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CELLULOSE ESTERS

Cellulose esters are based on one of the most abundant naturally occurring
biopolymers, namely cellulose. This polysaccharide represents a readily available,
sustainable feedstock alternative to petroleum-based materials. Although a broad variety of
cellulose esters can be made, this chapter only provides a general discussion on the
commercially available organic acid esters of cellulose: cellulose acetate (CA), cellulose
acetate propionate (CAP), and cellulose acetate butyrate (CAB).

Cellulose esters are the reaction product of combining organic acids and/or acid
anhydrides with the hydroxyl groups found on the anhydroglucose repeating units of a
cellulose molecule (Heyne, Whistler, 1948). In addition to esterification, several subsequent
processing steps are required in the manufacture of cellulose esters including hydrolysis to
obtain the desired residual hydroxyl level, filtration, precipitation, washing, dewatering,
drying, and screening. The final product is a dry, free-flowing powder in most instances,
although other physical forms can be produced when required.

Production of cellulose esters

For the production of coating-grade cellulose esters, three organic acids and
anhydrides are used, either separately or in combination with each other. Cellulose acetate
is the simplest cellulose ester since only acetic acid and acetic anhydride are used in the
esterification reaction. If two different organic acids and anhydrides are used
simultaneously, the resultant product is referred to as a mixed ester. Examples of mixed
cellulose esters are cellulose acetate butyrate and cellulose acetate propionate.

In addition to esterification and hydrolysis, several subsequent processing steps are


required in the manufacture of cellulose esters including filtration, precipitation, washing,
dewatering, drying, and screening. The final product is a dry, free-flowing powder in most
instances, although other physical forms can be produced. Unlike cellulose nitrate, organic
esters of cellulose are low in flammability and present no handling hazards.
Types of cellulose esters

Three types of cellulose esters are commercially available, including CA, CAP, and
CAB. Table 1 shows the types of commercially available cellulose esters. Cellulose acetate
butyrate is the most commonly used organic cellulose ester for coating applications.

Many types have been manufactured by varying acetyl/butyryl ratios, hydroxyl


content and molecular weight to meet the requirements of the applications for which they
were developed. Cellulose acetates are the least soluble and least compatible of the
cellulose esters, and they require strong solvents for dissolution. They have high glass
transition temperatures and produce tough and hard films with excellent chemical
resistance. CAPs have improved compatibility and solubility and are used in applications
where low odor is required. CAB esters are used as binders in protective and decorative
coatings for metal, wood, textiles, cloth, paper, plastic, human nail care, printing inks, trucks
and buses, polarographic oxygen electrodes, solid rocket propellants, and leather. They
provide excellent color and color retention, toughness, flexibility, flow control, as well as
good weather resistance. All three products are available with a range of substituents and
molecular weights that determine their solubility, compatibility, viscosity, and hardness.

Recently, Yuan et al. (2008) have investigated the permeability characteristics of


cellulose acetate butyrate coating films and their importance as semipermeable membranes
in osmotic drug delivery systems. Similar studies related to this end use include the use of
CAB as a matrix tableting and/or taste masking material when combined with CA and
hydroxypropyl cellulose. A novel technique for forming very thick but wrinkle-free membranes
that involves solvent-nonsolvent mixtures has been described. Table 1 contains a listing of
properties for commercial cellulose esters.

CAB esters are also useful as coatings additives where they can provide a significant
performance edge. Frequently, these polymers are described as versatile problem solvers
because cellulose esters provide qualities such as good flow and leveling, faster drying, sag
resistance, viscosity control, intercoat adhesion, and metal flake orientation.
Cellulose esters are typically supplied as dry, free-flowing fine powders and they
should be handled accordingly since any free-falling powder can generate static electricity.
Proper precautions should be taken when handling the dry-powder cellulose esters.

