Document LKj1o4DwOQE26a27wdde4xe5X
WORKING CONDITIONS AND MEASURES FOR THEIR IMPROVEMENT IN PRODUCTION AND USE OF VINYLCHLORIDE PLASTICS.
Tribukh, S.L., Tikhomirova, N. P., Levina, 5 V., Kozlov, L. A. Gigiena i Sanit, (10 ) 08-44(1949)
The production of vinylchloride plastics and also the different good; prepared from them gained in the last decade considerable importance* In the meanwhile from hygienical point of view, it was little studi d*
The basic raw material for the preparation of vinylchloride plastics is vinylchloride resin, which is prepared fron vinylchloride, a c lorless gas, condenses at 12 - 14 in liquid with a specific weight of 0,86 - 0,9'
Vinylchloride, on its turn, is prepared by the reaction of gaseous d eomp< sition products of petroleum vapors (vinyl) and gaseous chlorine. Subs quently, the vinylchloride condenses by using dichloroethane and is sub jected to polymerization in autoclaves. In this way, polyvinylchlorid resin is the product of vinylchloride polymerization. Due to the resist ance to alkali, diluted acids, ethers, benzin and lubricating oil,poly vinyl chloride resin is used for the preparation of acidresistant fillers fabrics for overalls, substituents to hides, etc.
At the preparation of various goods, the polyvinylchloride resin is plasticized with complex ethers of phthalic acid (dibutylphthalate), phos phoric acid (tricresylphosphate), mixture of diphenylchloride (sovol), or chlorinated naphthalenes (golowax). The selection of the plasticizer de pends on the assigned use of the plastic to be prepared.
According to the data of the literature, vinylchloride belongs to we; narcotics. Its narcotic concentrations for humans are within the limits of 75 to 250 mg/1, According to the data by Petropavlovskii (1942), vola tile substances, liberated, when vinylchloride resin and plasticizers are heated to 130-I650 cause in animals under the condition of one single in-
occulation, depending on the concentration, th
following phenomenal
UCC 057578
irritation of the ocular mucous membrane, respiratory disorders, damage of the central nervous system, breakdown in the coordination of movem nts, an death, after appearance of asphyxic convulsions.
Sovol and golowax, introduced into vinylchloride plastics, as plasti cizers, have general and local toxic effect. In their overall action on the organism, sovol and golowax are close to chlorinated fatty hydrocarbon Basically they attack the parenchemal organs. Severe toxic effect takes place in form of acute, or subacute yellow atrophy of the liver. In the literature, cases with lethal outcome are described, caused by th t xic effect during the production with vinylchloride naphthalenes (golowax! and diphenyls (sovol). The local action of sovol and golowax causes acne-type skin eruptions and erythematous-vesicular dermatitis.
We studied the working conditions at the finishing of vinyl chloride plastics under factory conditions in a vinylchloride plastic plant, using vinylchloride plastics as substituent for hides and for insulation of electric wires.
Production of vinylchloride plasticsi- In the vinylchloride plastics plant, the vinylchloride resin (a white powdery mass) is mixed with dibuty phthalate, or with sovol in mixing apparatus, at a temperature of 80-100. Then, the compound is transferred onto rollers, the surface of which is heated to 130-l6oV.
At the end of the rolling, the vinylchloride fabric is cut up in nar row tapes, which are further sorted and packaged in boxes.
UCC 057579
During the hygienical inspection of the vinylchloride plastic plant,
the air of the working place was examined on its sovol-. organochlorine
compound-, and hydrochloric acid vapor content. The obtained results ar
plotted in Table 1.
Table 1- Organochlorine compound, sovol and hydrogenchloride content in the air of vinylchloride plastic plant
1 Ko.iOerfTpam, a mi, i
Ha3Ba:ute OTAer.diiisi
/
Me" 3 B3BTHB npeSM l
xJOpopratiH- | tecK.ie coejH-1
HB lit*. B TOM !
Miic:ie coaoa *
3*
1
________ ^op*I'-r>Jii
Boaopoj 5h
PioaroTOBuTe-ibaoe
i.
