Good Manufacturing Practice for the Handling of Acetate General Description of Cellulose Acetate

Cellulose acetates are polymers of cellulose which has been esterified with acetic acid to form acetate group substituents. This is a class of polymers which comes from natural, renewable resources and was one of the first synthetic plastic materials. This group of polymers is differentiated according to : the composition the source of the raw material of cellulose and the use and application. Commercial sales grade cellulose acetate polymers are separated into two types: cellulose triacetate (CTA) in which (nearly) all hydroxyl groups of the cellulose are substituted with acetate groups. These polymers have a degree of substitution (DS) of at least 2.8 and cellulose diacetate (CA; synonyms: cellulose acetate or secondary acetate or 2.5 acetate). These polymers have a DS of 2.22 up to 2.76 (i.e. 74% up to 92% of the hydroxyl groups are substituted). 1 The source of the cellulose is another important distinction for cellulose acetate. The commercial cellulose acetate products have two different raw materials: wood pulp, from softwoods such as hemlock or from hardwoods such as eucalyptus or cotton linters. And for serving the different markets cellulose acetate is converted in different forms fibers in form of endless yarn for textile applications staple fibers for the nonwoven industry, tow for the manufacturing of cigarette filters or reservoirs films for photographic applications, optics and LCD screens granules and other shapes for different plastic applications.

ISO 2006:1999 "Textile - Man-made fibers - Generic names"

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In spite of different degrees of substitution or sources of cellulose which result in some variation in chemical and physical properties, the handling instructions and recommendations are generally valid for all cellulose acetate polymers.

General Scheme for Manufacturing

The production of cellulose acetate polymers takes place globally. The industrial processes used in the manufacture of cellulose acetates are very similar throughout the world. The cellulosic material reacts in acetic acid solution with acetic anhydride by an acid catalytic esterificiation reaction of the hydroxyl groups to form cellulose triacetate. The cellulose triacetate (CTA) is then precipitated into water, purified and dried. For the manufacturing of cellulose diacetate (CA), the first step, acetylation, is the same as described above, however, before the precipitation step, the CTA is treated with water in order to hydrolyze some acetate groups until the desired degree of substitution is reached. The cellulose diacetate polymer is then precipitated, purified and dried.

Figure 1:

Schematic scheme of the structures of CA and CTA

OH OH O HO O OH O O O HO OH

Cellulose

Ac 2 O

OAc OAc AcO O O OAc O O AcO OAc O

Cellulose Triacetate (CTA)

H 2O

OAc OAc AcO O O OH O O AcO OAC O

Cellulose Diacetate (CA)

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For both cellulose triacetate and cellulose diacetate, the polymer is precipitated from the acetylation solution and washed intensely in order to remove the residual acetic acid. In this washing process, the catalyst is also removed and neutralized in order to improve the stability of the cellulose acetate polymer. Therefore, the commercial acetates have a somewhat porous structure which enhances any re-dissolving step used to prepare acetate solutions, called dopes.

Size Commercial cellulose acetates are delivered in various forms such as flake: a form with low bulk density and a more porous structure grain: higher bulk density with similar solubility properties powder: a form prepared by milling or grinding of flakes or grain. The preferred form of polymer to use depends on the end use and customer manufacturing processes employed: For example, flake and grain are typically used in applications where the acetate will be dissolved in a solvent. The powder form is best suited for extrusion processes (after blending with plasticizers).

Figure 2:

Different forms of Cellulose Acetate

FLAKE

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GRAIN

POWDER

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Transport
Regulatory Requirements Cellulose acetate polymers are not classified as dangerous (hazardous) for transport or use. Therefore, there are no restrictions in terms of the dangerous goods regulations. However, as with storing these polymers, precautions should be taken in order to secure the integrity of the polymer for further use, by protecting the material during the transport from humidity, volatile or odoriferous substances and excessive heat.

Bulk transport Bulk transportation by gravity (plug flow) is preferred to pneumatic conveying due to safety hazards involving the generation of dust. If pneumatic transportation is required, consult and follow the relevant national regulations regarding the safe concentration based on the particle size of the dust. Furthermore, the following aspects should be considered: reduction of the possibility of electrostatic charging blanketing or smothering of the system with an inert gas filtering the emission for retaining dust

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Storage and Shelf Life

Recommendation for safe storage The requirements for the storage of cellulose acetate are recommended due to the desire to maintain product integrity, rather than from safety concerns. store in closed containers: the higher surface of cellulose acetate powder and even of the porous flakes might adsorb air impurities or volatile or odoriferous substances, which might interfere with its further use. store in dry areas: cellulose acetate absorbs moisture to the level of 5-6% humidity. store at ambient temperatures store away from ignition sources and oxidizing agents

Storage of polymer in high temperature and high humidity conditions can lead to hydrolysis and liberation of acetic acid.

