CN106248711B - The assay method of normal heptane the extractives content in polypropylene - Google Patents
The assay method of normal heptane the extractives content in polypropylene Download PDFInfo
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Abstract
The assay method of normal heptane the extractives content, comprises the following steps in a kind of polypropylene：(1) samples are classified；(2) sample pretreatments；(3) foundation of nuclear magnetic signals calibration curve；(4) test of testing samples nuclear magnetic signal；(5) calculates the normal heptane the extractives content of testing sample according to calibration curve.
Description
Technical field
The present invention relates to a kind of assay method of normal heptane the extractives content in polypropylene.In particular it relates to use low resolution
The method of normal heptane the extractives content in pulse nuclear-magnetism measure polypropylene.
Background technology
Normal heptane the extractives content is the important indicator that isotacticity is material property in polypropylene, is Mechanical Properties of PP
And one of determinant of application wholesomeness.Its conventional method is weight method, in testing using a large amount of organic solvents, is needed
The multistep manual operations such as weigh, extract, drying.During solvent it is larger to operating personnel and environmental hazard, and due to multistep
Manual presence, experimental result repeatability and repeatability are poor.Simultaneously as polypropylene high polymer long chain and crystalline texture
The parcel of component and solvent pair can be extracted, test data precision is poor.Weight method is generally 30h or so experimental period simultaneously,
Testing efficiency is relatively low, is unfavorable for the real-time monitoring of product quality.
Low pulse nuclear-magnetism of differentiating, using solid sample, is not required in the test application of polypropylene normal heptane the extractives content
Organic solvent is used, improves the Safety and Environmental Protection of test operation.Meanwhile the Sample Scan time is very short, greatly improves
Testing efficiency.But in previous methods, because different trade mark products can not be completely eliminated due to production process in sample pretreatment condition
In the thermal history brought, cause the difference of identical normal heptane the extractives content sample room nuclear magnetic signal.Corrected in previous methods bent
Line restricting condition for use is more, and the stability of analysis method is poor.2005《Analytical instrument》, 2005 (4)：20-23 (mq20 types
Application of the nuclear magnetic resonance spectrometer in polypropylene isotacticity measure) it is reported in using in small nuclear magnetic resonance spectrometer progress polypropylene isotacticity
Found during control analysis, with the change of the production T skill parameters such as control temperature, pressure, using same standard curve meeting
Cause measurement result inaccurate, in actual applications, the different trades mark will establish different standard curves.The same trade mark, batch
Difference, processing parameter have change, it is necessary on standard curve interpolation data point, curve is corrected again.And
Due to the sample slight change that microstructure occurs during nature regulation so that the reproduction tested within a certain period of time
Property is poor.2004《Analytical instrument》, 42 (1)：26—29《Low resolution pulse NMR method is analyzed in polypropylene isotacticity
Application in test》Report vacuum drying time, water bath time, vacuum drying temperature etc. have considerable influence to test result,
Data stability is poor.
The present invention has the following advantages compared with prior art：When the 1st, classifying to sample, go out from the basic structure of sample
Hair, is divided into HOPP, block copolymerization polypropylene and atactic copolymerized polypropene by sample, sample is simply divided into the same sex three
Class.Avoid and classified in the past with the sample trade mark, it is necessary to establish the cumbersome repeated work that thousands of kinds of calibration curves are brought.Improve survey
Try efficiency and measuring stability.When the 2nd, being pre-processed to sample, by sample pretreatment temperature setting more than fusing point, and maintain
For a period of time, sample identical thermal history is imparted, is eliminated between each product of identical normal heptane the extractives content due to producing
Nuclear magnetic signal difference caused by technological parameter difference in journey, the uncertain calibration curve that each technological parameter of each trade mark determines is simplified
To determine three HOPP, block copolymerization polypropylene and atactic copolymerized polypropene calibration curves by product structure.