3
o
B
mKijy
a.i
no;"peB
I cosoj* .........................
B cepiiiiae no^iiiu-:r! m
i ypoaue iMxa.nts pjfcwro
r
C-jetiieniiH n
Ba.tbtuaKit
io y cxtzHTdja bo speai i CMemeaei KO4no.ie.iTOi . .
6 To XB
,11 y cjuthtbjb so speua
1 0wrpy3ta KOMno3Maua . . .
ai
I ft Ha piloteu ster-e smw*
j aoant iKi..............................
a >i V cicci j.i* ociai'caero
j nnacTHtiri .............................
~] CnepaoBOB-iod
y pjlosero 14SCM caep-
! iOBOEKl ......................................
0,003 & He ofi.t.apyxeu
0.003
>
0,06-0,08 ;
0,0-3
C,01-0,08 0.2-0,97
oOaapyatea
0,27 19 He oGuapyxeu
0,005
1, Name of the department) 2. Place of the sample taking) 3. concentra
tion in mg/1) 3*. organochlorine compounds,included sovol^-j 3b. hydrogei
chloride)
preparation) 5 mixing and rolling) 6. the same) 7. dril
ling) 8. in the exhaust hood of the heated sovol) 9. in the middle of
the chamber, at the respiration level of the workers) 10, at th mixer
at the time when the components were mixed) 11. at the mixture, at the
time.when the components were discharged) 12. at the working place of
rolling) 13. at the deck for the cooled plastic compound) 14. at th
working place of the drill operator) 15. not detected).
In the air of the working places of the vinylchloride plastic plant,
as one can see this from the data of Table 1, the concentration of organo
chlorine compounds fluctuated between 0,005 to 0,27 mg/1. In the prepara
tion department sovol vapors formed at its heating, discharging and trans
portation. The concentrations of organochloride compounds, found in this
place (0,005 mg/1) can be attributed, most likely, in great part to sovol
On account of the insufficiently developed method to determine separateorganochlorine compounds, they were determined summarily.
UCC 057580
At the mixers the organochlorine compounds were found in an amount from 0,01 to 0,08 mg/1, and in the working place of the rolling - from 0,2 to 0,97 mg/1.
In the product sorting department the organichlorine compounds, usua ly, did not exceed 0,05 mg/1, we detected hydrogenchloride only in the di ferent samples in amounts, not exceeding thousandth' part of milligram.
In connection with the use of sovol, soiling the skin with ingredient in the composition of which sovol was introduced causes serious danger. Or th skin of the hands of the workers we found organochlorine compounds.
To fight the contamination of the air, the plant was mounted with influent and exhaust ventilation with automatic driving. The exhaust ven tilation was constructed on the principle of local exhaust from th hood?, placed over the basic sources of gas evolution.
The efficiency of the ventilation, as this was demonstrated by the sanitary-technical inspection,was insufficient, on account of the fact,the the air-feed was carried out with a rate of only 7-8 m/sec on the level of the shoulders of the workers. The unpleasant sensation, caused by si milar way of air feed, together with the infiltration and cooling of the compounds on the rollers forced the workers to overlay the damper of the sprinkling valves and already with this, the air current, escaping through th different leakages, decreased the work of the exhaust device, deviat ing the convective current, which got up from the rollers. 3esides, the closing of the influx nozzle, disrupted the balance between the influx anc the exhaust and attracted inorganized admission of contaminated air from the neighboring places.
UCC 057581
A significant defect of the ventilation system was th insufficient efficiency of the low-capacity hoods, arranged over the decks for the ready products and over the mixers. Much more effective are, according to our project executed orifices over the mixers in form of tents with open front wall (see the figure). At a productivity of 1 000 m^/hour these orifices
practically completely localized the separation of noxious gas*
f
Scheme of the tentlike openings of the mixer.
Use of vinvlchloride plastics as substituent for hidest- In the pro
duction of vinylchloride footwear, the basic raw material is polyvinyl
chloride resin, which is prepared by the polymerization of vinylchlorid
in a water-emulsion method. The temperature of the decomposition of this
resin is 130 - 150. As plasticizer here dibutylphthalate and as stabiliz
er potassium stearate is used.
