Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Terathane PTMEG/1,4-Butanediol
Terathane
polyether glycol
Chemical Reactions
Terathane polyether glycols and butanediol are dihydric alcohols and undergo the reactions typical of the hydroxyl group. The two commercially significant reactions are esterification with carboxylic acids and formation of urethanes with isocyanates. Reaction with acrylic acids results in the addition of a vinyl group that can be subsequently crosslinked.
Stability
Terathane polyether glycols contain oxidation inhibitors. After storage under nitrogen for one year at 70C (158F), Terathane polyether glycols still meet production specifications. Butanediol is also indefinitely stable in sealed containers.
Physical Properties
Table 1 lists Specifications and Typical Analyses for butanediol and the five grades of Terathane. Figure 1 shows the effect of temperature on viscosity for Terathane and 1,4-butanediol. The effect of temperature on density is shown in Figure 2.
17001900 19002100 66.059.1 150 max. 40 max. 2.01.0 59.153.4 150 max. 40 max. 2.01.0
487.8415.6 179.5166.2 118.1106.9 150 max. 40 max. 2.01.0 150 max. 50 max. 2.01.0 150 max. 40 max. 2.01.0
250 4070 50 (2332) 0.978 8.1 <0.001 <1 1.464 >163 (>325) <5
650 100200 1119 (5266) 0.978 8.1 <0.001 <1 1.464 >163 (>325) <5
1000 260320 2533 (7791) 0.974 8.1 <0.001 <1 1.464 39 22 90 >163 (>325) <5
1400 525600 2735 (8195) 0.973 8.1 <0.001 <1 1.464 >163 (>325) <5
1800 9401000 2738 (81100) 0.972 8.1 <0.001 <1 1.464 45 25 >163 (>325) <5
2000 9501450 2840 (82104) 0.972 8.1 <0.001 <1 1.464 47 26 109 >163 (>325) <5
2900 32004200 3043 (86109) 0.97 8.1 <0.001 <1 1.464 >163 (>325) <5
7073b 1920 (6668)c 1.014 8.4 ND* <0.2 1.445 68 38 159 155 (311)d <5
4 2900 2 1,000 8 6
Viscosity, cP (mPasec)
IN
2000
LT
1000
650
2 10 0 (32)
1,4-BDO
20 (68)
30 (86)
40 (104)
50 (122)
60 (140)
70 (158)
80 (176)
Temperature, C (F)
1.010
1,4-BDO
1.000
0.990
Density, g/mL
0.980
650 1000
0.970
2000 2900
0.960
0.950
0.940
0.930 20 (68) 30 (86) 40 (104) 50 (122) 60 (140) 70 (158) 80 (176) 90 (194) 100 (212)
Temperature, C (F)
Shipping Containers
Terathane polyether glycols are available in 5-gal (40-lb/18.1-kg net) steel pails and 55-gal (441-lb/ 200-kg net) steel drums. DuPont ships 1,4-butanediol in 55-gal (450-lb/ 205kg net) steel drums in USA and in 210-kg (462-lb) steel drums in Europe. This product is also shipped in stainless steel or resin-lined tank trucks that are insulated and equipped with heating coils. DuPont glycols are not regulated as hazardous materials by the Department of Transportation (DOT)(1) in the USA as of July 1998.
FDA Status
In the United States, Terathane, taken as alphahydro-omega-hydroxypoly (oxytetramethylene), is cleared as an indirect food additive under: 21 CFR 175.105, Adhesives 21 CFR 177.1680, Polyurethane resins Various medical devices based on 1,4-butanediol, Terathane or both have been approved by the FDA, including those used within the body. Formulators are cautioned, however, that FDA approval is not given generically for these devices; it must be applied for separately by each manufacturer of each device. In addition, copolyester elastomers made from Terathane, 1,4-butanediol and dimethyl terephthalate are acceptable under: 21 CFR 177.1590, Polyester elastomers 21 CFR 177.2600, Rubber articles intended for repeated use Also accepted under 21 CFR 177.2600 are polyurethane resins derived from 1,4-butanediol with adipic acid and diphenylmethane diisocyanate (MDI).
