CN105301031A - Method for determining hydrogen-containing silicone oil residual quantity in trisiloxane surfactant by one-dimensional hydrogen nuclear magnetic resonance method - Google Patents
Method for determining hydrogen-containing silicone oil residual quantity in trisiloxane surfactant by one-dimensional hydrogen nuclear magnetic resonance method Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 123
- 239000001257 hydrogen Substances 0.000 title claims abstract description 123
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 48
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 37
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000001225 nuclear magnetic resonance method Methods 0.000 title description 2
- 238000005481 NMR spectroscopy Methods 0.000 claims abstract description 51
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 40
- -1 methyl hydrogen Chemical class 0.000 claims abstract description 13
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001228 spectrum Methods 0.000 claims description 18
- 238000013459 approach Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 238000012113 quantitative test Methods 0.000 claims description 6
- 238000003556 assay Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 22
- 238000012360 testing method Methods 0.000 abstract description 22
- 230000005311 nuclear magnetism Effects 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000004445 quantitative analysis Methods 0.000 abstract description 5
- 239000000523 sample Substances 0.000 description 30
- 239000000126 substance Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 238000004448 titration Methods 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000009533 lab test Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GMVJKSNPLYBFSO-UHFFFAOYSA-N 1,2,3-tribromobenzene Chemical compound BrC1=CC=CC(Br)=C1Br GMVJKSNPLYBFSO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical group C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses a determination method of hydrogen-containing silicone oil residual quantity in a trisiloxane surfactant. The determination method comprises the following steps of adopting one-dimensional hydrogen nuclear magnetic resonance, and using single-peaked 1,3,5-tribromobenzene as a unified internal standard to perform quantitative analysis or concentration determination on the trisiloxane surfactant, wherein the quantitative analysis is performed by using the single-peaked internal standard as a one-dimensional nuclear magnetic resonance quantitative medium. The method not only can be used for determining the hydrogen content of methyl hydrogen silicone oil and block hydrogen silicone oil, but also can be used for the determination of the content of hydrogen-containing silicone oil in the trisiloxane surfactant. The concentration of each monomeric compound can be directly obtained through calculation according to a direct ratio relationship between the integral of a characteristic nuclear magnetism signal of a compound in a sample and the concentration thereof. According to the method, the problems that the determination is inaccurate and a test is complex due to overlapped signals of the trisiloxane surfactant are solved, and the experimental scheme of the method also has the possibility of accurately determining the content of multiple compounds in a mixture.
Description
Technical field
The invention belongs to chemical apparatuses analytical approach field, specifically, relate to the residual quantity that one-dimensional nuclear magnetic resonance hydrogen spectrometry measures containing hydrogen silicone oil in trisiloxane surfactant.
Background technology
Nuclear magnetic resonance technique has become a kind of requisite instrument in the qualitative examination of compound, because it can provide the most detailed, the most true and reliable chemical structure information.Along with the development of nuclear magnetic resonance technique, one-dimensional nuclear magnetic resonance is also usually used in quantitative test, because it has the advantage of many uniquenesses:
For the core determined, its signal intensity is directly proportional to the number of the core producing this signal, and has nothing to do with the chemical property of core.Utilize internal standard method or relative measurement method, in analysis of mixtures during a certain compound, without the need to the sterling standard in contrast of this compound.The narrower in width at NMR signal peak, much smaller than the difference of the chemical shift between each signal, thus in potpourri different component signal between less generation significantly overlapping.Nuclear magnetic resonance test experiments simply and do not destroy sample.
Described trisiloxane surfactant principal ingredient is 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD
hm, belongs to containing hydrogen silicone oil) a series of potpourris of being obtained by hydrosilylation from different allyl polyethers (number of different EO, PO segment, and different end-capping group, as methyl, acetyl group and hydroxyl etc.).In trisiloxane surfactant, residual containing hydrogen silicone oil can produce adverse influence to the packaging of product, and namely the residual meeting of containing hydrogen silicone oil causes having hydrogen to produce in product, is unfavorable for the packaging of product.For this reason, by formulating corresponding standard, making the product meeting corresponding index could be used for packaging, the production of three siloxy surface activating agents could be instructed so better.
