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HB-40 Monsanto Technical Bulletin No. P-104 July 1, 1952 Monsanto Chemical Company, Phosphate Division, St. Louis, Missouri Monsanto Technical Bulletin No. P-104 July 1, 1952 **** HB-40, a relatively non-toxic, high-boiling, colorless liquid is especially of interest for plasticizing polystyrene, vinyl resins, ethyl cellulose and asphaltic materials and for softening many rubber compounds. ' The product is reasonable in price and immediately available in commercial quantity. . Specific uses of HB-40 include: Plasticizer for polystyrene casting resins Plasticizer for polystyrene adhesives Plasticizer for molding polyvinylcarbazole Plasticizer for vinyl extrusions and adhesives Plasticizer for ethyl cellulose injection moldings Plasticizer for strip coatings for metals Plasticizer for floor tile compositions Plasticizer for asphalt base paints Lubricant for tin plate Diffusion pump oil High-temperature lubricant Heat-transfer medium **** The information contained in this bulletin is, t sutttteaHone we made without guarantee, since i Company dlsclsims any liability incurred in conn our best knowledge, true and at > conditions of use are beyond o onitrued as a recommendation t JJ4- 6 0557636 TOWOLDMONOQ36633 I. INTRODUCTION HB-40 is a partially hydrogenated mixture of isomeric terphenyls. The product is an almost colorless, oily liquid possessing a faint pleasant odor. It is relatively non-toxic to higher animals and does not seem to be injurious to foliage or plant life. The principal commercial uses for HB-40 are in the plastics, coating and adhesive fields. Selected applications are described under the heading "Uses for HB-40". II. PHYSICAL PROPERTIES OF HB-40 Appearance: Color: Odor: Specific gravity: Pounds per gallon: Refractive index: Viscosity: Pour Point: Freezing characteristics: Practically colorless, oily liquid. Less than ioo APHA Faint and pleasant. 1.004 0-003 25/15.6C. 8.37 (average) 1.5675 0.0075 @ 25C. 144 20 SUS 37-8C. (iooF.) 39 1 SUS @ 98.9C. (2ioF.) A. S. T. M. D-88 Minus 25C. 1 ( -- i3F. 2) A. S. T. M. D-97 -- 39 The product shows a strong tend ency to supercool. Some crystals are formed if the material is main tained at o to -- 5C. for a long period of time. The crystals redis solve at about 5C. Coefficient of expansion: Distillation range (corrected): 0.000741 cc/cc/C. Start 34O-3490C. (645-66oF.) 10% 345-358C. (653-6760F.) 50% 353-36oC. (667-68o0F.) 90% 362-389C. (684-732F.) 95% 37i-396C. (7oo-745F.) A. S. T. M. D-20 Flash point: Flame point: I74C. 6 (345F. 10) A. S. T. M. D92-24 I96C. 6 (385^. 10) A. S. T. M. D92-24 Vapor pressure: Temperature C. 150 200 250 300 350 ' 362 mm. Hg. 2 15 69 230 625 760 Evaporation Loss at iooC. for 6 hours: 0.033% Stability to heat: Appears stable at the boiling point in the absence of air. Stability to acid and alkali: Does not appear to undergo significant changes in composition when boiled with 10 percent aqueous solutions of sulfuric acid or sodium hydroxide. 4 I JJZ7 0557637 | TOWOLDMON0036634 III. ELECTRICAL PROPERTIES OF HB-40 Dielectric Constant: Power factor: DC Volume Resistivity. Dielectric strength: 2.6-2.7 at 6o and iooo cycles and 25C. 2.4-2.55 at 60 and 1000 cycles and iooC. less than 0.5% at 1000 cycles and iooC. less than 1.0% at 60 cycles and iooC. less than 0.1% at 1000 cycles and 25C. less than 0.5% at 60 cycles and 25C. greater than 1 x io12 ohm cm at iooC. greater than 50 x 1012 ohm cm at 25C. greater than 35 kv at 60 cycles and 25C. IV. SOLUBILITY AND COMPATIBILITY OF HB-40 HB-40 is not soluble in water, but is miscible at 