Chemwatch australian msds 23-5700

TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 1 of 16
Section 1 - CHEMICAL PRODUCT AND COMPANY IDENTIFICATION
PRODUCT NAME
TUFF PLUG A
PRODUCT USE
Isocyanate component used to make polyurethane.
SUPPLIER
Company: Tuff Drilling Solutions Pty Ltd
Address:
Unit 5 / 60 Coulson Street
Wacol
QLD, 4076
Australia
Telephone: +61 7 3271 2422
Emergency Tel: 1800 039 008 (24 hrs)
Fax: +61 7 3271 1344
Email: [email protected]
Section 2 - HAZARDS IDENTIFICATION
STATEMENT OF HAZARDOUS NATURE
HAZARDOUS SUBSTANCE. NON-DANGEROUS GOODS. According to NOHSC Criteria, and ADG Code.
POISONS SCHEDULE
S6
RISK
Risk Codes
• Irritating to eyes, respiratory system and skin.
• May cause SENSITISATION by inhalation and skin contact.
SAFETY
Safety Codes
• Do not breathe gas/ fumes/ vapour/ spray.
• Wear suitable protective clothing.
• Use only in well ventilated areas.
• Keep container in a well ventilated place.
• To clean the floor and all objects contaminated by thismaterial use water and detergent.
• Keep away from food drink and animal feeding stuffs.
• In case of contact with eyes rinse with plenty of waterand contact Doctor or Poisons Information Centre.
• If swallowed IMMEDIATELY contact Doctor or PoisonsInformation Centre (show this container or label).
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 2 of 16
Section 3 - COMPOSITION / INFORMATION ON INGREDIENTS
4, 4' - diphenylmethane diisocyanate (MDI) Section 4 - FIRST AID MEASURES
SWALLOWED
· For advice, contact a Poisons Information Centre or a doctor at once.
· Urgent hospital treatment is likely to be needed.
· If swallowed do NOT induce vomiting.
· If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to
maintain open airway and prevent aspiration.
· Observe the patient carefully.
· Never give liquid to a person showing signs of being sleepy or with reduced awareness; i.e. becoming
unconscious.
· Give water to rinse out mouth, then provide liquid slowly and as much as casualty can comfortably drink.
· Transport to hospital or doctor without delay.
EYE
• If this product comes in contact with the eyes:
· Wash out immediately with fresh running water.
· Ensure complete irrigation of the eye by keeping eyelids apart and away from eye and moving the eyelids by
occasionally lifting the upper and lower lids.
· Seek medical attention without delay; if pain persists or recurs seek medical attention.
· Removal of contact lenses after an eye injury should only be undertaken by skilled personnel.
SKIN
• If skin contact occurs:
· Immediately remove all contaminated clothing, including footwear.
· Flush skin and hair with running water (and soap if available).
· Seek medical attention in event of irritation.
INHALED
· If fumes or combustion products are inhaled remove from contaminated area.
· Lay patient down. Keep warm and rested.
· Prostheses such as false teeth, which may block airway, should be removed, where possible, prior to
initiating first aid procedures.
· Apply artificial respiration if not breathing, preferably with a demand valve resuscitator, bag-valve mask
device, or pocket mask as trained. Perform CPR if necessary.
· Transport to hospital, or doctor, without delay.
NOTES TO PHYSICIAN
• For sub-chronic and chronic exposures to isocyanates:
· This material may be a potent pulmonary sensitiser which causes bronchospasm even in patients without prior
· Clinical symptoms of exposure involve mucosal irritation of respiratory and gastrointestinal tracts.
· Conjunctival irritation, skin inflammation (erythema, pain vesiculation) and gastrointestinal disturbances · Pulmonary symptoms include cough, burning, substernal pain and dyspnoea.
· Some cross-sensitivity occurs between different isocyanates.
· Noncardiogenic pulmonary edema and bronchospasm are the most serious consequences of exposure. Markedly symptomatic patients should receive oxygen, ventilatory support and an intravenous line.
· Treatment for asthma includes inhaled sympathomimetics (epinephrine [adrenalin], terbutaline) and steroids.
· Activated charcoal (1 g/kg) and a cathartic (sorbitol, magnesium citrate) may be useful for ingestion.
· Mydriatics, systemic analgesics and topical antibiotics (Sulamyd) may be used for corneal abrasions.
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 3 of 16
Section 4 - FIRST AID MEASURES
· There is no effective therapy for sensitised workers. [Ellenhorn and Barceloux; Medical Toxicology]NOTE: Isocyanates cause airway restriction in naive individuals with the degree of response dependant on theconcentration and duration of exposure. They induce smooth muscle contraction which leads tobronchoconstrictive episodes. Acute changes in lung function, such as decreased FEV1, may not representsensitivity.
[Karol & Jin, Frontiers in Molecular Toxicology, pp 56-61, 1992].
Section 5 - FIRE FIGHTING MEASURES
EXTINGUISHING MEDIA
· Small quantities of water in contact with hot liquid may react violently with generation of a large volume
of rapidly expanding hot sticky semi-solid foam.
· Presents additional hazard when fire fighting in a confined space.
· Cooling with flooding quantities of water reduces this risk.
· Water spray or fog may cause frothing and should be used in large quantities.
· Dry chemical powder.
· BCF (where regulations permit).
· Carbon dioxide.
