Tiêu chuẩn iso 21561 2 2016

© ISO 2016 Styrene butadiene rubber (SBR) — Determination of the microstructure of solution polymerized SBR — Part 2 FTIR with ATR method Caoutchouc styrène butadiène (SBR) — Détermination de la micro[.]

Styrene-butadiene rubber (SBR) —

Part 2:

Ca utch uc styr ne-b tadiène (SB R) — Déte mination de la

microstructur du SB R p lymérisé en solution —

Partie 2: Méth de FTIR a e ATR

Fir t edition

2 16-0 -0

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© ISO 2016, P blshed in Sw itz rlan

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written permis ion Permis ion c n be req esed from either ISO at the ad r es below or ISO’s member bod y in the c u try of

F reword i v

1 Sc ope 1

2 Nor mati ve r eferenc es 1

3 Principle 1

4 A pparatus 2

5 Calbratio 2

5.1 FTIR 2

5.2 ATR 2

6 S mpl ng 2

7 Proc ed re for me sur ing ATR spectrum 2

8 Deter minatio of the micr ostructure of b tadiene and the styr ene c ontent 3

8.1 Measur ement of the a sor banc for each micr ostructur e comp nent 3

8.2 Calculation of micr os ructur es 4

8.2.1 General 4

8.2.2 Base lne correction of each a sor banc peak 5

8.2.3 Ratio of a sor banc 5

8.2.4 S con orde te ms 5

8.2.5 Styrene content an micr ostructur es in mas % b r eg r es ion formulae 5

8.2.6 Micr os ructures in mol % 6

9 Precision 6

10 Test rep rt 6

A nne x A (informative)Precision results fr om an inter laborator y test prog ramme 8

A nne x B (informative)Ac quisitio of r eg res io formula for micr ostr uctur e 10

A nne x C (informative) Determination of micr ostr uctur e b NMR spectrometry 12

Biblog raphy 16

ISO (he Int ernational Org nization for Stan ardization) is a worldwidefede ation of national s an ards

b dies (ISO membe b dies) The work of pr p ring Int ernational Stan ards is normaly car ied out

through ISO t ech ical committ ees Each membe b dy int er st ed in a subje t for w hich a t ech ical

committ ee has be n es a lshed has the right t o be r pr sent ed on that committ ee Int ernational

org nizations, g ove nmental an non-g ove nmental, in laison with ISO, also take part in the work

ISO cola orat es closely with the Int ernational Ele trot ech ical C mmis ion (IEC) on al matt ers of

ele trot ech ical s an ardization

The proc d r s used t o develo this document an those int en ed for it furthe maint enanc ar

desc ibed in the ISO/IEC Dir ctives, Part 1 In p rticular the dife ent a pro al c it eria ne ded for the

dife ent ty es of ISO document should be not ed This document was draft ed in ac ordanc with the

edit orial rules of the ISO/IEC Dir ctives, Part 2 ( e www.iso.org dir ctives)

A tt ention is drawn t o the p s ibi ity that some of the element of this document ma be the subje t of

p t ent right ISO shal not be held r sponsible for identifying any or al such p t ent right Detais of

any p t ent right identified d ring the develo ment of the document wi be in the Introd ction an / r

on the ISO ls of p t ent de larations r c ived ( e www.iso.org p t ent )

Any trade name used in this document is information given for the convenienc of use s an does not

cons itut e an en orsement

F or an ex lanation on the meaning of ISO spe ific t erms an ex r s ions r lat ed t o conformity

as es ment, as wel as information a out ISO’ s adhe enc t o the WTO principles in the Te h ical

Bar ie s t o Trade (TBT) se the fol owing URL: F or word - Sup lementary information

The committ ee r sp nsible for this document is ISO/TC 45, R ub e a d rub e produc ts , Subcommitt ee

SC 2, Tes tin a d a alys i s

This f irs edition of ISO 2 561- 2 canc ls an r plac s ISO 2 561:2 0 , w hich has be n t ech icaly

r vised It also incorp rat es Amen ment ISO 2 56 1:2 0 /Amd.1:2 1

ISO 2 56 1 consis s of the folowing part , un e the g ene al title St y rene -b tadiene ru be (SBR) —

Dete min tio o the mic ros truc tur o s olutio -p ly me i zed SB :

— Part 1:

1

H-NMR a d IR w ith c as t-fim meth d

— Part 2 : FTIR w ith ATR meth d

Styrene-butadiene rubber (SBR) — Determination ofthe

Part 2:

