Preventing polymer degradation during mixing.

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Preventing polymer degradation during mixing.

Author: Mazzeo, Russell A. Date: Feb 1, 1995 Words: 3164 Publicatio : Rubber World !""#: $$35%95&'

Degradation caused by oxyidation Elastomers, like most organic materials, are subject to atmospheric oxidation, even at moderate temperatures. The ease of susceptibility to degradation depends, to a large degree, upon structure and environmental exposure. For example, saturated polymers are inherently more stable than unsaturated polymers due to their stronger bonds, or lack of double bonds in their backbone. Therefore, it ould hold that EPD! and butyl rubber ould be more stable than "#$ or %$ against oxidative degradation. "ince this article deals primarily ith the prevention of polymer degradation during mixing, the mechanism and prevention of degradation of vulcani&ates by the actions of o&one and stress ill not be discussed at any great length. 'xidation is a complex process involving many reactions, each influenced by prevailing conditions such as singlet oxygen, o&one, mechanical shear, heat, light, metals and fatigue. Effects of oxygen, o&one and shear !ost elastomers are subject to oxidation and it is kno n that the addition of only ()*+ combined oxygen ill render a rubber article useless. 'xidation proceeds by t o mechanisms, - .hain scission )) $esults from the attack of the polymer backbone hich causes softening and eakening. /t is the primary mechanism observed for natural rubber and butyl oxidation. - .rosslinking )) #rittle compounds result due to radical crosslinking reactions, resulting in the formation of ne crosslinks and a stiffer material. This reaction occurs predominantly ith "#$, neoprene, nitrile and EPD!. /n most cases, both types of attack occur and the one hich prevails determines the final compound properties. /t has been found that loss of elongation is the most sensitive criterion for aging measurement regardless of mechanism, and it is favored over measure of tensile loss. Finally, cure system selection plays a role in determining aging resistance. The effect of type of sulfur crosslinks and ho they can be varied should be considered, but ill not be discussed in this article. Effects of heat 0s expected, heat accelerates oxidation. Therefore, the effects described previously are observed sooner and are more severe as temperature is increased. /n order to distinguish

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the effects of heat from those of oxidation, aging tests need to be carried out in an inert atmosphere. When this is done, in natural rubber for example, formation of more crosslinks occurs initially -- followed by reversion, as both crosslinks and the main polymer chain backbone are broken. For example, at 60 degrees!", it re#uires $.%& combined oxygen to reduce the tensile strength of conventionally cured natural rubber in half. 'owever, at $$0 degrees!", only 0.6(& oxygen is re#uired. 'ad similar agings been done at $$0 degrees! " in the absence of oxygen, essentially no tensile loss would have been observed. )ffect of light and weathering *.+. ,ight promotes free radical oxidation at the rubber surface which produces a film of oxidi-ed rubber. 'eat and humidity then accelerate a cra-ing or alligatoring effect, and this oxidi-ed layer can be rubbed off -- giving a chalking appearance. .lack compounds are more resistant to *.+. light than are light colored ones, and these lighter compounds re#uire addition of larger amounts of a nonstaining antioxidant to replenish that used up at the surface/ i.e. an antioxidant reservoir is re#uired. 0he problem is more severe with thin parts since product performance can suffer as well as being merely a cosmetic problem. )ffect of metals 'eavy metal 1principally cobalt, copper, manganese, iron2 ions are believed to cataly-e rubber oxidative reactions by influencing the breakdown of peroxides in such a way as to accelerate further attack by oxygen. 0he first corrective approach is to eliminate all sources of harmful metals. "ompounds of copper and manganese which are directly soluble in rubber 1stearates and oleates2 are particularly active, since they provide a direct source of heavy metal ions. )ven the less soluble forms such as the oxides can cause problems by reactions with fatty acids used in compounding to produce more soluble forms. 3lthough some antioxidants are active against cataly-ed oxidation of rubber, in general, the standard antioxidants do not give protection against the heavy metal ions. 4ince the activity of the metal depends on its being in an ionic form, it is possible to protect compounds by incorporating substances which react with ionic metals to give stable coordination complexes. )ffect of fatigue 5ne of the ma6or causes of failure in rubber is the development of cracks at the surface. 0he growth of these cracks under repeated deformation -- or fatigue -- leads to catastrophic failure. 0his fatigue failure is initiated at minute flaws where stresses are high and mechanical rupture at such points can lead to the development of cracks. 4imilarly, attack by o-one can cause cracks to occur at the surface whose rate of growth is directly proportional to the o-one concentration. 7any factors, both chemical and physical, are involved and as would be anticipated, corrective action often consists in re-design and recompounding to minimi-e excessive stress concentration. 8ifferent classes of antioxidants can have different effects and practical experience has led to the recognition that certain products -- known as antiflex cracking agents -- in addition to being antioxidants in a more normal sense, possess particular ability to reduce the rate of crack growth. 3nother factor to be considered with flexing is the effect of sulfur concentration. 0he rate of oxidation is proportional to the amount of combined sulfur, and with lower sulfur levels, we obtain better aging. 9t would appear, therefore, that it is better to compound with low sulfur. 'owever, these low sulfur cures yield poor fatigue resistance in natural rubber, but little