Factors affecting performance of cellulose esters in coatings

Performance attributes of cellulose esters are affected by the chemical composition


and the molecular weight of the ester. The larger size and lower polarity of the propionyl or
butyryl group on the molecule alters the packing density of the cellulose chains, causing
them to spread farther apart and lowering the attraction between the neighboring units. In
solution, these groups affect the configuration and conformation of the molecular chains
and thus alter properties. The extent to which these factors occur depends on the degree of
substitution (DS) and the particular substituents. DS is commonly used to quantify the
number of hydroxyls per anhydroglucose unit groups being replaced by acyl groups. The DS
ranges from 0 (cellulose) to 3 (tri-esters). CABs are the most commonly used cellulose esters
in coatings and are discussed in more detail below. As the butyryl content increases,
solubility, compatibility, flexibility, diluent tolerance, and moisture resistance are increased.
Lower butyryl levels are associated with increased chemical and grease resistance,
hardness, and melting range.

Most of the butyrates are manufactured with a hydroxyl content best suited for
general applications (about 1.5 %), permitting good solubility, compatibility, and
performance in coatings applications. Most CABs are soluble in esters, ke-tones, glycol
ethers, glycol ether esters, blends of alcohols, and aromatic hydrocarbons, and they are
quite tolerant of diluents such as aromatic hydrocarbons and alcohols. At levels around 5 %,
solubility in lower molecular weight alcohols occurs. At higher hydroxyl levels, reactivity
increases, providing cross-linking capability with amino and isocyanate resins. However, in
non-cross-linking systems, higher levels decrease moisture resistance due to increased
hydrophilicity.

When considering the hydroxyl functionality in the stoichiometry of a cross-linkable


coating system, the following calculations may be useful:

Hydroxyl number = 33 wt % hydroxyl


Hydroxyl equivalent wt = 1700 wt % hydroxyl

In general, CABs are compatible with most acrylics, polyesters, phenolics, ureas, and
isocyanates. They are also compatible with some epoxides and poly(vinyl acetates). CABs
are often incompatible with melamines, urea formaldehydes, and most alkyds.

The molecular weight (often related to as viscosity) of cellulose esters also influences
physical properties of the esters as well as coatings formulated with them. Increasing the
molecular weight slightly lowers its solubility and compatibility with other polymers, but it
does not affect hardness and density. Generally, toughness and flexibility are improved as
molecular weight is increased.

Cellulose esters as film formers, modifiers, or additives

serve as the primary film-forming polymer or as a modifying copolymer to impart a


specific property to the liquid or solid coating. There are four characteristics that explain the
benefits cellulose esters bring to coatings when they are used as additives.

1. Due to their rapid viscosity build, cellulose esters prevent film distortion and
craters, sags and runs, picture framing, poor metal flake orientation, color
separation in multipigment systems, pigment flooding and floating, inconsistent
gloss control with matting agents, and poor holdout.
2. Due to their Newtonian rheology, cellulose esters improve flow and leveling,
rheology control, reduction of surface defects such as pinholes and craters in
atomization, roll coat, and curtain coat applications.
3. Due to their high glass transition temperatures, cellulose esters provide rapid dry-
to-touch times and excellent hardness development.
4. Due to their cellulose backbone, cellulose esters have good UV stability and
dimensional stability.

Applications for cellulose esters in coatings

In the automotive industry, cellulose esters have been used for decades in both
original equipment manufacturer and refinish basecoats, refinish primers, clear coats, and
monocoats. They are often an integral component in enabling the formulator to achieve
desired color effects, particularly through consistent metallic flake orientation. CAB used in
the basecoat of a basecoat/clear-coat system provides improved flake alignment and
resistance to redissolve from the topcoat solvents. CAB is also used in pigment dispersions
for automotive applications to provide consistent tints and to achieve the maximum color
development from a given pigment. In addition to automotive metal coatings, CAB lacquers
are especially useful on structural aluminum, aluminum foil, stainless steel, chromium,
brass, silver, and tin, where protection of the metal surface and maintenance of the metallic
luster are desired. By appropriate selection of modifying resins, butyrate lacquers may be
formulated into clear or pigmented coatings that have good adhesion to metallic surfaces
and that are resistant to salt-fog, oxygen, and other tarnishing and corroding elements. CABs
used in metallic coil coatings reduce surface defects, improve metallic and pearlescent flake
alignment, as well as providing improved flow and leveling, better gloss consistency, and
purer white color value.

