CN105175707B - A kind of end alkynyl radical curing agent and preparation method thereof - Google Patents
A kind of end alkynyl radical curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN105175707B CN105175707B CN201510697784.2A CN201510697784A CN105175707B CN 105175707 B CN105175707 B CN 105175707B CN 201510697784 A CN201510697784 A CN 201510697784A CN 105175707 B CN105175707 B CN 105175707B
- Authority
- CN
- China
- Prior art keywords
- curing agent
- alkynyl radical
- radical curing
- end alkynyl
- follows
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyethers (AREA)
Abstract
The invention discloses a kind of end alkynyl radical curing agent, its structural formula is as follows：
Description
Technical field
The present invention relates to a kind of solid propellant end alkynyl radical curing agent, more particularly to it is a kind of containing urethano polyether chain
End alkynyl radical curing agent.
Background technology
Azido binder has positive generation heat, fast burning, energy height, combustion gas cleaning, heat endurance good and mechanical sensitivity
Low advantage, is the desired adhesion agent of high energy low characteristic signal propellant, gas generator propellant and highly filled propellant powder.Nitrine
The Typical Representative of adhesive is nitrine glycidol ether (GAP), and GAP has the advantages that above azido binder.GAP is when in use
Isocyanate cure systems typically are constituted with polyfunctionality isocyanate curing agent, react solid by terminal hydroxy group and NCO
Change, but the isocyanate curing agent in such curing system has high activity, Yi Yushui or Bronsted acid fast reaction generation
CO2, many stomatas are formed in the solidification process of propellant so that the density of propellant declines, and influences its mechanical property, simultaneously
So that the safety and reliability of propellant also declines.
In order to solve the above mentioned problem of isocyanate curing agent presence, scientific research personnel develops end alkynyl radical curing agent, and it can
Polytriazoles cross-linked elastomer is solidify to form with azido binder.Such as Thomas Keicher et al.《Isocyanate-free
curing of glycidyl-azide-polymer(GAP)with bis-propargyl-succinate》39th Int
Annu Conf of ICT, 2008 disclose a kind of end alkynyl radical curing agent, the i.e. propynyl ester of succinic acid two (BPS), and its structural formula is such as
Under：
BPS and two degree of functionality GAP (Mn=1570) and three-functionality-degree GAP (Mn=980) mixture carry out curing reaction,
When the degree of functionality GAP (Mn=1570) of BPS/ bis-/three-functionality-degree GAP (Mn=980) mass ratio be 8.97%/79.58%/
Solidify obtained film mechanical property when 11.45% as follows：Tensile strength is 0.215MPa, and elongation percentage is 44.68%, film
Mechanical property is relatively low.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of background technology there is provided a kind of higher end of mechanical property
Alkynyl curing agent and preparation method thereof.
Idea of the invention is that：The reason for BPS base polytriazole elastomer mechanical properties are relatively low is that BPS solidifies for small molecule
The interphase interaction of polytriazoles hard segment is weak in agent, the elastomer after solidification, is unfavorable between microphase-separated, and crosslinking points
Segment it is partially short.It is contemplated by the invention that：1) urethane group is introduced in alkynyl solidification agent molecule, is made using the hydrogen bond between urethane group
For promoting the microphase-separated of elastomer, mechanical strength is improved；2) polyglycol chain of flexibility is introduced in alkynyl curing agent, is carried
The elongation percentage of high resiliency body.
In order to solve the above-mentioned technical problem, the end alkynyl radical curing agent containing urethano polyether chain that the present invention is provided, it is tied
Structure formula is as follows：
Wherein, n=5~20, are integer.
The synthetic route of the present invention is as follows：
Wherein, n=5~20, are integer.
Particular technique approach：Using dibutyl tin laurate as catalyst, tetrahydrofuran is solvent, terminal hydroxy group polyethylene glycol
(PEG) react the isocyanate terminated polyethylene glycol of generation with toluene di-isocyanate(TDI) (TDI), states then up in reaction system
Add propilolic alcohol and carry out end capping reaction, form the end alkynyl radical curing agent (PrTPEG) containing urethano polyether chain.
Advantages of the present invention：1) urethane group is introduced in PrTPEG molecules, is promoted using the hydrogen bond action between urethane group
Enter the microphase-separated of crosslinked, improve mechanical strength；2) polyglycol chain of flexibility is introduced in PrTPEG, prolonging for elastomer is improved
Stretch rate.Tensile strength is 0.406MPa during 20 DEG C of the PrTPEG/GAP crosslinkeds of the present invention, and elongation percentage is 70.42%；And contrast
Tensile strength is 0.215MPa during 20 DEG C of BPS/GAP crosslinkeds in file, and elongation percentage is 44.68%.
