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BIPHENYL AS A DYE CARRIER FOR POLYESTER FIBERS 024*e?6 MONSANTO CHEMICAL COMPANY Organlo Chemlcale Division St. Louis 66, Missouri TOWOLDMONOQ27852 The Information in this bulletin Is, to our best knowledge, true and accurate,^ but ail recommendations or suggestions are made without guarantee, since the conditions of use are beyond our oontrol. The Monsanto Chemical Company disclaims any liability incurred in connec tion with the use of these data or suggestions. Furthermore, nothing contained herein shall be construed as a recom mendation to use any product In oonfliot with existing patents covering any material or Its use. I I I c TOWOLDMONOQ27853 3 BIPHENYL AS A DYE CARRIER FOR POLYESTER FIBERS 3 INTRODUCTION ] The well-known process of mercerizing depends largely on the ability of caustic soda to swell cellulose. But polyester fibers Buch as Dacron and Terylene present a more dlffloult problem. The polymers themselves are practically inert to most forms of chemical attack. ^* i As a result of a tremendous amount of work, a few compounds were found J to have some swelling action. These swelling agents, or "carriers" as they are usually oalled, are organic chemicals that have the property ! of greatly Increasing the rate of dyeing of polyester fibers when added -i to the dyebath. The. observation that certain chemicals behaved In this way was made during the Initial study of the dyeing of Terylene. since "I extensive searoh has been made for suitable oarrlers. J' A wide variety of organic compounds were found to aooelerate the rate of "J dyeing of disperse dyes on polyester fibers at temperatures up to 100C., Including aromatic hydrooarbons and chlorinated hydrocarbons Buoh as biphenyl, mono- and dlohlorobenzene, ohlorotoluenerf and phenollo derlva- tlves such as o- and p-phenylphenol (2- & 4-hydroxydlphenyl), oarboxy.110 j acids Buoh as benzolo, dlohlorobenzolo, salloyllo adds and amines suoh " as dlphenylamlne, . j Few compounds, however, have sufficiently attractive properties to Justify J their oommerolal use. Carriers now being used In the United Kingdom are mainly biphenyl, and to a lesser extent, o- & p-phenylphenol (2- & 4- Hydorxydlphenyl), mono- or dlohlorobenzene and mixtures of tetrahydro- * naphthalene with oyolohexanol. In thlB country, o- & p-phenylphenol, biphenyl, trlohlorobenzene, o-dlohlorobenzene and butyl benzoate are used. V _ . By employing a oarrler In the dyebath, full depths of shade may be ob tained In normal dyeing times from the majority of disperse dyestuffs. ~ Owing to the absence of chemically reactive groups from Dacron (duPont's j polyester fiber) and Terylene (i.C.I.'s polyester fiber), the classes of dyes available for Its coloration are In general, limited to the dls- perse dyes and certain azolo combinations. In addition, It Is possible to apply selected vat dyes at 130C., In an unreduced condition or as ' their sold leuoo compounds, while solubilized vat dyes--e.g., Soledons - (I.C.X.)jind Clbantlnes (Clba) oan be applied to Terylone-ootton fabrlos by padding. Pigment dispersions may also be padded on to Daoron and ^ Terylene fabrlos In conjunction with appropriate binders and fixed by ^ baking. ' - WHAT MAKES A GOOD CARRIER 02*6278 1 In determining the efficiency of a oarrler suoh factors as concentration reJ qulred in the dyebath, temperature of dyeing, effeot of variations In liquor* to goods ratio, effeot on the rate of dyeing and effeot on the bulld-up of : dyes must be considered. TOWOLDMONOQ27854 -2- Suooasaful oarrlor muse have the following propartlesi A. High efficiency B. Availability at low coat C. Little or no effect on the fastness properties of the dyed fiber D. No flmell or toxicity E. No degradation or dlsooloratlon of the fiber F. Ready removal after dyeing ' 0. Stability under dyeing conditions . K. Compatibility with the dyestuffs used . It Is believed that-biphenyl meets all the above qualifications