CAB has been used for many years in coatings for various plastic materials. Portions
of the surface of molded plastic articles are frequently coated with a lacquer that primarily
serves a decorative purpose; for example, metallic coatings on cell phones or casings for
DVDs. CAB polymers are effective as release coatings for silicone rubber molds used in
forming rigid polyurethane articles. The base release coating not only protects the mold from
attack by the poly-urethane components, it also becomes an integral part of the plastic
article and serves as a tie coat for other coatings on the molded article.

A major use of CAB is in wood coatings for furniture, plywood paneling, particleboard,
and hardboard, both in thermoplastic and thermoset systems. It can be formulated into
coatings (often a butyrate/acrylic composition) that are nonyellowing, possess good
durability, stain resistance, plasticizer migration resistance, depth of finish, color, and color
stability.

Crosslinking systems such as a CAB/urea-formaldehyde composition is frequently


used in coating kitchen cabinets, and high quality furniture finishes exhibiting outstanding
toughness and chemical resistance can be prepared by blending CAB with an isocyanate
prepolymer.

Flexible cloth lacquers made from CAB 381 are used in coating nonyellowing window
shades and flame-resistant artificial leathers. CAB is used with urethane elastomers to coat
fabrics used in the production of sportswear, rainwear, footwear, hats, coats, handbags,
luggage, and upholstery for furniture and automobiles. Blending CAB with these polymers
increases hardness, reduces tack, raises blocking point, improves slip, and reduces dirt
pickup of the coating.

Other applications include paper and lacquer emulsions for leather topcoats. CAB is
used worldwide in topcoats for leather items such as automotive upholstery, footwear, and
furniture. These topcoats containing CAB are tough and have good resistance to abrasion
and plasticizer migration.

Cellulose esters are used as additives in radiation curing (RC) systems as well. Here,
they provide similar benefits as in solvent-borne coatings, such as flow and leveling,
improved gloss control, adhesion, and reduction of surface defects. CAB 551 types are used
in overprint varnishes at levels of 15 %. In applying RC coatings, CABs can reduce or
eliminate holes in curtain coatings and reduce spattering in high-speed roll coat
applications. Most commonly, the CAB is dissolved in a monomer and then added to the
formulation. The viscosities of certain CABs in a variety of monomers are given in Table 2.

Cellulose esters are also used in graphic arts as thermoplastic and thermoset inks,
including over print varnishes. Guidance for selecting the appropriate cellulose ester is
provided in Table 3.
INTRODUCTION

Peanuts (Arachis hypogaea L.), also called as groundnuts and locally known as
mani, are the edible seeds of a legume and are high in protein, oil, and fiber. In 2015, the
Philippines has produced 29.2 million metric tons of peanuts (Selected Statistics on
Agriculture 2016, Philippine Statistics Authority). Peanuts are among the major crops
harvested in the Philippines and the most popular form for consuming peanuts are boiled,
roasted, fried, and processed into peanut butter (Garcia et al, 1990). The edible seeds are
protected by means of its shells which act as a natural protective covering against
mechanical damage and insect infestation. Peanut shells constitute about 21-29% of the
weight of whole peanuts (van Doosselaere, 2013), and are mainly composed of 39.86% -
40.67% alpha-cellulose, 10.33% - 58.10% moisture content, 47.78% lignin, and 2.03%
others (FTUD REPORT No. 044-14, Philippine Fiber Industry Development Authority,
2015; Code No. 17-0963, Adamson University Technology Research & Development
Center, 2017). But prior to processing, peanuts are usually stored in unshelled form.
This means that peanut shells are no longer of use and are either disposed of directly or
burned. However, these discarded peanut shells are lignocellulosic biomass material
and can be a renewable source of alpha-cellulose for producing valuable chemical
commodities such as cellulose acetate butyrate which is used by several industries.