Document 157KOL97zkx8B8g5n0KKvKbb5
BASF Wyandotte Corporation
June 19, 1975
Wyandotte, Michigan 48192
fl 313 282-3300
To:
2. Bell, PPG Industries, Inc. Mr. Milton Freifeld, Manufacturing Chemists Assn. Mr. W. Ronald Hoopes, Dewey & Almy Div., W.R. Grace & Co.
Subject: Vinylidene Chloride
Gentlemen:
This communication constitutes the recommendations of the Medical Surveillance ^arjd- Records Subcommittee to the Vinylidene Chloride Technical Panel.
The purpose was to provide a program of Pre-Employment Health Appraisal which will obviate the assignment of individuals with abdominal visceral defects to working in areas of possible contact with vinylidene chloride, and to provide a program of medical surveillance for each employee exposed to vinylidene chloride.
The objective is to avoid allowing an individual with pre-existing abdominal visceral disease the opportunity to develop further health deterioration, and to provide, as early as possible, medical data regarding the possible develop ment of abnormalities in individuals who work with vinylidene chloride.
At the time of the initial consideration for employment in an area where vinylidene chloride contact is possible, the following medical procedures, in addition to those required by routine Pre-Employment Health Appraisal, shall be performed:
1. A general physical examination, with specific attention to detecting enlargement or dysfunction of liver, spleen and kidneys, and for abnormalities in skin, connective tissues and pulmonary system.
2. A medical history, including the elicitation of information regarding the following topics: alcohol intake; liver disease; occupations; exposure to potential hepatotoxic agents, including drugs and chemicals; blood transfusions; hospitalizations.
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u>
SL 027905
2-
3. Laboratory investigations designed to evaluate liver function. The exact testing procedures are at the discretion of the medical admini stration of each organization. As guidelines, the following are suggested: Serum levels of total bilirubin, alkaline phosphatase, serum glutamic oxalacetic transaminase (SGOT), serum glutamic pyruvic transaminase (SGFT), and gamma glustamyl transpeptidase, and tecnetium sulfa colloid scan of liver and spleen.
The procedures listed in 1, 2, and 3 above, shall be performed every six (6) months in each individual who has been employed in vinylidene chloride manu facturing for ten (10) years or longer, and annually for all other such employees. Each employee exposed to an emergency shall be afforded appropriate medical surveillance. A statement of each employee's suitability for continued exposure to vinylidene chloride, including use of protective equipment and respirators, shall be obtained from the examining physician promptly after any examination. A copy of th physician's statement shall be provided each employee. If any employee's health would be materially impaired by continued exposur , such employee shall be withdrawn from possible contact with vinylidene chloride.
and Records Subcommittee /dr
cc: M. M. Johnson, M.D., B. F. Goodrich Co. J. R. McDonough, M.D., Tennessee Eastman Co. Harold Lovejoy, M.D., PPG Industries, Inc.
SL 027906
Vinylidene chloride monomer (VDC) is a versatile product used with other mo nomers to make a wide variety of copoly mer resins and latices.
Properly inhibited and protected from
exposure tp ait,.oxygen, water and light,
VDC is stableimljhipmept and storage at
m ambient ' tenlperatures,^porrect handling
'practices, outlined
must be fol-
Jowed at all
. y'-
flnO supplied .by ?PPG from its Lake
Charles, Louisiana, plant is inhibited with
hydroquinone monomethyl ether (HQMME or MEHQ) to prevent polymeri zation during shipment and storage. It is shipped under a nitrogen blanket to avoid contact with air and to prevent the formation of a peroxide that can act as a polymerization initiator.
For most applications, the MEHQ inhi bitor in PPG vinylidene chloride need not be removed. If uninhibited monomer is required, however, the MEHQ can be removed by distillation or alkali extrac tion.
PPG Industries operates two pilot reactors -- one of 500 gallons capacity, the other of 50 gallons -- for polymeri zation experiments at its Barberton, Ohio, Research Center. PPG researchers use these pilot plants to conduct poly merization studies involving VDC, vinyl chloride, and other monomers as well as PPG's peroxide polymerization initiators.
GRADES
.*.
The standard grade of VDC manufactured PPG is inhibited with hydroquinone nomethyl ether at approximately 200
parts per million. PPG can also supply, on request, a special grade inhibited with phenol at 0.6% to 0.8%.
USES
Vinylidene chloride monomer has been used for many years, primarily as a copolymer with such monomers as vinyl chloride, vinyl acetate, acrylonitrile, and acrylic acid esters. The copolymer resins and latices are formed into films, fibers, coatings and linings. VDC imparts to finished products quali ties of flame retardance, chemical resis-
tance, and impermeability to water vapor and gases.
Data on reactivity ratios of VDC copoly merizations with 36 monomers are presen ted in a booklet, "Vinylidene Chloride (Inhibited), handling, properties and reac tivity rates" Form A967, available on request from PPG Industries, Chemical Division.
