ANTIOXIDANTS

ANTIOXIDANTS

ANTIOXIDANTS

Degradation caused primarily by

Heat Oxygen What happens?
Oxygen combines with polymer under high temperature to form carbonyl compounds which leads to yellow & brown discoloration

ANTIOXIDANTS
Oxidation occurs in the polymer during # Manufacturing # Storage # Processing # End use Plastics are sensitive to oxidation

Stability against oxidation arise from # Chemical structure of polymers # Difference in the manufacturing process # Morphology (crystalline, orientation) # Commercial; polymer contains catalyst residue and functional groups which sensitize oxidation

ANTIOXIDANTS

ANTIOXIDANTS

ANTIOXIDANTS

Primary Stabilisers- Antioxidants Secondary stabilizers Peroxide decomposers

Chelating Agents- Metal deactivators

Special Stabilizers- Heat Stabilisers for halogenated polymers

ANTIOXIDANTS
C----H (Primary) 95kcal/mol C----H (Secondary) 90kcal/mol C----H (Tertiary) 85kcal/mol C----H (Allylic) 77kcal/mol O----H 110kcal/mol C==O 150kcal/mol Polymers with no C---H bonds PTFE Oxidation resistant Additives that interfere with oxidation Antioxidants Additives that interfere with small molecule elimination Stabilizers

ANTIOXIDANTS

Barrier to Polymer Degradation Activation Energy Low processing temperatures Low productivity Activation Entropy Availability of weak points Polymer design Competing Reactions Interference with degrading process Antioxidants

ANTIOXIDANTS Antioxidants are chemical entities, which retard oxidation and thus retard the resulting aging of the polymer. Usually, they are effective at concentration of a fraction of one percent. It is desirable to add the antioxidant as early as possible in the life cycle of a polymer. It is possible to use more than one antioxidant and this may give synergistic effect more than 200%. Antioxidant are of two types based on the function and mechanism: 1. Primary antioxidant (chain termination) Radical Scavengers 2. Secondary antioxidant (hydroperoxide decomposing)

ANTIOXIDANTS

ANTIOXIDANTS
Mechanism of Oxidation Initiation -----C----C--- -----C + ------C Main/side chain cleavage Shear ------C----H -----C Thermal instability, Oxygen attack Propagation -----C + O2 -----COO -----COO + ------C----H -----COOH + -----C -----COOH -----CO + OH -----CO + ------C----H -----COH + -----C OH + ------C----H H2O + -----C

ANTIOXIDANTS

Metal Poison -----COOH + Mn -----COO + H+ +Mn-1 -----COOH + Mn-1 -----CO +OH- +Mn ------------------------------------------------------------------2 -----COOH -----CO + -----COO + H2O ( Mn - Fe, Cu, Ni, Mn, Co, V, Ti) Catalyst Residues, Impurities in Fillers,TiO2(PVC)

ANTIOXIDANTS
-----C + ------C -----C----C---

Crosslink Formation under anaerobic condition Adverse effect on Processing, Service Polyethylene Fragmentation
-----C----C---C------ -----C=C--- + -----C----Rapid lowering of Molecular Weight Polypropylene, PMMA Cross linking followed by fragmentation R----CO R + C=O Decomposed products contains chromophores cause discoloration Water causes Hydrolytic degradation

ANTIOXIDANTS
Primary Antioxidants Interference with Propagation
-----C +A/O [-----CA/O ] Complex ------COO + A/O [-----COOA/O ] Decompose to regenerate A/O and slower polymer radical Abstract Hydrogen from H2O,OH,Polymer [-----CA/O ] ------C----H +A/O Radicals are electron deficient Hindered Phenolic Antioxidants CH3---A/O---OH + R RH +CH3----A/O---O. CH2----A/O----OH Dimerization 2 CH2----A/O----OH OH---A/O----CH2CH2----A/O----OH O=A/O=CH---CH=A/O=O Blocking of para position Not for polymers generating strong acids PVC Combination of a/o monophenols & bisphenols not recommended