The compound for the sole is prepared by mixing textile scraps, sa
turated with dibutylphthalate, and vinylchloride resin in the mix r. The
obtained compound is piled on the heater to 170 - 200 and rubbed through,
after this with Vaseline in the press mold. The, in this way filled press
form is closed, it is maintained for a few minutes, and then is placed fo:
a short time under the hot press.
UCC 057582
-o-
The composition for the upper footwear is obtain d by mixing a deter
mined amount of polyvinylchloride resin and dibutylphthalate in th mixer.
The mass is kept there for aging 12 hours at a temperature of 70 . After th aging the compound, is rolled at a temperature of 120-14-0 with the ad
dition of potassium stearate* The vinyl chloride plastic compound* btaine after the rolling is rapped in textile and pressed at a temperature of l6oc
The analysis of the air for noxious gas and vapor content in th plant
of vinylchloride footwear production is plotted in Table 2.
Table 2i- Concentretion of gases and vapors in the air of working plac s m vinylchloride footwear manufacturing plants in mg/1
MecTO unu
npo6
A
XjopopriHNie- 3
ckxb coeAHieuMi ~
HC1
7C (cyxvapHO)
CO
i KOHUeXTpIBMl B Ut/.I
t s 5! |j :
5*2
assa2* .s. 2x J<** 2 =x J*n
X : X X w ' XX X X
ac
SgL
* ft ft
xa xs
|& |s4aimasi
u :ii;axi
&;
y MJMtOB . .
lb y npeccos . .
ic
B BONemenxx
CMpoxuoft
0,14 0.48 0.35 0,038! 0,036 0.0320,07.0,350,2: 0.25 1,13 0,65. 0,008 0,036 0,0550.21:2.61 1.23| -
0,53 1,2 0.92 0,03 0 17 0,23 0,100.680,231 --
0,022 0,019
0,01
1. place of the sample taking} la. at the rollers; lb. at the press; lc. at the welding place?2.organochlorine content; 3. minimum; 4-. maximun 5. average; 6. concentration in mg/1; 7. total.
The organochlorine compounds, which evolve at the thermal finishing oi vinylchloride resins, represent cleaved molecules of vinylchloride in dif ferent quantitative chain compound compositions. In the air of the working places at the manufacturing of vinylchloride footwear, we found these com pounds in an amount from 0,14 to 1,2 mg/1. Here we found also vapors of hydrochloric acid in concentrations from 0,008 to 0,17 mg/l, hydrocarbon vapors (determined summarily) from 0,21 to 2,6l mg/1 and carbon monoxide vapors within the limits of 0,01 to 0,022 me/1.
UCC 057583
-7-
The contamination of the atmosphere toy organochlorine compounds and
vapors of hydrochloric acid increases in proportion with the temperature
increase at the heating during the different manufacturing operations.
The ventilation of the working place was carried out by means of a fe
exhaust devices, originally destined for local exhaustion. In spite of th
comparatively .
high frequency of air exchange (10 - 20), the effi
ciency of the ventilation was insufficient. Its basic imperfection was th
lack of local removal of the gas, evolved during the work at the pressing
rolling and welding of the fodwear.
The hood over the welding working benches, usually used in this kind
of production, was not efficient and could not be considered as a local ex
haust device, because at the welding of the vinylchloride footwear,.the
gases evolved on the level of the knee of the seated welder, in the imme
diate closeness to his face. A more radical device in the given case is a
vertical exhaust channel against each working place* The removal of the
air can be carried out through orifices in the platform of the working ben
the upper part of which, thus, should be used as planar exhaust channel.
Satisfactory effect can be observed also in case of exhaust through a
horizontal box, arranged on the surface of the working bench. The rate of
suction through the exhaust orifices should not be less than 6 m/sec.