The content of the invention
The present invention provides a kind of using normal heptane the extractives content in low resolution pulse nuclear magnetic resonance spectrometer test polypropylene product
Method, to improve the testing efficiency of this method and data stability.
The present invention provides a kind of assay method of normal heptane the extractives content in polypropylene, comprises the following steps：
(1) samples are classified
By correcting sample and testing sample according to HOPP, block copolymerization polypropylene and atactic copolymerized polypropene point
Class, a classes, b classes, c classes are denoted as respectively；
(2) sample pretreatments
A classes, b classes, the correcting sample of c classes and testing sample are pre-processed；
(3) foundation of nuclear magnetic signals calibration curve
Test to obtain nuclear magnetic signal corresponding to correcting sample with low resolution pulse nuclear magnetic resonance spectrometer, wherein, with the title of correcting sample
The normal heptane extract numerical value that weight method obtains is abscissa X, and the nuclear magnetic signal value of respective sample is Y, establishes a class polypropylene respectively
Nuclear magnetic signal calibration curve, b class polypropylene specimen normal heptanes the extractives content are corresponding corresponding to sample normal heptane the extractives content
Nuclear magnetic signal calibration curve, nuclear magnetic signal calibration curve corresponding to c class polypropylene specimen normal heptane the extractives contents；
(4) test of testing samples nuclear magnetic signal
Test to obtain nuclear magnetic signal corresponding to testing sample with low resolution pulse nuclear magnetic resonance spectrometer；
(5) calculates the normal heptane the extractives content of testing sample according to calibration curve
The nuclear magnetic signal of the testing sample measured in step (4) is substituted into respective nuclear magnetic signal school in step (3) respectively
Positive curve, calculate the normal heptane the extractives content of testing sample.
If testing sample is a classes, nuclear magnetic signal school corresponding to a class polypropylene specimen normal heptane the extractives contents is substituted into
Positive curve；If testing sample is b classes, nuclear magnetic signal school corresponding to b class polypropylene specimen normal heptane the extractives contents is substituted into
Positive curve；If testing sample is c classes, nuclear magnetic signal school corresponding to c class polypropylene specimen normal heptane the extractives contents is substituted into
Positive curve.
The assay method of normal heptane the extractives content in polypropylene of the present invention, wherein, a classes, b classes in step (2)
Or the correcting sample of c classes is respectively preferably 5~12 normal heptane the extractives content gradient samples.
The assay method of normal heptane the extractives content in polypropylene of the present invention, these, it is preferred in step (2)
The pretreatment includes：Sample is carried out to melt tabletting sample preparation, and carries out sample state regulation；By sample heating or cold after tabletting
But to test temperature and constant temperature regular hour.
The assay method of normal heptane the extractives content in polypropylene of the present invention, wherein, the tabletting of the sample and
Status adjustment condition is preferably：
Sample is subjected to MTG YBCO bulk at 190 DEG C~260 DEG C with tablet press machine, 1~20min of preheating time, the total head time 1~
20min, 1~30 DEG C/min of rate of temperature fall, demoulding temperature≤40 DEG C, sample regulation temperature≤40 DEG C, sample regulating time 0~
60h。
The assay method of normal heptane the extractives content in polypropylene of the present invention, wherein, sample after tabletting is heated
Or test temperature and constant temperature regular hour are cooled to, the test temperature is preferably 30~100 DEG C, and constant temperature time is preferably 3
~30min.
The assay method of normal heptane the extractives content in polypropylene of the present invention, these, it is preferred in step (2)
Correcting sample is identical with the pretreatment condition of testing sample.
The assay method of normal heptane the extractives content in polypropylene of the present invention, these, it is preferred in step (3)
Nuclear magnetic signal calibration curve, b class polypropylene specimen normal heptane extracts corresponding to a class polypropylene specimen normal heptane the extractives contents
Nuclear magnetic signal correction is bent corresponding to nuclear magnetic signal calibration curve corresponding to content and c class polypropylene specimen normal heptane the extractives contents
The coefficient correlation of line is >=0.95.