required In an excellent and eoonomloal dye carrier, A. HIOH EFFICIENCY From a quick look at Figure 1 -- the dye bath exhaustion of 3# Dlspersol Fast Scarlet B-150 powder fine oan be Increased from 48-80# at 100C and from 11-63# at 85C by the use of 8# emulsified biphenyl, during a dyeing time of 60 minutes. PERCENTAGE DYE8ATH EXHAUSTION FI0.1, The effect of emulsified biphenyl on the rate of dyeing of DlBperaol fast Scarlet B 150. TOWOLDMONOQ27855 -4- The ur.e of .biphenyl emulsifier, since It results In an Increase In diffusion rate also lnoreases the leveling power of the applied dyestuffs, I.C.I. claims that the leveling properties on Terylene fiber of disperse dyes, applied along with Tumesoal D (Z.C.Z. emulsified biphenyl) are oomparable with those of disperse dyes on nylon as shown In the following Table I, TABLE I LEVELING PROPERTIES OF BIPHENYL Fiber Terylene Terylene Nylon Conditions of Dvelnm 3# Dlspersol Fast Scarlet B-150 Powder Fine - No Carrier 3# Dlspersol Fast Scarlet B-150 Powder Fine - 8# Tumesoal D 3# Dlspersol Fast Scarlet B-150 Powder Fine Percentage Leveling In 1 hour 16 60 60 H Levellna Pyestuff on originally, white material x 1Q0 ^ Pyestuff on originally dyed material The white and dyed material used In the test are entered Into a blank dye bath under conditions similar to those whloh existed during the original dyeing. B. AVAILABILITY AT LOW COST 0*46281 A quick look at Table II below shows clearly that biphenyl Is the cheapest of the most popular dye carriers. (Ref. REVIEW OF THE DYEINO 6F POLYESTER FIBERS WITH DISPERSE DYES BY USING CARRIERS. Erich Frleserj Reyon, Zellwolle U, Chemlefasern 9, 378-83 (1959) C.A. 53, 2O01Of, 1959). In comparison with o-phenylphenol, biphenyl oosts naif as muoh for the production of the same oolor shades. TABLE II Carrier Cost Per Lb. Concentration In Bath 20 tl Cost Per 100 Lbs.Fabrlo Dyed In Dollars Biphenyl Trlchlorobenzane O-Phenylphenol Me thylsalIcylate Benzoic Aold. Latyl-Carrier A (duPont's) 0.1675 0.15 0.385 0.6025 0.37 1.24 4.0 g/l 5.0 g/l 3.2 g/i 10.0 g/1 20.0 g/1 5.0 gA 1.34 1.50 2.48 12.05 14.80 12.40 TOWOLDMONOQ27857 -5 * 0, LITTLE OR WO EFFECT ON THE FASTNESS PROPERTIES OF THE DYED FIBER Any xiraoss of biphenyl left on the fiber or the fabrlo has no detrimental effect whatsoever on the properties of the fiber or Its high fastness. O-phenylphenol effects the light fastness of many dyes. P- phenylphenol can have a very severe effect Indeed (an average reduction of 0.5 S.D.C. unit over the oomplete dispersion and duranol range). - The wet fastness properties show. In general, soma Improvement over corresponding dyeing with no carrier. The fastness- to nabbing and dry cleaning of dyeings carried out with emulsified biphenyl are generally superior to those oarrled out without the use of a carrier. D. SMELL OR TOXICITY The slightly phenolic odor of biphenyl In fabric dyed In the presence of biphenyl as a dye carrier could be objectionable sometimes If a trace Is left on the fiber. However, using the proper techniques, biphenyl residue should be completely removed. The normal procedure of vaouum drying of the fiber or the fabrlo at 70-80C Is sufficient. Laboratory and'practical Investigations have shown that biphenyl is completely harmless In quantities greater than that to which workers are normally exposed, (See pagel6). E. NO DEGRADATION OR DISCOLORATION OP THE FIBER Biphenyl has no detrimental effeot on the color of the fiber end fabric or the fiber and fabrlo themselves or their blends. In the presence of biphenyl as a dye carrier, shrinkage la much lesB pronounced than with o- or p-phenylphenol, P, READY'REMOVAL AFTER DYEINO The following table lists the vapor pressure of biphenyl and o-phenylphenol at various temperatures! , Temperature C F 70.6 90 ,, 101.6 117 152.5 204.2 251.9 286 - 159.1 194 215.2 242.6 306.5 211:1 .546.8 Biphenyl MM Pressure 1 0 5 10 40 200 760 0 ' " o-PP ' ' MM Pressure 0.4 0.7 1.45 3.1 14.8 88 0 760 TOWOLDMONOQ27858 -6- Based on the data on the preoedlng page, It Is easier to remove biphenyl than o-phenylphenol using,the vaouum oven drying method. 