Pro 250-42a Aqualon Ec

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AQUALON ®

Ethylcellulose (EC)

Physicaland

Chemical

Properties

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AQUALON ® EC

A Specialty Polymer With Broad Stability and Compatibility

CONTENTS PAGECOMPOSITION OF ETHYLCELLULOSE

TYPES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

FDA STATUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

OUTSTANDING CHARACTERISTICS . . . . . . . . . 5Color . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5Compatibility . . . . . . . . . . . . . . . . . . . . . . . . . . 5Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5Electrical Properties . . . . . . . . . . . . . . . . . . . . . 5Flexibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5Flammability . . . . . . . . . . . . . . . . . . . . . . . . . . 5Softening Point . . . . . . . . . . . . . . . . . . . . . . . . 5Solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5Stability to Chemicals . . . . . . . . . . . . . . . . . . . 5Stability to Water . . . . . . . . . . . . . . . . . . . . . . . 5Stability to Light . . . . . . . . . . . . . . . . . . . . . . . . 6Stability to Heat . . . . . . . . . . . . . . . . . . . . . . . . 6Taste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6Thermoplasticity . . . . . . . . . . . . . . . . . . . . . . . 6Toughness . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

PHYSICAL PROPERTIES(EFFECTS OF ETHOXYL CONTENTAND VISCOSITY) . . . . . . . . . . . . . . . . . . . . . . 7

VISCOSITY-CONCENTRATIONRELATIONSHIPS . . . . . . . . . . . . . . . . . . . . . . 8

BLENDING . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

How to Use the Blending Chart . . . . . . . . . . . . 8Limitations of Blending . . . . . . . . . . . . . . . . . . . 9

FORMULATIONSTABILIZATION OF ETHYLCELLULOSE . . . . . . 13

Hot-Melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13Clear Films . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

SOLVENTS AND SOLUBILITY . . . . . . . . . . . . . . 13Solubility Parameters . . . . . . . . . . . . . . . . . . . 13Effects of Ethoxyl Content . . . . . . . . . . . . . . . . 13Solvents for N-Type . . . . . . . . . . . . . . . . . . . . . 14Effects of Alcohols . . . . . . . . . . . . . . . . . . . . . 14Dilution With Petroleum Thinners . . . . . . . . . . . 15Rule 442—Exempt Solvents . . . . . . . . . . . . . . 15

Economy Through Solvent Choice . . . . . . . . . . 16Effects of Solvent Composition on

Film Properties . . . . . . . . . . . . . . . . . . . . . . 19Gasoline Resistance . . . . . . . . . . . . . . . . . . . . 21

RESINS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21Effects of Ethoxyl Content . . . . . . . . . . . . . . . . 21Compatibility With N-Type Ethylcellulose . . . . . 21Compatibility With K-Type Ethylcellulose . . . . . 22

PLASTICIZERS . . . . . . . . . . . . . . . . . . . . . . . . . 22Water-Sensitive Plasticizers . . . . . . . . . . . . . . 25Oils as Ethylcellulose Plasticizers . . . . . . . . . . 25Gasoline- and Oil-Resistant Plasticizers . . . . . 26

SPECIFIC APPLICATIONSLACQUERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

Hard Lacquers for Rigid Surfaces . . . . . . . . . . 27Tough Lacquer . . . . . . . . . . . . . . . . . . . . . . . . 27

Bronzing Lacquer . . . . . . . . . . . . . . . . . . . . . . 27Lacquer for Polystyrene Plastic . . . . . . . . . . . . 27Lacquer for Rubber . . . . . . . . . . . . . . . . . . . . . 27Specialty Wood Finishes . . . . . . . . . . . . . . . . . 28Water-White Wood Finish . . . . . . . . . . . . . . . . 28Alkali-Resistant Lacquer . . . . . . . . . . . . . . . . . 28Paper Lacquers . . . . . . . . . . . . . . . . . . . . . . . 28Flowback High-Gloss Lacquer . . . . . . . . . . . . . 28Solvent-Based Strip Coatings . . . . . . . . . . . . . 28

EMULSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

INKS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28Screen-Process Inks . . . . . . . . . . . . . . . . . . . . 28Magnetic Inks . . . . . . . . . . . . . . . . . . . . . . . . . 28Gravure and Flexographic Inks . . . . . . . . . . . . 28

VARNISHES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

ADHESIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

HOT-MELT APPLICATIONS . . . . . . . . . . . . . . . . 29

CASTING PLASTICS . . . . . . . . . . . . . . . . . . . . . 29

PIGMENT-GRINDING BASE . . . . . . . . . . . . . . . . 29

FILM AND FOIL . . . . . . . . . . . . . . . . . . . . . . . . . 29

PLASTICS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

FOOD CONTACT AND PHARMACEUTICALS . . . 30Tablets—Coatings . . . . . . . . . . . . . . . . . . . . . . 30Tablets—Binding . . . . . . . . . . . . . . . . . . . . . . . 30Encapsulation . . . . . . . . . . . . . . . . . . . . . . . . . 30

APPENDIXPRODUCT LISTING SUPPLEMENT . . . . . . . . . . 31

METHODS OF ANALYSIS . . . . . . . . . . . . . . . . . 32

PRODUCT SAFETY . . . . . . . . . . . . . . . . . . . . . . 32

© Aqualon, 2002.



Ethylcellulose is a cellulose ether distinguished by its versa-tility. It is very tough, soluble in a wide range of solvents,and flexible at low temperatures. Ethylcellulose can be for-mulated into lacquers, varnishes, inks, films, foils, adhe-sives, and plastics, and for food contact, animal feeds, andpharmaceutical goods.

Ethylcellulose is also characterized by low flammability andresistance to discoloration in sunlight. Ethylcellulose toughens,hardens, and reduces or even eliminates the surface tack ofcompositions in which it is compatible.

2

AQUALON ® ECA Specialty PolymerWith Broad Stability and Compatibility



Ethylcellulose is a cellulose ether made by the reactionof ethyl chloride with alkali cellulose, as expressed by thereaction: RONa + C2H5CI → ROC2H5 + NaCI, where Rrepresents the cellulose radical.

The structure that is most widely accepted for the cellulosemolecule is a chain of β anhydroglucose units joined to-gether by acetal linkages. This is indicated in Figure 1a.These long, oxygen-linked anhydroglucose-unit chains havegreat strength, which is passed on to cellulose derivativessuch as nitrocellulose, cellulose acetate, and ethylcellulose.The properties of flexibility and toughness in these deriva-tives are directly attributable to this long-chain structure.

From Figure 1a., it is seen that each anhydroglucose unithas three replaceable OH groups, all or part of which may

react as indicated in the reaction cited earlier. Complete sub-stitution of all three groups would give the triethyl ether pos-sessing a substitution value of 3, or 54.88% ethoxyl, which isillustrated in Figure 1b.

The completely substituted triethylcellulose has no commer-cial significance, however, because it lacks strength and flex-ibility, is not thermoplastic, and shows extremely limitedcompatibility and solubility. The commercial product, whichexhibits the remarkable combination of useful propertiescited in the introductory paragraphs, has a substitution valuebetween 2.25 and 2.60 ethoxyl groups per anhydroglucoseunit, or 44-52% ethoxyl content.

TYPESAqualon ® ethylcellulose is available in four ethoxyl types.These are listed in Table I, along with their degreeof substitution.

Each of these ethoxyl types is subdivided into viscositytypes, as indicated in Table II. The viscosity designation indi-cates the nominal viscosity in centipoises for a 5% weightconcentration in the Standard Viscosity Solvent. (See foot-note (b), Table II.) For example, K100 ethylcellulose wouldrefer to K-type of 45.0-47.2% ethoxyl content, and a viscos-ity of 100 cps in 5% solution. Thus, ethoxyl and viscositytypes can be readily specified as K100, N7, T200, andso forth.

HO H H

H HO

O

O

O

H

H

CH2OH

CH2OH

H

OH

H

H

OH

OH

OH

HH

H

H

H

CH2OH

OH

OH

OH

H

η-2

HO H H

H HO

O

O

H

H

CH2OC2H5

CH2OC2H5

H

OC2H5

H

H

OC2H5

OC2H5

OC2H5

HH

H

H

H

CH2OC2H5

OC2H5

OC2H5

OH

H

η-2

O

OO

3

COMPOSITION OF ETHYLCELLULOSE

FIGURE 1

COMPOSITION OF ETHYLCELLULOSE

Figure 1b. Structural Formula of Ethylcellulose With Complete (54.88%) Ethoxyl Substitution

Figure 1a. Structural Formula of Cellulose

Degree of Substitution

Ethoxyl of Ethoxyl Groups per

Type Content, % Anhydroglucose Unit

K-type 45.0-47.2 2.22-2.41

N-type 48.0-49.5 2.46-2.58

T-type 49.6-51.5 2.58-2.73

X-type 50.5-52.5 2.65-2.81

TABLE I—ETHOXYL TYPES



FDA STATUS

Aqualon ® K-, N-, and T-types of ethylcellulose (1) are incompliance with requirements of the U.S. Food and DrugAdministration for use in food and food-contact applications.These requirements are specified in the Code of FederalRegulations, Title 21, subject to the limitations and require-ments of each regulation under the following Sections:

175.105 Adhesives

175.300 Resinous and polymeric coatings

175.390 Zinc-silicon dioxide matrix coatings

176.170 Components of paper and paperboard incontact with aqueous and fatty foods

176.180 Components of paper and paperboard incontact with dry food

177.1210 Closures with sealing gaskets for foodcontainers

182.90 Substances migrating to food from paper andpaperboard products—ethylcellulose

573.420 Binder or filler in dry vitamin preparations tobe incorporated into animal feed

(1)Except plastic-peel-stabilized N100PP and N50S types.

In addition to the foregoing, the special NF drug grade ofN-type ethylcellulose meets other code requirements, allow-ing it to be used in other food contact and in pharmaceuticalapplications. These requirements are specified in the Code of

Federal Regulations, Title 21, subject to the limitations andrequirements of each regulation under the following Sections:

73.1(b) Diluents in color additive mixtures for markingfood: inks for marking food supplements in

tablet form, gum, and confectionery; inks formarking fruits and vegetables; diluents incolor additive mixtures for coloring shell eggs

73.1001 Diluents in color additive mixtures for druguse exempt from certification: ingested drugs;inks for branding pharmaceutical forms; exter-nally applied drugs

172.868 Ethylcellulose—for use as a binder and fillerin dry vitamin preparations, as a componentof protective coatings for vitamin and mineraltablets, and as a fixative in flavoring compounds

Ethylcellulose NF types also meet monograph requirementsin the National Formulary , current edition, and the United

States Food Chemicals Codex for Ethylcellulose . Ethylcellu-lose is included in the Cosmetic, Toiletry, and FragranceAssociation’s (CTFA) cosmetic ingredients dictionary.

The available types of NF ethylcellulose are:

(See section on Food Contact and Pharmaceuticals for addi-tional details.)

TABLE II—ETHOXYL AND VISCOSITY TYPES OF AQUALON ETHYLCELLULOSE

Ethoxyl Types Viscosity Types(b)

(* refers to types now produced)(a) (Viscosity on all types run at 5% concentration by weight and 25°C.)

K N T X45.0-47.2% 48.0-49.5% 49.6-51.5% 50.5-52.5%

Ethoxyl Ethoxyl Ethoxyl Ethoxyl Designation, cps Limits, cps

— * — — 4 3.0-5.5 — * — — 7 5.6-8.0

— * * — 10 8.0-11

— * — — 14 12-16

— * — *(c) 22 18-24

* * * — 50 40-52

* * * — 100 80-105

— * * * 200 150-250

— * * — 300 250-350(a)Blanks in the table indicate no demand at present for the particular type. However, this does not mean that these types cannot be produced.(b)Viscosity is determined in 80:20 toluene:ethanol by weight on a sample dried 30 min at 100°C. (See ASTM D 914.)(c)Viscosity is 18-35 cps.Note: “Ethanol” in this booklet refers to specially denatured (S.D.) ethyl alcohol, 2B, 190 proof.

NF Type Viscosity(d) Range, cps

N7 5.6 to 8.0

N10 8.0 to 11

N14 12 to 16

N22 18 to 24

N50 40 to 52

N100 80 to 105

(d)Determined using 5% ethylcellulose in 80 parts toluene: 20 partsethanol by weight.