FIRE FIGHTING
· Alert Fire Brigade and tell them location and nature of hazard.
· Wear breathing apparatus plus protective gloves.
· Prevent, by any means available, spillage from entering drains or water courses.
· Use water delivered as a fine spray to control fire and cool adjacent area.
· DO NOT approach containers suspected to be hot.
· Cool fire exposed containers with water spray from a protected location.
· If safe to do so, remove containers from path of fire.
· Equipment should be thoroughly decontaminated after use.
FIRE/EXPLOSION HAZARD
· Combustible.
· Moderate fire hazard when exposed to heat or flame.
· When heated to high temperatures decomposes rapidly generating vapour which pressures and may then rupture
containers with release of flammable and highly toxic isocyanate vapour.
· Burns with acrid black smoke and poisonous fumes.
· Combustion yields traces of highly toxic hydrogen cyanide HCN, plus toxic nitrogen oxides NOx and carbon Decomposition may produce toxic fumes of: isocyanates, hydrogen cyanide, nitrogen oxides (NOx).
May emit corrosive fumes.
When heated at high temperatures many isocyanates decompose rapidly generating a vapour which pressurisescontainers, possibly to the point of rupture. Release of toxic and/or flammable isocyanate vapours may thenoccur.
FIRE INCOMPATIBILITY
• Avoid contamination with strong oxidising agents as ignition may result.
HAZCHEM
None
Personal Protective Equipment
Gas tight chemical resistant suit.
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 4 of 16
Section 6 - ACCIDENTAL RELEASE MEASURES
MINOR SPILLS
· Remove all ignition sources.
· Clean up all spills immediately.
· Avoid breathing vapours and contact with skin and eyes.
· Control personal contact by using protective equipment.
· Contain and absorb spill with sand, earth, inert material or vermiculite.
· Wipe up.
· Place in a suitable, labelled container for waste disposal.
MAJOR SPILLS
• Chemical Class: cyanates and isocyanates
For release onto land: recommended sorbents listed in order of priority.
DGC: Not effective where ground cover is denseR; Not reusableI: Not incinerable continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 5 of 16
Section 6 - ACCIDENTAL RELEASE MEASURES
P: Effectiveness reduced when rainyRT:Not effective where terrain is ruggedSS: Not for use within environmentally sensitive sitesW: Effectiveness reduced when windy Reference: Sorbents for Liquid Hazardous Substance Cleanup and Control; R.W Melvold et al: Pollution Technology Review No. 150: Noyes Data Corporation 1988.
· Liquid Isocyanates and high isocyanate vapour concentrations will penetrate seals on self contained breathing apparatus - SCBA should be used inside encapsulating suit where this exposure may occur.
· Treat isocyanate spills with sufficient amounts of isocyanate decontaminant preparation.
· Typically, such a preparation may consist of: sawdust: 20 parts by weight Kieselguhr 40 parts by weight plus a mixture of {ammonia (s.g. 0.880) 8% v/v non-ionic surfactant 2% v/v water 90% v/v}.
· Let stand for 24 hours.
· Avoid contamination with water, alkalies and detergent solutions.
· Material reacts with water and generates gas, pressurises containers with even drum rupture resulting.
· DO NOT reseal container if contamination is suspected.
· Open all containers with care.
· DO NOT touch the spill material.
Moderate hazard.
· Clear area of personnel and move upwind.
· Alert Fire Brigade and tell them location and nature of hazard.
· Wear breathing apparatus plus protective gloves.
· Prevent, by any means available, spillage from entering drains or water course.
· Stop leak if safe to do so.
· Contain spill with sand, earth or vermiculite.
· Collect recoverable product into labelled containers for recycling.
· Neutralise/decontaminate residue.
· Collect solid residues and seal in labelled drums for disposal.
· Wash area and prevent runoff into drains.
· After clean up operations, decontaminate and launder all protective clothing and equipment before storing · If contamination of drains or waterways occurs, advise emergency services.
EMERGENCY RESPONSE PLANNING GUIDELINES (ERPG)
The maximum airborne concentration below which it is believed that nearly all individuals could be exposed
for up to one hour WITHOUT experiencing or developing
irreversible or other serious effects or symptoms which could impair an individual's ability to take other than mild, transient adverse effects without perceiving a clearly defined odour is: American Industrial Hygiene Association (AIHA) Ingredients considered according to the following cutoffs where percentage is percentage of ingredient found in the mixture Personal Protective Equipment advice is contained in Section 8 of the MSDS.
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 6 of 16
Section 7 - HANDLING AND STORAGE
PROCEDURE FOR HANDLING
· DO NOT allow clothing wet with material to stay in contact with skin.
· Avoid all personal contact, including inhalation.
· Wear protective clothing when risk of exposure occurs.
· Use in a well-ventilated area.
· Avoid contact with moisture.
· Avoid contact with incompatible materials.
· When handling, DO NOT eat, drink or smoke.
· Keep containers securely sealed when not in use.
· Avoid physical damage to containers.
· Always wash hands with soap and water after handling.
· Work clothes should be laundered separately. Launder contaminated clothing before re-use.
· Use good occupational work practice.
· Observe manufacturer's storing and handling recommendations.
· Atmosphere should be regularly checked against established exposure standards to ensure safe working
conditions are maintained.
SUITABLE CONTAINER
· Polyethylene or polypropylene container.
· Packing as recommended by manufacturer.
