5706 5710.output

* GB786114 (A)
Description: GB786114 (A) ? 1957-11-13
Improvements in or relating to method of making a split metal sleeve and the
resulting product
Description of GB786114 (A)
PATENT SPECIFICATION
Iv 17 ento, CHARLES H COLLETT 786 A 114 Date of Application and filing
Complete Specification Aug 19, 1955.
No 23937/55.
Complete Specification Published Nov 13, 1957.
Index at Acceptance:-Classes M 4, i 3 E 4 i; 83 ( 2), A 122 (l F Jl);
85, AIC; and 99 ( 2), K 2.
International Classification: -B 23 p E 2 llb F'06 b, 1.
COMPLETE SPECIFICATION
Improvements in or relating to method of making a Split Metal Sleeve
and the resulting product We, BETTIS RUBBER COMPANY, a corporation
organised under the laws of the State of California, United States of
America, of 1557 South Esperanza, Los Angeles 23, California, United
States of America, do hereby declare the invention, for which we pray
that a patent may be granted to us, and the method by which it is to
be performed, to be particularly described in and by the following
statement: -
This invention relates to split metal sleeves, and while it finds its
principal advantageous use as a protective device on drill pipes in
the drilling of oil wells land the lilke, it is also advantageous in
other uses such as for collars is and bushings.
For instance, it is conventional practice in rotary well drilling to,
mount on the drill pipe rubber sleeves to prevent frictional wearing
engagement of the drill pipe with the well casing, and t 6 centre the
pipe in the casing, particularly since the drill holes are often
crooked Heretofore it has been the practice to utilize one-piece
rubber sleeves which must be stretched and applied fu-ially over the
drill pipe but this is time consuming, requires expensive equipment,
and also requires that the pipe lengths be disconnected at the joints.

While attempts have been made to provide split sleeves for the
purpose, such attempts have not been fully successful for several
reasons One reason is that they are incapable of embracing the drill
pipe sufficiently tightly to prevent them from slipping axially of the
pipe Another difficulty with prior art split sleeves has been that
they have necessarily been of such construction as to render them
incapable of withstanding the tremendous stresses to which they are
subjected in normal use The segments either become separated or the
means provided for holding the segments together about the pipe
seriously weaken the devices.
Th resent invention provides the method of making a split metal sleeve
adapted to snugly and resiliently embrace a member of round
cross-section, comprising the sequential steps of providing a length
of metallic tubing having an inner radius of curvature smaller than
the radius of curvature of the member which the sleeve is to embrace,
heat treating the length of tubing to render the same resilient, and
then flame-cutting said length of tubing along lines separating it
into two segments having interengaging side edge portions, each
segment, including its side-edge portion or portions having a total
arcuate length exceeding in curvature.
The present invention also provides a split metal sleeve for a drill
pipe of cylindrical crosssection, said sleeve being adapted to be
disposed about said pipe in embracing relationship thereto, and to
resiliently and snugly embrace said pipe in a manner automatically to
compensate for reduction in the original outside diameter of said
pipe, and comprising a pair of opposed interengaging resilient
metallic semi-cylindrical segments, one side edge of each of which has
a circtumferentially disposed slot, and the other side edge of each of
which has a circumferentially extending slot-engaging tongue portion,
each segment, including its side edge portions, having a total arcuate
length exceeding 1800 in curvature, the tongue portion having an axial
length not greater than the axial length of the entrance portion of
the said slot.
It is an object of the invention to provide a novel method of maling a
resilient split metal sleeve.
It is a further object of the invention to provide a split metal
sleeve which is easy to install and remove, which sufficiently tightly
embraces the pipe to resist slipping along the pipe and which is
sufficiently strong and durable to withstand all the abuses to which
it is subjected in normal usage.
The invention has additional but more subordinate objects and
advantages which will appear hereinafter.
Without intending thereby to limit the broader scope of the invention
as defined by the appended claims what has been found to be presently

preferred embodiments thereof shall now be described, for which
purpose reference will be made to the accompanying drawings, wherein.
Fig 1 is a view partly in section and partly in side elevation,
showing one of the split sleeves installed on a conventional drill
pipe:
Figs 2 and 3 are, respectively, enlarged sections taken on lines 2-2
and 3-3 of Fig 1; Fig 4 is a perspective view showing the sleeve
segments separated; Fig 5 is a side elevation of the segments showing
them about to be assembled; Fig 6 is a perspective of a locking key
which is utilized; Fig 7 is a fragmentary plan view showing a wedge in
place; Figs 8 and 9 are, respectively, sections taken on lines 8-8 and
9-9 of Fig 7; Fig 10 is a side elevation showing a modified form of
the split sleeve; Fig 11 is a section taken on line 11-11 of Fig 10;
Fig 12 is a side elevation of a further modified form of the
invention; Fig 13 is a side elevation showing another modified form of
device; and Fig 14 is a section taken on line 14-14 of Fig 13.
In general, in carrying the invention into practice, we provide two
segments composed of resilient metal, each of the segments being
curved in excess of 1800 in cross-section from one side edge to the
other, so that each segment must be sprung over the diameter of the
drill pipe or other member on which it is to be mounted However, to
enable the two segments, when assembled in opposed relationship about
the pipe, to resiliently embrace the pipe about its 3600
circumference, we provide for the interengaging or interfitting of
contiguous side edge portions of the segments, the interengagement
being by means of tongue and slots and being such as to make the
circumference of the combined interengaged segments substantially 3600
This interengagement may be provided at each side edge portion or only
at one side edge portion of the segments To insure a tight frictional
engagement of the segments about a pipe or drill stem or the like, the
radius of each segment is made slightly smaller than the radius of the
member onto which it is to fit We may also provide positive locking
means to secure the segments against separation in a circumferential
direction However, we have not found such locking means essential
because the resiliency of the segments and the fact that each embraces
the pipe in excess of 1800 is sufficient to prevent such separtion
under all normal conditions of use When we use the split sleeve for
the purpose, of preventing frictional wear between, for instance, a
drill pipe or drill stem and a well casing, we provide each 70 segment
with a compressible or soft rubberlike outer covering However, the
split sleeve is adapted for many uses which do not require such
covering For instance, it finds advantageous use as a bushing, sleeve
or collar in other 75 fields, and also may be used to great advantage
in sealing leaks in fluid lines, because of its ease of application In