Uses
The main uses for DuPont glycols involve the reaction of the hydroxyl groups with either organic acids or isocyanates. The glycols become segments or building blocks in a variety of elastomers, such as polyurethanes, copolyesters and polyamides.
Safety Precautions
In accordance with good industrial hygiene practice, avoid contact with eyes or skin. Wear chemical splash goggles. Gloves should also be worn, because these glycols may be hot when liquid. Wash thoroughly after handling.
First Aid
In case of skin contact with Terathane, wash with soap and water. For the eyes, immediately flush with water for 15 min, and call a physician.
Both the ether, Terathane, and low molecular weight polyester glycols such as poly(butylene adipate) glycol yield very good polyurethanes, and in most uses either can be used as the soft segment. However, the need for the ultimate in some particular property will often dictate the use of one or the other.(5) Terathane gives urethanes with superb resistance to low temperatures, fungus attack and hydrolysis.(4, 6) They also have excellent dynamic properties. For example, Terathane 2000 gives a higher resilience than any other commercially available soft segment in many polyurethane formulations. Terathane imparts a low specific gravity, and both the polyether glycol itself and its prepolymers have low viscosities, leading to easier handling. The prepolymers have long shelf lives.
1,4-Butanediol
Butanediol is used to make a variety of esters, including monomeric plasticizers, the engineering plastic polybutylene terephthalate and low molecular weight polyester glycols. The polyester glycols, made by reacting butanediol with various dibasic acids such as adipic and sebacic acid, are used as soft segments in polyurethanes. Details of the preparation are available on request. Polyesters such as poly(butylene adipate) glycol yield urethanes with excellent resistance to oils, solvents and ultraviolet light. These urethanes also have very good mechanical properties at room and elevated temperatures as well as high resistance to flexing and abrasion. Urethanes made from polyester glycols are quite polar and show generally better metal adhesion than those derived from polyethers. In addition to its use in the soft segments of polyurethanes, butanediol is used in the hard segments of some polyurethanes, particularly those made with MDI. In the hard segment, butanediol produces a good balance between hardness and low temperature flexibility. Butanediol is also used as a reaction solvent.
References* have recently come to light describing explosions apparently caused by the peroxidation of 1,3-butanediol and 2-butanol. Both are secondary alcohols. 1,4-Butanediol is not, and we are not aware of any hazard of this nature ever occurring with it. Nevertheless, it can peroxidize, causing product discoloration. Store 1,4-butanediol under an oxygen-free atmosphere; do not store in materials with a low barrier to oxygen, such as polyethylene. Transient exposure to air, e.g., when pumping between vessels, probably need not be avoided. Water spray, alcohol-resistant foam, dry chemical or CO2 extinguishers may be used to fight butanediol or Terathane fires. When water or foam is used, frothing may occur.(8)
Butanediol may also be dried under reduced pressure at about 75C (170F). An alternative drying technique involves passing butanediol through a zeolite bed such as Zeolon(9) 500, which can produce a water concentration of less than 0.01% in the treated product. Further assistance in planning drying operations may be obtained by calling the DuPont office (see back cover).
Transportation Emergencies
Terathane and 1,4-butanediol are not regulated as Hazardous Materials by the Department of Transportation (DOT).(1) If a transportation emergency arises in the continental United States, call (800) 424-9300 toll free. You will be connected with the Chemical Manufacturers Associations Chemical Transportation Emergency Center (Chemtrec) in Washington, DC. The Chemtrec telephone is attended around the clock to make expert help immediately available. Chemtrec specialists relay handling and hazard information and report the accident to the shipper.