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fatigue loss upon aging is experienced. SBR, on the other hand, exhibits both good aging and good fatigue resistance with low sulfur cures (ref. 1). Polymer degradation Polymeric degradation typically occurs ia a free radical process. !hemical bonds, whether they are within the main chain of the polymer or in side groups, can be dissociated by energy resulting from heat, mechanical shearing or radiation to create a free radical, "R.sup.#$. %he formation of ("R.sup.#$) can occur in any one of the arious phases of a polymer&s life cycle' polymeri(ation, processing and end use, and is called the initiation reaction. Propagation, the second stage of the degradation process, occurs when atmospheric oxygen reacts with ("R.sup.#$) to form a peroxy radical ("R)).sup.#$), as shown in e*uation 1. %he propagation stage is usually *uite rapid compared to initiation. %his peroxy radical can further react with labile hydrogens of the polymer to yield unstable hydroperoxides. %hese hydroperoxides decompose to al+oxy and hydroxy radicals which, in turn, abstract more hydrogens generating more polymer radicals and the cycle becomes autocatalytic, as shown in e*uations , through -, which illustrate some, but not all, of the reactions which can occur during the propagation stage. (1) "R.sup.#$ . ").sup.,$ "right arrow$ R)) (,) "R)).sup.#$ . R/ "right arrow$ R))/ . "R.sup.#$ (0) R))/ "right arrow$ "R).sup.#$ . "sup.#$)/ . (1) "R).sup.#$ . R/ "right arrow$ R)/ "R.sup.#$ (-) "/).sup.#$ . R/ "right arrow$ /)/ "R.sup.#$ 2utoxidation will progress until termination results from the formation of stable products. 3 entually, propagating radicals combine or disproportionate to form inert products and the process is terminated, as shown in e*uations 4 through 15. (4) , R# "right arrow$ R6R (7) "8athematical 3xpression )mitted$ (9) , "R.sub.0$ !))# "right arrow$ "R.sub.0$!))!"R.sub.0$ . ").sub.,$ (:) , R)# "right arrow$ R))R (15) R))# . #)/ "right arrow$ R)/ . ").sub.,$ 3*uations 4, 9 and : represents crosslin+ing, and increase the molecular weight of the polymer; this type of degradation manifests itself as brittleness, gelation and decreased elongation. !hain scission, e*uations (7) and (15), results in a decrease in molecular weight leading to increased melt flow and reduced tensile strength. %he manner in which arious common elastomers degrade is listed in table 1.
Table 1 - degradation of elastomers Natural rubber Scission (softens) Polyisoprene Scission (softens) Polychloroprene Crosslinking and scission (hardens) SB Crosslinking and scission (hardens) NB Crosslinking (hardens)

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Preventing polymer degradation during mixing.