The present invention can be also summarized as follows：
To achieve these goals, according to an aspect of the invention, there is provided normal heptane extract in a kind of polypropylene
The instrumentation method of testing of content, comprises the following steps：According to sample structure feature to sample in HOPP, block copolymerization
Classification in the range of polypropylene and atactic copolymerized polypropene；Correcting sample and testing sample are pre-processed, eliminated not same
Product are because thermal history difference is on influence caused by test result；It is corresponding to establish different type polypropylene specimen normal heptane the extractives content
Nuclear magnetic signal calibration curve；Test the nuclear magnetic signal of testing sample；The normal heptane of testing sample is calculated according to calibration curve
The extractives content.
Polypropylene normal heptane the extractives content nuclear-magnetism test calibration curve is established, is obtained by following steps：A. 5 are taken respectively
HOPP, atactic copolymerized polypropene and the block copolymerization polypropylene sample of~12 different normal heptane the extractives contents carry out pre-
Processing；B. using the nuclear magnetic signal of nuclear magnetic resonance spectrometer test pretreatment post-equalization sample；C. correcting sample positive heptan is established respectively
Matched curve is associated between alkane the extractives content and nuclear magnetic signal, obtains correlation function.Curve correlation coefficient need to be more than 0.95.
Testing sample is heated or cooled to instrument test temperature, 30~100 DEG C of Range of measuring temp, incited somebody to action after reaching temperature
Sample is put into 3~30min of constant temperature in instrument.
Testing sample is put into low resolution pulse nuclear magnetic resonance spectrometer, nuclear magnetic signal is measured, brings into correction function, be calculated
The normal heptane the extractives content of sample.
Embodiment
The technical scheme in embodiments of the invention will be described in detail below, but following examples be only to
Understand the present invention, and the present invention can not be limited, the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
Correcting sample：
In the present invention, correcting sample is not particularly limited, the correcting sample of a classes, b classes or c classes in usual step (2)
Respectively 5~12 normal heptane the extractives content gradient samples, correcting sample number can also be more, but can not be less than 5；If step
Suddenly the correcting sample of a classes, b classes or c classes is respectively to be less than 3 normal heptane the extractives content gradient samples in (2), due to correcting sample
Product are very few, and calibration curve is representative poor, causes test result error larger；And in step (2) a classes, b classes or c classes correction sample
Product are respectively to be more than 12 normal heptane the extractives content gradient samples, because sample is excessive, cause workload larger.
Tabletting and status adjustment condition：
In the present invention, tabletting and status adjustment condition are not particularly limited, the tabletting of the usual sample and state
Adjusting condition is：Sample is subjected to MTG YBCO bulk, 1~20min of preheating time, total head time with tablet press machine at 190 DEG C~260 DEG C
1~20min, 1~30 DEG C/min of rate of temperature fall, demoulding temperature≤40 DEG C, sample regulation temperature≤40 DEG C, sample regulating time 0
~60h；
If MTG YBCO bulk temperature is less than 190 DEG C, because MTG YBCO bulk temperature is too small, cause sample plasticizing incomplete, nothing
Sample thermal history is completely eliminated in method, and causes experimental error；And MTG YBCO bulk temperature is more than 260 DEG C, due to MTG YBCO bulk temperature
It is excessive, cause sample oxidation degraded to destroy, have no other beneficial effects；
If preheating time is less than 1min, because preheating time is too short, causes sample plasticizing incomplete, can not be completely eliminated
Sample thermal history, and cause experimental error；And preheating time is more than 20min, because preheating time is long, the time is caused to waste,
And sample oxidation degraded can occur and destroy, it is effective to have no other；
If the total head time is less than 1min, because the total head time is too short, causes sample plasticizing incomplete, can not be completely eliminated
Sample thermal history, and cause experimental error；And the total head time is more than 20min, due to total head overlong time, the time is caused to waste,
And sample oxidation degraded can occur and destroy, it is effective to have no other；
If rate of temperature fall is less than 1 DEG C/min, because rate of temperature fall is too short, cause sample thermal history is complex to cause reality
Test error；And rate of temperature fall is more than 30 DEG C/min, because rate of temperature fall is excessive, cause sample temperature gradient is too high to cause sample not
Uniformly, it is effective that other are had no；
If demoulding temperature is more than 40 DEG C, because demoulding temperature is too high, sample cooling is caused not exclusively to cause test result
Error, have no other beneficial effects；
If sample regulation temperature is more than 40 DEG C, because sample regulation temperature is too high, the thermal history for causing sample new causes
Test result error, have no other beneficial effects；
If sample regulating time is more than 60h, because sample regulating time is long, the time is caused to waste, may band sample
The new thermal history of product causes experimental error, has no other beneficial effects.