Use of vinylchloride plastics for the insulation of electric.wiresi-
In the factory, where vinylchloride plastics are used as insulating mat ri.
for electric wires, the covering of the wires with vinylchloride envelope,
is carried out on extruders.
During the time, when the vinylchloride plastic compound is dried in
the drying chambers, and also at its fusion and at the discharge of th
wires from the hot envelope from the head of the extruder, in the air of
the working space we found the following volatile substances (Table 3).
UCC 057584
Tabl 3
MecTO B3t)Ttta npo6
y uinpHa^taniH m a 30He j'juxa.tna paOoiero . . . Haj npoaojjM. noicpuTUM 4 ropaieii tuacTuaccoii. . B cepeamie noeuienHa//
XaopopraHHiecKHe coeo^MCHHa
J
1j
HC1
!C | (cyMMapHO)
it
i
Ko-ueHTpaiwa a Mr/a
CO
z3*:=
* a
U*s.
4s
n
at I 5 5
I 0,003 0,1
i1 a S3 am n=*
o.oo:
'i V
Uamxa *a*sJm
a
X
2m a=
0,06 0.3
10GK 1j i <
oa49s
JX S*
1j
'
5 ii
i `
;
0,6
=| 4aas san. --1
0,:+ 0,65 He 1 pyxe^a
0.0011 0,080 To xe
--
(
- 0.017 0,05
0,11 :
0.02
Hai cymiubHUM mita<J>0M 0,0 0.14 -- 0,016 0.0, C,21 1
71
--
__
1. Place of the sample taking! 2. organoehlorine compounds! 3, concentra tion in mg/l! 4. summarily! 5. at the extruder in the zone of the workers respiration! 6. over the wire coated with hot plasties! 7. over th drying chent. S. was hot tfeteetodi 9. minimum! 10. maximum 11. in the center of the place.
In the composition of the volatile substances, evolved at the heating
of the vinylchloride plastics, up to 120 - 140t there is an organochlo-
rin content of 0,003 to 0,6 mg/l, vapors of free hydrochloric acid from 0,001 to 0,06 mg/l, hydrocarbon vapors from 0,08 to 0,6 mg/l, and carbon
monoxide vapors from 0,01 to 0,05 mg/l. The ventilation of the plant was accomplished by means of exhaust
hoods, arranged on the telescopic downstroke over each extruder head. The gases, evolving at the drying of the plastic compound in the drying chest and at the cooling of the vinylchloride wire after discharging from the extruder head, arrived in the atmosphere of the working places,maintaining in them a considerable concentration of toxic substances.
UCC 057585
Results of the medical examination of the workersi- A randomly se
lected group of workers in the inspected plant was subjected to medical ej
amination. In the vinylchloride plant 48 men were examined, mainly roller
workers. At the rhino-larynx examination, in a great number
of the
workers, in the upper respiratory tracts (in the nose, larynx, and thrache
white films of dust were observed, which were formed as a result of th
mixture of dust with the mucus. These films were compacc at the touch and
could be removed from the surface of the mucous membrane only with diffi
culty. In 1? men hyperemia of the mucous membrane of the upper respirator
tract was found. Chronic bronchitis was detected in 13 len. As to the
change in blood circulating organs, one must mention vascular hypotonia
(90 - 100/45 - 50) in 13 men, moderate hypertonia in one, arterio-cardio-
sclerosis - in 5. The condition of the gastro-intestinal tract was charac
terized in 10 examined workers by chronic gastritis and in 2 by chronic
colitis. In 15 workers there were alterations in the liver in form of
more or less pronounced hepatitis, accompanied in 2 examined workers by cholecystitis.
Regarding the blood, 29 examined workers had low hemoglobin count; or*
- 46$, 22 50-5595, and 6 56-60#. The blood picture and the ROE w re with
*
out peculiarities.
One must pay attention to the skin diseases (acne, bleakheads), es
pecially on the face, the neck and the chest, found in the examined group.
The skin injuries were found not only on the face of those who w r in
contact with sovol, but also on those, who were not in direct contact with
it, but were working inthe same place. Evidently, the skin disease was
caused by the action of sovol, when its vapor was sorbed.