· Check all containers are clearly labelled and free from leaks.
STORAGE INCOMPATIBILITY
· Avoid reaction with water, alcohols and detergent solutions.
· Isocyanates and thioisocyanates are incompatible with many classes of compounds, reacting exothermically to
release toxic gases. Reactions with amines, strong bases, aldehydes, alcohols, alkali metals, ketones,
mercaptans, strong oxidisers, hydrides, phenols, and peroxides can cause vigorous releases of heat. Acids
and bases initiate polymerisation reactions in these materials.
· Isocyanates easily form adducts with carbodiimides, isothiocyanates, ketenes, or with substrates containing
activated CC or CN bonds.
· Some isocyanates react with water to form amines and liberate carbon dioxide. This reaction may also
generate large volumes of foam and heat. Foaming in confined spaces may produce pressure in confined spaces
or containers. Gas generation may pressurise drums to the point of rupture.
· Do NOT reseal container if contamination is expected
· Open all containers with care
· Base-catalysed reactions of isocyanates with alcohols should be carried out in inert solvents. Such
reactions in the absence of solvents often occur with explosive violence,
· Isocyanates will attack and embrittle some plastics and rubbers.
· A range of exothermic decomposition energies for isocyanates is given as 20-30 kJ/mol.
· The relationship between energy of decomposition and processing hazards has been the subject of discussion;
it is suggested that values of energy released per unit of mass, rather than on a molar basis (J/g) be used
in the assessment.
· For example, in "open vessel processes" (with man-hole size openings, in an industrial setting), substances
with exothermic decomposition energies below 500 J/g are unlikely to present a danger, whilst those in
"closed vessel processes" (opening is a safety valve or bursting disk) present some danger where the
decomposition energy exceeds 150 J/g.
BRETHERICK: Handbook of Reactive Chemical Hazards, 4th Edition.
STORAGE REQUIREMENTS
• for commercial quantities of isocyanates:
· Isocyanates should be stored in adequately bunded areas. Nothing else should be kept within the same
bunding. Pre-polymers need not be segregated. Drums of isocyanates should be stored under cover, out of
direct sunlight, protected from rain, protected from physical damage and well away from moisture, acids and
alkalis.
· Where isocyanates are stored at elevated temperatures to prevent solidifying, adequate controls should be
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 7 of 16
Section 7 - HANDLING AND STORAGE
installed to prevent the high temperatures and precautions against fire should be taken.
· Where stored in tanks, the more reactive isocyanates should be blanketed with a non-reactive gas such as nitrogen and equipped with absorptive type breather valve (to prevent vapour emissions).
· Transfer systems for isocyanates in bulk storage should be fully enclosed and use pump or vacuum systems. Warning signs, in appropriate languages, should be posted where necessary.
· Areas in which polyurethane foam products are stored should be supplied with good general ventilation. Residual amounts of unreacted isocyanate may be present in the finished foam, resulting in hazardous atmospheric concentrations.
Rotate all stock to prevent ageing. Use on FIFO (First In-First Out) basis.
Section 8 - EXPOSURE CONTROLS / PERSONAL PROTECTION
EXPOSURE CONTROLS
Source
diisocyanate (MDI)(Isocyanates, all (as-NCO)) EMERGENCY EXPOSURE LIMITS
MATERIAL DATA
TUFF PLUG A:
• None assigned. Refer to individual constituents.
• Some jurisdictions require that health surveillance be conducted on occupationally exposed workers. This demography, occupational and medical history and health advice · completion of a standardised respiratory questionnaire· physical examination of the respiratory system and skin· standardised respiratory function tests such as FEV1, FVC and FEV1/FVC.
• for diphenylmethane diisocyanate (methylene bisphenyl isocyanate; MDI)Odour Threshold Value: 0.39 ppmIDLH Level: 10 mg/m3Mean MDI exposures of less than 0.003 ppm appear to have no acute or chronic effect on pulmonary function.
MDI produces identical toxicological responses to those produced by TDI and the recommended TLV-TWA is identical for the two isocyanates. Exposure at or below the recommended value is thought to protect theworker against pulmonary function decrements as well as to minimise the potential for respiratory tractsensitisation. Individuals who may be hypersusceptible or otherwise unusually responsive to exposure tocertain industrial chemicals may not adequately protected from adverse health effects caused by MDI at therecommended TLV-TWA. Ceiling values recommended by NIOSH and OSHA are synonymous with normal excursionsallowable for exposures to the TLV-TWA (in excess of 3 x TLV-TWA for no more than a total of 30 minutesduring a work day but in any case not exceeding 5 x TLV-TWA).
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 8 of 16
Section 8 - EXPOSURE CONTROLS / PERSONAL PROTECTION
PERSONAL PROTECTION
EYE
· Safety glasses with side shields.
· Chemical goggles.
· Contact lenses may pose a special hazard; soft contact lenses may absorb and concentrate irritants. A
written policy document, describing the wearing of lens or restrictions on use, should be created for eachworkplace or task. This should include a review of lens absorption and adsorption for the class ofchemicals in use and an account of injury experience. Medical and first-aid personnel should be trained intheir removal and suitable equipment should be readily available. In the event of chemical exposure, begineye irrigation immediately and remove contact lens as soon as practicable. Lens should be removed at thefirst signs of eye redness or irritation - lens should be removed in a clean environment only after workershave washed hands thoroughly. [CDC NIOSH Current Intelligence Bulletin 59].
