The Use of Antiozonants in Rubber Compounding

The Use of Antiozonants in Rubber Compounding

Through the years, rubber compounders have struggled with the problem of cracking of rubber goods in storage and in use. The chief cause of this cracking is the effects of oxygen and flexing. Fortunately (Slide 1), products broadley Slide 1 identified as antidegradants have been developed that limit or retard the effects of oxygen, ozone and flexing attack. Ozone is a special and very active form of oxygen. Antiozonants (Slide 2 considered by this presentation are Slide 2), chemically, p-Phenylenediamines. Antiozonants are the reaction products of keytone and dinitroaniline. This

presentation provides (Slide 3 a history of antiozonants, some of the differences in antioxidants and antiozonants used Slide 3) in the elastomer industry, discusses how antiozonants and antioxidants work, reviews the effects of compounding ingredients on antiozonant effectiveness, looks at some antiozonant toxicity issues and, finally, gives brief consideration to applications. In the early fifties at the beginning of the Korean War, the U.S. Army (Slide 4 had a problem, the tires on Slide 4) mothballed vehicles were all cracked, worthless. Through work done at UOP and the U.S. Army Arsenals, the substituted p-phenylenediamines were found to be effective in preventing the formation of cracks in rubber vulcanizates. UOP and Du Pont made p-phenylene diamines which were gasoline antioxidants. Research work at UOP established that

UOP No. 5 had very useful properties in protecting rubber goods against premature cracking. However, it was found
that UOP No. 5 was too active a species to be used in rubber compounding. It caused skin problems to workers and it was too volatile in the cured and uncured stocks. Based on this early work, UOP developed the first rubber antiozonants, UOP 88 and then UOP 288. These two chemicals have been successfully used in hundreds of applications involving rubber products. Despite much research that has been done through the years, these two chemicals continue to be made and sold by UOP. They are still the preferred antiozonants in many compounds. As stated earlier antidegradants used by the elastomer industry include materials that limit or retard the effects of oxygen, ozone and flex cracking attack. Since ozone is a particularly active form of oxygen, it might be suspected that ozone attack would be similar to oxygen attack. This is not generally true. Oxygen (Slide 5 is relatively slow acting. It Slide 5)

penetrates rubber goods and slowly deteriorates the vulcanizate throughout the piece. Oxygen deterioration (Slide 6 is Slide 6) characterized by softening (as in natural rubber) or hardening (as in SBR) and deterioration of other physical properties. In contrast, the reaction of ozone with SBR, nitrile and natural rubber vulcanizates is so rapid that the reaction is almost exclusively a surface reaction. Ozone attack is characterized by a surface frosting effect on relaxed vulcanizates and by cracking perpendicular to the direction of applied stress in rubber articles. A wide variety of chemicals have been found that exhibit antioxidant activity in elastomers. These materials vary widely in their antioxidant potency. Typical antioxidants include substituted phenols, diphenylamine-acetone reaction products, and tris(nonyl phenyl) phosphite (Slide 7 Amine materials are generally the most effective. These Slide 7). materials also have a tendency to stain. Other antioxidants, while perhaps less potent, are equally useful because of low discoloring properties, economics, polymer solubility, etc. Effective antiozonants (Slide 8 however, are almost exclusively limited to one class of compounds, the Slide 8), N,Ndisubstituted-p-phenylenediamines. The symmetrical N,NDialkyl-p-phenylenediamine antiozonants are most effective under static conditions. The unsymmetrical N-alkyl, N-aryl-p-phenylenediamines are good antiozonants in both static and dynamic conditions. The di-aryl derivatives have very low antiozonant effectiveness, however, they are very effective as antiflexcracking agents. Slide 8 shows specific examples of each of three types of antiozonants. Slides 9, 10 and 11 show commercially available symmetrical dialkyl antiozonants such as UOP 88, UOP 288 and UOP 788. Chemically, they are highly reactive. They are effective antiozonants in purely static applications. They tend to make a rubber stock scorchy. Note that there are several antiozonant suppliers for these three antiozonants. Why so many antiozonants? There are differences in each chemical type, of course there is competition and, finally, formulator preference. Each of the three symmetrical antiozonants are about equal in antiozonant potency. However, Slide UOP 88 (Slide 9 has a bright red stain, while UOP 288 (Slide 10 stains a more acceptable brown. UOP 788 (Slide 11 Slide 9) Slide 10) Sli 11) stains less than UOP 88, but more than UOP 288. UOP 288 is extremely scorchy; UOP 88, much less so. UOP 788 is intermediate in scorch. The commercial symmetrical diaryl antiozonants shown in Slide 12 are much less chemically reactive as antiozonants. They are, however, excellent antioxidants and antiflex-cracking agents and are less migratory than alkyl or alkylaryls. The alkyl-aryl derivatives are intermediate to the other groups (Slides 13, 14 and 15). They show good
1