25C. with many solvents and oils, of which the following are typical: Solvent or Oil Solubility Abalyn Acetone Benzene Carbon tetrachloride Castor oil Diethyl ether Ethyl acetate Ethyl alcohol Linseed oil Mineral oil Petroleum oil Skellysolve B Solvent naphtha Turpentine Miscible Miscible Miscible Miscible Miscible Miscible Miscible 6 mi. of HB-40 will dissolve in 100 ml. of alcohol @ 25C. Miscible Miscible Miscible Miscible Miscible Miscible The solubility of waxes and resins in HB-40 is given in the following tabulations: Soluto Acrawax C Aroplaz 905 Beeswax Candelilla Carnauba Cerese AA Ceresin Yellow Coumar MH %lA Dallawax No. 70 Dallawax No. 89 Loba B Montan Naphthalene Nonaethylene glycol hexaricinoleate Petrosene Piccolite S-8? Polypale Santowax M Santowax 0 Santowax OSA Santowax P Santowax R Santowax R Stroba S & W Fused Congol Velsicol Grams/100 grams HB-40 <2.0 <2.0 2.0 5.0 2.0 2.0 5.0 >10.0 2.0 <2.0 5.0 30.0 ><0.0 2.0 >5.0 > 10.0 >10.0 >30.0 5- 5-o 5-o 25.0 2.0 <2.0 2.0 Tamp. 100 100 45 46 5 51 60 25 66 42 IOO 56 35 25 55 25 25 25 25 44 61 38 100 IOO IOO 45 nr * 055763B | TOWOLDMONOQ36635 HB-40 is compatible with a number of resins or plastics materials, of which the following are typical: 7 Parts HB-40/100 Plastics Parts Plastics Butvar, low or high PVOH (polyvinyl butyral) Cellulose nitrate 20-30 sec., 11% N. Chlorinated rubber Ethyl cellulose (Dow Standard) Formvar, type E (polyvinyl formal) Polymethyl methacrylate Polystyrene Vinylite VYNW 50 10 100* 100 30 20 100* 30 *Forms a sticky product; may be even more compatible. It is important to point out that HB-40 is compatible with Gilsonite and asphaltic compounds, polyvinyl carbazole, Vistanex, Geon and similar plastics. In general, it is compatible with most aliphatic and aromatic hydrocarbons. V. PLASTICIZING PROPERTIES Low Temperature Flexibility: The low temperature behavior of HB-40 in Butvar and ethyicellulose as compared with the similar value for other plasticizers is indicated in the following tabulation: Plasticizsr (SO Parts) Dibutyl sebacate Santicizer B-16 Dimethyl phthalate HB-40 Tricresyl phosphate Dibutyl sebacate Santicizer B-16 Dimethyl phthalate Tricresyl phosphate HB-40 Rasin (100 Parts) Butvar Butvar Butvar Butvar Butvar Ethyicellulose Ethyicellulose Ethyicellulose Ethyicellulose Ethyicellulose Flex. Temp. C. about --60 -- 2Q.O -27.5 -14.5 -8.5 below - 50 -37 -33-5 -16.5 -*3-5 Brittle Poi: C. below -70 "33 -39 -8 -7 -6$ -31 -35 -21 -21 Volatility: ^ Test sheets for volatility determinations were 1x3 inches with gauge varying from 0.019 to 0-025 inches and were placed on a metal foil. A 24 hour time interval was found sufficient to give the proper volatility relationships. The circulating oven used in these tests had an air flow of about 150-200 ft/min. and a temperature of io5C. was used. The following comparative tabulation indicates the volatility of tne various plasticizers from Butvar and ethyicellulose sheets using 50 parts of plasticizer and 100 parts of resin. Plasticiser Percent Plasticiser Lost Percent Plasticizer Loet From Butvar From Ethyicellulose Dimethyl phthalate HB-40 Santicizer M-!7 Dibutyl sebacate Santicizer B-16 Tricresyl phosphate 93*4 55*3 39-7 27.5 16.9 2.4 81.4 5i*7 44-4 31-8 12.7 5-i Water Absorption: Samples 1x3 inches by 0.019-0.025 inches were conditioned at 50C. for 24 hours, weighed and placed in beakers of distilled water for 24 hours at 25C., then weighed and finally reconditioned at 50C. for 24 hours and reweighed. Comparative water absorption values for various plastici zers used at a level of 50 parts in 100 parts of Butvar and ethyicellulose