Embodiment
With reference to embodiment, the present invention is described further.
Tester：
Number-average molecular weight
Equipment：Britain's PL companies GPC-50 type gel permeation chromatographs；
GPC test conditions：Chromatographic column is connected for PLgel MIXED-E；Mobile phase is THF；Column temperature is 40 DEG C；Detector
For differential refraction detector.
Film mechanical property
Equipment：The type universal testing machines of Instron companies of U.S. Instron 4505；
Method of testing：According to GB/T528-1998.
Embodiment 1
One be furnished with mechanical agitation, reflux condensing tube, thermometer, the 500ml four round flask of dropping funel according to
Secondary addition 200ml tetrahydrofurans, 100g (0.25mol) PEG400 and 7.4ml (0.0125mol) dibutyl tin laurate, are stirred
Mix uniform, be heated to 40 DEG C, then add 87.08g (0.5mol) TDI, 43 DEG C~45 DEG C reaction 6h.Again to above-mentioned reaction system
After middle dropwise addition 29.4g (0.525mol) propilolic alcohol, completion of dropping 8h is reacted at 80 DEG C~82 DEG C.Room temperature is cooled to, is eaten with saturation
Salt solution is extracted, upper liquid revolving, after vacuum drying, obtains pale yellow transparent viscous liquid 193.7g, yield 90.1%.
Structural Identification：Infrared (KBr, cm-1)：3309 (≡ C-H), 3067 (C-H on phenyl ring), 2965 (- CH3),2846(-
CH2), 2110 (C ≡ C), 1728 (C=O), 1107~1115 (C-O-C).
Theoretical number-average molecular weight is 860, and actual measurement number-average molecular weight is~849.
Above-mentioned analyze data confirms that synthesized compound is exactly PrTPEG.
The application performance of the present invention
(1) with the compatibility of azido binder
It is adhesive from GAP, has investigated the compatibility and reactivity of PrTPEG curing agent and adhesive.
The PrTPEG curing agent of the present invention has good compatibility with GAP adhesives, and mixture is as clear as crystal, is formed
Mixed liquor curing reaction can be smoothly carried out at 50~60 DEG C.
(2) mechanical property of crosslinked
GAP adhesives are generated into crosslinked with BPS curing agent and the reaction of the PrTPEG curing agent of the present invention respectively, its is corresponding
Mechanical property be shown in Table 1：
Influence (20 DEG C) of the curing agent of table 1 to crosslinked mechanical property
| Curing agent | Tensile strength, MPa | Elongation percentage, % |
| The present invention | 0.406 | 70.42 |
| Correlation technique | 0.215 | 44.68 |
It can be seen that, the mechanical property for the crosslinked that the present invention is formed is substantially better than the mechanical property of BPS base crosslinkeds.
Claims (2)
1. a kind of application of end alkynyl radical curing agent in azido binder solidification, it is characterised in that the end alkynyl radical curing agent structural formula
It is as follows：
Wherein, n=5~20, are integer.