HANDS/FEET
• NOTE:
· The material may produce skin sensitisation in predisposed individuals. Care must be taken, when removing
gloves and other protective equipment, to avoid all possible skin contact.
· Contaminated leather items, such as shoes, belts and watch-bands should be removed and destroyed.
Suitability and durability of glove type is dependent on usage. Important factors in the selection of glovesinclude: such as:· frequency and duration of contact,· chemical resistance of glove material,· glove thickness and· dexteritySelect gloves tested to a relevant standard (e.g. Europe EN 374, US F739).
· When prolonged or frequently repeated contact may occur, a glove with a protection class of 5 or higher (breakthrough time greater than 240 minutes according to EN 374) is recommended.
· When only brief contact is expected, a glove with a protection class of 3 or higher (breakthrough time greater than 60 minutes according to EN 374) is recommended.
· Contaminated gloves should be replaced.
Gloves must only be worn on clean hands. After using gloves, hands should be washed and dried thoroughly.
Application of a non-perfumed moisturiser is recommended.
· Do NOT wear natural rubber (latex gloves).
· Isocyanate resistant materials include Teflon, Viton, nitrile rubber and some PVA gloves.
· Protective gloves and overalls should be worn as specified in the appropriate national standard.
· Contaminated garments should be removed promptly and should not be re-used until they have been · NOTE: Natural rubber, neoprene, PVC can be affected by isocyanates.
· DO NOT use skin cream unless necessary and then use only minimum amount.
· Isocyanate vapour may be absorbed into skin cream and this increases hazard.
OTHER
• All employees working with isocyanates must be informed of the hazards from exposure to the contaminant and
the precautions necessary to prevent damage to their health. They should be made aware of the need to carry
out their work so that as little contamination as possible is produced, and of the importance of the proper
use of all safeguards against exposure to themselves and their fellow workers. Adequate training, both in the
proper execution of the task and in the use of all associated engineering controls, as well as of any
personal protective equipment, is essential.
Employees exposed to contamination hazards should be educated in the need for, and proper use of, facilities,
clothing and equipment and thereby maintain a high standard of personal cleanliness. Special attention should
be given to ensuring that all personnel understand instructions, especially newly recruited employees and
those with local-language difficulties, where they are known.
· Overalls.
· P.V.C. apron.
· Barrier cream.
· Skin cleansing cream.
· Eye wash unit.
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 9 of 16
Section 8 - EXPOSURE CONTROLS / PERSONAL PROTECTION
The local concentration of material, quantity and conditions of use determine the type of personal protectiveequipment required. For further information consult site specific CHEMWATCH data (if available), or yourOccupational Health and Safety Advisor.
ENGINEERING CONTROLS
· All processes in which isocyanates are used should be enclosed wherever possible.
· Total enclosure, accompanied by good general ventilation, should be used to keep atmospheric concentrations
below the relevant exposure standards.
· If total enclosure of the process is not feasible, local exhaust ventilation may be necessary. Local exhaust ventilation is essential where lower molecular weight isocyanates (such as TDI or HDI) is used orwhere isocyanate or polyurethane is sprayed.
· Where other isocyanates or pre-polymers are used and aerosol formation cannot occur, local exhaust ventilation may not be necessary if the atmospheric concentration can be kept below the relevant exposurestandards.
· Where local exhaust ventilation is installed, exhaust vapours should not be vented to the exterior in such · Spraying of material or material in admixture with other components must be carried out in conditions conforming to local state regulations.
· Local exhaust ventilation with full face positive-pressure air supplied breathing apparatus (hood or helmet · Spraying should be performed in a spray booth fitted with an effective exhaust system which complies with · The spray booth area must be isolated from unprotected personnel whilst spraying is in progress and until NOTE: Isocyanate vapours will not be adequately absorbed by organic vapour respirators.
Refer also to protective measures for the other component used with the product. Read both MSDS before using;store and attach MSDS together.
Section 9 - PHYSICAL AND CHEMICAL PROPERTIES
APPEARANCE
Dark amber viscous liquid; does not mix with water.
PHYSICAL PROPERTIES
Liquid.
Section 10 - CHEMICAL STABILITY AND REACTIVITY INFORMATION
CONDITIONS CONTRIBUTING TO INSTABILITY
· Presence of incompatible materials.
· Product is considered stable.
· Hazardous polymerisation will not occur.
· Presence of elevated temperatures.
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 10 of 16
Section 10 - CHEMICAL STABILITY AND REACTIVITY INFORMATION
For incompatible materials - refer to Section 7 - Handling and Storage. Section 11 - TOXICOLOGICAL INFORMATION
POTENTIAL HEALTH EFFECTS
ACUTE HEALTH EFFECTS
SWALLOWED
• Accidental ingestion of the material may be damaging to the health of the individual.
Ingestion may result in nausea, abdominal irritation, pain and vomiting.
EYE
• This material can cause eye irritation and damage in some persons.
SKIN
• This material can cause inflammation of the skin oncontact in some persons.
The material may accentuate any pre-existing dermatitis condition.
Skin contact with the material may damage the health of the individual; systemic effects may result following
absorption.
Open cuts, abraded or irritated skin should not be exposed to this material.
Entry into the blood-stream, through, for example, cuts, abrasions or lesions, may produce systemic injury
with harmful effects. Examine the skin prior to the use of the material and ensure that any external damage
is suitably protected.