0. STABILITY UNDER DYEINQ CONDITIONS Biphenyl Is one of the most stable organic compounds -- slnoe It has no functional groups It does not enter Into any chemical reaction with dyes used for polyester fibers nor chemloals normally used In dyeing baths, Hydrophobic dye carriers are moBt desirable. H. COMPATIBILITY WITH DYESTUFFS - It may be stated that the effect of the carrier In the fiber does not depend directly on the type used but on the number of molecules present In the fiber. Thus, the Bteeper the distribution curve of a substance, l.e., the more hydrophoblo this subBtance Is, the more suitable It will be as a oarrler. Biphenyl Is hydrophoblo, contrary to o-phenylphenol. Some very Important qualifications for a good oarrler ares 1. Insolubility In dye bath - biphenyl is extremely Insoluble In water. ' 2. Solubility of dye In the oarrler - biphenyl Is an excellent solvent for many dyes. 3. Solubility of the fiber In the dye oarrler. At high temperatures, biphenyl Is an excellent solvent for fibers. Patent No. 2,710,849 describes a method for homo geneously dyeing aromatlo polyesters in the presence of biphenyl as a solvent. V In Table IV on the following page, three related carriers are oompared in praotloal behavior and it will be seen that many oonfllotlng faotors must be considered before staking a final oholow for a particular purpose. *>2*6283. TOWOLDMONOQ27859 G tabus IV PRACTICAL PROPERTIES OF THREE RELATED CARRIERS P Proporty Biphenyl o-Phenylphenol p-Phenylphonol 1; Molting point T10. 5*o0. 165C. H Method of Use L-l Aqueous emulsion n ^ Quantity employed 6-10 on fiber wt. P' l: Forms of Terylene on Loose staple, whloh mainly used slubblng, yarn, D half-hose Na salt oonverted to phenol during dyeing Aq.dispersion,or Na salt oonvorte to phenol during dyeing. 2-4 parts/1000 parts of dye liquor. . 2-4 parts/1000 parts of dye llq Loose staple, slub., yarn, half-hose, knitted fabrlo and woven oloth, Terylenewool yam. Terylene-wool oloth, subJ. to light fastness limitations. P suitable equipment n w Bpooial Precautions H .. Method of Removal r*i LT . Chief Drawbacks D G Open back, olroulatlng maohlnery, paddle maohlnery. Keep dyeing temp. >0OO, otherwise oarrler may solidi fy. Add portionwise. Dry heat, storage Unlevel dyeing ft smell In few Instances Open book, circu lating maoh., paddle maoh.. Jig , winoh, star-frame. All types Liberate phenol slowly None at 1000. NaOH & Llssapol 0 at 70-100C. will, remove oarrler from fiber surface. Slight effeot on light fastness; oomplex dyeing prooess As o-Phenylpheno Appreciable effeot on light fastness. |j 'Bxoept for Terylone-wool oloth. 0 *0 D TOWOLDMONOQ27860 The RELATIVE PRACTICAL MERITS OF'THC most WIDELY uses CARRIERS ARC SUMMARIZED IN TABLE V. TABLE_V PROPERTIES OP EXISTING CARRIERS Carrier ErriciENCY on Weight Basis Effect on Light Fastness Biphchyl High Mono- 1 Dichlorobehzckcs High ' None None Poss 1 BLC Hazards Slight Toxic . Methyl Salicylate o-Phehylphehol p-Phcnylphcrol Phenylmethylcarb1NOL (4 Acetophenone) - High 'Medium Midium Low-Medium Tctrahyorohaphthalcnc (4 Cyclohcxanol) Benzoic Acio High Low Salicylic Acid o > > CD Ul Lov None Slight Appreciable None Appreciable Nome None Slight Slight Slight Slight Toxic Slight Slight Smell Ease of Removal Level-Dyeing Properties Intense Moderate Intense Moderate Slight Intense Mooeratc Moderate Usually Good East , Usually Gooo IN ENCLOSED MACHINES Difficult Usually Good Mooerate Usually Good Difficult Good East Usually Good, HAY KARSHEIt THE F1BER " Mooerate Can be poor None None Easy Mat cause SPECKS Difficult Easy May cause SPECKS TOWOLDMONOQ27861 -9- In the very few Instances where biphenyl gives unlevel dyeing, certain dyeing assistants lnorease leveling action by slowing down the rato of absorption, Sodium hydrooarbon sulfonates, such as Avltone T, (duPont) and nonlonlo