In trisiloxane surfactant, the residual quantity of silicone oil represents by this index of hydrogen content.The residual quantity of hydrogen content lower explanation containing hydrogen silicone oil is fewer.
The existing report measuring certain containing hydrogen silicone oil raw material hydrogen content before this, main method of testing has chemical method, infra-red sepectrometry and hydrogen nuclear magnetic resonance spectroscopy.Wherein chemical titration Chang Zuowei sets up the benchmark measuring all kinds of containing hydrogen silicone oil hydrogen content method.Although there is the report of nuclear magnetic resonance internal mark method determination silicone oil raw material hydrogen content, the method that have not been reported containing hydrogen silicone oil residual quantity in the nuclear magnetic resonance internal mark method determination trisiloxane surfactant of the residual quantity of containing hydrogen silicone oil in nuclear magnetic resonance internal mark method determination mixture system-namely have not been reported.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, there is provided a kind of simply, efficiently one-dimensional nuclear magnetic resonance hydrogen spectrometry measure the residual quantity of containing hydrogen silicone oil in trisiloxane surfactant, affect the accurate quantitative analysis of certain compound due to signal overlap to solve in conventional hydrogen spectrum and test loaded down with trivial details problem.Solving this quantitative problem is production in order to instruct trisiloxane surfactant better, makes the trisiloxane surfactant product obtained not easily produce bubble after packaging, thus the possibility of breaking after avoiding packaging.
In order to realize above-mentioned object, the present invention adopts following technical scheme:
The invention provides the method that one-dimensional nuclear magnetic resonance hydrogen spectrometry measures containing hydrogen silicone oil residual quantity in trisiloxane surfactant.The key of the method is to select suitable internal standard compound matter, thus avoid corresponding quantitative overlap of peaks cause cannot be quantitative problem, make this internal standard compound matter can play a bridge beam action in quantitatively, can by and undertaken converting by quantitative material and draw the concrete content of test substance.
The assay method of containing hydrogen silicone oil residual quantity in a kind of trisiloxane surfactant, comprise the steps: to adopt one-dimensional nuclear magnetic resonance hydrogen spectrum, with unimodal 1,3,5 ?tribromo-benzene be mark in unified, quantitative test or concentration determination are carried out to trisiloxane surfactant, uses unimodal interior mark to carry out quantitative test as the medium that one-dimensional nuclear magnetic resonance is quantitative.
As preferably, in said determination method, use one-dimensional nuclear magnetic resonance hydrogen spectrum to be quantivative approach, within be designated as bridge, measure the hydrogen content of Methyl Hydrogen Polysiloxane Fluid or block containing hydrogen silicone oil.
As preferably, in said determination method, use one-dimensional nuclear magnetic resonance hydrogen spectrum to be quantivative approach, within be designated as bridge, the residual quantity of containing hydrogen silicone oil in the trisiloxanes class surfactant of quantitative different molecular weight or different structure.
One-dimensional nuclear magnetic resonance method is used to measure the application in blend sample in compound concentration, owing to measuring the relative concentration ratio of some compound in potpourri, when calculating the result of relative concentration ratio gained, have nothing to do with the concentration of interior sample body, energy Accurate Determining often plants concentration or the relative scale of monomeric compound.The present invention measures the content of certain particular compound in potpourri, adopts one-dimensional nuclear magnetic resonance hydrogen to compose quantitative analytical approach, surely needs quantitative compound by mapping in suitable.