the latter use the sleeve should have a compressible lining.
Referring now to the drawings, in Fig 1 80 we show one of the split
sleeve devices, eenerally denoted 5, installed upon a conventional
drill pipe P within a well casings C in a drill hole.
The split sleeve device in the embodiment of 85 Figs 1-9, consists of
two segments 15 16.
Each segnent has a mnain, semi-circular body Portion 18 curved
substantially 1800 but not in excess of 1800, while one of its side
ed-es ha a circumferentia I dovetailed extension or 90 tongue 19
curved substantially 300 The curvature of the body Portion nhis its
tonave s in excess of 1800 but nrefernblv not in excess of 215 -it
being preferred that said combined curvature be of the order of 2100
The 95 opposite edge portion of each segment presents a dovetailed
slot 20 at least of the depth of the tongue of the other segment It
will be understood, of course, that the tongue 19 of one segment
enoages in the slot 20 of the 100 other segment initially with a loose
fit-that is, the minor length portion of each slot is slightly greater
than the major length Portion of each tonaue, as shown best in Fig 5
This is to enable the tongue to be circumferen 105 tiallv inserted in
the slot The ends of each segment are preferably rounded as shown at
22 It will be seen that the circumferential extent of each tongue and
slot are such that when interengaged, the sleeve produced by the 110
segments is not in excess of 3600.
Each of the segments 15, 16 has an outer covering of soft rubber or
like compressibl P material which is bonded to the outer surface of
the segment, the outer surface of each seg 115 ment preferably having
a plurality of indentations 26 to facilitate bonding of the rubber
covering thereto.
To install the segments upon a drill pipe it is only necessary to
apply them to opposite 120 surfaces of the pi-e and force them into
position wherein each of the tongues 19 enters a slot 20 Since the
segments all composed of resilient metal, each segment can be
sufficiently sprung to force it over the pipe even 125 though each
segment is curved to an extent greater than 1800.
Due to the fact that each segment is curved in excess of 1800, the
sleeve, when assembled on the pipe, will sufficiently resist any 13 '0
786,114 ments there is provided a semi-circular recess in each end
wall 46 of each slot and a corresponding semi-circular recess 52 in
the contiguous surface 44 of the tongue The two recesses mate to
provide a round hole for the 70 reception of a set screw 53 which is
threaded into the hole, or may be threaded into a hole drilled in the
drill pipe.
In the embodiment of Fig 12, the sleeve is as described in connection
with Figs 10 and 75 11 except that in lieu of the set screws 53 and

recesses 50, it is provided in each end wall of each slot an undercut
60, providing an inwardly facing shoulder 61 while it is provided on
each of the tongues, at each end, a 80 protubertance 62 substantially
conforming to the shape of the undercut We also provide
circumferentially disposed slots 64 in each tongue adjacent its ends
Thus a pair of resilient portions 66 of each tongue are pro 85 vided,
which enable the tongues to yield sufficiently to be forced into the
slot After the protuberances 62 pass the shoulders 61, the portions 66
flex into normal position to bring the protuberances 62 behind the
shoulders 61 90 In Figs 13 and 14 we show another embodiment
comprising two segments 71, 72 each of which has one straight side
edge 73, the straight side edges abutting each other Segment 71 is
curved in cross-section in excese 95 of 1800 but preferably not in
excess of 215 and has in its opposite side edge a circumferentially
opening slot 75 of a depth at least equal to the extent to which the
curvature of the segment exceeds 1800 The corners of 100 the slot are
preferably curved Segment 72 has a body portion 77 curved in
cross-section not in excess of 1800 and has at its opposite side edge
portion a circumferentially disposed tongue or extension 74, which
extends sub 105 stantially 300, or equal the depth of slot 75 into
which it extends To facilitate removal of the split sleeve from a
drill pipe or the like, we provide in the side edge of the tongue 74 a
slot 76 into which a tool (not shown) of 110 rectangular cross-section
may be inserted and rotated to spring the segments apart Here, a
soft-rubber-like outer covering 78 extends about the two segments, the
rubber covering extending over the abutting straight side edges 115 73
to hingedly connect the two segments together at that point, and being
split along a line following the opposite side edges of the segments.
In each of the embodiments, the inner 120 radius of each of the
segments should be slightly smaller, preferably approximately /,,th
inch smaller, than the outer radiuq of the drill pipe onto which the
sleeve is to fit, to insure a snug spring fit 125 In making the split
sleeve, we first cut steel tubing stock to length and round the end
edges Next we heat treat the cut tubing to make it resilient Next
there is used a flame cutter to cut the tubing into the two segments
130 normal stresses tending to separate the segments, However, as a
positive lock, to positively insure the segments remaining in
assembly, it is preferred to provide at one end of each slot, between
the adjacent end wall of the slot and the adjacent end surface of the
interfitting tongue 19, a key 30 As best shown in Figs 6-9, each key
has flat side surfaces 30 a and has a medial longitudinal split 30 b
opening through its inner end portion The inner end surface 30 c at
one side of the split is beveled in one direction while the inner end
surface 30 d at the other side of the split is beveled in the opposite

direction (Fig 6) As best shown in Figs 7-9, the opposite surfaces of
the end wall of the slot 20 and the end wall of the interfitting
tongues 19 are each undercut as shown at 32.
Thus, after the segments are assembled on the pipe with the tongues 19
engaging in the respective slots 20, as each key 30 is driven inwardly
between the end wall of the slot and the contiguous end surface of the
tongue 19, they bend outwardly in opposite directions as the beveled
surfaces engage the periphery of the pipe P, as shown in Figs 8 and 9,
preventing escape It is preferred, although it is not essential, to
insert one of the keys 30 into each slot.
When the segments are thus assembled and secured in interlocked
position, the key 30 forces the opposite end of the tongue 19 against
the opvosite end wall of the slot 20, so that said opposite end wall
of the slot overhangs the contiguous end wall of the tongue to
positively prevent withdrawal of the tongues from the slots in a
circumferential direction and consequently to positively prevent
separation of the segments when installed on a pipe.
It will be understood, of course, that if the sleeve is to be used
simply as a bushing or collar instead of as a drill pine protector in
the boring of a well, the rubber covering 25 may be omitted-the rubber
covering being omitted from the device as shown in Fig.
5.
In the embodiment of Figs 10 and 11, the device consists of two
segments 40, 41 each comprising a main body portion 42 which is curved
substantially but not in excess of 1800, while one side edge of each
segment has a tongue or extension 43 whose end edges 44 are straight
or normal to the longitudinal axis of the segment and parallel, while
the other side edge of each segment is provided with a slot 45 whose
end walls 46 are also straight and parallel The curvature of each
segment, together with its tongue is of the order of at least 2100 but
preferably not greater than 215 , so that the resilient segments may
be sprung over the diameter of the nipe and so that they thus
resiliently embrace the pipe.
To positively prevent separation of the seg786,114 4 786,114 having
the tongues and slots (Figs 1-12) or tongue and slot (Figs 13, 14) The
tubing is cut into the segments after heat treating because if the
tubing were heat treated after the cutting it would tend to flatten
out The interengaging side edge portions of the segments not only
prevent relative axial movement of the segments and facilitate
positive locking of the segments against relative circumferential
separative movement of the segments, but the interengaging side edge
portions, wehich define the extent to which the segments exceed 1800
each in curvature, are of substantially the same length That is, the
tongue has an axial length of approximately half the axial length of

the sleeve, while those portions of the other segment which bound the
ends of the tongue-receiving slot are of approximately equal length
and their combined axial length equals approximately the other half of
the axial length of the sleeve, so as not only to provide an effective
and dependable gripping of the pipe but also to evenly distribute the
gripping force.
To further insure that the split sleeve will not slide upon the pipe
after being applied thereto, it is our preference to knurl the inner
surface of each segment as shown at 70 (Fig 4).
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* 5.8.23.4; 93p
* GB786115 (A)
Description: GB786115 (A) ? 1957-11-13
Improvements relating to vehicle wheels, more especially for use on vehicles
usuallyoperating on soft, easily penetrable ground
786,115 i 71 A M % Date of Application and filing Complete
Specification: Sept 1, 1955 No 2514 i
Complete Specification Published: Nov 13, 1957.
Index at acceptance:-Classes 144 ( 1), AD( 1:3:5); and 144 ( 2), C 5 C
3.
International Classification:-B 62 f, g.
Improvements relating to Vehicle Wheels, More Especially for Use on
Vehicles Usually Operating on Soft, Easily Penetrable Ground I 555.
I, WILLIAM MILNE CATCHPOLE, a British Subject of Mothersoles,
Bardwell, Bury St.