Shelf Life The shelf life of cellulose acetate depends on the storage conditions, i.e. the humidity and the temperature, but also from some product-related properties. Some general characteristics are: Cellulose triacetate (CTA) is generally more stable than cellulose diacetate (CDA). Typically, the manufacturer of cellulose acetate will specify a shelf life from the date of manufacturing for properly stored materials. Moisture regain by a respective longer storage in an open environment might affect the processing behaviour, therefore the polymer should be analyzed before processing.

The suitability of acetate in case of improper storage might be checked by the determination of acetic acid present. This analysis is typically performed by the titration of aqueous extracts. For most purposes, an acetic acid content in the flake of 0,2 g/kg is acceptable.

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Handling and Processing

Handling Cellulose acetate is not classified as dangerous and the handling of these polymers does usually not require any specific personal safety measures. However, measures should be taken to avoid the formation and the release of dust for safety reasons as well as for environmental protection and industrial hygiene. Dust generation is dependent on the handling processes employed as well as the material used. The various physical forms of cellulose acetate polymers have different characteristics regarding the formation and release of dust, with grain being the least likely to generate dust. Bulk transportation by gravity (flow) produces less dust than any pneumatic conveying.

Processing The melting temperature for cellulose acetates is above 230C. At higher temperatures, cellulose acetate starts to decompose, begins to yellow and to carbonize.

Therefore, the processing of the acetate is based on an acetate solution in solvents or a thermal processing with plasticizers, Common solvents for CA: acetone, acetic acid CTA: dichloromethane, dimethylsulfoxide (DMSO). Common plasticizers for CA: dimethylphthalate (DMP), diethylphthalate (DEP), triacetin, esters from citric acid and similar products. CTA: triacetin, triphenylphosphate, diethylphthalate (DEP) and similar products.

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Flammability and Fire Prevention

Flammability The risk of flammability when using cellulose acetate is quite low due to its low ignition properties and is accordingly given the following classifications: Hazardous Materials Identification System (HMIS) Degree of Flammability Hazard: 1 with degree of 1 defined as "materials that must be preheated before ignition can occur" 2 Ignition number ("Brennzahl") BZ:3; i.e. "localized combustion or glowing with practically no spreading"3 Cellulose acetate is not designated as a flammable substance under the Japanese Fire Defense Law.

Flakes and grains are not explosive and have higher ignition temperatures than dust. However, depending on its size and surface, cellulose acetate polymer dust has the ability for the generation of dust explosions, even from low ignition energy sources in the case of higher concentrations of dust.

Fire prevention Therefore, in the case of the handling of powder or the formation of dust, any ignition sources such as open flames, hot surfaces, sparks from rotating parts, and foreign metallic objects must be eliminated.

National Fire Prevention Association, NFPA, -704 Codes, 2007 Edition. Remark: materials in this degree 1 require considerable preheating, under all ambient temperature conditions, before ignition and combustion can occur. VDI 2263, part 1: "Dust Fires and Dust Explosions; Hazards, Assessments, Protective Measures; Test Methods for the Determination of the Safety Characteristics of Dust"

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Dust Prevention
Industrial Hygiene Cellulose acetate polymers are not water soluble and not accessible to biological systems. Therefore, these acetate polymers are not hazardous nor bio-available. However, as with all non-water soluble materials, the formation of dust during the handling should be avoided, particularly where the dust could be inhaled or come into contact with the eye or skin. Non-water soluble dust might be irritating to the eyes and to the skin, by mechanical action irritating to the mouth and throat if inhaled and initiating inflammations in the lungs if respired . When handling powder or flakes with a high concentration of dust, the wearing of breathing masks, or respirators, is highly recommended as a general measure and might be required in cases where the national threshold limits for the respirable / inhalable dust fraction might be exceeded. Further personal protection equipment and devices might be needed (such as closed safety gloves) depending on the exposure and the working conditions.

Process safety The explosive properties of dust should be taken into account. When handling acetate polymers in powder or flake form with a high concentration of dust, the following measures are appropriate: elimination of all ignition sources taking of precautions against electrostatic charging by using conductive and grounded materials, respectively coatings with low disruptive voltages (< 4kV) for the transport installations and by reducing the transportation speed. blanketing or smothering of the system with an inert gas

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Disclaimer Although the information in this Generic Guidelines is presented in good faith and is believed to be correct, neither GAMA, the GAMA Members, nor those acting on behalf of GAMA or its Members (such as their employees, officers or directors) make any representations or warranties as to its completeness or accuracy. Use of the Generic Guidelines is conditional on users making their own determination as to its suitability for their purposes prior to use. In no event will GAMA, the GAMA Members, nor those acting on behalf of GAMA or its Members be responsible for damages of any nature resulting from the use of or reliance upon the Generic Guidelines. Users agree that use of the Generic Guidelines is entirely at their own risk and that they will not be entitled to make any claims against GAMA, the GAMA Members, nor those acting on behalf of GAMA or its Members. Nothing contained in this Generic Guidelines is to be construed as a recommendation to adopt or refrain from any course of action.