surfactants, such as Alkanol KCS surfaco-aotlvo agont, (duPont) both have the effect, particularly with blue disperse dyes. At 1.5 g/l, AVitone T gives fairly good retarding and leveling, but where a greater effect is required, 0.25 to 0.5 g/l of Alkanol HC3 should be used. ' MOPES OP OPERATION OP DYE CARRIERS Various theories have been put forward to explain the mode of operation of dye carriers, . Vlkerstaff has described possible modes of carrier action such as lnoreaslng the solubility of dye in water, swelling or plasticizing the fiber, or forming new dye sites. He differentiates between water* soluble oarrlers like benzoio aold and water-insoluble oarrlers like biphenyl. . Vlkerstaff ooncludes that carriers merely Berve the same purpose as raising the temperature. In that the molecular structure Is loosened and the rate of dyeing Increased. Experimental work by Peters and Sumner leads to the following conclusions! 1, Water-BOluble agents are first adsorbed by the fiber, which Is thereby swollen or plasticized, so that dyeing can take place more quickly. These agents compete with dye for available slteB In the fiber and the equilibrium exhaustion of dye Is reduced. This phenomenon was observed for benzole aold by Remington and Schuler, 2. Water-Insoluble agents, In addition to plastlolzlng the fiber, also serve to* surround It with a solvent layer in which dye Is highly soluble. Dyeing Is further accelerated owing to the increased concentration gradient. METHODS OF USING BIPHENYL . The water- and alkali-insoluble agents like biphenyl and mono- & dl- chlorobenzene are added to the dyebath as aqueous emulsions or dis persions; agents like benzoio aold and o-phenylphenol oan also be used In this way, but It Is more usual to predlssolve them with sodium hydroxide (or to use the ready-made sodium Balt) and liberate the free aold or phenol at the desired rate by gradually adding a weak aold during the dyeing process. . The main drawback to the liberation of the free dye carrier acids or o- and p-phenylphenol Is the difficulty lb maintaining the proper pH during the dyeing. It Is well known that the performance dyes in the dye bath are sensitive to the pH of liquors. Any slight ohange in the pH oould effeot the reproduction of oorreot shades. 0246286 TOWOLDMONOQ27862 10 EMULSIFIERS According to various theories by experts In the dye carrier field, the most reoommended emulsifiers for biphenyl or hydrophobic carriers Is the nonlonlo type (condensation products of alkylphenols with ethylene oxide). However, a small amount of anionic emulsifier such as sodium saltB of naphthalene sulfonlo acid, formaldehyde condensation produots, Bodlum lignin sulfonate and sulfonated turkey oil and other alkylar/1 sulfonates should be present to maintain an excellent level dyeing,. Two procedures are suggested for the preparation of the emulsion: 1, Dry Mix - To dry mix the biphenyl and the nonlonlc and anlonlo emulsifiers In the proper ratios, generally the biphenyl contains . from 10 to 30% emulsifiers depending on the conditions used. To the above pre-prepared dry mix, 1 part,Is added 4 parts of water. This mixture Is then brought to boll with constant agitation until emulsification Is complete. The time of boiling necessary for the preparation of emulBlon 1b rarely longer than two-minutes. This emulsion Is now ready for pumping Into the dye bath. 2, Liquid Emulsion - A mixture of approximately biphenyl 30-50 parts, nonionic and anionic emulsifier 10-20 parts and any suitable solvent such as toluene (most preferred) xylene, o-dlohlorobenzene, tetralln, decalin and ethyl benzene, 20-40 parts Is prepared as stock for biphenyl. This liquid mixture Is then added to dye bath at 150-l60F. where It quickly emulsifies with the dye llquore. RECOMMENDED BIPHENYL CONCENTRATIONS The concentration of biphenyl in the dye bath depends on the shade of the fiber dr fabric required to achieve. Concentrations of approxi mately 4-12# of the weight of the fiber or fabric are recommended, as Its action Is comparatively Insensitive to the llquor-to-goods ratio employed. Because biphenyl may have the tendency to condense on the"cooler parts of the equipment and drop baok Into the dye liquors where it may cause spots on the fabric, It is reoommended to steam or preheat that Section to avoid any condensation, CONCLUSIONS Biphenyl, If properly emulsified, Is the cheapest and most efflolent dye oe.rrler on the market today. 