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

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

Polyester resin
The most important esters are those derived from carboxylic acids Polyesters are defined as polymers containing recurring CO-O- groups in the main chain A large number of polyesters is commercially available:
Unsaturated polyesters Poly(allyl ester)s PET etc

Unsaturated Polyesters resin


Linear polyester containing aliphatic unsaturation which provides sites for subsequent cross-linking First became available in USA, 1946 Prepared from diethylene glycol and maleic anhydride and could be cross-linked by reaction of styrene The polymers was of interest for the preparation of glassfibre laminate by technique which did not involve high pressure The commercial production of GFR polyester established 1949 mainly for large structures such as boat hulls, sports car bodies and roofing.
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Unsaturated Polyesters resin


1950, Bulk Moulding Compounds were developed 1960, Sheet Moulding Compounds were developed. During the past few years the use of polyester moulding compositions has grown significantly, particularly in the transportation field

Unsaturated Polyesters resin


Linear unsaturated polyesters are prepared commercially by the reaction of a saturated diol with a mixture of an unsaturated dibasic acid and a modifying dibasic acid (or corresponding anhydrides). In principle, unsaturation desired in a polyester can be derived from either an unsaturated diol or an unsaturated acid For economic reason, unsaturated acid is invariably preferred

Unsaturated Polyesters resin


Unsaturated acid provides sites for subsequent crosslinking The function of the modifying acid is to reduce the number of reactive unsaturated sites along the polymer and hence to reduce the cross-linking intensity and brittleness of the final product. Some acids and anhydrides which are used to modify polyesters are, in fact, unsaturated but the double bonds are not sufficiently reactive to represent sites for subsequent cross-linking

Unsaturated Polyesters resin


Diols Propylene glycol Is the diol most widely used for manufacture of linear unsaturated polyesters It is prepared by the hydration of propylene oxide Commonly, the reaction is carried out without catalyst at about 200C and 2 MPa Propylene glycol is isolated by distillation under reduced pressure.

Unsaturated Polyesters resin

Preparation of propylene glycol

Unsaturated Polyesters resin

Propylene glycol is the preferred diol because it forms polyester which are compatible with styrene and which show little tendency to crystallise and readily available at low cost.

Unsaturated Polyesters resin

Other diols Diols other than propylene glycol are utilised to a lesser extent Typical examples of other diols are: Diethylene glycol Neopentylene glycol Ethylene glycol

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Unsaturated Polyesters resin

Unsaturated acids and anhydrides Typical examples are: Maleic anhydride Phthalic anhydride

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Unsaturated Polyesters resin

Maleic anhydride Most important unsaturated component used in manufacture of linear unsaturated polyesters Mostly obtained by the oxidation of benzene

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Unsaturated Polyesters resin

Maleic anhydride The reaction is carried out in the vapour phase by passing a mixture of benzene and excess of air over a vanadium pentoxide catalyst at 350C - 450C The effluent is cooled and most of the maleic anhydride is condensed The non-condensed material passes to a scrubber where the remaining anhydride is hydrolysed to maleic acid

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Unsaturated Polyesters resin

The maleic anhydride solution is then passes to evaporators for concentration and dehydration High purity anhydride is ontained by distillation under reduced pressure Because of rise in price of benzene, increasing amounts of maleic anhydride are being obtained from cheaper nbutane

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Unsaturated Polyesters resin

Reaction:

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Unsaturated Polyesters resin

Maleic anhydride is a white crystalline solid, m.p. 52C53C Maleic anhydride is preferred to maleic acid since it is more reactive and give rise to less water on esterifation

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Unsaturated Polyesters resin

Other acids (Fumaric acid)


Trans-isomer of maleic acid is sometimes preferred to maleic anhydride as it is less corrosive and gives lightercoloured Chloromaleic acid and chlorofumaric acid may be used in the production of self-extinguishing resins

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Unsaturated Polyesters resin

Modifying acids and anhydrides


Phthalatic anhydride The most important modifying component used in manufacture of linear unsaturated polyester The anhydride is generally obtained by the oxidation of oxylene

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Unsaturated Polyesters resin

Modifying acids and anhydrides


Production of Phthalatic anhydride

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Unsaturated Polyesters resin

Modifying acids and anhydrides


Production of Phthalatic anhydride The reaction is carried out in the vapour phase by passing a mixture of o-xylene and air over a catalyst such as vanadium pentoxide supported on silica and promoted with titanium dioxide at about 400C The exit gas is cooled and the phthalic anhidride is collected and purified by distillation under reduced pressure

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Unsaturated Polyesters resin

Modifying acids and anhydrides


Production of Phthalatic anhydride Older processes based on the air-oxidation of naphthalene (obtained from coal) are now of minor importance Phthalic anhydride is a white crystalline solid mp. 131C Phthalic anhidride gives polyester which are compatible with styrene and the crosslinked products are hard and rigid.

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Unsaturated Polyesters resin

Other acids and anhydrides


Modifying components other than phthalic anhydride are frequently used in the preparation of unsaturated polyesters in order to impart special properties to the final product Adipic and sebacic acids are employed to give flexible materials and isophthalic acid is used for tough products with higher heat distortion temperatures

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Unsaturated Polyesters resin

Other acids and anhydrides


The use of endo-methylenetetrahydrophthalic anhydride, the dies-Alder reaction product of cyclopentadiene and maleic anhydride leads to a substantial improvement in heat resistance Flame resistance materials are obtained by the use of chlorinated acids and anhydrides, e.g. tetrachlorophthalic anhydride and chlorendic acid

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Unsaturated Polyesters resin Cross-linking monomers


It is possible to cross-link unsaturated linear polyester chains directly one to another, however, reaction is slow and low degree of cross-linking is achieved. These limitations are overcome by the introduction of a material which forms bridges between the chains. The materials most commonly used to cross-link unsaturated linear polyesters in this way are vinyl monomers

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Unsaturated Polyesters resin

Cross-linking monomers
The addition of a liquid vinyl monomer to the polymer also leads to a reduction in viscosity and this facilitates the impregnation of glass-fibre in the preparation of laminates. Styrene is the most widely used cross-linking monomer, being preferred because of its compatibility, low viscosity, ease of use and low price.

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Unsaturated Polyesters resin Cross-linking monomers


Other materials are sometimes employed when special properties are required. For example, methyl methacrylate is used, often in conjunction with styrene, for the preparation of translucent sheeting. Diallyl phthalate and triallyl cyanurate (solid) is used for heat resistance products. Partially polymerized diallyl phthalate (solid) is used as the cross-linking agent in moulding powders (the socalled alkyd polyester moulding powders) based on linear unsaturated polyester

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Unsaturated Polyesters resin Preparation of linear unsaturated polyester


Linear unsaturated polyesters are prepared batch-wise by heating a mixture of the appropriate acidic and hydroxy components in a reactor jacketed for heating and cooling and fitted for distillation. A typical formulation for general-purpose material might be as follows:

Propylene glycol
Maleic anhydride Phthalic anhydride

100 parts by weight


72 parts by weight 54 parts by weight

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Unsaturated Polyesters resin Preparation of linear unsaturated polyester


The molar ration of the ingredients shown above is 1.2:0.67:0.33 The excess of glycol is to allow for loss during the reaction and to restrict the molecular weight of the polymer. The mixture is heated at 150C-200C for 6-16 hours and water is continuously distilled from the reactor. Sometimes xylene is added to the reaction mixture to assist in the removal of water by azeotropic distillation and sometimes catalyst such as p-toulenesulphonic acid is added to reduce the reaction time.

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Unsaturated Polyesters resin Preparation of linear unsaturated polyester


In order to prevent discolouration, the reaction is carried out in an inert atmosphere of either carbon dioxide or nitrogen. Heating is continued until the average molecular weight of the polyester reaches about 1000-2000. The polymer is then cooled to about 90C and pumped into a blending tank containing vinyl monomer to which has been added an inhibitor such as hydroquinone. In a general purpose material, the weight of styrene used is about half that of the polymer

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Unsaturated Polyesters resin Preparation of linear unsaturated polyester


The blend (which is commonly referred to as polyester resin) is then allowed to cool to room temperature. The reaction between hydroxy-compound and anhydride proceeds in two distinct steps. In the first step, esterification of the anhydride occurs to form a free acid group which is then esterified in the second step. Typical reaction;

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Unsaturated Polyesters resin Preparation of linear unsaturated polyester

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Unsaturated Polyesters resin Preparation of linear unsaturated polyester


The first step proceeds more rapidly than the second since the anhydride group is more reactive than the free acid group. Clearly, a diol and an anhydride may interact through a sequence of reactions of the foregoing type to yield a linear polyester. Thus a segment of the polyester obtained from propylene glycol, maleic anhydride and phthalic anhydride might have the following structure:

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Unsaturated Polyesters resin Preparation of linear unsaturated polyester

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Unsaturated Polyesters resin Preparation of linear unsaturated polyester


Appreciable cis-trans isomerization generally occurs during the polyesterification of unsaturated dibasic acids and anhydrides. Such isomerization is particularly marked with maleic anhydride, which becomes incorporated into the polymer chains mostly from fumarate groups. The extent of isomerization is governed by several factors including the structure of diol, the reaction conditions, the catalyst used (if any) and the molecular weight of the polymer

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Unsaturated Polyesters resin Preparation of linear unsaturated polyester


The polymerzation of maleic anhydride with propylene glycol gives almost entirely poly(propylene fumarate) but in most other cases the final polymer contains 70-90% fumarate groups and 10-30% maleic groups. It is fortunate that maleated-fumarate isomerization does occur because the fumarate group shows much greater reactivity towards vinyl monomers than the maleated group; hence subsequent cross-linking proceeds more readily.

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Unsaturated Polyesters resin Cross-linking of linear unsaturated polyester

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