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Патент USA US2407495

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SePt- 10, 1946- '
5.2, 1941
4 Sheets-Sheet 2
Sept; 10, 1946.
Filed Jan. 2, 1941
4 Sheets-Sheet 3v
h 4
Sept. 10, 1946.
Filed Jan. 2, 1941
4 Sheets-Sheet 4
@412 ’
Patented Sept. 10, 1946
Harman Hartvigsen, Scotch Plains, .N. J ., assign
or, 'by mesne assignments, to Jasco, Incorpo-l
rated, a corporation of Louisiana
Application January 2, 1941, Serial No. 372,947
'7 Claims.
(Cl. 260-84)
This invention relates to polymeric materials
of the ole?nic type; relates particularly to meth
ods for the polymerization of ole?nic materials;
of ‘catalyst into the reactant ,mix lbefore unde
sirable reactions occur.
The present invention provides a powerful stir
‘ring device of the propeller type, which is
equipped with channels adjacent the trailing
edge of the p-ropellen-through which the catalyst,
either gaseous or liquid solution, is discharged
into the .eddy zone behind the trailing edge of
the propeller, in whichzone dispersal .forces far
and relates especially to a polymerization device
for‘conducting the polymerization of the ole?ns
by the controlled and rapid addition and disper
sion of ‘the catalyst into the ole?nic reactants.
Various ole?nic mixtures ,are- readily polymer?
ized into very high molecular weight substances
by the application vto the role?nsrat Very low tem 10 more powerful than are obtainable ‘by any sim
peratures of active halide, or Friedel-Crafts, type
ple stirring procedure are utilized for ‘the dis
catalyst; especially .isobutylene vat temperatures
persal of the catalyst intorthereactant
It is
ranging from-0° C‘. to -l00° C., under the in?uence
found that under such conditions, a suf?ciently
of a catalyst such as boron ‘tri?uoride, in the
rapid dispersingof the catalyst into the reactant
presence of diluent-refrigerants ‘such as liquid
mix occurs to avoidsubstantially all of .the un
desired reactions which otherwise occur in sim
p-le mixing of the catalyst andreactan'ts.
Thus an object of the 'inventionis to polymer
propane, liquid ethane, liquid ethylene and the
like; and 'ole?nic mixtures such as iso-ole?ns of
the type of isobutylene in admixture with di-ole
?ns such .as butadiene, isoprene, p-entadiene, di
ize an ole?n-containing mixture . at vlow temper
methyl butadiene and the like, in the‘ presence __.
of similar diluent-refrigerants, and '
the application to the mixed ole?ns of a Friedel
Crafts ‘type catalyst such as aluminum chloride
dissolved in va =1ow :freezing solvent such as ethyl
chloride‘or methyl-chlorideor carbon disul?de or
the like.
In this polymerization process, however, diffi
culty has (been experienced in the incorporation
of the catalyst into the reactant mixture. The
reaction is very rapid, and to obtain an optimum
molecular weight, especially optimum molecular
weight with satisfactory heteropolymerization
from the mixed olefin and (ii-ole?n reactants,
‘there is required a very ‘rapid :and .completedis
vpersal of the catalyst into the reactant-refriger
ant diluent mixture. When gaseous ‘boron :tri
fluoride-is ibubbled into ‘the reactantmix, ‘the :in- ~
"terface vloe'tween the surface of the vbubbles and
the reactant-‘mixture 11s a location or relatively
high catalyst concentration, and the polymeriza
'tion occurs in the neighborhood ,of 'the interface
‘under :conditions ‘of low concentration of react
ants ‘in jproportionto the vconcentration of cata
rlyst,v~-and :the vcatalystrei‘?ciency is markedly re
duced. Similarly when-the v(liquid catalyst solu
tion-of aluminum chloride is :added to the react
.a-similarjinteriace occurs between the
catalyst solution and the ‘reactant “mix, until the
catalystsolution has vbeen :fully dispersed into the
‘lreactant mixture. :In consequence, a similar
condition/of reaction in the presence of arela
itively low quantity of reactants occurs, and even
ature .by-the ultra rapid dispersal of catalyst or
catalyst solution Pinto and through ,the- eddy zone
in the reactants behind a propeller type mixing
stirrer. .Other objectsand details of the inven
tion will be apparent .from the following de
r ,scription when read in connection with the ac
companying drawings wherein
.Fig. 1 is a view in vertical section through a
polymerization reactor equipped with a catalyst
.disperseraccording to the invention.