OUTSTANDING CHARACTERISTICSThe outstanding physical and chemical properties that distin-guish Aqualon ® ethylcellulose, together with some of its indi-cated uses, are described briefly in the paragraphs that follow.

ColorEthylcellulose is practically colorless, and retains this condi-tion under a wide range of uses. Neither sunlight nor ultra-violet light affects the color. Accurate color control throughthe use of dyes and pigments is readily attained in protectivecoatings, plastics, and other compositions where close colorcontrol is often important.

CompatibilityEthylcellulose is compatible with an unusually wide range of

resins and plasticizers, including oils and waxes. This widerange of compatibility makes it easy to develop economicalformulations in the great variety of uses to which it is adapt-able. Small additions of ethylcellulose to waxes toughen theirtexture and raise their melting point. In varnishes, its usereduces tackiness and increases drying rate.

It is quite useful in printing inks. Plastics with rigid or softproperties can be readily formulated.

DensityThe low density of ethylcellulose makes it possible to getgreater coverage and greater volume per unit weight thanwith the other cellulose derivatives. For example, it hasabout 45% greater coverage than nitrocellulose and 20%greater coverage than cellulose acetate in coatings and

adhesives of similar weight composition. In plastics, film, andfoil, the low density of ethylcellulose gives the same corre-sponding advantages of greater volume for a given weight.

Lacquers are generally formulated with N4, N7, and N10types, where a minimum viscosity is desired for a maximumsolids content. Higher viscosities would be used, however,for maximum toughness.

Electrical PropertiesThe excellent electrical properties of ethylcellulose, com-bined with its good thermal stability and outstanding flexibil-ity and toughness, led to its early and continued use in cablelacquers, where conditions requiring these properties areencountered. It also has been used in plastics for electricalinsulation for many purposes.

FlexibilityThe great flexibility of ethylcellulose over a wide range oftemperatures is one of its most marked characteristics. Itsretention of flexibility at very low temperatures is especiallynotable, for many compositions remain flexible even at

–70°C. Ethylcellulose also retains a large measure of itsinitial flexibility, even after long exposure to temperaturesapproaching its softening point (156°C).

This flexibility is carried over into many compositions, suchas protective coatings, adhesives, foil, and plastics. It is aproperty that is desirable, for example, in plastics for high

impact resistance at low temperatures, in furniture lacquersfor prevention of cold-checking, in fabric coatings for goodflexibility and cold-crack resistance at low temperatures, andin hot-melt compositions and plastics for sustained toughen-ing action after compounding.

FlammabilityEthylcellulose flammability is of as low an order as that ofany other cellulosic material. If it is held in an open flame, itwill catch fire and burn, but its formulations can be made fireresistant by proper choice of plasticizer and other flame-proofing agents.

Softening PointThe softening point (156°C) of ethylcellulose is relatively lowand, if desired, can be made even lower by proper adjustment

of plasticizers. These factors permit ease of working andapplication, as in hot-melt application of adhesives, calendarapplication on cloth, and in injection and extrusion plastics.

SolubilityEthylcellulose is soluble in a wide variety of solvents, thusmaking it easy to formulate this versatile material for anypurpose where solvent application is desirable. Among theuseful solvents are the esters, aromatic hydrocarbons, alco-hols, ketones, and chlorinated solvents. Inexpensive solventcombinations can be used with ethylcellulose. Among themost generally useful combinations are 70-90% aromatichydrocarbons or synthetic aromatics (dehydrogenated naph-thenes and cyclicized hydrocarbons of varied kauri-butanolvalues, depending on grade and manufacturer) with 30-10%alcohols. Although such combinations are relatively low incost, they can be made even more economical by the addi-tion of petroleum distillates such as heptane or VM&P naph-tha. In some cases, as much as 50% of the total solvent canbe replaced with such low-priced mineral spirits.

Stability to ChemicalsOf all cellulose derivatives, none is more stable to chemicalsthan ethylcellulose. It is resistant to alkalies, both dilute andconcentrated, and to salt solutions.

Ethylcellulose is more sensitive to acidic materials than arecellulose esters; however, lacquer coatings satisfactorilywithstand the action of dilute acids for limited exposureperiods. It is resistant to oxygen under high pressures atroom temperature for extended periods of time, and to anozonized atmosphere for one to two weeks with no detectabletrace of degradation. Oxygen at temperatures above thesoftening point of ethylcellulose has a marked degradingeffect unless the compositions are stabilized with antioxidants.

Stability to WaterThe types of ethylcellulose discussed here are not affectedby water. It takes up very little water from moist air or dur-ing immersion, and that small amount evaporates readily,leaving the ethylcellulose unaltered. Dimensional stability,which is related to water absorption, is unusually good.Thisproperty can be especially valuable in many applicationsof ethylcellulose.



Stability to LightLight, visible or ultraviolet, has no discoloring action on ethyl-cellulose. Clear films transmit practically all the visible lightof the spectrum and varying amounts of ultraviolet light,depending on the stabilizers and plasticizers used in formu-lation. Figure 2 shows the ultraviolet absorption character-istics of ethylcellulose: (a) the effect of film thickness onabsorption, and (b) the effect of certain stabilizers known toreduce the embrittling effect of ultraviolet light on ethylcellu-lose. (See Stabilization of Ethylcellulose, page 13.)

Ethylcellulose, because of its light transmission, togetherwith its flexibility, great toughness, and chemical resistance,is an unusual material when properly used in protectivefilms. Such films can be applied from solution, from hot-melt,by calendering, or by lamination.

Stability to HeatApplication of heat up to its softening point has little effecton ethylcellulose. At higher temperatures, embrittlement anddiscoloration may occur unless the ethylcellulose is pro-tected by antioxidants. Acidic materials such as high-acid-number resins have a degrading effect on ethylcellulose,particularly at elevated temperatures, and thus should not beused in plastics, in adhesives, or in other hot-melt applica-tions of ethylcellulose.

When properly formulated and stabilized, ethylcellulosecompositions have remarkably good resistance to high tem-peratures, so plastic compounding, molding operations, andhot-melt compounding and application can be carried outwithout degrading the ethylcellulose. Similarly, this resistance

to heat makes ethylcellulose useful in formulations subjectto heat, as in lacquers for electric cable. See page 13 fora discussion of modifiers contributing to the heat stabilityof ethylcellulose.

TasteEthylcellulose has no taste. It has been used as a coating forpaper, film, and foil in contact with food. (See section onFood Contact and Pharmaceuticals.) Plastic uses also arepossible in the food-packaging field.

ThermoplasticityEthylcellulose possesses excellent plastic flow characteris-tics; it is possible to process plastics completely in heatedBanbury mixers or on heated two-roll mills without the aid ofvolatile solvents, thus making compounding more economi-

cal. This characteristic is essential for injection, extrusion,lamination, and calendering operations, as well as for hot-melt compounding and application of adhesives, paper coat-ings, and casting plastics.

ToughnessThe high tensile strength of ethylcellulose is worthy of note.Combined with its excellent flexibility over a wide tempera-ture range, this results in unusual toughness. Toughness, athigh and low temperatures, is one of the most useful quali-ties of ethylcellulose. In this respect, it has marked advan-tages over synthetic resins. It is superior in this property toother cellulose derivatives. The toughening action that ethyl-cellulose imparts can be of fundamental importance for pro-tective coatings, plastics, and adhesives.

FIGURE 2ULTRAVIOLET ABSORPTION STUDY OF

ETHYLCELLULOSE FILMS

100

80

60

40

20

0220 260 300

Wavelength, mµ

L i g h t T r a n s m i s s i o n ,

%

340 380

Ethylcellulose Film,2 mils Thick

Ethylcellulose,10 mils Thick

a. Effect of ethylcellulose film thickness on light transmission.

100

80

60

40

20

0220 260 300

Wavelength, mµ

L i g h t T r a n s m i s s i o

n ,

%

340 380

Ethylcellulose Film

EthylcelluloseWith 1% Ionol Ethylcellulose

With 0.5%Each of Ionoland Uvinul 400

b. Examples of how ultraviolet light stabilizers can affect light transmission ofethylcellulose film. All films were 3 mils thick.



PHYSICAL PROPERTIES (EFFECTS OFETHOXYL CONTENT AND VISCOSITY)

As in the case of the other cellulose derivatives, there arecertain properties of ethylcellulose that depend somewhaton the degree of substitution (ethoxyl content). For example,the effect of substitution on softening point, hardness, waterabsorption, solubility in ethanol, and solubility in 80:20tolune:ethanol is given in Figure 3. The effect of substitutionon solubility in different solvents is discussed at length later.

Conversely, there are certain other properties such as ten-sile strength, elongation, and flexibility that are not greatlyaffected by the degree of substitution, but depend largelyon the degree of polymerization, which can be measuredby viscosity. Table III (page 8) presents data on the tensile

strength, elongation, and flexibility of various viscositygrades of N-type ethylcellulose. Figure 4 shows thesedata in graphic form.

It will be seen that there is a marked leveling off of thecurves (Figure 4) for tensile strength and elongationbetween N50 and N100 types. This means that very littleadditional tensile strength or elongation can be gained byusing viscosity types higher than about N100. On the otherhand, there is no break in the flexibility curve within therange shown to indicate what the ultimate folding enduranceof ethylcellulose might be.

The softening point of unplasticized ethylcellulose is notgreatly affected by the viscosity.

Within the substitution range offered, N-type ethylcellulose(48.0-49.5% ethoxyl content) meets most requirements andis usually specified because it exhibits the most generallyuseful combination of properties. The other types areselected when special requirements must be met. Forinstance, K-type is usually selected for special uses requir-ing harder, higher melting compositions having better resis-tance to certain solvents and oils. K-type should be selectedfor injection molding because it can be injected without surface-lamination or similar mold defects, and yields plastics of bet-ter resistance to distortion under heat. K-type is used whereoil- and gasoline-resistance is important. T- and X-types areuseful where extreme dilution with straight-chain hydrocar-bon solvents is desirable, and where maximum water resis-tance is important.

The physical properties of N-type ethylcellulose are pre-sented in Table IV. A study of these data will show this mate-rial to be unusual in many respects.

FIGURE 3

THE EFFECT OF SUBSTITUTION ON PHYSICAL

PROPERTIES OF ETHYLCELLULOSE

190

180

170

160

150

140

5

4

3

2

1

0

110

105

100

95

90

8542 43 44 45 46

Ethoxyl of Ethylcellulose (50-cps Type), %

Range of Ethanol Solubility

Range of 80:20 Toluene:Ethanol Solubility

M o

i s t u r e A b s o r p t i o n a t 1 9 ° C

a n

d 7 0 % R

e l a t i v e H u m i d i t y

47 48 49 50 51

S h o r e H a r d n e s s ,

R S c a l e

S o f t e n i n g P o i n t , ° C

SofteningPoint

Hardness, Shore

MoistureAbsorption(e)

FIGURE 4TENSILE STRENGTH AND ELONGATION

40

30

20

10

2,400

2,000

1,600

1,200

800

400

11,000

10,000

9,000

8,000

7,000

6,000

5,000

4,000

3,000

2,000

1,000

T e n s i l e S t r e n g t h ,

l b s / i n . 2

Viscosity(f) of N-Type Ethylcellulose (Log Scale), cps

F l e x i b i l i t y ,

M I T D o u b l e F o l d s

E l o n g a t i o n a t R u p t u r e ,

%TensileStrength

4 6 810 507

1009

3002005

302040

Elongation

MITFolds

(e)The moisture absorption of ethylcellulose decreases as the ethoxyl con-tent increases over the 43-51% range.Within this same range, softeningpoint and hardness are at a minimum at 48% ethoxyl content. Ethanoldissolves ethylcellulose at 45-49% ethoxyl, while a mixture of 80:20toluene:ethanol is a solvent for the product over the 43-51% ethoxyl range.

(f)Viscosity of ethylcellulose has a marked effect on flexibility over the entirerange studied. Also, viscosity has a marked effect on tensile strength andelongation up to 50 to 100 cps, at which zone there is a noticeable level-ing off in effect.



VISCOSITY-CONCENTRATIONRELATIONSHIPS

Typical viscosity-concentration curves for N-type ethylcellu-lose are shown in Figure 5 (page 10). These curves shouldprove useful in the control of the viscosity of solutions sincethey show the viscosity concentration for the different vis-cosity types of N-type ethylcellulose. From this chart, oneobserves how the viscosity of the solution of a given typevaries when the concentration of ethylcellulose is changed. Italso shows how the viscosity of a given solution changes if a

different viscosity type of ethylcellulose is substituted in thesame concentration. This same viscosity-concentration rela-tionship holds for other ethoxyl types of ethylcellulose.

