Morpholine

1

MORPHOLINE

Introduction ..................................................................... 2Sales Specifications/Analytical Procedures ..................... 2Applications .................................................................... 3

Rubber Chemicals .................................................... 3Catalysts .................................................................. 3Corrosion Inhibitors .................................................. 3Separating Agents .................................................... 4Optical Brighteners ................................................... 4Pharmaceutical Chemicals ....................................... 4Bactericides, Fungicides, and Herbicides .................. 5Antioxidants .............................................................. 5Wax Emulsifiers and Surface-Active Agents ............. 5Miscellaneous Applications ....................................... 6

Physical Properties ......................................................... 7Solubility ................................................................... 7pH Value of Aqueous Morpholine .......Figure 1 ........ 8Flash Point of Aqueous Morpholine ....Figure 2 ........ 9Freezing Point of Aqueous

Morpholine ...................................Figure 3 ........ 9Refractive Index of Aqueous

Morpholine at 20°C ......................Figure 4 ...... 10Specific Gravity of Aqueous

Morpholine at 20°C ......................Figure 5 ...... 11Specific Gravity of Morpholine

Versus Temperature ....................Figure 6 ...... 12Surface Tension of Aqueous

Morpholine at 20°C ......................Figure 7 ...... 13Vapor-Liquid Equilibria for Aqueous

Morpholine at AtmosphericPressure ......................................Figure 8 ...... 14

Vapor Pressure Versus Temperatureof Morpholine ............................... Figure 9 ...... 15

Viscosity of Aqueous Morpholineat 20°C ........................................ Figure 10 .... 16

Chemical Properties ...................................................... 17Reaction with Acids and Acid Derivatives ................ 17Reaction with Isocyanates and Isothiocyanates ...... 18Reaction with Amines and Amides .......................... 18The Mannich and Related Reactions ...................... 18Reaction with Aldehydes ........................................ 19The Leuckart-Wallach Reaction .............................. 19Alkylation ................................................................ 19Arylation ................................................................. 19Addition to Unsaturation ......................................... 20Reaction with Epoxides and Imines ........................ 20Willgerodt Reaction ................................................ 20Reaction with Oxidizing Agents............................... 21The Hofman Degradation ....................................... 22Direct Chlorination .................................................. 22Complex Formation ................................................ 22Miscellaneous Reactions ........................................ 22

Handling and Storage ................................................... 23General .................................................................. 23Maintaining Specifications ...................................... 23Transfer Lines ........................................................ 23Pumps .................................................................... 24Unloading in Cold Weather ..................................... 24New Facilities and Cleaning.................................... 24

Shipping Information ..................................................... 25Safety and Toxicity ........................................................ 26Huntsman Sales Offices ................................................ 28

Quality PolicyHuntsman Corporation is committed to providing prod-ucts and services that consistently conform to ourcustomers’ requirements.

To fulfill this commitment, the employees of Hunts-man Corp. are dedicated to “being the best” throughcontinuous improvement.

In implementing its quality policy, Huntsman Corp.is committed to the use of statistical methods.

Product Safety PolicyIt is the product safety policy of Huntsman Corporationto provide our customers with information on the safehandling and use of our products. The Material SafetyData Sheet (MSDS) should always be read and under-stood thoroughly before handling the product, andadequate safety procedures should be followed. Infor-mation on the toxicity, environmental, and industrialhygiene aspects of our products may be found in theMSDS.

2

INTRODUCTION

Morpholine, CAS Number 110-91-8, is a colorless, mobile,hygroscopic liquid with a characteristic amine-like odor. Itis completely miscible with water and a large number oforganic solvents, and is itself a solvent for a large varietyof organic materials, including resins, dyes, waxes,shellac, and casein.

Morpholine is an extremely versatile chemical withmany important applications. It is used as an intermediatein the manufacture of rubber chemicals and opticalbrighteners. It is also used extensively as a corrosioninhibitor in steam boiler systems.

Fatty acid derivatives of morpholine are used asemulsifiers in the manufacture of waxes and polishes.Other derivatives have found applications as bactericides,pharmaceutical chemicals, and antioxidants for lubricatingoils. Morpholine derivatives are particularly useful in thetextile industry, where they are employed as textilelubricants and sizing emulsifiers.

Chemically, morpholine is an amino ether. The etherfunction of the molecule is typically inert and most of thereactions of morpholine involve the secondary aminegroup.

SALES SPECIFICATIONS/ANALYTICAL PROCEDURES

Sales SpecificationsThe following sales specifications are subject to changewithout notice. Appropriate analytical procedures for thesespecifications may be found to the right.

Method ofDetermination

Appearance Clear liquid, ST-30.1substantiallyfree fromsuspendedmatter

Color, Pt-Co scale 15 max. ST-30.12

Morpholine, wt. % 99.0 min. ST-35.77

Water, wt. % 0.3 max. ST-31.53Procedure 6

Analytical ProceduresAbbreviated forms of the standard methods of test for usewith morpholine specifications are presented here. Copiesof the methods in detail are available from our TechnicalServices Section in Austin, Texas, upon request.

APPEARANCE (Method No. ST-30.1) is determinedby visual inspection of DIGLYCOLAMINE agent in a100-ml tall-form Nessler tube.

COLOR (Method No. ST-30.12) is determined visuallyin a 40-ml tube with APHA color disc standards, or in a100-ml tall-form Nessler tube with liquid platinum cobalt(APHA) standards.

MORPHOLINE ASSAY (Method No. ST-35.77) is usedto determine morpholine and impurities by gas chromatog-raphy.

WATER (Method No. ST-31.53) is determined by thestandard Karl Fischer method, the end point being de-tected electrometrically.

3

APPLICATIONS

Rubber ChemicalsA major use of morpholine is as an intermediate in theproduction of delayed-action type rubber accelerators.Accelerators are added to rubber before fabrication toincrease the rate of vulcanization. Since during fabricationthere is a danger of prevulcanization, particularly if hightemperatures are involved or if furnace black rather thanchannel black is present, delayed-action accelerators arehighly desirable.

Morpholine-based delayed-action accelerators areusually made by reacting morpholine with 2-mercapto-benzothiazole. Several other morpholine-based accelera-tors have been reported in the literature.

CatalystsMorpholine has been employed as a catalyst for thecondensation of aldehydes and ketones which containactive methyl or methylene groups. The condensates maybe hydrogenated to polyhydroxy compounds which can besulfated to form surface-active agents.

Small quantities of morpholine are used in the emul-sion polymerization of monomers, such as butadiene andisoprene, as well as their copolymerization with styrene,acrylonitrile, and the like.

