INTERNATIONAL ISO

STANDARD 24076
First edition
2021-02

Plastics — Polypropylene (PP) —

Determination of isotactic index by
low-resolution nuclear magnetic
resonance spectrometry
Plastiques — Polypropylène (PP) — Détermination de l'indice
isotactique par spectrométrie de résonance magnétique nucléaire à
basse résolution

Reference number
ISO 24076:2021(E)

© ISO 2021
ISO 24076:2021(E)

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 ISO 24076:2021(E)

Contents Page

Foreword ........................................................................................................................................................................................................................................ iv
Introduction .................................................................................................................................................................................................................................. v
1 Scope ................................................................................................................................................................................................................................. 1
2 Normative references ...................................................................................................................................................................................... 1
3 Terms and definitions ..................................................................................................................................................................................... 1
4 Principle ........................................................................................................................................................................................................................ 1
5 Apparatus ..................................................................................................................................................................................................................... 2
6 Preparation of sample .................................................................................................................................................................................... 2
6.1 ........................................................................................................................................................................................................... 2
General

6.2 Re ference s amp les ............................................................................................................................................................................... 2

7 Method A — Ratio method ......................................................................................................................................................................... 2
7.1 .................................................................................................................................................................................................... 2
Pro cedure

7.1 .1 M eas urement o f f re erence s amp les by n- hep tane extractio n .................................................. 2
7.1 .2 LR- N M R meas urement p ro cedure o f f re erence s amp les .............................................................. 3
7.1 .3 LR- N M R meas urement p ro cedure o f tes t s amp les ............................................................................. 3
7.2 .................................................................................................................................................................................................. 3
C alculatio n

7.2 .1 C alib ratio n curve ............................................................................................................................................................. 3

7.2 .2 C alculatio n of is o tactic index II ........................................................................................................................ 4
na

8 Method B — Absolute method ................................................................................................................................................................ 4

8.1 .................................................................................................................................................................................................... 4
Pro cedure

8.1 .1 M eas urement o f f re erence s amp les by n- hep tane extractio n .................................................. 4
8.1 .2 LR- N M R meas urement p ro cedure o f f re erence s amp les .............................................................. 4
8.1 .3 LR- N M R meas urement p ro cedure o f tes t s amp les ............................................................................. 4
8.2 .................................................................................................................................................................................................. 4
C alculatio n

8.2 .1 C alib ratio n curve ............................................................................................................................................................. 4

8.2 .2 C alculatio n of is o tactic index IInb ........................................................................................................................ 5
9 Expression of results ........................................................................................................................................................................................ 5
10 Test report................................................................................................................................................................................................................... 5
Annex A f (in o rmative) Example of a calibration curve for method A................................................................................. 7
Annex B f (in o rmative) Example of a calibration curve for method B ................................................................................. 8
Bibliography ................................................................................................................................................................................................................................ 9

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ISO 24076:2021(E)

Foreword
ISO (the International Organization for Standardization) is a worldwide federation o f national standards
bodies (ISO member bodies). The work o f preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters o f
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular, the di fferent approval criteria needed for the
di fferent types o f ISO documents should be noted. This document was dra fted in accordance with the
editorial rules o f the ISO/IEC Directives, Part 2 (see www.iso .org/directives).
Attention is drawn to the possibility that some o f the elements o f this document may be the subject o f
patent rights. ISO shall not be held responsible for identi fying any or all such patent rights. Details o f
any patent rights identified during the development o f the document will be in the Introduction and/or
on the ISO list o f patent declarations received (see www.iso .org/patents).
Any trade name used in this document is in formation given for the convenience o f users and does not
constitute an endorsement.
For an explanation o f the voluntary nature o f standards, the meaning o f ISO specific terms and
expressions related to con formity assessment, as well as in formation about ISO's adherence to the
World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT), see www.iso .org/
iso/foreword .html.
This document was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 9,
Thermoplastic materials.
Any feedback or questions on this document should be directed to the user’s national standards body. A
complete listing o f these bodies can be found at www.iso .org/members .html.

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 ISO 2 4076:2 02 1(E)

Introduction

T he L R-N M R me tho d i n th i s do c ument i s a relative me tho d e s tabl i she d with I S O 91 1 3 a s the ab s olute

me tho d . T he me tho d a nd concep t o f i s o tac tic i nde x o f p olyprop ylene a re s p e c i fie d i n I S O 9 1 1 3 , th at i s ,

the p olyprop ylene s ample i s s ep arate d i nto the e xtrac table a nd the u nex trac table matter b y n-hep ta ne

ex trac tion, and the p ercentage o f u ne xtrac tab le matter i n the s a mple i s c a lc u late d a s i s o tac tic i ndex.