Edmunds, Suffolk, do hereby declare the invention, for which I pray
that a patent may be granted to me, and the method by which it is to
be performed, to be particularly described in and by the following
statement: This invention relates to skeleton type vehicle wheels,
more especially for use on tractors, agricultural implements,
agricultural carriers and like vehicles usually operating on soft,
easily penetrable ground.
According to the invention, a skeleton type vehicle wheel comprises
two separate, narrow and completely smooth tread surfaces of annular
form constituted respectively by the outer peripheries of two annular
rim elements of the wheel whose crosssection, at any point along the
element, in a plane radial to the wheel and containing the rotational
axis thereof is elongated in the direction radially of the wheel and
whose form is such that the line of the major axis of said
cross-section is either truly normal to said rotational axis or at an
angle thereto not less than 80 ', which rim elements are spaced apart
from one another axially of the wheel with the intervening space
between them, for the full depth of the elements radially of the
wheel, completely devoid of any parts projecting into it from any part
of the wheel, the mutually opposed faces of said rim elements being
completely smooth and there being no part of the wheel projecting
radially thereof beyond said tread surfaces.
Further according to the invention, the rim elements of the improved
wheel may carry ground engaging lugs projecting from the elements
axially of the wheel and in spaced relation to one another therearound
from the outer side faces of the elements.
Virtually the improved wheel of this invention is a twin-wheel
consisting in effect of two narrow wheels spaced apart with their
ground contacting surfaces and also their mutually opposing faces
completely smooth and free from projections of any kind In this way it
is possible to provide a wheel 50 which effectually overcomes the
tendency of all previous types of steel wheels to collect sticky soil
and gradually build it up on their engaging surfaces until they are
rendered ineffective for the purpose of which they are 55 designed The
ability thus of the new type of wheel according to this invention to
run free from adhering soil, however sticky may be, opens up vast new
fields for the operation of, for example, wheeled agricultural 60
tractors, although as later more particularly described, the invention
is by no means limited to this particular field.
It will be understood that no part of the ground engaging lugs of the
improved wheel 65 of this invention projects beyond the line in the
side elevation of the wheel of the ground engaging surfaces of the rim
elements This is important, as the smooth circumference of the rim
portion of the wheel 70 (constituted by the two rim elements)

exercises a very strong control over the extent to which the wheel
penetrates into the ground surface This strong control of penetration
persists even when the wheel, 75 while being used as a driving wheel
as in the case, for example, of an agricultural tractor, is slipping
or spinning relative to the ground surface The wheel of the present
invention does not, by slipping when being used as a 80 driving wheel,
dig itself into the surface of the ground and bog itself down under
unfavourable conditions This digging action of wheels constructed, up
to the present time, of steel or a combination of cast iron and 85
steel, has been a main limiting factor in their usefulness and it has
been entirely overcome by the present invention.
In the improved wheel of the present invention the division of the
wheel, as regards 90 786,115 the rim portion thereof, into two
separate Vim elements which leave a substantially undisturbed strip of
ground between them as the wheel runs, results in the wheel load being
applied to the ground surface in such a way that it is spread over a
relatively large area of the subsoil section in a plane normal to the
ground surface and containing the rotational axis of the wheel.
Thus in the case of a wheel of the known skeleton structure type
having only one rim element, said rim element being of the same
general form as that of the rim elements of the present invention, the
wheel load is supported by a mass of subsoil (considering a section
therethrough in a plane as aforesaid normal to the ground surface and
containing the rotational axis of the wheel) of wedge shape, the apex
of the wedge being uppermost and the included angle of the wedge
varying with the relative friction of the soil particles In the case
of the improved wheel of the present invention the wheel load is
supported on two such masses of subsoil spaced apart from one another
axially of the wheel, with the result that the degree of penetration
of the wheel into the ground is less than that of the known single rim
skeleton 'wheel, which is of great benefit when the wheel load is
heavy and the surface conditions are soft.
The advantages of the improved wheel of the present invention apply
equally whether the wheel is used purely as a load carrier, as a
driving wheel of a self-propelled vehicle, e.g, an agricultural
tractor, or as a wheel of a trailed carriage operatively connected to
mechanism on the carriage to be driven by the wheel, through the
intermediary of suitable chain drive or other gearing.
The invention will now be further described with reference to the
accompanying drawings, which illustrate it by way of example.
In these drawings:Fig 1 is a side view of the improved wheel of the
invention according to one preferred form thereof; Fig 2 is a
corresponding end view looking in the direction of the arrow A in Fig
1; Fig 3 is a fragmentary side view of the improved wheel illustrating

a possible modification as regards the form of the ground engaging
lugs of the wheel:
Fig 4 is a corresponding fragmentary end view looking in the direction
of the arrow B in Fig 3, the view illustrating a further possible
modification hereinafter more particularly described: and 6 O Fig 5 is
a fragmentary plan view of the improved wheel illustrating a further
possible modification still as regard the ground engaging lugs of the
wheel.
Like reference numerals are applied to like parts in the various
figures.
The wheel shown in the drawings comprises two annular rim elements 1,
2, disposed coaxially with one another and spaced apart axially of the
wheel These rim elements carry narrow and completely smooth 70 ground
contacting surfaces 3, 4, and between the rim elements is a space 5
which is completely devoid of any parts projecting into it from any
part of the wheel, the mutually opposed faces of the rim elements
being 75 completely smooth and free from all projections of any kind.
Carried upon the rim elements are ground engaging lugs 6 As shown,
these lugs project from the rim elements axially of the 80 wheel and
in spaced relation to one another therearound from the outer side
faces 7 of the elements It will also be seen that the lugs at one side
of the wheel are staggered with respect to those at the other side
there 85 of.
The rim elements 1 2 are of adjustable spacing axially of the wheel
and they are connected to a hub element of the wheel in such a manner
as to be adjustable as to 90 position axially of the wheel with
respect thereto.
More particularly described, the rim elements, 1, 2 are respectively
connected to a pair of wheel centre elements 8, 9 which in 95 turn are
connected to a hub element 10 common to them both, said hub element
being adapted to be mounted upon a wheel axle (not shown).
Both the rim elements 1, 2 and the wheel 100 centre elements 8, 9 are
constituted by rings of thin rectangular section, the rings 1 2 being
rigidly connected to the rings S 9 by radial spokes 11, also of thin
rectangular section 105 The hub element 10 is located intermediate the
wheel centre elements 8, 9 and the latter are connected to the hub
element bv bolts 12 which extend parallel to the rotational axis of
the wheel, the wheel centre 110 elements 8, 9 being of adjustable
position with respect to one another along these bolts and the hub
element being also adjustable therealong.
Thus the bolts 12 carry respectively sets 115 of spacers in the form
of short sleeves 13 threaded on to the bolts and intervening between
the hub element 10 on the one hand and the wheel centre elements 8, 9
on the other, the arrangement being such that one 120 or more of the