02*6287 TOWOLDMONOQ27863 - 11 In praotlce, the choice of the best carrier from those available Is by ease of application and affeot on light fastness. Biphenyl Is used today very successfully on loose stable, Blubbing and yarn in circu lating machinery and for piece dyeing on the Jig, winch and beok dyeing machines. .. 0- or p-phenylphenol affeots the light fastness of many valuable disperse dyes on polyester fibers. Even with o-phenylphenol, which affects the light fastness to a lesser extent than does the para Isomer, spotting troubles are not unknown and the strictest oontrol of the rate and the temperature at which the free phenol Is released 1b essential to obtain satisfactory results on 100# Terylene and Dacron. The problem of producing speok-free dyeings with o-phenylphenol on Terylene-wool or Daoron-wool blended fabrics 1b even more aoute. BIPHENYL AS A CARRIER IN STRIPPING BATHS Despite all the care taken to Insure perfect dyeing, an average of about'2# of material has to be redyed for a variety of reasons ranging from nonuniformity -or nonmatohlng to a swltoh In fashion making the color obsolete. Reduolng agents are most effective strippers. The strip Is usually alkaline with 6# o.w.f. sodium carbonate and 4# reduoer (sodium hydro sulfite or zinc BUlfoxylate formaldehyde) at 200F. The more hydrophoblo fibers)need carriers to allow the reducer to penetrate the fiber and attaok the dye-fiber bond. Biphenyl Is an excellent and efflolent carrier for this purpose. SUGGESTIONS FOR DYEINO OF VARIOUS BLENDS OF POLYESTER FIBERS VISCOSE-DACRON BLENDS ' These are dyed with direct and disperse dyes In a one-bath or, preferably, a two-bath pethod wherein the Dacron Is dyed first with biphenyl as carrier, the fabric sooured to remove the oarrler, the bath dropped and the viscose dyed In a fresh bath. The one-bath process saves time but the two-bath usually provides better shade oontrol and light fastness. ARNEL . ' Arnel dyes slower than acetate with disperse dyes but faster than Dacron or staple Orion. The disperse dyes are selected for their fastness to light, gas, and ozone fading, washing, and sublimation (the LOWS fast dyes). Carriers and high temperatures (205F plus) are needed to obtain satisfactory penetration and diffusion within the fiber. Biphenyl, properly used, Is a suitable Arnel dye oarrler. Xn blends with Daoron or the aorylloe, biphenyl oan also be used.. 02*6288 TOWOLDMONOQ27864 - 12 - emulsions of biphenyl must-be stable,or spotting, praatloally Im possible to'remove, will ooour. Exoeselve amounts of emulsifier will reduce oa.rrler action. Minimum dyeing temperature Is 205? at which light-medium shades will dye without carrier In 3-6 hours and dark shades with carrier In 4-6 hours. Arnel oan be dyed, especially dark shades, with developed In situ azoic dyes provided conditions are modified to compensate for slower plok-up of components and dlazotlzatlon. ARNEL-COTTON BLENDS For union dyeing the heat treatment follows the dyeing. For best results on crossdyelng the heat treatment Is run before mercerizing, the oOtton dyed with vats and the Arnel finally with disperse dyeB using biphenyl as the carrier. If the cotton Is stained, strip with 0.5-1*0# o.w.s. sodium hypochlorite oold, followed by rinsing and a 0.1$ o.w.s. sodium bisulfite antlohlor. Vat classes IK and IW stain Arnel the least. ARNEL-DACRON BLENDS These require a biphenyl carrier for disperse dyeB selected from those recommended for Dacron, a scour to remove Arnel Btalns and