The JEFFAMINE Polyetheramines - Huntsman …

1 The JEFFAMINE Polyetheramines JEFFAMINE polytheramines are a part of an JEFFAMINE DIAMINES. expanding family of Huntsman products. They (D, ED, and EDR series). contain primary amino groups attached to the end JEFFAMINE diamines include the D, ED, and of a polyether backbone. The polyether backbone EDR series products. The D signifies a diamine, is normally based on either propylene oxide (PO), ED signifies a diamine with a predominately PEG. ethylene oxide (EO), or mixed PO/EO. Thus they backbone, and EDR designates a highly reactive, are called Polyetheramines . Historically, the PEG based diamine. As with the M series, the JEFFAMINE polyetheramine family consisted of number represents the approximate molecular monoamines, diamines, and triamines based on weight. this core structure. Recently, the addition of secondary, hindered, high-conversion, and JEFFAMINE D Series polytetramethylene glycol (PTMEG) based JEFFAMINE D series products are amine Polyetheramines has increased the utility of this terminated PPGs with the following representative unique product range.

2 The JEFFAMINE . structure: Polyetheramines undergo typical amine reactions, often imparting increased flexibility, toughness, low viscosity, and low color. The wide range of molecular weight, amine functionality, repeating H2N ( O. ) NH2. unit type, and distribution can provide flexibility in x the design of new compounds or mixtures. CH3 CH3. JEFFAMINE MONOAMINES (M series). JEFFAMINE monoamines are designated as JEFFAMINE x MW*. the JEFFAMINE M series. The letter M signifies a D-230 ~ 230. monoamine and the number represents the D-400 ~ 430. approximate molecular weight. D-2000 ~33 2,000. JEFFAMINE M series products are prepared D-4000 (XTJ-510) ~68 4,000. by reaction of a mono-alcohol initiator with EO. and/or PO, followed by conversion of the resulting JEFFAMINE ED Series terminal hydroxyl groups to amines. M series JEFFAMINE ED series products are polyether products have the following representative diamines based on a predominantly PEG.

3 Structure: backbone. PEG imparts complete water solubility to each of the products in this series. The O NH2 JEFFAMINE ED products have the following H3C O representative structure: x y R H2N. ( ) (O ) (O ) NH2. O. x y z R= H for (EO), or CH3 for (PO) CH3 CH3 CH3. JEFFAMINE PO/EO mol ratio MW* JEFFAMINE y x+z MW*. M-600 (XTJ-505) 9/1 600 HK-511 ~ 220. M-1000 (XTJ-506) 3/19 1,000 ED-600 (XTJ-500) ~ ~ 600. M-2005 29/6 2,000 ED-900 (XTJ-501) ~ ~ 900. M-2070 10/31 2,000 ED-2003 (XTJ-502) ~39 ~ 2,000. * MW = approximate molecular weight JEFFAMINE EDR Series JEFFAMINE M-600 and JEFFAMINE M-2005 JEFFAMINE EDR-148 (XTJ-504) and Polyetheramines are predominately polypropylene JEFFAMINE EDR-176 (XTJ-590) amines are much glycol (PPG) based, whereas JEFFAMINE M-1000 more reactive than the other JEFFAMINE diamines and JEFFAMINE M-2070 Polyetheramines are and triamines. They are represented by the predominately polyethylene glycol (PEG) based following structure: and are therefore more hydrophilic.

4 JEFFAMINE Base Product MW*. H2N. (CH2) O. O. ( CH2) NH SD-231 (XTJ-584) D-230 315. x 2 SD-401 (XTJ-585) D-400 515. x SD-2001 (XTJ-576) D-2000 2050. ST-404 (XTJ-586) T-403 565. JEFFAMINE x MW. EDR-148 (XTJ-504) 148 EXPERIMENTAL AMINES. EDR-176 (XTJ-590) 176 This next series of amines includes monofunctional amines similar to the M series. These products can be used in a number of They are oleophilic and not water soluble. applications since they are unhindered diamines miscible in a wide variety of solvents. Reactions XTJ-435 Chemical Intermediate typical of aliphatic diamines (polyamide formation through reaction with dibasic acids, epoxy resin CH3. curing, polyurea formation through reaction with isocyanates) may be expected with these products. H3C. ( CH2 ) O. NH2. 12 O.. JEFFAMINE TRIAMINES (T series) CH3. JEFFAMINE T series products are triamines prepared by reaction of PO with a triol initiator, XTJ-435 is a monoamine derived from a PO.

5 Followed by amination of the terminal hydroxyl adduct of a C12-14 alcohol. This product is groups. They are exemplified by the following restricted and may only be used as a chemical structure: intermediate. CH 3 XTJ-436. ( H2C ). (O ) CH3. y NH 2. n C 9H19. H2N. ( ) (O ) NH 2 (O ) NH2. O x z CH 3 R CH 3. Moles PO XTJ-436 is a 1000 molecular weight, JEFFAMINE R n (x+y+z) MW* nonylphenol initiated, polypropylene glycol derived T-403 C2H5 1 5-6 440 monoamine. T-3000 (XTJ-509) H 0 50 3000. T-5000 H 0 85 5000 Slower Amines Slower amines analogous to JEFFAMINE D- 230 and JEFFAMINE T-403 Polyetheramines are JEFFAMINE Secondary Amines now available under the names XTJ-568 and XTJ- 566, respectively. These unique materials are (SD Series, ST Series) primary amines created by amination of butylene The SD Series and ST Series products consist oxide (BO) capped alcohols. This method results in of secondary amine versions of the JEFFAMINE . primary amines with the terminal end group core products.

