Study of antioxidant migration into surface layer of diene elastomers

Małgorzata Piaskiewicz*

Teresa Kleps*

Teresa Parys*

Aneta Stępkow ska*

Study of antioxidant

migration into surface layer of diene elastomers

T h e m ig r a tio n o f a n tio x id a n ts in to th e s u r fa c e la y e r o f e la s to m e r s h a s b e e n in v e s tig a te d . T h e m a in a im o f th e in v e s tig a tio n w a s to e v a lu a te o f th e m ig r a tio n o f c o m m o n a n tio x id a n ts u s e d f o r ru bber. D e r iv a t iv e s o f p h e n o l, su c h a s 2 ,2 '-

-

d a n ts h a s b e e n e v a lu a te d f r o m th e c h a n g e s o f B K F o r I P P D c o n te n t in th e s u r fa c e la y e r a f te r d iffe r e n t tim e o f e la s to m e r s s to r a g e . C o n c e n tr a tio n o f a n ti­

o x id a n ts h a s b e e n d e te r m in e d b y F o u r ie r T r a n s fo r m e r I n f r a r e d S p e c tr o s c o p y w ith a tte n u a te d to ta l re fle c tio n (F T -IR A T R ) a n d g a s c h r o m a to g r a p h y (G C ) m e th o d s . I t w a s f o u n d th a t th e c o n c e n tr a tio n o f a n tio x id a n ts in th e s u r fa c e la y e r h a s g r a d ie n t p r o f ile a n d d e p e n d s o n th e tim e o f s t o r a g e o f e la s to m e r s .

Key words:

Badania migracji przeciwutleniaczy do warstwy wierzchniej elastomerów dieno- wych

Z b a d a n o m ig r a c ję p r z e c iw u tle n ia c z y d o w a r s tw y w ie r z c h n ie j w y r o b u g u ­ m o w e g o . S k o n c e n tr o w a n o s ię n a b a d a n ia c h m ig r a c ji p r z e c iw u tle n ia c z y p o ­ w s z e c h n ie s to s o w a n y c h w te c h n o lo g ii g u m y - p o c h o d n y c h f e n o lo w y c h (2 ,2 '- - m e ty l e n o - b is - ( 4 - m e ty lo - 6 - te r t- b u ty lo f e n o l) (B K F ) ) i a m in o w y c h (N - iz o p r o - p y l o - N ' - f e n y lo -p - fe n y le n o d ia m in a ) (I P P D )

w

k a n iz a c ji. Z m ia n y s tę ż e n ia p r z e c iw u tle n ia c z y

w

w

w

Słowa kluczowe:

1. Introduction

B a se on rubber te c h n o lo g y p ra ctice it is k n o w n that the fo rm a tio n o f thin la y ers o f an y c o m p o n e n ts on the su rfa ce o f rubber v u lc a n iz a te s (b lo o m in g ) e x e r ts an a f­

fe c t on a d h e siv e p ro p erties o f v u lc a n iz a te s , its r e s is ­ tan ce to a g in g , th erm al sta b ility and fin a lly th eir a p ­ p earan ce. C h e m ic a l c o m p o s itio n , stru ctu re and m o r ­ p h o lo g y o f the su rfa ce la y e r h a v e s ig n ific a n t in flu e n c e on the c o n d itio n s o f p r o c e s s in g o f ru b b er an d o ft e n ­ tim es d e c id e s on the q u a lity o f v u lc a n iz a te s .

* The Research Rubber Institute “Stom il”, Piastów, Poland

A slig h t m ig ra tio n o f a n tio z o n a n ts and a n tio x id a n ts su b s ta n c e s on th e o n e h an d h as a p o s itiv e e ffe c t d u e to th e in c r e a s e s o f r e s is ta n c e to th erm al o x id a tio n and o z o n e a g in g [ 1 , 2 ] but on th e oth er h and th e m igration o f h ig h q u an tity o f th e s e su b s ta n c e s lea d s to the fo rm a ­ tio n o f d is tin c t b lo o m that m a y d is q u a lify p rod u cts in term s o f th eir a p p lic a tio n and p r o c e s s in g .

