CN105175707A - Alkynyl-terminated curing agent and preparation method thereof - Google Patents
Alkynyl-terminated curing agent and preparation method thereof Download PDFInfo
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- CN105175707A CN105175707A CN201510697784.2A CN201510697784A CN105175707A CN 105175707 A CN105175707 A CN 105175707A CN 201510697784 A CN201510697784 A CN 201510697784A CN 105175707 A CN105175707 A CN 105175707A
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- solidifying agent
- alkynyl
- curing agent
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- 0 Cc(c(NCl(Cl**)=[Fl])c1)ccc1NC([U]CCI#*)=C Chemical compound Cc(c(NCl(Cl**)=[Fl])c1)ccc1NC([U]CCI#*)=C 0.000 description 3
- RAFNJGITJKPZLT-UHFFFAOYSA-N Cc(cc1)c(C)cc1NC[U]CC#C Chemical compound Cc(cc1)c(C)cc1NC[U]CC#C RAFNJGITJKPZLT-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an alkynyl-terminated curing agent of which the structural formula is disclosed in the specification, wherein n is a whole number ranging from 5 to 20. The preparation method comprises the following steps: reacting hydroxyl-terminated polyethyleneglycol and toluene diisocyanate by using dibutyltin dilaurate as a catalyst and tetrahydrofuran as a solvent to generate isocyanate-terminated polyethyleneglycol, and adding propiolic alcohol into the reaction system to perform termination reaction, thereby forming the alkynyl-terminated curing agent containing urethano polyether chain. The alkynyl-terminated curing agent is mainly used for solid propellants.
Description
Technical field
The present invention relates to a kind of solid propellant end alkynyl radical solidifying agent, particularly relate to a kind of end alkynyl radical solidifying agent containing urethano polyether chain.
Background technology
Azido binder has positive Heat of Formation, burning is fast, energy is high, combustion gas is clean, Heat stability is good and the advantage such as mechanical sensitivity is low, is the desired adhesion agent of high energy low characteristic signal propellant, gas generator propellant and highly filled propelling charge.The Typical Representative of azido binder is nitrine glycidyl ether (GAP), and GAP has the advantage of above azido binder.GAP in use general and polyfunctionality isocyanate curing agent forms isocyanate cure systems, by terminal hydroxy group and the solidification of isocyanic ester radical reaction, but the isocyanate curing agent in this type of curing system has high activity, Yi Yushui or protonic acid rapid reaction generate CO
2, in the solidification process of propelling agent, form a lot of pore, the density of propelling agent declined, affects its mechanical property, make the safety and reliability of propelling agent also decline simultaneously.
In order to solve the problems referred to above that isocyanate curing agent exists, scientific research personnel develops end alkynyl radical solidifying agent, and it can solidify to form polytriazoles cross-linked elastomer with azido binder.People " Isocyanate-freecuringofglycidyl-azide-polymer (GAP) withbis-propargyl-succinate " 39thIntAnnuConfofICT such as such as ThomasKeicher, 2008 disclose a kind of end alkynyl radical solidifying agent, i.e. succinic acid two propynyl ester (BPS), its structural formula is as follows:
The mixture of BPS and two functionality GAP (Mn=1570) and three-functionality-degree GAP (Mn=980) is cured reaction, the film mechanical property obtained is solidified as follows: tensile strength is 0.215MPa when BPS/ bis-functionality GAP (Mn=1570)/three-functionality-degree GAP (Mn=980) mass ratio is 8.97%/79.58%/11.45%, unit elongation is 44.68%, and the mechanical property of film is on the low side.
Summary of the invention
Technical problem to be solved by this invention is the deficiency overcoming background technology, end alkynyl radical solidifying agent providing a kind of mechanical property higher and preparation method thereof.
Design of the present invention is: the reason that BPS base polytriazole elastomer mechanical property is on the low side is BPS is small molecules solidifying agent, and in the elastomerics after solidification, the interphase interaction of polytriazoles hard segment is weak, is unfavorable for microphase-separated, and segment between cross-linking set is partially short.The present invention imagine: 1) in alkynyl solidifying agent molecule, introduce urethano group, utilize urethano roll into a ball between hydrogen bond action to promote elastomeric microphase-separated, improve mechanical strength; 2) in alkynyl solidifying agent, introduce flexible polyglycol chain, improve elastomeric unit elongation.
In order to solve the problems of the technologies described above, the end alkynyl radical solidifying agent containing urethano polyether chain provided by the invention, its structural formula is as follows:
Wherein, n=5 ~ 20 are integer.
Synthetic route of the present invention is as follows:
Wherein, n=5 ~ 20 are integer.