spacers 13 (considering any of the sets thereof) may be removable from
the wheel to adjust thec spacing of the rim elements thereof axially
of the wheel or the hub element 10 may be located between any 125 two
of the spacers (considering any of the sets thereof) to adjust the
nosition of the rim elements relatively to the hub element axially of
the wbeel.
The hub element 10 is of dished elate 130 786,115 form with a
peripheral flange 14 to which the wheel centre elements 8, 9 are
secured through the intermediary of the bolts 12 and associated
spacers 13, the whole unit constituting the wheel and comprising, as
will be appreciated, the two rim elements 3, 4 the lugs 6 thereon, the
wheel centre elements 8, 9 the spokes 11, the hub element 10, the
bolts 12 and the associated spacers 13, being bolted up solidly to the
form of a rigid entity which, as such, is mountable upon the wheel
axle and securable thereto by means of blots (not shown) extending
through holes 15 provided for their reception in the base portion of
the dished plate 10.
It will be seen, therefore, that the construction illustrated is one
in which the wheel centre elements 8, 9 are connected to the hub
element 10 at a position therealong (i e, axially of the element and
therefore of the wheel) removed from the position at which the hub
element is mountable from the position at which the hub element is
mountable upon the wheel axle, and the arrangement is such that the
hub element is reversible in the wheel so as to vary the position
axially of the wheel of the rim elements 3, 4 relatively to the wheel
axle.
It will be appreciated that with a con30struction of the foregoing
description it is possible, by simply varying the position of the
flange 14 of the hub element 10 along the bolts 12, i e, by
re-arranging the spacers 13 therealong, to vary the track of the
wheels when fitted to the extremities of an axle, or alternatively,
the track of the wheels when fitted to the extremities of an axle may
be varied by reversing the position of the hub element 10, without
alteration of the arrangement of the spacers 13 along the bolts 12, or
the track may be varied by a combination of these methods It will be
seen, therefore, that in this respect the improved construction of
wheel according to the invention provides a highly flexible system as
regards possibility of varying the track of a pair of the wheels when
fitted to the extremities of an axle.
It will further be seen that the distance between the rim elements 1,
2 may be varied merely by altering the number of spacers 13 threaded
over the bolts 12 This is an important consideration when it is a
case, for example, of wheels designed to run between, or to straddle
very narrow rows of plants.

In this connection it may be remarked that, during agricultural crop
husbandry, much cultivation work is carried out on the soil surface
between plants grown in parallel rows With some types of plants the
rows are of necessity very close together, and it is impossible to
arrange existing types of tractor and implement wheels to run in the
inter-row spaces without damage to the plants The employment of wheels
of the improved construction according to the present invention, owing
to the fact that the twin rim elements and the lugs thereon can be
effectively constructed with relatively narrow overall width, coupled
with the fact 70 that the wheel can be arranged to straddle one or
more rows, makes it possible to run comparatively heavy tractors in
narrow inter-row spaces in a manner not hitherto possible 75 Moreover,
in the type of application where the wheel straddles the row or rows
with its pair of rim elements, the complete absence of any tendency of
the wheel to lift or pick up soil between the rim elements 80 is of
great value In the case of very small or shallow rooting plants any
lifting of the soil would immediately sever and destroy the roots of
the plants, which would result in the probable loss of the crop 85
Referring now to the ground engaging lugs 6 of the improved wheel, the
actual style of these lugs depends on the work which it is desired to
perform with the wheels It also depends on the type of surface condi
90 tions which are likely to be encountered in the use of the wheels
To effect, for example, the very minimum disturbance of easily
penetrable surfaces the faces of the lugs which are directed
rearwardly of the wheel 95 (i.e, in a direction away from the
direction in which the axle of the wheel is travelling when the wheel
is running along the ground), assuming the lug to be at its lowermost
position in the wheel (i e, at the point of tan 100 gency of the
periphery of the wheel with the ground surface), may be arranged at a
suitable angle ' (see Fig 1) to a line drawn from the centre of the
wheel to the radially outer edge of the lug, the direction of the 105
inclination of the lug with respect to said radial line and the
magnitude of such inclination being such that as the wheel rotates,
the lugs penetrating the soil in succession, the said rear faces of
the lugs leave the 110 ground in or near a vertical position-thereby
producing the very least possible displacement of the soil.
Fig 3 illustrates a construction in which the lugs are of V-section
form, with the bot 115 tom of the V directed away from the rotational
axis of the wheel Lugs of this form leave larger depressions in the
soil surface, but they enable the wheel to support greater weights
when running on soft surfaces 120 Under conditions where it is
desirable, for the purposes of developing traction, to limit the
shearing action of the lugs on the soil, lugs of the flat plate type,
as employed in the wheel illustrated in Figs 1 and 2 may be 125 set

obliquely to the general plane of the rim element upon which they are
carried, Fig.
illustrating this possible modification.
In certain soil structures where clay predominates, the repeated
passage to and fro 130 786,115 of wheeled tractors and wheeled
implements during agricultural cultivation work has a harmful
consolidating elfect upon the soil.
It is found, however, that wheels constructed in accordance with the
invention with ground engaging lugs of the type used in the
construction according to Figs 1 and 2 or of the type used in the
construction according to Fig 5, eliminate for all practical purposes
this harmful consolidating effect of clay type soils At the same time
wheels of this description can both carry loads and develop traction
when the soil conditions are so adverse that any normal type of wheel
of existing design will be completely ineffective, due either to
loading up with sticky soil or to sinking in too deep into the ground
or again to failure to effect an adequate grip on greasy surfaces.
Fig 4 illustrates an alternative form for the rim elements according
to which the the elements, as regards the mutually opposed faces
thereof, are splayed radially outwardly with respect to one another in
the axial section of the wheel at a small angle ri which may be, for
example, in the neighbourhood of 5 ' Such splaying of the mutually
opposed faces of the rim elements decreases the ability of the wheel
to penetrate the surface of the ground and is advantageous where
conditions tend to allow the rim elements of a wheel embodying this
invention to penetrate the surface too freely.
In other respects the wheel of Fig 4 is similar to the wheel of Figs 1
and 2 and any of the various forms of ground engaging lugs described
above may be employed in the wheel.
The ground engaging lugs of the improved wheel of this invention may
be either permanently affixed to the rim elements which carry them or
detachably mounted thereon, and they may be either of fixed position
relatively to the rim elements or of adjustable position with respect
thereto e g of adjustable position as regards the angle ' in the case
of lugs of the type shown in Figs.
1 and 2.
Finally, it will be appreciated that the wheel may be constructed of
any suitable material, although it will generally be constructed of
steel.
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* 5.8.23.4; 93p
* GB786116 (A)
Description: GB786116 (A) ? 1957-11-13
A process for preparing epoxidized condensation polymers and the resulting
products
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amongst the following family members:
BE540982 (A) CH341647 (A) FR1136342 (A) NL103509 (C)
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
786 J 116 Date of Application and filing Complete Specification Sept
1, 1955.
No 25150155.
Application made in United States of America on Sept 3, 1954.
Complete Specification Published Nov 13, 1957.
Index a: Acceptance:-Classes 2 ( 5)1 R 3 C( 8: 9 110: 1 l 12), R 31 M(
1: 2 A 2 B: 2 C: 3: 4: 5: 6: 9:10:
11 12: 1: I 50:17:18), 13 (P 3: T 2), R 7 C( 8: D: 10: 11:12), R 7 (P:
T 2), ROC( 3: 0: 10: 1 1: 12), R 9 (P: T 2), R 14 C( 8: 9: 10: 11:
12), R 14 (P: T 2), R 22 C 8 ( 9: D: DAZ:1 12), R 22 (D D 2: P:72), R
27 K 3 (C 8:C 1 l:M 6:M 7), R 275 t 1462 ( 89: 10 e 1 Lll 12), P 127