S o m e c h e m ic a l su b s ta n c e s a d d ed to rubber c o m ­ p o u n d w e ll th e s e su b s ta n c e s w h ic h are fo rm ed during th e v u lc a n iz a tio n p r o c e s s can u n d erg o th e m igration in to the su rfa ce layer. B lo o m in g o n to rubber su rfa ce is th e resu lt o f th e m ig ra tio n o f lo w m o le c u la r w e ig h t c h e m ic a l s u b s ta n c e s from th e b u lk o f rubber v u lc a n i­

z a tes.

S&a&twt&ity nr 6 listopad - grudzień 2006 r. TOM 10

migracja pnecim tleniaczy

T ab le 1. T h e p a r a m e te r s o f s o lu b ility o f th e a n tio x id a n ts a n d r u b b e r s s t u d ie d T ab ela 1. P a r a m e tr y r o z p u s z c z a ln o ś c i b a d a n y c h p r z e c iw u tle n ia c z y i k a u c z u k ó w

Antioxidants rubber

Parameters of solubility 5, 103 J0,5/™1'5

according to Hoftyzer - Van Krevelen method [5] Literature [6,7]

8

d

p 5h 5

2,2’-methylene-bis-(4-methyl-6-tert-butylphenol) (BKF) 18.0

10.5 20.9 -

N-isopropyl-N’-phenyl-p-phenylenediamine (IPPD) 18.0 1.5 5.3 18.9 -

c/s-l,4-polyisoprene (IR) 14.6

14.6 16.3-^18.4

Styrene-butadiene rubber (SBR) 23,5% of bounded

styrene 17.5 0.7

17.5 17.5

T e n d e n c y to w a rd s th e m ig ra tio n o n to th e su rfa ce s h o w s up for th e c r y s ta llin e su b s ta n c e s o f lim ite d s o lu ­ b ility in e la s to m e r s w h ic h c o n cen tra tio n in rubber e x ­ c e e d s th eir s o lu b ility lim it as w e ll as fo r the a m o rp h o u s s u b s ta n c e s that d o n o t d is s o lv e in rubber and fo rm p h y s ic a l m ix tu res.

A c c o r d in g to literature data [3, 4] th e m e c h a n ism o f b lo o m in g o f c r y s ta llin e su b s ta n c e s o n to th e su rfa ce o f rubber v u lc a n iz a te is rela ted to th e rep ro d u ctio n o f a c r y sta llin e p h a se after c o o lin g .

C h e m ic a l r e a c tiv it y o f s u b s ta n c e s , in p a rticu la r their c o m p lia n c e to o x id a tio n w h ic h occu r, fo r e x a m p le , as th e resu lt o f th e rea ctio n o f o z o n e w ith p -p h e n y l- d ia m in e (P P D ) in f lu e n c e s th e m e c h a n ism o f m ig ra tio n . A s th e resu lt o f rea ctio n th e su rfa ce g ra d ien t o f P P D co n cen tra tio n is fo rm ed . T h e gra d ien t o f co n cen tra tio n is r e s p o n s ib le fo r th e in itia tio n o f m ig ra tio n p r o c e ss o f P P D to w a rd s th e su rfa ce o f rubber v u lc a n iz a te s and fo rm a tio n o f fit, o z o n e p r o te c tiv e la y er o f P P D o x id a ­ tion p ro d u cts on th e su rfa ce.

In th e p resen t w o rk , th e m ig ra tio n o f lo w m o le c u la r w e ig h t c o m p o n e n ts o f rubber c o m p o u n d s to w a rd s the su rfa ce la y er o f rubber p ro d u cts h as b een attem p ted to study.

T h e m a in to p ic o f th e stu d y is the e v a lu a tio n o f the m ig r a tio n o f t e c h n o l o g i c a l a n t io x id a n t s - 2 , 2 ’-m e - th y le n e -b is -(4 - m e th y l-6 -te r t -b u ty lp h e n o l) (B K F ), and N - is o p r o p y l- N ’- p h e n y l - p - p h e n y l e n e d ia m i n e ( I P P D ) c o m m o n ly u s e d in d ie n e e la s to m e r s - sty r e n e -b u ta ­ d ie n e (S B R ) and is o p r e n e (IR ) rubber.

T h e a n a ly s is o f s o lu b ility p aram eters o f rubbers (5 ) s h o w s (T a b le 1) that S B R h as h ig h er p o la rity than IR.

