CN106198594A - A kind of characterizing method of polymer molecular weight - Google Patents
A kind of characterizing method of polymer molecular weight Download PDFInfo
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- CN106198594A CN106198594A CN201610442944.3A CN201610442944A CN106198594A CN 106198594 A CN106198594 A CN 106198594A CN 201610442944 A CN201610442944 A CN 201610442944A CN 106198594 A CN106198594 A CN 106198594A
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Abstract
The invention provides the characterizing method of a kind of polymer molecular weight, by the polymer solution of known molecular amount being carried out the two-dimensional molecular diffusion experiment (2D DOSY) in nuclear magnetic resonance technique, obtain diffusion coefficient, and set up the standard curve of polymer molecular weight and diffusion coefficient；Then the polymer solution to be measured of unknown molecular amount is carried out two-dimensional molecular diffusion experiment, obtain diffusion coefficient, and according to the molecular weight of this base polymer and the standard curve of diffusion coefficient, be calculated molecular weight and the distribution thereof of polymer to be measured；Wherein, according to molecular size, control the concentration of described polymer solution to be measured 0.2～1.5mg/mL and experimental temperature at 90 DEG C to 150 DEG C；The method is simple to operate, and required sample size and quantity of solvent are all little, characterize low cost, and test result is accurate, and while characterizing polymer molecular weight and molecular weight distribution, can distinguish two or more different types of polymer of close molecular weight in polymer.
Description
Technical field
The present invention relates to field of polymer technology, particularly relate to the characterizing method of a kind of polymer molecular weight.
Background technology
The molecular weight of high polymer has material impact with distribution to the character of macromolecular material, thus becomes polymer science
Characteristic index necessary in research process.But, some only comprises the non-polar polymer of carbon hydrogen element without functional group, and
Room temperature does not dissolves in ordinary organic solvents (such as oxolane), is the most only dissolved in high temperature (more than 100 DEG C) severe toxicity three
This type of high molecular molecular weight parameter could be obtained in chlorobenzene equal solvent and then by the means of high temperature GPC.
The principle of high temperature GPC uses high temperature trichloro-benzenes to dissolve polymer exactly and flushing makes it walk in chromatographic column, then
Determined by various sizes of molecule residence time in the chromatography column and count all and weight average molecular weight, and then calculating molecular weight divides
Cloth.But, the shortcoming of existing GPC characterized by techniques molecular weight of high polymer has three: the test of the molecular weight of (1) average each sample
Needing highly toxic trichloro-benzenes 60ml, about sample size 20mg, and the purification of trichloro-benzenes reclaims relatively difficult, thus cost is high；
(2) use of a large amount of trichloro-benzenes is more serious to the damage ratio at environment especially water source；(3) chromatographic column needs often to change, and enters one
Step increases testing cost.Therefore it provides a kind of polymer without functional group that characterizes eco-friendly, that testing cost is low divides
The method of son amount is to be presently required to solve the technical problem that.
Summary of the invention
In view of this, the technical problem to be solved is to provide the table of a kind of polymer molecular weight and distribution thereof
Levying method, the method that the present invention provides is environmentally friendly, and experimental cost is low.
The invention provides the characterizing method of a kind of polymer molecular weight, including:
By polymer solution to be measured by two-dimensional molecular diffusion experiment in nuclear magnetic resonance technique, obtain diffusion coefficient, root
According to molecular weight and the standard curve of diffusion coefficient of the polymer set up, it is calculated the molecular weight of polymer to be measured and divides
Cloth,
The concentration of described polymer solution to be measured is 0.2～1.5mg/mL.
Preferably, dissolving the deuterated reagent of polymer in described polymer solution to be measured is deuterated o-dichlorohenzene, deuterated
Sym-tetrachloroethane, deuterated toluene, deuterated benzene or deuterated DMSO.
Preferably, the temperature of described detection is 90～150 DEG C.
Preferably, the compound method of described polymer solution is:
Polymer is mixed with deuterated reagent, and dissolves 15～36 hours at 90～150 DEG C, obtain polymer solution.
Preferably, the pulsed gradient intensity of described detection is 2% and 95%.
Preferably, the diffusion time of described detection is 80～120ms.
Preferably, the gradient pulse duration of described detection is 100～10000 μ s.
Preferably, described polymer to be measured is the polymer only containing carbon hydrogen element.
Preferably, the number-average molecular weight of described polymer to be measured is less than or equal to 500kg/mol.