Morpholine has been used as a temperature sensitivepolymerization inhibitor. Small amounts permit completeimpregnation of porous materials with molten vinylpyrrole-type monomers just above their melting points, but stillallow complete polymerization at slightly higher tempera-tures.

Morpholine has also been used as a gelling agent inthe preparation of alumina catalysts for the treatment ofhydrocarbons. Catalysts of fine particle size suitable forfluidized solid techniques result from this procedure.

Corrosion InhibitorsMorpholine is widely used as a neutralizing amine incombating carbonic acid corrosion in condensate returnlines of steam boiler systems. The morpholine volatilizeswith the steam from the boiler and condenses when thesteam does, thereby affording protection to the lines,which otherwise would be subjected to corrosion by thecarbonic acid present in the steam condensate.

Morpholine vapors protect silver and other metalsagainst corrosion and tarnish by acid fumes, such assulfur dioxide and hydrogen sulfide. The morpholine issupplied by evaporation from solution in a solid, such ascamphor, or by sublimation from morpholiniumN,N'-oxydiethylenecarbamate.

Morpholine is a component of a corrosion inhibitorsystem that prevents decomposition of a chlorinatedhydrocarbon in a composition containing the chlorinatedhydrocarbon and a large amount of water.

Corrosion of metal aerosol containers and valves canbe prevented by the use of low levels of morpholine.

Morpholine is one of several amines employed asphosphates for inhibiting the corrosive action of grease-proof paper on steel and other metals. Di-4-morpholinylpolysulfides have been claimed as corrosion inhibitors tobe added to mineral lubricating oils. Turbine oils, espe-cially, are quickly contaminated with water, and to protectthe machinery against rusting, 4,4'-alkylidenedimorpho-lines and poly (4-morpholinylmethyl) phenols have beenused. Storage tanks, pipes, and other devices for handlingpetroleum distillates must be protected against corrosion,and for this purpose 4,4'-butylmercaptomorpholine,morpholinium mahogany sulfonates, and morpholine inconjunction with ammonium mahogany sulfonates havebeen suggested.

4

Separating AgentsThe physical and chemical properties of morpholine makeit useful in various purification procedures. Marked differ-ences in the solubility of the methyl amines in morpholinehave led to a convenient extractive method for separatingthese volatile amines. The addition of morpholine tostyrene-containing hydrocarbon mixtures makes possiblethe isolation of substantially pure styrene by azeotropicdistillation. It is claimed that aldehydo or keto derivativesof morpholine, e.g., 4-formylmorpholine, are useful forseparating low-viscosity components from mineral, animal,vegetable, and fish oils. It is reported that morpholine isthe preferred amine to use in an oil-amine mixture forscrubbing organic sulfur compounds from fuel gas.Morpholine is also used in the purification of acetylene andcertain olefins.

Optical BrightenersMorpholine is an important intermediate in the manufac-ture of optical brighteners. Optical brighteners are em-ployed by the soap and detergent industry in thecompounding of detergents. The diaminostilbene triazinetype brightener with morpholine as a substituent on one ofthe triazine rings is particularly effective on cellulosics.Having greater stability to chlorine bleaches than othertypes of brighteners, they are particularly suitable forhome laundry detergents.

APPLICATIONS

Pharmaceutical ChemicalsThe physiological activity of the morpholine nucleus isattested by the number of pharmaceutical applicationswhich have been found for it.

The hydroperiodide is suitable for incorporation inointments for the treatment of skin disorders, such asathlete’s foot.

A number of morpholine derivatives have beendescribed as analgesics and local anesthetics. The4-benzyl morpholines are particularly effective. 4-(4-Bromobenzyl) morpholine, for instance, is reported to beonly 25% as toxic as procaine, but almost equal to it inactivity.

Several morpholine-derived chemicals are useful asrespiratory and vasomotor stimulants. TheN,N'-ethylenebis (N-alkyl-4-morpholinecarboxamides) areespecially valuable, since the ratio of active dose to toxicdose is low. The dibutyl derivative, for example, shows 12times the activity of nikethamide.

Other pharmaceutical fields in which morpholine hasfound application include choleretics, antispasmodics,analeptics, and antimalarials. In addition, the use ofmorpholine as a peptizing agent for preparing aqueousdispersions of phenothiazines for anthelmintic purposeshas been claimed. Likewise, the use of morpholine inpreparing soluble salts of certain sulfanilamides has beenpatented, and various derivatives are claimed to havetherapeutic value.

5

APPLICATIONS

Bactericides, Fungicides, and HerbicidesA number of morpholine derivatives have been shown topossess bactericidal activity. For example, morpholiniumsalts of certain acylated sulfonamides possess strongbacteriostatic or bactericidal properties, and morpholinehydroperiodide has been used as a water disinfectant.

The reaction of morpholine with 3,4,5-trichloro-2,6-pyridinedicarbonitrile yields a product which is useful in thecontrol of fungi.

Morpholine is used in preparing compounds that areexcellent herbicides and that can be applied either to thesoil before the weeds emerge or to the growing plants.

AntioxidantsIn addition to its use as a corrosion inhibitor, 4-t-butylmercaptomorpholine has been employed as anantioxidant for lubricating oils. Di-4-morpholinylmonosulfide has been claimed as a lubricating oil stabi-lizer, and multifunctional oil additives that possess antioxi-dant properties can be prepared from wax-phenols,formaldehyde, and morpholine.

Small quantities of morpholine and 1-ascorbic acid areclaimed to show marked synergistic antioxidant propertiesfor use in fatty products. The morpholine salt of gallic acidis an oil-soluble antioxidant for glyceridic oils and astabilizer for vitamin A and carotene, and 4-alkylmorpholines have been found to act as stabilizers for2-chlorothiophene.

Wax Emulsifiers and Surface-Active AgentsWhen morpholine is reacted with fatty acids, it formssoaps possessing excellent emulsifying properties. Theoleic soap is a particularly important emulsifier used in theformulation of self-polishing waxes and polishes. One ofthe main advantages of morpholine-based emulsifiers isthe similar boiling points of morpholine and water. Whenthe loosely bound fatty acid-morpholine compound breaksdown, the morpholine component evaporates at approxi-mately the same rate as the water. Consequently, theresultant wax film is left dry and void of morpholine, and isthen highly water resistant. This is a very desirable featurein household and automobile waxes and polishes.

The reaction products of morpholine and tung oil orlinseed oil have been found to be good emulsifying anddispersing agents. Also, the quaternary alkyl ammoniumsulfates of Mannich bases from morpholine and mono- orpolyhydric phenols have been patented as emulsifyingand wetting agents.