Compared with prior art, the present invention has following beneficial effect:
1. preparation of samples is simple: one of key factor of the method uses a kind of unimodal compound of solid that contains as single universal dosed interior mark.Adopt single interior mark, only need mix and can get out nuclear-magnetism sample to be measured.Testing mixture sample dissolution is mixed directly can carry out nuclear magnetic resonance experiment with the mother liquor of interior mark normal concentration.
2. the experiments of measuring time is relatively short: the time (5-10min) using single interior target nuclear-magnetism sample to carry out testing is less than the minute (40min) of chemical titration.
The method not only may be used for the mensuration of Methyl Hydrogen Polysiloxane Fluid and block containing hydrogen silicone oil hydrogen content, also can be applied to the mensuration of containing hydrogen silicone oil content in trisiloxane surfactant, and general method can only be used for the hydrogen content measuring Methyl Hydrogen Polysiloxane Fluid or block containing hydrogen silicone oil.The concentration of each monomeric compound can per sample in the integration of feature nuclear magnetic signal of compound and the proportional relation of its concentration directly calculate acquisition.This method solve trisiloxanes class surfactant signal overlap to cause measuring inaccurate and testing loaded down with trivial details problem, the experimental program of this invention also has the possibility of compound multiple in potpourri being carried out to accurate quantitative analysis.If only pay close attention to the relative concentration ratio between compound, adopt this invention experimental program, the result obtained is not by the impact of general interior target concentration.
Accompanying drawing explanation
Fig. 1 is MD
hm and interior target one-dimensional nuclear magnetic resonance hydrogen spectrogram, choose MD
hthe Si-H proton peak of M is as quantitative foundation, and its chemical shift is about 4.6ppm.Interior target chemical shift is about 7.6ppm, and using this chemical shift as quantitative peak, Fig. 1 uses internal mark method determination MD
han illustration of the hydrogen content of M.
Fig. 2 is MD
hm and interior target canonical plotting, the related coefficient quantitatively obtained is 0.99976, illustrates that the interior mark used can the content of accurate quantitative analysis containing hydrogen silicone oil.In order to the method checking proton nmr spectra quantitative further, we use chemical determination MD
hthe hydrogen content of M, with the value of the hydrogen content of chemical determination containing hydrogen silicone oil for standard.
Fig. 3 is that to measure mean molecular weight be MD in the trisiloxane surfactant of about 612 to embodiment 2
hthe one-dimensional nuclear magnetic resonance hydrogen spectrogram of the content of M.
Fig. 4 is embodiment 3 determining molecular weight is MD in the trisiloxane surfactant of about 674
hthe one-dimensional nuclear magnetic resonance hydrogen spectrogram of the content of M.
Fig. 5 is embodiment 4 determining molecular weight is MD in the trisiloxane surfactant of about 807
hthe one-dimensional nuclear magnetic resonance hydrogen spectrogram of the content of M.
Embodiment
Below in conjunction with accompanying drawing, further illustrate essentiality content of the present invention with embodiments of the invention, but do not limit the present invention with this.
1, nuclear magnetic resonance experiment:
The nuclear magnetic resonance test experiments of the embodiment of the present invention and collection of illustrative plates process and data analysis are carried out by the following method:
Nuclear magnetic resonance test experiments: all nuclear magnetic resonance experiments involved by invention all at 25 DEG C (298K), model be BrukerAVANCE400 nuclear magnetic resonance spectrometer on carry out.The experiment of one-dimensional nuclear magnetic resonance hydrogen spectrum adopts Bruker standard pulse sequence to be " zg30 ".
In order to ensure the accuracy of integrating peak areas, then need to consider that conversion is counted SI, spectrum width SW, scanning times NS, stand-by period D1 and the isoparametric optimization of sampling time AQ.
Conversion count must be 2 even number power, as inputted 2K, the such conversion of 32K is counted, and in nmr quantitative experiment, on resonance peak halfwidth, only has 5 when describing point, the accuracy that guarantee is quantitative.