Concrete technological approaches: take dibutyl tin laurate as catalyzer, tetrahydrofuran (THF) is solvent, terminal hydroxy group polyoxyethylene glycol (PEG) and tolylene diisocyanate (TDI) react and generate isocyanate terminated polyoxyethylene glycol, then in above-mentioned reaction system, add propiolic alcohol and carry out end capping, form the end alkynyl radical solidifying agent (PrTPEG) containing urethano polyether chain.
Advantage of the present invention: 1) introduce urethano group in PrTPEG molecule, utilize urethano roll into a ball between hydrogen bond action to promote the microphase-separated of crosslinked, improve mechanical strength; 2) introduce flexible polyglycol chain in PrTPEG, improve elastomeric unit elongation.During PrTPEG/GAP crosslinked of the present invention 20 DEG C, tensile strength is 0.406MPa, and unit elongation is 70.42%; And tensile strength is 0.215MPa during BPS/GAP crosslinked 20 DEG C in documents, unit elongation is 44.68%.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Testing tool:
Number-average molecular weight
Equipment: Britain PL company GPC-50 type gel permeation chromatograph;
GPC test condition: chromatographic column is PLgelMIXED-E series connection; Moving phase is THF; Column temperature is 40 DEG C; Detector
For differential refraction detector.
Film mechanical property
Equipment: American I nstron company Instron4505 type universal testing machine;
Testing method: according to GB/T528-1998.
Embodiment 1
Be furnished with in 500ml tetra-mouthfuls of round-bottomed flasks of mechanical stirring, reflux condensing tube, thermometer, dropping funnel at one and add 200ml tetrahydrofuran (THF), 100g (0.25mol) PEG400 and 7.4ml (0.0125mol) dibutyl tin laurate successively, stir, be heated to 40 DEG C, then 87.08g (0.5mol) TDI is added, 43 DEG C ~ 45 DEG C reaction 6h.In above-mentioned reaction system, drip 29.4g (0.525mol) propiolic alcohol again, at dropwising latter 80 DEG C ~ 82 DEG C, react 8h.Be cooled to room temperature, with saturated aqueous common salt extraction, upper liquid revolves steaming, after vacuum-drying, obtains pale yellow transparent viscous liquid 193.7g, productive rate 90.1%.
Structural Identification: infrared (KBr, cm
-1): 3309 (≡ C-H), 3067 (on phenyl ring C-H), 2965 (-CH
3), 2846 (-CH
2), 2110 (C ≡ C), 1728 (C=O), 1107 ~ 1115 (C-O-C).
Theoretical value average molecular weight is 860, and actual measurement number-average molecular weight is ~ 849.
Compound synthesized by above-mentioned analytical data confirms is exactly PrTPEG.
Application performance of the present invention
(1) with the compatibility of azido binder
Select GAP to be tackiness agent, investigate compatibility and the reactivity of PrTPEG solidifying agent and tackiness agent.
PrTPEG solidifying agent of the present invention and GAP tackiness agent have good compatibility, and mixture is as clear as crystal, and the mixed solution formed can be cured reaction stably at 50 ~ 60 DEG C.
(2) mechanical property of crosslinked
Reacted with BPS solidifying agent and PrTPEG solidifying agent of the present invention respectively by GAP tackiness agent and generate crosslinked, its corresponding mechanical property is in table 1:
Table 1 solidifying agent is on the impact (20 DEG C) of crosslinked mechanical property
| Solidifying agent | Tensile strength, MPa | Unit elongation, % |
| The present invention | 0.406 | 70.42 |
| Correlation technique | 0.215 | 44.68 |
Visible, the mechanical property of the crosslinked that the present invention is formed obviously is better than the mechanical property of BPS base crosslinked.
Claims (2)
1. an end alkynyl radical solidifying agent, is characterized in that structural formula is as follows:
Wherein, n=5 ~ 20 are integer.
2. end alkynyl radical solidifying agent according to claim 1, it is characterized in that preparation method is as follows: take dibutyl tin laurate as catalyzer, tetrahydrofuran (THF) is solvent, terminal hydroxy group polyoxyethylene glycol and tolylene diisocyanate react and generate isocyanate terminated polyoxyethylene glycol, then in reaction system, add propiolic alcohol carry out end capping, form the end alkynyl radical solidifying agent containing urethano polyether chain.