A number of other morpholine-containing compoundshave been used as wetting agents, and it is said thatmorpholinium linoleate is an especially good surfacetension depressor for use in rust-preventive compositionsbecause it tends to harden the rust-preventive film.

The morpholine salt of a polymeric maleamic acid hasbeen used in compositions for coating paper, cloth, etc.Small quantities of morpholine have been incorporated infireproofing materials, and the stability of certain asphaltemulsions has been improved by the addition ofmorpholine. This amine has also been used as an equaliz-ing and dispersing agent in dye baths and printing pastes,and its quaternary alkyl ammonium sulfates have beenpatented as general surface-active agents.

6

Miscellaneous ApplicationsMorpholine derivatives have found application in the textileindustry. Thus, a biquaternary compound derived from4,4'-ethylenedimorpholine is suitable as a softening agentfor natural or regenerated cellulose. In viscose spinning,small amounts of quaternary morpholine derivatives,introduced into either the viscose solution or regeneratingbath, prevent fouling of the spinnerets during extrusion.Compounds of this type are also useful as textile lubri-cants and sizing emulsifiers. A superior whitening agentfor textiles includes morpholine in the formula, and α-4-morpholinylacrylic esters have been claimed as textileadjuvants.

A compound prepared from sulfur dioxide andmorpholine is useful in photographic developers, and asmall amount of morpholine in the recipe improves thekeeping qualities of a fine grain developer.

Morpholinium salts of sulfonated azo dye componentsare used in dry mixtures for the production of dye imagesby electrolytic recording methods.

Morpholine is used in an ink eradicator formulationthat is used to remove a graphic arts ink. The eradicator

APPLICATIONS

enables the user to modify his original graphic representa-tion almost immediately.

A strongly basic ion-exchange resin can be preparedby treating a polymerized 4,4'-diallylmorpholinium bromidewith alkali, and it is reported that a quaternary morpho-linium ethosulfate is useful as a hair conditioner anddeodorant in popular wave formulations. The ethosulfateis also found in shampoos and mouthwashes. A processfor citric acid by fermentation includes a small quantity ofmorpholine in the mash, and it has been found thatdimorpholinium oxalate is an excellent precipitant fortrivalent gold. A rapid test for acrylates and acrylonitriledepends upon reaction with morpholine as a first step.

Morpholine may be used alone to thermally stabilizecellulose materials. Electric graded kraft papers treatedwith morpholine will retain a higher degree of their originaltensile strength after subjection to heat aging.

Morpholine is used to prevent the deterioration ofpaper, especially in books. The paper is impregnated withgaseous morpholine, thereby raising the pH of the paperand removing the acidic conditions which cause itsdeterioration.

7

PHYSICAL PROPERTIES

The following physical properties are for the pure com-pound.

Autoignition temperature, °F 590Boiling point, 760 mm Hg, °C 128.3Conductivity, mho/cm x 1010 6Density, 20°C, g/cc 0.999Dielectric constant, esu 7.176Dipole moment, Debyes 1.58Flash point, TCC, °F 95Freezing point, °C -4.9Heat capacity, 25°C, cal/mol/deg 41.6Heat of vaporization, 45-129°C, cal/mol 9510

SolubilityThe solvent power of morpholine is said to exceed

that of benzene, pyridine, and dioxane. Listed below arethe solubilities of some commom materials in morpholine.

g Solute in g Solute in g Solute in100 g 100 g 100 g

Morpholine Morpholine MorpholineSubstance at 25 °C Substance at 25 °C Substance at 25 °CAcetone ∞ 2-Ethylbutanol ∞ Paraffin wax (hot) >5Beeswax <1 Ethylene glycol ∞ Pine oil ∞Benzene ∞ Ethyl ether ∞ Polyvinyl acetate >5Benzyl cellulose >5 Methyl glycol ether ∞ Polyvinyl butyral >5Butyl ether ∞ n-Heptane ∞ Polyvinyl chloride >5Carbon tetrachloride ∞ 2-Hexanone ∞ Resin >5Castor oil ∞ Linseed oil ∞ Shellac >5Cellulose acetate >5 Methanol ∞ Sulfur <5Cellulose nitrate >5 Methylamine (gaseous) 33 Toluene ∞Copal gum >5 Methylcyclohexanol ∞ Trimethylamine (gaseous) 34Dimethylamine (gaseous) 109 Naphtha >5 Turpentine ∞Ester gum >55 Paraffin oil <1 Water ∞Ethanol ∞ Xylene ∞

Molar polarization, P ∞ in benzene 75.3Molecular weight 87.12pKb 5.64Refractive index, nD, 20°C 1.4545Specific gravity, 20/20°C 1.0017Surface tension, 20°C, dynes/cm 37.5Vapor pressure, 20°C, mm Hg 7Viscosity, 20°C, centipoises 2.23Weight, 20°C, Ib/gal 8.3

8

Additional physical properties pertinent to the han-dling and use of morpholine are presented in the pagesthat follow.

Property Figure

pH Value of Aqueous Morpholine ...................................................................................................................................... 1

Flash Point of Aqueous Morpholine ................................................................................................................................... 2

Freezing Point of Aqueous Morpholine .............................................................................................................................. 3

Refractive Index of Aqueous Morpholine at 20°C............................................................................................................... 4

Specific Gravity of Aqueous Morpholine at 20°C................................................................................................................ 5

Specific Gravity of Morpholine Versus Temperature .......................................................................................................... 6

Surface Tension of Aqueous Morpholine at 20°C .............................................................................................................. 7

Vapor-Liquid Equilibria for Aqueous Morpholine at Atmospheric Pressure......................................................................... 8

Vapor Pressure Versus Temperature of Morpholine .......................................................................................................... 9

Viscosity of Aqueous Morpholine at 20°C ........................................................................................................................ 10