6 The SD signifies a secondary structure represented below: diamine and ST signifies a secondary triamine. The amine end-groups are reacted with a ketone ( NH2. acetone) and reduced to create hindered secondary amine end groups represented by the following terminal structure: CH3. H3C NH. Higher Conversion Amines Methods have been developed to increase CH3 CH3 functionality and conversion to primary amines for several of the core JEFFAMINE Polyetheramines . One reactive hydrogen on each end group Two such products are currently available: a high provides for more selective reactivity and makes conversion 440 molecular weight diamine (XTJ- these secondary di- and triamines useful for 582), and a high conversion 2000 molecular weight intermediate synthesis and intrinsically slower diamine (XTJ-578). The higher functionality and reactivity compared with the primary JEFFAMINE conversion are beneficial in polymerizations such amines. as polyamide formation.

7 JEFFAMINE Polyetheramine Properties Typical Properties Sales Specifications JEFFAMINE Product Avg. Density, Melting Color Primary Total Amine Max AHEW 25oC, g/ml Point C Pt-Co Amine Meq/g % Water g/eq ( ) APHA (% Min). (Max). Monoamines M-600 (XTJ-505) 291 -40 75 95 M-1000 (XTJ-506) 489 29 75 90 Min M-2005 1045 -36 75 95 Min M-2070 1040 17 75 95 Min Diamines D-230 60 - 25 97 HK-511 62 - 75 - D-400 115 - 50 97 XTJ-582 (HC*) 110 - 50 98 D-2000 514 - 25 97 XTJ-578 (HC*) 500 - 40 98 D-4000 (XTJ-510) 1000 - 75 95 Diamines (EO-Based). ED-600 (XTJ-500) 132 -10 75 95 ED-900 (XTJ-501) 250 22 100 95 ED-2003 (XTJ-502) 575 43 75 95 Diamines (PTMEG-Based). XTJ-542 260 9 50 98 XTJ-548 380 33 400 - XTJ-559 355 16 50 98 Diamines (High Reactivity). EDR-148 (XTJ-504) 37 - 50 98 (% Min TEGDA). EDR-176 (XTJ-590) 44 - 50 99 Min Triamines T-403 81 - 50 90 T-3000 (XTJ-509) 530 - 75 97 T-5000 952 - 75 97 Secondary Amines SD-231 (XTJ-584) 158 - 100 <5 . SD-401 (XTJ-585) 258 - 100 <5.

8 SD-2001 (XTJ-576) 1025 - 100 <5 ST-404 (XTJ-586) 189 - 100 <5 . Experimental Amines XTJ-435 157 - 100 96 XTJ-436 525 - 100 97 XTJ-566 77 - 75 90 XTJ-568 55 - 75 93 Min * HC = High Conversion (products have specification for high conversion of alcohol to amine). Proposed Sales Specification After standing for several months will partially crystallize at room temperature Not EINECS/ ELINCS registered Measured at 38oC. Measured at 50oC. CHEMICAL REACTIONS. JEFFAMINE Polyetheramines undergo reactions typical of primary amines. General reactions which have proven to be useful include those listed below in the form: JEFFAMINE Amine + Reactant Product. Reactant Product Epoxy reactions occur by the non-catalyzed addition of epoxides to JEFFAMINE amines. C C. This alkoxylates each NH functionality to produce aminoalcohols. O. Epoxides Aminoalcohols ( epoxy resins ). Polyurea linkages are formed from the rapid, uncatalyzed reaction of JEFFAMINE amines with polyisocyanates.

9 When applied to a RIM. or spray process, this reaction has found great commercial utility in a variety of applications including castings, coatings, and sealants. Isocyanates Ureas The Michael addition of an activated double bond compound to a JEFFAMINE amine is a reversible reaction1. Acrylonitrile Cyanoethylated amines Substituted ureas are formed by heating JEFFAMINE amines with urea at temp- eratures of 125-175 C, while removing ammonia. This will result in mono- and di- substituted ureas. Urea Substituted ureas Amides can be formed from JEFFAMINE . amines by an acid-catalyzed reaction with carboxylic acids, lactams, anhydrides, or by ester-amide interchange reactions. Carboxylic acids Amides (or esters, anhydrides, etc.). Imines are formed by reacting JEFFAMINE amines with aldehydes or ketones, at elevated temperatures, while removing water. Aldehydes Imines or ketones + - + - Salts of JEFFAMINE amines may be readily H X RNH3 X. formed with a variety of organic and inorganic Acids Salts acids.

10 1. Acylonitrile addition leads to a cyanoethylated product that can be catalytically hydrogenated to a non-reversible and stable aminopropylated polyetheramine. STORAGE AND HANDLING. Materials of Construction At temperatures of 75-100 F (24-38oC). Tanks Carbon steel Lines, valves Carbon steel Pumps Carbon steel Heat exchange Surfaces Stainless steel Hoses Stainless steel, polyethylene, polypropylene, TEFLON 1. Gaskets, packaging Polypropylene or TEFLON 1 (elastomers such as neoprene, Buna N, and VITON 1 should be avoided). Atmosphere Nitrogen or dry air At temperatures above 100 F (38oC). Tanks Stainless steel Lines, Valves Stainless steel Pumps Stainless steel or Carpenter 20 equivalent Atmosphere Nitrogen 1. Registered trademark of Dupont JEFFAMINE Polyetheramines may be stored under air at ambient temperatures for extended periods. A nitrogen blanket is suggested for all storage, however, to reduce the effect of accidental exposure to high temperatures and to reduce the absorption of atmospheric moisture and carbon dioxide.