KIS(D: E), Rt 271 K; 5 C(: 9: 10: 11: 12), R 27 K 5 (D E); R 271 M (
8:0910: 1: 112), R 27 K 6 (D: E), R 27 K 7 C( 8: 9:10:
11: 12), R 27 K 7 (D: E), R 33 C( 80: 9 0: 111: 12), R 3113 (P: T 2);
2 ( 6), P 2 A, P 2 DW(AX), P 2 X( 4: 9), P 2 T 2 X, P 4 A, P 4 D 3
(C: X), P 4 K 2, P 9 A, P 9 DIB( 1:
2: 3), PM 1 ( 2: 3), PO(K 2:TW); and 2 ( 7), T( 11 I:)3 X: 3).
International Classification: -CO 8 f, g.
A process for p-ee-:aring E Loxidized Condensation Polymers and tiie
resutiing prodeucts We, N V DE BATAAFSCHE PFTROLEUM MAATSCRAPPIJ, a
Company organised under the Laws of The Netherlands, of 30, Carel van
Bylandtlaan, The Hague, The NetherS lands, do hereby declare the
invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly
described in and by the following statement: -
This invention relates to a process for preparing new epoxidized
polymeric products, to the resulting products and to the use of these
new epoxidized products, particularly in the preparation of improved
coating compositions.
Unsaturated polymeric condensation products, such as unsaturated alkyd
resins and unsaturated polyamides, are useful in applications such as
surface coating and laminating, as they can be cured through the
unsaturated linkages to form insoluble infusible products.
Many of these materials, however, and par.
ticularly those wherein the double bonds are in a non-conjugated
relationship, have only limited utility because they are difficult to
cure In addition, many of these unsaturated polymeric products have
only limited solubility in oils and solvents and limited compatibility
with other film forming materials and this places a considerable
limitation on the amount of such materials that can be tolerated in
coating compositions Many of these products are also unsuited for use
in other applications, such as the formation of fibres, as they are
relatively inert to further treatment such ^ dyeing.
It has now been discovered that these and other drawbacks may be
avoided by the novel products of the present invention which comprise
epoxidized polymeric products obtained by epoxidizing unsaturated
condensation polymers having a plurality of non-terminal ethylenically
or acetylenically unsaturated linkages, at least two of said
unsaturated linkages per molecule being converted during the 0 A
epoxidation to -C-C groups in a polymer chain containing, in addition
to carbon, at least one of the following elements: oxygen, nitrogen,
silicon, phosphorus, and sulphur, present in at least two different
locations in the said chain These epoxidized polymeric products have
been found to possess many unusual and unexpected properties not

possessed by the unsaturated polymeric products and are suitable for
many applications in the chemical and related industries The
epoxidized polymeric products described above, for example, have
greatly improved solubility and compatibility characteristics and can
be combined in much larger amounts with coating solvents and synthetic
resins than was possible with the unsaturated polymeric products In
addition, the epoxidized polymeric products may be easily modified
through reaction with monofunctional agents, such as drying oil fatty
acids and monoamines, to form polymeric products having new and
improved properties Furthermore, these epoxidized polymeric products
or their modified derivatives may be easily cured by treatment with
polyfunctional epoxy curing agents such as polycarboxylic acids,
polyamines and polymercaptans, to form harder and more resistant
coatings.
Thus there is provided in accordance with the present invention a
process for preparing an epoxidized product, in which an unsaturated
condensation polymer containing in the molecule a plurality of
non-terminal ethylenically or acetylenically unsaturated linkages anti
containing, in a polymer chain, in addition to carbons at least one of
the following elements:
oxygen, nitrogen, silicon, phosphorus and sulphur, present in at least
two different locations in the said chain, is reacted with an
epoxidizing agent in an amount sufficient to convert at least two of
the unsaturated carbon-to-carbon linkages per molecule to epoxy groups
The present invention also includes the resulting epoxidized products,
a process for hardening the same and the resulting hardened products.
The unsaturated polymeric products to be epoxidized according to the
present invention are the unsaturated condensation polymers possessing
a plurality of non-terminal ethylenically or acetylenically
unsaturated linkages The unsaturated linkages are preferably ethylenic
linkages but may be of the acetylenic type By the expression "
condensation polymer " is meant those polymers fromed by elmination of
a molecule of a component such as, for example, water or hydrogen
chloride, from two molecules of reactant These condensation polymers
will have polymer chains containing, in addition to carbon other
elements, and particularly at least one of the following elements:
oxygen, nitrogen, silicon, phosphorus and sulphur present in at least
two different locations in the said chain The expression " polymer "
as used herein refers generically to homopolymers as well as
copolymers.
Unsaturated polymeric products which may be epoxidized according to
the present invention include the unsaturated allkvd resins, i e.
reaction products of polybasic acids or anhydrids and polyhydric
alcohols, both mod 1fled and unmodified In this case, the main carbon