Spills
Liquid spills may be absorbed with a material such as vermiculite and handled as nontoxic solid waste. Small spills of butanediol, and the residue left after absorbing butanediol in vermiculite, may be flushed with water to a sewer, because butanediol is miscible with water and biodegradable. A larger spill should be temporarily diked and roped off. If fluid, it may be pumped into drums for later salvage or disposal by burning under controlled conditions. If the spill has solidified because of low temperature, it may be shoveled into drums for disposal or recovery. Terathane spills can be frozen for this purpose by flushing with cold water. Spills should not be allowed to get into water courses or uncontrolled sewers because federal, state and local regulations may govern this situation.
Drying
Occasionally, it may be necessary to dry Terathane or butanediol; for example, when the product has accidentally picked up additional moisture in storage or some process requirement dictates a moisture content lower than what is typically received. Gross amounts of water may be removed from Terathane by azeotropic distillation with toluene. Further reduction in water content may be achieved by heating (120150C [238302F]) for a few hours at reduced pressure (less than 20 mmHg). The vessel used as a drier must be clean and free of air to minimize contamination and oxidation.
* Supplied on request
required. To safely receive tank trucks, the unloading areas should include: A serviceable roadway to the unloading station Vertical clearances of at least 13.5 ft (4.1 m) An open area at the unloading station that permits normal maneuverability for a trailer and a level surface capable of supporting 34,000 lb (15,400 kg) per tandem axle Securely anchored and heated or well insulated receiving line with connections at normal working levels Low pressure steam (50 psig [350 kPa]) to heat trailer contents when required Dry nitrogen supply with pressure control A static electricity grounding cable Tank Placement and Unloading Plant personnel should: be sure the storage tank can take the entire delivery; make certain the truck unloading hose is securely attached to the proper receiving line; check safety shower or provide water hose; be sure that all valves in the line to the storage tank are open; be sure that the storage tank is adequately vented to accommodate gas displaced from the tank and any gas blown from the truck when the transfer is completed; operate or supervise the operation of all the plant equipment involved in the unloading. Driver will: 1. position the trailer properly, chock the wheels, and prepare it for unloading; 2. connect the unloading hose to the plant receiving line; 3. operate or supervise the operation of all truck equipment as needed to unload the truck, including clearing the unloading line. A typical tank truck unloading and storage system is shown in Figure 3. The unloading procedure continues as follows: 1. Connect static electricity grounding cable. 2. Heat the unloading lines if necessary 30 min before unloading. 3. Connect a flexible steam hose from a low pressure source (about 50 psig/350 kPa) to the
4.
5.
6. 7.
8.
9. 10. 11.
12.
13. 14.
heating coil if heating is required; this will seldom be necessary in summer. Leave steam on the heating coils until the temperature of the contents as measured on the trailer thermometer is above approximately 40C (l04F) for butanediol and 50C (120F) for Terathane. Connect dry nitrogen supply to the vent connection on the top of the trailer. For pump unloading, positive venting of the cargo tank is essential. A nitrogen flowmeter (or for closed loop unloading, a vent gas flowmeter) of 015 cfm (07 L/sec) capacity is recommended. A pumped flow of 100 gpm (6.3 L/sec) must be balanced with a 13.3 cfm (6.3 L/sec) gas rate to avoid a vacuum in the cargo tank. Open nitrogen valve, and adjust the regulator to maintain 1020 psig (70140 kPa) on the trailer. Never permit this pressure to exceed 30 psig (200 kPa) in order to avoid opening the pressure relief valves. Operate valves as necessary to route flow from the trailer to the specified storage tank. Start unloading pump, and check the level gauge on storage tank to verify that material is flowing. To prevent vacuum from collapsing the tank, check the nitrogen flowmeter to be sure of an adequate flow. When unloading is completed, make certain the cargo tank is empty by checking the gain in storage tank inventory. Shut off the nitrogen valve to the trailer, and permit the nitrogen pressure in the cargo tank to vent off through the storage tank. Open manway, and visually verify that the cargo tank is empty. Close valves on the trailer and receiving line, and reset as necessary for normal operation. If steam was used, close steam valve and relieve the pressure via the condensate drain valve. Disconnect unloading hose, and drain any residue into a bucket for disposal. Wash and hang hose on rack. Disconnect grounding cable. Disconnect and place nitrogen hose in storage rack. Clean up any spills.