BR IIR EPM EPDM Crosslinking (hardens) Scission (softens) Crosslinking and scission (hardens) Crosslinking and scission (hardens)

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<nhibition of degradation 2ntioxidants do not completely eliminate oxidati e degradation, but they mar+edly retard the rate of autoxidation by interfering with radical propagation. =epending on the types and combinations used, antioxidants can pro ide suitable polymer protection during the phases of its life cycle. %wo general classifications can be used to categori(e antioxidants 66 primary (chain terminating) and secondary (peroxide decomposing). Primary antioxidants /indered phenols and secondary aryl amines act as primary antioxidants by donating their reacti e hydrogen (>6/, )6/) to free radicals, particularly peroxy radicals, as shown below' "R)).sup.#$ . 2/ R))/ . "2.sup.#$ <n order to sufficiently terminate the oxidati e process, the antioxidant radical ("2.sup.#$) must be rendered stable so as not to continue propagation of new radicals. %hese radicals, in most cases, are stabili(ed ia their electron delocali(ation, or resonance. Phenolics /indered phenolics, because of their non6staining *ualities, are the most preferred type of primary antioxidant for light colored applications such as footwear. %his group can be further categori(ed into' simple phenolics (1), bisphenolics (,). polyphenolics (0), and thiobisphenolics (1) (figure 1). 2mines Secondary aryl amines function by hydrogen donation, similar to the phenols; howe er, at higher temperatures. they are also capable of decomposing peroxides. %his single feature, which will be discussed later, eliminates. most times. the need for a secondary antioxidant in combination with an amine antioxidant, which is more so the case with phenolic 2lthough the amine class of primary antioxidants is usually more effecti e than the phenols, because of their ability to act both as chain terminators and peroxide decomposers, their use is generally limited to those applications where their discoloring characteristic can be tolerated or mas+ed. %he amines are perhaps most used in unsaturated polymers containing carbon blac+. 8ost notable amine antioxidants are those deri ed from diphenylamine and p6 phenylenediamines. Some of the al+ylated diphenylamines are less discoloring than the phenylenediamines and find application in plastics. ?or example, 1,1&bis (alpha, alpha6 dimethylben(yl)diphenylamine is widely used in flexible polyurethane foams and polyamide hot melt adhesi es. %he p6phenylenediamines are more recogni(ed for their acti ity as antio(onants. Secondary antioxidants

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%his class of antioxidants consists of arious tri alent phosphorus and di alent sulfur containing compounds, most notable of which are organo phosphites and thioesters. %hese antioxidants are also termed pre enti e stabili(ers, because they pre ent the proliferation of al+oxy and hydroxy radicals by destroying hydroperoxides. Phosphites Phosphites function by reducing hydroperoxides to alcohols, and thus, con erting themsel es to phosphates. ""8athematical 3xpression )mitted$ >ot only are phosphites non6discoloring, but they are color stabili(ing, in that they inhibit the formation of the discoloring *uinoidal structures of phenolic antioxidants. %he most popular stabili(er is tris(nonylphenyl) phosphite (%>PP). %he introduction of %>PP re olutioni(ed the area of non6discoloring rubber stabili(ation. 2 serious drawbac+ of phosphites is their sensiti ity to hydrolysis. %he commercially a ailable phosphites ary significantly in their resistance to hydrolysis. Se eral phosphites are a ailable with arious additi es present to decrease susceptibility to hydrolysis. /ydrolysis of phosphites can ultimately had to the formation of phosphorous acid which can cause corrosion of processing e*uipment. Phosphite stabili(ers beha e synergistically with hindered phenolics and pro ide good processing protection, and some cases, enhance stability during ultra iolet exposure. %hey are the recommended secondary antioxidants for use in combination with the primary phenolic antioxidants %hioesters 2liphatic esters of B6thiodipropionic acid are highly effecti e peroxide decomposers for long term heat exposure application when used in combination with phenolics. %hey are more widely used in thermoplastic polymers, where sulfur will not interfere in a ulcani(ation process. %he ma@or thioester stabili(ers are dilauryl thiodiproprionate (=A%=%) and distearyl thiodiproprionate (=S%=P) (ref. ,). Polymer degradation during mixing >atural rubber Bhen we spea+ of natural rubber, we are concerned with an elastomer in which nature has pro ided naturally occuring antioxidants or stabili(ers. %hese stabili(ers protect the uncured hydrocarbon ery effecti ely. %he presence of oxidation inhibitors in the natural polymer has been demonstrated. 3arly in estigators extracted natural rubber with acetone and found that the rate of oxygen ta+en up in the extracted rubber was measurably increased. Reincorporation of the acetone extract into the extracted polymer restored the oxygen absorption rate to the original low le el (figure ,). Similar tests were made with ulcani(ed rubber (figure0). Remo al of acetone extractable material from the ulcani(ate lowered the resistance to oxidation. 2dding the original acetone extract to the extracted ulcani(ate and also to the unextracted ulcani(ate, impro ed the resistance to oxidation considerably, but not as greatly as hydro*uinone, a man made antioxidant. <t is e ident that the natural inhibitor in the acetone extract is a good deal more effecti e in the raw polymer than in the ulcani(ate. %his phenomenon is generally recogni(ed, and the addition of more powerful antioxidants for ulcani(ate protection is common practice. Synthetic rubber

