mechanical property of propellant.

Should have following condition from mechanical property and energy point of view, ideal curing agent is improved: 1) sticky liquid Body；It 2) is primary isocyanate groups；3) degree of functionality >=3；4) energy group is had；5) with adhesive, nitrate ester plasticizer phase Dissolubility is good.

European patent EP 0 296 310 discloses two kinds of macromolecular liquid based on nitrine glycidol ether (GAP) The preparation method of nitrine curing agent, but without reporting that specific mechanical performance data, structure are as follows:

《Synthesis and properties ofpoly-isocyanate energetic curing agent》 Polymer Bulletin, 2006,56 (6): 563~569, one kind is disclosed using pentaerythrite as initiator, and degree of functionality is 4 Azide polyethers type energetic curing agent Ec01~Ec03, structure are as follows:

Above-mentioned macromolecular energetic curing agent is the GAP and hexamethylene-diisocyanate with low relative molecular mass (HDI) through made from addition reaction.Since corresponding GAP is with chains such as 1,4- butanediol, trimethylolpropane, pentaerythrites Shape fatty alcohol is initiator, therefore highly polar group is free of in these GAP strands, this also leads to final resulting nitrine solidification Agent the defects of there are highly polar group contained in strand is less, and the active force of molecule interchain is smaller, so above-mentioned curing agent is simultaneously The mechanical property of azido binder system is not set to have more apparent improvement.

Summary of the invention

The technical problem to be solved by the present invention is to overcome the shortcomings of background technique, provide that a kind of mechanical property is higher to be contained Energy terminal isocyanate group curing agent and preparation method thereof.

Insight of the invention is that 1) introduce highly polar group azepine ring structure list in terminal isocyanate group solidification agent molecule Member improves the mechanical property of elastomer by enhancing intermolecular active force；2) it is introduced in terminal isocyanate group curing agent Polyether chain flexible improves the elongation percentage of elastomer；3) azido and itrate group are introduced in terminal isocyanate group curing agent It rolls into a ball to improve the energy of elastomer.

In order to solve the above technical problem, the present invention provides containing can terminal isocyanate group curing agent, structural formula is as follows It is shown:

Wherein, x, y, z are 2~6 positive integer.

Synthetic route of the invention is as follows:

Wherein, x, y, z are 2~6 positive integer.

Specifically includes the following steps:

1) with 1,3,5- trihydroxyethyl isocyanuric ester for initiator, boron trifluoride etherate is catalyst, dichloro Ethane is solvent, and 3- azido-methyl -3- nitrate methy oxetane is monomer, by cation ring-opening polymerization mechanism, synthesis Terminal hydroxy group 3- azido-methyl -3- nitrate methy oxetane polyethers；The 1,3,5- trihydroxyethyl isocyanuric ester and 3- The molar ratio of azido-methyl -3- nitrate methy oxetane is 1:6~18,1,3,5- trihydroxyethyl isocyanuric ester and three The molar ratio for being fluorinated diethyl etherate is 2:1, and reaction temperature is 12 DEG C~15 DEG C.

2) in ethyl acetate medium, triphenyl bismuth is catalyst, terminal hydroxy group 3- azido-methyl -3- nitric acid ester methyl oxa- Cyclobutane polyethers reacts to form the terminal isocyanate group curing agent containing energy with isophorone diisocyanate；The terminal hydroxy group 3- nitrine The molar ratio of methyl -3- nitrate methy oxetane polyethers and isophorone diisocyanate is 1:3.1, and reaction temperature is 82 DEG C~85 DEG C.

Beneficial effects of the present invention:

1) contain the highly polar group azepine ring structure list similar with hexogen (RDX), octogen (HMX) structure Member can improve the active force of azido binder system network molecule interchain, the mechanics of nitrine polyurethane elastomer finally can be improved Performance；2) contain energy group, the molecular weight of azido binder and curing agent can be allowed to have variation by a relatively large margin, so that promoting Agent prescription adjusting has relatively large freedom degree；3) there is the backbone structure similar with azido binder and nitric acid ester adhesive, together When there is nitrate group identical with nitrate ester plasticizer, therefore curing agent of the present invention and azido binder, nitrate bond Agent and nitrate ester plasticizer suffer from good intermiscibility, have the necessary condition for adjusting mechanical property.

Specific embodiment

The present invention will be further explained with reference to the examples below.

Number-average molecular weight test

Equipment: Britain's PL company GPC-50 type gel permeation chromatograph；

GPC test condition: chromatographic column is PLgel MIXED-E series connection；Mobile phase is THF；Column temperature is 40 DEG C；

Detector is differential refraction detector.

Film Mechanics Performance Testing

Equipment: 4505 type universal testing machine of Instron company, U.S. Instron；

Test method: according to GB/T528-1998.