In th e c a s e o f S B R th e v a lu e o f p ola r c o m p o n e n t o f the s o lu b ility p a ram eter Sp is 0 .7 , w h erea s in the c a s e o f IR it is zero . T h e B K F and IP P D a n tio x id a n ts are ch a ra c­

te r iz e d by h ig h e r v a lu e s o f s o lu b ility p a ram eters in c o m p a r iso n to th e rubbers te s te d and th e v a lu e o f p olar and h y d r o g e n c o m p o n e n ts o f th e s o lu b ility p aram eters are d ifferen t. D iffe r e n t v a lu e s o f s o lu b ility p aram eters and th eir c o m p o n e n ts a llo w to fo r e s e e lim ite d s o lu b ility o f B K F and IP P D a n tio x id a n ts in IR and S B R . W ith re sp e c t to that th e s e g r e g a tio n o f a n tio x id a n ts o n to the su rfa ce o f rubber o u g h t to b e d ifferen t, b e in g d ep en d on

th e c h e m ic a l stru ctu re and p o la rity o f ela s to m e r s and th e r e a c tiv ity o f a n tio x id a n ts.

In th e litera tu re [8 -1 1 ] th ere are a lo t o f in fo rm a tio n a b o u t th e in v e s tig a t io n s on th e m ig ra tio n and su rfa ce se g r e g a tio n o f c h e m ic a l su b s ta n c e s, u sed as the c o m p o ­ n en ts o f e la s to m e r s m a teria ls, b y u sin g F ou rier T ran s­

fo rm er In frared S p e c tr o s c o p y w ith atten u ated total re­

fle c tio n (F T -IR A T R ).

In our w o rk the m igration o f an tioxid an ts into sur­

fa c e la y er o f d ie n e ela sto m ers has b een stu d ied by m ea n s FT-IR A T R an d G C m eth o d s w h ich w a s u sed ad d ition ­ ally to a n a ly z e o f extracts from their surface layer.

2. Experimental

2.1. Materials

T h e su b je c ts o f in v e s tig a tio n h a v e b een a n tio x i­

dan ts b e lo n g in g to p h e n o l d e r iv a tiv e s grou p - 2 ,2 ’-m e - t h y le n e -b is -(4 - m e th y l-6 -te r t -b u ty lp h e n o l) (B K F ) an d to a m in e s d e r iv a tiv e s - N - iz o p r o p y l- N ’-p h e n y l-p -p h e - n y le n e d ia m in e (I P P D ). T h e y h a v e b een ad d ed to rubber c o m p o u n d s c o n ta in in g is o p r e n e rubber (IR ) or sty ren e- b u ta d ie n e ru b b er (S B R ). T h e c o m p o u n d s h a v e c o n ­ ta in ed 2 .5 phr o f B K F or IP P D and c r o ss lin k in g s y s te m w h ic h c o n s is te d o f z in c o x id e , stearic a cid , a ccelera to r o f v u lc a n iz a t io n - C B S ( N - c y c lo h e x y lb e n z o lilo s u l- p h e n a m id e ) and sulphur. T h e co m p o u n d s h a v e b een v u lc a n iz e d at 1 6 0 °C .

2.2. Methods

• E x tra ctio n o f th e p la tes o f v u lc a n iz a te s (1 4 0 x 1 4 0 x 2 m m ) w a s p erfo rm ed w ith a c e to n e du rin g 5 m in at ro o m tem p era tu re after 7 , 3 0 , 6 0 and 9 0 d a y s o f v u lc a n i­

za tio n

• G a s c h r o m a to g ra p h y (G C ), th in -la y er ch ro m a to ­ g rap h y (L T C ) and F o u rier T ran sform er Infrared S p e c ­ tr o s c o p y F T IR - w e r e a p p lied for the d eterm in a tio n o f a n tio x id a n ts in a c e to n e ex tracts

• F o u rier T ran sfo rm er Infrared S p e c tr o s c o p y w ith a tte n u a te d to ta l r e fle c tio n a tta c h m e n t (F T -IR A T R )