PHYSICAL PROPERTIES

pH V

ALU

E

MORPHOLINE, wt. %

0 10 20 30 40 50 60 70 80 90 100

12

11

10

9

8

7

ConcentrationMorpholine pH

0 7.00.001 8.80.01 9.40.1 10.01.0 10.6

10.0 11.2

Figure 1pH Value of Aqueous Morpholine

9

PHYSICAL PROPERTIES

Figure 2Flash Point of Aqueous Morpholine

FR

EE

ZIN

G P

OIN

T, °C

MORPHOLINE, wt. %

0 10 20 30 40 50 60 70 80 90 100

0

–5

–10

–15

–20

–25

–30

–35

–40

–45

–50

–55

–60

0

–5

–10

–15

–20

–25

–30

–35

–40

–45

–50

–55

–60

Figure 3Freezing Point of Aqueous Morpholine

FLA

SH

PO

INT,

°F

MORPHOLINE, wt. %

100 95 90 85 80 75 70 65 60 55 50

190

180

170

160

150

140

130

120

110

100

90

10

PHYSICAL PROPERTIES

Figure 4Refractive Index of Aqueous Morpholine at 20 °C

RE

FR

AC

TIV

E IN

DE

X

MORPHOLINE, wt. %

0 10 20 30 40 50 60 70 80 90 100

1.50

1.48

1.46

1.44

1.42

1.40

1.38

1.36

1.34

1.32

11

PHYSICAL PROPERTIES

Figure 5Specific Gravity of Aqueous Morpholine at 20 °C

SP

EC

IFIC

GR

AVIT

Y

MORPHOLINE, wt. %

0 10 20 30 40 50 60 70 80 90 100

1.050

1.045

1.040

1.035

1.030

1.025

1.020

1.015

1.010

1.005

1.000

0.995

0.990

12

PHYSICAL PROPERTIES

Figure 6Specific Gravity of Morpholine Versus Temperature

SP

EC

IFIC

GR

AVIT

Y

TEMPERATURE, °C0 10 20 30 40 50 60 70 80 90 100

1.040

1.030

1.020

1.010

1.000

0.990

0.980

0.970

0.960

0.950

0.940

0.930

0.920

0.910

0.900

13

PHYSICAL PROPERTIES

Figure 7Surface Tension of Aqueous Morpholine at 20 °C

SU

RFA

CE

TE

NS

ION

, dyn

es/c

m

MORPHOLINE, wt. %

0 10 20 30 40 50 60 70 80 90 100

90

80

70

60

50

40

30

20

10

0

14

PHYSICAL PROPERTIES

Figure 8Vapor-Liquid Equilibria for Aqueous Morpholine at Atmospheric Pressure

WAT

ER

VA

PO

R, M

OLE

%

WATER IN LIQUID, MOLE %

0 10 20 30 40 50 60 70 80 90 100

100

90

80

70

60

50

40

30

20

10

0

15

PHYSICAL PROPERTIES

Figure 9Vapor Pressure Versus Temperature of Morpholine

VAP

OR

PR

ES

SU

RE

, mm

Hg

TEMPERATURE, °C0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

1000900800700

600

500

400

300

200

1009080

70

60

50

40

30

20

10

16

Figure 10Viscosity of Aqueous Morpholine at 20 °C

PHYSICAL PROPERTIES

VIS

CO

SIT

Y, c

p

MORPHOLINE, wt. %

0 10 20 30 40 50 60 70 80 90 100

13.00

12.00

11.00

10.00

9.00

8.00

7.00

6.00

5.00

4.00

3.00

2.00

1.00

17

CHEMICAL PROPERTIES

Because of the chemical inertness of ethers in general,most of the chemical reactions of morpholine involve thesecondary amine function of the molecule. An outline ofthe chemistry of morpholine is given in the followingsections. Reaction yields are given where they areavailable.

Reaction with Acids and Acid DerivativesLike most secondary amines, morpholine reacts withcarboxylic acids and their anhydrides, chlorides, andesters to give the corresponding morpholides.

It is interesting that in the particular case cited, othersecondary amines, such as diethylamine or diphenyl-amine, were essentially unreactive.

Ethylene carbonate reacts smoothly with morpholineat temperatures below 100°C to give β-hydroxyethylN,N'-oxydiethylenecarbamate.

A morpholide is not formed, however, with β-propio-lactone or ethyl acetoacetate.

NH + CH3CHCOOCH3O ON

OH

CH3CHCO350C

OH

83%

NH +O NCOOCH2CH2OHOO O 96%

O

NH +O NCH2CH2COOHO

O

O

NH + CH3COCH2COOC2H5O NCO

CH3

CHCOOC2H5

The last reaction is an important one, for it offers aclean-cut route to mono-substituted acetoacetic esters viaalkylation of the β-4-morpholinylcrotonic ester. Alkylhalides or sulfates are satisfactory alkylation reagents.The mechanism of alkylation of ethyl β-4-morpholinyl-crotonate permits the attack of only one alkyl group andtreatment of the adduct with hot water leads to themono-alkyl acetoacetic ester.

Although reaction of morpholine with dialkyl sulfatesand trialkyl phosphates results in 4-alkyl morpholines, therelated acid chlorides lead to morpholides.

It is expected that ethyl chlorosulfonate would reactwith morpholine in a similar manner.

Dibenzyl phosphite undergoes oxidation when treatedwith morpholine and carbon tetrachloride and yields thecorresponding phosphoramidate.

Morpholine reacts with carbon dioxide to form acarbamate that sublimes unchanged at about 95 to 100°C.Carbon disulfide gives the corresponding dithiocarbamate.

The action of potassium ferricyanide on the dithiocar-bamate yields N,N,N',N'-bis (oxydiethylene) thiuramdisulfide.

NCSSH • O HN O + K3Fe(CN)6 NCS4CO N O

NH + CS2O NCSSH • O HN O

NH + (C6H5CH2O)2POH + CCl4O

ON (C6H5CH2O)2PO 86%

NH + (C2H5)2NSO2ClO ON 97% (C2H5)2NSO2

NH + (C2H5O)2POCIO ON (C2H5O)2PO 79%

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CHEMICAL PROPERTIES

In the presence of certain water-soluble cyanides andoxidizing agents, N,N,N',N'-bis (oxydiethylene) thiuramsulfide is obtained from the dithiocarbamate salts.

The monosulfide can also be obtained by treating thedisulfide with potassium cyanide.

Reaction with Isocyanates and IsothiocyanatesReactions of morpholine with isocyanates give the corre-sponding substituted ureas, and isothiocyanates yieldthioureas.

Reaction with Amines and AmidesMannich bases, such as β-dimethylaminopropiophenone,and Betti bases, e.g.,1-α-dimethylaminobenzyl-2-naph-thol, undergo amine exchange when heated withmorpholine.

The amine function of certain amides, too, can becaused to exchange with morpholine. Heating the latterwith urea in a nitrogen atmosphere gives 4-morpholine-carboxamide.

Morpholine also reacts with 2-benzothiazolesulfen-amide to give the substituted sulfenamide.

The Mannich and Related ReactionsMorpholine has been found to enter into the Mannichreaction in the broadest sense. Thus, phenols, ketones,nitroalkanes, and amides react with morpholine andformaldehyde to give corresponding 4-morpholinylmethylcompounds.