chain will contain a plurality of -COlinkages, and the unsaturated
linkages to be epoxidized may be contained in the acid and/ or alcohol
portion of the molecule and/or in the modifier portion of the
molecule.
A preferred group of such unsaturated alkyd resins are those obtained
by using unsaturated polybasic acids or anhydrides.
Examples of these unsaturated acids are maleic acid, aconitic acid,
2-butenedioic acid, 4-cyclohexene-1, 2-dicarboxylic acid,
endomethylene 3,6-tetra-hydrophthalic acid,
3-acetoxy-4-cyclohexene-1,2-dicarboxylic acid,
3-heiyl-4-cyclohexene-1, 2-dicarboxylic acid, 4,5-dinethyl-4
cyclohexene-1,2-dicarboxylic acid, 1,4-cyclohexadiene-1,2-dicarboxylic
acid, 6-ethyl-1,4cyclohexadiene-1,2-dicarboxylic acid,
3-butyl1,4-cyclohexadiene-1,2-dicarboxylic acid,
3,6dimethyl-1,4-cyclohexadiene-1,2 dicarboxylic acid, 3 methyl 3,5
cyclohexadiene 1,2 dicarboxylic acid,
1,2-dimethyl-3,5-cyclohexadiene-12 dicarbcjvylic acid, 3 -ct 1
ecenylsuccinic acid, eicosenyl-succinic acid, hexadeca 65
dienylsuccinic acid, octadecadienylsuccinic acid, dimerized linoleic
acid, 8,10-eicosodi neioic acid, 8,14-eicosadienedioic acid, and
8,12cctaclecdenediscic uacid.
Preferred unsaturated polycarboxylic acids 70 to be used in preparing
the above-noted alkyd resins comprise the mono and rfv Ptnazally
unsaturated aliphatic dicarboxylic acids containing not more than 25
carbon atoms in the molecule and the mono and poly-ethylen c 75 allv
unsaturated cycloaliphatic dicarboxny'ic acids containing not more
than 15 carbon atoms in the molecule Of snecial interest are the
alkendioic acids, alkadienedioic acids containing from 4 to 12 carbon
carbon atoms in 80 the molecule.
The polyhydric alcohols to be reacted with the above-noted unsaturated
Dolycarboxylic acid may be any di-, tri or higher polyhydric alcohol
Examples of such alcohols are ethylene 85 glycol, diethylene glycol,
triethylene glycol, 1,5 pentanediol, 1,6 hexanediol, 3
ethylhexanediol-1,3, glycerol allyl ether, glycerol phenyl ether,
butanediol-1,4, thiodipronanol, sulphonyl-dinropanol, glycerol
mnonoacetate, 90 2,5-dimethyl-2,6-hentanediol, glycerol, hexanetriol,
pentaerythritol, mannitol, methyltripentaerythritol, polyallyl
alcohol, polyvinyl alcohol, 3,5-dithfiiooctanetriol and the polyols 95
formed by the condensation of bis-phenols with epichlorohydrin
Particularly preferred alcohols comprise the aliphatic and
cycloaliphatic dihydric alcohols containing not more than 10 carbon
atoms in the molecule and 100 especially the alkanediols and
cycloalkanediols containing no more than 8 carbon atoms in the
molecule.

Another preferred group of unsaturated alkyd resins are those obtained
by reacting an 105 unsaturated polyhydric alcohol with a
polvcarboxylic acid or anhydride Examples of such unsaturated
polyhydric alcohols are:
2-buteme iic 1-1 42-(hyd'r=-lme;hv l) lnrtopen3-ol,
2-(hydroxymethyl)-1-buten-3-ol, 2-( 1 110 hydroxyethyl)-1-buten-3-ol,
1-butene-3,4-diol, 1-penten-3,5 diol, 1 pentene 3,4 diol, 2
methyl-l-butene-3,4-diol, 1,5-hexadiene-3,4diol, 2-(hydroxymethyl)-2
butene 4 ol, 2 methyl-2-pentene-1,4-diol, 2,3 dimethyl 2 115 butene-1
A-diol, 2-pentene-1,5-diol, 3-hexene2,6-diol, 2,5 dimethyl 3 hexene
2,5-diol, 1 hexene 5,6 diol, 1-heptene 4,6-7-triol, 2,6 dimethyl 6
octene 2,3,8 triol, 2,6 dimethyl 7 octene 2,3,6 triol and 120
cyclohexenediol-2,5 The most preferred unsaturated colyh'iiric
alcohols are the aliphatic and cycloaliphatic ethyleneically
unsaturated di-, tri and higher polyhydric alcohols containing not
more than 18 carbon 125 atoms in the molecule, and more preferably the
open-chain aliphatic ethylenically unsaturated di and trihydric
alcohols containing not more 786,116 utilized in amounts varying from
1 % to 90 % by weight of the alkyd resin.
The water formed during the reaction is preferably removed during the
course of the reaction substantially as fast at is is formed 70
therein Care should be taken during the reaction to avoid converting
the resins to a step beyond that of being fusible This may occur if
the reaction mixture is overheated or heated too long Ordinarily the
heating is continued 75 until the viscosity of the reaction mixture
has reached the desired value and the acid number ,as been reduced to
a value between about 3 and 30.
Thie preparation of two examples of the 80 above-described unsaturated
alkyd resins is given below.
POLYESTER A About 560 parts of dimerized linoleic acid was mixed with
74 parts of ethylene glycol and} 5 1 part of p-toluene sulphonic acid
and the mixture heated up to 1700 C and then held in the range of 170
C to 2500 C until the reaction was complete A slow stream of carbon
dioxide was sent through the charge to 90 eliminate the air and carry
away the water of esterification The excess glycol was then removed
under reduced pressure The resulting product was a brown solid alkyd
resin having acid No 9 95 POLYESTER B About 146 parts of adipic acid
and 113 parts of 2-butenediol-1,4 were mixed together and the mixture
heated to 200 C and held at that temperature until the reaction is
complete A 100) slow stream of carbon dioxide was sent through the
charge to elminate the air and carry away the water of esterification
The excess butenediol-1,4 was then removed under reduced pressure The
resulting product was a brown solid 1 i 5 resin.
Another group of unsaturated polymeric products, related to the

above-described unsaturated alkyd resins, which may be epoxidized
according to the process of the present l 10 invention include the
polyesters obtained by polymerizing hydroxy substituted acids.
Hydroxy-substituted acids that may be used in preparing these
polyesters include, among others, 4-hydroxy-2-butenoic acid, 5-hydroxy
115 3-heptenoic acid and 4,6-dihydroxy-3dodecenoic acid Particularly
preferred members of this group comprise the hvdroxy-substituted
alkenoic acids containing not more than 10 carbon atoms in the
molecule 120 Another group of unsaturated polymeric products which may
be epoxidized according to the present invention include the
unsaturated polyamides, i e reaction products of polybasic acids and
polyamines 125 A preferred group of such unsaturated polyamides are
those obtained by reaction of unsaturated polybasic acids with
polyamines.
There polybasic acids are exemplified by the than 12 carbon atoms in
the molecule Coming under special consideration are the alkenediols
and the alkenetriols containing up to 8 carbon atoms in the molecule.
The polybasic acids and anhydrides to be reacted with the
above-described unsaturated polyhydric alcohols may be any di-, tri or
higher polycarboxylic acid or anhydride thereof Examples of such
polybasic acids are: malonic, succinic, glutaric, suberic, citric,
cyclohexanedicarboxylic, phthalic, isophthalic, terephthalic,
1,8-naphthalenic, adipic, sebacic, azelaic, pimelic, chlorosuccinic,
dichlorophthia lic, tetrachloro phthalic, hexachloro endomethylene
tetrahydro phthalic acid, benzophenone-2,4 '-dicarboxylic acid,
thiodipropionic acid, sulphonyldipropionic acid, oxydipropionic acid,
4,6-dithiododecanedioic acid, 8,10-dioxadodecanedcriic acid dir
rboxydiberzvlbenzene, di(carboxyphenylethyl) isopropylbenzene, and
their mixtures.
Other alkyd resins that may be used in the preparation of the novel
epoxidized products are those obtained by employing an unsaturated
polycarboxylic acid or anhydride as described above with an
unsaturated polyhydric alcohol described above, or by reacting a
mixture of saturated and unsaturated polycarboxylic acids or
anhydrides with a saturated or unsaturated polyhydric alcohol, or
alternatively by reacting a saturated or unsaturated polycarboxylic
acid or anhydride with a mixture of saturated and tnsaturated
polyhydric alcohols.
If desired, the above allvd resins may be modified Examples of the
modifiers which may be used are propanol, butanol, allyl alcohol,
tertiary butanol, hexanol, octanol, dodecanol, dodecenol,
cyclohexenol, methyl cyclohexanol, and monocarboxylic acids, such as
lactic acid, benzoic acid, chlorobenzoic acid, salicylic acid,
tert-butylbenzoic acid, acrylic acid, cyclohexanecarboxylic acid,

