CN104181184B - The reactivity sequential determination method of active hydrogen component and hardening agent is contained in propellant - Google Patents
The reactivity sequential determination method of active hydrogen component and hardening agent is contained in propellant Download PDFInfo
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- CN104181184B CN104181184B CN201310200525.5A CN201310200525A CN104181184B CN 104181184 B CN104181184 B CN 104181184B CN 201310200525 A CN201310200525 A CN 201310200525A CN 104181184 B CN104181184 B CN 104181184B
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Abstract
The present invention is a kind of reactivity sequential determination method for containing active hydrogen component and hardening agent in the propellant of aerospace fuel nmr analysis.The steps include: to determine detected object, preparation detects sample, selects testing conditions, implements sample detection, detects data processing; It is to mix system for detected object containing active hydrogen component with toluene diisocyanate in propellant.Detection sample is mixed by radical concentration proportioning, grouping, choose appropriate amount of sample, is placed in chromatogram bottle.Adopt low-field nuclear magnetic resonance spectrometer, choose testing conditions.Detect spin spin relaxation time <i>T</iGreatT.Gr eaT.GT
2with the change curve in reaction time, each curve ordinate is normalized, the speed degree of the front slope change that tends towards stability according to curve, draws the reactivity order of each component and toluene diisocyanate (TDI).The advantage that the present invention also has that simple to operate, experiment safety, expense are saved, data are reliable, testing conditions optimization, testing process simplify.
Description
Technical field
The present invention relates to a kind of nmr analysis method of organic chemistry filed of aerospace fuel, specifically in a kind of propellant, contain the reactivity sequential determination method of active hydrogen component and hardening agent.
Background technology
Chinese periodical " solid-rocket technology " the 33rd volume the 5th phase in 2010 reports the document curing reaction Kinetics research of active hydrogen component " in the NEPE propellant ", this document propose and adopt chemical titration to measure respectively under different temperatures end hydroxy polyether (PEG)/phenylisocyanate (PI), bonding agent (NPBA)/PI, the polymerization kinetics curves that in stabilization agent (MNA)/PI system, the concentration of-NCO changed with the reaction time, and then calculate corresponding system reaction rate constant at different temperatures and energy of activation, by comparing the size of reaction rate constant and energy of activation, obtain end hydroxy polyether (PEG), bonding agent (NPBA) and stabilization agent (MNA) with the reactivity order of phenylisocyanate (PI) are respectively: MNA>PEG>NPBA.Chemistry titration needs in measuring to use toluene/dimethyl sulfoxide (DMSO), di-n-butylamine/toluene solvant.
Chinese periodical " Push Technology " the 29th volume the 6th phase in 2008 reports the document reactivity research of active hydrogen component " in the HTPB propellant curing system ", this document propose and adopt chemical titration to measure respectively under different temperatures end hydroxy butadiene (HTPB)/phenylisocyanate (PI), bonding agent (BA25)/PI and antioxidant H (N, N '-diphenyl-para-phenylene diamine) in/PI system the concentration of-NCO with the change in reaction time, calculate reaction rate and the energy of activation of corresponding system, by comparing the size of reaction rate constant and energy of activation, obtain containing active hydrogen component HTPB, the reactivity order of BA25 and antioxidant H and PI is: the amido in the hydroxyl > antioxidant H on the upper amido >HTPB of bonding agent (BA25) on hydroxyl >BA25.Chemistry titration needs in measuring to use toluene/dimethyl sulfoxide (DMSO), di-n-butylamine/toluene solvant.
Above-mentioned open source literature reflects the state of the art containing active hydrogen component and hardening agent reactivity sequential determination method in propellant, and its defect existed is: operating process is loaded down with trivial details, and experiment needs reagent, and testing conditions is harsh, detects data and can only be used for indirectly comparing.
Summary of the invention
The object of the invention is to provide a kind of reactivity sequential determination method containing active hydrogen component and hardening agent in propellant, it can simplify the operation step, reliably optimum detection condition effectively, reflects reactivity intuitively sequentially.
Technical scheme of the present invention is:
Design a kind of reactivity sequential determination method containing active hydrogen component and hardening agent in propellant, comprise following five steps: determine detected object, preparation detects sample, select testing conditions, implement sample detection, detect data processing, it is characterized in that: determining in detected object process: detected object is the spin spin relaxation time T mixing hydrogen in system in propellant containing active hydrogen component with toluene diisocyanate TDI
2; Detect in sample in preparation: mix by radical concentration proportioning, grouping, choose appropriate amount of sample, be placed in chromatogram bottle; In selection testing conditions process: adopt low-field nuclear magnetic resonance spectrometer, choose detected parameters, setting sampling number and sampling termination time; In detection data handling procedure: detect spin spin relaxation time T
2with the change curve in reaction time, each curve ordinate is normalized, the speed degree of the front slope change that tends towards stability according to curve, draws the reactivity order of each component and toluene diisocyanate TDI.