NH + KCNS + HClO ONNH2CS

NH + CH2 O ON CH2 CHCH2NCS CHCH2NHCS

NCSSNa + O NaCN + (NH4)2S2O8 NCS3CO N O

NH + C6H5COCH2CH2N(CH3)2O

ONC6H5COCH2CH2 78%

NH + H2NCONH2O NCONH2O 96%

NH +O ONS

N

S

N

CSNH2 CS

NH +O

OH ON

+ HCHO82%

CH2

OH

NH + CH3COCH3 + HCHOO NCH2CH2COCH3O

NH + CH3CH2CH2NO2 + HCHOO

NCH2CHCH2CH3O

NO2

68%

NH + H2NCONH2 + HCHOO NCH2NHCONH2O 92%

NH + C2H5OOCNHNO2 + HCHOO

NCH2NCOOC2H5O

NO2

19

No reaction occurs with a simple aliphatic nitrile, butif the effect of the nitrile group is augmented by that of aphenyl group, reaction does occur. Thus, phenylaceto-nitrile reacts, but acetonitrile does not.

Alcohols enter this reaction to give 4-morpholinyl-methyl ethers.

Reaction with AldehydesTwo molecules of morpholine condense with an alde-hyde to form a 4,4'-alkylidenedimorpholine. When thealdehyde bears an alpha hydrogen atom, the appropri-ate enamines form upon gentle heating.

The Leuckart-Wallach ReactionThe addition of formic acid to a mixture of morpholineand aldehyde leads to reductive alkylation of themorpholine. This is the Leuckart-Wallach reaction.

Some ketones, e.g., cyclohexanone, can be usedinstead of aldehydes.

AlkylationIn addition to the Mannich and Leuckart-Wallach reac-tions, morpholine can be alkylated by several othermethods. Dialkyl sulfates, trialkyl phosphates, alkylhalides, and cyanhydrins are effective reagents for

preparing 4-substituted morpholines. Certain activatedethers also react with morpholine to give morpholinederivatives and, under vigorous conditions,polymethylene glycols have been found to give lowyields of ω -4-morpho-linylalkanols and 4,4'-polymethylenemorpholines. Examples of these reactionsare:

ArylationMorpholine can be arylated by aryl halides that possessrelatively labile halogens.

Morpholine reacts more slowly than does piperidinein this respect, but it is equally favored by the absence ofby-products and the morpholine derivatives are, ingeneral, higher melting.

CHEMICAL PROPERTIES

NH + C2H5OH + HCHOO NCH2OC2H5O 59%

NH + n - C3H7CHOO NCHO ON

NCHO

C3H7

95% CHC2H5

NH + (CH3)2CHCHO + HCOOHO

NCH2CH(CH3)2O 73%

NH + (C2H5O)2SO2 + NaOHO NC2H5O

NH + CH3CHCNO NCHCNO

CH3OH

KCN

NH + n - C12H25Br + K2CO3O NC12H25O

NH + CH3OCH2CH2CNO NCH2CH2CNO150 - 2300C

NH + HO(CH2)8OHO N(CH2)8OHO

N(CH2)8O ON

Catalyst

Heat Pressure

26%

+ 41%

NHO Cl NO2 + Na2CO3+

NO NO2

reflux

20

Aryl halides characterized by reduced aromaticity,e.g., halogenated anthraquinones or2-chloro-6-methoxy-benzothiazole, also arylatemorpholine.

Addition to UnsaturationLike most secondary amines, morpholine adds to α, β-unsaturated ketones, esters, and nitriles in a mannerpresumed to be typical 1,4-addition.

In certain instances, however, apparently as aconsequence of enolization, reaction occurs at an allylicposition rather than at the normal olefinic linkage.

In the presence of cuprous chloride, morpholinereacts with phenylacetylene to give 3-(4-morpholinyl)-1,4-diphenyl-1-butyne.

Reaction with Epoxides and IminesMorpholine reacts with alkylene oxides to give thecorresponding β-4-morpholinylalkanols.

Polyoxyethylene derivatives also can be obtained.

Ethylenimine and morpholine yield 4-(2-aminoethyl)-morpholine.

Willgerodt ReactionAs originally reported, yellow ammonium sulfide wasemployed in the Willgerodt reaction to convert aryl alkylketones to ω -aryl fatty acid amides. The volatility ofammonium polysulfide required that the reaction becarried out in a closed vessel at 150°C. The disadvan-tage was overcome when morpholine and sulfur weresubstituted for the volatile sulfide. Since then, thereaction has been the subject of considerable investiga-tion, much of it employing morpholine, although otherhigh-boiling amines can be used.

The nucleus may be heterocyclic as well as homo-cyclic. Thus, 4-acetylpyridine gives4-pyridylthioacetomor-pholide.

CHEMICAL PROPERTIES

NH + CH2 O

NCH2CH2COOC2H5O

reflux

86%

CHCOOC2H5

NH + C6H5CO NCHCO

CH2C6H5

Cu2Cl2CH CC6H5

NH + CH2 O NCH2CH2OHOCH2

O

NH + CH2 O NCH2CH2NH2OCH2 H2SO4

HN

55%

NH + O COCH3 + SN CH2CSNreflux ON 76%

NH +O NCO

N

S

N

SOCH3 OCH3

CIC reflux58%

NH + C6H5COCHO

ONC6H5COCH2CHCH2

COC6H5

COC6H5

CCH3

NH + (n + 1) CH2O N(CH2CH2O)nCH2CH2OCH2

O

OH

21

Acetylphenylacetylene and benzalacetone havebeen found to behave as typical aryl alkyl ketone, givingγ-phenylethylthioacetomorpholide and γ-phenylvinylthio-acetomorpholide, respectively.

When α-tetralone is the ketone employed, nothiomorpholide is possible without ring rupture and theproduct is 4-(2-naphthyl)-morpholine.

In addition to aryl alkyl ketones, the reaction hasbeen found to be applicable to aldehydes, alcohols,mercaptans, amines, olefins, and acetylenes. Thus,benzaldehyde, benzylamine, and benzylmercaptan givebenzothiomorpholide when refluxed with equivalentquantities of morpholine and sulfur.

Styrene and vinylnaphthalene yield the correspond-ing aryl acetothiomorpholides under the conditions of theWillgerodt reaction.

CHEMICAL PROPERTIES

NH + C6H5CO

ONC6H5C 51%

refluxCCOCH3 + S

CCH2CS

NH +OON

O

+ Sreflux

Acetylene gives 54% dithioöxalomorpholide and45% acetothiomorpholide.