Fig. 2 isa top view of the device of Fig. 1.
.Fig. 3 is a View in vertical section of an .alter
native ‘embodiment of the polymerization reac
tor and catalyst disperser of the invention, and
Fig. 4 is a view in side elevation of thepropeller
on Car .disperserof the invention.
Referring .to Figs. _1 and,2,'.thereis_shown,a de
sirable embodimentof the invention includinga
polymerization reactor 1 carried upon appropri
ate support members ‘,2 and equipped with pipe
lines ,3 passing through a cover _4 ,for the delivery
to the reactor of the various components of the
, reaction ~mixture including the ole?nio mate
rialrand the-diluent refrigerant, Within .the re
‘ ctor chamber there is provided the catalyst dis
perser of the presentinvention which includes a
hollowshaft?, which shaft is cylindrical in for
mation and supported by set screw ll] carried in
thepulley 9, upon the thrust bearing ll , the ,inner
cylinder 5,, the outer cylinder ,6a._,an.d the lock
nuts M, which are respectively connected to the
top member or cover 4 of the reaction vessel. “The
roller bearings (‘l .areheld in ,place by set screws
the most powerful stirring of the reactant mix
,8.‘ Acollar la and the set screw I it are a means
for adjusting .this assembly.
.is not adequate todisperse the necessary amount
.As is clearly. shown by Fig. .1, the ‘body portion
of the hollow shaft is provided with propeller type
hollow blades l5 which have openings H5 at the
trailing edges of the blades through which the
catalyst is dispersed as it passes through the in
ner opening I‘! of the shaft, after delivery thereto
through a catalyst delivery pipe 3a.
In the operation of this embodiment of the
invention, a suitable quantity of the refrigerant,
which may be liquid propane or liquid ethane
or liquid ethylene, is delivered through the sup
ply pipe line 3 to the reactor l. The reactor,
which is preferably glass lined or enamel lined,
is cooled rapidly by volatilization of the refrig~
erant (aided by the cooling effect of liquid eth
ylene in the refrigerant jacket [8) , and the vola
tilized gas is discharged through an exit pipe
line l9. for condensation and recycling or other
terials through a bottom outlet such as a gate
valve I 2, aided by a push rod H3; or by scoop
ing out the solid polymer, or by other means.
By this procedure there is thus readily obtained
a Very high molecular weight poly-isobutylene.
If liquid ethylene is used for the diluent refrig
erant, giving temperature of approximately ~98“
C. (ethylene alone boils at approximately -l03°
C.) and high purity isobutylene is used with boron
tri?uoride as catalyst, this reactor equipped with
the catalyst disperser as shown in Fig. l is capa
ble of producing poly-isobutylene having molecu
lar weights‘ranging from 100,000 up to 450,000
or ‘above, substantially free from undesirably low
molecular weight materials.
This embodiment of the invention is particu
larly advantageous for the preparation of copoly
,mers or interpolymers or heteropolymers of mixed
use. When the reactor and other members of
ole?ns such as isobutylene with a diole?n to give
the device are cooled to the desired low tempera
ture, the desired quantity of ole?n, which may 20 a plastic elastic material of high molecular Weight,
and loW unsaturation, which can be cured with
desirably be liquid isobutylene, is delivered
through another delivery pipe line 3 to the re
actor. At any convenient time up to this point,
For this use, the reactor is desirably equipped
with side wall scrapers 5a, which may be mount
9 is put into operation, to rotate the shaft 5 and 25 ed on, and driven by the catalyst'tube 5, but are
a power source associated with the driving pulley
the propeller blades [5; When the desired charge
of reactant mix has been built up in the reactor,
and the propeller blades l5 are revolving rapidly,
the catalyst is delivered to the hollow shaft 5
from the associated pipe line 3a. This catalyst
may be gaseous boron tri?uoride, under low pres
sure. especiallv when the reactant mixture in the
reactor contains only isobutylene as the reaction
material. The gaseous catalyst is then discharged
through the hollow blades I5 as shown and flows
outward through perforations at the trailing
edges of the blades. The speed of rotation of
the stirring propeller desirably ranges between
400 R. P. M. and 1500 R. P. M., depending upon
the character of the reactants. the relative sizes
of the reactor and the propeller and the char
acter and rate of delivery of the catalyst. The
preferably independently mounted and driven
in an oscillatory manner, as by a packed shaft
passing through the bottom of the reactor.