Figure 3. Typical Tank Truck Unloading and Outdoor Storage System for DuPont Glycols
Conservation Vent Emergency Vent on Manway Cover
Dry Nitrogen Supply (See Figure 4) Level Transmitter High Level Alarm Vent Flowmeter External Steam Heating Panels
To Process
D TE K LA TAN U E INS AG OR T S
Ground Wire
Filter
Low Pressure Steam Source (Optional) Unloading Hose Grounding Cable Ground
Nitrogen Gauge (Do Not Exceed 20 psig Pressure) Pressure Reducing Valve
Bleed Valve Nitrogen Supply Rotameter Nitrogen Shut-Off Valve Pop Valve (Set at 30 psig)
Notes: Use a 015 cfm (07 L/sec) nitrogen rotameter to balance nitrogen flow with liquid pumping rate. This maintains positive pressure on cargo tank. Flow rate of 13.3 cfm is equivalent to a glycol flow rate of 100 gpm (both 6.3 L/sec). CautionThe cover over the nitrogen valves on the dome of a tank car is hinged and a potential pinch point.
Tank Cars DuPont ships glycols in tank cars with connections that permit either top or bottom unloading. Refer to the step-wise procedure above under Truck Placement and Unloading for key points that apply equally to unloading glycol tank cars. Top unloading with a self-priming pump is preferred to minimize the amount spilled in the event of a valve or line leak. Prepare for unloading as follows: 1. Make sure car is properly positioned, brakes set and the wheels chocked. 2. Connect static electricity grounding cable. 3. Place metal sign* (white lettering on blue background) on track at open ends of siding to warn persons approaching: StopTank Car Connected. Signs that have a stand and lock conforming to DOT requirements are available from safety equipment suppliers.
The storage tank must be provided with external or internal heating to maintain a temperature of about 40C (104F) for butanediol or about 50C (120F) for Terathane. Insulation, required to conserve heat, should be properly sealed and weatherproofed for outdoor service. Steam bayonet-type heaters may be used. The glycol may be circulated in the tank using a mixing eductor such as those manufactured by Schutte & Koerting in the United States. The temperature in the tank should be monitored. A 0150C (32300F) industrial-type dial thermometer can be used, with a 30-cm (12-in) stem length in a thermowell. The bulb should extend 15 cm (6 in) inside the straight side of the tank. If remote temperature indication is desired, a thermocouple or temperature transmitter can be installed near the bottom of the tank in a thermowell. The tank must be pressure-tight and structurally capable of supporting the various forces applied to it. Tanks should be designed and built in accordance with good industrial practice and appropriate federal, state and local codes. Large tanks designed for low pressure service, both positive and negative, require a dry nitrogen blanket, properly sized conservation vents, and a regular inspection program to ensure proper vent function. Vents and emergency vents should be heat traced and insulated to prevent plugging by solidified glycol. The tank should be equipped with a manway to facilitate entry and cleaning when required. The tank foundation must carry the load of the tank and its accessories plus the weight of the stored glycol. Other factors such as wind load. snow, floods, etc., should be included in the foundation design. The tank level can be monitored by use of a dip tube with a nitrogen purge to a local or remote manometer system. If a remote indicator is desired, a differential pressure transmitter system is recommended.