A comparison of the viscosity-concentration relationships forthe low-viscosity lacquer types of N-type ethylcellulose andnitrocellulose is given in Figure 6 (page 11).

BLENDING

On occasions when the stock of a certain viscosity type ofethylcellulose is not on hand, or a use may be developed foran ethylcellulose of a viscosity differing from any standardtype, it is useful to know that different viscosity types can beblended to produce a product of the desired viscosity. Theprinciple of blending is based on the Arrhenius equation,which relates viscosity and concentration. It can be conven-iently expressed as follows:

Log Vs =n log V1 + (100 – n)log V2

100

where Vs = viscosity sought

n = % of first component of blend having aviscosity V1

V2 = viscosity of second component of blend

All viscosities must be expressed in the same unit.

Blends can be calculated directly from this equation.However, it is more convenient to use the blending chart(Figure 7, page 12). With this chart, it is possible to deter-mine, without calculation, the percentage of any two ethyl-celluloses of different viscosities that must be blended tosecure a desired intermediate viscosity. Likewise, it is possi-ble to determine the viscosity that will result from makingany blend.

This chart is set up on semilogarithmic plotting papermarked off so that the divisions on the horizontal axis repre-

sent percentages from 0 to 100, while the divisions on thevertical axis represent viscosity in centipoises from 2 to 500for standard 5% solutions of ethylcellulose as indicated inTable II (page 4). The position of each of the standard vis-cosity grades is shown on the chart.

How to Use the Blending ChartThe exact procedure can be described most easily by theuse of specific examples. Suppose you wish to obtain anethylcellulose having a viscosity of 150 cps in a 5% solution,and the materials available consist of Type 100 (80 to 105cps with an exact viscosity of 99 cps in 5% solution) andType 200 (150 to 250 cps with an exact viscosity of 200 cpsin 5% solution). The diagonal line (corresponding to astraightedge) connects Type 100 at the 99-cp point, on theleft side of the chart (V1), with Type 200, on the right (V2).

The diagonal intersects the horizontal line corresponding to150 cps at the vertical line marked 60%, point A.

This means that 60% of Type 200 and 40% of Type 100should be mixed to obtain 150-cps ethylcellulose. Similarly,other blends can be obtained. It is not necessary to drawlines; merely use a straightedge and read directly. Remem-ber that the percentage read from the diagonal refers to theethylcellulose type indicated on the right-hand axis (V2).

Viscosity(h)Tensile Flexibility,

Centipoises Intrinsic Strength Elongation MITin 5% Solution (η), dL/g(i) lbs/in.2 at Rupture, % Double Folds

8 0.73 6,800 10 160

9 0.79 7,000 14 200

13 1.04 7,300 19 330

24 1.40 8,100 28 595

43 1.70 9,500 32 1,000

94 2.16 10,400 35 1,480

184 2.53 10,500 35 2,020(g)Films 0.003 in. thick were cast from solution in 80:20 toluene:ethanol, dried 16 hrs at 70°C, conditioned 48 hrs at 70°F and 65% relative humidity, and tested.(h)Solvent was 80:20 toluene:ethanol. (All solvent values in this book are in terms of wt%.)(i)These intrinsic viscosity values are appropriate. They were obtained by measuring the relative viscosities at several concentrations, calculating the reduced

viscosities, and extrapolating to zero concentration, using the Martin equation, log10ηsp /c=log[η] + k [η]c , where c is concentration in g/dL in a solvent of 80:20toluene:ethanol.

TABLE III —EFFECTS OF VISCOSITY ON PHYSICAL PROPERTIES OF N-TYPE ETHYLCELLULOSE(g)



The chart also can be used to calculate the viscosity thatwill result by blending predetermined weights of two vis-cosity types. Suppose that equal weights of the same Type100 and the same Type 200, used to illustrate the firstexample, were mixed. What would be the viscosity of theresulting blend?

The vertical 50% line intersects the diagonal at point B onthe horizontal viscosity line, designating 140 cps.

Limitations of BlendingCertain cautions to be observed in blending should bepointed out. First, the two viscosity types selected for theblend should be as close together as possible. If widelyseparated viscosity types are blended, there is danger thatthe resulting blend may yield a lumpy or granular solution.Second, different substitution types should not be blended,because lumpy, granular or even incompatible solutionscan result.

TABLE IV —PHYSICAL PROPERTIES(j) OF N-TYPE ETHYLCELLULOSE

Bulking density, lbs/gal, in granular form 2.6-2.8

Bulking value, gal/lb, in solution 0.099-0.104

Color, Hazen, in solution, ASTM D 365 2-5Discoloration by sunlight Very slight

Electrical properties

Dielectric constant at 25°C, 1 Mc 2.8-3.9

Dielectric constant at 25°C, 1 kc 3.0-4.1

Dielectric constant at 25°C, 60 cyc 2.5-4.0

Dielectric strength, V/mil, 10-mil film, ASTM D 149-64, step by step 1,500

Power factor at 25°C, 1 kc 0.002-0.02

Power factor at 25°C, 60 cyc 0.005-0.02

Volume resistivity, ohm/cm 1012-1014

Elongation at rupture, %, 3-mil film, conditioned at 77°F and 50% RH 7-30

Flexibility, folding endurance, MIT double folds, 3-mil film 160-2,000

Hardness index, Sward, 3-mil film 52-61

Light transmission, practically complete, nm 310-400

Light transmission, better than 50% complete, nm 280-310Moisture absorption, by film in 24 hrs at 80% RH, % 2

Odor, flake Slight

Refractive index, cast film 1.47

Softening point, °C 152-162

Specific gravity 1.14

Specific volume, in.3 /lb in solution 23.9

Taste None

Tensile strength, lbs/in.2, 3-mil film, dry 6,800-10,500

Tensile strength, wet (% of dry strength) 80-85

Water vapor transmission, g/m2 /24 hrs, 3-mil film, ASTM E 96. Procedure E 890

(j)Values shown are not routinely determined and are not to be construed as sales specifications.



100,000

50,000

10,000

5,000

1,000

500

100

50

10

5

4

3

2

1

V i s c o s i t y , c p

s

1,000,000

500,000N200

N100

N50

N22

N14

N10

N7

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28

Concentration of Ethylcellulose by Weight

FIGURE 5VISCOSITY-CONCENTRATION CURVES (WT%) FOR AQUALON ® N-TYPE ETHYLCELLULOSE (DISSOLVED IN

80:20 TOLUENE:ETHANOL AND MEASURED AT 25 ± 0.1°C)



FIGURE 6VISCOSITY-CONCENTRATION COMPARISONS FOR AQUALON ® ETHYLCELLULOSE AND HERCULES ® RS

NITROCELLULOSE (MEASURED AT 25°C)

5,000

4,000

3,000

2,000

1,000

500

RS nitrocellulose, 1 / 2-sec RS nitrocellulose, 1 / 4-sec

100

50

10

5

4

3

2

1

.50 5 10 15 20 25 30 35

Concentration, wt%

V i s c o s i t y , c p s

N7 ethylcellulose

N22 ethylcellulose

Solvents: For ethylcellulose, 4:1 toluene:ethanol.

For nitrocellulose, 3:1 butyl acetate:ethanol.



FIGURE 7ETHYLCELLULOSE BLENDING CHART(k)

500

400

300

250

200

150

100

8070

60

50

40

30

20

15

10

8

76

5

4

3

2

Ethylcellulose V2 in Blend, %

V i s c o s i t y o f V 1 , c p s

500

400

300

250

200

150

100

8070

60

50

40

30

20

15

10

8

76

5

4

3

2

V i s c o s i t y o f V 2 , c p s

0 10 20 30 40 50 60 70 80 90

B A

100

0 10 20 30 40 50 60 70 80 90 100

Viscosity Type 7

Viscosity Type 10

Viscosity Type 14

Viscosity Type 22

Viscosity Type 50

Viscosity Type 100

Viscosity Type 200

Viscosity Type 300

Viscosity Type 4

(k)Based on 5% solutions of N-type in standard 80:20 toluene:ethanol mixed solvent, with viscosities run at 25 ± 0.1°C. (V1 and V2 represent the low- and high-viscosity types, respectively, to be blended.)



FORMULATION

STABILIZATION OF ETHYLCELLULOSEEthylcellulose formulations, if not stabilized, are subject tooxidative degradation in the presence of sunlight or ultravio-let light and at elevated temperatures, especially above thesoftening point of ethylcellulose (156°C). Ethylcellulose thusoxidized becomes brittle, and the surface can become badlycrazed. Discoloration generally occurs during prolongedexposure at excessive temperatures.

Investigation has shown that the harmful effects of oxidationcan be inhibited for extended periods of time by the use ofantioxidants and by the proper selection of resins, plasticiz-ers, and other modifiers.

The use of antioxidants is the most effective and generally

the easiest method of inhibiting oxidative degradation. Ethyl-cellulose compositions that are subjected to high tempera-tures during compounding or subsequent use and that maybe exposed to ultraviolet light or sunlight should always containan antioxidant. Acid acceptors should be added to ethylcellu-lose formulations containing components such as chlori-nated resins and plasticizers, which form acidic degradationproducts. Epoxy types are especially useful because of theirexcellent capacity to absorb free acids. Stabilizers of thesetypes should always be incorporated when ethylcellulose isused in hot-melts, in plastics, and in clear-film applications.

Additional studies show that compounds that absorb lightwaves in the range of 230 to 340 nm are effective stabilizersagainst light-catalyzed oxidation. A typical ultraviolet lightabsorber of this type is 2,4-dihydroxybenzophenone

(Uvinul 400).

Usually, the addition of one part of antioxidant or a blendwith equal parts of a light absorber or epoxy stabilizer foreach 100 parts of ethylcellulose is sufficient to obtain long-term ethylcellulose stability. Larger quantities of stabilizerresult in very small increased benefits, and as little as0.25 part will give marked improvement over unstabilizedethylcellulose compositions.

Stabilization studies in Aqualon laboratories have shown thatstabilizer activity is often dependent on the type of ethylcel-lulose composition. Some specific examples:

Hot-MeltsDiamyl phenol, 2,6-di-tert -butyl-para -cresol (BHT), and octylphenol are suitable antioxidants for a satisfactory compro-mise between color and viscosity retention. Diethyl oxalateand dibutyl tartrate give good results in hot-melts when usedprimarily as color stabilizers during formulation and applica-tion. An acid acceptor should be used with the antioxidant toabsorb acidic degradation products caused by the high pro-cessing temperature of the melt.

PlasticsStabilizers effective in hot-melts, such as diamyl and octylphenols, are also useful in plastics. Diamyl phenol demon-strates excellent stabilizing action in a heated ethylcellulosedisk test with respect to color and embrittlement.

Clear FilmsOutdoor exposures of clear ethylcellulose films show that acombination of antioxidant, light absorber, and acid acceptoris more effective than a single stabilizer. As antioxidants,Pentaphen 67 (para -tert -amylphenol), BHT (2,6-di-tert -butyl-para -cresol), and Antioxidant 2246 [2,3-methylene bis (4-methyl-6-tert -butyl) phenol] are effective. An example of alight absorber is 2,4-dihydroxybenzophenone. Useful acidacceptors are epoxy compounds used either as plasticizersor solely as stabilizers.

Some of the substituted phenols, such as diamyl phenol, areplasticizers as well as stabilizers, and can be used eitheralone or as a component of a mixed plasticizer. Likewise,some materials ordinarily considered as plasticizers have astabilizing effect. Some single or mixed plasticizers that havebeen found to contribute stability to ethylcellulose compo-sitions during outdoor exposure are listed in the order oftheir effectiveness:

1. Tricresyl phosphate with diamyl phenol, 70:30.2. Tricresyl phosphate with triphenyl phosphate, 70:30.3. Tricresyl phosphate with diphenyl phosphate, 70:30.4. Diamyl phenol.5. Diphenyl phosphate.6. Phenyl diglycol carbonate.

Most pigments protect ethylcellulose against degradation dur-ing outdoor exposure. In pigmented systems where addedstability is desired, antioxidants are more effective than ultravi-olet light absorbers, because light is excluded by the pigment.