Aryl alkyl ethers give β-aryloxypropiothiomorpholideswhen refluxed with morpholine and sulfur, but vinylethers and esters are cleaved at the oxygen to givethioaceto-morpholide.

Reaction with Oxidizing AgentsMorpholine reacts with aqueous sodium hypochlorite inthe cold to give a quantitative yield of4-chloromorpholine. Sodium hypobromite reacts simi-larly.

Essentially quantitat ive yields of 4-cyanomorpholineresult when a cold ethereal solution of morpholine istreated with cyanogen bromide.

On the other hand, if a benzene solution ofmorpholine and cyanogen chloride is refluxed, theproduct is the hydrochloride of1,1,3,3-bis(oxydiethylene)-quanidine. The hydrobromideof the same base results from reaction of 4-cyanomorpholine with morpholine hydrobromide.

Morpholine reacts with aqueous hydrogen peroxideto give low yields of 4-hydroxymorpholine.

NH + C6H5CHO + SO ONC6H5CSreflux

NH + C6H5CHO ONC6H5CH2CSreflux

52%CH2 + S

NH + NaOClO NClO

NH + C4H9OCHO ONCH3CSCH2 + S

NH + CNBrO NCNO

NH + CNClO NCO O • HClN

NH

reflux

NH + H2O2O NOHOO0C

22

CHEMICAL PROPERTIES

Oxidative condensation of morpholine with2-mercap-tobenzothiazole in the presence of iodineyields 2-(4 mor-pholinylmercapto)-benzothiazole.

The Hofman DegradationThermal decomposition of quaternary morpholiniumhydroxides may result in either retention or rupture of themorpholine ring.

Direct ChlorinationAn excess of morpholine reacts with chlorine to form4-chloromorpholine and an equivalent amount of mor-pholinium chloride.

Complex FormationThe addition of certain metallic halides to hot morpholineresults in the formation of addition complexes whichcontain two moles of morpholine per mole of metallichalide. The complexes are sensitive to moisture, but in

NH +OS

N

OHS

N

CSH + I2 CS 86%

NO NCH2O

CH

OH-+

CH2

NO

OH-+

NCH2CH2OCH CH2

NH + Cl2O NH2ClON - Cl +O2

NH + CCl3CHOO NCHO + CHCl3O 92%

NH + C6H5N2ClO C6H5N ONN

anhydrous condition some of them are stable to tem-peratures in excess of 200°C. The decompositiontemperatures of several of the halide complexes are:

Halide Decomposition Halide DecompositionComplex Range, °C Complex Range, °C

CdBr2 250-252 ZnCI2 200-210Cdl2 205-210 ZnBr2 230-240

HgBr2 131-135 SnCI4 215-235

Cuprous chloride combined in a 1:1 molecular ratiowith aqueous morpholine hydrochloride at temperaturesbelow 50°C gives a 90% yield of a complex which meltswith decomposition at 110.5 to 112°C. Cupric chloride,under the same conditions, gives a complex containingtwo moles of morpholine hydrochloride per mole ofcupric chloride. This complex melts at 160°C.

Miscellaneous ReactionsMorpholine attacks chloral in the same fashion as doessodium hydroxide; the products are chloroform and4-formylmorpholine.

The latter is formed in equally good yield frommorpholine and formic acid.

Aryl diazonium salts treated with morpholine give4-aryl-azomorpholines. These compounds are readilypurified and are reported to be remarkably stable in thesolid state.

23

an GeneralThe handling and storage of morpholine presents nounusual problems. Huntsman Corporation's TechnicalService Section is available to assist those who maydesire additional information.

Commercial morpholine is liquid at room tempera-ture, but will solidify at approximately 23°F.

The vapor pressure of morpholine is less than 7 mmof mercury at 20°C. Being an organic compound, it willundergo combustion, and it is classified as flammable bythe Department of Transportation. Although not consid-ered poisonous, morpholine is moderately toxic andshould not be ingested or allowed to come in contactwith the skin. In case of contact with the eyes, flushimmediately with plenty of water for at least 15 minutesand obtain medical attention. (See toxicity statement onpages 26-27.)

Maintaining SpecificationsMorpholine is hygroscopic and, if its water content is tobe minimized, a dry gas pad under a few ounces ofpressure should be used on storage tanks. Sincemorpholine is basic, it will react with acidic gases, hencecarbon dioxide and natural gas containing acidic sulfurcompounds cannot be used. Nitrogen is quite suitable.Nitrogen should also be used if low color is important,since absorbed atmospheric oxygen will causemorpholine to develop color.

Morpholine will react with copper to form complexsalts. Because of this, the use of copper and alloyscontaining copper should be avoided in equipment whichwill contact morpholine or its aqueous solutions.

Other factors that should be considered in theinstallation of storage and handling facilities are thesolvent properties and alkaline nature of morpholine.Storage tanks constructed according to a recognizedcode, using carbon steel as a material of construction,generally are satisfactory. In those cases where lowcolor is needed, stainless steel or aluminum should beused. However, aluminum should not be used if the

temperature of the morpholine will exceed 150°F.Neither should it be used in contact with aqueousmorpholine solutions at any temperature.

In areas where the temperature is expected to fallbelow 23°F, steam coils of a suitable area to heat thetank contents using low-pressure steam should be builtinto the tank about 6 inches above the floor. The coilsshould be constructed in such a manner as to allow thecondensate to drain. Stainless steel is the preferredmaterial of construction for the coils, particularly whenlow color of the morpholine is important. When steamheat is to be used continuously to prevent freezing of themorpholine, a temperature regulator that throttles eitherthe steam or condensate should be installed.

In situations where the ambient temperature is low,insulation of the tank will probably be desirable. Thetemperature of the morpholine in the tank should notexceed 100°F if the low color is to be maintained.

If a dry gas pad is used, pressure relief and vacuumrelief valves of suitable capacities should be installed.The dry gas system may consist of a cylinder of nitrogenand a line to the top of the storage tank. Tanks shouldbe diked and electrically bonded and grounded.

Transfer LinesTransfer lines, preferably not less than 2 inches indiameter, constructed of carbon steel and joined bywelds or flanges are suitable. Screwed joints are subjectto failure unless back-welded. Morpholine will leachconventional pipe dopes. However, threads can bewrapped with Teflon tape. Garlock 7021 gasket material,or its equivalent, is satisfactory for use with flangedconnections in morpholine service.