Wherein, determining in detected object process, comprising containing active hydrogen component in propellant: stearic acid (YS); 2,2,4-trimethyl-1,2-dihyaroquinoline condensate (RD); N, N '-diphenyl-para-phenylene diamine (antioxidant H); α, alpha-alpha-dimethyl phenmethylol (PB).
Wherein, detect in sample in preparation, select in propellant containing in the hydroxyl of active hydrogen component or amido and toluene diisocyanate (TDI)-NCO group, molar concentration is than 1:1 mode proportioning; Often kind of active hydrogen component is taken 3g, is placed in beaker, mix with toluene diisocyanate (TDI); Choose appropriate amount of sample, be positioned in 2ml chromatogram bottle, height of specimen about 2cm.
Wherein, in selection testing conditions process, the testing conditions chosen is: resonant frequency 21.800MHz, magnet strength 0.51T, coil diameter is 10mm, and sampling bandwidth SW is 200kHz, and starting sampling time D3 is 75 μ s, repeating stand-by period TR is 1000ms, digital gain RG1 is 20, and analog gain RG2 is 3, and repeated sampling times N S is 2, half echo time tau is 100 μ s, echo number EchoCnt is 5000; At 80 DEG C, every 1min or 5min, sampling should be carried out, until T
2change curve tends towards stability in time.
The invention has the beneficial effects as follows: because testing process have employed low-field nuclear magnetic resonance spectrometer, thus improve accuracy and the science of testing process, avoid that the operating process of chemical titration complexity, frequently reagent are selected, troublesome temperature test.Simultaneously because data processing have employed the normalization of each curve ordinate, thus the reactivity order reflecting each component and toluene diisocyanate (TDI) intuitively be can form, loaded down with trivial details chemical reaction rate constant and the computation process of energy of activation avoided.The advantage that the present invention also has that simple to operate, experiment safety, expense are saved, data are reliable, testing conditions optimization, testing process simplify.
Accompanying drawing explanation
Fig. 1 is the T of YS and TDI reaction
2curve map;
Fig. 2 is the T of RD and TDI reaction
2curve map;
Fig. 3 is the T that antioxidant H and TDI react
2curve map;
Fig. 4 is the T of PB and TDI reaction
2curve map;
Fig. 5 is the T that in propellant, four kinds are reacted with TDI respectively containing active hydrogen component
2curve is always schemed.
In figure, YS is stearic acid; RD is 2,2,4-trimethyl-1,2-dihyaroquinoline condensate; Antioxidant H is N, N '-diphenyl-para-phenylene diamine; PB is α, alpha-alpha-dimethyl phenmethylol; TDI is toluene diisocyanate; T
2for the spin spin relaxation time of hydrogen, represent with ordinate, unit is millisecond (ms); Horizontal ordinate is the reaction time, and unit is minute (min); T
2/ T
maxfor each bar curve ordinate normalization result, i.e. the T of each bar curve each detection time of point
2with this curve first T put detection time
maxratio.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Step one, determines detected object: detected object is the spin spin relaxation time T mixing hydrogen in system in propellant containing active hydrogen component with toluene diisocyanate TDI
2.Comprise containing active hydrogen component in propellant: stearic acid (YS); 2,2,4-trimethyl-1,2-dihyaroquinoline condensate (RD); N, N '-diphenyl-para-phenylene diamine (antioxidant H); α, alpha-alpha-dimethyl phenmethylol (PB).
Step 2, preparation detects sample: radical concentration proportioning, grouping mixes, and chooses appropriate amount of sample, is placed in chromatogram bottle.Select in propellant containing in the hydroxyl of active hydrogen component or amido and toluene diisocyanate (TDI)-NCO group, molar concentration is than 1:1 mode proportioning.Often kind of active hydrogen component is taken 3g, is placed in beaker, mix with toluene diisocyanate (TDI).Choose appropriate amount of sample, be positioned in 2ml chromatogram bottle, height of specimen about 2cm.
Step 3, selects testing conditions: adopt low-field nuclear magnetic resonance spectrometer, choose detected parameters, setting sampling number and sampling termination time.Described testing conditions is: resonant frequency 21.800MHz, magnet strength 0.51T, coil diameter is 10mm, and sampling bandwidth SW is 200kHz, and starting sampling time D3 is 75 μ s, repeating stand-by period TR is 1000ms, digital gain RG1 is 20, and analog gain RG2 is 3, and repeated sampling times N S is 2, half echo time tau is 100 μ s, echo number EchoCnt is 5000; At 80 DEG C, every 1min or 5min, sampling should be carried out, until T
2change curve tends towards stability in time.
Step 4, examinations process: nmr spectrometer experimental temperature is set to 80 DEG C, after instrument is warming up to 80 DEG C and is constant, according to the testing conditions in step 3, carries out the automatic collection of nuclear magnetic data.Gather to obtain after terminating each hydrogeneous component respectively with the spin spin relaxation time T of TDI mixed system
2with the change curve in reaction time.