SOLVENTS AND SOLUBILITY

Solubility ParametersSolubility parameters provide a convenient method for deter-mining the best solvent or solvent system for a film-formersuch as ethylcellulose.

The solubility parameter of a polymer can be establishedindirectly from the solubility parameter of solvents that dis-solve the polymer. Data on the solubility parameters ofAqualon ® ethylcellulose, for three classes of solvents, aregiven in Table V. Additional information can be found in CSL-204, Solubility Parameter Maps of Aqualon Film-Formers.

Effects of Ethoxyl ContentThe solubility of Aqualon ethylcellulose in organic solventsmerits careful consideration in its extensive application inlacquers and coating compositions. The effect of substitutionon solubility is illustrated by the data given in Table VI. It willbe seen from this data that there are relatively few singlesolvents for the lower substitution types. Solubility in allclasses of organic solvents improves with increased ethoxylcontent until an optimum level is reached within the rangeof substitution of the N-, T-, and X-types. Above this level ofsubstitution, solubility again becomes more restricted, beinglimited in the highest levels of substitution to highly nonpolarcompounds such as the aromatic hydrocarbons.



Solvents for N-TypeIt was pointed out that the variety of solvents for N-typeethylcellulose is unusually wide. The solubility of this type inorganic solvents is indicated in Table VII (page 17). It will beseen that the aliphatic or straight-chain hydrocarbon class isthe only one having essentially no solvent power to dissolveN-type ethylcellulose. This wide range of solvents greatly sim-plifies the task of selecting solvents for specific applications.

A comparison of the solubility of ethylcellulose, N22 type,with RS nitrocellulose, 1/2-sec, is given in Table VIII (page 18).

Effects of AlcoholsAlthough there are special uses that may require singlesolvents, for general use, they are inadvisable. Almost allketone, ester, and hydrocarbon solvents for ethylcellulose

can be greatly improved by mixing them with relatively smallquantities of the lower aliphatic alcohols such as ethanol orbutanol. Such binary mixtures are much better solvents forethylcellulose than is either component alone, and they haveseveral advantages.

These binary solvents will completely dissolve a much widerrange of substitution types of ethylcellulose than will singlesolvents. For example, toluene alone is a good solvent onlyfor the range of substitution covered by the T-type. However,N-type, although soluble, does not always form a good solu-tion in toluene alone, as evidenced by the fact that it is diffi-cult to duplicate the viscosity in successive solutions of thesame concentration, indicating incipient gel formation.

Low degree of substitution types are poorly soluble in toluene

alone. But a solvent combination of 80:20 toluene:ethanolwill completely dissolve all substitutions from 43.4% to 50%.In general, the quantity of alcohol required with the esters,ketones, and hydrocarbons to make good binary solventsincreases as the degree of substitution becomes lower. Forexample, 90:10 toluene:ethanol is a good solvent for theN-type, but to obtain comparable results with the K-type andits ethoxyl content of 46.1%, one would need a ratio of 70:30toluene:ethanol.

The alcohols are especially valuable in improving the solventpower of the so-called “toluene substitutes”—proprietaryproducts derived in many cases by catalytic dehydrogena-tion of naphthenes and cyclicized hydrocarbons. They arecharacterized by having kauri-butanol values between 40and 70, and alone show considerably poorer solvency for

ethylcellulose than do the aromatic hydrocarbons suchas toluene and xylene. However, the toluene substitutesbecome excellent solvents for all substitution types of ethyl-cellulose when they are mixed in a ratio of 70:30 toluenesubstitute:ethanol. Some are better solvents than others; ingeneral, the higher the kauri-butanol value, the less ethanolis required to obtain good solvency. Butanol is somewhatless effective than ethanol in these binary mixtures, which isreflected by the fact that viscosities at a given concentrationare higher.



Marked reduction in solution viscosity is another advantageto be gained by using a binary solvent mixture in which oneof the lower aliphatic alcohols is a constituent of the solventmixture. This is brought out clearly by the curves in Figure 8.

An evident advantage to be derived from use of a mixedsolvent is the possibility of obtaining more concentratedsolutions without encountering objectionable gelation orgranulation. Control of viscosity in such binary solvents is mucheasier because the solutions are less sensitive to smallchanges in concentration or temperature. Other advantagesto be gained by using binary solvents containing an alcoholare improved clarity of solution, freedom from the granula-tion or gelation encountered when poor or lean solvents areused, and improved tolerance for petroleum thinners.

Dilution With Petroleum ThinnersThe tolerance of ethylcellulose solutions for dilution withnonsolvent petroleum thinners is unusually good; it becomes

progressively better with increased ethoxyl content. Suchdilution, however, is affected not only by the potency of theactive solvent being diluted but also by the degree of substi-tution of the ethylcellulose. A poor or lean solvent will obvi-

ously tolerate less dilution than a rich or active solvent. TableIX (page 18) shows the effect of substitution on dilution withVM&P naphtha of the 70:10 toluene:ethanol solvent mixture.

Rule 422—Exempt SolventsSince N-type and T-type ethylcellulose have a high tolerancefor alcohols and aliphatic hydrocarbons, the formulation ofexempt lacquers and inks generally presents no seriousproblems. Suggested approaches can be found in CSL-204,Solubility Parameter Maps for Aqualon Film-Formers.Suggested acceptable solvent blends can be foundin CSL-173.

15

Class I Class II Class III(Weakly Hydrogen-Bonded) (Moderately Hydrogen-Bonded) (Strongly Hydrogen-Bonded)

Range Midpoint Range Midpoint Range Midpoint

Aqualon ®

K100 ethylcellulose Insoluble 8.5-10.8 9.6 9.5-11.4 10.4

Aqualon

N22 ethylcellulose 8.1-11.1 9.6 7.4-11.0 9.2 9.5-14.5 12.0

Aqualon

T10 ethylcellulose 8.5-9.5 9.0 7.8-9.8 8.8 9.5-11.4 10.4

TABLE V —SOLUBILITY PARAMETERS

Relative Solubility

Solvent Used K-Type N-Type T-Type X-Type

Toulene g s cs cs cs

Xylene g i cs cs cs

80:20 Toluene:Alcohol cs cs cs cs

Ethyl acetate vhs vhs vhs vhs

Butyl acetate g s vhs vhs vhs

Acetone i vhs vhs vhs

Methanol vhs hs i i

Ethanol hs hs hs hs

Butanol i hs hs hs

Isopropanol (91% by volume) hs hs hs hs

Ethylene glycol monobutyl ether g s — i i

Ethylene dichloride hs cs cs cs

Carbon tetrachloride g cs cs cs

Methylene chloride cs cs cs cs

Key: c = clear; g = gelled mass; h = hazy; i = insoluble, although some particles might be gelled; s = solution; v = very.

(1)Each test was made at 15% concentration, by weight, of ethylcellulose in the solvent.

TABLE VI —SOLUBILITY OF ETHYLCELLULOSE (EFFECTS OF ETHOXYL SUBSTITUTION(1)

)



Economy Through Solvent ChoiceMany ethylcellulose solvent mixtures are relatively inexpen-sive —for example, mixtures of aromatic hydrocarbons withethanol and mixtures of the toluene substitutes with ethanol.These mixtures can be made even more economical by dilu-tion with heptane, VM&P naphtha, or some other petroleumthinner, using the appropriate boiling range. The degree towhich such dilution can be practiced with true economy willvary with the concentration of the solution to be diluted.

The viscosity data in Figure 9 illustrate graphically theeffects of solvent composition.

Curve 2 in Figure 9 shows that substituting heptane for33.3% of the toluene in Formula 1 solvent is real economybecause there has been no appreciable change in viscosity,

and solvent cost is appreciably lower. On the other hand,substitution of heptane for 50% of the alcohol present inFormula 1 solvent (Curve 3, Figure 9) or for 50% of the alco-hol plus 33.3% of the toluene in Formula 1 solvent (Curve 4,Figure 9), or for 66.7% of the toluene (Curve 5, Figure 9)results in a marked increase in the viscosity with a neces-sary lower solids content at any viscosity level, and withouta probably sufficient compensating saving in cost over theFormula 2 solvent (Curve 2, Figure 9) to represent any realeconomy. It can be stated, therefore, that dilution with apetroleum thinner can be practiced with real economy bysubstituting it for a limited quantity of the aromatic hydro-carbon, but not for the alcohol, in a binary solvent.

16

FIGURE 8

ALCOHOL-TOLUENE VISCOSITY CURVES(5 G OF ETHYLCELLULOSE N-22 IN

95 G SOLVENT)

150140130120110100908070605040

3020100100 80 60 40 30 20 10 0

Toluene, %

V i s c o s i t y

o n H o r i z o n t a l V i s c o m e t e r , s e c

tert -Butyl alcohol-toluene

Methanol-toluene

When ethylcellulose is dissolved in a binary solvent system composed ofone of the lower alcohols in the proper amount and an aromatic hydrocar-bon, viscosity of the solution is greatly lowered, allowing better viscositycontrol and the use of more concentrated solutions.

FIGURE 9EFFECTS OF SOLVENT COMPOSITION(m)

10,000

1,000

100

10

120 30 40

Aqualon® N-7 Ethylcellulose, wt%

V i s c o s i t y ( S t o r m e r V i s c o m e t e r ) a

t 2 5 ° C , p o i s e s

5

4

3

2

1

Solvent Formulas1. 60:40 Toluene:Ethanol2. 40:40:20 Toluene:Ethanol:Heptane3. 60:20:20 Toluene:Ethanol:Heptane4. 40:20:40 Toluene:Ethanol:Heptane5. 20:40:40 Toluene:Ethanol:Heptane

(m)In solvent formulas for ethylcellulose coating compositions, part of thetoluene (up to 331 ⁄ 3%, but not as much as 662 ⁄ 3%) can be replaced by hep-tane without causing any appreciable increase in viscosity; similar replace-ment of the alcohol by heptane causes a much greater viscosity increase(Curves 1, 4, and 5).



Solvents Solubility

AlcoholsMethanol sEthanol sPropanol sIsopropanol swButanol sAmyl alcohol sCyclohexanol psBenzyl alcohol sDiacetone alcohol sw

Chlorinated HydrocarbonsMethylene chloride sChloroform sCarbon tetrachloride sEthylene dichloride sTrichloroethylene psPentachloroethane s

EstersMethyl acetate sEthyl acetate sPropyl acetate sIsopropyl acetate sButyl acetate sAmyl acetate sMethyl Cellosolve acetate s

Cellosolve acetate sGlycol diacetate psBenzyl acetate sCyclohexyl acetate psMethyl formate sEthyl formate sEthyl lactate sButyl lactate s

EthersEthyl ether sMethyl Cellosolve psCellosolve sButyl Cellosolve sCarbitol sw

Key: i = insoluble; ps = partly soluble, but contains gel and granula-tion; s = soluble (films obtained from these solutions were clear,although some might appear slightly hazy to others); sw =swollen, but granules not merged into cohesive gel.

(n)These solvent mixtures are the most generally useful because theycombine good clarity with low viscosity and are economical.

Solvents Solubility

HydrocarbonsToluene sXylene sHi-Flash naphtha psCyclohexane psTetralin sDipentene No. 122 ® psTurpentine swAromatic petroleum distillates —

dehydrogenated naphthenes and

cyclicized hydrocarbons psPetroleum ether iHexane iVM&P naphtha iVarsol i

KetonesAcetone sMethyl ethyl ketone sDipropyl ketone psHexone sCyclohexanone sMethyl cyclohexanone s

Miscellaneous SolventsDichloroethyl ether psDioxane s

Pine oil sMixed Solvents80:20 Toluene:ethanol(n) s80:20 Xylene-butanol(n) s662 ⁄ 3:331 ⁄ 3 Ether:ethanol s15:1 Ethanol:camphor s70:30 Turpentine:butanol s70:30 Dipentene No. 122 to butanol s70:30 Aromatic petroleum distillates

(dehydrogenated naphthenes andcyclicized hydrocarbons:butanol) s

Nitroparaffins1-Nitropropane s2-Nitropropane sNitroethane ps

Nitromethane i

TABLE VII —SOLUBILITY OF N-TYPE ETHYLCELLULOSE IN REPRESENTATIVE ORGANIC SOLVENTS(15 G ETHYLCELLULOSE IN 85 ML SOLVENT)

17



N22 RS Nitrocellulose,Solvents Ethylcellulose 1/2-sec

Methanol s sEthanol s iButanol s iCyclohexanol ps iDiacetone alcohol sw s

Methylene chloride s iEthylene dichloride s iChloroform s i

Carbon tetrachloride s iPentachloroethane s i

Methyl acetate s sEthyl acetate s sButyl acetate s sEthyl lactate s sButyl lactate s sMethyl Cellosolve

acetate s sCellosolve acetate s s

N22 RS Nitrocellulose,Solvents Ethylcellulose 1/2-sec

Ethyl ether s trDioxane s sMethyl Cellosolve s sCellosolve s s

Toluene s iXylene s iDipentene No. 122 ® ps iTurpentine sw i

Hexane i iVM&P naphtha i i

Acetone s sMethyl ethyl ketone s sCyclohexanone s s

1:15 Camphor:ethanol s s2:1 Ethyl

ether:ethanol s s80:20 Toluene:ethanol s i70:30 Xylene:ethanol s i90:10 Methylene

chloride:ethanol s i90:10 Ethylene

dichloride:ethanol s i

TABLE VIII —SOLUBILITY OF AQUALON ® N22 ETHYLCELLULOSE —COMPARISON WITH

RS NITROCELLULOSE, 1/2-SEC

Key: i = insoluble; ps = partly soluble, but contains gel and granulation; s = soluble; sw = swollen, but granules not merged into cohesive gel; tr = particlesbecome translucent, but not swollen.