Test temperature：
In the present invention, test temperature is not particularly limited, sample after tabletting is generally heated or cooled to test temperature
Spend and constant temperature regular hour, the test temperature are 30~100 DEG C；
If test temperature is less than 30 DEG C, because test temperature is too small, equalized temperature is caused to be difficult to control；And test temperature
More than 100 DEG C, because test temperature is too high, causes the obvious thermal history of polymer samples to influence test result, it is effective to have no other
Fruit.
Constant temperature time：
In the present invention, constant temperature time is not particularly limited, sample after tabletting is generally heated or cooled to test temperature
The simultaneously constant temperature regular hour is spent, the constant temperature time is 3~30min；
If constant temperature time is less than 3min, because constant temperature time is too short, cause non-uniform temperature constant temperature effect poor；It is and permanent
The warm time is more than 30min, because constant temperature time is long, causes the time to waste, thereby increases and it is possible to sample can be made to produce new thermal history and led
Test error is caused, it is effective to have no other.
The coefficient correlation of calibration curve：
In the present invention, the coefficient correlation of calibration curve is not particularly limited, a class polypropylene samples in usual step (3)
Savor nuclear magnetic signal calibration curve corresponding to normal heptane the extractives content, corresponding to b class polypropylene specimen normal heptane the extractives contents
The phase relation of nuclear magnetic signal calibration curve corresponding to nuclear magnetic signal calibration curve and c class polypropylene specimen normal heptane the extractives contents
Number is >=0.95；If nuclear magnetic signal calibration curve, b corresponding to a classes polypropylene specimen normal heptane the extractives content in step (3)
Nuclear magnetic signal calibration curve corresponding to class polypropylene specimen normal heptane the extractives content and c class polypropylene specimen normal heptane extracts
The coefficient correlation of nuclear magnetic signal calibration curve is respectively less than 0.95 corresponding to content, due to a class polypropylene specimens positive heptan in step (3)
Nuclear magnetic signal calibration curve corresponding to alkane the extractives content, nuclear-magnetism letter corresponding to b class polypropylene specimen normal heptane the extractives contents
The coefficient correlation mistake of nuclear magnetic signal calibration curve corresponding to number calibration curve and c class polypropylene specimen normal heptane the extractives contents
It is small, larger test error is caused, has no other beneficial effects.
Embodiment 1：
The measure of the normal heptane the extractives content of HOPP sample 1.
12 HOPP samples are stripped with normal heptane, choosing 5 normal heptane extracts by weight method contains
Gradient sample is measured as nuclear-magnetism method correcting sample.
5 correcting samples respectively take 6g, and sample is carried out into MTG YBCO bulk, preheating time 5min, total head at 210 DEG C with tablet press machine
Time 10min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, sample regulating time 6h.
Correcting sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 5min in instrument after temperature.
The corresponding nuclear magnetic signal value of correcting sample will be obtained in nuclear magnetic resonance spectrometer.
The normal heptane extract numerical value obtained with the weight method of correcting sample is abscissa X, the nuclear magnetic signal of respective sample
It is worth for Y, establishes standard curve, be shown in Table 1.Fitting correlation function is Y=368+142X, coefficient correlation 0.98.