Preferably, described standard curve prepares in accordance with the following methods:
The detection method that the polymer solution of a series of known molecular amounts provides according to the present invention is detected, is divided
Son amount and the standard curve of diffusion coefficient,
The concentration of the polymer solution of described known molecular amount is 0.2～1.5mg/mL.
Compared with prior art, the invention provides the characterizing method of a kind of polymer molecular weight, by be measured being gathered
Polymer solution carries out the two-dimensional molecular diffusion experiment (2D DOSY) in nuclear magnetic resonance technique, obtains diffusion coefficient, then according to building
The molecular weight of vertical polymer and the standard curve of diffusion coefficient, be calculated molecular weight and the distribution thereof of polymer to be measured；Its
In, by the concentration of the described polymer solution to be measured of control 0.2～1.5mg/mL, use two-dimensional diffusion sequence nuclear-magnetism altogether simultaneously
The method of shaking detects, and obtains diffusion coefficient, and then obtains molecular weight and the distribution thereof of polymer to be measured；This method is simple to operate, institute
Needing sample size and quantity of solvent all little, characterize low cost, test result is accurate, and is characterizing molecular weight and the molecule of polymer
While amount distribution, it is also possible to distinguish two or more different types of polymer of close molecular weight in polymer.
Accompanying drawing explanation
Fig. 1 is the curve chart that the intensity of magnetization changes with gradient intensity；
The 2D DOSY spectrum of No. 4 sample P E4 that Fig. 2 provides for embodiment 1；
Fig. 3 is the standard curve of peak molecular weight and diffusion coefficient；
Fig. 4 is the standard curve of number-average molecular weight and diffusion coefficient；
Fig. 5 is the standard curve of weight average molecular weight and diffusion coefficient；
Fig. 6 is the 2D DOSY spectrum that the embodiment of the present invention 2 prepares；
Fig. 7 be concentration be the 2D DOSY spectrum that the polyethylene solution of 2mg/mL obtains.
Detailed description of the invention
The invention provides the characterizing method of a kind of polymer molecular weight, including:
Polymer solution to be measured is carried out nuclear magnetic resonance, NMR two-dimensional molecular diffusion experiment, obtains diffusion coefficient, according to foundation
The standard curve of molecular weight and diffusion coefficient of polymer, be calculated molecular weight and the distribution thereof of polymer to be measured,
The concentration of described polymer solution to be measured is 0.2～1.5mg/mL.
According to the present invention, polymer solution to be measured is carried out nuclear magnetic resonance, NMR two-dimensional diffusion experiment by the present invention, is spread
Coefficient, then according to molecular weight and the standard curve of diffusion coefficient of the polymer set up, is calculated dividing of polymer to be measured
Son amount and distribution thereof；Wherein, described polymer to be measured is preferably the most only containing the polymer of carbon hydrogen element, more preferably polyethylene,
One or more in polystyrene, norborene, polypropylene and norbornene derivative, the molecular weight of described polymer to be measured
It is preferably less than and is equal to 500kg/mol, more preferably 5～450kg/mol, most preferably 10～350kg/mol, more preferably 15
～200kg/mol；The concentration of described polymer solution preferably 0.3～0.9mg/mL, more preferably 0.5～0.8mg/mL；Described
The temperature of detection is preferably 90～150 DEG C, more preferably 100～120 DEG C, and wherein, in order to make test result accurate, this dissolving is treated
The boiling point of deuterated reagent surveying polymer should be greater than 40K with difference DELTA T of detection temperature；The pulsed gradient intensity of described detection is excellent
Elect 1～2% and 90～99% as, more preferably 2% and 95% or 1% and 98%；The diffusion time of described detection is preferably 80
～500ms, more preferably 100～400ms, most preferably 100～200ms；The gradient pulse duration of described detection is
100～10000 μ s, more preferably 300～8000 μ s, most preferably 500～5500 μ s.
The present invention does not has particular/special requirement to the compound method of polymer solution to be measured, the most in accordance with the following methods preparation: will
Polymer mixes with deuterated reagent, and dissolves 15～36 hours at 90～150 DEG C, promotes molecule fully to dissolve, obtains polymer
Solution.Described deuterated reagent is preferably deuterated o-dichlorohenzene, deuterated sym-tetrachloroethane, deuterated toluene, deuterated benzene or deuterated DMSO.