I s o tac tic i nde x i n I S O 9 11 3 s ou nd s s i m i lar to tac ticity (i s o tac ticity or s tere o tac tic ity) o f p olymer ch ai n,

but the concep t and re s u lt a re d i fferent. T he res u lt i s relate d to but no t e qua l to the tac tic ity (i s o tac ticity

or s tere o tac ticity) o f mole c u lar ch ai n, wh ich c an b e de term i ne d b y h igh re s olution c a rb on-1 3 nucle ar

magne tic re s onance and i n frare d me tho d . T he re s u lt o f I S O 9 11 3 i s a l s o relate d to c r ys ta l l i z ation,

mole c u la r weight, chai n entanglement o f the s ample, s olvent s olubi l ity a nd o ther e ffe c ts .

For s ol id p olymers , ex trac tion a lways ta ke s a long ti me for the d i ffu s ion o f long mole c u lar cha i n from
p olymer to s olvent. To i mprove te s t e ffic ienc y, relative me tho d s are develop e d . T h i s do c u ment provide s

a relative non- de s truc tive me tho d for the de term i nation o f i s o tac tic i nde x by low-re s olution nucle ar

magne tic re s onance s p e c trome tr y th rough a c a l ibration c u r ve e s tab l i s h i ng with magne tic s igna l a nd

i s o tac tic i ndex de term i ne d b y I S O 9 11 3 . No s olvent i s u s e d, and the de term i nation e fficienc y i s i mprove d

du ri ng s ample s me a s u rement pro ce du re excep t for the c a l ibration p a r t.

© ISO 2021 – All rights reserved v

INTERNATIONAL STANDARD ISO 24076:2021(E)

Plastics — Polypropylene (PP) — Determination of

isotactic index by low-resolution nuclear magnetic
resonance spectrometry
1 Scope
This document specifies a relative method for the determination o f polypropylene (PP) isotactic index
by low-resolution pulsed nuclear magnetic resonance spectroscopy (LR-NMR).
This method enables the identification and coding o f types H propylene (PP-H) plastics according to
ISO 19069-1.
This method is suitable for base polymers and is not applicable for mixtures.
NOTE The direct method for the determination o f polypropylene isotactic index is specified in ISO 9113.

2 Normative references
The following documents are re ferred to in the text in such a way that some or all o f their content
constitutes requirements o f this document. For dated re ferences, only the edition cited applies. For
undated re ferences, the latest edition o f the re ferenced document (including any amendments) applies.
ISO 9113, Plastics — Polypropylene (PP) and propylene-copolymer thermoplastics — Determination of
isotactic index

3 Terms and definitions

For the purposes o f this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https://www.iso .org/obp
— IEC Electropedia: available at http://www.electropedia .org/
3.1
isotactic index
II
percentage mass fraction o f unextractable matter content in polypropylene, which cannot be extracted
from polypropylene by boiling n-heptane

4 Principle
The sample is placed in LR-NMR. A fter electromagnetic equilibration in the static magnetic field o f
the NMR spectrometer and application o f a 90° radio frequency pulse, the magnetization decay signal
curve from the protons o f the sample is recorded. The signal o f the un-extractable matter in the sample
drops much faster than that o f extractable matter. In the signal curve, initial signal corresponds to
the whole sample including the un-extractable and the extractable matter, and later slower dropping
signal corresponds to the extractable matter in the sample. So, the magnetization decay signal and the
isotactic index o f the sample are related.
The isotactic index is either calculated from the ratio between the magnetization decay signal o f the
un-extractable part and the entire sample detected by a ratio probe (method A ratio method), or from

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ISO 24076:2021(E)

the ratio between the magnetization decay signal o f the extractable part and the mass o f the sample-
detected by an absolute probe (method B absolute method), using an appropriate calibration. The
calibration curve is constructed using the magnetization decay signal and isotactic index determined
by n-Heptane extraction method specified in ISO 9113.

5 Apparatus
Usual laboratory apparatus and glassware and, in particular, the following.
5.1 LR-NMR, o f frequency 18 MHz to 25 MHz, typical o f 20 MHz and 23 MHz; a probe o f 10 mm
diameter for method A, or a probe o f 26 mm diameter for method B; temperature o f probe and magnet
field being 40 °C ± 0,1 °C.
NOTE The probe o f other diameter can also be used according to instrument parameters.