HOPP testing sample 6g is taken, sample is subjected to MTG YBCO bulk, preheating time with tablet press machine at 210 DEG C
5min, total head time 10min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, when sample is adjusted
Between 6h.
Testing sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 5min in instrument after temperature.
The corresponding nuclear magnetic signal value 1025 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of testing sample is brought into fitting function and calculated, obtains testing sample normal heptane extract
Content value 2.4%.
Table 1, correcting sample weight method normal heptane the extractives content numerical value and corresponding nuclear magnetic signal value
| Normal heptane extract, % | Nuclear magnetic signal value | |
| 1 | 1.6 | 610 |
| 2 | 2 | 655 |
| 3 | 2.3 | 670 |
| 4 | 2.9 | 780 |
| 5 | 3.4 | 862 |
Embodiment 2：
The measure of the normal heptane the extractives content of HOPP sample 2.
HOPP testing sample 5g is taken, sample is subjected to MTG YBCO bulk, preheating time with tablet press machine at 210 DEG C
5min, total head time 10min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, when sample is adjusted
Between 6h.
Testing sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 4min in instrument after temperature.
The corresponding nuclear magnetic signal value 621 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of HOPP sample to be measured is brought into embodiment 1 to obtained fitting function Y=368+
Calculated in 142X, obtain testing sample normal heptane the extractives content numerical value 1.8%.
Embodiment 3：
The measure of the normal heptane the extractives content of HOPP sample 3.
HOPP testing sample 5.5g is taken, sample is subjected to MTG YBCO bulk, preheating time with tablet press machine at 210 DEG C
5min, total head time 10min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, when sample is adjusted
Between 6h.
Testing sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 4min in instrument after temperature.
The corresponding nuclear magnetic signal value 718 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of HOPP sample to be measured is brought into embodiment 1 to obtained fitting function Y=368+
Calculated in 142X, obtain testing sample normal heptane the extractives content numerical value 2.5%.
Embodiment 4：
The measure of the normal heptane the extractives content of block copolymerization polypropylene sample 1.
15 block copolymerization polypropylene samples are stripped with normal heptane, choosing 12 normal heptanes by weight method extracts
Thing concentration gradients sample is as nuclear-magnetism method correcting sample.
12 correcting samples respectively take 6g, and sample carried out into MTG YBCO bulk at 200 DEG C with tablet press machine, preheating time 3min, entirely
Press time 6min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, sample regulating time 12h.
Correcting sample is heated to 30 DEG C of instrument test temperature, reaches and sample is put into constant temperature 3min in instrument after temperature.
The corresponding nuclear magnetic signal value of correcting sample will be obtained in nuclear magnetic resonance spectrometer.
The normal heptane the extractives content numerical value obtained with the weight method of correcting sample is abscissa X, the nuclear-magnetism of respective sample
Signal value is Y, establishes standard curve, is shown in Table 2.Fitting correlation function is Y=650+89X, coefficient correlation 0.98.
Block copolymerization polypropylene sample 6g to be measured is taken, sample is subjected to MTG YBCO bulk, preheating time with tablet press machine at 200 DEG C
3min, total head time 6min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, sample regulating time
12h。
Block copolymerization polypropylene sample to be measured is heated to 40 DEG C of instrument test temperature, reaches and sample is put into instrument after temperature
Constant temperature 5min in device.
The corresponding nuclear magnetic signal value 2154 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of testing sample is brought into fitting function and calculated, obtains the extracting of the normal heptane of testing sample two
Thing content 16.9%.
Table 2, correcting sample normal heptane the extractives content numerical value and corresponding nuclear magnetic signal value
| Normal heptane extract, % | Nuclear magnetic signal value | |
| 1 | 4.7 | 932 |
| 2 | 7.9 | 1406 |
| 3 | 10.3 | 1753 |
| 4 | 14.6 | 1934 |
| 5 | 19.9 | 2348 |
| 6 | 23.2 | 2644 |
| 7 | 27.1 | 2931 |
| 8 | 29.4 | 3412 |
| 9 | 31.2 | 3450 |
| 10 | 33.6 | 3637 |
| 11 | 35.8 | 3849 |
| 12 | 39.4 | 4161 |
Embodiment 5：
The measure of the normal heptane the extractives content of block copolymerization polypropylene sample 2.