WARNING — Per o s using this part of ISO 21561 sho ld be famiiar with normal laboratory

practice This part of ISO 21 61 does not purport to addres al the safety problems, if any,

as ociated with its use It is the respo sibi ity of the use to establsh appropriate safety and

he lth practices and to ensure compl ance with any national re ulatory conditions

CAUTION — Certain proced res specified in this part of ISO 21561 might inv lve the use or

g eneration of su stances, or the g eneratio of waste, that co ld co stitute a local enviro mental

hazard Reference sh uld be made to ap ro riate documentation o safe handlng and disposal

after use

This part of ISO 2 561 spe ifies proc d r s for the q antitative det ermination of the mic os ructur

of the butadiene an the cont ent of s yr ne in solution-p lyme iz d SBR ( S-SBR) b F ourie Trans orm

Infrar d Spe trometry (FTIR) with A tt en at ed Total R efle tion (ATR) method The s yr ne cont ent is

ex r s ed in mas % r lative t o the w hole p lyme The viny l, trans an cis cont ent ar ex r s ed in

mol % r lativet o the butadiene cont ent Thismethod isonly a plca le t o raw rub e s

NOTE 1 Precision as shown in An e A may not b o tained for S-SBRs containing polystyrene block or

styrene content more than 45 mas %

NOTE 2 Only “vin l”, “trans” an “ is” , are used in this part of ISO 2 56 1 However, the e pres ion of viny l,

trans an cis me n as fol ows in g neral

— viny l: vin l u it,vin lb n , 1,2-u it, 1,2-b n , 1,2-viny l-u it or 1,2-viny l-b n ;

— trans: 1,4-trans u it, 1,4-trans b n , trans-1,4 u it or trans1,4 b n ;

— cis: 1,4-cis u it, 1,4-cis b n , cis-1,4 u it or cis-1,4 b n

2 Normati ve r eferences

The folowing document , in w hole or in p rt, ar normatively r fe enc d in this document an ar

in ispensa le for it a pl cation F or dat ed r fe enc s, only the edition cit ed a pl es F or u dat ed

r fe enc s, the lat es edition of the r fe enc d document ( inclu ing any amen ment )a pl es

ISO 1 9 , R ub e ,raw n tural a d raw sy nthetic — S mpln a d f rthe pr p rati ve procedur s

The IR spe trum of the S-SBR sample is measur d b FTIR with ATR The a sorb nc s that ar

charact eris ic of each mic os ructur component an s yr ne at the spe if ied wa elengths ar used

t o det ermine the cont ent of each component b using the spe ific formulae pr sent ed in this p rt of

ISO 2 561

4 A pparatus

4.1 FTIR , of the folowing spe ifications:

— Det ect or: Deut erium Tri-Glycine Sulfat e (DTGS) or Tri-Glycine Sulfat e (TGS);

— Sample pr s ur clamp:A conca e or a flat-sha ed clamp w hich is ca a le of maintaining a cons ant

pr s ur on the sample The use of a t orq e wr nch is pr fe a le

5 Cal bration

5.1 FTIR

Adjus the o tical bench al gnment of FTIR spe tromete ac ording to the man factur r’s

ins ruction man al

5.2 ATR

S t ATR in the sample chambe of FTIR an adjus the o tical algnment of ATR ac ording t o the

man factur r’s ins ruction man al

6.1 Pr ep r e the tes sample in ac or danc with ISO 1 9

NOTE The e traction of ordinary e ten er oils by solvent is not neces ary

6.2 Cut out a tes pie e fr om the tes sample The tes pie e shal ha ve a flat surfac to g iveg ood contact

with the ATR c ys al and be a pr ox imately the same siz as the c ystal, usualy a few sq ar e mi imetr es

7 Proc edure for measuring ATR spectrum

7.1 S t up FTIR ac or ding to the man factur er’s ins ruction man al

7.2 S t ATR in a sample chambe of FTIR

7.3 Measure the b ckg r ou d spe trum with thecon itions shown in 4.1

7.4 P t the tes pie e on the ATR c ys al an contact it as completely as p s ible to the c ys al surfac ,

pr eferably using the clampspe ified in 4.2 The contact betwe n the tes pie e an the c ystal afe ts the