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In contrast to natural rubber, synthetic polymers require the addition of antioxidants to guard against oxidative degradation. It is a general practice to add the antioxidant stabilizer during the manufacturing process and prior to the drying operation. This practice ensures that the polymer is adequately protected from the heat of the drying equipment. In the case of styrene butadiene rubber (SB !, incidences are "no#n #here improperly stabilized polymer has actually ignited in the drying oven. Simple oven aging tests reveal the effectiveness of oxidation inhibitors in SB polymer. Temperatures in the range of $%%&$'%(degrees)* are ordinarily used in the aging tests. +ithin as little as '% minutes at $'%(degrees)*, inadequately protected polymer #ill sho# the effects of oxidation by the formation of a melting surface film. ,pon cooling, the melted layer resinifies into a hard surface film #hich brea"s easily #hen the polymer sample is stretched slightly. The time required to form a fracturable film is ta"en as the -resinification time.- .ffective antioxidants usually inhibit resinification for several hours at $'%(degrees)*, the time depending on the effectiveness of the inhibitor. The initial melting and subsequent surface hardening indicate that both chain scission and cross&lin"ing reactions occur as the polymer is oxidized. /ooney viscosity determinations on polymers heated for varying periods of time reveal some interesting differences in the behavior of natural rubber and SB . In figure 0, the /ooney viscosities of natural rubber smo"ed sheet, pale crepe and of an unstabilized sample of SB are plotted. It is apparent that the predominant effect of heat on natural rubber is in the direction of lo#er viscosity (chain scission! #hereas #ith SB , the predominant effect is that of /ooney viscosity increase (cross&lin"ing!. The effects of several antioxidants on the /ooney viscosity curves of SB are sho#n in figure 1. The rising /ooney viscosity curves #ith unprotected SB is indicative of an oxidative cross&lin"ing reaction and the formation of higher molecular #eight polymer. This theory is confirmed by solubility and gel determinations. 2el is defined as the benzene insoluble portion of the polymer. Table 3 sho#s the effects of $'%(degrees)* oven aging on an oil extended SB polymer. These data #ere ta"en from a study comparing the effectiveness of several stabilizers in controlling gel development in SB . (T4B,54 64T4 3 7/ITT.6) 4n interesting study #as performed by +illiams and *arlton on the effect of '1%(degrees)8 internal mixer mastication and gel build&up in SB . In table ', the changes in /ooney viscosity and gel are sho#n after several periods of mastication at '1%(degrees)8. The milled samples #ere subsequently passed three times through a cold mill #hich is capable of redispersing at least part of the gel produced in the hot mixing treatment. edispersible gel is referred to as -loose- gel, #hereas gel that remains insoluble in benzene after the cold mill treatment is called -tight- gel. It is interesting to note that after six minutes, considerable loose gel #as produced9 #hereas after nine and t#elve minutes a great deal of tight gel #as found in the polymer.
Table 3 - effect of 350[degrees]F mixer mastication on gel formation Time Mooney % gel (remilled - 3 passes (min. !iscosity % gel t"ro#g" a cold mill 3 55 0 0 $ 5% &% 0 ' () %( %0 &% 3$ 3( 30