5.2 Sample tube , o f glass with outer diameter 10 mm ± 0,25 mm, wall thickness 0,9 mm ± 0,25 mm,
and length at least 150 mm, for method A; o f glass with outer diameter 26 mm ± 0,25 mm, wall thickness
1,3 mm ± 0,25 mm, and length at least 200 mm, for method B.
NOTE The sample tube o f other size can also be used according to probe parameters.

5.3 Oven, shall be capable o f being maintained at the temperature o f 140 °C ± 2 °C, provided with
vacuum lines o f 25 kPa or less.

5.4 Thermostatic apparatus , shall be capable o f being maintained at the temperature o f 40 °C ± 0,1 °C.

5.5 Balance, shall be accurate to the nearest 0,000 1 g, only for method B.

6 Preparation of sample
6.1 General
The test sample and the re ference sample can be in the form o f powder or pellets. Place at least 10 g o f
the sample in a glass container, and put it in the oven (5.3) for 2 h at 140 °C ± 2 °C under 25 kPa nitrogen
vacuum or less for complete drying and annealing, then cool in a desiccator to room temperature.

6.2 Reference samples

At least five re ference samples with di fferent isotactic index shall be used. The isotactic index o f
re ference samples shall cover the general range, and its distribution shall be homogeneous as far as
possible.
NOTE The isotactic index o f re ference samples can be 94 % to 99 %. The re ference samples can be collected
by the user or o ffered by spectrometer manu facturer.

7 Method A — Ratio method

7.1 Procedure

7.1.1 Measurement of reference samples by n-heptane extraction

The isotactic index o f re ference samples shall be measured by extraction method specified in ISO 9113.

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 ISO 2 4076: 2 02 1 (E)

7.1 .2 LR-NMR measurement procedure of reference samples

7.1 .2 .1 Put the re ference sample into a sample tube (5.2), with a depth o f between 30 mm and 50 mm.
NOTE The sample amount can be specified by the spectrometer manu facturer which matches to the
probe height.
7.1 .2 .2 Put the tube in thermostatic apparatus (5.4) for a minimum o f 30 min to achieve temperature
equilibration.

7.1 .2 .3 Trans fer the tube to LR-NMR probe (5.1) within 15 s. Hold for 15 min to achieve temperature
equilibration.
NOTE Experience shows that it is easy to trans fer a tube from thermostatic apparatus to LR-NMR probe
within 15 s.

7.1 .2 .4 Measure the magnetization decay signal. The typical signal range corresponding to the sample
is 7 μs to 9 μs, and that o f extractable matter is 50 μs to 90 μs.
NOTE For exact magnetization decay signal time, re fer to the spectrometer manu facturer’s instructions.

7.1 .3 LR-NMR measurement procedure of test samples

Shall be the same as that o f re ference samples (see 7.1.2 ) except that the re ference sample is replaced by
the test sample.

7.2 Calculation

7.2 .1 Calibration curve

Prepare calibration curve by plotting II' obtained from extraction method against LR-NMR signal. An
example o f a calibration curve for method A is shown in Annex A .
The Formula (1) is obtained by linear regression method according to the calibration curve.
II ′ = a ×
N′
1a − N′

N′
2a
+b (1)
1a

where
II' is the isotactic index o f the re ference sample determined by n-heptane extraction specified in
ISO 9113, expressed in percent (%);
N'1a is the average magnetization decay signal o f the re ference sample measured by method A;
N'2a is the average magnetization decay signal o f the extractable matter in the re ference sample
measured by method A;
a is the slope o f the calibration curve;
b is the intercept o f the calibration curve.

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ISO 24076:2021(E)

7.2.2 Calculation of isotactic index IIna

Isotactic index IIna is given by the Formula (2) .
− N2 a
II
na = a×
N
1a
N
+b (2)
1a

where
IIna is the isotactic index o f the test sample determined by method A, expressed in percent (%);
N1a is the average magnetization decay signal o f the test sample;
N2a is the average magnetization decay signal o f the extractable matter in the test sample;
a is the slope o f the calibration curve;
b is the intercept o f the calibration curve.

8 Method B — Absolute method

8.1 Procedure

8.1.1 Measurement of reference samples by n-heptane extraction

See 7.1.1.
8.1.2 LR-NMR measurement procedure of reference samples

8.1.2.1 Weigh approximately 5 g o f the re ference sample, to the nearest 1 mg, put them into a sample
tube (5.2 ) within the height of LR-NMR probe.
NOTE The sample amount can be specified by the spectrometer manu facturer which matches to the
probe height.
8.1.2.2 See 7.1.2.2.
8.1.2.3 See 7.1.2.3.
8.1.2.4 Measure the magnetization decay signal. The typical signal range corresponding to extractable
matter is 100 μs to 120 μs
NOTE For exact magnetization decay signal time, re fer to spectrometer manu facturer's instructions.