After Fourier conversion is counted and determined, the digital resolution of spectrogram has just been decided.Computing formula is as follows:
Formula 1
Spectrum width SW is general only relevant with the chemical shift of sample, and in one-dimensional nuclear magnetic resonance hydrogen spectrum of the present invention test, unified spectrum width is SW=10ppm.
In nuclear magnetic resonance test, need by excited sample repeatedly and collect the quality that signal that sample sends improves spectrogram, this repeatedly excited sample the number of times collecting sample signal is called scanning times.
In nmr quantitative experiment, have document to prove to need to ensure signal to noise ratio (S/N ratio) S/N >=150, the uncertainty of quantitative result could about 1%.
Through groping condition, can determine that scanning times NS=32 can meet quantitative requirement.
In nuclear-magnetism test process, stand-by period D1 is comparatively large on quantitative impact, need by constantly attempting determining D1.
Follow-up nuclear-magnetism test experiments setting D1=4s.
Sampling time AQ, on quantitatively accurately having important impact, will ensure that free relaxation decay (FID) is complete in the dosing process, and setting AQ=4s can meet.
Other parameters as gain RG, sky sweeps number of times DS, probe temperature TE is less to quantitative effect, can by instrument setup parameter.
The selection at quantitative peak has two reference principle: (1) high s/n ratio S/N, and (2) are without the independent resonance peak of other assorted peak interference.
With reference to above two principles, the proton peak of Si-H can be selected as quantitative peak, and Si-H chemical shift is at about 4.6ppm; Inside be designated as unimodal, select this quantitative peak of unimodal conduct, chemical shift is at about 7.6ppm.
Integrating peak areas interval is also the quantitative important data processing step of impact, and in all process data, quantitative interval is respectively 4.7-4.5 and 7.7-7.5.
2, collection of illustrative plates process and data analysis:
Before quantitative test, MestReNova software is used to carry out baseline correction and automatic phase adjustment to the collection of illustrative plates of Fourier transform.
?
1in H-NMR, resonance peak area or peak height are directly proportional to the proton number of this resonance peak of generation, and this is quantitative foundation.That is:
Formula 2
A
s: the integral area at the quantitative peak of sample; n
s: the proton number that the quantitative peak of sample comprises;
M
s: the molecular mass of sample; A
r: the integral area at the quantitative peak of internal standard compound matter;
N
r: the proton number that the quantitative peak of internal standard compound matter comprises; M
r: the molecular mass of internal standard compound matter;
M
r: the interior mark quality taken; W
r: interior target purity; m
s: the quality of sample;
Hydrogen content: the grams of Si-H key contained by every 100g silicone oil, represents with H%.
The formula of proton nmr spectra internal mark method determination containing hydrogen silicone oil hydrogen content can be derived by the definition of hydrogen content:
Formula 3
M
samplefor the quality of sample, m
infor interior target quality;
A
samplefor the integrated peak areas of sample, A
infor the peak area that interior scalar product is divided;
The size of hydrogen content can reflect the residual quantity of containing hydrogen silicone oil in trisiloxane surfactant, for this reason, instructs the production of trisiloxane surfactant by this method of testing.
Embodiment 1:
One-dimensional nuclear magnetic resonance hydrogen spectrometry and chemical determination MD
hthe consistency analysis of M hydrogen content:
In order to verify the feasibility using one-dimensional nuclear magnetic resonance hydrogen spectrum internal mark method determination containing hydrogen silicone oil hydrogen content analytical approach, the present invention uses the hydrogen content of chemical titration containing hydrogen silicone oil as a comparison, and uses chemical titration too as a comparison in the mensuration of other embodiments.