\jCC
In the chemical plant 25 female workers were examin d, mainly those* working at the presses and welding with a long working record of 3 - 6 years in the said professions. In some of them, examined for ear - laryr different degree of hyperemia of the mucous membrane of the upper respira tory tract was observed* on its whole extent, or only on the organic parte Chronic bronchitis was found in 5* mildly expressed emphysema of the lunge in 3 and remaining signs of pleurisy in 2,
As to the cardio-vascular system in 14 men vascular hypotonia (R/R 90 - 110/55-65) and in 4 mildly expressed hypertonia (R/fe 140 - 165/ 085) was detected. Thudding sound of the heart, its enlargement and th data of the ECGi Low T-wave of heart, not less than by 2 basic abc'uctior and the roundness of the S - T interval, gave foundation* in som cases, to diagnose distrophy of the myocardium.
In the examined group, in 6 workers hepatitis was diagnosed. At the same time,in some persons,'simultaneously liver and stomach disease was de tected* Not in one of the liver disease cases could we find in the anam nesis, or at the examination*signs of jaundice. Neither did we detect any bile pigment in the urine. In a considerable number of the examined work ers small swelling of the liver, without characteristic pain and sensitiv; ty at palpation was observed.
Analyzing the results of the medical examination, one must remark, that in a known part of the workers, changes in the upper and deeper res piratory tracts were detected. These findings are confirmed als by th data of the literature.
One must pay attention to the high percentage of skin injuries, which is, no doubt connected ethiologically to the action of sovol.
UCC 057587
The presence of hepatitis in some workers, in contact with vinylchlo
ride resin and vinylchloride plasticizers deserves serious consideration
Therefore further dynamic observations on the state of the health of the
workers, who are in contact with vinylchloride resin and its plasticizers
*
are necessary, to prevent the development of severe liver damage,. .
Results . 1, - Into the composition of volatile substances, which f rm at th
thermal finishing of vinylchloride resins and plasticizers, during the manufacturing organo-chlorine compounds, hydrocarbons, vapors of free hydrochloric acid and of carbon monoxide enter.
2, The action of these volatile substances are manifested in the ir ritation of the mucous membrane, mainly of the upper respiratory tracts*
lengthy influence of finely dispersed dusts and vinylchloride resin vapor
cause, besides, dryness and atrophy of the mucous membrane of the upper
respiratory tracts, and is also responsible for the development of chroni
bronchitis.
3, A considerable number of hepatitis among the examined work rs,
and also the change in the upper respiratory tracts, raise the question
of the necessity for further dynamic research on the state of th health
of the workers and to take a series of therapeutic-prophylactic measures,
in particular by organizing
heat and moisture*inhalation of drugs for
the workers,
4, At the use of vinylchloride sovol, as plasticizer, on most worker acne type skin injuries, with preferable location on the face and neck, were observed.
5, For the prophylaxis of skin diseases at the work with sovol, the following complex sanitary measures have to be taken* 1) securing for the
workers work underwear and outfit: *)
' (alkaline)
2) construction of sanitary showers
UCC 057588
with separate undressing for home and work cloths. At the sanitary pas sage, there must be a vapor chamber for the low temperature steaming of underwear and work outfit, at a temperature of 110-120<, for one hour. The plant should be equipped with wash basins with hot and cold running water.
6. For the sanitation of the atmosphere, it is necessary to decrease as much as possible, the degree of vinylchloride resin decomposition at i* thermal finishing. This must be attained by standardizing its heat re sit tance, and also by controlling the temperature when the rollers, the presses and other equipment are heated, not to exceed 120-130.
Of extremely great importance is the rationally equipped ventilation system, calculated on maximum screening-off the source of gas-, vapor- anc dust separation.
In connection with the fact, that in some factories the inflammation of the condensate was observed, which occurred in the exhaust ventilation tubes in contact with open flame, the exhaust apparatus must be proj cted by observing the conditions, adopted by the construction legislation for construction , designated for the mixing of inflammable gaseous mixtures.
UCC 057589