are given as follows: m 0557639 TOWOLDMONOQ36636 Plasticizers Dimethyl phthalate Santicizer M-17 HB-40 Santicizer B-16 Tricresyl phosphate Dibutyl sebacate Percent Weight Loss Butvar Ethyl 3-31 9-5 1.23 4.8 o*53 0.31 0.15 0.08 0.03 0.24 0.0 0.13 Tensile Strength and Elongation: All tensile strength measurements were made on a Scott IP-4 tilt table using a one inch jaw separator; 200 r.p.m. and a fifty pound weight. The samples were Y% inches wide and 0.020 to 0.025 inch gauge. The following is a comparative tabulation of the tensile strength and elongation values for HB-40 and various other plasticizers used at a level of 50 parts in 100 parts of Butvar and ethylcellulose: Tensile Strength Percent Plasticizer Resin p.s.i. at 25 C. Elongation HB-40 Santicizer M-17 Tricresyl phosphate Santicizer B-16 Dimethyl phthalate Dibutyl sebacate HB-40 Santicizer M-17 Tricresyl phosphate Santicizer B-16 Dimethyl phthalate Dibutyl sebacate Butvar Butvar Butvar Butvar Butvar Butvar Ethylcellulose Ethylcellulose Ethylcellulose Ethylcellulose Ethylcellulose Ethycellulose 1800 1720 1300 800 620 560 2310 2070 2550 1420 1080 830 230 280 *35 35 345 380 80 84 82 77 70 80 Effect on Rubber: HB-40 has a pronounced swelling action on many rubber compounds. This is illustrated by the following results of a 68 hour test conducted at room temperature: Name of Rubber Composition Source Buna S Hycar OR Koroseal Neoprene Paranite Perbunan Monsanto Chemical Co. Monsanto Chemical Co. B. F. Goodrich Co. Gates Engineering Co. Manhattan Rubber Co. Monsanto Chemical Co. Percent Swelling Length Thickness 17.5 15.2 1.2 1.2 00 11.2 7*5 00 13.6 8.5 The following are presumably compositions of natural rubber: D173K215 T-50-P-58 9215 Goodyear Tire & Rubber Goodyear Tire & Rubber Goodyear Tire & Rubber 10.8 4.5 26.3 8.9 7-9 24-3 Color Stability: To determine the color stability of HB-40 with reference to several other plasticizers, the follow ing tests were made using the Gardner Standards for comparing the colors. For color after heating, 5 ml. of the plasticizer was placed in a Pyrex tube and heated in an oil bath for 2 hours at 2$oC. For color changes after exposure to light 5 ml. of plasticizer was placed in a quartz test tube and exposed to a G. E. Sunlamp for 50 hours. The bulb was 6 inches above the turntable and the bottom of the test tube was 5.5 inches from the center of the turn table and at a 45 degree angle. m- to 0557640 TOWOLDMONOQ36637 Plasticiser Dimethyl phthalate. Dibutyl sebacate Santicizer B-16 Dibutyl phthalate Santicizer M-17 Tricresyl phosphate HB-40 Santicizer 8 Original Color o o o o o o o 3 Color after Heating 0 1 1 2 2 5 11 13-14 Color after Light o o o 0 1 7.8 7-8 I3-H VI. TOXICOLOGY Information submitted from a reliable source indicates that HB-40 is practically non-toxic. Rats and rabbits survived acute doses of 25 grams per kilo. Chronic experiments with six grams per kilo, ingested daily for four months produced no toxicity. Preliminary results of experimental work with HB-40 in the horticultural field indicate a low order of phytotoxicity. HB-40 does not seem injurious to plant leaves. VII. USES FOR HB-40 Plasticiser Field (General Comments): In the plastics field HB-40 is particularly of interest for use with polystyrene, vinyl resins, ethylcellulose and asphaltic compounds. It is also of interest as a "softener" or swelling agent for rubber type compounds. HB-40 plasticizer imparts good tensile strength, good elongation and good moisture resistant qualities to these plastics. Moreover, the plasticizer has good electrical properties which is very important