Scorch: The premature curing or cross-linking of the rubber compound before it is completely mixed or processed.

antiozonant properties with added antiflex and antioxidant properties. These compounds are the preferred materials for dynamic applications. Therefore, this is the type of antiozonant used in tires. The unsymmetricals are less scorchy than the symmetricals and they tend to stain a purple to gray. The unsymmetrical antiozonants also show differences within their group UOP 688 (Slide 16 is the least Slide 16) staining and the IPPD type is the most staining. UOP 688 also seems to mute the stain of other antiozonants when it is used in blends. In this group, IPPD is the most active antiozonant, but it is the most toxic and it has the highest tendency to water leach. This product is used in tires in other parts of the world, but it is not used in the United States because of its toxicity. UOP 588 has slightly lower antidegradant properties than IPPD. The antidegradant properties of

UOP 588 and UOP 688 are similar. The biggest drawback with UOP 588 is its physical state. It can be made into a solid
by using special chilling and crystal seeding techniques. If it is sold as a liquid, it must be kept above its melting point of 48C. This type of antiozonant is used by most of the large tire companies in the world.

UOP 688 has the best combination characteristics of all of the previous materials. It is a liquid at room
temperature. Its antiozonant properties are similar to the other alkyl-aryl-p-PDAs, it is low in scorch, and it has the lowest staining and water-leaching characteristics. It is the least toxic of all the antiozonants. Blends shown on Slide 17 are a way of providing a combination static and dynamic application product. Flexzone 3-C is an IPPD type, but rather than the common isopropyl, it is normal propyl. A wide divergence of opinion exists as to how antiozonants react to provide vulcanizate protection (Slide 18 In Slide 18). the early 50s when these antiozonants were first introduced, Bob Shaw of the Rock Island Arsenal proposed that the antiozonants were scavengers. They are so reactive that ozone will react preferentially with the pPDA rather than the rubber hydrocarbon. It was shown that in an inert solvent containing antiozonant and rubber, five to six mols of ozone were consumed by the antiozonant reaction before attack on the rubber started (Slide 19 Other mechanisms have Slide 19). been proposed. British workers using electron microscope pictures concluded that a protective film develops on antiozonant protected polymers which prevents further attack on the body of the vulcanizate. If reaction of antiozonant and rubber hydrocarbon does occur, it most surely will occur at the double bond, thus reducing the vulnerability of the sites for oxygen attack. It has also been proposed that the ozone attacks the rubber double bond, and then the antiozonant reacts with the ozonized rubber. Recently, Dr. C. K. Rhee and co-workers at BFGoodrich have carefully analyzed products found at the surface of rubber protected with pPDA antiozonant. Their results clearly show that ozone scavenging is a mechanism by which pPDA antiozonants act. It is our feeling that no one reaction mechanism can account for the protection provided by pPDA antiozonants, and that both scavenging and chemical reaction involving ozone, antiozonant and rubber hydrocarbon occur.