If the ambient temperature is low, the transfer lineshould be steam-traced and insulated. Steam-tracingcan be accomplished by affixing copper tubing, approxi-mately 3/8-inch diameter, to the underside of the line,insulating, and using low-pressure steam in the tubing.For flexible connections, stainless steel metal hose ispreferred to rubber, since rubber will generally deterio-rate in morpholine service.

HANDLING AND STORAGE

24

Systems which are insulated and steam-tracedshould be preheated in cool weather before being putinto service. Normally,15 to 30 minutes of applyingsteam to the tracing will adequately warm, but notoverheat, the system.

Transfer piping and pumps may be equipped with aninert gas padding system so that the morpholine can bepressured out of the lines when an extended idle periodis due. This practice will help to reduce losses andincreases in color that would result if the morpholine wasallowed to remain in the lines.

PumpsRotary or centrifugal pumps of all-iron construction canbe used with morpholine, although a centrifugal pump ispreferred. Rotary pumps should be equipped withexternally lubricated bearings. John Crane Type 9Mechanical Seal is suitable. Where pump packing isneeded, Garlock 234, Garlock 239, or equivalent isconsidered satisfactory. Provision should be made forpreheating pumps that are exposed to the cold. This canbe done by playing live steam on the uninsulated pump,or by having the pump wrapped with copper tubing andinsulated, then applying low-pressure steam to thetubing.

Unloading in Cold WeatherThawing a tank or tank car of morpholine is accom-plished by applying steam at 50 pounds maximumpressure to the coils of the tank or tank car. The liquidtemperature should be kept below 100°F to avoiddiscoloring the product.

As the morpholine melts, solids will remain in thebottom and on the sides of the tank while the warmerliquid rises. The thawing may be accelerated by using aliquid circulating pump. As soon as the flow of steam tothe coils is discontinued, they should be blown free ofcondensate with dry air to prevent freezing of thecondensate and rupturing of the coils.

Morpholine which has frozen in drums may bethawed in a hot room at about 100°F. The thawingshould be expected to require two days.

New Facilities and CleaningPrior to putting storage vessels into service, it is some-times desirable to purge with inert gas to remove oxygenfrom the tank atmosphere. Although cleaning tanks andtransfer lines frequently is not recommended, it issometimes necessary as the result of contamination oraccumulation of foreign material in the system. For suchcleaning, a water wash is generally satisfactory.

Tank cleaning is normally accomplished by thor-oughly sluicing the interior of the tank with a water jetand following this with cloth or chamois drying. Unlessexcessive rust scale makes it necessary, the interior ofthe tank should not be wire-brushed or sand-blastedbecause the oxides of iron are relatively inert tomorpholine. Once clean and dry, the tank should besealed and purged with dry inert gas to avoid unduecondensation and rust formation.

New systems frequently introduce line scale, rust,and the like, which will be a source of contamination andpossible plugging. These solids can be effectivelyremoved with either a “y” strainer, using a 150-200 meshstainless steel screen, or with a commercial-type clothfilter. A good grade of woven cotton canvas,12-ounce orheavier, is suitable as a cloth filter medium. Wool andsynthetic fibers have been found to be unsatisfactory.

Most of what has just been described concernscommercial, essentially anhydrous, morpholine. Itsaqueous solutions have lower freezing points and lowerviscosities, so storage and handling may be simplifiedconsiderably by dilution in storage if the morpholine is tobe used as an aqueous solution.

HANDLING AND STORAGE

25

SHIPPING INFORMATION

Packing Group III flammable liquid, does not address thepotential dermal corrosivity hazards of morpholine.Huntsman has recently sponsored DOT dermalcorrosivity studies using morpholine which indicate thatmorpholine should be reclassified as a Packing Group Idermal corrosive. On the basis of these studies, Hunts-man has petitioned the DOT for a change in the Hazard-ous Materials Table entry for morpholine, from PackingGroup III flammable liquid to Packing Group I corrosiveliquid with a subsidiary hazard of flammability. Until theDOT rules on our petition for this change, we will con-tinue to identify morpholine as a Packing Group IIIflammable liquid on our MSDS, product labels, andshipping papers, to minimize any confusion which couldresult from a discrepancy between our DOT PackingGroup determination and the existing DOT classificationfor morpholine. However, to ensure employee, cus-tomer and public safety, Huntsman will handle andtransport morpholine as a Packing Group I corro-sive, using appropriate shipping containers andhandling procedures.

For further information, please refer to the MaterialSafety Data Sheet (MSDS) for this product.

Delivery of morpholine can be made in 10,000- and20,000-gallon tank cars. These cars are constructed ofwelded carbon steel, and have bottom-unloading fittingsand steam coils. In areas within reasonable proximity ofbulk storage points, deliveries can be made in full orcompartmented, insulated, stainless-steel tank wagonswith steam coils. If requested, tank wagons can beequipped with unloading pumps and hoses. Drums ofmorpholine can be shipped promptly from local ware-houses in carload, truckload, or smaller quantities. Thenet weight of a drum is 460 pounds, approximately 55gallons per drum. Drums are UN1A1 or UN1H1, nonre-turnable.

Under US Department of Transportation (DOT) andCanadian Transportation of Dangerous Goods (TDG)regulations, the proper shipping name for this product is“morpholine,” identification number UN 2054. Thisproduct is considered a flammable material (TDG hazardclass 3.3) and requires a “FLAMMABLE” label forshipping. Please note: The Department of Transporta-tion (DOT) classification for morpholine, UN 2054, as a

26

HANDLING AND STORAGE

MORPHOLINE FDA CLEARANCES UNDER 21 CFR

Direct Additives172.235 173.310

Indirect Additives175.105 176.210175.300 177.1200176.170 177.1210176.180 178.3120176.200 178.3300

TOXICITY STUDIES

Acute ToxicityThe results of acute toxicity testing using morpholineindicate that this product is moderately toxic by singleoral and single dermal exposures. The oral LD50 in ratsand the dermal LD50 in rabbits are 1.05 g/kg and 1.21 g/kg, respectively.

Acute irritation studies have shown this product tobe extremely irritating/corrosive to the skin of rabbits,with a Draize dermal irritation score of 8.0 (maximumscore 8.0). Rabbit eye irritation studies using morpholinehave shown that this product is extremely irritating to theeyes, with a Draize ocular irritation score of >80 (maxi-mum score 110).

Chronic ToxicityA chronic inhalation (vapor) study of morpholine wasconducted using Sprague-Dawley rats at exposureconcentrations of 0, 10, 50, and 150 ppm for 6 hours perday, 5 days per week, over a period of 104 weeks.