when these plastics are used in the electrical field. The low temperature characteristics of HB-40 are about average and its volatility is somewhat higher than average, but substantially lower than that of a number of widely used plasticizers. HB-40 does not have the outstanding resistance to discoloration possessed by several other com mercial plasticizers when exposed to elevated temperatures and ultraviolet rays. However, in the case of certain plastics where HB-40 is used in combination with other plasticizers, it is known that the plastics possess good light stability. The very low order of toxicity of HB-40, and its availability at relatively low cost are also im portant factors in the commercial use of this plasticizer. With reference to the above named plastics, the properties of HB-40 indicate that the material is especially of interest for casting resins, plastics emulsions, including adhesives, plastics paint coatings and plastics extrusions. It is also indicated that HB-40 should be used as a co-plasticizer or as an extender for primary plasticizers selected to give outstanding low temperature and low volatility characteristics. HB-40 for Polyatyren Casting Resins: HB-40 is highly compatible with polystyrene and imparts the type of plasticizing action desired in the use of polystyrene and related plastics for casting resin purposes. This is illustrated by the National Bureau of Standards Casting Resin, which is an outgrowth of wartime research on such devices as the radio proximity fuse. A representative formula is as follows: Compounds Percent by Weight 2,5-dichlorostyrene Poly 2,5-dichlorostyrene Styrene monomer Polystyrene HB-40 Solution containing 60% divinylbenzene 33.0 21.5 21.0 11.00 13.0 0.5 100.0 i\ UL ft o`>*lb''v TOWOLDMONOQ36638 The following are some of the measured mechanical and electrical properties of the N. B. S. Casting Resin, cured at 5oC., employing o.i percent of benzoyl peroxide catalyst: Compressive strength, p. s. i. Izod impact, ft.-lb./in. of notch Coefficient of thermal expansion per C. Water absorption (24 hr. immersion) Volumetric shrinkage or polymerization Density of monomer Heat distortion, C. Power factor (at 100 megacycles and 50% R. H.) Dielectric constant (at 100 megacycles and 50% R. H.) ^ Dielectric strength in. sample; volts/mil) _ Volume resistivity (megohm-cm.) 17,100 0.228 iixio"5 (approx.) 0.01% 8.0% t.13 68-70 0.0004-0.0008 *5 610-660 > io17 The liquid resin may be stored at oC.for a few months without a catalyst, and for a few weeks with a catalyst, before the viscosity increases to a point where pouring is difficult. At room temperature, the catalyzed casting resin gradually increases in viscosity and must be used in a day or two. The cured polymer may be drilled or turned on a lathe. HB-40 Plasticizer for Polystyrene Emulsion Adhesives: Emulsified HB-40 is added to the extent of about 30-35 percent to styrene monomer which is then emulsified in water using oil base emulsifying agents such as triethanolamine oleate or stear ate. The emulsified styrene monomer and HB-40 combination is then polymerized using selected peroxide catalysts to produce the desired adhesive emulsion. The polymerization reaction is carried out in an autoclave under carefully controlled conditions so that the emulsion will not break. Dibutyl phthalate may be used in combination with HB-40 as a co-plasticizer in this process. HB-40 -- Polystyrene Adhesive Formulations: Combinations of HB-40? Aroclors, Lustron A (polystyrene), ethylcellulose, Santowax and other selected resins and plastics make good adhesives. a. Label Adhesives: A satisfactory adhesive for brush application to labels when quick drying and non-wrinkling are required consists of: Ingredients Lustrex, LM-3 HB-40 Aroclor 5460 Ethylenedichloride-butylchloride mixture Acetone Percent by Weight j10 15 10 50 For mechanical application when slower drying and non-wrinkling are required, it is suggested to use a 50-50 mixture of acetone and toluene instead of acetone alone, as described in the above formula. b. Pressure Sensitive Adhesive Formulae: Ingredients Formula 1 Lustrex, LM-3 Aroclor 1254 HB-40 Ethylcellulose N-100 Formula. 2 Lustrex, LM-3 Aroclor 5460 HB-40 Ethylcellulose N-100 Percent by Weight 28 35 35 2 28 35 35 2 JJjr 05676*2 TOWOLDMON0036639 HB-40 Plasticiser for Molding PolyvinylcarbasoU: Polyvinylcarbazole is a thermoplastic material possessing electrical qualities comparable to polystyrene. The material has a heat distortion point at about !5oC. and is too brittle for practical molding operations. Relatively small amounts of HB-40 lower the molding temperature to practical values and im prove the properties of the finished plastics. The product has a very small temperature coefficient and a dielectric constant about 3.0. Its dielectric strength is high up to temperatures of about I50C. Made under the tradename Polectron, the material is being used in specialized electrical applica tions including the impregnation of some electrical condensers. Pofechtron polymer plasticized with 50% to 100% of HB-40 is used in various plastics applications. HB-40 Plasticiser for Vinyl Extrusions: HB-40 is especially recommended for Geon and similar vinyl plastics extrusions. In this operation it is desirable to use HB40 at a level of about 25 percent based on the total weight of the plasti cizers. When HB-40 is used in combination with dtoctyl phthalate or certain other selected plasti cizers, the volatility characteristics of the plasticizer combinations are entirely satisfactory for vinyl extrusion work. The finished plastics possess good light stability qualities. HB-40 plasticizes Vinylite without seeming to soften it excessively. The finished plastics Has a dry feel instead of a greasy feel. HB-40 Plasticiser for Vinyl and Vistanax Rosin Adhosivo Tapes: HB-40 is attractive for use as a co-plasticizer in making vinyl and Vistanex resin base adhesive tapes. Used in combination with tricresyl phosphate, dibutyl phthalate or Santicizer B-16, HB-40 offers interesting properties at a saving in cost. When used as the only plasticizer for these compositions, HB-40 gives properties similar to those derived from tricresyl phosphate and dibutyl phthalate. Vinyl Aeotato Adhoaivoo: HB-40 with dibutyl phthalate or with combinations of Aroclor 1260 and dibutyl phthalate makes excellent co-plasticizer mixtures for polyvinyl acetate base adhesives. HB-40 for Ethylcsllulos# Injection Molding: HB-40 has proved satisfactory as a plasticizer for the injection molding of ethylcellulose. Although HB-40 is not more outstanding for this purpose than certain other plasticizers, nevertheless its good efficiency at lower costs makes it more attractive. The practice is to use about 15 percent of HB-40 in the ethylcellulose molding powder. Strip Coating for Matals: The following formulation containing HB-40 plasticizer and ethylcellulose is a good strip coating for metals: Ingredients Percent by Weight Ethylcellulose N-100 HB-40 Aroclor 5460 Paraffin Staybelite Ester No. 10 Age Rite Alba (stabilizer) 25 14 20 3i 10 1 101 Synthetic Rubber Latex: HB-40 used at a level of 15 to 30 percent improves the miscibility of synthetic rubber latex with