Use reagent and sample preparation: purity is the MD of 99%
hm is purchased from West Asia Reagent Company, the deuterochloroform (CDCl of 99.9%
3) be purchased from CIL (CambridgeIsotopeLaboratories, Massachusetts, USA).Sodium thiosulfate (AR), potassium iodide (AR), soluble starch (AR) and the concentrated sulphuric acid (AR) are all purchased from Tianjin great Mao chemical reagent work, potassium dichromate (PT) is purchased from Ke Miou Reagent Company, 1,3,5-tribromo-benzene (AR) is purchased from Aladdin Reagent Company.The weighing precision of the plum Teller analytical balance used is scholar 0.1mg.
Chemical determination containing hydrogen silicone oil hydrogen content:
Take sample in the iodine flask of 250mL, add 20mL phenixin respectively, Br that 10mL volumetric molar concentration is about 0.2mol/L
2-CH
3cOOH and 0.25mL deionized water, the beyond the Great Wall stopper of iodine flask, fluid-tight.Vibration shakes up and is placed on dark place reaction 30min.Adding 25mL massfraction after reaction terminates is 10%KI solution, uses deionized water rinsing bottleneck.During by calibrated sodium thiosulfate solution titrated close to terminal, add the starch indicator that 1mL mass concentration is 10g/L, be titrated to blue disappearance.
The calculating of chemical determination silicone oil hydrogen content is as shown in Equation 4:
M be sample quality/g, c are calibrated Na
2s
2o
3concentration/(mol/L);
V
0for blank consumes Na
2s
2o
3volume/mL, V
1for sample consumes Na
2s
2o
3volume/mL;
Formula 4
Through 3 parallel laboratory tests, record MD
hthe average hydrogen content of M is 0.440% (theoretical hydrogen content is 0.448%, does not in fact reach, and relative error is 1.78%, and relative average debiation is 0.23%), using 0.440% as MD
hthe true value of M hydrogen content.
The preparation of 1,3,5-tribromo-benzene (interior mark) standard solution: take 0.0600g1,3,5-tribromo-benzene, in 5mL volumetric flask, adds deuterochloroform and ultrasonic dissolution, is settled to 5mL after dissolving, and concentration is 12mg/mL.When preparing sample, pipette this standard solution of 0.25mL in nuclear magnetic tube with liquid-transfering gun at every turn, then with MD
hm solution is mixed to 0.5mL.
MD
hthe preparation of M standard solution: take 0.1600gMD
hm, in 2mL volumetric flask, uses deuterochloroform constant volume.Shift out 1mL in another volumetric flask with liquid-transfering gun, then be settled to 2mL with deuterochloroform, repeat above-mentioned steps, obtain the containing hydrogen silicone oil solution of 80mg/mL, 40mg/mL, 20mg/mL, 10mg/mL, 5mg/mL, 2.5mg/mL.Pipette this 0.25mL standard solution to mix with above-mentioned inner mark solution at every turn.The hydrogen content of containing hydrogen silicone oil is measured under above-mentioned nuclear magnetic resonance test condition.
MD in potpourri
hm and interior mark peak area obtain by using nuclear-magnetism software MestReNova to carry out process, in one-dimensional nuclear magnetic resonance hydrogen spectrum, choose the proton peak on interior mark phenyl ring and MD
hthe Si-H proton peak of M is as quantitative peak.In FIG, the integrating peak areas at interior mark and sample amounts peak is respectively 3.000 and 0.406, can calculate MD according to known interior target concentration according to formula 3
hthe hydrogen content of M is 0.430%.Obtaining hydrogen content respectively by 3 parallel laboratory tests is 0.430%, 0.434% and 0.435%, and the average of its three parallel laboratory tests is 0.433%, and relative average debiation is 0.46%.Based on chemical titration repeatedly replicate experiments, measure MD
hthe hydrogen content of M is 0.440%.Therefore the relative error of above-mentioned three tests is 1.59%.The containing hydrogen silicone oil of 6 variable concentrations gradients and interior mark potpourri are measured by above-mentioned nuclear magnetic resonance test condition, obtains the peak area ratio of a series of one-dimensional nuclear magnetic resonance hydrogen spectrum.