Survival, body weight gains, organ weights, hematol-ogy/clinical chemistry blood parameters, gross pathol-

SAFETY AND TOXICITY

ogy, and histopathology were normal in the exposedgroups and comparable to the control animals. Therewere no exposure-related adverse changes in the liver,kidney, brain, intestine, lung, or any other internal organor tissue. The incidences of neoplasia were comparableamong all groups (including controls), and were typicalfor the strain and age of rat used in this study. Notunexpectedly, irritation of the eyes, nose, and skin wasobserved during the course of this study. Chronicexposure to morpholine vapors produced inflammationof the cornea (keratitis) at the highest exposure concen-tration.

Nasal effects included nasal cavity irritation andnecrosis at the highest exposure concentration. Poste-rior nasal structures (trachea, bronchial tree, and lungs)were histologically normal.

The results of this chronic exposure study demon-strate that morpholine is neither carcinogenic norsystemically toxic. These exposures did result in local(ocular, nasal, and dermal) irritation, consistent with theknown irritation properties of morpholine.

Genetic ToxicityA battery of in vitro genetic toxicity studies, employing anAmes assay, a Cell Transformation assay, an Unsched-uled DNA Synthesis (UDS) assay, and a Sister Chroma-tid Exchange (SCE) assay, were equivocal in theirresponses to morpholine. Morpholine was negative inthe Ames and UDS assays, and weakly positive in theMouse Lympho-ma Forward Mutation and SCE assays.Morpholine was active (positive) in the Cell Transforma-tion assay. The interpretation of these assays may beconfounded by the contribution of the pH of the testmedium (after introduction of morpholine) to the ob-served genotoxic activity in these assays. The possiblepresence of nitrosating agents in the test system may

27

SHIPPING INFORMATIONSAFETY AND TOXICITY

also contribute to genotoxic activity in these assays, dueto the potential formation of genetically active nitro-samines.

Aquatic ToxicityThe acute toxicity (LC50) of morpholine to freshwater fishhas been reported to range from 180 to 380 mg/l (Salmospecies). The acute toxicity (LC50) to freshwater crusta-ceans (Daphnia species) has been reported to rangefrom 100 to 119 mg/l. The toxicity threshold (EC50) toalgae has been reported to be 1.7 to 28 mg/l.

HUMAN HEALTH EFFECTS AND FIRST AIDOn the basis of these animal toxicity studies, the princi-pal health hazard from accidental exposures tomorpholine is a moderate to severe irritation/corrosionof the eyes, skin, and mucous membranes.Chemical-type goggles with face shield must be wornduring handling or use of the undiluted product orconcentrated solutions. Contact lenses should not beworn. Protective clothing and gloves resistant to chemi-cals and petroleum distillates must be worn.

Should accidental eye contact occur, flush eyes withlarge amounts of water for at least 15 minutes, afterwhich a physician should be consulted. During flushingof the eyes, eyelids should be held apart to permitrinsing of entire surface of eye and lids.

For skin contact, immediately flush skin with largeamounts of water for at least 15 minutes. Clothing wetwith the product must be removed immediately andlaundered before reuse. Morpholine has been known to

produce dermal sensitization (allergic skin reaction) insensitive exposed individuals.

If morpholine is accidentally ingested and theindividual is conscious and can swallow, he or sheshould be given two large glasses of water, after which aphysician should be consulted. Since this product isexpected to produce severe irritation/corrosion ofmucous membranes, vomiting should not be induced,due to the possibility of lung damage from aspiration ofthe product into the lungs during vomiting.

Under usual circumstances, exposure to harmfulquantities of vapor should not be a health problem;however, exposure to appreciable concentrations ofmorpholine vapors can result in irritation to the eyes,nose, and throat, and may produce temporary andreversible hazy or blurred vision. These symptomsdisappear when exposure to morpholine is terminated.Adequate ventilation should be provided where a largequantity of product is exposed, or where mists or vaporsare generated. Spills in confined areas should becleaned up promptly, using appropriate personal protec-tive equipment.

The Threshold Limit Value (TLV ) for morpholine, asestablished by the American Conference of Governmen-tal Industrial Hygienists (ACGIH) is 20 ppm (71 mg/m3),calculated as an 8-hour time weighted average (TWA).The TLV for morpholine also includes a “skin” notation,warning of the potential significant contribution to theoverall exposure by the cutaneous route. The Occupa-tional Safety and Health Administration (OSHA) hasestablished a Permissible Exposure Limit (PEL) formorpholine at 20 ppm, and a Short Term Exposure Limit(STEL) of 30 ppm. Exposures should be kept belowthese values to avoid symptoms of irritation to eyes,nose, and throat.

For further information, please refer to the MaterialSafety Data Sheet (MSDS) for this product.

28

Copyright © 2005 1080-0905Huntsman CorporationHuntsman Corporation warrants only that its products meet the specifications stated herein. Typical properties, where stated, are to be considered asrepresentative of current production and should not be treated as specifications. While all the information presented in this document is believed to be reliableand to represent the best available data on these products, NO GUARANTEE, WARRANTY, OR REPRESENTATION IS MADE, INTENDED, OR IMPLIED ASTO THE CORRECTNESS OR SUFFICIENCY OF ANY INFORMATION, OR AS TO THE SUITABILITY OF ANY CHEMICAL COMPOUNDS FOR ANYPARTICULAR USE, OR THAT ANY CHEMICAL COMPOUNDS OR USE THEREOF ARE NOT SUBJECT TO A CLAIM BY A THIRD PARTY FOR INFRINGE-MENT OF ANY PATENT OR OTHER INTELLECTUAL PROPERTY RIGHT. EACH USER SHOULD CONDUCT A SUFFICIENT INVESTIGATION TOESTABLISH THE SUITABILITY OF ANY PRODUCT FOR ITS INTENDED USE. Products may be toxic and require special precautions in handling. For allproducts listed, user should obtain detailed information on toxicity, together with proper shipping, handling, and storage procedures, and comply with allapplicable safety and environmental standards.Main Offices: Huntsman Corporation / 10003 Woodloch Forest Dr. / The Woodlands, Texas 77380 / 281-719-6000Technical Services Section: 8600 Gosling Rd. / The Woodlands, Texas 77381 / 281-719-7780

HUNTSMAN CORPORATION10003 Woodloch Forest Dr.The Woodlands, TX 77380Tel: 281-719-6000Fax: 281-719-7555

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Emergency AssistanceFor transportation emergencies only,call CHEMTREC 1-800-424-9300.

For all other emergencies,call 409-722-8381, our 24-houremergency number in Port Neches,Texas.

FOR MORE LITERATURE OR INFORMATIONPlease Call the Nearest Huntsman Corporation Office