There is more general agreement on how an antioxidant reacts (Slide 20 Free radicals develop in a polymer Slide 20). system. These react with oxygen yielding a free radical peroxy. This free radical, in turn, reacts with a C-H linkage yielding a peroxide and another free radical. This is the chain reaction which continues until it is halted. Chain termination reactions occur as shown. It is generally agreed that antioxidant-free radicals are not reactive and are, thus, effective chain stoppers. In a more practical vein, let us look at the effect of some compounding ingredients on antiozonant effectiveness (Slide 21 First, antiozonants are used with unsaturated polymers susceptible to ozone attack, i.e. natural rubber, SBR, Slide 21). polybutadiene and nitriles (Slide 22 Some antiozonant is reacted or lost in curing, presumably by direct reaction with Slide 22). certain compound ingredients. The amount so consumed is determined by the specifics of the compound. The reinforcing agent (carbon black) is responsible for some antiozonant loss. The extent of such loss is related directly to the oxygen content of the black. Thus, furnace blacks which are low in oxygen content consume little antiozonant while channel blacks, which are higher in oxygen content, consume appreciably more antiozonant. Sulfenamide accelerators react only sparingly, if at all, with antiozonants (Slide 23 Thiazole accelerators have Slide 23). little effect on antiozonants and guanadines also react only modestly. The ultra accelerators cause significant antiozonant loss during cure (Slide 24 They are not recommended for use with pPDA antiozonants, although 0.1-0.2 Slide 24). parts as a kicker shows little antiozonant loss and can be tolerated. Naturally, antiozonants are not used with peroxide cures (Slide 25 Slide 25). Waxes should be used in ozone susceptible systems if possible. Wax offers much static protection by forming a protective surface barrier that it should be a part of the degradation package. Waxes migrate freely in the rubber stock and help bring fresh antiozonant to the surface of the goods. The pPDA antiozonants are organic bases. Thus, the reduction of acidic components is a plus for antiozonant effectiveness. A high ZnO to stearic acid ratio is good. Acidic softeners, i.e. pine tar, are bad. Also, a highly crosslinked cure will generally require more antiozonant, the antiozonant cannot migrate so readily. Peroxides react preferentially with antiozonants, leaving no antiozonant functionality. Just as the particulars of the compound affect the antiozonant, so the antiozonant affects the compound. The first and obvious effect of the antiozonant is the staining and discoloring it imparts to a rubber stock. Thus, the antiozonant, for all practical purposes is limited to black reinforced stocks. Secondly, the antiozonant affects cure and scorch, but to a varying degree in compounds. Frequently, accelerator reduction is possible when an antiozonant is introduced into a formula. If necessary, retarders may be used to reduce the antiozonant induced scorch. Depending on the effects just mentioned, level of 2-4 parts antiozonant per hundred parts rubber will cover most situations. Two parts

of wax is about the desired level for most applications. Such protection will greatly increase the useful life of the vulcanizates. Finally, safety is always important and it is an ever increasing concern (Slide 26). A few words are in order Slide 26 concerning the toxicity of pPDAs and their safe use. Unsubstituted para phenylenediamine is an extremely toxic substance. Thus, its derivatives have been suspect. To complicate early problems, back around 1951-52, an extremely effective antioxidant, N,N-di-sec-butyl-pphenylenediamine (UOP No. 5) was found to be a powerful antiozonant. At that time, UOP, Du Pont and Eastman sold this material as an antioxidant for gasoline. We knew that this material was a skin irritant. The resulting plant trial was a disaster. Most, if not all, of the tire builders developed skin rash or burns, some requiring hospitalization. It was UOP who offered the first safe effective pPDA antiozonant. This slide shows the acute toxicity as LD50. LD50 stands for

Lethal Dose for 50% of the test animals. This test provides a scale for measuring the relative toxicity of a group of chemicals. It should be remembered that other more elaborate tests are required before statements concerning actual toxicity can be made. The third compound is UOP 788. The rubber industry has used millions of pounds of this compound with no trouble. The third compound from the bottom is IPPD (N-isopropyl-N-phenyl-P-phenylenediamine). This product is an extremely effective antiozonant, but it is not used in the U.S. because of its tendency to cause skin problems and its potentially hazardous nature. Next to the bottom on the slide is UOP 588 (Monsanto-Santoflex 13, Uniroyal-Flexone 7L, Bayer 4020, etc.) It has been proven to be safe and effective. It is the most widely used antiozonant in the world. Finally, at the bottom is