In the present invention, before detecting the diffusion coefficient of polymer, the present invention is the most also to NMR (Nuclear Magnetic Resonance) spectrum
Instrument is calibrated, and the content of described calibration includes: by using the deuterated DMSO standard specimen of 80% ethylene glycol, rectify an instrument 300-
The temperature of 380K scope；Use containing GdCl399%D2O/1%H2The self-diffusion coefficient of water is tested in the circulation of O standard specimen repeatedly, directly
It is 1.872e-9 to water diffusion coefficient under the conditions of 298K, thus realizes the correction to gradient.
The molecular weight of the polymer of described foundation and the standard curve of diffusion coefficient are by relational expression diffusion coefficient and to divide
Relational expression M=A D between son amountx, by the data of the polymer of known molecular amount with the diffusion coefficient recorded can obtain A and
X, thus obtain standard curve, wherein, M is peak molecular weight Mp, number-average molecular weight MnOr weight average molecular weight Mw, D is diffusion coefficient,
Concrete, the method for Criterion curve of the present invention is: the polymer solution of a series of known molecular amounts is carried out two-dimensional molecular
Diffusion experiment, obtains a series of diffusion coefficient, obtains the standard curve of molecular weight and diffusion coefficient, it is known that polymer expands
The testing conditions dissipating coefficient is identical with the testing conditions of the diffusion coefficient of polymer to be measured, and this condition includes the dense of polymer solution
Degree, the temperature of detection, the pulsed gradient intensity of detection, it differs only in diffusion time, the persistent period of gradient pulse and survey
The polymer of examination is different.And, in the present invention, for polymer and the polymer to be measured of known molecular amount, diffusion experiment
Experimental temperature error need to be less than 0.1 DEG C.
It addition, the relational expression M=A D between diffusion coefficient and molecular weightxDraw based on following theory: molecule spreads
Coefficient D=kBT/6 π η r, wherein kBFor Boltzmann constant, T is the absolute temperature of sample, and η is the diffusion coefficient of solvent, and r is for dividing
Sub-radius.The same class polymer of analog structure is dissolved in the same solvent of same volume with identical quality, and protects
The temperature of card nuclear-magnetism experiment keeps highly consistent.So, under these conditions, molecular radius is only relevant with its diffusion coefficient.Point
Sub-radius reflection molecular dimension, i.e. molecular size, show as molecular weight indirectly.
The characterizing method of the polymer molecular weight that the present invention provides, by carrying out nuclear magnetic resonance, NMR by polymer solution to be measured
Two-dimensional molecular diffusion experiment (2D DOSY) in technology, obtains diffusion coefficient, then according to set up polymer molecular weight with
The standard curve of diffusion coefficient, is calculated molecular weight and the distribution thereof of polymer to be measured；Wherein, described to be measured poly-by controlling
The concentration of polymer solution is 0.2～1.5mg/mL；This method is simple to operate, and required sample size and quantity of solvent are all little, characterize cost
Low, test result is accurate, and while characterizing the molecular weight and molecualr weight distribution of polymer, it is also possible to by existing simultaneously
One-dimensional1Two or more different types of polymer of close molecular weight in the lane place segregation compound of H H NMR spectroscopy signal peak.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
GPC: high-temperature gel permeation chromatography (Gel-Permeation Chromatography), a kind of polymer of measuring divides
The method of son amount；Mn:Number-average molecular weight；Mw:Weight average molecular weight；MWD: molecular weight distribution (molecular weight
Distribution), its value is equal to Mw/Mn.；DOSY: molecule diffusion spectrum (Diffusion-Ordered SpectrocopY).
Embodiment 1
Test instrunment is Bruker Ascend series 400MHZ Liquid NMR spectrometer, pops one's head in high into BBFO wideband
Resolution fluid is popped one's head in, and Z-Gradient field is 5.35G/mm.
1) instrument calibration
Use the deuterated DMSO standard specimen of 80% ethylene glycol, the temperature of the 300-380K scope that rectifies an instrument.
Use containing GdCl399%D2O/1%H2The self-diffusion coefficient of water is tested in the circulation of O standard specimen repeatedly, until water exists
Diffusion coefficient under the conditions of 298K is 1.872e-9, thus realizes the correction to gradient.
2) linear polyethylene molecular weight and the mensuration of molecular distribution
A) acquisition of standard curve
Select a series of known molecular amounts of table 1 display and the Hi-fax of distribution.Weigh 3mg sample and be dissolved in 10mm
In the glass tubing of bore, add the deuterated sym-tetrachloroethane of 6mL, seal, be subsequently placed in the oil bath pan of 120 DEG C, high-temperature digestion 24
Hour, promote it fully to dissolve.Then from the glass tubing fully dissolved, take out the polymer solution (i.e. 0.5mg/mL) of 0.6mL
Sample as nuclear-magnetism experiment.Repeat said process, obtain the sample of this series polymer experiment.