INHALED
• The material can cause respiratory irritation in some persons. The body's response to such irritation can
cause further lung damage.
The vapour/mist may be highly irritating to the upper respiratory tract and lungs; the response may be severe
enough to produce bronchitis and pulmonary oedema. Possible neurological symptoms arising from isocyanate
exposure include headache, insomnia, euphoria, ataxia, anxiety neurosis, depression and paranoia.
Gastrointestinal disturbances are characterised by nausea and vomiting. Pulmonary sensitisation may produce
asthmatic reactions ranging from minor breathing difficulties to severe allergic attacks; this may occur
following a single acute exposure or may develop without warning for several hours after exposure. Sensitized
people can react to very low doses, and should not be allowed to work in situations allowing exposure to this
material. Continued exposure of sensitised persons may lead to possible long term respiratory impairment.
Inhalation hazard is increased at higher temperatures.
CHRONIC HEALTH EFFECTS
• Long-term exposure to respiratory irritants may result in disease of the airways involving difficult
breathing and related systemic problems.
Inhaling this product is more likely to cause a sensitisation reaction in some persons compared to the
general population.
Skin contact with the material is more likely to cause a sensitisation reaction in some persons compared to
the general population.
There has been some concern that this material can cause cancer or mutations but there is not enough data to
make an assessment.
Substance accumulation, in the human body, may occur and may cause some concern following repeated or long-
term occupational exposure.
Persons with a history of asthma or other respiratory problems or are known to be sensitised, should not be
engaged in any work involving the handling of isocyanates. [CCTRADE-Bayer, APMF].
Isocyanate vapours are irritating to the airways and can cause their inflammation, with wheezing, gasping,
severe distress, even loss of consciousness and fluid in the lungs. Nervous system symptoms that may occur
include headache, sleep disturbance, euphoria, inco-ordination, anxiety, depression and paranoia. Digestive
effects include nausea and vomiting. Breathing difficulties may occur unpredictably after a period of
tolerance and after skin contact. Allergic inflammation of the skin can occur, with rash, itching, blistering,
and swelling of the hands and feet. Sensitive people can react to very low levels and should not be exposed
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 11 of 16
Section 11 - TOXICOLOGICAL INFORMATION
to this material.
Respiratory sensitisation may result in allergic/asthma like responses; from coughing and minor breathingdifficulties to bronchitis with wheezing, gasping.
TOXICITY AND IRRITATION
4,4'-DIPHENYLMETHANE DIISOCYANATE (MDI):
POLYMERIC DIPHENYLMETHANE DIISOCYANATE:
• unless otherwise specified data extracted from RTECS - Register of Toxic Effects of Chemical Substances.
• The substance is classified by IARC as Group 3: NOT classifiable as to its carcinogenicity to humans.
Evidence of carcinogenicity may be inadequate or limited in animal testing.
• unless otherwise specified data extracted from RTECS - Register of Toxic Effects of Chemical Substances.
Oral (Rat) LD50: >2000 mg/kgDermal (Rabbit) LD50: >2000 mg/kgInhalation (Rat) LC50: 490 mg/m³/4h [Manufacturer]• Contact allergies quickly manifest themselves as contact eczema, more rarely as urticaria or Quincke'soedema. The pathogenesis of contact eczema involves a cell-mediated (T lymphocytes) immune reaction of thedelayed type. Other allergic skin reactions, e.g. contact urticaria, involve antibody-mediated immunereactions. The significance of the contact allergen is not simply determined by its sensitisation potential:the distribution of the substance and the opportunities for contact with it are equally important. A weaklysensitising substance which is widely distributed can be a more important allergen than one with strongersensitising potential with which few individuals come into contact. From a clinical point of view, substancesare noteworthy if they produce an allergic test reaction in more than 1% of the persons tested.
Asthma-like symptoms may continue for months or even years after exposure to the material ceases. This may bedue to a non-allergenic condition known as reactive airways dysfunction syndrome (RADS) which can occurfollowing exposure to high levels of highly irritating compound. Key criteria for the diagnosis of RADSinclude the absence of preceding respiratory disease, in a non-atopic individual, with abrupt onset ofpersistent asthma-like symptoms within minutes to hours of a documented exposure to the irritant. Areversible airflow pattern, on spirometry, with the presence of moderate to severe bronchial hyperreactivityon methacholine challenge testing and the lack of minimal lymphocytic inflammation, without eosinophilia,have also been included in the criteria for diagnosis of RADS. RADS (or asthma) following an irritatinginhalation is an infrequent disorder with rates related to the concentration of and duration of exposure tothe irritating substance. Industrial bronchitis, on the other hand, is a disorder that occurs as result ofexposure due to high concentrations of irritating substance (often particulate in nature) and is completelyreversible after exposure ceases. The disorder is characterised by dyspnea, cough and mucus production.
Allergic reactions involving the respiratory tract are usually due to interactions between IgE antibodies andallergens and occur rapidly. Allergic potential of the allergen and period of exposure often determine theseverity of symptoms. Some people may be genetically more prone than others, and exposure to other irritantsmay aggravate symptoms. Allergy causing activity is due to interactions with proteins.
Attention should be paid to atopic diathesis, characterised by increased susceptibility to nasal inflammation,asthma and eczema.