Solubility

Solvent N-Type T-Type X-Type

Toluene:ethanol:

VM&P naphtha7:3:90 swollen swollen swollen14:6:80 swollen v. sl. hazy partly soluble

21:9:70 sl. hazy v. sl. hazy v. sl. hazy28:12:60 sl. hazy v. sl. hazy v. sl. hazy49:21:30 v. sl. hazy clear clear

63:27:10 clear clear clear

TABLE IX —TOLERANCE OF LOW-VISCOSITY ETHYLCELLULOSE FOR

PETROLEUM THINNERS (EFFECT OF ETHOXYL SUBSTITUTION)



Figure 10 shows that raising the temperature of applicationgreatly reduces viscosity, thus allowing correspondinglyincreased solids concentration at any given viscosity level.There are many applications where this principle can bepracticed with real economy.

Effects of Solvent Composition on Film PropertiesThe physical properties of ethylcellulose films depend some-what on the composition of the solvent from which they aredeposited. Care must be exercised, therefore, in properselection of solvents to ensure the preparation of strong,flexible films. In general, flexible films of maximum tensilestrength are obtained when nonpolar solvents such astoluene or xylene (which have no affinity for water) or butylacetate or methyl isobutyl ketone (which have little affinityfor water) constitute a major portion of the solvent at themoment the film sets to a gel. Brittle films with relativelypoorer tensile strength usually result when polar solventssuch as acetone or alcohol, which are miscible with water inall proportions, are present in major amounts at the momentof gelation.

FIGURE 10TEMPERATURE AND VISCOSITY(o)

20 30 40

Solvent – 60:40 Toluene:Ethanol

25°C

35°C

Aqualon® N7 Ethylcellulose, wt%

V i s c o s i t y ( S t o r m e r V i s c o m e t e r ) a t 2 5 ° C , p o i s e s

10,000

1,000

10

1

50°C

(o)The viscosity of an ethylcellulose solution is lowered by an increase in itstemperature. This allows the application, at the higher temperature, of amore concentrated solution at a given viscosity.



Figure 11 illustrates the effects on tensile strength and flexi-bility when highly nonpolar solvents are used. It is clearlyevident from these graphs that a suitable solvent mixtureshould contain not more than about 30-40% of a low-boiling,water-miscible solvent such as ethanol or acetone. Theremainder should consist of solvents such as xylene,toluene, toluene substitute, butyl acetate, or butanol. Waterin relatively small amounts in a solvent mixture is known tohave a pronounced effect on the physical properties of films.This water either may be present in the solvent initially ormay be introduced into the film solution by condensationbrought about by the rapid rate of cooling during thedrying period.

The foregoing discussion has been based on the suppositionthat most applications are carried out under ordinary atmos-pheric conditions where no control of relative humidity isexercised. It should be pointed out that strong, flexible filmscan be obtained from any good solvent mixture, even thoughthey are composed wholly of water-miscible solvents, pro-vided care is taken to use anhydrous solvents and to controlthe moisture content of the air and the rate of evaporation.This requires special drying rooms or cabinets equipped withair-conditioning apparatus.

20

FIGURE 11EFFECT OF SOLVENT SYSTEM ON FLEXIBILITY AND STRENGTH OF ETHYLCELLULOSE FILM

1,000

800

600

400

200

0

8,000

7,000

6,000

5,000

4,000

8,000

7,000

6,000

5,000

4,000

1,000

800

600

400

200

0100 80 60 40 20 80 60 40 20 80 60 40 20 0

0 20 40 60 80 20 40 60 80 20 40 60 80 100

Butanol Ethanol Ethanol

0 20 40 60 80 20 40 60 80 20 40 60 80 100

Butanol Ethanol Ethanol

Xylene Toluene Acetone

100 80 60 40 20 80 60 40 20 80 60 40 20

Xylene Toluene Acetone

M I T F o l d

i n g E n d u r a n c e

T e n s i l e S t r e n g t h

T e n s i l e S t r e n g t h

M I T F o l d

i n g E n d u r a n c e

The charts illustrate how the flexibility and tensile strength of ethylcellulose film can be affected by the composition of the solvent system from which the film is cast.Best films are generally obtained when the major part of the solvent is nonpolar at the moment the film sets to a gel.



Gasoline ResistanceThere are special uses for ethylcellulose compositions wherewide solubility in solvents and great tolerance for diluentsare not advantageous properties. One such use is in coat-ings for automotive and aviation ignition cables, where gaso-line resistance is an important requisite. Aviation engines, inparticular, are frequently washed with high-test gasoline con-taining an appreciable amount of aromatic hydrocarbons.Reference to Table X shows that resistant compositions forthis use can be prepared best by resorting to the use of thelower-substitution K-type ethylcellulose (which shows thelowest solubility in aromatic hydrocarbons and tolerates theleast dilution with petroleum thinners) and compounding itwith gasoline-resistant plasticizers.

Many situations arise where special conditions must be met.

Shown here is one such situation (the need for gasolineresistance), which was handled by making use of the specialproperties peculiar to one type of ethylcellulose. Other situa-tions calling for special properties can also be facilitated bybecoming familiar with the properties of ethylcellulose dis-cussed in this booklet.

RESINS

Resins are used as modifying agents in ethylcellulose com-positions for many applications. In coating compositions,they impart hardness, gloss, adhesion, and improved waterresistance. In plastics, they impart hardness, improved waterresistance, and, in some cases, better dimensional stability.

Conversely, ethylcellulose diminishes tack and impartstoughness to resins. Such beneficial effects, however,are obtained only when the resin is compatible withthe ethylcellulose.

Effects of Ethoxyl ContentIt is seen from Table XI that N-type ethylcellulose, with asubstitution of 48.0-49.5% ethoxyl content, is compatiblewith more classes of resins than is any other substitutionrange. Compatibility becomes more restricted with bothlower and higher substitution types. These data show thatAqualon ® ethylcellulose of all substitution types is compatiblewith rosin (which is made up largely of isomeric resin acids)and Paraplex RG-2. It is further apparent that there are com-patible resin types for all ethylcellulose types, from K throughX, thus simplifying the task of the formulator.

Compatibility With N-Type EthylcelluloseSince N-type ethylcellulose is more generally used than areother types, compatibility data with a majority of the availablelacquer resins have been obtained with this type. Table XII A.

(page 23) lists resins that have been found to give clearfilms with this type in all proportions, up to and including1:1 resin:ethylcellulose.

Some partially compatible resins produce clear films withethylcellulose in proportions up to and including 0.3-0.5:1resin:ethylcellulose. In higher proportions of resin, incompati-bility develops. Table XII B. (page 23) lists resins with suchlimited compatibility.

In Table XII C. (page 23) are listed resins that failed to giveclear films with ethylcellulose in any proportion tested.

Table XII data show that N-type ethylcellulose is generallycompatible with resin acids and the glycerol, glycol, anddiethylene glycol esters of resin acids; with varnish-type pure

phenolics of both the oil-soluble and oil-reactive classes;with rosin-modified phenolics; with many natural resins, sev-eral of which were compatible only after heat treatment orother special treatment such as dewaxing; and with toluene-sulfonamide-formaldehyde resins.

21

Condition of Film(p) After 72-hr

Types of Ethylcellulose Plasticizer Immersion in Test Solvent

1. K100 (46.1-47.2% ethoxyl) None Slight curl

2. N100 (48.0-49.5% ethoxyl) None Softened

3. T100 (49.6-51.5% ethoxyl) None Gelled and partly dissolved

4. K100 Paraplex RG-2 Badly curled

5. K100 Baker’s Pale No. 16 castor oil Soft, curl

6. K100 Dimethoxyethyl phthalate Soft, curl, exudation

(p)Film: 60 parts ethylcellulose to 40 parts plasticizer; tests were made in a solvent composed of 60 parts 100-octane gasoline, 5 parts benzene, 15 partsxylene, and 20 parts toluene.

TABLE X —GASOLINE RESISTANCE OF ETHYLCELLULOSE FILMS



N-type ethylcellulose shows restricted compatibility withmaleic-modified rosin esters; urea-formaldehyde resins;coumarone-indene resins; alkyds modified with phenolics,rosin, or oils; cycloparaffins; and zinc resinates. This re-stricted compatibility is usually controlled by the degree ofresin modification. For instance, compatibility becomes morerestricted as the percentage of maleate is increased, as themelting point of the coumarone-indene resins increases, andwith increased zinc content in the zinc resinate. Compatibilitywith modified alkyds becomes less restricted with increasedoil or fatty acid modification, or with increased phenolic orrosin modification.

N-type ethylcellulose is incompatible in all proportions withall pure alkyds based on glycerol phthalate, and short oilmodifications of such alkyds, acrylates and methacrylates,polystyrene, polyisobutylenes, and vinyl acetate resins.

With some specific resins of borderline compatibility, theremay be inconsistencies in compatibility data, depending onminor variations in the resin from lot to lot or other factorsnot strictly controlled. Consequently, it is possible that otherinvestigators may find discrepancies between their resultsand those reported here. However, the table gives an accu-rate idea of the kinds of resins that are compatible or incom-patible with ethylcellulose.

Note that many resins normally incompatible with ethylcellu-lose alone can be usefully incorporated into compositionscontaining ethylcellulose by employing a mutually compatiblethird ingredient to prevent separation, with its resultant dull-ness or haze. Solvent plasticizers often serve in this capac-

ity. Cellulose nitrate is also effective.

Compatibility With K-Type EthylcelluloseK-type ethylcellulose is used in both plastics and protectivecoatings because of such special properties as its highermelting point, special molding characteristics, and restrictedsolubility and compatibility. It is interesting, therefore, to con-sider the resins that can be used to modify this type of ethyl-cellulose. Table XIII (page 24) gives a list of resins that arecompatible in all proportions, up to and including 1:1resin:K-type ethylcellulose.

Many urea-formaldehyde and melamine resins show arestricted compatibility with K-type ethylcellulose, but are ofinterest within their limited sphere of compatibility becausethey are colorless resins and because they possess ther-mosetting characteristics.

The list of resins in Table XIII is incomplete because many ofthe resins listed in Table XII are compatible in ethylcellulose,K-type as well as N-type.

PLASTICIZERS

Ethylcellulose alone yields very tough films of excellent ten-sile strength, flexibility, and elongation characteristics; yetsuch films lack suppleness. Also, ethylcellulose alone soft-ens and flows at too high a temperature to be practical inmolding operations or in other applications requiring goodthermoplasticity. Therefore, plasticizing or softening agentsare added to ethylcellulose to obtain the proper degreeof suppleness, to lower the softening point, and toimprove thermoplasticity.

Compatibility Data for Different Types of Ethylcellulose

Resin(q) K-Type N-Type T-Type X-Type

Ester gum 80 i c c c

Wood rosin c c c c

Dewaxed dammar c c c c

Aroplaz 1351 c c i i

Paraplex RG-2 c c i i

Key: c = compatible; i = incompatible.

(q)Each resin listed is representative of a general class. Ratio: 1:1 ethylcellulose:resin.