With A
s/ A
rto m
s/ m
rmapping, obtain typical curve as shown in Figure 2, the equation obtained is y=0.51612x-0.00095, and related coefficient is 0.99974.Linear relationship, the repeatability of nuclear magnetic resonance measuring containing hydrogen silicone oil hydrogen content are fine, describe one-dimensional nuclear magnetic resonance hydrogen spectrometry and measure MD
hthe feasibility of M hydrogen content.
This method is also applicable to Methyl Hydrogen Polysiloxane Fluid (category-A, MD
hm belongs to one wherein) and the mensuration of block containing hydrogen silicone oil (category-B) hydrogen content.
Wherein Methyl Hydrogen Polysiloxane Fluid and block containing hydrogen silicone oil are purchased from Nanchang Tian Run new material company limited.
Embodiment 2:
Measuring mean molecular weight is MD residual in the trisiloxane surfactant of 612
hthe content of M
In the storage and production run of reality, MD
hm places and just has hydrogen generation after a while.Because three siloxy surface activating agents can remain MD aborning
hm, residual a certain amount of MD
hm can cause packaging bag to be heaved even breaking.Therefore, MD in three siloxy surface activating agents
hthe detection of M content has important directive function to production.
In mensuration three siloxy surface activating agent during the content of containing hydrogen silicone oil, the size by hydrogen content represents MD
hthe size of M residual quantity.
The preparation of inner mark solution: take 0.0600g1,3,5-tribromo-benzene is in 5mL volumetric flask, add deuterochloroform and ultrasonic dissolution, 5mL is settled to deuterochloroform, concentration is 12mg/mL, pipettes this standard solution of 0.25mL at every turn in nuclear magnetic tube, then is mixed to 0.5mL with three siloxy surface activator solutions.Unspent inner mark solution need seal refrigeration, to treat that next time uses.
The preparation of trisiloxane surfactant solution: the three siloxy surface activating agent samples taking 0.8000g, in 2mL volumetric flask, are settled to 2mL with deuterochloroform, pipette this solution 0.25mL and mix in nuclear magnetic tube with inner mark solution, ultrasonic 30s.
Test by above-mentioned nuclear-magnetism test condition, obtaining one-dimensional nuclear magnetic resonance hydrogen spectrum and integral area, as shown in Figure 3, is the one-dimensional nuclear magnetic resonance hydrogen spectrogram of trisiloxane surfactant.The result of three replicate determination peak areas is 1.475,1.476,1.476, can calculate hydrogen content according to formula 3 is 0.014%, 0.014% (0.0141%), 0.014% (0.0141%), mean value is 0.014% (0.0141%), basically identical with the result 0.014% (mean value 0.0142%) of chemical titration.Bring above-mentioned peak area and the ratio of interior mark peak area into typical curve equation y=0.51612x-0.00095, then can show that every 100mg trisiloxanes sample contains 2.87mgMD in conjunction with formula 2
hm, converts as hydrogen content is substantially consistent with the result measured.
Embodiment 3: the expansion measuring containing hydrogen silicone oil residue in the trisiloxane surfactant of different molecular weight
In order to verify that the method measures the feasibility of containing hydrogen silicone oil residual quantity in trisiloxane surfactant further, the trisiloxane surfactant potpourri that the present invention uses EO chain number different is as quantitative examination object.The preparation of inner mark solution is consistent with pipetting same embodiment 2.The preparation of sample solution is consistent with pipetting same embodiment 2.
By above-mentioned nuclear-magnetism test condition test, obtain one-dimensional nuclear magnetic resonance hydrogen spectrum, as shown in Figure 4, for mean molecular weight is the one-dimensional nuclear magnetic resonance hydrogen spectrogram of the trisiloxane surfactant of 674.The result of three replicate determination peak areas is 0.658,0.654,0.653, can calculate hydrogen content according to formula 3 is 0.006% (0.0063%), 0.006% (0.0062%), 0.006% (0.0062%), mean value is 0.006%, basically identical with the result 0.006% (0.0059%) of chemical titration.Bring above-mentioned peak area and the ratio of interior mark peak area into typical curve equation y=0.51612x-0.00095, then can show that every 100mg trisiloxanes sample contains 1.27mgMD in conjunction with formula 2
hm, converts as hydrogen content is substantially consistent with the result measured.