TOM 10 listopad - grudzień 2006 r. Sta&toM&ity nr 6

migracja pneciwutleniarzy

migracja przeciwmmniaczg

eq u ip p ed w ith th e cry sta ls o f d ifferen t refra ctiv ity in d i­

ces: G e - n = 4 .0 and Z n S e - n = 2 .4 , w a s a p p lie d to stu d y the c o m p o s itio n o f th e su rfa ce la y er at th e d ep th o f 0 .9 9 -r 0 .4 5 pm in the c a s e o f G e cry sta l and 2 .5 0 - 1 .3 9 pm in th e c a s e o f Z n S e o n e r e s p e c tiv e ly as c a lc u la te d a c ­ co rd in g to H arrick ’s eq u a tio n [1 2 ] fo r sp ectra l re g io n

1 5 2 0 -r 8 3 6 c m '1.

T h e co n trib u tio n in d e x o f a n tio x id a n ts w a s d e fin e d as the relation o f a b so rb a n ce o f s o m e b a n d s c h a ra c­

teristic for c h e m ic a l g ro u p s w h ic h are in a n tio x id a n ts and in p rod u cts o f their rea ctio n w ith o x y g e n or o z o n e to the su m o f c o rresp o n d in g a b so rb a n ce b an d s c h a ra c­

teristic for rubber and a n tio x id a n ts p r e se n t in th e s a m ­ ple.

T h e f o llo w in g fo rm u la m a k e s it p o s s ib le to c a lc u ­ late the co n trib u tio n in d e x (X ) o f B K F and IP P D an ti­

oxid an ts:

w here:

X

~

X

-

A

Ap

Ar+b k f

> Ap+fppD -

dant ( 1 3 8 0 cm "1 fo r IR + B K F and IR + IP P D , 1 4 4 7 c m ' 1 for S B R + B K F and 1 3 1 0 - 1 2 9 5 cm "1 fo r S B R + IP P D )

3. Results and discussion

3.1. The solvent extraction / Gas chromatography method

It w a s r e c o g n iz e d that th e a n a ly s is o f s o lv e n t e x ­ tracts o b ta in ed from the su rfa ce o f v u lc a n iz a te s o u g h t to g iv e s o m e in fo rm a tio n a b ou t the c h a n g e s o f a n tio x id a n t q uantity in their su rfa ce layer.

It w a s a ss u m e d that d u rin g a v ery sh o rt tim e o f so lv e n t a ctio n o n th e su rfa ce o f v u lc a n iz a te p la tes - 5 m in at ro o m tem p eratu re - o n ly o rg a n ic lo w m o le c u la r w e ig h t su b sta n ces in c lu d e d in s id e th e su r fa c e la y er w ill be extra cted but th e su b s ta n c e s in c lu d e d in th e b u lk o f v u lca n iza te w ill n o t b e e x tra cted b e c a u s e o f a v ery sh ort tim e o f ex tra ctio n and lo w tem p eratu re.

T h e resu lts fro m F ig . 1 s h o w that th e c o n te n t o f extracted su b s ta n c e s is d iffe r e n t d e p e n d in g o n th e p o ­ larity o f rubber. T h e s o lv e n t ex tra cts fro m th e su rfa ce layer o f S B R v u lc a n iz a te s w e r e h ig h e r th en extra cts

F ig . 1.

Surface layer extracts from IR (A) and SBR (B) vulcanizates

R y s. 1.

Ekstrakt z warstwy wierzchniej wulkanizatów IR (A) i SBR (B)

T ab le 2.

Chemical substances in the surface layer ex­

tracts ofIR and SBR vulcanizates identified by TLC and FT-IR methods

T ab ela 2.

Substancje zidentyfikowane metodą TLC i FT- IR

ekstraktach z warstwy wierzchniej wulkanizatów

Vulcani­

zates

Anti­

oxidant added to

rubber com­

pounds

Chemical substances identified in the surface layer extracts

IR IPPD

IPPD, mercaptobenzothiazole, track quantities of p-phenylenediamine derivatives, hydrocarbons, zinc stearate

IR BKF

BKF, mercaptobenzothiazole, track quantities of p-phenylenediamine derivatives, hydrocarbons, zinc stearate

SBR IPPD

IPPD, mercaptobenzothiazole, track quantities of p-phenol derivatives, hydrocarbons, zinc stearate

SBR BKF

BKF, mercaptobenzothiazole, track quantities of p-phenol derivatives, hydrocarbons, zinc stearate

fro m IR v u lc a n iz a te s , ir r e sp e c tiv e o f th e k in d o f a n ti­

o x id a n ts - B K F or IP P D .