2. a kind of application of the end alkynyl radical curing agent according to claim 1 in azido binder solidification, it is characterised in that
The end alkynyl radical curing agent preparation method is as follows：Using dibutyl tin laurate as catalyst, tetrahydrofuran is solvent, and terminal hydroxy group gathers
Ethylene glycol is reacted with toluene di-isocyanate(TDI) and generates isocyanate terminated polyethylene glycol, and propine is then added into reaction system
Alcohol carries out end capping reaction, forms the end alkynyl radical curing agent containing urethano polyether chain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510697784.2A CN105175707B (en) | 2015-10-23 | 2015-10-23 | A kind of end alkynyl radical curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510697784.2A CN105175707B (en) | 2015-10-23 | 2015-10-23 | A kind of end alkynyl radical curing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105175707A CN105175707A (en) | 2015-12-23 |
| CN105175707B true CN105175707B (en) | 2017-08-08 |
Family
ID=54898192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510697784.2A Active CN105175707B (en) | 2015-10-23 | 2015-10-23 | A kind of end alkynyl radical curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105175707B (en) |
Families Citing this family (9)
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4227007A (en) * | 1977-01-31 | 1980-10-07 | Basf Aktiengesellschaft | Diurethanes |
| US4276211A (en) * | 1980-03-10 | 1981-06-30 | Troy Chemical Corporation | Stabilization composition for coating composition |
| CN102241820A (en) * | 2011-03-03 | 2011-11-16 | 华东理工大学 | Novel polytriazole elastomer and preparation method thereof |
| CN102702536A (en) * | 2012-05-14 | 2012-10-03 | 华东理工大学 | Synthetic method of triblock polymer |
| CN103865073A (en) * | 2014-03-31 | 2014-06-18 | 东南大学 | Method for preparing polyethylene glycol network hydrogel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62249961A (en) * | 1986-04-21 | 1987-10-30 | Showa Highpolymer Co Ltd | Unsaturated urethane compound and production thereof |
-
2015
- 2015-10-23 CN CN201510697784.2A patent/CN105175707B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4227007A (en) * | 1977-01-31 | 1980-10-07 | Basf Aktiengesellschaft | Diurethanes |
| US4276211A (en) * | 1980-03-10 | 1981-06-30 | Troy Chemical Corporation | Stabilization composition for coating composition |
| CN102241820A (en) * | 2011-03-03 | 2011-11-16 | 华东理工大学 | Novel polytriazole elastomer and preparation method thereof |
| CN102702536A (en) * | 2012-05-14 | 2012-10-03 | 华东理工大学 | Synthetic method of triblock polymer |
| CN103865073A (en) * | 2014-03-31 | 2014-06-18 | 东南大学 | Method for preparing polyethylene glycol network hydrogel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105175707A (en) | 2015-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105175707B (en) | A kind of end alkynyl radical curing agent and preparation method thereof | |
| Cornille et al. | Room temperature flexible isocyanate-free polyurethane foams | |
| Cornille et al. | Syntheses of epoxyurethane polymers from isocyanate free oligo-polyhydroxyurethane | |
| CN105294948B (en) | One kind is applied to supercritical CO2Fluorochemical urethane thickener of thickening and preparation method thereof | |
| Asemani et al. | Synthesis and evaluation of non-isocyanate polyurethane polyols for heat-cured thermoset coatings | |
| Sardon et al. | Homogeneous isocyanate-and catalyst-free synthesis of polyurethanes in aqueous media | |
| Liu et al. | Synthesis and properties of non-isocyanate polyurethane coatings derived from cyclic carbonate-functionalized polysiloxanes | |
| Liu et al. | Synthesis and properties of POSS-containing gallic acid-based non-isocyanate polyurethanes coatings | |
| CN110229310B (en) | Curing agent for modified waterborne epoxy resin and preparation method thereof | |
| CN105038684A (en) | Method for preparing environment-friendly polyurethane adhesive for plastic track | |
| Wang et al. | Synthesis and properties of cyclic carbonates and non-isocyanate polyurethanes under atmospheric pressure | |
| CN108822288A (en) | A kind of alkenyl polyether is containing can nitric acid ester adhesive and its synthetic method | |
| CN106750077A (en) | A kind of preparation method of side chain type hydrophobic oleophobic fluorochemical urethane | |
| CN105968303A (en) | Preparation method of water-based epoxy resin curing agent | |
| CN112341349A (en) | Functional group-containing benzoxazine oligomer, low-temperature crosslinked benzoxazine resin and preparation method thereof | |
| CN105199653A (en) | High-strength low-viscosity island modified polyurethane resin | |
| CN105753799B (en) | One kind end alkynyl radical curing agent containing energy and preparation method thereof | |
| CN108276939B (en) | Energy-containing adhesive for room temperature curing and synthesis method thereof | |
| CN109942805A (en) | The poly- 3- nitric acid ester methyl -3- methy oxetane prepolymer of end alkynyl radical | |
| CN110511372A (en) | One kind terminal isocyanate group curing agent containing energy and its synthetic method | |
| CN109355061B (en) | Epoxy soybean oil adhesive with function of modifying polyurethane by amine curing agent and preparation method thereof | |
| KR20170063583A (en) | Nco-free compounds and usage thereof in a curable composition | |
| CN109837053A (en) | A kind of polyene-based polytetrahydrofuran adhesive and its synthetic method | |
| Wang et al. | Performance properties of self-curing aqueous-based PU system with tri-glycidyl phosphate curing agent | |
| Kozakiewicz et al. | New family of functionalized crosslinkers for heat-curable polyurethane systems—A preliminary study |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |