Huntsman Corporation · NYSE:HUN
Huntsman — Technical Presentation (December 2008)
36 slides from Huntsman's technical presentation, December 2008
Slide 1: BHEMA: A Versatile Amine for Metalworking Formulations
BHEMA A Versatile Amine for Metalworking Formulations
Slide 2: Outline
Outline What is BHEMA? What is the EHS profile? What are the performance attributes? Summary Performance Products
Slide 3: Huntsman Amines for Metalworking
Huntsman Amines for Metalworking H2N CH2 CH2 NH2 HOCH2CH2OCH2CH2NH2 CH O CH x DIGLYCOLAMINE® agent CH3 CH3 Product x HOCH2CH2NH2 (HOCH2CH2)3N JEFFAMINE® D-230 amine 2-3 JEFFAMINE® D-400 amine 5-6 MEA TEA CH2[OCH2CH(CH3)]NH2 x CH3CH2 CH2[OCH2CH(CH3)]NH2 [OCH2 CH(CH3 )]13 NH2 y CH2[OCH2CH(CH3)]NH2 z x
Slide 4: Specialty Amines
Specialty Amines Amines provide alkalinity for corrosion control Amines are often blended (primary + tertiary) and mixed with fatty acids for buffering Performance Products
Slide 5: Commonly Used Amine Derivatives
Commonly Used Amine Derivatives Carboxylate salts - buffering and lubricity Boric acid salts and condensates - high pH buffer Carboxamides - lubricity, secondary emulsifier, corrosion control Acid phosphate salts - cleaning, corrosion control (vibratory acid) Performance Products
Slide 6: BHEMA: bis-(Hydroxyethyl)methylamine
BHEMA bis-(Hydroxyethyl)methylamine CH3 N HO OH A strong tertiary amine Produced by the pKa = 8.61 ethoxylation of methyl pH (5%) = 10.7 amine BP = 247 °C Typical assay = 99.5% FP = 240 °F TSCA, EINECS, DSL Melt point = -21°C CAS# 105-59-5 Performance Products
Slide 7: Industry Concerns Influenced by Amine Selection
Industry Concerns Influenced by Amine Selection Environmental, Health and Safety Issues Toxicity (environmental and worker effects) Misting and Volatility Registration Issues Performance Issues Reserve Alkalinity pH Stability Corrosion Protection (Ferrous and Non-Ferrous) Tool Life Ext
Slide 8: Physical Properties of Metalworking Amines
Physical Properties of Metalworking Amines DGA® agent MEA DEA TEA BHEMA Equivalent weight 105 61 105 151 119 pKa, 20°C 9.45 10.03 8.88 7.76 8.6 pH, 5% solution 10.68 11.87 10.34 9.64 10.7 Boiling Point, °C 223 171 268 340 247 Vapor Pressure, mm Hg, 20°C 0.0036 0.36 <0.01 <0.01 <0.01 Freezing Point,
Slide 9: Volatility of Common Metalworking Amine Solutions
Volatility of Common Metalworking Amine Solutions* A m ine in Vapor P hase, w t% 1.5 1.3 1.1 0.9 AMP 0.7 MIPA 0.5 MEA 0.3 DGA®agent 0.1 DEA, TEA BHEMA -0.1 25 35 45 55 65 75 85 95 Temperature, °C *Plots correspond to a 10 wt% aqueous amine sample and were constructed using data obtained in vapor-liq
Slide 10: BHEMA Environmental Profile
BHEMA Environmental Profile Test Value Interpretation Octanol:water partition Very water soluble; low chance of - 1.08 coefficient bioaccumulation Fish Toxicity LC50 760-2000 Practically nontoxic 3 species ppm Aquatic Invertebrate Toxicity LC50 Practically nontoxic (Daphnia) 230 ppm LC50 Algae EPA s
Slide 11: Toxicity of BHEMA
Toxicity of BHEMA Test Result Interpretation Rabbit LD50 >2000 mg/kg Practically nontoxic None–> slightly Skin Contact irritating Eye Contact Irritating BHEMA is alkaline Chronic skin contact LOAEL Localized skin lesions- reversible 6hr/d, 90-day 250 mg/kg/d Genotoxicity negative Data Source : IUCLI
Slide 12: Salt Registrations
Salt Registrations TSCA, DSL and EINECS Pending CORFREE® M1 acid, BHEMA Salt 843644-84-8 Tall-Oil Fatty acids, BHEMA Salt 843644-82-6 Neodecanoic acid, BHEMA Salt 842129-84-4 Nonanoic acid, BHEMA Salt 842126-27-6 Decanoic acid, BHEMA Salt 842126-13-0 CORFREE® is a trademark of Invista Performance Pr
Slide 13: Amine Performance Profile
Amine Performance Profile Reserve alkalinity CI rust testing Copper leaching Cobalt leaching Aluminum staining Performance Products
Slide 14: Titration Curves with Decanoic Acid
Titration Curves of Metalworking Amines with Decanoic Acid 50 g of a 5% decanoic acid solution with various amines 10 9 8 7 pH 6 5 4 3 0 20 40 60 80 100 mL of 5% amine solution DGA(R) Agent MEA AMP BHEMA TEA Performance Products
Slide 15: Titration Curves with CORFREE M1 Acid
Titration Curves of Metalworking Amines with CORFREE® M1 Acid 50 g of a 5% CORFREE® M1 acid solution with various amines 11 10 9 8 pH 7 6 5 4 3 0 20 40 60 80 100 120 140 mL 5% of amine solution DGA(R) Agent MEA AMP TEA BHEMA CORFREE® is a trademark of Invista Performance Products
Slide 16: Titration Curves with Isononanoic Acid
Titration Curves of Metalworking Amines with Isononaoic Acid 50g of a 5% acid solution with various amines 11 10 9 8 pH 7 6 5 4 3 0 20 40 60 80 100 120 140 160 mL of 5% amine solution TEA DGA(R) Agent MEA AMP BHEMA Performance Products
Slide 17: BHEMA Benefit
BHEMA Benefit BHEMA is a fairly strong tertiary amine that has good reserve alkalinity (8.32 meq HCl/g amine) Suggests that BHEMA may be useful to formulate “single amine” products that have no MEA or TEA. Simplifies the formulation with a desirable environmental profile. Performance Products
Slide 18: Cobalt Leaching by Commonly Used Metalworking Amines
Cobalt Leaching by Commonly Used Metalworking Amines 1000 900 800 Dissolved Cobalt, ppm 700 600 500 400 300 200 100 0 pH = 8.5 pH = 9.0 er t en P at pH = 9.5 e M w A ag in A A M EA am TE ® E EA A H A D A 0 IP B G M IP 5 D M -1 D A X® O FF JE Amine Amine Performance Products
Slide 19: Copper Leaching by Commonly Used Metalworking Amines
Copper Leaching by Commonly Used Metalworking Amines 160 140 Dissolved Copper, ppm 120 100 80 60 40 20 0 nk nt bla ge P te r A AM ne wa A® a mi EM A A DG 50 BH TE A 1 ME DE A A- PA ® MI DIP A FOX F JE Amine pH not adjusted pH = 9.0 Performance Products
Slide 20: Copper Corrosion/Leaching
Copper Corrosion/Leaching Aqueous solutions of amines and amine-based additives can contribute to copper corrosion/leaching. 1% aqueous amine solutions (pH adjusted to desired level with acetic acid) are being tested using a modified ASTM D130 test. Copper coupons (3 ½ x 1/16 inch) are submerged i
Slide 21: BHEMA Benefits
BHEMA Benefits BHEMA leaches more copper than TEA but less than MEA Suggests that a typical blend of MEA/TEA in a formulation may have a leaching characteristic similar to a single amine formulation based on BHEMA BHEMA leaches less cobalt than MEA or TEA especially at higher pH – Suggests no pitf
Slide 22: Aluminum Staining/Corrosion
Aluminum Staining/Corrosion Tests include aluminum wrought alloys 2024, 6061 and 7075 and cast alloy 390. Test procedure: • Aluminum coupons (1 x 3 x 1/16 in.) are partially submerged in the test solution inside a closed jar. • Test solution = 2.5 wt% aqueous amine, the pH of each solution is adjust
Slide 23: Aluminum Staining/Corrosion
Aluminum Staining/Corrosion Amine Dissolved Al (ppm) Al 7075 Al 6061 Al 2024 Al 390 DGA® agent 5 5.5 7.6 9 AMP 9 7.9 12 11.5 TEA 155 195 235 215 JEFFOX® A-150 11 9.3 14 14 amine BHEMA 7.2 4.8 8.6 9 DEA 7.9 9.3 10 11 MEA 10 Blank <1 <1 <1 <1 Test conditions: 2.5 wt% aqueous solution of amine, test ti
Slide 24: Aluminum Staining/Corrosion
Aluminum Staining/Corrosion DGA® agent AMP TEA JEFFOX® A-150 amine BHEMA DEA Blank 2.5 wt% aqueous solution of amine, test coupon = Al 6061, test time = 24 hours, pH = 8.8 Performance Products
Slide 25: Aluminum Staining/Corrosion
Aluminum Staining/Corrosion Amine Dissolved Al (ppm) Isononanoic Al 7075 Al 6061 Al 2024 Al 390 acid salt DGA® agent 3.1 3.8 2.8 1.3 AMP 4.7 5.5 3.6 4.5 TEA 40 39 34 32 JEFFOX® A150 3.3 4.8 3.7 4.0 amine BHEMA 1.6 2.2 1.4 1.8 DEA 2.5 3.8 1.2 2.7 MEA 2.7 4.2 2.6 2.7 Blank 2.3 4.0 1.8 2.5 Test conditi
Slide 26: Aluminum Staining/Corrosion
Aluminum Staining/Corrosion DGA® agent AMP TEA JEFFOX® A-150 amine BHEMA DEA MEA Blank aqueous solution of amine- isononanoic acid salt, test coupon = Al 6061, test time = 24 hours, pH = 8.8 Performance Products
Slide 27: Aluminum Staining/Corrosion Summary of Results
Aluminum Staining/Corrosion Summary of Results Of the amines tested, BHEMA has the lowest aluminum corrosion rate and a very desirable staining characteristic Aluminum staining/corrosion is highly affected by the presence of other common additives (especially fatty acids) Solutions of TEA show
Slide 28: Performance of a Simple BHEMA Formulation
Performance of a Simple BHEMA Formulation % SURFONIC® POA-17R2 surfactant 5.4 BHEMA 11.9 Water 69.2 CORFREE® M1 acid 4.2 Neodecanoic acid 6.4 Oleic acid 2.9 pH, as is 9.1 Cast iron chip test Break point, 40:1 dilution (0.3% fatty acid) Falex wear 42 teeth, 23 inch-pounds, 50:1 dilution 16 teeth, 19
Slide 29: Benefits of BHEMA
Benefits of BHEMA BHEMA has low mammalian toxicity and low toxicity to aquatic species is very mild to skin but is irritating to eyes (similar to other strong amines); it is not a dermal sensitizer is not classified as corrosive under DOT BHEMA has low volatility, pour point and viscosity, a
Slide 30: Ester Derivatives of BHEMA
Ester Derivatives of BHEMA Interesting polymeric esters possible for nontraditional EP- type agents Esters tend to be low foaming Possible lubricity agents Candidates for formulating additives for hydraulic fluids Performance Products
Slide 31: Esterification
Esterification Typical conditions 150-160°C, no catalyst, 5 hrs, remove water of reaction Branched (neo) acids hard to react Typical assay (Sebacic-based) Residual acid number = <10 mg KOH/g Mono ester = ± 12% Di-ester = ± 87% Performance Products
Slide 32: Esterification reaction
Esterification reaction O OH O C R O H3C N + HO C R H3C N O OH O C R 150°C, Mol Ratio 1:1 or 1:2 Performance Products
Slide 33: BHEMA Esters: Viscosity vs. Temperature
BHEMA ESTERS Viscosity vs. Temperature 600 500 Isostearic Viscosity, cSt Oleic 400 Sebacic 300 Tofa 200 Decanoic 100 0 0 20 40 60 80 100 120 Temperature, °C Performance Products
Slide 34: Ester Physical Properties
Ester Physical Properties ESTER Decanoic Isostearic Oleic TOFA Sebacic* Solubility Water I I I I I Canola S D D S I Naphthenic S S S S I Paraffinic S S S S I Pour Point, -24 -24 -22 -29 -29 °C *Some residual amine present Performance Products
Slide 35: Summary
Summary BHEMA is a versatile tertiary amine with a desirable environmental and performance profile BHEMA is outstanding for aluminum machining formulations and should be considered as a replacement for TEA BHEMA can be formulated to produce effective single amine formulations Performance Produ
Slide 36: Trademark Notices
Trademark Notices DIGLYCOLAMINE®, DGA®, JEFFAMINE®, SURFONAMINE®, JEFFOX® and SURFONIC® are registered trademarks of Huntsman Corporation or an affiliate thereof in one or more, but not all, countries. Performance Products