A n a ly s is o f th e su rfa ce la y er ex tra cts from IR and S B R v u lc a n iz a te s s h o w s th e p r e se n c e o f a n tio x id a n ts

SCaAtruH&Uf, nr 6 listopad - grudzień 2006 r. TOM 10

added to rubber c o m p o u n d s , and oth er su b s ta n c e s su ch as m e r c a p to b e n z o th ia z o le and z in c stearate as w e ll as trace q u a n tities o f p -p h e n y le n e d ia m in e d e r iv a tiv e s in the c a s e o f IR and p -p h e n o l d e r iv a tiv e s in th e c a s e o f S B R c o m p o s ite s (T a b le 2 ).

P r o b a b ly v e r y s m a ll a m o u n ts o f d e r iv a tiv e s o f p -p h e n y le n e d ia m in e s and o f p -p h e n o l o rig in a te from an tia g in g su b s ta n c e s u s e d to p ro tect raw rubbers, w h ile m e r c a p t o b e n z o th ia z o le and z in c stea ra te fo r m e d as a resu lt o f c h e m ic a l rea ctio n o f c o m p o n e n ts o f c r o ss - lin k in g sy s te m d u rin g v u lc a n iz a tio n .

A c c o r d in g to th e literature data [3] th e s o lu b ility o f zin c stea ra te in ru b b er in c r e a s e s in th e p r e se n c e o f a m in es d u e to the fo rm a tio n o f z in c -a m in e c o m p le x . In a c o n s e q u e n c e o f th is it is in fa v o u r o f m ig ra tio n and

F ig. 2. C o n te n t o f I P P D a n d B K F a n tio x id a n ts in s u r ­ f a c e la y e r s e x tr a c ts fr o m IR (A ) a n d S B R (B ) v u lc a n i-

z a te s d e te r m in e d b y G C m e th o d

R ys. 2. Z a w a r to ś ć p r z e c iw u tle n ia c z y I P P D i B K F o z n a ­ c zo n a m e to d ą G C w e k s tr a k ta c h z w a r s tw p o w ie r z c h ­ n io w y c h w u lk a n iz a tó w IR (A ) i S B R (B )

form ation o f th e b lo o m o f zin c stearate on th e su rfa ce o f v u lc a n iz a te s. In th is re sp e c t it is very d iffic u lt to lo o k for a d irect r e la tio n sh ip b e tw e e n th e m ig ra tio n o f stu ­ died su b s ta n c e s and th e v a lu e d e r iv e d from s o lv e n t e x ­ tracts o b ta in e d after v a r io u s tim e o f sa m p le s sto ra g e after v u lc a n iz a tio n .

In sp ite o f th is p r o b le m th e e v a lu a tio n o f c o m p o s i­

tion o f th e su r fa c e ex tra cts, u sin g G C m eth o d , g iv e n in F ig. 2, c le a r ly s h o w s that th e m ig ra tio n o f IP P D a n tio x i­

dant w a s h ig h e r th en o n e o f B K F . H o w e v e r , it is d if fi­

cult to e s ta b lis h th e in f lu e n c e o f sto ra g e tim e on the m igration o f a n tio x id a n ts stu d ied .

F ig . 3. C o n tr ib u tio n in d e x o f I P P D (A ) a n d B K F (B ) a n tio x id a n ts in th e s u r fa c e la y e r o f IR v u lc a n iz a te s d e ­ te r m in e d b y F T -IR A T R m e th o d

R y s. 3. W s k a ź n ik u d z ia łu p r z e c iw u tle n ia c z y I P P D (A ) i B K F (B ) w w a r s t w i e w ie r z c h n ie j w u lk a n iz a tó w IR ( o z n a c z o n y m e to d ą F T-IR A T R )

F ig . 4. C o n tr ib u tio n in d e x o f I P P D (A ) a n d B K F (B ) a n tio x id a n ts in s u r fa c e la y e r o f S B R v u lc a n iz a te s d e te r ­ m in e d b y F T-IR A T R m e th o d