HOPP testing sample 6.3g is taken, sample is subjected to MTG YBCO bulk, preheating time with tablet press machine at 200 DEG C
3min, total head time 6min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, sample regulating time
12h。
Testing sample is heated to 30 DEG C of instrument test temperature, reaches and sample is put into constant temperature 3min in instrument after temperature.
The corresponding nuclear magnetic signal value 1453 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of HOPP sample to be measured is brought into embodiment 4 to obtained fitting function Y=650+89X
In calculated, obtain testing sample normal heptane the extractives content numerical value 9.0%.
Embodiment 6：
The measure of atactic copolymerized polypropene normal heptane the extractives content.
13 atactic copolymerized polypropene samples are stripped with normal heptane, choosing 8 normal heptanes by weight method extracts
Thing concentration gradients sample is as nuclear-magnetism method correcting sample.
8 correcting samples respectively take 5.7g, and sample carried out into MTG YBCO bulk at 190 DEG C with tablet press machine, preheating time 1min, entirely
Press time 1min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, sample regulating time 8h.
Correcting sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 5min in instrument after temperature.
Correcting sample is put into nuclear magnetic resonance spectrometer and obtains corresponding nuclear magnetic signal value.
The normal heptane the extractives content numerical value obtained with the weight method of correcting sample is abscissa X, the nuclear-magnetism of respective sample
Signal value is Y, establishes standard curve, is shown in Table 3.Fitting correlation function is Y=26+259X, coefficient correlation 0.96.
Atactic copolymerized polypropene testing sample 5.7g is taken, sample is subjected to MTG YBCO bulk at 220 DEG C with tablet press machine, during preheating
Between 3min, total head time 12min, 25 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample regulation 25 DEG C of temperature, sample regulation
Time 8h.
Testing sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 3min in instrument after temperature.
The corresponding nuclear magnetic signal value 1502 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of testing sample is brought into fitting function and calculated, obtains testing sample normal heptane extract
Content 5.7%.
Table 3, correcting sample weight method normal heptane the extractives content numerical value and corresponding nuclear magnetic signal value
| Normal heptane extract, % | Nuclear magnetic signal value | |
| 1 | 1.2 | 529 |
| 2 | 2.9 | 724 |
| 3 | 3.4 | 838 |
| 4 | 4.7 | 1099 |
| 5 | 5.3 | 1269 |
| 6 | 6.9 | 1874 |
| 7 | 7.4 | 2045 |
| 8 | 8.2 | 2197 |
Embodiment 7：
The measure of the normal heptane the extractives content of atactic copolymerized polypropene sample 2.
Take HOPP testing sample 5g, 190 DEG C of progress MTG YBCO bulks, preheating time 1min, total head time 1min, drop
Warm 30 DEG C/min of speed, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, sample regulating time 8h.
Testing sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 5min in instrument after temperature.
The corresponding nuclear magnetic signal value 1269 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of HOPP sample to be measured is brought into embodiment 6 to obtained fitting function Y=26+259X
In calculated, obtain testing sample normal heptane the extractives content numerical value 4.8%.
Embodiment 8：
The measure of the normal heptane the extractives content of atactic copolymerized polypropene sample 3.
HOPP testing sample 5.2g is taken, sample is subjected to MTG YBCO bulk, preheating time with tablet press machine at 190 DEG C
1min, total head time 1min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature, sample 25 DEG C of temperature of regulation, sample regulating time
8h。
Testing sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 5min in instrument after temperature.