Embodiment 4:
Measure mean molecular weight be the residual quantity inner mark solution of containing hydrogen silicone oil in the trisiloxane surfactant of 807 preparation with pipette all consistent with embodiment 2.The preparation of sample solution is consistent with pipetting same embodiment 2.
By above-mentioned nuclear-magnetism test condition test, obtaining one-dimensional nuclear magnetic resonance hydrogen spectrum, as shown in Figure 5, is the one-dimensional nuclear magnetic resonance hydrogen spectrogram of trisiloxane surfactant.The result of three replicate determination peak areas is 0.610,0.612,0.614, the mean value that can calculate hydrogen content according to formula is 0.006% (0.0058%), 0.006% (0.0058%), 0.006% (0.0059%), mean value is 0.006%, basically identical with the result 0.006% (0.0058%) of chemical titration.Bring above-mentioned peak area and the ratio of interior mark peak area into typical curve equation y=0.51612x-0.00095, then can show that every 100mg trisiloxanes sample contains 1.19mgMD in conjunction with formula 2
hm, converts as hydrogen content is substantially consistent with the result measured.
The present invention is suitable for the detection of containing hydrogen silicone oil residual quantity in a series of trisiloxane surfactant; shown in the following structural formula of chemical constitution of described trisiloxane surfactant, i.e. the polyethers of the allyl polyether of hydroxyl terminal, methyl or acetyl blocked allyl polyether and this three classes different molecular weight and MD
hthe trisiloxane surfactant that M is obtained by reacting.This provides a comparatively simple, fast method of testing for actual production.
5≤n≤20，0≤m≤10，R＝H、CH
3、CH
3CO。
Claims (3)
1. the assay method of containing hydrogen silicone oil residual quantity in a trisiloxane surfactant, it is characterized in that comprising the steps: to adopt one-dimensional nuclear magnetic resonance hydrogen spectrum, with unimodal 1,3,5-tribromo-benzene is marked in unified, quantitative test or concentration determination are carried out to trisiloxane surfactant, uses unimodal interior mark to carry out quantitative test as the medium that one-dimensional nuclear magnetic resonance is quantitative.
2. method according to claim 1, is characterized in that using one-dimensional nuclear magnetic resonance hydrogen spectrum to be quantivative approach, within be designated as bridge, measure the hydrogen content of Methyl Hydrogen Polysiloxane Fluid or block containing hydrogen silicone oil.