In conducting this polymerization, the reac
tor is charged with an appropriate quantity of
liquid ethylene to bring the temperature to the
desired .low value and to provide in the reactor
a substantial quantity of residual liquid ethylene,
sufficient to maintain the desired low tempera
ture through the entire reaction. To this quan
tity of liquid ethylene there is then added an ap
propriate quantity of a mixture of isob-utylene
and a diole?n such as butadiene, isoprene, penta
diene, or dimethyl butadiene (as above men
tioned) in the proportion of from '70 to 99 parts
of the isobutylene with 30 to 1 parts of the di
ole?n, together with from 200 to 500 parts of
the liquid ethylene. At any convenient stage
rapidly churning eddies produced at the trailing
during the preparation of this mixture, the pro
edge of the propeller disperse the catalyst into
the reaction mixture at an exceedingly rapid rate, 45 peller shaft 5 is put into rotation and with it the
blades 15 are likewise rotated. The speed of ro
probably in time intervals. measured in thou
tation is desirably about 1000 R. P. M.
sandths of a second. and the catalyst is dispersed
Meanwhile a catalyst solution consisting of
in bubbles or droplets so small that they are com
AlCls dissolved in methyl chloride to aconcentra
pletely dissolved through the solution in+erface
tion of 0.5 gm. per 100 cc. is prepared and chilled
into ‘the reactant mix before the polymerization
to about -—78° C. and admitted to the top of the
reaction has proceeded to such an extent as to
hollow shaft 5 at a rate of about 100 cc. per min
make any substantial change in the concentra
ute. The catalyst solution flows down the walls
tion of the reactants adjacent the interface of
of the hollow shaft through the opening at the
the bubble.
To the present it has not been possible to de- ;' ' bottom I‘! into the hollow blade l5 where it is
thrown out into the reactant mix, through the
termine the size of bubbles or droplets produced
opening it at the trailing edge of the blades H5.
by this device, nor has it been possible to measure
The liquid catalyst is thrown out through the
the reaction rate, but inspection of the equip
trailing edge of the propeller blades under con
ment in operation indicates that the reaction
rate is very rapid and the bubbles or droplets (50 ditions of relatively high pressure because of the
centrifugal force developed by the speed of ro
exceedingly small.
The delivery of the catalyst through the pro
tation and it is thrown in relatively small streams
peller blades is continued until the desired amount
into the eddy zones behind the trailing edge of
of polymerization has been obtained. When this
the blades and the reaction between the stream
stage is reached, as determined by inspection of
of catalyst solution and the vigorous eddies re
the reactant mix through the sight glass 4a, the
sults in a very rapid dispersal of the catalyst in
delivery of catalyst is stopped and the reaction
to exceedingly small droplets which are absorbed
is desirably quenched by the application to the
in a very short period of time into the body of the
reaction mixture of an oxygenated organic liq
solution. The rapid stirring of the main body of
uid such as an alcohol, or aldehyde, or even an
the solution, together with the high degree of
acid, or water, or alkaline solution, or ammonia,
dispersal of the catalyst solution results in a
or other suitable catalyst-quenching material.
highly advantageous polymerization condition.
The reactor may then be discharged in any
convenient .manner such as by draining the re
In consequence
a relatively high molecular
sidual diluent refrigerant and unpolymerized me 75 Weight polymer is obtained which also is substan
:p‘lacing jliquid around the shaft '22 to seal the
reaction vessel 1-8. ‘For conducting‘the low :tem
perature polymerization reactions it is not .nec
.essary'to‘have the lantern ring assembly in the
reaction apparatus. However, in conducting ,re
actionszother?than those‘ of low temperature, this
tially free from ‘undesirable, :lowmolecular weight
.The .reaction of the mixed .iso-ole?nic and .di
vole?nic‘materials in'theppresence of the dissolved
aluminum chloride catalyst occurs at a slower
rate than the reaction with the iso-olefin alone,
and the diole?n exerts a marked poisoning effect
upon the vpolymerization reaction. Accordingly
‘conditions of stirring and ‘temperature which
produce a very high molecular weight simple
poly-.isobutylene produce a considerably lower
molecular weight interpolymer which may range
from 65,000 to 200;,000. Alsozit is usually desir
able that ‘the reaction ‘be :quenched when from
lantern :ring assembly is essential and practical
for purposes of equalizing the pressure in the
packing gland so as to seal the shaft. A feed
line'29 ‘is provide‘d'to carry the liquid stored in
the cylinder 30 ‘into the lantern ring ‘28. ,‘A vent
3:! is provided in the form of a cylindrical tube
with ‘a small bore to balance the ‘pressure be
'~.tween'the lantern ring 28 and reaction vessel l8.