UOP 688, the least toxic of all the commercial antiozonants. We feel that UOP 688 offers the best combination of
properties of any antiozonant on this list. Most applications require the rubber compound to have some kind of stringent resistance property. For example, windshield wiper blades (Slide 27 have very critical requirements. In the past, wiper blades were nearly Slide 27) exclusively natural rubber. Other polymers are being used now, but antiozonants are still important to the application. Wiper blades are thin. This results in high surface-to-volume ratios. They also have sharp edges. These sharp edges crack easily and the high surface-to-volume ratios thus provide little antiozonant where it is needed. These blades must be protected by a very high antiozonant loading. They cannot contain wax since the wax would tend to smear onto the glass. The antiozonant must resist water and windshield solvent leaching. Finally, the staining characteristic of the antiozonant is important since the color can bleed onto the automobile finish and discolor light paints. Wiper blades are

also finished by a chlorine treatment which forms a thin chlorinated rubber layer on the blade. This is done to reduce wiper blade drag and squeaking. Unfortunately, it also changes the blooming characteristics of the antiozonant. UOP 688 is widely used for wiper blades because of its excellent antiozonant properties, its good resistance to water leaching, plus, its low stain.

11/27/96

Antiozonants

Antidegradants

Deterioration by: Oxygen (O2) Ozone (O3 ) Flexing

Combat with: Antioxidants Antiozonants Selected Antiozonants

Slide 1

Antiozonants
Generic p-PHENYLENEDIAMINE

H R1 N

H N R2

Ketone + dinitroaniline

cat

H R1 N

H N R2

pressure

R1 and R can be alkyl or aryl and 2 equal or different

Slide 2

Antiozonants

I. II. III. IV. V. VI. VII. VIII. IX. X.

Background Antidegradants Som e symm etrical di-alkyls Som e diaryls Som e alkyl-aryls How Do AOZs function AOs AOZ interaction with Comp. Ingred. Toxicity Applications
Slide 3

Antiozonants

Historical: Early 50s UOP & Army Arsenal UOP 5 (for gasoline) UOP 88, 288

Slide 4

Antiozonants

Ozone Attack Rapid, at Surface Surface frosting, cracking perpendicular to applied stress

Oxygen Attack Slow, internal SBR, NBR harden NR, softening

Slide 5

Antiozonants
Antiozonant and Antioxidant Differences
Antiozonant N,N-di-substituted Para phenylenediamines Surface Reaction Antioxidant Phenols, Organic Phosphates Diphenylamine-acetone reaction products, et al Reactions both at surface and in the polymer body

Reactions Usually Involve Reacts with Oxygen - Polymer Ozone Reaction Products Scavenger - Surface Film Mechanisms Peroxide Decomposer or Reacts with Free Radicals

Retards Cracking on Prevents Chain Splitting (NR) Stressed Polymer Surface and Crosslinking (SBR) Affects Cure Staining No Effect on Cure Staining or Non-Staining
Slide 6

Antiozonants

Typical Antioxidants I. Substituted Phenols II. Diphenylamine-Acetone Reaction Products III. Tris (Nonylphenyl) Phosphite

Slide 7

Antiozonants
Para-Phenylene Diamines
Dialkyl-Phenylenediamine (UOP 288)

CH C-C-C-C-C-C-C-N

HC N-C-C-C-C-C-C-C

(symmetrical alkyl static)

Alkyl-Aryl-Phenylenediamine (UOP 688)

H N

HC N-C-C-C-C-C-C-C

(unsymmetrical, alkyl-aryl dynamic)

Diaryl-Phenylenediamine (Wingstay 100 Type)

H N

H N R

(symmetrical diaryl antiflex crack, also AO)