Exogenous allergic alveolitis is induced essentially by allergen specific immune-complexes of the IgG type;cell-mediated reactions (T lymphocytes) may be involved. Such allergy is of the delayed type with onset up tofour hours following exposure.
Isocyanate vapours are irritating to the airways and can cause their inflammation, with wheezing, gasping,severe distress, even loss of consciousness and fluid in the lungs. Nervous system symptoms that may occurinclude headache, sleep disturbance, euphoria, inco-ordination, anxiety, depression and paranoia. Digestiveeffects include nausea and vomiting. Breathing difficulties may occur unpredictably after a period oftolerance and after skin contact. Allergic inflammation of the skin can occur, with rash, itching, blistering,and swelling of the hands and feet. Sensitive people can react to very low levels and should not be exposedto this material.
The material may be irritating to the eye, with prolonged contact causing inflammation. Repeated or prolongedexposure to irritants may produce conjunctivitis.
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 12 of 16
Section 11 - TOXICOLOGICAL INFORMATION
Dermal (rabbit) LD50: >9400 mg/kgInhalation (rat) LC50: 490 mg/m³/4h Inhalation (rat) LC50: 178 mg/m³/4h DermalSensitiser *Oral (mouse) LD50: 2200 mg/kg RespiratorySensitiser (g.pig) *Dermal (rabbit) LD50: >6200 mg/kg * [* = BayerCCINFO 2133615]Oral (Rat) LD50: 9200 mg/kg• for diisocyanates:In general, there appears to be little or no difference between aromatic and aliphatic diisocyanates astoxicants. In addition, there are insufficient data available to make any major distinctions betweenpolymeric (<1000 MW) and monomeric diisocyanates. Based on repeated dose studies in animals by the inhalationroute, both aromatic and aliphatic diisocyanates appear to be of high concern for pulmonary toxicity at lowexposure levels. Based upon a very limited data set, it appears that diisocyanate prepolymers exhibit thesame respiratory tract effects as the monomers in repeated dose studies. There is also evidence that botharomatic and aliphatic diisocyanates are acutely toxic via the inhalation route. Most members of thediisocyanate category have not been tested for carcinogenic potential. Though the aromatic diisocyanatestested positive and the one aliphatic diisocyanate tested negative in one species, it is premature to makeany generalizations about the carcinogenic potential of aromatic versus aliphatic diisocyanates. In theabsence of more human data, it would be prudent at this time to assume that both aromatic and aliphaticdiisocyanates are respiratory sensitisers. Diisocyanates are moderate to strong dermal sensitisers in animalstudies. Skin irritation studies performed on rabbits and guinea pigs indicate no difference in the effectsof aromatic versus aliphatic diisocyanates.
For monomers, effects on the respiratory tract (lungs and nasal cavities) were observed in animal studies atexposure concentrations of less than 0.005 mg/L. The experimental animal data available on prepolymericdiisocyanates show similar adverse effects at levels that range from 0.002 mg/L to 0.026 mg/L.
There is also evidence that both aromatic and aliphatic diisocyanates are acutely toxic via the inhalationrouteOncogenicity: Most members of the diisocyanate category have not been tested for carcinogenic potential.
Commercially available Poly-MDI was tested in a 2-year inhalation study in rats. The tested materialcontained 47% aromatic 4,4'-methylenediphenyl diisocyanate (MDI) and 53% higher molecular weight oligomers.
Interim sacrifices at one year showed that males and females in the highest dose group (6 mg/m3) hadtreatment related histological changes in the nasal cavity, lungs and mediastinal lymph nodes. The incidenceand severity of degeneration and basal cell hyperplasia of the olfactory epithelium and Bowman's glandhyperplasia were increased in males at the mid and high doses and in females at the high dose following thetwo year exposure period. Pulmonary adenomas were found in 6 males and 2 females, and pulmonaryadenocarcinoma in one male in the high dose group. However, aliphatic hexamethylene diisocyanate (HDI) wasfound not to be carcinogenic in a two year repeated dose study in rats by the inhalation route. HDI has notbeen tested in mice by the inhalation route.
Though the oral route is not an expected route of exposure to humans, it should be noted that in two yearrepeated dose studies by the oral route, aromatic toluene diisocyanate (TDI) and 3,3'-dimethoxy-benzidine-4,4'-diisocyanate (dianisidine diisocyanate, DADI) were found to be carcinogenic in rodents. TDI induced astatistically significant increase in the incidence of liver tumors in rats and mice as well as dose-relatedhemangiosarcomas of the circulatory system and has been classified by the Agency as a B2 carcinogen. DADI wasfound to be carcinogenic in rats, but not in mice, with a statistically increase in the incidence ofpancreatic tumors observed.
Respiratory and Dermal Sensitization: Based on the available toxicity data in animals and epidemiologicstudies of humans, aromatic diisocyanates such as TDI and MDI are strong respiratory sensitisers. Aliphaticdiisocyanates are generally not active in animal models for respiratory sensitization. However, HDI and continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 13 of 16
Section 11 - TOXICOLOGICAL INFORMATION
possibly isophorone diisocyanate (IPDI), are reported to be associated with respiratory sensitization inhumans. Symptoms resulting from occupational exposure to HDI include shortness of breath, increasedbronchoconstriction reaction to histamine challenges, asthmatic reactions, wheezing and coughing. Two casereports of human exposure to IPDI by inhalation suggest IPDI is a respiratory sensitiser in humans. In viewof the information from case reports in humans, it would be prudent at this time to assume that both aromaticand aliphatic diisocyanates are respiratory sensitisers. Studies in both human and mice using TDI, HDI, MDIand dicyclohexylmethane-4,4'-diisocyanate (HMDI) suggest cross-reactivity with the other diisocyanates,irrespective of whether the challenge compound was an aliphatic or aromatic diisocyanate. Diisocyanates aremoderate to strong dermal sensitisers in animal studies. There seems to be little or no difference in thelevel of reactivity between aromatic and aliphatic diisocyanates.
