Formulation and raw material selection

Safe preparation of polyester resins from polyfunctional monomers (Fn > 2) without gelation requires careful optimization of average functionality and calculation of the degree of polymerization at the gel point (Pgel). Wallace Carother and P. J. Flory have made significant contributions in this area; however, a detailed discussion is outside the scope of this book.

A wide range of raw material is available to design polyesters with a broad spectrum of properties. In addition to the polyols listed in the section on alkyd resins (Section 2.3), other specialty diols are also used in polyester synthesis. Some important polyols are listed in Table 2.4.

Various polybasic acids are used in polyester synthesis, including aro­matic acids as well as aliphatic acids. Some important acids used in poly­ester synthesis and their primary characteristics are shown in Table 2.5.

In addition to polybasic acids, some monobasic acids including lower MW synthetic branched fatty acids and monobasic aromatic acids are also used for controlling functionality and MW of polyesters.

Table 2.4: Important polyols for polyesters

Polyol

Fn

Remarks

Neopentyl glycol

2

Hardness, heat resistance, impact resistance, chemical resistance

TMPD

2

Good heat resistance, solubility, compatibility, low viscosity

1,6-hexanediol

2

Flexibility, impact resistance

CHDM

2

Reactivity, thermal stability, good balance between hardness and flexibility

BEPD

2

Low viscosity, better solubility and compatibility, exterior durability, hydrolysis resistance, corrosion resistance, hydrophobicity

HBPA

2

Excellent solvent and chemical resistance, durability, high expense

TMP and TME

3

Branching, hardness, reactivity, durability

Pentaerythritol

4

Branching, too much functionality to handle, hardness, durability

Fn = number average functionality; TMPD = 2,2,4-trimethyi-1,3-pentanedioi; CHDM = cyclohexane dimethanoi; BEPD = 2-butyi-2-ethyi-1,3-propanedioi; HBPA = hydrogenated bisphenoi A; TMP = trimethyioi propane; TME = trimethyioi ethane

Подпись: Table 2.5: Important polybasic acids for polyesters Polybasic acid Remarks Phthalic anhydride Cost-effective, hardness, poor in exterior durability Isophthalic acid Good mechanical properties, chemical resistance Terephthalic acid Improved heat resistance, good mechanical properties, strong crystallizing tendency of polymer, hence solubility problem TMA Trifunctionality, useful for water-reducible polyesters and acid-functional polyesters for powder coatings CHDA Excellent flexibility - hardness balance, better corrosion resistance than linear diacids, good thermal resistance, excellent durability HHPA, THPA Better hydrolysis resistance, yellowing resistance (HHPA) Linear diacids* Flexibility, durability Succinic acid Sustainability CHDA = cyclohexane dicarboxylic acid, HHPA = hexahydrophthalic anhydride; THPA = tetrahydrophthalic anhydride; TMA = trimellitic anhydride * Adipic acid, azelaic acid, sebacic acid and related acids

Some examples of such monobasic acids are benzoic acid, p-tert — butylbenzoic acid, hexahydrobenzoic acid, 2-ethylhexanoic acid and isononanoic acid.

Подпись:Another interesting material often used in polyester resins is the glycidyl ester of versatic acid (Figure 2.14), a synthetic satura­ted monocarboxylic acid of highly branched C10 isomers. The highly branched alkyl group provides excellent wetting, exterior dura­bility, hydrophobicity, flexibility and impact resistance, and acid etch resistance, and low viscosity.

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