vinylacetic acid, allylacetic acid, ethyl propionic acid, vinyl
acrylic acid, sorbic acid, butyric acid, stearic acid, palmitic acid,
glycolic acid, chloroacetic acid and chloropropionic acid.
Other modified unsaturated alkyd resins that may be used are those
obtained by polymerizing the above-noted unsaturated alkyd resins with
polyunsaturated monomers, such as pentadiones and butadienes.
The unsaturated alkyd resins described above may be prepared by any
suitable process.
They are preferably prepared by merely heating the desired polybasic
acid, or anhydride.
polyhydric alcohol and modifying agent (if desired) preferably in an
inert atmosphere, if desired, in the presence of a catalyst such as
p-toluenesuiphlonic acid.
The proportions of reactants to be used in the alkyd formation will
vary depending upon the properties desired in the finished product.
Preferably one reacts the acid with an excess up to 50 % excess of the
alcohol In modifying 6,5 agents are employed, they are preferably
786,116 786,116 same acids listed above for use in preparing
unsaturated alkyd resins.
The polyamines to be reacted with the above-noted unsaturated
polycarboxylic acids may be any di-, tri or higher polyamine.
Examples of such amines are: 1,4-butanediamine, 1,5-pentanediamine,
1,6-hex anediamine, 1,4-cyclohexanediamine, 1,3-benzenediamine,
1,2,3-benzenetriamine, 3,31-diphenyldiamine, 3,4-diphenyldiamine,
diethylenetriamine, 2,6diaminopyridine, 2,5-diamino-1,3,4-thiadiazole,
2.5-diaminopyrrole, 3-chloro-1,5-pentanedimin and 4 -v
kro-octanediaarnc Particularly preferred polyamines of this type to be
used are the aliphatic, cycloaliphatic and aromatic diamines
containing not more than 12 carbon atoms, particularly not more than
10 carbon atoms in the molecule.
Other preferred unsaturated polyamides to be used in preraring the
novel eto'tid; 7 ed nolymeric products are those obtained bv reacting
an unsaturated polyamrine vith a rclybasic acd as descr-ibed ab Pve
Examniles er these unsaturated amines include, among others:
2-pentene-1,5-diamine, 3-pentene-1,5-diamire.
2-hexene-1,6 diamine, 3 cyclohexene 1,4 diamine, 3-chloro-4-octene 1,8
diamine, 3 hexene-1,6-diamine, 3 dodecene 1 A 4,10 triamine and
2-methoxy-4-octene-1,8-diamine.
The preferred unsaturated pzlyawing Lo be used for this purpose
include the aliphadic and cyclo-aliphatic ethylenically unsaturated
diand triamines containing not more than 18 carbon atoms in the
molecule, and more particuiarly tlv opzn-zhaa nt> e l-ecliy
unsaturated diamines having the amine groups on terminal carbon atoms
and containing not more than 12 carbon atoms in the molecule.

Other unsaturated polyamides that may hused in the preparation of the
novel epoxidized products but are less preherrd than the
abovedescribed polyamides are those obtained by employing an
unsaturated polycarboxylic acid with an unsaturated polyamine, or by
reacting a mixture of saturated and unsaturated polycarboxylic acids
with a Saturated or Unsaturated polyamine, or alternatively by
reacting a saturated or unsaturated polycarboxylic acid wvith a
mixture of saturated and unsaturated polyamines.
Tle unsaturated polyamides described above may be prepared by any
suitable method They are preferably prepared by merely reacting the
polyamine or pol-ybasic acid together at reaction temperatures varying
from about 100 ' C to 300 C and removing the vwate' forned during the
reaction substantially as fast as it appears therin Derivatives of
polybasic acids, such as their lower alkyl esters and acid chlorides
may be used in this reaction If desired, the reaction may be carried
out in the presence of a catalyst Preferably one reactr the acid with
an excess to 30 % excess or the -olyamine.
It is preferable to block off any remaining acid or armine groups
before proceeding wvil the epoxidation step By fumher reaction on the
polyamide with acetic anht rilde or 1- eve the reactive amine gou Ps
will bcetverted t O amides Ethylene oxidie, all, Ilyrcidy e? and other
epoxides can be used to convert tk es.
polyamides with reactive carbuvv 4 c groups,il hydroxy esters or
reaction with mononia r-iiite will form the terminal amide linkage.
The preparation of one of the abovedescribed unsaturated polyamides is
given below.
POLIAMIDE A 11.6 parts of fumaric acid was heated with 18 narts of
dcametlhvlene diamine and 30 80 parts of phenol for 30 minutes at
150-160 ' C an t 'or O minnutes at 150-160 ' C.
un-er 1-2 mrni absolute pressure to remove tile mnc- A
jiight-colouread 'esin was obtained which melts at 45-50 C 85 Another
group of polyamides that may be opoxidized according to the process of
the present invention are those obtained by polymerization of
unsaturated aminocarboxylic acids Amino-substituted acids that may be
90 used in Preparing thes polyamides include 4amino-2-butenoic acid,
4-amino-5-octenoic acid and 4,6-diamino-3-dodecanoic acid Particularly
preferred inembers o' t^s gruw con Mpr 1: e the am-ino-substitute ail
Toc acids oalaing 95 not more than 12 carbon atolm in tll tuci Ccule
The polyamides riay ab prepared frenm these arnino-substitute-d acids
in the same manner as described above ior the preparation of the
unsaturated polyamides 100 Also coming within the scope of tihe
present invention are the unsaturated nolyester-polyarudes such as
those obtained by reacting polybasic acids w-,-ith-amino substituted
alcohois In this case, he unsaturated linmage may be pre 105 sent in