"The-pressure inthe lantern ring forces the liquid
~-65% to 5.95% of the mixed reactants have poly- ,
merized. ‘For this purpose the reactionis desir
fromrthe supply cylinder past the packing instead
ably quenched by the addition of an alcohol or
other oxygenated liquid or wateror alkali, as
above indicated. ‘The interpolymer resulting
from this polymerization reaction has a relative 20
ly .low iiodine number, preferably ranging be
tween :1 and 9; yet'it is reactive with sulphur for
a curing reaction which develops in it ‘an elastic
limit and a de?nite tensile strength. For this
purpose .the polymer as removed from the ‘reac-
tor is desirably washed with water in a Werner
and P?eiderer type of kneader to remove residual
traces of catalysts and quenching liquids. It is
then compounded with sulphur in approximate
ly the proportion of '3 parts, zinc oxide in the
proportion of 3 parts, stearic acid in the propor
tion of 3 parts, and a vulcanizer in'the form of
“Tuads” (tetra methyl thiuram disul?de) one
part, per hundred parts of the polymer, and if
desired, with from 50 to 200 parts of carbon black.
cured under heat and pressure for a time inter
val ranging from 15 to 60 minutes at a tempera
ture ranging from 135"v C. to 165° C. The result
ing cured polymer has a tensile strength ranging
from 3000 pounds to 4600 pounds per square inch
and an elongation at break ranging from 900%
In this reaction considerable heat‘ is liberated
which is removed by vaporization of the liquid
ethylene refrigerant-diluent. Also the quality
ing surface .on one side for the shaft .22'and an
opening provided around that shaft on the oppo
site side, including an aperture through the hol
low :side :of the conveyor leading to the outside-of
‘the‘reaction vessel. The outside surface around
thesbearing side of the hub is threaded to afford
means of tightening and sealing the member 33
and packing gland 24 to the reaction vessel It
with the necessary gaskets in between. .Above
the apertureileading to thehub there is provided
a bolt "to help seal :the .hub.
The propeller ‘blade housings?hasa solid core
drilled to ‘?t the shaft 22 and is provided with
impeller blades 31. This housing has enough
clearance between it'and the member 33 to allow
the housing to revolve. Openings 36 through the
3. housing to the hollow blades 3'! connect to open
The resulting compound may be moulded and
to 1250%.
of ."the gaseous reactants'in thereaction vessel.
.Athollow zconveyor:33 :is provided having a bear
ings 38 in the trailing edges to permit the dis
persion of the catalyst solution. A removable
cap .39 is threaded at the open end so that it can
"be screwed into the propeller blade housing 35
g particularly when not feeding ‘the-catalyst solu-‘
tion. .An opening 34-which is tapped for a plug
‘is provided as a "means :of "tightening the set
screws in the propeller ‘blade housing. ‘This
opening is :tappedand plugged so as to sealthe
of the product is an inverse function of temper
member 33. ‘The catalystrstored incontainer All
is conveyed ithrougha pipe‘M to the aperture of
the trailing edge of blade :31. ‘The opening '42
ature, thereby necessitating a well-controlled '
permits the'?ow of gases or vapor through the
unit ,so :as to accelerate the "polymerization re
reaction to insure against localizedoverheating.
If the-catalyst is added me; stream, or added too 50 iactionparticularly'in the case where the gaseous
catalyst in the reaction vessel is distributed
rapidly the reaction becomes unduly ‘violent with
throughout the liquid reactants in the reaction
evolution of more heat than can be removed by
the vaporization of liquid ethylene, resulting in
‘ vessel.
in vthe operation of this embodiment of the
a vlowered molecular Weight and poorer quality .
product. By using the dispersion blades: for cat— --_ invention, the reactor is ?lled with the desired
mixture of diluent-refrigerant and reactants,
alyst introduction, a smooth, well-controlled re
action is obtained as evidenced by the manner in
which the copolymer forms and by the excellent
quality of the ?nished product.