Table 0 sho#s the effect of mixing temperature on gel formation. 4t lo#er temperatures

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little gel was formed. Mixing at 325[degrees]F and above produced appreciable gel, and at higher temperatures the gel became the indispersible tight variet . !illiams also studies the effect of gel build"up on the ph sical properties of vulcani#ates prepared from these mixer masticated pol mers. $he data are given in table 5. %t lower mastication temperatures where little gel was produced, the ph sical properties were best, whereas at higher temperatures, the development of gel resulted in deterioration of the ph sical properties. !ith increasing temperatures we see an increase in the modulus and decreases in the tensile and elongation. $he &eMattia flexing data are especiall interesting. 't is apparent that gel in the pol mer ma have a dramatic effect in lowering the flex crac(ing resistance of )*+ ,ref. 3-.
Table 4 - effect of mastication on gel formation 12' mixer at temperature indicated Mastication Mooney % gel temperature, [degrees] !iscosity % gel "remilled# 22$ 4% & & 2$& 44 & & 2'$ %( & & %&& 4$ & & %2$ 4) 2% & %$& $4 %4 2$ %'$ 42 41 4&

[$%*./%+ &%$% 5 0M'$$1&] 2reventing pol mer degradation First and foremost, the use of a properl stabili#ed pol mer or an elastomer containing an ade3uate amount of antioxidant will immensel assist the rubber compounder and4or processor because it will5 6 2revent gel build"up "" which is detrimental to the development of good ph sical properties and of good flexing resistance as has been shown. 6 2revent viscosit increase or decrease "" which interferes with the processing after mixing. $he result will be observed in better handling on calenders, extruders, in7ection molding machines, etc. 6 2revent discoloration and staining "" especiall minimi#es ellowing of )*+ and 8*+ compounds which are (nown to ellow when sub7ected to high heat during mixing, processing and vulcani#ation. )econdl , mixing speeds and temperatures must be (ept as low as possible since these factors have been shown to contribute to gel build"up in even properl stabili#ed elastomers. 9onclusions $he selection of the proper antidegradants for elastomers and rubber compounds should be based upon a careful assessment of the elastomers utili#ed, mixing and processing conditions, the normal service re3uirements expected from the derived compounds, and the environment in which the vulcani#ates are to perform. 0nl then can one choose the ideal antioxidant or combination of antidegradants. )ince the degradation of rubber proceeds via several mechanisms, it must be emphasi#ed that it is essential to choose and utili#e the combination of antidegradants which will inhibit all of the described mechanisms of degradation.

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[FIGURE 1 TO 5 ILLUSTRATION OMITTED] References [1.] Barnhart, R.R., Ant!"#!$ants an$ ant!"%"nants, Un!r"&a' (he)!ca' (")*an&, Inc. 1+,,. [-.] .a"'!n", ..R., Ant!$e/ra$ants, Un!r"&a' (he)!ca' (")*an&, Inc., A*r!' -0, 1+1+, *resente$ at the -,th Ann2a' A3r"n R244er Gr"2* Lect2re Ser!es. [5.] 62nter, B.A., (he)!ca' *r"tect!"n a/a!nst $e/ra$at!"n "f h&$r"car4"n *"'&)ers, Un!r"&a' (he)!ca' (")*an&, Inc., 1+,,.
(O.7RIG6T 1++5 L!**!nc"tt 8 .et", Inc. ("*&r!/ht 1++5, Ga'e Gr"2*. A'' r!/hts reser9e$. Ga'e Gr"2* !s a Th")s"n ("r*"rat!"n (")*an&.

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