TABLE XI —ETHYLCELLULOSE-RESIN COMPATIBILITY —EFFECTS OF ETHOXYL SUBSTITUTION



NaturalBatu, runCongo, runDammar, dewaxed BataviaElemiKauriManila gum, all gradesMastic gumPontianak, run, mixed boldRosin, woodSandaracShellac, dewaxedVinsol ®

AlkydAroplaz 1271Paraplex RG-2, RG-8

Coumarone-IndeneCumar P10, R28

Phenolic ResinsSuper-Beckacite 1001

Rosin- and Terpene-BaseAbalyn ®

Abitol ® ECellolyn ® 21, 102MEster gum 8DHercolyn ® DLewisol ® 28Pentalyn ® A, H, 830, 856Pentrex ® 28Poly-pale ® 10 esterPoly-pale resinStaybelite ®

Staybelite 3, 10 esterVinsol ® ester gumZinarZirexZitro

MiscellaneousOrlonPiccolastic ® A-5

23

TABLE XII —COMPATIBILITY OF RESINS WITH N-TYPE ETHYLCELLULOSE

A. Resins Compatible In All Proportions Up to 1:1 Resin:Ethylcellulose

NaturalWhite shellac

Coumarone-IndeneCumar R-3, R-11

Rosin- and Terpene-BaseUni-Rez 7200

MiscellaneousChlorowax 70(r)

B. Resins Compatible In All Proportions Up to 0.3-0.5:1 Resin:Ethylcellulose

(r)This resin is compatible at 1:10 resin:ethylcellulose.

NaturalAccroidesCongo Ester No. 10

East India Macassar, paleEast India Singapore, paleOrange shellac

AlkydBeckosol 12-021Paraplex G-20

Rosin BaseUni-Rez 7200Metalyn ®

Pentalyn ® G, K

Urea- and Melamine-FormaldehydeBeckamine 21-510Resimene

Uformite MM-55

MiscellaneousAcryloid C10LV, F10, B72Dow Corning Fluid 200Epon 1004KeltrolVinylite VAGH

C. Resins Incompatible Even at Ratios as Low as 1:10 Resin:Ethylcellulose



The variety of plasticizing agents for ethylcellulose is unusu-ally large, and includes, with two exceptions, all classes ofcompounds that have been offered as softening or flexibil-izing agents for coatings or plastics. The two exceptionscomprise the heat-bodied vegetable oils and the highlyunsaturated drying oils such as tung, perilla, andoiticica oils.

Table XIV lists a large number of plasticizing agents compat-ible with ethylcellulose. Note that the fatty acids derived fromincompatible oils are compatible with ethylcellulose. In gen-eral, it has been observed that air-bodying an oil improvesits compatibility over that exhibited by the raw oil.

Practically all of the compounds listed can be used withall substitution types of ethylcellulose, from K-type through

T-type. Both vegetable and mineral oils, however, show amore marked tendency to exude from compositions basedon the lower-substitution K-type; also, solid plasticizers, suchas triphenyl phosphate, tend to crystallize from ethylcelluloseplastics if used in an excessive proportion: they show agreater tendency to crystallize from K-type compositionsthan from the other ethylcellulose types.

Tests for compatibility were made by preparing solutionscontaining both ethylcellulose and plasticizer, makingflowouts of the solutions on glass plates, drying them, andexamining the dry films. Strangely enough, in spite of itswide compatibility, ethylcellulose is actually insoluble at roomtemperature in almost all plasticizers. For example, if pow-dered ethylcellulose is added to a liquid plasticizer such asdioctyl phthalate, the particles do not even become swollen

at room temperature; at 100°C, a solution is formed and theethylcellulose remains in solution when the composition iscooled. In commercial practice, ethylcellulose compositionsare always compounded by a solvent process or by hot-milling or hot-melt procedures. This unusual property of widecompatibility, along with very limited room-temperature solu-bility, may explain why ethylcellulose lacquers and plasticsare much more resistant to oils and greases, to plasticizermigration, and to contaminating influences generally thanone would expect.

Ethylcellulose is somewhat softer than nitrocellulose and cel-lulose acetate, and therefore requires proportionately lessplasticizer than either of these to attain the desired degreeof softening for any particular purpose. Both cellulose

acetate and nitrocellulose plastics normally require from30-35% plasticizer by weight for most plastics applications.Ethylcellulose plastics, on the other hand, normally requireonly 15-20% plasticizer to obtain comparable hardness.Nitrocellulose lacquers frequently contain as much as onepart plasticizer to two parts nitrocellulose. Ethylcellulose lac-quers seldom contain more than one part plasticizer to fourparts ethylcellulose at comparable hardness.

TABLE XIV —PLASTICIZERS FOUND COMPATIBLE

WITH ETHYLCELLULOSE

Resins compatible in all proportions,up to 1:1 resin:ethylcellulose

Boea, run Wood rosinCellolyn ® 102M(s) Zitro resinParaplex RG-2

(s)Completely compatible in all proportions, up to 0.3-0.5:1resin:ethylcellulose.

TABLE XIII —COMPATIBILITY OF RESINSWITH K-TYPE ETHYLCELLULOSE

Phosphate EstersTricresyl phosphateTriethyl phosphateTriphenyl phosphate

Phthalate EstersBenzyl methyl phthalateCyclohexyl butyl phthalateCyclohexyl ethyl phthalateCyclohexyl methyl phthalateDiamyl phthalateDibutyl phthalateDicapryl phthalateDicyclohexyl phthalateDiethyl phthalateDiisobutyl carbinyl phthalateDiisopropyl phthalate

Dimethyl phthalateDinonyl phthalateDioctyl phthalateDiphenyl phthalate(t)

Diethoxyethyl phthalateDibutoxyethyl phthalateDimethoxyethyl phthalate

Miscellaneous EstersAbalyn ® methyl abietateAcetyl tributyl citrateAcetyl triethyl citrateMonoplex DIOA (diisooctyl adipate)Amyl oleateFlexricin P-3 (butyl ricinoleate)Benzyl benzoateButyl and glycol esters of fatty acids

Butyl diglycol carbonateButyl oleateButyl stearateDi(β-methoxyethyl) adipateDibutyl sebacateDibutyl tartrateDiisobutyl adipateDihexyl adipateFlexol 3GH [triethylene glycol di(2-ethyl butyrate)]Tegmer 804 [polyethylene glycol di(2-ethyl hexoate)]Hercoflex ® 600 monomeric PE esterHercolyn ® D hydrogenated methyl ester of rosinMethoxyethyl oleateButoxyethyl stearate

(t)Solid plasticizers that exhibit a tendency to crystallize from the filmwhen they are used as the sole plasticizing agent.



TABLE XIV —PLASTICIZERS FOUND COMPATIBLE WITHETHYLCELLULOSE (CONTINUED)

Table XV gives evaluation data for a number of plasticizer-ethylcellulose compositions. The compositions consisted ofone part plasticizer to four parts ethylcellulose, with twoethoxyl types of ethylcellulose, N100 and K100, beingtested. Tensile strength, elongation, and flex life were mea-sured for 5-mil films of each composition.

Water-Sensitive PlasticizersEthylcellulose has been tested and found compatible witha number of materials that were not included in Table XIVbecause their excessive water sensitivity detracts from theirgeneral usefulness. These materials include triethyl citrate,glyceryl triacetate, glyceryl diacetate, triethylaconitate, triethylcarballylate, and a number of partially esterified glycol, diethyl-ene glycol, and glycerol compounds made with the higher fattyacids. Examples of the latter compounds are ethylene glycolmono-ricinoleate, -laurate, -oleate, and -stearate; and glycerylmono- and di-ricinoleates, -laurates, -oleates, and -stearates.These are mentioned because there may be special useswhere such water-sensitive softening agents could be useful.

Oils as Ethylcellulose PlasticizersThe oils, both mineral and vegetable, are relatively inexpen-sive plasticizing agents, and can play a unique and impor-tant part in the plasticization of ethylcellulose. Unlike thehigh-boiling solvent esters, they possess very little activesolvent action for ethylcellulose unless heated to tempera-tures approaching the softening point of ethylcellulose. Theoils possess much less softening action on the ethylcellulosethan do the more active high-boiling esters, and they can beused in the development of compositions requiring a degreeof toughness not possible with the high-boiling estersbecause of their excessive softening action.

Refined mineral oil can be cited as one example. It is usedextensively either as the sole plasticizer or as an importantconstituent of plasticizer blends in the preparation of extru-sion and injection plastics where low water resistance, good

dimensional stability under adverse temperature and humid-ity conditions, and low-temperature toughness and flexibilityare important requisites. Mineral oils of refined and lubricat-ing grades can be used in amounts up to about 20-23% byweight in an ethylcellulose composition without excessiveexudation being encountered at ordinary temperatures.

Castor oil is unique among the vegetable oils compatible withethylcellulose in that it does not exude from compositions evenwhen it is present in proportions as high as equal parts of oiland ethylcellulose. All of the other vegetable oils exude whenpresent in such high proportions (1:1 ratio). This tendency toexude is lessened somewhat if the oil is air-blown. Oil blendscontaining castor oil, Hercolyn ® D hydrogenated ester of rosin, orone of the chemical esters as a component of the blend alsohave a reduced tendency to exude. However, vegetable oils,

such as corn, soybean, cottonseed, and linseed, can be incor-porated into ethylcellulose compositions up to 30-40% by weightbefore objectionable exudation is encountered. Linseed and soy-bean oils exude less readily than do corn and cottonseed oils.

It is appropriate at this point to call attention to the toughen-ing type of plasticizers. In addition to the vegetable oils, thesebacic acid type of alkyd resins and very long oil-extendedalkyds impart suppleness to ethylcellulose plastics with aminimum effect on softening point and toughness. Variousmixtures of the vegetable oils with these alkyd resins canalso serve as valuable toughening plasticizers that can beused in proportions as high as 50% by weight of the plasticwithout exudation or stickiness. Such compositions form thebasis for cable coatings and calendered coatings.

Miscellaneous Esters (Continued)Tributyrin (glycerol tributyrate)Triethylene glycol dipelargonatebeta-(p-tert- amylphenoxy) ethanolbeta-(p-tert- butylphenoxy) ethanolbeta-(p-tert- butylphenoxyethyl) acetateBis(β-p-tert- butylphenoxydiethyl) etherCamphorCumar R-3, R-14Diamyl phthalate(Diamylphenoxyl) ethanolDiphenyl oxide

Amides

Bis(dibutyl) adipamideDibutyllauramideDiethyldiphenylurea

Mineral OilsDutrex 25Gloria white mineral oilLubricating oil, practically all gradesMineral oils, refinedNecton 45Nujol

Fatty AcidsLinseedOleicRicinoleicStearic

Tung and many others

Fatty AlcoholsCetylMyristylStearyl and others

Vegetable OilsBlown castor oil, Baker’s No. 15 and 30, and Pale 4, 16, 1000Castor oil, rawCorn oil, raw and air-blownCottonseed oil, raw and air-blownLinseed oil, raw and air-blownSoybean oil, raw and air-blown

Miscellaneous TypesAbitol ® E technical hydroabietyl alcoholBeckolin

Chlorinated paraffin, 40% chlorine contentPiccolastic ® A-5Glycerol alpha -methyl alpha -phenyl etherHalowax 1013 (chlorinated naphthalene)HB-40MonoamylphthalateNevillac 10o -Nitrodiphenyl



Acetyl triethyl citrate

Baker’s Pale No. 16

Benzyl ether of glycerol

Dimethyl phthalate

Diphenyl phthalate

PhosFlex CEF [tri(beta -chloroethyl) phosphate]

Dimethoxyethyl phthalate

Paraplex RG-2 (sebacic alkyd)

Triacetin (glycerol triacetate)

Triethyl citrate

With the exception of castor oil, all of the compatible veg-etable oils form rigid gels with relatively minor amounts (3-5% by weight) of ethylcellulose. Such gels are prepared ashot-melt mixtures by dissolving the ethylcellulose in the oil atabout 180° to 200°C and then permitting the mixture to coolto room temperature.

Gasoline- and Oil-Resistant PlasticizersEarlier in this booklet (page 21), the subject of gasolineresistance was dealt with in showing how certain problemscould be met by employing special formulations. Table XVIlists a somewhat more inclusive group of plasticizers resis-tant to petroleum hydrocarbons and oils.