a sor banc of ATR spe tra

7.5 Measur e thesample spe trum w ith the con itions shown in 4.1.

7.6 T e atmosphere ofthe sample chambe for FTIR shal be kept consis ent d r ing the b ckgrou d and

tes pie e measurement in orde to a void the influenc s of a sor banc at 6 8 cm

8 Determination of the microstructur e ofbutadiene and the styr ene c ontent

8.1 Measurement of the absor banc e for each micr ostructur e c omponent

Measur thea sorb nc v lues at the wave n mbe s cor esp n ing t o themic os ructur component

as spe if ied in Ta le 1 F or cis, the a sorption peaks ar weak an the wa e n mbe of the peaks is

afe t ed b the s yr ne cont ent of the polyme

Table 1 — Me surement of absorbances for e ch mic ostructure compo ent of S-SBR

T e wave n mb r at his pe k ma imum is afected by the nature of the

polymer, such as the styrene cont ent When the pe k ma imum is visible,

re d of the a sorb nce at he pe k ma imum from 72 cm

−1

t o 73 cm

−1

If the styrene cont ent is over 3 %,the pe k of the cis b n is hid en

b tween the two larg styrene a sorptions at arou d 75 cm

Figure 1 — ATR spectrum of a ty ical S-SBR

8.2 Calculation of micr ostructur es

8.2.1 General

The mic os ructur of S-SBR is calculat ed b using r gr s ion formulae an the measur d a sorb nc

v lues of the ATR spe tra of each sample The r gr s ion formulae we e de ived from a s atis ical s u y

on the ATR spe tra of v rious S-SBR samples with k own mic os ructur s Aft er adjus ing the b selne

of the ATR spe tra, the a sorb nc ratio v luesof r spe tive a sorptions ar o tained as the p ramet er

v lue for mic os ructur calculation The mic os ructur r sult ar calculat ed b subs ituting these

p ramet er v lues in the r gr s ion formulae

8.2.2 Base lne c orrectio of e ch absor banc e pe k

Obtain the a sorb nc of each of the peaks A1 to A6 with cor e ted b se lnes by using

8.2.3 Ratio of absor banc e

Obtain the ratios of thea sorb nc s A 12 t o A 62 b using F ormulae (7) t o (1 ):

8.2.4 S c ond orde ter ms

Calculat e the se on orde t erms w hich ar thesq ar s of A1 t o A62

8.2.5 Styrene c ontent and microstr uctur es in mas % b reg r es io for mula

The cont ent (mas % ) of each mic os ructur comp nent is ex r s ed b the folowing r gr s ion

V = 3 , 9 + 5,3 × (A1 ) – 1 ,9 × (A1 ) – 1 3,6 × (A2 ) + 1 1 8,4 × (A2 ) + 1 ,2 × (A3 ) – 5 2,5

is the s yr ne cont ent of the S-SBR, in mas %;

V is the viny l cont ent of the S-SBR, in mas %;

T is the trans cont ent of the S-SBR, in mas %;

C

m

is the ciscont ent of the S- SBR, in mas %

8.2.6 Micr ostructures in mol %

Thecont ent (mol % ) in butadiene is ex r s ed b F ormulae (1 ) t o (1 ):

V is theviny l cont ent of the butadiene p rtion of the S-SBR, in mol %;

T is thetrans cont ent of the butadiene p rtion of the S-SBR, in mol %;

C is thecis cont ent of the butadiene portion of the S-SBR, in mol %

1) a ful desc iption of the sample an it origin;

2) if a pro riat e, method of pr p ration oft es pie e from the sample;

b) a r fe enc t o this p rt of ISO 2 561, i.e ISO 2 56 1- 2;

c) t es detais inclu ing any detai s of any proc d r s not pe if ied in this p rt of ISO 2 56 1;

d) t es r sult :

1) the n mbe of t es pie es used;

2) the r sult of the det ermination, ex r s ed in % an roun ed t o one plac of de imals;

e) dat e() of t es

A nnex A

Precision results from an inter laborator y test prog ramme

A 1 General

The folowing int erla orat ory t es pro ramme (ITP) was initialy car ied out in 2 14

Al calculations t o pro ide r peata i ity an r prod cibi ty v lues we e pe formed in ac ordanc with