Dermal Irritation: Skin irritation studies performed on rabbits and guinea pigs indicate no difference in theeffects of aromatic versus aliphatic diisocyanates. The level of irritation ranged from slightly to severelyirritating to the skin. One chemical, hydrogenated MDI (1,1-methylenebis-4-isocyanatocyclohexane), was foundto be corrosive to the skin in guinea pigs.
Contact allergies quickly manifest themselves as contact eczema, more rarely as urticaria or Quincke'soedema. The pathogenesis of contact eczema involves a cell-mediated (T lymphocytes) immune reaction of thedelayed type. Other allergic skin reactions, e.g. contact urticaria, involve antibody-mediated immunereactions. The significance of the contact allergen is not simply determined by its sensitisation potential:the distribution of the substance and the opportunities for contact with it are equally important. A weaklysensitising substance which is widely distributed can be a more important allergen than one with strongersensitising potential with which few individuals come into contact. From a clinical point of view, substancesare noteworthy if they produce an allergic test reaction in more than 1% of the persons tested.
Asthma-like symptoms may continue for months or even years after exposure to the material ceases. This may bedue to a non-allergenic condition known as reactive airways dysfunction syndrome (RADS) which can occurfollowing exposure to high levels of highly irritating compound. Key criteria for the diagnosis of RADSinclude the absence of preceding respiratory disease, in a non-atopic individual, with abrupt onset ofpersistent asthma-like symptoms within minutes to hours of a documented exposure to the irritant. Areversible airflow pattern, on spirometry, with the presence of moderate to severe bronchial hyperreactivityon methacholine challenge testing and the lack of minimal lymphocytic inflammation, without eosinophilia,have also been included in the criteria for diagnosis of RADS. RADS (or asthma) following an irritatinginhalation is an infrequent disorder with rates related to the concentration of and duration of exposure tothe irritating substance. Industrial bronchitis, on the other hand, is a disorder that occurs as result ofexposure due to high concentrations of irritating substance (often particulate in nature) and is completelyreversible after exposure ceases. The disorder is characterised by dyspnea, cough and mucus production.
Allergic reactions involving the respiratory tract are usually due to interactions between IgE antibodies andallergens and occur rapidly. Allergic potential of the allergen and period of exposure often determine theseverity of symptoms. Some people may be genetically more prone than others, and exposure to other irritantsmay aggravate symptoms. Allergy causing activity is due to interactions with proteins.
Attention should be paid to atopic diathesis, characterised by increased susceptibility to nasal inflammation,asthma and eczema.
Exogenous allergic alveolitis is induced essentially by allergen specific immune-complexes of the IgG type;cell-mediated reactions (T lymphocytes) may be involved. Such allergy is of the delayed type with onset up tofour hours following exposure.
Isocyanate vapours are irritating to the airways and can cause their inflammation, with wheezing, gasping,severe distress, even loss of consciousness and fluid in the lungs. Nervous system symptoms that may occurinclude headache, sleep disturbance, euphoria, inco-ordination, anxiety, depression and paranoia. Digestiveeffects include nausea and vomiting. Breathing difficulties may occur unpredictably after a period oftolerance and after skin contact. Allergic inflammation of the skin can occur, with rash, itching, blistering,and swelling of the hands and feet. Sensitive people can react to very low levels and should not be exposedto this material.
The material may produce moderate eye irritation leading to inflammation. Repeated or prolonged exposure toirritants may produce conjunctivitis.
Inhalation (human) TCLo: 0.13 ppm/30 mins Eye (rabbit): 0.10 mg moderate CARCINOGEN
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 14 of 16
Section 11 - TOXICOLOGICAL INFORMATION
for Research on Cancer(IARC) - AgentsReviewed by the IARCMonographs (IARC) - AgentsReviewed by the IARCMonographs Section 12 - ECOLOGICAL INFORMATION
Refer to data for ingredients, which follows: 4,4'-DIPHENYLMETHANE DIISOCYANATE (MDI):TUFF PLUG A:• DO NOT discharge into sewer or waterways.
• Hydrolysis would represents the primary fate mechanism for the majority of the commercial isocyanatemonomers, but, is tempered somewhat by the lack of water solubility. In the absence of hydrolysis, sorptionto solids (e.g., sludge and sediments) will be the primary mechanism of removal. Biodegradation is minimalfor most compounds and volatilisation is negligible. Atmospheric degradation is not expected with removalfrom air occurring by washout or dry deposition. Volatilisation from surface waters (e.g., lakes and rivers)is expected to take years. In wastewater treatment this process is not expected to be significant.
Review of the estimated properties of the isocyanates suggest that sorption is the primary removal mechanismin the ambient environment and in wastewater treatment in the absence of significant hydrolysis. Sorption tosolids in wastewater treatment is considered strong to very strong for most compounds. Sorption to sedimentsand soils in the ambient environment is very strong in most instances. Migration to groundwater and surfacewaters is not expected due to sorption or hydrolysis.
