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Viscosity Index Improvers and Thickeners

The engine lubricants are the largest commercial application of VI improvers However they are also widely used in other lubricant formulations such as: Automatic transmission fluids, multipurpose tractor transmission fluids, power steering fluids, shock absorber fluids, hydraulic fluids, manual transmission fluids, rear axle lubricants, industrial gear oils, turbine engine oils and aircraft piston engine oils.

Poly Methacrylates (PMAs) Poly(ethylene propylene) Olefin Copolymers (OCPs) Hydrogenated Poly(styrene-co-butadiene) or (isoprene) Esterified Poly(styrene-co-maleic anhydride) Combination of PMA/OCP

Poly methacrylates
Poly methacrylate-based VI improvers used in engine oil are usually copolymers of three methacrylic acid esters: Short chain alkyl methacrylates Intermediate chain alkyl methacrylates long- chain alkyl methacrylates

Methyl and butyl (n-butyl, isobutyl or mixtures of the two) methacrylates Derived from 2-ethylhexyl alcohol, isodecyl alcohol and alcohol mixtures which may be C8C10, C12C14 or C12C15 long-chain alkyl esters are based on either C16C18 or C16C20 mixtures

Polymethacrylate VI improvers are free-radical initiated solution copolymers The process solvent is usually mineral oil in a viscosity/volatility range compatible with the use of the end product The primary criteria for a solvent Selection Relative freedom from significant chain transfer activity Boiling point compromise between the reaction temperature Ease of solvent transfer at the end of the reaction

The products produced are random copolymers Since reactivity ratios of all of the alkyl methacrylate monomers are almost the same No special steps are required for specific monomer distribution

Applications
Free-radical solution polymerization can produce a broad range of molecular weights and compositions Poly methacrylates are used in almost all lubricant areas where viscosity/temperature modification is required including both mineral oil-based applications and synthetic fluids

Olefin Copolymers
Olefin copolymer-based VI improvers are primarily derived from ethylene and propylene Ethylene contents of OCP VI improvers are normally in the 4060 wt% The ethylene/propylene ratio for VI improvers is a compromise between thickening efficiency and low-temperature solubility. The best thickening effect is achieved at high ethylene content, but too much ethylene leads to polymer crystallinity and insolubility at low temperatures

Objective of optimizing the ethylene/ propylene ratio is to minimize propylene content to achieve the best possible oxidative stability Another concern is the sequence distribution of ethylene and propylene units in the polymer Microcrystalline regions resulting from ethylene units can also interact with wax at low temperatures, resulting in undesirable low-temperature properties

Olefin copolymer VI improvers are produced by solution polymerization of ethylene and propylene catalyzed by soluble ZieglerNatta catalysts The most commonly used catalyst is an aluminium alkyl halide with a soluble vanadium compound Polymerization is carried out in relatively dilute hexane solution at low temperature Excess ethylene and propylene are removed and the solutions are washed with water to coagulate the polymer

Applications
The excellent thickening ability of OCPs has led to their extensive use in engine oils However, the relatively poor low temperature viscosity behaviour of OCPs and difficulty of achieving the lower molecular weights have hindered significant use in most other speciality lubricants

Hydrogenated Styrene Diene Copolymers


Styrenediene copolymers are produced by anionic solution polymerization, typically using s-butyl lithium in Cyclohexane at 60 120C Small amounts of an amine such as N,N,N,N Tetramethylethylene diamine or an ether, such as tetrahydrofuran may act as promoter in polymerization reactions

These compounds may be either random, block polymers or star shaped molecules For random polymers, all of the monomers may be charged together in the solution For blocks, one of the monomers is polymerized, and then the second is added to the living polymer to make an AB block

In case of stars, the arms are polymerized first and then divinyl benzene is added to the living polymer arms to form the basic structure. The living polymer is then terminated by addition of an alcohol or by the subsequent hydrogenation The polymers are hydrogenated in solution using a homogeneous catalyst such as Trialkyl aluminium and an Organo-nickel compound, such as nickel Octanoate or Acetylacetonate. Finally, the polymers are washed with water to remove the salts and to coagulate the polymer

Applications
Hydrogenated styrenediene and star-shaped diene VI improvers have found their widest utility in gasoline and diesel engine oils They are also used in other applications which have moderate requirements for shear stability, such as tractor transmission fluids and aircraft piston engine oils

Esterified Poly(styrene-co-maleic anhydride)


The copolymer of styrenemaleic anhydride is mixed in mineral oil and Esterified to about 70% with a C818 alcohol mixture, using an acid catalyst at 150160C Esterification is then carried to 95% using nbutanol N-(3-aminopropyl)-morpholine is finally added to react with the remaining acidity

Applications
These products are used almost exclusively in automatic transmission fluids and multipurpose tractor fluids

Concentrate-Compatible PMA/OCP Blends


A conventional methacrylate monomer mixture is polymerized by free-radical initiation in an oil solution of about 1015% of an OCP VI improver at a temperature of 120 140C When methacrylate conversion is complete, additional solid OCP VI improver is added to bring the total OCP content up to the desired level

The final product is then diluted with ester solvent to invert the phases, and sufficient additional mineral oil is added to reach the final product solids These products are only used commercially in gasoline and diesel engine oils