The pulse train that 1D DOSY uses is ledbpg2s1d, and regulation parameter diffusion time (D20) is 100ms, gradient arteries and veins
Rushing the persistent period changes between 300-1800us with molecular size range.Pulsed gradient intensity is respectively set to 2% and 95%.Must
Make its under conditions the intensity of magnetization meet shown in Fig. 1 with gradient intensity change curve, Fig. 1 is the intensity of magnetization to be changed with gradient intensity
Curve chart；
Utilize above-mentioned optimal parameter diffusion time (D20), pulse duration (P30) and intensive parameter (GPZ6), utilize
Same sample pipe does the DOSY experiment of its two dimension, it is thus achieved that they 2D DOSY spectrums under the conditions of 110 DEG C, and then obtains diffusion coefficient.
The 2D DOSY spectrum of No. 4 sample P E4 that 2D DOSY spectrum such as Fig. 2, Fig. 2 provide for embodiment 1, wherein, F1 dimension is sample1H
H NMR spectroscopy, F2 dimension is diffusion axle, it can be seen that wherein 1.40ppm is polyethylene1H NMR signal peak, 6.0ppm is
The signal of deuterated reagent.On two dimensional surface two signals the most respectively to should polyethylene specimen and solvent under this experiment condition
Diffusion signal, diffusion rate is respectively 1.331*10-9m2/ s and 5.32*10-9m2/s。
The molecular weight parameter of the known Hi-fax of table 1 and diffusion coefficient
According to the relational expression M=A D between diffusion coefficient and molecular weightx, the series data be given by table 1 can obtain A
And X, thus obtaining standard curve, result is shown in the standard curve that Fig. 3～Fig. 5, Fig. 3 are peak molecular weight and diffusion coefficient, and it obtains
Formula be log Mp=-1.224logDs-5.959, the slope i.e. simulating straight line is-1.224, and standard error is 0.047；Directly
Line intercept is-5.959, and standard error is 0.405；Fig. 4 is the standard curve of number-average molecular weight and diffusion coefficient, its public affairs obtained
Formula is log Mn=-1.223logDs-5.82, the slope i.e. simulating straight line is-1.223, and standard error is 0.089；Linear intercept
For-5.820, standard error is 0.773；Fig. 5 is the standard curve of weight average molecular weight and diffusion coefficient, and its formula obtained is
log Mw=-1.276logDs-6.231, the slope i.e. simulating straight line is-1.276, and standard error is 0.032；Linear intercept is-
6.231, standard error is 0.283.
B) sign of polymer molecular weight to be measured
The Hi-fax sample that a part amount is unknown is made into the solution of same concentrations, under the conditions of 110 DEG C, is 2D
DOSY tests, and recording its diffusion coefficient is 1.05x10-8m2/ s, substitutes into regression formula, obtains Mn=145.0kg/mol, Mw=
167.2kg/mol,Mp=159.0kg/mol；
Meanwhile, being tested the Hi-fax sample of this unknown by high temperature GPC, the data obtained are Mn=134.0kg/
mol,Mw=153.2kg/mol, Mp=169.0kg/mol, it is seen then that compared with the method that the present invention provides is tested with GPC, both
Difference is (5.9-9.1%) in rational range of error, thus proves that the method that the present invention provides may be used for polymer molecule
The test of amount.
Embodiment 2
The pulse train that 1D DOSY uses is still ledbpg2s1d, and regulation parameter diffusion time (D20) is 100ms, gradient
Pulse duration changes between 300-1800us with molecular size range.Pulsed gradient intensity is respectively set to 1% and 98%.Right
Sample P E4 does two dimension DOSY experiment, it is thus achieved that its 2D DOSY spectrum under the conditions of 110 DEG C, and then obtains diffusion coefficient.2D DOSY
As shown in Figure 6, wherein, F1 dimension is sample to spectrum1H H NMR spectroscopy, F2 dimension is diffusion axle, it can be seen that wherein 1.40ppm
For polyethylene1H NMR signal peak, 6.0ppm is the signal of deuterated reagent.On two dimensional surface, two signals are the most respectively to should
Polyethylene specimen and solvent diffusion signal under this experiment condition, diffusion rate is respectively 1.332*10-9m2/ s and 5.32*
10-9m2/ s, basically identical with the DOSY of PE4 shown in Fig. 2 spectrum, diffusion rate is the most equal.Visible, in pulsed gradient intensity, GPZ6 is
Can change between 0-98%.Under conditions of ensureing signal to noise ratio, signal intensity declines 1%-5% and 90-98% respectively
Between be all feasible.