8.1.3 LR-NMR measurement procedure of test samples

Shall be the same as that o f re ference samples (see 8.1.2) except that the re ference sample is replaced
by the test sample.

8.2 Calculation
8.2.1 Calibration curve
Prepare calibration curve by plotting II' obtained from extraction method against LR-NMR signal. An
example o f a calibration curve for method B is shown in Annex B .

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 ISO 2 4076: 2 02 1 (E)

The Formula (3) is obtained by linear regression method according to the calibration curve.
II ′ = a ×
N′

m′
2b
+b (3)
where
II' is the isotactic index o f the re ference sample determined by n-heptane extraction specified in
ISO 9113, expressed in percent (%);
N'2b is the average magnetization decay signal o f the extractable matter in the re ference sample
measured by method B;
m' is the mass o f the re ference sample, expressed in grams (g);
a is the slope o f the calibration curve;
b is the intercept o f the calibration curve.

8.2 .2 Calculation of isotactic index IInb

Isotactic index IInb , is given by the Formula (4) :

II
nb = a×
N
2b
m
+b (4)
where
IInb is the isotactic index o f the test sample determined by method B, expressed in percent (%);
N2b is the average magnetization decay signal o f the extractable matter in the test sample meas -
ured by method B;
m is the mass o f the test sample, expressed in grams (g);
a is the slope o f the calibration curve;
b is the intercept o f the calibration curve.

9 Expression of results

Express the result as the arithmetic mean o f the two determinations. Report the result to one decimal
place. The absolute di fference between two determinations shall be within 0,2 %. I f this condition is
not fulfilled, repeat the test.

1 0 Test report

The test report shall include the following particulars:

a) a re ference to this document. i.e. ISO 24076:2021;
b) the method used (method A or method B);
c) all in formation necessary for the complete identification o f the test sample;
d) details o f the LR-NMR used;
e) results o f calibration: number and isotactic index o f re ference samples, magnetization decay signals
used for calculation, calibration curve and coe fficients;

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ISO 2 4076:2 02 1(E)

f) the i nd ividua l re s u lts , thei r me an va lue a nd the ab s olute d i fference b e twe en two de term i nation s ,

for more than two i nd ividua l va lue s the re s u lts ob ta i ne d;

g) any op eration no t s p e ci fie d i n th i s do c u ment or rega rde d as a n op tion;

h) the date o f the de term i nation .

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 ISO 2 4076: 2 02 1 (E)

Annex A

(informative)
Example of a calibration curve for method A

An example o f a calibration curve obtained from six re ference samples for method A is given below.
a) Number o f re ference samples: 6
b) Isotactic index o f re ference samples (tested in accordance with ISO 9113): 96,2 %, 96,8 %, 97,2 %,
98,4 %, 98,9 %, 99,2 %;
c) Magnetization decay signals range used for calculation (re fer to spectrometer manu facturer's
instructions): 7,5 μs to 9,5 μs for N1a, 47,5 μs , to 87,5 μs for N2 a;
d) Calibration curve and coe fficients: Prepared by plotting the isotactic index II' versus (N' 1a - N' 2a)/
N' 1a as shown in Figure A.1 , intercept −5,97, slope 1,14, linear correlation coe fficient 0,998.

Figure A.1 — E xample of a calibration curve for method A

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ISO 2 4076: 2 02 1 (E)

Annex B

(informative)
Example of a calibration curve for method B

An example o f a calibration curve obtained from seven re ference samples for method B is given below.
a) Number o f re ference samples: 7
b) Isotactic index o f re ference samples (tested in accordance with ISO 9113): 94,7 %, 95,3 %, 96,1 %,
96,9 %, 97,7 %, 98,0 %, 98,5 %;
c) Magnetization decay signals range used for calculation (re fer to spectrometer manu facturer's
instructions): 100 μs , to 120 μs for N2b;
d) Calibration curve and coe fficients: Prepared by plotting the isotactic index II' versus N' 2b/m ' as
shown in Figure B.1, intercept 107, slope −0,0076, linear correlation coefficient −0,996.

Figure B .1 — E xample of a calibration curve for method B

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 ISO 2 4076: 2 02 1 (E)

Bibliography

[1] I S O 19 0 6 9 -1 , Plastics — Polypropylene (PP) moulding and extrusion materials — Part 1: Designation
system and basis for specifications

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ISO 2 4076:2 02 1(E)

ICS 83.080.20
Price based on 9 pages

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