PROPERTIES
Chemical Names: Vinylidene chloride; vinylidene chloride monomer; 1,1-dichloroethylene
Chemical Formula: CH2CC12; Jjc-dg
Molecular Weight: 96.95. Contains 73.14% chlorine.
Description:
At ordinary handling temperatures, below its boiling point of 88.9F (31.6C), vinylidene chloride is a liquid. It is clear and
colorless and has a sweet odor. Vinylidene chloride is highly volatile and its vapor is toxic and extremely flammable.
Boiling Point, C F
+31.6 +88.9
Freezing Poin.t, oCp
-122.5 -188.5
Explosive Limits, volume % in air 7 to 16
Flash Point, Cleveland open cup, C -15 F +5
Autoignition Temperature, C F
570.0 1058
Critical Pressure, atmospheres 51.3
Critical Temperature, C "F
222 432
Absolute Viscosity at 20C, cps 0.330
Specific Gravity, 20/20C
1.213
Density at 20C, pounds/gallon 10.1
Refractive Index, no at 20C 1.4247
Vapor Pressure, mm Hg, at 20C 475.1
Solubility, water in monomer, weight %
0.035
Solubility:
Vinylidene chloride is practically insoluble in water but soluble in most organic solvents.
Reactivity:
Uninhibited, or inhibitor-depleted, vinylidene chloride may poly merize very slowly even in the absence of oxygen. To further retard polymerization, the uninhibited monomer should be main tained in darkness below 14F (-10C)
Uninhibited, or inhibitor-depleted, vinylidene chlorlde reacts readily with oxygen or air to form a peroxide at temperatures as low as-40F rC.
SL 027907
Specification for regular grade: Appearance Color, maximum APHA Vinylidene Chloride, minimum weight % ^Bexcluding inhibitor) J^tylene, Acetylides, as C2 H2, maximum ppm
Other Chlorinated Hydrocarbons, no one to exceed this maximum weight %
Acidity, as HQ, maximum ppm Peroxide, as H202, maximum ppm
clear, free of suspended matter 25 99.6
25 0.25
10 10
Water, maximum ppm
50
Inhibitor, HQMME*, ppm
Hydroquinone monomethyl ether is sometimes referred to as MEHQ (monomethyl ether f hydroquinone).
180 to 220
TOXICITY Inhibited vinylidene chloride is irritating to the eyes and skin. Upon evaporating, the inhibitor can cause' local skin irrita tions r bums unless washed off thoroughly.
Vinylidene chloride is highly volatile and Us vapor is heavy. Its odor-warning pro perties are not adequate. Overexposure to vapor can lead to anesthesia, irrational behavior and-if continued-to unconscious ness, In all cases of overexposure, medical attention should be obtained. Prolonged or repeated exposures can cause damage ^^iver and kidneys.
toxicity of vinylidene chloride vapor ^^onsidered to be greater than that of ethylene dichloride but less than that of carbon tetrachloride. Vapor concentra tions in work areas should not exceed 25 ppm as a time-weighted average atmo spheric concentration for an 8-hour day to avoid adverse effects on workmen. Above a level of 200 ppm, respiratory protection is recommended. Workmen cleaning up spills or stopping leaks should have self-contained or air-supplied breathing apparatus.
More information appears in "Industrial Hygiene and Toxicology," second revised edition, volume 11, edited by Irish and Fassett, Interscience Publishers, New Y rk, N.Y., 1967, pages 1305-1307,/j^
HANOLING AND STORAGE
If tank car valves are defective or leaky, d not unload. Telephone the PPG Chem-
icals plant at Lake Charles, Louisiana, 318-882-1200.
Nitrogen used with vinylidene chloride should have a maximum oxygen content of 10 ppm.
Information on unloading tank cars and drums, handling spills and leaks, construc tion materials, storage tanks and transfer lines is presented in a booklet on "Vinyli dene Chloride (inhibited), "Form A967 available on request from PPG Industries Chemical Division.
Fire hazard
Vinylidene chloride vapor is extremely flammable and bums vigorously at con centrations between 7 and 16% by vol ume in air. Proper ventilation and the elimination of ignition sources are manda tory in areas where vapor concentrations may reach a flammable level due to spills or leaks. Firemen should be warned that the pro ducts of combustion include toxic hydrogen chloride and that vinylidene chloride vapors in high concentrations are toxic. Carbon dioxide or dry chemical agents can extinguish fires effectively, also water spray or foam may be used. Water may also be sprayed to cool equip ment. No one without proper protective respiratory equipment should enter an area where there has been a fire until the area has been adequately ventilated.
Explosion hazard
The peroxide compound that forms when uninhibited vinylidene chloride has been
exposed to atmospheric oxygen is poten tially dangerous. This peroxide can also form if the inhibitor content has been depleted. Depletion can result from any of several causes including distillation or exposure to oxygen due to improper storage. The presence of peroxide can be detected by sharp, acrid odors or by the precipitation of a white flocculant poly mer.