Comparative example 1
The solution that the polyethylene specimen that number-average molecular weight is 63.5kg/mol is configured to 2mg/mL does 2DDOSY spectrum, result
See Fig. 7, Fig. 7 be concentration be the 2D DOSY spectrum that the polyethylene solution of 2mg/mL obtains, it can be seen that polyethylene is with molten
The diffusion coefficient of the deuterated sym-tetrachloroethane of agent is respectively 1.477x10-8m2/ s and 1.485x10-8m2/ s, shows polymer molecule segment
And exist between solvent molecule and interact.Although macromolecule and solvent molecular weight difference are very big, but both diffusion coefficients are basic
Unanimously, and too high.Obviously, this diffusion coefficient data is not suitable as standard curve data, it is seen then that survey using high temperature 2DDOSY
When trying the molecular weight of high molecular polymer, the concentration of polymer solution selects the most crucial.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out
Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. a characterizing method for polymer molecular weight, including:
By polymer solution to be measured by the two-dimensional molecular diffusion experiment in nuclear magnetic resonance technique, obtain diffusion coefficient, according to
The molecular weight of the polymer set up and the standard curve of diffusion coefficient, be calculated molecular weight and the distribution thereof of polymer to be measured,
The concentration of described polymer solution to be measured is 0.2～1.5mg/mL.
Detection method the most according to claim 1, it is characterised in that dissolve polymer in described polymer solution to be measured
Deuterated reagent be deuterated o-dichlorohenzene, deuterated sym-tetrachloroethane, deuterated toluene, deuterated benzene or deuterated DMSO.
Detection method the most according to claim 1, it is characterised in that the temperature of described detection is 90～150 DEG C.
Detection method the most according to claim 1, it is characterised in that the compound method of described polymer solution is:
Polymer is mixed with deuterated reagent, and dissolves 15～36 hours at 90～150 DEG C, obtain polymer solution.
Detection method the most according to claim 1, it is characterised in that the pulsed gradient intensity of described detection is 2% He
95%.
Detection method the most according to claim 1, it is characterised in that the diffusion time of described detection is 80～120ms.
Detection method the most according to claim 1, it is characterised in that the gradient pulse duration of described detection is
100～10000 μ s.
Detection method the most according to claim 1, it is characterised in that described polymer to be measured is only containing carbon hydrogen element
Polymer.
Detection method the most according to claim 1, it is characterised in that the number-average molecular weight of described polymer to be measured is little
In equal to 500kg/mol.
Detection method the most according to claim 1, it is characterised in that described standard curve is prepared in accordance with the following methods
Arrive:
By the polymer solution of a series of known molecular amounts according to the detection described in claim 1～claim 9 any one
Method is tested, and obtains the standard curve of molecular weight and diffusion coefficient,
The concentration of the polymer solution of described known molecular amount is 0.2～1.5mg/mL.
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| CN107044994A (en) * | 2017-01-09 | 2017-08-15 | 南京工业大学 | The method of crystalline polymer molecular weight and its distribution is calculated using thermometric analysis |
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| CN108445034A (en) * | 2018-03-22 | 2018-08-24 | 中国科学院长春应用化学研究所 | A kind of method of fast quantitative analysis polymer chain architecture and composition |
| CN109655480A (en) * | 2018-12-19 | 2019-04-19 | 万华化学集团股份有限公司 | A kind of assay method of polyether polyol |
| CN109696451A (en) * | 2019-03-03 | 2019-04-30 | 中国科学院山西煤炭化学研究所 | A kind of NMR measuring method of PAMAM to guest molecules adsorbance |
| CN109696451B (en) * | 2019-03-03 | 2020-08-28 | 中国科学院山西煤炭化学研究所 | NMR determination method of PAMAM (polyamidoamine) on guest small molecule adsorption quantity |
| CN111690478A (en) * | 2020-07-23 | 2020-09-22 | 常州兰迪科技有限公司 | Composite formula of cleaning solution for melt-blown cloth spinning die |
| CN112630251A (en) * | 2020-12-31 | 2021-04-09 | 南京欧纳壹有机光电有限公司 | Novel method for calculating molecular weight of conjugated polymer by adopting diffusion ordered nuclear magnetic resonance spectrum |
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