Slide 8

Antiozonant UOP 88
N, N-BIS-(1-ETHYL-3-METHYL PENTYL) p-PHENYLENEDIAMINE
CH2CH3 CH 3CH 2CHCH 2CH CH 3 NH

NH CH 3CHCH 2CH 2CH CH 3 CH2CH3

Competition Antiozite 2 Flexzone 8L Application Static, Stains Bright Red Scorchiness: 88<788<288 Water leaching
Slide 9

Vanderbilt Uniroyal

Antiozonant UOP 288

N, N-BIS-(1-METHYL HEPTYL) p-PHENYLENEDIAMINE
C H3 C H(C H 2) 5C H 3 NH

NH C H(C H 2) 5C H 3 C H3

Competition Antiozite 1 Vanderbilt

Application Primarily Static, Stains Brown Scorchiness: 88<788<288 Water leaching

Slide 10

Antiozonant UOP 788

N,NBIS-(1,4-DIMETHYL PENTYL) p-PHENYLENEDIAMINE
CH3 CHCH2CH2CHCH3 NH CH3

NH CHCH2CH2CHCH3 CH3 CH3

Competition Vulkanox 4030 Santoflex 77 Flexzone 4L Applications Primarily static, stains color intensity between UOP 88 and UOP 288 Scorchiness: 88<788<288 Water Leaching
Slide 11

Mobay Flexsys Uniroyal

Antiozonants

Commercially Available Diaryl Antiozonants

Diaryl-Phenylenediamine

H N
(symmetrical diaryl

H N

R
antiflex crack, also AO)

Wingstay 100

Goodyear

Aniline-Hydroquinone-o-toluidine Reaction Product

Winstay 200

Goodyear

Xylidines-Hydroquinone-o-toluidine Reaction Product

Slide 12

Antiozonants
Commercially Available Antiozonants

NO UOP
N-Isopropyl-N-Phenyl p-Phenylenediamine

NH

NH CH3CHCH3 Competition Flexzone 3C Santoflex IP Vulkanox 4010 NA Uniroyal Monsanto Mobay

Application This is IPPD. Staining. Very volatile. Highly Toxic, Most Water Leach, Most Active, Tires for non-USA
Slide 13

Antiozonant UOP 588

N-1,3-DIMETHYL BUTYL-N-PHENYL p-PHENYLENEDIAMINE

NH

NH CH 3 CHCH 2CHCH 3 CH 3

Competition Antiozite 67 Flexzone 7-L Santoflex 13 Wingstay 300 Vulcanox 4020 Vanderbilt Uniroyal Flexsys Goodyear Mobay

Application Dynamic, stain brown, semi-solid, less scorchy than symmetricals, for liquid store at 48C+, type use in tires
Slide 14

Antiozonant UOP 688

N,1-METHYL HEPTYL,N-PHENYL p-PHENYLENEDIAMINE

NH

NH C H (C H 2) 5 C H 3 C H3

Competition None Application Least toxic, low scorchiness, least staining, least water leaching, liquid at room temperature
Slide 15

Antiozonants

Alkyl-Aryl Notes
UOP 688
First offered by UOP as replacement for IPPD. Low toxicity and does not irritate skin. Antidegradant properties slightly lower than IPPD. Little migration stain. Good water leachable properties.

UOP 588
Antidegradant properties slightly lower than IPPD. Biggest drawback is physcial state -- sometimes liquid, sometimes solid at room temperature.

Slide 16

Antiozonants

Blends
To take advantage of the high static antiozonant activity of UOP 88, 288 and 788,and high dynamic activity of UOP 588 and 688.

Flexone 3-C
An alkyl-aryl PPDA. Excellent antiozonant, antioxidant and anti-flexcracking properties. Alkyl portion is n-propyl, IPPD is i-propyl. Has high migration stain. Not generally recommended today because of high toxicity and poor water leachable properties.