Dried polymer residues may contain ad
sorbed peroxide which can be exploded
by a slight mechanical shock or by heat.
These residues should be handled with
extreme caution. Adding water that is at
room temperature to polymer residues
containing peroxide renders them inactive.
However, the hazard may return if the
water evaporates. The peroxide can be
destroyed by several washes with fresh
5% sodium bisulfite solution or with 10%
sodium hydroxide solution that is at
room temperature. Vinylidene chloride
monomer that contains peroxide may be
purified by washing in the same manner.
Separation and handling of precipitated
polymer, and its potentially dangerous
adsorbed peroxide, must be done with
extreme caution.
* .
Equipment not used continually should be filled with water when shut1 down.
PACKAGING AND SHIPPING
PPG Industries ships vinylidene chloride (inhibited) in tank cars of 10,000-galloif (105,000-pound) capacity from Lake Charles, Louisiana, and in 55-gallon, (500-pound) drums from Bayonne, Nes/ Jersey.
SAMPLES AND SERVICE
,
Samples of Vinylidene Chloride are avail
able, on request in 1 pint and 5 gallon
containers. The technical service staff of
PPG Industries Chemical Division is avail
able for consulting on handling, storage
and use.
3 nXa
l V-
1
INDUSTRIES
A--1001 2.&M 470
PPG INDUSTRIES, Inc. Chemical Division One Gateway Center Pittsburgh, Pa. 15222
||||*,1I,J l
$Statements and methods presented ere based upon the best Information'an^*'
practices known 10 PPG industries, inc, put arc not representations or ianties of performance or result nor do they imply any recommendations/^' infringe any patent or an offer of license under any patent. With respect its product?, PPG industries* Inc. warrants only that they conform to its^> quality standards.
Some of the materials mentioned above may be hazardous in nature and should bo handled with care Read the label carefully and observe and com ply with all the label warnings and precautionary directions. Although these materials are not fntendod for household use, they, as all potentially hazard ous materials, must be kept out of the reach of .children.
SL 027908
Printed in Ll.S.A.
BASF Wyandotte Corporation
June 19, 1975
Wyandotte, Michigan 48192 313 282-3300
To:
Dr, Z. Bell, PPG Industries, Inc. Mr. Milton Freifeld, Manufacturing Chemists Assn. Mr. W. Ronald Hoopes, Dewey & Almy Div., W.R. Grace & Co,
Subject: Vinylidene Chloride
Gentlemen:
This communication constitutes the recommendations of the Medical Surveillance and Records Subcommittee to the Vinylidene Chloride Technical Panel.
The purpose was to provide a program of Pre-Employment Health Appraisal which will obviate the assignment of individuals with abdominal visceral defects to working in areas of possible contact with vinylidene chloride, and to provide a program of medical surveillance for each employee exposed to vinylidene chloride.
The objective is to avoid allowing an individual with pre-existing abdominal visceral disease the opportunity to develop further health deterioration, and to provide, as early as possible, medical data regarding the possible develop ment of abnormalities in individuals who work with vinylidene chloride.
At the time of the initial consideration for employment in an area where vinylidene chloride contact is possible, the following medical procedures, in addition to those required by routine Pre-finployment Health Appraisal, shall be performed:
1. A general physical examination, with specific attention to detecting enlargement or dysfunction of liver, spleen and kidneys, and for abnormalities in skin, connective tissues and pulmonary system.
2. A medical history, including the elicitation of information regarding the following topics: alcohol intake; liver disease; occupations; exposure to potential hepatotoxic agents, including drugs and chemicals; blood transfusions; hospitalizations.
SL 027909
o
3. Laboratory investigations designed to evaluate liver function. The exact testing procedures are at the discretion of the medical admini stration of each organization. As guidelines, the following are suggested: Serum levels of total bilirubin, alkaline phosphatase, serum glutamic oxalacetic transaminase (SGOT), serum glutamic pyruvic transaminase (SGPT), and gamma glustamyl transpeptidase, and tecnetium sulfa colloid scan of liver and spleen.
The procedures listed in 1, 2, and 3 above, shall be performed every six (6) months in each individual who has been employed in vinylidene chloride manu facturing for ten (10) years or longer, and annually for all other such employees. Each employee exposed to an emergency shall be afforded appropriate medical surveillance. A statement of each employee's suitability for continued exposure to vinylidene chloride, including use of protective equipment and respirators, shall be obtained from the examining physician promptly after any examination. A copy of the physician's statement shall be provided each employee. If any employee's health would be materially impaired by continued exposure, such employee shall be withdrawn from possible contact with vinylidene chloride.
and Records Subcommittee /dr
cc: M. M. Johnson, M.D., B. F. Goodrich Co. J^R. McDonough, M.D., Tennessee Eastman Co.
j/'tiarold Lovejoy, M.D., PPG Industries, Inc.
0279'-