then seleoted disperse dyes with biphenyl applied for shading the Arnel. Carriers will Improve dyeing, but'no more than 2# o.w.f, should be used or excessive swelling will weaken fibers and oauBe shrinkage. DACRON Best results are obtained with disperse dyes. For pastels and light shades they are used alone. Heavier shades require biphenyl as a carrier at the boll. DACRON-SILK BLENDS -----------------------------------------,-------------------------- . . These can be dyed union or contrasting shades using selected disperse dyes for the Dacron and add dyes for the silk. A two-bath method must be used, dyeing the Daoron first with the carrier beoause the silk must be stripped, slnoe It dyes almost as..dpp as the Daoron bjut with poor fastness properties. Slnoe the Btrlp Is never oomplete, deeper or duller than normal acid dyeings are required for the silk to aohleve a satisfactory dyeing. < DACRON-CELLULOSIC BLENDS These blends are dyed union or cross In one- or two-bath processes using oarrler-applled seleoted disperse dyes for the Daoron and dlreot dyes for the cellulose. Resin treatments applied to the high oelluloslo oontent blends lnorease the dlreot dye fastness* but vats must replaoo the dlreots for best wash fastness. 02M>*ee TOWOLDMONOQ27865 - 13 - In the single-bath method with direct dyes, biphenyl could be used as a carrier. After the Daoron Is dyed at the boll, 10-30;, sodium chloride is added to exhaust the dlreot dyes. Tha temperature Is lowered to 170-l80P to help exhaust the deeper shades. Nonlonlo surface active agents.should be used so that the disperse dye staining of vIsoobo is not Increased and to decrease the dlreot dye color value. DACRON-NYLON BL.'.NDS These are dyed union, cross, or heather by one- or two-bath pro cedures. The one-bath method uses the technique normally used to dye nylon adding disperse dyes and carrier to dye the DacrOn.- The more widely used two-bath method allows an Intermediate scour of caustlo soda and hydrosulfite after dyeing the Daoron with biphenyl as the oarrler to reduoe the amount of disperse dye staining the nylon. DACRON-ORLON BLENDS These blends can be dyed union or tone-on-tone In a one-bath method or In a two-bath process where the Dacron Is dyed with disperse dyes. Normally, the goods scoured at l80-200F with a surfactant (the Orion will still be stained slightly), and then the Orion Is dyed with catlonlo dyes. Any catlonlo dye staining of the Dacron oan be re moved by a l/lO to 1/4 strength stripping bath. SUGGESTED METHOD FOR DYEINO ARNEL IN COVERED BECK WITH DISPERSE DYSS KUS CTr'RYEr" (Yeroentages o.w.f.} ..................... 1. Load Singed and boiled off goods on winch. 2. Scour 30 minutes In 1,5-2# detergent (Igepon T). 3. Make up dyebath at 105F containing 4# seleoted disperse dyes, 1# gas-fading Inhibitor and 0.5# Igepon T and 8# emulsified biphenyl. . 4. Run doth In dye bath 30 mlnuteB at 105F, 30 minutes at 150?, raise to 205?, olose book and run 5 hours at 205?, 5. Rinse ' 6. soour 30 minutes at 120? In 0.5# Eraulphor ELA-719* 7. Rinse and dry. 8. Heat treat 10-30 seoonds.at 400-435?, *46?90 TOWOLDMONOQ27866 - 1ft - DACRON CARRIER DYED . 1. Soour 15-80 minutes at 160-1&JF. 2. ,Rlnse thoroughly. 3. Set bath at 120-l40F with O.O3-O.O556 o.w.e. surfactant and 0.03# o.w.s, softner. 4. Add, oompletely emulsified biphenyl 4-12$6, depending on shade required, at 160-180F. ' 5. Mix well at 160-180F for one-half hour. 6. Add disperse dyes' pasted with dispersing In hot water. 7. Raise temperature to boll. 8. Boll 2 hours. 9. Rinse ' 10, Soour 11. Dry, preferably at 3OO-35O0? to sublime off residual biphenyl. 0246291 TOWOLDMON0027867 - 15 - SOLUBILITY TABLE FOB TECHNICAL DIPHENYL Type of Solvent Hydrocarbon Hydroxy Derivative Solvent Mineral Spirits Gasoline (Texaoo) Kerosene Benzene Xylene Turpentine Toluene Methyl Alcohol Ethyl Alcohol (3-A) n-Butyl Alcohol Amyl Alcohol Glycerine 90# Phenol Solubility In gme. biphenyl/ IOC co. Solvent 16.9 24.1 17.5 81.5 56.9 24.2 62.0 7.45 6.7 9.1 10.3 . Insol, 17.8 Te0mN^* p, 26 26 27 27 27 24 18 24 28 27 22 Rm. Temp 28 Ethere Ethyl Ether Cellosolve Aoetate 57.8 50.3 24 25 Ither Aloohol . Cellosolve Carbltol Diethylene Olyool 22.5 14.5 Insol. 