Slide 17

Antiozonants

How Does an Antiozonant Work? I. Scavenger II. Protective Film III. Reaction with Double Bonds IV. Reaction with Ozonized Rubber

Slide 18

Antiozonants

Reactions with Ozone

H C8H17 N H NO O O C8H17 N Adduct (I) Adduct (IV) N-Hydroxylamine (III)
-

Amine Oxide (II)

N-Hydroxylamine Oxide (V)

Nitrosoaryl (VI) (MW234)

Nitroaryl (VII) (MW250)

Slide 19

Antiozonants

How Does an Antioxidant Work?

RRH + Initiator R + O2 ROO + RH R + R R + ROO ROO + ROO ROO

Free Radical ROO ROOH + R

Inert Products Inert Products Inert Products Inert Products Inert Products

+ AH

R + AH

Slide 20

Antiozonants

Compound Ingredients I. Polymer II. Reinforcing Agent-Carbon Blacks III. Accelerator IV. Peroxides V. Wax VI. Acidic-Basic Components
Slide 21

Antiozonants

Compound
Polymer Use with highly unsaturated polymers, SBR, NBR, NR, etc. EPDM and EPR do not need. Some AOZ lost to double bonds during curing.

Carbon Black Channel blacks are high in oxygen, consume AOZ. Thus, furnace blacks preferred.

Non-Black Fillers AOZ can be used with some but, not if non-black compound is the target.
Slide 22

Antiozonants
Compound
Selected Accelerators

N C-SH S
Thiazole Accelerators

N C-S-S-C S

Thiazole Accelerators

S C-S-N N

CH2 CH2 CH2 CH2 O

Sulfenamide Accelerators

Slide 23

Antiozonants
Compounds
Selected Accelerators

C2H5

C2H5 NCSSCN C2H5 S S C2H5

- - - - Thiuram Ultra Accelerators

CH3 CH3

N C S Cu S C N S CH3 S
Dithiocarbamate Ultra Accelerators

- - -

- - -

CH3

Not recommended at greater than 0.2 pphr as kicker. Ultras result in significant AOZ loss.

Slide 24

Antiozonants

Compound
Peroxides Do not use AOZ.

Wax Used with p-phenylene diamines. Waxes are migrators, carry AOZ to the surface.

Acidic-Basic Components pPDA antiozonants are organic bases. Minimize acidity. Use high ratio of ZnO to stearic acid.

Slide25

Antiozonants
LD50 of PPDA ANTIOZONANTS

R1

H N

H N-R

Antiozonant R1 R2 C 2 -CC 3 -CC 6 -CC 7 -CC 8 -CC 2 -CC 5 -CC 7 -C-C-C 2 -C-C 3 -C-C 6 -C-C 7 -C-C 8

LD 50 MG/KG

200 500 (UOP 5) 1600 (UOP 788) 2500 4000 500 (IPPD) 2000 (UOP 588) 3500 (UOP 688)

Slide 26

Antiozonants

Applications

Windshield Wiper Blades Tires Many others: Seals, Gaskets Hosecover, Elastic Thread

Slide 27

L O C A T I O N S

For Customer Service and general inquiries, please call 1-877-427-4255 or go to www.hallstar.com. International customers, please call +1-312-385-4494. Corporate and Executive Offices Address: 120 South Riverside Plaza Suite 1620 Chicago, IL 60606 Chicago Manufacturing and Technical Center Address: 5851 West 73rd Street Chicago, IL 60638 Stow Order Fulfillment Center Address: 4460 Hudson Drive Stow, OH 44224 Memphis Manufacturing and Order Fulfillment Center Address: 2500 Channel Avenue Memphis, TN 38113 Hackettstown Customer Service & Sales Office Address: 1500 Rte 517 Suite 305 Hackettstown, NJ 07840 Anderson Warehouse Address: 407 River Heights Circle Anderson, SC 29621 The information presented herein is believed to be accurate and reliable, but no warranty or guaranty, expressed or implied, is made regarding the information or the performance of any product. Further, nothing contained herein shall be taken as any inducement or recommendation to use, manufacture or sell that may infringe any patents or any other proprietary rights now or hereafter in existence.