Hydrolysis of the N=C=O will occur in less than hours in most instances and within minutes for more than 90%of the commercial isocyanates. However, the low to very low solubility of these substances will generallylessen the effectiveness of hydrolysis as a fate pathway. But hydrolysis should be considered one of the twomajor fate processes for the isocyanates.
Aerobic and/or anaerobic biodegradation of the isocyanates is not expected to occur at significant levels.
Most of the substances take several months to degrade.
Degradation of the hydrolysis products will occur at varying rates depending on the moiety formed.
POLYMERIC DIPHENYLMETHANE DIISOCYANATE:Aquatic toxicity:Fish (Brachydanio rerio) 96h LC0: >1000 mg/l *(Daphnia) 24h EC50: >1000 mg/l *Bacterial toxicity (activated sludge microorganism) 3h EC50: >100 mg/l * 4,4'-DIPHENYLMETHANE DIISOCYANATE (MDI):• Half- life Soil - High (hours): • Half- life Surface water - High (hours): • Half- life Surface water - Low (hours): • Half- life Ground water - High (hours): • Half- life Ground water - Low (hours): • Aqueous biodegradation - Aerobic - High (hours): • Aqueous biodegradation - Aerobic - Low (hours): • Aqueous biodegradation - Anaerobic - High (hours): • Aqueous biodegradation - Anaerobic - Low (hours): continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 15 of 16
Section 12 - ECOLOGICAL INFORMATION
• Photooxidation half- life air - High (hours): • Photooxidation half- life air - Low (hours): • First order hydrolysis half- life (hours): Ecotoxicity
Ingredient
Section 13 - DISPOSAL CONSIDERATIONS
· DO NOT recycle spilled material.
· Consult State Land Waste Management Authority for disposal.
· Neutralise spill material carefully and decontaminate empty containers and spill residues with 10% ammonia solution plus detergent or a proprietary decontaminant prior to disposal.
· DO NOT seal or stopper drums being decontaminated as CO2 gas is generated and may pressurise containers.
· Puncture containers to prevent re-use.
· Bury or incinerate residues at an approved site.
Section 14 - TRANSPORTATION INFORMATION
HAZCHEM:
None
NOT REGULATED FOR TRANSPORT OF DANGEROUS GOODS: ADG7, UN, IATA, IMDG Section 15 - REGULATORY INFORMATION
POISONS SCHEDULE
S6
REGULATIONS
Regulations for ingredients
polymeric diphenylmethane diisocyanate (CAS: 9016-87-9) is found on the following regulatory
lists;
"Australia High Volume Industrial Chemical List (HVICL)","GESAMP/EHS Composite List - GESAMP Hazard Profiles","IMO IBC Code Chapter 17: Summary of minimum
requirements","IMO MARPOL 73/78 (Annex II) - List of Noxious Liquid Substances Carried in Bulk","International Agency for Research on Cancer (IARC) - Agents
Reviewed by the IARC Monographs","OECD Representative List of High Production Volume (HPV) Chemicals"
4,4'-diphenylmethane diisocyanate (MDI) (CAS: 101-68-8,26447-40-5) is found on the following
regulatory lists;
"Australia - Queensland Hazardous Materials and Prescribed Quantities for Major Hazard Facilities","Australia Hazardous Substances","Australia High Volume
Industrial Chemical List (HVICL)","Australia National Pollutant Inventory","GESAMP/EHS Composite List - GESAMP Hazard Profiles","IMO IBC Code Chapter 17:
Summary of minimum requirements","IMO MARPOL 73/78 (Annex II) - List of Noxious Liquid Substances Carried in Bulk","International Agency for Research on Cancer
(IARC) - Agents Reviewed by the IARC Monographs","International Air Transport Association (IATA) Dangerous Goods Regulations","OECD Representative List of High
Production Volume (HPV) Chemicals"
No data for TUFF PLUG A (CW: 23-5700)
continued.
TUFF PLUG A
Chemwatch Independent Material Safety Data Sheet
Issue Date: 1-Jun-2010
CHEMWATCH 23-5700
NC317ECP
Version No:2.0
CD 2010/2 Page 16 of 16
Section 16 - OTHER INFORMATION
Denmark Advisory list for selfclassification of dangerous substances
Substance
INGREDIENTS WITH MULTIPLE CAS NUMBERS
Ingredient Name
4, 4' - diphenylmethane diisocyanate (MDI) • Classification of the preparation and its individual components has drawn on official and authoritative sources as well as independent review by the Chemwatch Classification committee using available literature references.
A list of reference resources used to assist the committee may be found at: www.chemwatch.net/references.
• The (M)SDS is a Hazard Communication tool and should be used to assist in the Risk Assessment. Many factors determine whether the reported Hazards are Risks in the workplace or other settings. Risks may be determined by reference to Exposures Scenarios. Scale of use, frequency of use and current or available engineering controls must be considered.
This document is copyright. Apart from any fair dealing for the purposes of private study, research, review orcriticism, as permitted under the Copyright Act, no part may be reproduced by any process without writtenpermission from CHEMWATCH. TEL (+61 3) 9572 4700. Issue Date: 1-Jun-2010Print Date: 1-Jun-2010

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