R y s. 4. W s k a ź n ik u d z ia łu p r z e c iw u tle n ia c z y I P P D (A ) i B K F (B ) w w a r s tw ie w ie r z c h n ie j w u lk a n iz a tó w S B R ( o z n a c z o n y m e to d ą F T-IR A T R )

TOM 10 listopad - grudzień 2006 r. £ćaa£<Mieny nr 6

migracja przeciwutleniaczy

3.2 Fourier Transformed Infra­

red Spectroscopy with attenu­

ated total reflection (FT-IR ATR)

V a lu es o f co n trib u tio n in d e x fo r e x a m in e d a n tio x i­

dants p resen t in th e su rfa ce la y er o f v u lc a n iz a te s , c a lc u ­ lated from FT-IR A T R sp ectra u sin g G e and Z n S e c r y s ­ tals are p resen ted in F ig . 3 -4 .

In th e c a s e o f rubber c o n ta in in g B K F or IP P D an ti­

o x id a n ts it w a s s h o w n that th e c o n c e n tr a tio n g ra d ien t o f the a n tio x id a n ts in the su rfa ce la y e r o f v u lc a n iz a te s is presen t. C o n cen tra tio n o f a n tio x id a n ts in IR sa m p le s, e v a lu a ted on th e b a se o f co n trib u tio n in d e x w a s h ig h e r at su rfa ce la y er o f 0 .9 9 -r 0 .4 5 p m than at 2 .5 0 -r 1 .3 9 pm . T h e co n cen tra tio n c h a n g e d w ith th e tim e o f sto r­

ag e. It m a y te s tify on th e c o n tin u o u s d iffu s io n o f a n ti­

o x id a n ts tow ard s the su rfa ce la y er o f v u lc a n iz a te s . T h e co n cen tra tio n o f a n tio x id a n ts in S B R s a m p le s w a s sm a ller at 0 .9 9 - 0 .4 5 p m than at 2 .5 0

+

O n e x te n s io n o f the sto ra g e tim e o f S B R s a m p le s up to 6 0 d a y s the in c r e a s e o f a n tio x id a n ts c o n c e n tr a tio n at 0 .9 9 -i- 0 .4 5 pm w a s fo u n d to b e h ig h e r in co m p a r iso n to 2 .5 0 -r 1 .3 9 p m d ep th d u e to th eir c o n tin u o u s m ig ra ­ tion tow a rd s the su rfa ce la y er o f v u lc a n iz a te s .

4. Conclusion

• T h e resu lts o b ta in ed p o in te d at on th e su rfa ce g ra ­ d ien t o f a n tio x id a n ts c o n c e n tr a tio n p r e se n t for e x ­ a m in ed v u lc a n iz a te s. T h e g ra d ien t c h a n g e s in tim e.

• C h a n g es o f the c o n c e n tr a tio n o f B K F and IP P D a n tio x id a n ts in th e su rfa ce la y er o f IR and S B R v u lc a n iz a te s d ep en d o n sto r a g e tim e after v u lc a n i­

za tio n and m a y te s tify on th e c o n tin u o u s m ig ra tio n o f a n tio x id a n ts fro m th e b u lk o f v u lc a n iz a te m a te ­ rial o n to its s u r fa c e , d e s p ite s im u lt a n e o u s c o n ­ s u m p tio n p r o c e ss d u e to rea ctio n w ith o x y g e n or o z o n e .

• C o n cen tra tio n g ra d ien t o f a n tio x id a n ts in th e su r­

fa c e la y er d ep en d s on w h ic h p r o c e s s d o m in a te s - m ig ra tio n or o x id a tio n .

• T h e k in e tic s o f m ig ra tio n o f th e a n tio x id a n ts stu ­ d ied d ep en d s on m a n y fa cto rs su c h as th e c h e m ic a l structure o f e la s to m e r and a n tio x id a n t, th e a m ou n t o f a n tio x id a n t in c o m p o u n d , its c h e m ic a l c o m p o s i­

tion as w e ll as on m u tu al in tera ctio n b e tw e e n the c o m p o n e n ts. In r e sp e c t to that it is d iffic u lt to e s ­ ta b lish th e strict m e c h a n is m o f m ig ra tio n o f a n ti­

o x id a n ts in v u lc a n iz a te s. It w ill b e th e su b ject o f further stu d ies.

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