Figs. 3 and 4 show an alternative embodiment i,
of the invention in which the propeller is inserted
through the side wall of the reactor, carried on a
solid shaft in a horizontal position.
Referring to- these ?gures, this alternative em
bodiment of the catalyst disperser of the in
vention includes a motor 2| connected to the
shaft 22 on which are mounted the stirring blades
which latter may be the simple iso-olefin such as
isobutylene or may consist of the mixed ole?ns
such as isobutylene and a diole?n as above de
scribed. ‘When the reactor and its attachments
have been cooled to the desired'low temperature
(‘with the'aid of a refrigerating jacket as in Fig. 1
if desired), and the mixture in the desired pro
portions as above indicated fully prepared in the
reactor, the stage of addition of the catalyst is
reached. The propeller blade mixer is previ
ously put into rotation, and the flow of catalyst
may then ‘be started. The catalyst may consist
ofv gaseous boron tri?uoride from the cylinder 43,
the shaft 22 into the reaction vessel 31:8. A
jacket 23 around the packing gland .24 is .used 3-. which passes through the ?tting 33 to the blade
frame, .and thence through the openings 38 in
for circulating water to remove .the heat due to
.the trailing edge of the blades 3'! into the eddy
friction. -A soft packing 25 seals ‘the shaft 22 and
behind the blade where it is rapidly and power
the free coupling 26 prevents distortion of the
,fully dispersed :into the reactant mixture.
packing which is adjusted or tightened by means
of cap 21'. 'The lantern ring L28 is a {means of 75 Alternatively a liquid catalyst may be used
31. A packing gland 24 ‘is provided for sealing,
such as the above described solution of aluminum
chloride in a low freezing solvent. In this in
stance also the liquid catalyst solution is dis
charged from the cylinder 4%! through the pipe 4 l ,
' the ?tting 33 to the propeller hub 35 and the
blades 31 and the openings 38, into the eddy be
catalyst, either gas or liquid, moved in the above
described embodiments. The same procedure,
and the same apparatus may be used for treating
naphthas, oils, etc, with reagents such as alkali
solutions, doctor solutions, solvent extraction
liquids and the like. The apparatus and proce
dure are similarly useful for alkylation reactions,
hind the trailing edge of the blade where it is
the acid and isoparaiiins being agitated with and
rapidly dispersed as above described to produce
dispersed into the hydrocarbons through the ed
the desired polymers.
The embodiments of the invention above de 10 dies behind the trailing edges of the blades as
above described. In this instance, after the acid
scribed utilize a propeller type of stirrer im
and isoparamns have been added, the material
mersed in a simple cylindrical type of reactor
the reactor chamber may be recirculated as
container. It is not, however, necessary that
a mixture, thru the propeller blades and into the
they be so immersed. Alternatively the propeller
‘eddies behind the trailing edges thereby obtain
type stirrer may be placed within a circulating
ing a very satisfactory, long continued, intimate
tube exterior to the main reactor container, the
contact between the acid and hydrocarbon
propeller type stirrer being utilized to withdraw
portions of the reaction mixture from the body
While there are above disclosed but a limited
within "a reaction chamber and to discharge the
number of embodiments of the device of the in
'mixture after dispersing the catalyst therein back
vention, it is possible to provide still other em
into the main reaction chamber. If desired, the
bodiments without departing from the inventive
main reactor may be equipped with a travelling
concept herein disclosed and it is therefore de
strainer for removing the solid polymer from the
sired that only such limitations be imposed upon
reaction mixture as it accumulates in the main
the appended claims as are stated therein or re
reactor container, thus minimizing the length of
quired by the prior art.
