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EBB 427 Application and Technology of Engineering Polymers (Second Half) THERMOSETTING POLYMERS: Preparation, Properties, Processing, Application

and Future Direction


Dr. Hazizan Md Akil School of Materials and Mineral Resources Engineering Engineering Campus, USM.

Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester Involve the reaction between the unsaturated sites in polymer chain and vinyl-type monomer As carried commercially, cross-linking of unsaturated polyester is invariably a free radical reaction Two types of initiating systems are commonly employed for this reaction, namely those effective at elevated temperature and those effective at room temperature. The most important initiators used at elevated temperatures are peroxides, which liberate free radicals as a result of thermal decomposition.

Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester A peroxide which is widely used in this way is benzoyl peroxide. Other peroxides include 2,4-chlorobenzoyl peroxide, ditert-butyl peroxide and lauroyl peroxide Mixtures of polyester resin and this type of peroxide are comparatively stable at room temperature but rapidly cross-link at temperature ranging from about 70 150C. Such peroxides are used principally in processes employing moulding compositions, when short curing times are required

Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester Initiating systems which are effective at room temperature normally consist of mixtures of a peroxy compound and an activator (accelerator) In the presence of accelerator, the peroxy compound rapidly decomposes without the application of heat into free radicals The two most important peroxy materials now used for the cold curing of polyester resin are methyl ethyl ketone peroxide (MEKP) and cyclohexane peroxide. In reality, MEKP and cyclohexane peroroxides are hydroperoxides

Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester The most common accelerators for MEKP and cyclohexane peroxide are salts of metals which exhibit more than one valency. The most widely used metal of this kind is cobalt, although salts of cerium, iron, manganase, tin, vanadium also find some application. In order to be effective as an accelerator a metal salt must be soluble in the polyester resin The most commonly used salts are naphthenates, which are readily soluble, octoate may also be used

Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester The decomposition of a hydroperoxide (ROOH) by a metal salt such as cobalt napthenate to give free radicals proceeds according to the following:

Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester The cycle is repeated until all hydroperoxide has been decomposed. Cobalt napthenate-methyl-ethyl-ketone peroxide or cyclohexane peroxide systems are very extensively used in the production of large glass-fibre laminates by hand lay-up and cured at room temperature. It may be noted that the foregoing metal-based accelerators, which are highly reactive towards hydroperoxides, have little influence on the decomposition of peroxide especially those used for curing polyester at elevated temperature

Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester However, peroxide do decompose rapidly at room temperature into free radicals in the presence of tertiary amines. Amines such as dimethylaniline, diethylaniline, and dimethyl-p-toluidine react violently with benzoyl peroxide or tertiary amine. Polyester resin cured with benzoyl peroxide-tertiary amine tend to discolour and craze on ageing

Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester The reaction between benzoyl peroxide and tertiary amine is thought to proceed via a one-electron transfer from nitrogen, as shown in the following example involving dimethylaniline:

Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester The cross-linking of an unsaturated polyester by means of a vinyl monomer such as styrene may be represented as:

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Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester The average value of n in the structure may be deduced from both spectroscopic and degradation studies. Both the spectroscopic and degradation studies indicate that in a typical cured general purpose polyester resin the cross-links contain 1-3 styrene units. Determination of the molecular weight of the polymer enables estimation of the average of chains linked together by a continuous cross-link

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Unsaturated Polyesters resin


Cross-linking of linear unsaturated polyester Typically such copolymers have Mn ~2500 which indicates that each continuous styrene-fumarate copolymer chains passes through 6-10 cross-link sites in the un-degraded cured polyester. It will be noted that the cross-linking of linear unsaturated polyester by vinyl monomers does not involve the elimination of any volatile by-products. Hence, it is possible to cure the resin without the application of pressure. It is also possible to cure the resins without the application of heat, they are very useful in the manufacture of large structure such as boat hulls
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Unsaturated Polyesters resin


Properties of cross-linked polymers Cross-linked unsaturated polyesters are rigid, infusible and insoluble. There are so many varieties of polyester resins now commercially available that it is difficult to give typical values for physical properties of cured materials. Furthermore, polyester resin are mostly used in conjunction with glass fibre and the physical properties of the final product greatly depend on the type and quantity of glass fibre incorporated. Cross-linked polyesters have good heat stability, showing little weight loss up to about 200C.

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Unsaturated Polyesters resin


Properties of cross-linked polymers The mechanical strength of general purpose materials begins to decline at about 100C and the maximum service temperature of glass-fibre laminates and mouldings is about 150C; for heat resistance grades of resins these temperature are of the order of 160C and 200C. The electrical insulating properties of cured polyester are satisfactory for many purposes but the polar nature of the ester group results in a relatively high power factor and dielectric constant and so the use of the resins in high frequency applications is limited.

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Unsaturated Polyesters resin


Properties of cross-linked polymers Cross-linked polyesters are resistant to a wide range of organic solvents but they are attacked by chlorinated hydrocarbons (e.g. chloroform, ethylene dichloride and trichloroethylene), esters (e.g. ethyl acetate) and ketones (e.g. acetone and MEK). The ester groups in the polymer provide sites for hydrolytic attack and strong alkalis cause appreciable degradation. The polymer is, however, resistant to most inorganic and organic acids, with exception of strong oxodising acids.

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