mineral oil to a marked degree. This suggests the use of HB-40 in other commercial applications where improvement in the mis cibility of petroleum hydrocarbons with rubber compounds and plastics materials is desired. HU /J 0*576*3 TOWOLDMONOQ36640 HB-40 Non-Plaaticiaw Lubricant for Calluloao Acatata: In the manufacture of cigarette cases, rattles and toys from cellulose acetate sheets, it is desirable to have a non-plasticizing lubricant to prevent the acetate sheets from sticking together during the hot-stamping operation. Because of its lack of plasticizing action on cellulose acetate, HB-40 is ideal for this purpose. Floor-Tila: HB-40 plasticizer is especially good for a variety of resinous materials used in making floor-tile. This includes asphaltic materials, certain oil-proof resins, vinyls, coumar resins, PiccoUte, Poly pale resins, Aroclors and rosin derivatives. Asphalt Basa Paints: HB-40 works well as a plasticizer for maintenance paints with asphalt or Gilsonite bases. The addition of about 2 percent of HB-40 to a high melting asphalt compound for molding pur poses gives a very high gloss. HB-40 for Enamel Finishes: HB-40 imparts considerable flow to enamel films and increases gloss. It is quite effective as an anti-skinning agent, but in this connection it tends to retard the drying of alkyd enamels. HB-40 apparently has no deleterious effect relative to after yellowing or the water resistance of enamel paints. The product is valuable for use in four hour enamels to ease brushing, increase flow and prevent skinning without imparting odor. HB-40 Lubrication for Tin Plats: As a tin plate lubricant in place of oils, such as palm oil, HB-40 offers improvements particularly where phenolic coatings are applied. The enamel adhesion is good and HB-40doefc not impart objectionable taste or toxicological problems which are important factors in cans intended for food products. Diffusion Pump Oil: Processed HB-40j i. e>) after removal of about xo percent of the lowest boiling fraction, is a good oil for use in diffusion pumps. It is possible to reach a pressure as low as io-4 mm. and the oil may be operated in conventional type units with a pressure on the vapor column of over 5 mm. of mercury without decomposition. Unprocessed HB-40 appears to be suitable for use in booster-type vacuum pumps. HB-40 High-Tsmpsraturs Lubricant: HB-40 is used as hieh-temperature lubricant for chain drives on bakery ovens. Its lubricity, non toxic qualities and Tack of odor make HB-40 particularly attractive for uses of this type. Hsst-Transfsr Medium: HB-40 is a very satisfactory liquid for melting-point baths, particularly where temperatures exceeding jooC. are not desired. It is also of interest as an actuating medium for thermostatic controls provided that the operat ing temperatures are not beyond the range in which HB-40 can be used satisfactorily. --9-- 0557644 TOWOLDMON0036641 SV94SS0 /VISCOSITY, SAYBOLT UNIVERSAL SECONDS_ _ _ <? f 1EMKUT1K. DEUCES FAHRENHEIT si 0 n i i w in n n w w m VISCOSITY. SAYBOLT UNIVERSAL SECONDS VISCOSITY of HB-40 fCW/rh--3M--8--1 50 TOWOLDMONOQ36643 /-- Monsanto Chemicals-Plastics _______ For further information about HB-40, write, wire or call the neorest Monsanto office. MONSANTO CHEMICAL COMPANY ST. LOUIS AKRON BIRMINGHAM BOSTON CHARLOTTE CHICAGO CINCINNATI CLEVELAND * DETROIT HOUSTON LOS ANGELES NEW YORK PHILADELPHIA SAN FRANCISCO SEATTLE MONSANTO (CANADA) LTD. MONSANTO (AUSTRALIA) PTY LTD. Montreal Toronto Vancouver Melbourne MONSANTO CHEMICALS LTD. London Representatives in the Principal Cities of the World. # 0557647 TOWOLDMONOQ36644