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ANTIOXIDANTS

ANTIOXIDANTS
Secondary Antioxidants

Phosphite Esters : ---COOH + (R---O---)3P: ----C---OH + (R---O---)3P=O Alcohol more stable Divalent sulfur compounds ---C---OOH + (--COCH2CH2)2S ----C---OH + (--COCH2CH2)2S=O ---C=C---C=O + (R---O---)3P: ----C---C---C----OR (R---O---)3P=O ---C=C---C=O + S ----S----C---C---C=O Preserves color & process safety Regenerate primary a/o [-----COOA/O ] + (R---O---)3P: A/O +(R---O---)3P=O +---CO [-----COOA/O ] + ---S--- A/O + ---S=O +---CO Hydrolysis (R---O---)3P: + H2O (RO)2POH +ROH (R---O---)2P---OH (RO)2PH=O Good reducing agents

ANTIOXIDANTS
Amine Antioxidants
-----C + O2 + A/O [--C A/OO2] ArNH---Ar---NH---Ar Ar---N=Ar=N---Ar +2COOH Ar---NO---Ar---NO---Ar + 2---COH Highly colored & Staining Phenolic + Aminic A/O Reduced effectiveness & Highly colored compounds Mercaptobenzimidazoles synergism with Aminic & Bisphenolic A/O

ANTIOXIDANTS
Metal Deactivators By chelation of metal EDTA, ArCH=NNHCOCONHN=CHAr Hydrazide ArCH2CH2CONHNHCOCH2CH2Ar Hydrazine ArCH2CH2COOCH2CH2NHCOCONHR Oxamide Metal completely surrounded by ligands antioxidant-metal deactivator 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine

ANTIOXIDANTS
By capturing chloride & replacing the ligand by electron donating Alkaline earth stearates Complexes the metal Chloride scavenging by hydrtalcite synthetic clay platy magnesiumaluminium hydroxide structure

ANTIOXIDANTS

ANTIOXIDANTS

STABILIZERS
FOR HALOGENATED POLYMERS Scavenge HCl Arrest autocatalytic chain reactions Prevent free radical processes eg, Oxidation, X-linking, Scission Displace labile groups with stable substituents Terminating development of unsaturation Break conjugation thus discoloration Provide antioxidant protection

STABILIZERS
Basic Lead Carbonate: Pb(OCOOPbOH)2 Dibasic Lead Phosphite: PbOOP(OPbPOH)2H Stable . 300 c Color stability Dibasic Lead Searate: Lubricant Stabilizer Combination with Ba Stearate more effective Forms complexes with allylic chloride Scavenge HCl Terminate developing conjugated unsaturation Provide a/o protection Phosphite,Pb(+2) to Pb(+4)

STABILIZERS

STABILIZERS

STABILIZERS

STABILIZERS
Organo Metallic Stabilizers R2SnX2 : Solubility Parameter close to PVC. Increasing chain length decreases volatility. Laurates, Maleates Maximum clarity, Low odor R2Sn(SCH2COOC8H17)2 ; Mercaptides Better nucleophile & a/o SSn2(CH3)2(SCH2CH2OOCC17H33)4: Thiobis[monomethyltin bismercaptoethyloleate Antimony analogs

STABILIZERS

STABILIZERS

STABILIZERS

STABILIZERS
Mixed Metal Stabilizers Pairs of compatible salts Primary Stabilizer: Zn,Cd Stearates Displace labile chloride Secondary Stabilizer: Ba,Ca Stearates Provides ligand in exchange Synergism with Organic Phosphites.Improved color retention

STABILIZERS
HCl Scavengers Epoxidised Soyabean oil :Costabilizer with Metal Chloride.Oxirane rings functions as scavenger catalyzed by metal Limited solubility Exudation Hydrous Zeolites :More efficient. EOS not necessary. Affects clarity Hydrtalcite: More efficient. EOS not necessary. Affects clarity

STABILIZERS