time during which the solid catalyst is in contact
I claim:
with the reaction mixture, thereby further mini
1. In the low temperature polymerization of
mizing the production of undesired low molecu
iso-ole?ns to high molecular weight polymeriza
lar weight polymer. This embodiment may be
operated upon successive batches of reactive mix 30 tion products which are formed as solids under
the reaction conditions by addition of a suitable
ture, or it may be operated in continuous manner
polymerization catalyst to a. cold liquid medium
by discharging into the reactor the necessary
containing said iso-ole?n at temperatures be
continuous supply of reactant mixture contain
tween 0° C. and ~100° 0., an improved method of
ing the reactants and refrigerants in the pro
portions in which they are removed by the re
Alternatively the same type of propeller dis
perser may be utilized within a pipe conduit by
operation comprising turbulently agitating the
liquid medium by a rotating member therein hav
ing a trailing edge, delivering a, ?uid Friedel
Crafts polymerization catalyst through the trail~
ing edge of the said rotating member, and intro
from a supply chamber, the catalyst dispersed by 4-0 ducing said ?uid polymerization catalyst through
said trailing edge into the cold reaction medium
the propeller type disperser into the stream of
to cause rapid dispersion of the catalyst therein
reactant mixture in the conduit, and the whole
with immediate formation of solid polymeriza
discharged into a reaction chamber together with
tion products which are projected away from the
a supply of catalyst-quenching agent, the solid
zone of catalyst introduction by the driving ac
polymer being removed by a travelling strainer,
tion of the said rotating member.
and the residual liquids fractionally distilled to
2. Process according to claim 1, in which said
recover the various components for recycling.
iso-o-le?n is isobutylene and in which the said
Thus the invention provides a new process by
catalyst is a Friedel-Crai'ts catalyst solution.
which a catalyst is dispersed at low temperature
3. Process according to claim 1, in which said
into an eddy zone behind a propeller type stirrer
iso-oleiin is isobutylene and said catalyst is boron
for the ultra rapid and thorough dispersion of or
incorporation into a reactant mix for the poly
4. In the low temperature copolymerization of
merization of the reactant mix with a minimum
which a fresh reactant mixture is withdrawn
of undesired polymers; and a device consisting
of a propeller type stirrer having ducts at the
trailing edge of the propeller blade for the dis
iso-butylene with a conjugated diole?n of 4 to 6
carbon atoms per molecule to high molecular
weight copolymerization products which are
formed as solids under the reaction conditions by
charge of catalyst‘ directly into the eddy behind
addition of a suitable polymerization catalyst to
the trailing edge of the stirrer blade.
a cold liquid medium containing said reagents at
The apparatus above disclosed is intended pri
marily for the incorporation of catalyst, either 60 temperatures within the range between 0° C. and
-103° C., an improved method of operation com
as gas or as a solution, into a reactant mixture of
prising turbulently agitating ‘the liquid medium
ole?ns, with the powerful dispersing effect of
by a rotating member therein having a perforat
the eddies at the trailing edges of the blades be
ed trailing edge, delivering a fluid Friedel-Crafts
ing utilized to incorporate the catalyst into the
catalyst through the said openings through the
reaction mixture in the shortest possible time.
trailing edge or" the said blades, and introducing
The advantages of this powerful incorporating
said ?uid polymerization catalyst through the
and dispersing effect are not, however, limited
perforated edges in said rotating member into
to such ole?nic reaction mixtures at low temper
the cold reaction medium to cause rapid disper
ature. The same apparatus (made in stainless
sion of the catalyst therein with immediate for
steel or other non~corrosive metal) may be used
mation of solid polymerization products which
for‘the acid absorption of re?nery ole?ns; the
are projected away from the zone of catalyst in
acid being stirred into, dispersed in and caused
troduction by the driving action of the rotating
to react with the ole?ns by passing thru the
hollow blades into the eddies behind the trailing
5. Process according to claim 4, in which said
edges, in substantially. the same way in which the 75
catalyst is a Friedel-Crafts catalyst dissolved in a
solvent which is liquid at the reaction tempera
6. Process according to claim 4, in which‘ said
catalyst comprises a solution of aluminum chlo
ride in methyl chloride.
7. A low temperature polymerization process
comprising the steps of cooling isobutylenic ma
terial to a, temperature between its liquefaction
point and -100° 0., rotating 5;, stirrer therein at
a speed between 400 and 1500 R. P. M. to develop
a turbulence zone in the isobutylenic material
adjacent the trailing edge of the stirrer and de
livering into the turbulence zone a polymeriza
tion' catalyst to initiate polymermization of the
isobutylenic material in the turbulence zone.
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