Storage
DuPont glycols are hygroscopic and can oxidize. They should be stored in completely enclosed tanks under a dry nitrogen blanket. Do not store in materials with a low barrier to oxygen, such as polyethylene. Storage Tank Either horizontal or vertical tanks may be used. Vertical tanks are usually less expensive to install and require less area per unit of storage. The tank size should be about 50% larger than the load to be delivered. Mild steel tanks, designed and manufactured according to the local requirements for pressure vesselsASME, TUV, STOOMWEZEN, etc. are usually satisfactory. Steel tanks lined with phenolic resin such as Plasite(10) or Unichrome(11) and stainless steels such as type 304 may also be used. Phenolic resin liners are available in Europe through SAKAPHEN in Gladbeck, Germany. Tanks should be pressure tested and equipped with a pressure vacuum relief conservation vent and an emergency vent.
*U.S. Federal Regulation 49 CFR 174.67
Pumps
Glycols should be transferred from the tank using centrifugal or gear pumps such as a Viking model KK 4125 R, capacity 55 gpm (3.5 L/sec) at a discharge pressure of 150 psig (1,032 kPa) at 520 rpm. The motor is 10 HP, 1750 rpm with a reducer ratio of 4.19 to 1. Gear pumps require a spring-loaded bypass relief valve to prevent damage to the equipment. Pump shafts may be packed with braided Teflon fluorocarbon or equipped with mechanical seals such as a John Crane Type 9. Piping, Gaskets, Valves and Hoses Piping may be electric-resistance-welded (ERW) carbon steel or stainless steel. Nozzles should be Schedule 80 pipe with 150-lb design standard flanges. Gaskets such as John Crane #888, or equivalent, give good service life. All piping should be heat-wire traced and insulated. Ball, plug, globe or check valves can be used. Flexonics #RW401M (or equivalent) Type 321, 57 cm (23 in) stainless-steel flexible hose with screwed ends may be used for unloading. A neoprene or butyl-rubber lined hose may also be used. Ever-Tite(12) or Kamlok(13) adapters may be used for quick-disconnect hose couplings.
Cleaning of Equipment
New equipment should be cleaned before use to avoid contamination. New steel tanks should be brushed or sandblasted to free the surfaces of rust and scale before placing them in service. Tank walls and floor should be vacuumed carefully. Make sure tank is dry. The tank is then ready for service. After disconnecting from the tank, piping can be cleaned by pumping a detergent solution through it to remove loose scale and organics. The lines and pump should then be flushed thoroughly with water and dried before reconnecting. Experience has shown that storage tanks can be used for years without need for subsequent cleaning. No corrosion problems have been encountered using materials described in the Equipment section. However, should the tank need cleaning, laboratory studies indicate that hot water and detergent, followed by careful drying, should be sufficient. All lines should be thoroughly flushed with water and dried before beginning work. Note: Suppliers of equipment for glycol service in each geographical area can be obtained by contacting our Customer Service Center. (See back cover for phone numbers and address.)
10
We make the grades We have the specialties Now meet the PEOPLE
For superior polyurethanes, nothing beats Terathane PTMEG from DuPont for hydrolysis resistance, low temperature flexibility, and excellent dynamic properties. Superior polyols for demanding applications!
Available grades Terathane 250 Terathane 1400 Terathane 1800 Terathane 650 Terathane 1000 Terathane 2000 Terathane 2900 Other high performance specialties include Hylene PPDI and Hylene TPEs
Contact us with your needs and meet our people. We will take that extra step to solve your problem. Europe: P. R. China: Japan: Korea: Taiwan: Australia: All other Asia: Americas: 49-6172-871306 86-21-6386-6366 81-3-5434-6124 82-2-222-5306 886-2-514-4419 61-2-9923-6194 82-2-222-5306 800-441-9598 fax: 49-6172-871962 fax: 86-21-6386-6333 fax: 81-3-5434-6189 fax: 82-2-222-5319 fax: 886-2-514-4364 fax: 61-2-9923-6099 fax: 82-2-222-5319 fax: 302-992-2500