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| CN201510697784.2A CN105175707B (en) | 2015-10-23 | 2015-10-23 | A kind of end alkynyl radical curing agent and preparation method thereof |
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| CN105175707B CN105175707B (en) | 2017-08-08 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753799A (en) * | 2016-03-28 | 2016-07-13 | 西安近代化学研究所 | Energy-containing terminal alkynyl curing agent and preparation method thereof |
| CN106366306A (en) * | 2016-09-07 | 2017-02-01 | 西安近代化学研究所 | Acetylene-terminated ethylene oxide tetrahydrofuran copolyether containing carbamic acid ester units and synthesis method thereof |
| CN106397756A (en) * | 2016-09-07 | 2017-02-15 | 西安近代化学研究所 | Carbamate element terminate propargyl polycaprolactone and synthesis method thereof |
| CN106397639A (en) * | 2016-09-07 | 2017-02-15 | 西安近代化学研究所 | Synthesis method of alkynyl-terminated polybutadiene containing carbamate element |
| CN108503795A (en) * | 2018-04-19 | 2018-09-07 | 西安近代化学研究所 | Crosslinked glycidyl azide polymer of triazoline key and preparation method thereof |
| CN108587544A (en) * | 2018-03-28 | 2018-09-28 | 西安近代化学研究所 | A kind of end azido polycaprolactone adhesive and its synthetic method |
| CN109161012A (en) * | 2018-09-13 | 2019-01-08 | 西安近代化学研究所 | A kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether and its synthetic method containing carbamate structures unit |
| CN109942805A (en) * | 2019-04-02 | 2019-06-28 | 西安近代化学研究所 | The poly- 3- nitric acid ester methyl -3- methy oxetane prepolymer of end alkynyl radical |
| CN114989393A (en) * | 2022-06-28 | 2022-09-02 | 岳阳凯门水性助剂有限公司 | Polyurethane associated thickener, preparation method and application thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753799B (en) * | 2016-03-28 | 2018-01-23 | 西安近代化学研究所 | One kind end alkynyl radical curing agent containing energy and preparation method thereof |
| CN105753799A (en) * | 2016-03-28 | 2016-07-13 | 西安近代化学研究所 | Energy-containing terminal alkynyl curing agent and preparation method thereof |
| CN106366306A (en) * | 2016-09-07 | 2017-02-01 | 西安近代化学研究所 | Acetylene-terminated ethylene oxide tetrahydrofuran copolyether containing carbamic acid ester units and synthesis method thereof |
| CN106397756A (en) * | 2016-09-07 | 2017-02-15 | 西安近代化学研究所 | Carbamate element terminate propargyl polycaprolactone and synthesis method thereof |
| CN106397639A (en) * | 2016-09-07 | 2017-02-15 | 西安近代化学研究所 | Synthesis method of alkynyl-terminated polybutadiene containing carbamate element |
| CN106397639B (en) * | 2016-09-07 | 2018-12-11 | 西安近代化学研究所 | A kind of synthetic method of the end alkynyl radical polybutadiene of amido-containing acid ester unit |
| CN108587544A (en) * | 2018-03-28 | 2018-09-28 | 西安近代化学研究所 | A kind of end azido polycaprolactone adhesive and its synthetic method |
| CN108587544B (en) * | 2018-03-28 | 2020-11-10 | 西安近代化学研究所 | Azido-terminated polycaprolactone adhesive and synthesis method thereof |
| CN108503795B (en) * | 2018-04-19 | 2020-10-27 | 西安近代化学研究所 | Triazoline bond crosslinked poly-azido glycidyl ether and preparation method thereof |
| CN108503795A (en) * | 2018-04-19 | 2018-09-07 | 西安近代化学研究所 | Crosslinked glycidyl azide polymer of triazoline key and preparation method thereof |
| CN109161012A (en) * | 2018-09-13 | 2019-01-08 | 西安近代化学研究所 | A kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether and its synthetic method containing carbamate structures unit |
| CN109161012B (en) * | 2018-09-13 | 2021-01-05 | 西安近代化学研究所 | Azido terminated ethylene oxide-tetrahydrofuran block copolyether containing carbamate structural unit and synthetic method thereof |
| CN109942805A (en) * | 2019-04-02 | 2019-06-28 | 西安近代化学研究所 | The poly- 3- nitric acid ester methyl -3- methy oxetane prepolymer of end alkynyl radical |
| CN109942805B (en) * | 2019-04-02 | 2021-05-18 | 西安近代化学研究所 | Alkynyl-terminated poly-3-nitrate methyl-3-methyloxetane prepolymer |
| CN114989393A (en) * | 2022-06-28 | 2022-09-02 | 岳阳凯门水性助剂有限公司 | Polyurethane associated thickener, preparation method and application thereof |
| CN114989393B (en) * | 2022-06-28 | 2024-03-26 | 岳阳凯门水性助剂有限公司 | Polyurethane association thickener and preparation method and application thereof |
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