The corresponding nuclear magnetic signal value 1469 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of HOPP sample to be measured is brought into embodiment 6 to obtained fitting function Y=26+259X
In calculated, obtain testing sample normal heptane the extractives content numerical value 5.6%.
Embodiment 9：
The measure of atactic copolymerized polypropene normal heptane the extractives content.
13 atactic copolymerized polypropene samples are stripped with normal heptane, choosing 6 normal heptanes by weight method extracts
Thing concentration gradients sample is as nuclear-magnetism method correcting sample.
6 correcting samples respectively take 5g, and sample carried out into MTG YBCO bulk at 260 DEG C with tablet press machine, preheating time 20min, entirely
Press time 20min, 1 DEG C/min of rate of temperature fall, 40 DEG C of demoulding temperature, sample 40 DEG C of temperature of regulation, sample regulating time 60h.
Correcting sample is heated to 100 DEG C of instrument test temperature, reaches and sample is put into constant temperature in instrument after temperature
30min。
Correcting sample is put into nuclear magnetic resonance spectrometer and obtains corresponding nuclear magnetic signal value.
The normal heptane the extractives content numerical value obtained with the weight method of correcting sample is abscissa X, the nuclear-magnetism of respective sample
Signal value is Y, establishes standard curve, is shown in Table 4.Fitting correlation function is Y=26+259X, coefficient correlation 0.97.
Atactic copolymerized polypropene testing sample 5g is taken, sample is subjected to MTG YBCO bulk, preheating time with tablet press machine at 260 DEG C
20min, total head time 20min, 1 DEG C/min of rate of temperature fall, 40 DEG C of demoulding temperature, sample 40 DEG C of temperature of regulation, when sample is adjusted
Between 60h.
Correcting sample is heated to 100 DEG C of instrument test temperature, reaches and sample is put into constant temperature in instrument after temperature
30min。
The corresponding nuclear magnetic signal value 2253 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of testing sample is brought into fitting function and calculated, obtains testing sample normal heptane extract
Content 5.7%.
Table 4, correcting sample weight method normal heptane the extractives content numerical value and corresponding nuclear magnetic signal value
| Normal heptane extract, % | Nuclear magnetic signal value | |
| 1 | 2.9 | 1086 |
| 2 | 3.4 | 1257 |
| 3 | 4.7 | 1649 |
| 4 | 5.3 | 1904 |
| 5 | 6.9 | 2811 |
| 6 | 7.4 | 3068 |
Embodiment 10：
The measure of the normal heptane the extractives content of HOPP sample 1.
12 HOPP samples are stripped with normal heptane, choosing 5 normal heptane extracts by weight method contains
Gradient sample is measured as nuclear-magnetism method correcting sample.
5 correcting samples respectively take 6g, and sample is carried out into MTG YBCO bulk, preheating time 5min, total head at 210 DEG C with tablet press machine
Time 10min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature.
Correcting sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 5min in instrument after temperature.
The corresponding nuclear magnetic signal value of correcting sample will be obtained in nuclear magnetic resonance spectrometer.
The normal heptane extract numerical value obtained with the weight method of correcting sample is abscissa X, the nuclear magnetic signal of respective sample
It is worth for Y, establishes standard curve, be shown in Table 5.Fitting correlation function is Y=368+142X, coefficient correlation 0.98.
HOPP testing sample 6g is taken, sample is subjected to MTG YBCO bulk, preheating time with tablet press machine at 210 DEG C
5min, total head time 10min, 30 DEG C/min of rate of temperature fall, 25 DEG C of demoulding temperature.
Testing sample is heated to 40 DEG C of instrument test temperature, reaches and sample is put into constant temperature 5min in instrument after temperature.
The corresponding nuclear magnetic signal value 1025 of testing sample will be obtained in nuclear magnetic resonance spectrometer.
The nuclear magnetic signal value of testing sample is brought into fitting function and calculated, obtains testing sample normal heptane extract
Content value 2.4%.