ISO/TR 9 7 Pr cision conc pt an nomenclatur ar also given in ISO/TR 9 72

A 2 Precision results fr om the ITP

A 2.1 Prog ramme detai s

The ITP was org niz d an cond ct ed b Ja an in 2 14 Tes samples we e pr p r d in one la orat ory

an sent t o al 1 p rticipating la orat ories

Two S-SBRs we e used in the t es designat ed asS-3 an S-34

The n mbe of la orat ories on w hich pr cision data for each pro e ty is b sed is given in the ta les of

pr cision r sult (Ta les A.1 t o A.4) The n mbe of p rticipating la orat ories as not ed in these ta les is

the final n mbe aft er identifying c rtain la orat ory v lues as outle s

The ITP t es ing was cond ct ed o e a pe iod of two seq ential we ks On a spe ified week, the

b ckgrou d an det ermination t es s for each ty e of rub e (n = 1 × 2) we e pe formed in a da One

we k aft er Da 1, the blank t es an the det ermination t es s we e r peat ed (n = 1 × 2) Al the analy ses

we e cond ct ed on the basis of these t es r sult

A 2.2 Precision r esults

The pr cision r sult ar l st ed in Ta les A.1 t o A.4

R epeata i ity: The r peata i ty, r, of the t es method has be n es a lshed as the a pro riat e v lue

ta ulat ed in Ta les A.1 t o A.4 Two single t es r sult that dife b mor than the v lue shal be

conside ed suspe t an sugg es that some a pro riat e inves ig tive action be taken

R eprod cibi ity: The r prod cibi ity, R, of the t es method has be n es a l shed as the a pro riat e

v alue ta ulat ed in Ta les A.1 t o A.4 Two single t es r sult that dife b mor than the v lue shal be

conside ed suspe t an sugg es that some a pro riat e inves ig tive action be taken

The pr cision r sult as det ermined b this ITP should not be a pled t o ac eptanc or r je tion

t es ing for any group of mat erials or prod ct without documentation that the r sult of this pr cision

ev luation actualy a ply t o the prod ct or mat erials t est ed

Explanation of symb ls for Ta les A.1 to A.4:

s

r

within-la oratory stan ard deviation (in me surement u its);

r repe ta ility (in me surement u its);

(r) repe ta ility (in per ent of me n level);

s

R

b tween-la orat ory stan ard deviation (in me surement u its);

R reprod cibility (in me surement u its);

( R) reprod cibility (in per ent of me n level)

Table A.1 — Precisio data for Styrene content of S-SBR

Number of laboratories afer outler deleted (otal n mber of laboratories in ITP:16)

Table A.2 — Precisio data for V iny l co tent of S-SBR

Number of laboratories afer outler deleted (otal n mber of laboratories in ITP:16)

Table A.3 — Precisio data for Trans co tent of S-SBR

Number of laboratories afer outler deleted (otal n mber of laboratories in ITP:16)

Table A.4 — Precision data for Cis co tent of S-SBR

A nne x B

B.1 The r eg r es ion formulae for dete mining the micros ructur e wer e o tained b Partial Leas

C-NMR spe trometry The content of s yr ene, vinyl, trans an cis wer e dete mined in

ac ordanc w ith A nnex C The measur ement wer e con ucted in thr ee la or atories, an the results were

a ver ag ed T ese v lues b NMR spe tr ometry wer e used as resp nse v ria les in PLS r eg res ion analysis

B.3 ATR spe tra of these samples were measured in ac or danc with Clause 7 The measur ement

wer e car ied out onc in seven la oratories

B.4 The measur ed a sor banc s of ATR spe tr a wer e conve ted to ratio in ac or danc with 8.1to 8.2.3

B.5 C lculate the se on orde te ms which ar e the sq ar e of A 12 to A 62 A 12 to A 62, an the sq ar e

v lues of these six , ar e used as the ex lanatory v ria lesin PLS r eg res ion analysis ( e 8.2.4.)

B.6 The r eg r es ion Formulae (1 ) to (1 ) for dete mining the micr os ructur e in Clause 8 wer e o tained

as folows

a) Of-the-shelf sof war of PLSr gr s ion (JMP®

1)

b SAS Ins itut e Inc was a pled

b) The v luesof s yr ne, viny l, trans an cis of 1 samples o tained b NMR methods in B.2 we e used

as r sp nse v ria les in PLS

c) The v lues in B.5 de ived from a sorb nc of ATR spe tra b r spe tive la orat ories wer used as

ex lanat ory v ria les in PLS

d) The coefficient de ived b the PLSr gr s ion analy sis cor esp nd t o those in the F ormulae (1 )t o

(1 ) for s yr ne, viny l, transan cis ( e 8.2.4)

Table B.1 — Mic ostructures of samples used for PLS re res io analy sis

C NMR spe t omet y

1) Example of a suitable prod ct a vaila le commer cialy T is information is g iven for the con enience of user of

this document an do s not constitute an en or ement by ISO of this pr od ct