The number of plasticizing agents possessing these specialproperties is sufficiently extensive so that the formulator hasa relatively wide latitude of choice in developing suitable for-mulations for resistance to petroleum hydrocarbons and oils.The proper selection of ethylcellulose for such use should bemade from the lower-substitution K-types.

N100 Ethylcellulose

Tensile

MIT Flex, Strength, Elongation,

Plasticizer Double Folds lbs/in.2 %

Dibutyl phthalate 2,000 5,500 45

Tegmer 804 1,400 5,000 50

Raw castor oil 1,200 6,700 42

Tricresyl phosphate 980 6,400 38

Aroplaz 1351 910 5,850 66

Diamyl phthalate 880 6,400 42

Paraplex RG-2 600 7,150 37

Baker’s Pale No. 16 600 6,700 35

Diisobutyl carbinyl phthalate 560 6,400 37

HB-40 520 7,200 32

beta -(p-tert -butylphenoxy) ethanol 430 6,950 38

Dutrex 25 400 6,800 26

Diphenyl phthalate 400 6,200 39

Pentaphen 360 7,850 27

Butyl diglycol carbonate 145 2,650 13

Piccolastic ® A-5 110 8,200 19

Butoxyethyl stearate 105 2,700 19

TABLE XV —EVALUATION OF PLASTICIZERS IN ETHYLCELLULOSE FILMS (APPROXIMATELY 5 MILS THICK —1:4 PLASTICIZER:ETHYLCELLULOSE)

TABLE XVI —ETHYLCELLULOSE PLASTICIZERS

INSOLUBLE IN PETROLEUM

HYDROCARBONS AND OILS



SPECIFIC APPLICATIONS

Experience has shown that ethylcellulose can be used inmany ways. A large and growing accumulation of data inAqualon laboratories points the way to numerous specificuses, and those who have tested ethylcellulose are continu-ally finding new applications.

The following brief notes are intended to aid potential usersin more definitely determining where and how ethylcellulosecan fit their needs.

LACQUERS

Satisfactory formulation of ethylcellulose lacquers and theirgood performance depend largely on selection of the properkind and proportion of modifying agents to meet the require-ments of each case.

Ethylcellulose has been found to yield lacquers of excellenttoughness and flexibility. These properties are retained overa temperature range extending from low to high. Ethylcellu-lose lacquers, for example, can be formulated to be unusu-ally resistant to cold-checking. Furthermore, they can beformulated to retain their color extremely well on exposureto sunlight.

Tests and experience indicate that properly formulated ethyl-cellulose lacquers are as durable as conventional nitrocellu-lose lacquers, and their specific properties make them adesirable choice for use over metal, wood, leather, and rubber.

In general, the solvent system for ethylcellulose lacquersconsists of 80% aromatic hydrocarbons and 20% alcohols.

The hydrocarbon portion is composed of toluene and xyleneor mixtures of these two materials; the remainder is com-posed of ethanol, isopropanol, and butanol or mixtures ofthese alcohols.

For some coatings applications, such as those on asphalttile and polystyrene plastics, it is necessary to use specialsolvent combinations instead of the cited mixtures. Thesespecial solvent compositions may give higher viscosities andsomewhat hazy solutions, but the lacquers dry to clear filmsand can be used without difficulty if the lower solids neces-sary with these solvents can be tolerated.

Examples of the varied uses of ethylcellulose lacquers areas follows:

Hard Lacquers for Rigid SurfacesSuch lacquers will give satisfactory service where a tough,crack-resistant coating is desired on a rigid surface, evenwhen it is exposed to the extremes of outdoor temperature.For such applications, ethylcellulose is modified with hardresins and plasticizers.

Tough LacquerMany lacquer applications on nonrigid surfaces require, asbasic desired properties, toughness, wear resistance, goodadhesion, resistance to discoloration and alkali, and flexibility.Such properties are required in lacquers for paper, linoleum,cellophane, surgical tape, wet or dry sandpaper, and lac-

quers for the decoration of textiles. Properly plasticized andstabilized ethylcellulose lacquers meet these requirements.

Bronzing LacquerMany ethylcellulose compositions are substantially free fromdiscoloration and gelation in copper and aluminum bronzelacquers. Resin choice is an important consideration; in anexperimental series, dewaxed dammar developed less colorin the lacquer than other resins tested. Citric acid (1% basedon the ethylcellulose) is an effective stabilizer against thedevelopment of any green color.

Lacquer for Polystyrene PlasticThe solvent combination is an important factor in any suc-cessful coating for polystyrene plastic. In an ethylcelluloselacquer for this plastic, alcohols must constitute the major

portion of the solvent, although a small amount of an activesolvent for the plastic is desirable to get some “bite” into themolded part. A suitable active solvent would be an ester,ketone, or aromatic hydrocarbon. For further details, seeCSL-61, A Report on Lacquer for Plastics.

Lacquer for RubberWhether the emphasis is on gloss, adhesion, or flexibility,coatings can be formulated to give the desired properties.Ethylcellulose lacquers have met these requirements whenapplied to either cured or uncured rubber, and yield a finishwith outstanding adhesion and good flexibility.

Discoloration Sensitivity Sensitivity Sensitivity Temperatureby Ultraviolet to to to Sward Change,

Light Water 5% HCl 5% NaOH Hardness Cycles

Formula Formula Formula Formula Formula FormulaA B A B A B A B A B A B

Cumar R-29 (coumarone-indene) v b v b sl blis t bl OK v sl t OK t bl 54 36 47 50 –

Dewaxed Batavia dammar v sl sl blis v sl bl v v sl r v v sl r v v v v 82 84 35 5(natural resin) r v sl r sl r sl r

Composition of Formulas A B

Ethylcellulose 10 10

Resin 5 10

Key: b = bad(ly); bl = blush;blis = blistered; m = moderate; r = rust; sl = slight(ly); t = temporary; v = very.

TABLE XVII —EFFECTS OF RESINS ON SELECTED PROPERTIES OF ETHYLCELLULOSE COMPOSITIONS



Specialty Wood FinishesEthylcellulose lacquers containing high proportions of low-cost resins and a small proportion of high-viscosity ethylcel-lulose are economical, air-drying coatings. Although the filmsmay be somewhat soft, their flexibility and toughness aresufficient to make them interesting for applications such asdrawer coatings or backboards for chests.

Water-White Wood FinishWhen ethylcellulose films are exposed to ultraviolet light,they tend to bleach rather than discolor. This tendency indi-cates that they have a place in water-white wood finishes.K-type ethylcellulose without a plasticizer produces a water-white composition hard enough to stand some rubbing andpolishing. An 80:20 nitrocellulose:ethylcellulose lacquer alsoshows reasonably good color retention.

Alkali-Resistant LacquerBecause there is an increasing interest in maintenancepaints that have good alkali resistance, work has been doneon the use of stabilized ethylcellulose compositions in thisfield. It was found that the use of epoxide-type stabilizers,plus antioxidants, produces ethylcellulose coatings of veryhigh alkali resistance.

Ethylcellulose lacquers applied to steel panels were found tobe unaffected after 100 days at room temperature in either a5% caustic solution or a 1% ammonia atmosphere. A morespectacular test showed these coatings to be unaffected,even though they remained immersed in a 70% caustic solution at 76°C (170°F) for 19 days.

Paper LacquersBecause of the varied special properties that ethylcellulosemakes possible in paper lacquers, it is used widely in thisfield. Achievable with this material are: light initial color andgood color retention under sunlight and aging exposures,heat-sealing, good gloss, resistance to blocking, resistanceto heat discoloration, flexibility over a wide range of tempera-tures, and alkali resistance.

Reconstituted cigar wrappers are flexible, yet tough, whenthey are formulated with ethylcellulose.

Flowback High-Gloss LacquerOther interesting ethylcellulose lacquers are flowback papercoatings. These formulations are designed to give especially

high gloss when the coating is reflowed by application ofheat at about 177°C (350°F) for a few seconds after the lac-quer is applied and dried in a normal manner.

Solvent-Based Strip CoatingsIn recent years, there has been much interest in temporaryprotective coatings that can later be stripped from the sur-face they protect. The major volume of these coverings hasbeen deposited from hot-melts, but a growing market isdeveloping for the solvent-based products.

EMULSIONSEthylcellulose emulsions can be formulated for environmen-tal concerns and low cost. Ethylcellulose emulsions weredeveloped for use as a permanent sizing agent for textilesto replace starch and various water-soluble gums.

The method of preparation, choice of materials, stability, andsample formulations are discussed in CSL-76.

INKS

Screen-Process InksThe use of ethylcellulose in screen-process inks has grownsubstantially. Ethylcellulose is soluble in organic solventsthat are not injurious to lacquer stencils, and it has wide

compatibility with many resins and plasticizers. Compositionsare usually based on one part by weight of ethylcelluloseand a few parts of plasticizer and resin. A heavy loading ofpigment and inert ingredients is possible.

Magnetic InksBecause of the high dielectric constant of ethylcellulose, itcan also be used for formulating magnetic inks. These haveunique adhesion and holdout properties.

Gravure and Flexographic InksEthylcellulose is being used in both gravure and flexographicinks. It contributes good scuff resistance, pigment disper-sion, and holdout features, and controls viscosity. Com-patibility with ink resinates is good. Pigments are easilyincorporated by adding ethylcellulose color chips or flushed

colors, or by any of the usual methods of grinding. Typically,one to three parts by weight of an N-, T-, or X-type are used.

Flexographic inks are commonly formulated with shellac, orcombinations of shellac and hard resins, in alcohol solutions.Ethylcellulose is added to promote adhesion and toughnessand provide other features, the same as with rotogravure inks.

VARNISHES

Use of ethylcellulose in certain types of varnishes givesthem the inherent toughness and quick-drying propertiesassociated with the cellulose derivatives. Addition of ethylcel-lulose to some varnishes shortens drying time appreciably,increases toughness, reduces the amount of metallic driernecessary, decreases surface tack, and improves resistance

to rapid temperature changes.There are two different procedures for adding ethylcelluloseto varnishes. The simplest and most foolproof is the coldcutmethod. Ethylcellulose is first dissolved in its usual solventcombination, then added to a varnish that has been thinnedwith a solvent rich enough to hold the ethylcellulose in solu-tion. If the varnish contains the usual solvent of mineral spir-its or other aliphatic hydrocarbon, the ethylcellulose willprecipitate on being added to the varnish.



The hot-melt procedure involves the addition of ethylcellu-lose flake to the hot varnish. Careful temperature control isnecessary to avoid degradation of the ethylcellulose.

The quantity of ethylcellulose added will control the proper-ties of the coating, but 10%, based on resin and oil, is ade-quate for most purposes. The type of ethylcellulose can beeither N or T, with the T-type having a slight advantage. Theviscosity can vary from 10 to 200 cps, depending on theamount of extra bodying desired in the varnish.

ADHESIVES

In adhesives, ethylcellulose contributes:

• Low-temperature flexibility.

• A broadening of the critical melting range with a resul-tant decrease in plastic flow.

• Strength.

• An increase in melting point of the mixture.

• A decrease in sweating of plasticizers.

• Better control of tackiness in adhesive film.

Hot-melt adhesives incorporating ethylcellulose have quicktack while still molten, but harden quickly on cooling.Furthermore, there is no residual solvent odor or taste.

Solvent-type ethylcellulose adhesives are useful in places whereethylcellulose film or plastic must adhere to another surface.

HOT-MELT APPLICATIONS

Hot-melt applications of ethylcellulose have received consid-erable attention. This is because ethylcellulose is a productwith an unusual combination of properties, which makes iteasily adaptable to this mode of application. It can be madestable to heat; it has excellent thermoplasticity; it dissolvesreadily in many hot resins, plasticizers, oils, and wax mix-tures; and of particular interest is the fact that it imparts tosuch mixtures a remarkable toughness. Furthermore, allhot-melt compositions are economical to apply. No volatilesolvents are involved. Application is usually a simple, one-operation procedure.

A variety of such compositions is now in use. Some of theapplications are relatively well known and have been in usefor years. Others are new, have interesting possibil ities, and

are expanding rapidly. Examples of well-known uses areshellac substitutes, potting compounds used in electricalinsulation work, and decalcomania transfer compositionstoughened with ethylcellulose. Numerous possibilities existfor the hot-melt coating of paper with resin and plasticizermixes toughened with ethylcellulose.

Compositions based on ethylcellulose can be tailored to spe-cific requirements such as nonblocking, flexibility over a widetemperature range, high gloss, or pale color. Ethylcellulosehot-melt strip coatings provide protection during both ship-ping and storage. Detailed information is available.