21 27 Rm. Temp Be ter Methyl Acetate Ethyl Acetate ' Butyl Acetate Amyl Acetate Ethyl Laotate Diethyl Phthalate Trlcresyl Phosphate 48.4 56.6 73.4 55.4 25.6 30.2 50.0 24 22 29 27 25 26 34 Chloro Derivative ', Chloroform Carbon Tetrachloride Ethylene Dlchlorlde Trichloroethylene Tetrachloroethane Monochlorobenzene Orthene 110.0 66.4 111.0 95-2 106.2 93.2 103.0 19 22 23 23 22 23 29 ietone Aldehyde .mine Tying Oli elde Acetone 40# Formaldehyde Aniline Pyridine Tung Oil . Linseed Cll Acetic Acid Oletlc Acid 55.8 Insol. 44.6 . 40.0 36.2 22.8 15.8 20.2 19 Rm. Temp 22 25 * ON** 26 26 25 lacellaneous Nitrobenzene Carbon Disulfide 81.4 149.6 Tnnnl. 25 26 Rkrmi. Ttoemmpu* TOWOLDMONOQ27868 ] - 16 3 the toxicity of biphenyl and o-phenylphenol 1 The following data was extracted for toxicity studies by R. 0. TomklnB and F. A. Isherwood, Analyst, 1945, 70, 330, 1 - INGESTION OF SINGLE DOSES (a) Biphenyl suspended in gum acacia solution or dissolved in nut oil has been given by stomach tube to cats in doses up to 1 g/kg. of body weight without oausing any visible ill effect, (b) O-phenylphenol, similarly administered, was more toxic, the mean- lethal dose being about ,0.5 g/kg. for cats, and about 3 G/kg. for rats. The picture of acute, intoxication was one of general depression, with death following through respiratory failure; in cats hemorrhage was , obsorvod post mortem in the lungs, liver, alimentary canal and myocardium. Sub-lethal doses of o-phenylphenol usually produoed no obvious signs of. poisoning. INGESTION OF REPEATED DOSES With many aromatlo compounds the effeots produced by their repeated, administration are quite unlike those produced by a single dose; the blood forming tissues, in particular, are often poisoned by prolonged exposure to concentrations far below those immediately lethal. For this reason it Ib always necessary to determine the chronic as well as the acute toxi h city of any substance which may be administered repeatedly to man. Young ratB are suitable test objects for this purpose, since any cumulative effeot on the substances might be manifested in a departure from the normal D growth rate. . . (a) Biphenyl - Sixty male white rats, weighing between 35 and 75 g. were divided into four equal groups of the same mean weight and fed ad libitum on the stock laboratory diet. Each rat was given 0.005 ml. of nut oil per g. of body weight daily by mouth and was weighed every second day. Group 1 received no biphenyl. The oil administered to groups 2, 3 and 4 contained 0.4 and 40 mg/ml respectively of biphenyl; the dally Intake of the compound was thus 2, 20, 200 mgAg for these three groups. There was no significant difference between the mean growth rates of the 4 group# during the four weeks of the test, and no animal Bhowed any sign of ill health attributable to the biphenyl feeding. At the end of the test, the blood of six rats from Group 1, and six ratB from Group 4, was examined. Hemoglobin content, total white cell oount and differential white cell count were normal In all cases. (b) O-phenylphenol - The effect of chronic administration of thlB sub stance Xas tested in an experiment on sixty young male white rats lasting thirty-two days; the method of administration and the dOBage levels were exaotly the same as in the biphenyl experiment. The mean growth rate was again praotleally identical in the four groups. There were no signs of 0 0Z*bi93 TOWOLDMONOQ27869 3 3 - 17 - l . j L..J --a c m -- c m -- u . i i . i ! ; . j Ui health attributable to the o-pnenylphenol, and examination of the blood of eight rats from Group 1 and 4 at the end of the experiment showed no significant effect of the treatment on the hemoglobin or white oell level. PARENTERAL ADMINISTRATION (a) Biphenyl - No sign of Irritation followed the Injection of 0.5 ml of a 4jii solution Into the skin of a rabbit's ear, or the rubbing of such a solution Into the skin of the forearm of two human subJeotB. The lntra- perltoneal lnjeotlon of 0,5 g/kg Into a rabbit In the form of an oily solution or aoaola-sallne suspension had no 111 effeot. (b) O-phenylphenol - The tests for cutaneous Irritation described for biphenyl were negative for this oompound also. By lnt'raperltpneal lnjeotlon o-phenylphenol Is somewhat more toxlo than by mouth, the mean lethal dose for rats being about 1,5 g/kg with the'oily solution and about 0.5 gAg with the aoaola-sallne suspension, INHALATION OF VAPOR ' The vapor pressure of both compounds Is, at ordinary temperature, so low that the risk of a toxic quantity entering the body through the lungs seems remote, A mouse kept for six hour periods on two suooesslve days In air saturated with biphenyl vapor at 20C showed signs of discomfort during the exposure, but appeared normal soon after being removed from the chamber, and showed no sign of Injury later. A Bimllar experiment with o-phenyl phenol at 25C gave the same result, 1 These experiments emphasize the low toxlolty of both compounds, expeclally J of biphenyl, which appears to be pharmacologically nearly Inert. The doses given to the animals In these tests were, of course, far greater than would ever be Ingested by anyone eating oranges from treated wraps. Thus, sup - posing that the peel of such oranges contained uniformly 20 mg/100 g of biphenyl or 30 mg/100 g of o-phenylphenol (the highest concentrations found " by Tomkins and Isherwood), and supposing also that the rat and man are . equally sensitive to these oompounds, then a 60-kg man eating the peels of ca. 400 oranges a day would still not be getting enough preservative to do him any harm. The amounts of the substances In orange pulp, and In marmalade , made from treated oranges are still more negligible. The low toxlolty of the compounds when given by lnjeotlon or Inhalation shows that the handling of ' treated oranges and wraps is not dangerous to health. J1 ' DESCRIPTION AND PROPERTIES OP BIPHENYL , 1 Biphenyl; Diphenyl; Phenyl Benzene; C6H5.C5H5 or CipHjoJ The oompound ' Is indexed by the Amerloan Chemloal Soolety as "Biphenyl" rather than "Diphenyl" to ponform to the nomenolature adopted by the Soolety. The ; formula is preferably written as CgH^.C/dfe to distinguish It from aoe- J naphthene which has the same moleoular formula of 012U10. 0 Z*62`>1' TOWOLDMONOQ27870 18 Moleeular weight 154.20. Contains by theory 93.46j6 oarbon and 6.54# hydrogen. Biphenyl Is formed by the linking together of two benzene nuoleln, or In effect, a hydrogen atom of benzene 1b replaoed by phenyl. PROPERTIES OP PURE BIPHENYL Molecular Weight Bolling point at 760 mm Bolling point at 10.5 mm Crystallizing point Melting point Solution point ' Specific gravity at 77/4C Specific gravity at 20/40 Refractive Index 77.10 Viscosity at 100C . Viscosity at 70C Surfaoe Tension at 129,2G Solubility In Water ,, Solubility In abs. alo. at 19.5 0 Solubility in IOO56 Methanol 19.5C Benzene at 27.9C Heptane at 26.5C Flash point F (method) Fire point F Heat of combustion Kg-cal, (15) latent heat of fusion Latent heat Of vap. at 69.2C Specific heat at 40C Critical temperature Critical pressure Pounds per gal. at 77C 154.20 255C 118 69.oc 690c 0.9896 1.041 D-l.58822 28.8 Say. Sec. 31.2 Say. Sec. 39.5 dyne/cm 9.98 0. 100 g. sol. Seidell 6.57 k/100 g. solvent 137 g/100 g. Solvent 25.1 g/100 g. Solvent 235F - closed cup 255F - open cup per gm. mol. - 1504.4 28.8 gm. oa l/gm. or 53.1 BTU/lb. 190.0 BTU per lb. 1.61 Joule/gm 8,23 lbs. per gal. MONSANTO SPECIFICATIONS Appearanoet Colorless to pale yellow orystalllzed solid or flake Freezing Points Distillation Rang*1 68.7C minimum 2,5C raxlmum Including 255C 0246295 MONSANTO CHEMICAL COMPANY ORGANIC CHEMICALS DIVISION 800 NORTH LINDBERQH BLVD. ST. LOUIS 66, MISSOURI TOWOLDMONOQ27871