Table 5, correcting sample weight method normal heptane the extractives content numerical value and corresponding nuclear magnetic signal value
| Normal heptane extract, % | Nuclear magnetic signal value | |
| 1 | 1.6 | 610 |
| 2 | 2 | 655 |
| 3 | 2.3 | 670 |
| 4 | 2.9 | 780 |
| 5 | 3.4 | 862 |
Claims (5)
1. the assay method of normal heptane the extractives content, comprises the following steps in a kind of polypropylene：
(1) samples are classified
Correcting sample and testing sample are classified according to HOPP, block copolymerization polypropylene and atactic copolymerized polypropene, point
A classes, b classes, c classes are not denoted as；
(2) sample pretreatments
A classes, b classes, the correcting sample of c classes and testing sample are pre-processed；
(3) foundation of nuclear magnetic signals calibration curve
Test to obtain nuclear magnetic signal corresponding to correcting sample with low resolution pulse nuclear magnetic resonance spectrometer, wherein, with the weight method of correcting sample
Obtained normal heptane extract numerical value is abscissa X, and the nuclear magnetic signal value of respective sample is Y, establishes a class polypropylene specimens respectively
Nuclear magnetic signal calibration curve corresponding to normal heptane the extractives content, core corresponding to b class polypropylene specimen normal heptane the extractives contents
Nuclear magnetic signal calibration curve corresponding to magnetic signal calibration curve, c class polypropylene specimen normal heptane the extractives contents；
(4) test of testing samples nuclear magnetic signal
Test to obtain nuclear magnetic signal corresponding to testing sample with low resolution pulse nuclear magnetic resonance spectrometer；
(5) calculates the normal heptane the extractives content of testing sample according to calibration curve
It is bent that the nuclear magnetic signal of the testing sample measured in step (4) is substituted into respective nuclear magnetic signal correction in step (3) respectively
Line, calculate the normal heptane the extractives content of testing sample；
Being pre-processed described in step (2) includes：Sample is carried out to melt tabletting sample preparation, and carries out sample state regulation；By tabletting
Sample is heated or cooled to test temperature and constant temperature regular hour afterwards；
The tabletting of the sample and status adjustment condition are：
Sample is subjected to MTG YBCO bulk at 190 DEG C~260 DEG C with tablet press machine, 1~20min of preheating time, the total head time 1~
20min, 1~30 DEG C/min of rate of temperature fall, demoulding temperature≤40 DEG C, sample regulation temperature≤40 DEG C, sample regulating time 0~
60h。
2. the assay method of normal heptane the extractives content in polypropylene according to claim 1, it is characterised in that step
(2) correcting sample of a classes, b classes or c classes is respectively 5~12 normal heptane the extractives content gradient samples in.
3. the assay method of normal heptane the extractives content in polypropylene according to claim 1, it is characterised in that by tabletting
Sample is heated or cooled to test temperature and constant temperature regular hour afterwards, and the test temperature is 30~100 DEG C, and constant temperature time is
3~30min.
4. the assay method of normal heptane the extractives content in the polypropylene according to any one of claims 1 to 3, step (2)
Middle correcting sample is identical with the pretreatment condition of testing sample.
5. the assay method of normal heptane the extractives content in the polypropylene according to any one of claims 1 to 3, its feature exist
In nuclear magnetic signal calibration curve, b class polypropylene specimens corresponding to a classes polypropylene specimen normal heptane the extractives content in step (3)
Core corresponding to nuclear magnetic signal calibration curve corresponding to normal heptane the extractives content and c class polypropylene specimen normal heptane the extractives contents
The coefficient correlation of magnetic signal calibration curve is >=0.95.
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| JPH09235325A (en) * | 1996-02-29 | 1997-09-09 | Mitsui Toatsu Chem Inc | Polypropylene and oriented film using the same |
| PT1141982E (en) * | 1998-10-28 | 2008-04-29 | Treofan Germany Gmbh & Co Kg | Biaxially oriented sheeting for electrical insulation with improved shrinkage at elevated temperatures |
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