TABLE XVIII —TYPICAL DATA FORETHYLCELLULOSE HOT-MELT

CASTING PLASTIC

Rockwell hardness, M scale – 50-+50Izod impact, ft-lbs/in. notch 0.5-5.0Softening point, ring-and-ball

method, °C 130-170Scratch hardness, by pencil 4B-HTensile strength, lbs/in.2 1,000-4,000Compressive strength, lbs/in.2 3,000-10,000Flexural strength, lbs/in.2 3,000-10,000Modulus of elasticity, lbs/in.2 100,000-350,000Mold shrinkage, in./in. 0.0025-0.015Coefficient of expansion,

in./in./ °C × 10 – 5 5-15

Distortion under heat, °C 28-50Specific gravity 1.08-1.33Water absorption, % gain after 48

hrs’ immersion at 21°C 0.15-0.75

CASTING PLASTICS

Table XVIII gives typical data obtained on formulationsdesigned for hot-melt casting applications. Such composi-tions are composed of resins, plasticizers, waxes, and min-eral fillers toughened with ethylcellulose.

This type of plastic can be cast in bronze, brass, iron,aluminum, wood, or plaster molds. Some mold materials,such as wood and plaster, require a sealer coat. Remarkablyaccurate surface reproduction is possible with these hot-melt

plastic castings. They are used for the preparation of dies, jigs, and tools in the aircraft industry, and hold promise ofwide use in other industrial applications.

PIGMENT-GRINDING BASE

Ethylcellulose has been found to be an excellent base forpigment grinding. Because of its low melting point, ethylcel-lulose, plasticized or unplasticized, can be colloided readilyon either the two-roll or the Banbury mill. Plastic thus pro-duced is very tough and sticky while hot, and is well adaptedto pulling apart pigment agglomerates. The high tempera-tures at which ethylcellulose can be worked without de-composition ensure uniform grinding and dispersion ofpigment particles.

FILM AND FOIL

In film form, ethylcellulose is well suited in properties andappearance as a wrapping material and as electrical insu-lation. Unplasticized film can be produced to have a highdegree of toughness and flexibility. Unplasticized film 0.001in. thick, for example, can be flexed over 2,000 times on theMIT fold tester before failure occurs. Even at – 70°C the filmhas a high degree of flexibility. Tensile strength is on theorder of 7,000 to 11,000 lbs/in.2, while elongation runs 10-35%. Moisture absorption in highly humid atmospheres runsto approximately 2%, but has no appreciable effect on thedimensional stability of the film. In fact, ethylcellulose film isnot noticeably affected even after long immersion in water,followed by drying.



PLASTICSEthylcellulose plastic belongs to the group known as thermo-plastic materials —that is, those that can be shaped by pres-sure while hot, and that, when cool, retain the impressedform. A plastic make from ethylcellulose has the usual oper-ating advantages of other thermoplastics —i.e., reuse ofscrap; adaptability to fast, low-cost injection and extrusionprocesses; ready workability with hand or machine tools; andeasy finishing.

An outstanding characteristic of ethylcellulose plastic is itshigh impact resistance at low temperatures. It has the lowestspecific gravity of any of the cellulosic thermoplastics nowavailable, and, with the exception of nitrocellulose, it showsthe lowest water pickup of these thermoplastics. This mater-

ial has the highest alkali resistance and also has fair resis-tance to acid.

Ethylcellulose plastic easily meets all ordinary requirementsof practical strength properties at temperatures between

– 57°C and 77°C ( – 70°F and 170°F). Use of ethylcelluloseplastic is indicated where hardness, combined with tough-ness, close dimensional tolerance, ability to hold dimensionsduring immersion in water, and high impact strength at lowtemperatures, is required.

Military rocket tapes and molded parts can be made from apremium grade of K-type ethylcellulose. This is a result of alow ash content, critical to the shelf life of the product.

FOOD CONTACT AND PHARMACEUTICALS

Tablets—CoatingsNF -grade ethylcellulose produces durable tablet coatingsthat offer good adhesion and function to control the rate atwhich the ingested medication is released. Typically, thetablet is spray-coated from a solvent system.

Pharmaceutical manufacturers also treat products with anEC-based aqueous polymer dispersion that is spray-coatedonto the tablets, thus avoiding solvent systems that aresometimes undesirable. In either case, the coating masksbitter tastes and improves stability. Further details on aque-ous dispersions can be found in U.S. Patent 4,963,896,FMC Corporation.

Tablets—Binding

Ethylcellulose has long been used as a binder and filler intablets of vitamin, mineral, and prescription drugs for bothhumans and animals. It helps produce a stable, attractivetablet without significantly affecting the dissolution rate.

EncapsulationMicroencapsulation of drug particles with NF -grade ethyl-cellulose offers pharmaceutical manufacturers anothermeans of controlling solubility rates.The coacervationprocess with a solvent is found in U.S. Patent 3,567,650,NCR Corporation.



PRODUCT LISTING SUPPLEMENTThe following list of products, along with their chemical iden-tity and source of supply, may be helpful to the reader who isunfamiliar with some of the products referred to in this book.

Read and understand the Material Safety Data Sheets(MSDSs) before using these products.

Product Chemical Identity Manufacturer

Abalyn ® Methyl ester of rosin Hercules

Abitol ® E Hydroabietyl alcohol Hercules

Acryloid B72, Flexible acrylic ester resins Rohm & HaasC10LV

Acryloid F10 Mineral-thinner-soluble Rohm & Haas

acrylic ester resin

Antioxidant 2246 2,3-methylene bis (4-methyl- Ciba Geigy6-tert -butyl) phenol

Aroplaz 1351 Nonoxidizing alkyd resin Reichhold

Aroplaz 1271 Long oil phthalic alkyd Reichhold

Baker’s castor oilNo. 1 5, 30; Pale Processed castor oil CasChemNo. 4, 16, 1000

Beckacite, Oil-soluble pure ReichholdSuper-, 1001 phenolic resin

Beckamine 21-510 Urea-formaldehyde resin ReichholdBeckolin Synthetic oil Reichhold

Beckosol 12-021 Alkyd resin Reichhold

Butyl Cellosolve Ethylene glycol monobutyl Union Carbideether-solvent

Carbitol Diethylene glycol Union Carbidemonoethyl ether

Cellolyn ® 21 Rosin-derived alkyd HerculesCellolyn 102M Modified ester of rosin Hercules

Cellosolve Ethylene glycol monoethyl Union Carbideether-solvent

Cellosolve Ethylene glycol monoethyl Union Carbideacetate ether acetate-solvent

Chlorowax 70 Chlorinated paraffin U.S. IndustrialChemicals

Cumar P10 Plastic-grade coumarone- Nevilleindene resin Chemical

Cumar R-3, R-11, Coumarone-indene resins NevilleR-14, R-28, R-29 Chemical

BHT 2,6-di-tert -butyl-para -cresol Ashland

Dipentene No.122 ® Solvent, C10H16 HerculesDow Corning Silicone dimethyl fluid Dow Corning

Fluid 200

Dutrex 25 Petroleum-derived plasticizer ShellEpon 1004` Polymer of bisphenol and Shell

epichlorohydrin

Ester Gum 8D Glycerol ester of rosin Hercules

Flexol 3GH Triethylene glycol di(2-ethyl CP Hallbutyrate)

Flexricin P-3 Butyl ricinoleate CasChem

Gloria White mineral oil Sonneborn

Halowax 1013 Chlorinated naphthalene resin Bakelite

HB-40 Hydrogenated terphenyl Monsanto

Hercoflex ® 600 Monomeric PE ester Hercules

Hercolyn ® D Hydrogenated methyl esters Herculesof rosin

Hercules ® RS – Herculesnitrocellulose

Product Chemical Identity Manufacturer

Hi-Flash naphtha Solvent hydrocarbon Allied Signal

Ionol Oxidation inhibitor Shell UK

Keltrol Fatty oil-vinyl toluene Reichholdcopolymer

Lewisol ® 28 Maleic-modified ester Herculesgum resin

Metalyn ® Distilled methyl ester of Herculestall oil

Methyl Cellosolve Ethylene glycol monomethyl Union Carbideether

Methyl Cellosolve Ethylene glycol monomethyl Union Carbideacetate ether acetate

Monoplex DIOA Diisooctyl adipate CP Hall

Necton 45 Petroleum lubr icating oil base Exxon

Nevillac 10 Phenol-indene-coumarone Nevilleresins Chemical

Nujol Liquid paraffin oil Schering

Orlon Acrylic synthetic fiber E. I. du Pontde Nemours

Paraplex G-20 Sebacic, unmodified, CP Hallnonoxidizing alkyd resin

Paraplex RG-2, Sebacic, oil -modif ied alkyd CP Hal lRG-8 resins

Pentalyn ® A Pentaerythritol ester of rosin Hercules

Pentalyn G Modified pentaerythritol Hercules

ester of rosin

Pentalyn H Pentaerythritol ester of Herculeshydrogenated rosin

Pentalyn K Pentaerythritol ester of Herculesmodified rosin

Pentalyn 830, Hard, pale, thermoplastic Hercules856 resins

Pentaphen 67 para-tert -amylphenol Atochem

Pentrex ® 28 Maleic-modified glycerol Herculesester of rosin

PhosFlex CEF Tri(beta -chloroethyl) Akzo Chemiephosphate

Piccolastic ® A-5 Styrene resin Hercules

Pine oil – Hercules

Poly-pale ® 10 Ester of polymerized rosin Herculesester

Poly-pale resin Polymerized rosin Hercules

Resimene Melamine resin Monsanto

Staybelite ® Hydrogenated rosin Hercules

Staybelite 3, Esters of hydrogenated Hercules10 ester rosin

Tegmer 804 Polyethylene glycol CP Halldi-2-ethylhexoate

Tetralin Tetrahydronaphthalene E. I. du Pontde Nemours

Triacetin Glycerol triacetate Bayer AG

Tributyrin Glycerol tributyrate EastmanChemical

Uformite MM-55 Melamine-formaldehyde resin Reichhold

Uni-Rez 7200 Hard maleate resin Union Camp

Uvinul 400 2,4-dihydroxybenzophenone BASF

Varsol Petroleum thinner Exxon

Vinsol ® Dark, hard pine resin Hercules

Vinsol ester gum Glycerol ester of Vinsol Hercules

Vinylite VAGH Vinyl resin Union Carbide

Zinar, Zirex, Zitro Zinc resinates Arizona

31

APPENDIX



METHODS OF ANALYSISProduct specifications are based on Aqualon test methods.The following standard test methods are essentially equivalentto the Aqualon test methods, except where indicated:

Ethylcellulose —Standard GradesASTM D 914(2)

Ethylcellulose —NF GradesNational Formulary (current edition)• Ethylcellulose Official

Monograph

(2)Viscosity —The Aqualon test method utilizes the Hercules horizontal capil-lary viscometer, in accordance with ASTM D 914, for ethylcellulose typeshaving a viscosity of 250 cps or less. For viscosities greater than 250 cpson the horizontal capillary viscometer, the following test method is used:

ApparatusBrookfield viscometer Model LVF

ProcedurePrepare the viscosity solution in accordance with ASTM D 914 procedurespecified for “Hercules horizontal capillary viscosity.” After the solution iscomplete by visual inspection, place it in a 12-oz bottle, adjust the tempera-ture to 25°C, and measure the viscosity, using a Brookfield viscometer ModelLVF (No. 2 spindle, 30 rpm).

CalculationMultiply the 3-min dial reading by 10 to obtain viscosity in centipoises.

PRODUCT SAFETY

Read and understand the Material Safety Data Sheet(MSDS) before using this product.



Cellulose and Its Derivatives



HERCULES INCORPORATED

Aqualon Division

Hercules Plaza

1313 North Market Street

Wilmington, DE 19894-0001

www.aqualon.com

(800) 345-0447

ORDER PLACEMENT INFORMATION

(800) 334-8426

PRODUCT AND TECHNICAL INFORMATION

(800) 345-0447

The products and related information provided by Hercules are for manufacturing use only. Hercules makes no express, implied, or other representation,warranty, or guarantee concerning (i) the handling, use, or application of such products, whether alone, in combination with other products, or otherwise,(ii) the completeness definitiveness or adequacy of such information for user ’s or other purposes (iii) the quality of such products except that such

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