3. method according to claim 1, is characterized in that using one-dimensional nuclear magnetic resonance hydrogen spectrum to be quantivative approach, within be designated as bridge, the residual quantity of containing hydrogen silicone oil in the trisiloxanes class surfactant of quantitative different molecular weight or different structure.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106501296A (en) * | 2016-10-18 | 2017-03-15 | 广州天赐高新材料股份有限公司 | The detection method of silicon hydrogen content in organosilicon polymer |
| CN107300564A (en) * | 2017-08-17 | 2017-10-27 | 中国农业科学院农业质量标准与检测技术研究所 | Application of the Dimetridazole as internal standard compound in hydrogen nuclear magnetic resonance technology |
| CN111610214A (en) * | 2019-02-25 | 2020-09-01 | 苏州纽迈分析仪器股份有限公司 | Standard substance and standard sample for testing solid fat content and preparation method thereof |
| CN113588705A (en) * | 2021-08-05 | 2021-11-02 | 肇庆市高要晋益纤维有限公司 | Process for accurately judging texture of colored yarn |
| CN115508400A (en) * | 2022-11-23 | 2022-12-23 | 中国石油大学(华东) | Method for determining content of benzyl quinoline quaternary ammonium salt dimer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125481A (en) * | 1994-03-11 | 1996-06-26 | 川崎制铁株式会社 | Method of evaluating siloxane used for forming insulation coating, coating fluid used for forming insulation coating, process for producing the fluid, process for forming insulation coating for....... |
| US6436715B1 (en) * | 1999-07-01 | 2002-08-20 | Degussa Huls Ag | Method for determining silicone concentrations |
| WO2013087077A1 (en) * | 2011-12-12 | 2013-06-20 | Nanonord A/S | A method of determining catalytic fines in an oil |
| US20140349406A1 (en) * | 2013-05-21 | 2014-11-27 | Agilent Technologies, Inc. | Solvent Extraction Using Environmentally-Friendly Siloxane Solvents |
| CN104237282A (en) * | 2014-09-25 | 2014-12-24 | 中国科学院青岛生物能源与过程研究所 | Additive for nuclear magnetic resonance spectrum and method for analyzing mixture by virtue of additive |
| CN104535596A (en) * | 2014-06-30 | 2015-04-22 | 哈尔滨工业大学 | Method using silicon hydroxyl relative content for analysis of silicone rubber aging degree |
-
2015
- 2015-12-01 CN CN201510870182.2A patent/CN105301031B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125481A (en) * | 1994-03-11 | 1996-06-26 | 川崎制铁株式会社 | Method of evaluating siloxane used for forming insulation coating, coating fluid used for forming insulation coating, process for producing the fluid, process for forming insulation coating for....... |
| US6436715B1 (en) * | 1999-07-01 | 2002-08-20 | Degussa Huls Ag | Method for determining silicone concentrations |
| WO2013087077A1 (en) * | 2011-12-12 | 2013-06-20 | Nanonord A/S | A method of determining catalytic fines in an oil |
| US20140349406A1 (en) * | 2013-05-21 | 2014-11-27 | Agilent Technologies, Inc. | Solvent Extraction Using Environmentally-Friendly Siloxane Solvents |
| CN104535596A (en) * | 2014-06-30 | 2015-04-22 | 哈尔滨工业大学 | Method using silicon hydroxyl relative content for analysis of silicone rubber aging degree |
| CN104237282A (en) * | 2014-09-25 | 2014-12-24 | 中国科学院青岛生物能源与过程研究所 | Additive for nuclear magnetic resonance spectrum and method for analyzing mixture by virtue of additive |
Non-Patent Citations (1)
| Title |
|---|
| 吴美玉 祈争健: "有机硅匀泡剤及相关聚有机硅氧烷的核磁共振研究", 《全国聚氨酯行业协作组第七次年会论文集》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106501296A (en) * | 2016-10-18 | 2017-03-15 | 广州天赐高新材料股份有限公司 | The detection method of silicon hydrogen content in organosilicon polymer |
| CN106501296B (en) * | 2016-10-18 | 2018-08-24 | 广州天赐高新材料股份有限公司 | The detection method of silicon hydrogen content in organosilicon polymer |
| CN107300564A (en) * | 2017-08-17 | 2017-10-27 | 中国农业科学院农业质量标准与检测技术研究所 | Application of the Dimetridazole as internal standard compound in hydrogen nuclear magnetic resonance technology |
| CN111610214A (en) * | 2019-02-25 | 2020-09-01 | 苏州纽迈分析仪器股份有限公司 | Standard substance and standard sample for testing solid fat content and preparation method thereof |
| CN113588705A (en) * | 2021-08-05 | 2021-11-02 | 肇庆市高要晋益纤维有限公司 | Process for accurately judging texture of colored yarn |
| CN115508400A (en) * | 2022-11-23 | 2022-12-23 | 中国石油大学(华东) | Method for determining content of benzyl quinoline quaternary ammonium salt dimer |
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