Step 5, detect data processing: be normalized by each curve ordinate, tend towards stability according to curve the speed degree of front slope change, show that the reactivity of each component and toluene diisocyanate TDI is sequentially: antioxidant H >RD>YS>PB.
Claims (4)
1. in a propellant, contain the reactivity sequential determination method of active hydrogen component and hardening agent, comprise following five steps: determine detected object, preparation detects sample, select testing conditions, implement sample detection, detect data processing, it is characterized in that: determining in detected object process, detected object is the spin spin relaxation time mixing hydrogen in system in propellant containing active hydrogen component with toluene diisocyanate (TDI)
t 2; Detect in sample in preparation, by radical concentration proportioning, grouping mixes, and chooses appropriate amount of sample, is placed in chromatogram bottle; In selection testing conditions process, adopt low-field nuclear magnetic resonance spectrometer, choose detected parameters, setting sampling number and sampling termination time; In detection data handling procedure, detect spin spin relaxation time
t 2with the change curve in reaction time, each curve ordinate is normalized, the speed degree of the front slope change that tends towards stability according to curve, draws the reactivity order of each component and toluene diisocyanate (TDI).
2. contain the reactivity sequential determination method of active hydrogen component and hardening agent in propellant according to claim 1, it is characterized in that: determining in detected object process, comprise containing active hydrogen component in propellant: stearic acid (YS); 2,2,4-trimethyl-1,2-dihyaroquinoline condensate (RD); N, N '-diphenyl-para-phenylene diamine (antioxidant H); A, a-dimethylphenylcarbinol (PB).
3. in propellant according to claim 1, contain the reactivity sequential determination method of active hydrogen component and hardening agent, it is characterized in that: detect in sample in preparation, select in propellant containing in the hydroxyl of active hydrogen component or amido and toluene diisocyanate (TDI)-NCO group, molar concentration is than 1:1 mode proportioning; Often kind of active hydrogen component is taken 3g, is placed in beaker, mix with toluene diisocyanate (TDI); Choose appropriate amount of sample, be positioned in 2ml chromatogram bottle, height of specimen 2cm.
4. in propellant according to claim 1, contain the reactivity sequential determination method of active hydrogen component and hardening agent, it is characterized in that: in selection testing conditions process, the testing conditions chosen is: resonant frequency 21.800MHz, magnet strength 0.51T, coil diameter is 10mm, sampling bandwidth SW is 200kHz, starting sampling time D3 is 75ms, repeating stand-by period TR is 1000ms, digital gain RG1 is 20, and analog gain RG2 is 3, and repeated sampling times N S is 2, half echo time tau is 100ms, and echo number EchoCnt is 5000; At 80 DEG C, every 1min or 5min, sampling should be carried out, until
t 2change curve tends towards stability in time.
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Citations (4)
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| JPH04231849A (en) * | 1990-05-18 | 1992-08-20 | Aerojet General Corp | Prediction of quality of product by analysis of basic factor of spectrum of reacting body |
| US7246939B1 (en) * | 2003-10-23 | 2007-07-24 | Gultekin David H | Measurement of thermal diffusivity, thermal conductivity, specific heat, specific absorption rate, thermal power, heat transfer coefficient, heat of reaction and membrane permeability by nuclear magnetic resonance |
| CN101659893A (en) * | 2009-09-28 | 2010-03-03 | 浙江大学 | Poly (methyl) acrylic acid ferrocene acyloxy ethyl ester burning-rate accelerator and propellant containing same and preparation method thereof |
| CN102728408A (en) * | 2012-07-02 | 2012-10-17 | 南京师范大学 | Core-shell nano-catalyst for composite propellant and preparation method thereof by stepwise grafting |
-
2013
- 2013-05-27 CN CN201310200525.5A patent/CN104181184B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04231849A (en) * | 1990-05-18 | 1992-08-20 | Aerojet General Corp | Prediction of quality of product by analysis of basic factor of spectrum of reacting body |
| US7246939B1 (en) * | 2003-10-23 | 2007-07-24 | Gultekin David H | Measurement of thermal diffusivity, thermal conductivity, specific heat, specific absorption rate, thermal power, heat transfer coefficient, heat of reaction and membrane permeability by nuclear magnetic resonance |
| CN101659893A (en) * | 2009-09-28 | 2010-03-03 | 浙江大学 | Poly (methyl) acrylic acid ferrocene acyloxy ethyl ester burning-rate accelerator and propellant containing same and preparation method thereof |
| CN102728408A (en) * | 2012-07-02 | 2012-10-17 | 南京师范大学 | Core-shell nano-catalyst for composite propellant and preparation method thereof by stepwise grafting |
Non-Patent Citations (2)
| Title |
|---|
| 1H NMR analysis of the tolylene-2,4-diisocyanate–methanol reaction;Peng Fei Yang et al.;《Chinese Chemical Letters》;20100731;第21卷(第7期);853-855 * |
| HTPB–异氰酸酯体系的固化反应机理研究进展;邱磊;《化学推进剂与高分子材料》;20120831;第10卷(第4期);1-6 * |
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