Lhe acid portion and/or the amino alcohol portion of the molecule
Suitable unsaturated polybaric acids are exemnlified by those
described above for preparing the unsaturated polyesters and the
amino-alcohols 110 saturated and unsaturated, are exemplified by the
following 3-amhnobutanol, 4-aminohexanol.
3-aminooctanoi, 3,5-diaminododecanol, 4aruno-2-burenol,
5-ajr-nino-3-octenoi and 4amino-5,7-dodecadieno'i These polyester-polv
115 amides may be prepared under the conditions described hereinabove
for preparing the polyamides.
Still another group of unsaturated polymeric products that may bc
opoxidized according to 120 the present invention include the
unsaturated polycarbamates, i e polymers having recurring units of the
following structure:O H H O -OR-O G-N-R,-N 9 c-O-Rwhere R or R, are
bivalent organic radicals 125 either or both of which contain
unsaturated linkages These polycarbamates may be prepared by reacting
polyhydric alcohols with 786,116 polyisocyanates or by reacting
polyamines with chloroformates, either or both of such reactants
containing the necessary unsaturated linkages.
A preferred group of these unsaturated polycarbamates are those
obtained by reacting polyamines with chloroformates of unsaturated
polyhydric alcohols in the presence of material capable of absorbing
the released hydrogen chloride The polyamines used in the preparation
of these unsaturated carbamates may be any of those described
hereinabove for the preparation of the polyamides and are preferably
the aliphatic and cyclo-aliphatic saturated polyamines containing not
more than 18 carbon atoms, such as 1,4-hexanediamine,
1,8-octanediamine, 1,10-decanediamine, 1,18-octadecanediamine,
1,4-cyclohexanediamine and 1,3,5hexanetriamine.
The chloroformates of the unsaturated polyhydric alcohols are
preferably those of the following formula:
0 O Cl-C-R-O-O-C-C 1 wherein R is derived from an unsaturated
polyhydric alcohol by removing the hydroxyl groups Examples of such
unsaturated polyhydric alcohols are:
2-butene-diol-l,4,2(hydroxymethyl)-l-propen-3-ol, 2
(hydroxymethyl)-1-buten-3-ol, 1,5-hexadiene-3,4-diol,
2-butene-1,3-diol, 2,5-dimethyl-3-hexen-2,5diol,
cyclohexenediol-2,5,3-chloro-cyclohexenediol-2,5 and
3-methyl-cyclohexenediol-2,5.
Preferred unsaturated polyhydric alcohols used for this purpose
include the aliphatic ethylenicaily unsaturated dihydric alcohols
containing not more than 12 carbon atoms in the molecule.
These unsaturated polycarbainates are preferably prepared by a method
described in U.K Patent Specification No 701,238, wherein a solution
of the chloroformate in a waterimmiscible organic solvent is dispersed

in an aqueous diamine solution in the presence of a water-miscible
organic solvent, and the reaction between the bis-chloroformate and
the polyamine is caused to take place to produce the 45 unsaturated
polycarbamate.
The preparation of an unsaturated polycarbamate by the above method is
illustrated below.
POLYCARBAMATE A 50 A solution of 17 6 parts by weight of
tetramethylene diamine in 500 parts by weight of water was neutralized
to ai pit of 3-5 To his solution were added 450 parts by weight of
water and 673 parts by weight of acetone and 55 the solution cooled to
0 to 20 C A solution of 42 parts by weight 2-butenediol-1,4 bis
chloroformate in 1082 parts by weight of toluene was added to the
cooled diamine solution and the mixture stirred vigorously to form a
dispersion 60 While continuing the stirring, there was added 250 parts
by weight of a 3 24 normal aqueous Na OH solution and the stirring
continued for an additional 10 minutes The dispersion is permitted to
stand to allow the polymer to 65 separate, the polycarbamate is
filtered off, purified by slurrying alternately with water and acetone
and dried at 100-110 C in vacuum.
The preparation of an unsaturated polycar 70 bamnate by reaction of an
unsaturated alcohol with a diisocyanate is illustrated below.
POLYCARBAMATE B 880 parts of 2-butenediol-1,4 is combined with 1620
parts of benzene diisocyanate and 75 1000 parts of dioxane and the
mixture heated to 1000 C Dioxane was removed and the product
concentrated to form a resinous polycarbamate.
Another group of unsaturated polymeric 80 products that may be
epoxidized according to the process of the present invention are the
unsaturated polymers containing sulphur linkages A preferred group of
these polymers include those obtained by reacting unsaturated 85
organic diahalides and sodium sulphide, a reaction which may be
represented thus: CI-R-CG +Na S->-S-R-S-R-S-R +Na Cl, to form a high
molecular weight polymer containing a plurality of sulphide linkages.
Unsaturated organic halides used for this purpose are exemplified by
1,4-dichloro-2-butene, 1,5-dichloro-3-pentene, 1,6-dichloro-4-hexene,
dichloroallyl ether, 1,5-pentanediol dichloroacrylate, 1,4-butenediol
dichloropropionate and 1,3,4-trichlorocyclohexene-2 Other dihalides,
such as the saturated dihalides and aromatic dihalides may also be
employed in combination with the above-described unsaturated dihaldes.
Examples of these other dihalides are: ethylene dichloride, propylene
dichloride, dichloroethyl ether, triglycoldichloride, glycerol
dichlorohydrin, dichloroethyl formal and dichloropropionic acid.
Other sulphur-containing polymers may be o Lc-ined by reacting
unsaturated polymercaptans, such as the alkenepolythiols as
2buteneditbiol, 41 octenedithiol, 4,6-octadienedithiol,

5-dodecenedithiol, and 2-cyclohexene1,4-dithiol and oxy-containing
polymercaptans as oxydibutenethiol, oxydihexenethiol and
oxydidodecenethiol, with organic dihalides, polycarboxylic acid
halides and polycarboxylic acids.
Other sulphur-containing polymers to be used in the process of the
present invention include sulphur-containing polyesters, polyamides or
polyester-polyamides wherein one or more of the reactants contain
sulphur-linkages Sulphur-containing polycarboxylic acids that may be
used in preparing such polymers include, among others: 3,3
'-thiodipropionic acid, 4,41-thiodibutyric acid,
4,41sulphonyl-dibutyric acid, 4,4-thiodipentenoic acid and
7,8-dithia-1,10-decanedioic acid.
Sulphur-containing polyhydric alcohols that may be used in preparing
these polymers are:
bis( 2-methyl-4-hydroxybutyl) sulphide, bis( 2S ethyl-5-hydroxyhexyl)
sulphide, bis( 2-hydroxyethyl) sulphide, bis( 2-ethyl 4-hydroxyoctyl)
sulphide, 5,7-dhydroxy-4-thiadecan-1,o I,
7hydroxy-2,4-dithiadodecan-1-ol Sulphur-containing polyamines that may
be used in preparing these polymers are: 4,6-dithiaoctane1,8-diamine,
6-thiaheptane-1,7-ihamine and 5-thia-8-dodecenediamine-1,10 These
polymers may be prepared by the methods described above for the
preparation of the other polyesters, polyamides and
polyamide-polyesters.
The preparation of an unsaturated polymer containing sulphur linkages
is illustrated below.
UNSATURATED SULPHUP-CONTAINING POLYMER About 267 parts of 4,4
'-thiodibutanol and 116 parts of maleic acid and 1 part of
ptoluenesulphonic acid were mixed together and the mixture heated to
about 1800 C and held at that temperature until the acid number had
been reduced below 30 A slow stream of carbon dioxide was sent through
the charge to elminate the air and carry away the water of
esterification The excess 4,4 '-thiodibutanol was removed under
reduced pressure The resulting product was a light yellow resin.
Preferred silicon-containing polymers are those obtained by reacting
silicon-containing polcarboxylic acids, such as
dicarboxyphenyldimethylsilane (HOOCC GH 4)2 (Si(CHE)),, with
unsaturated polyhydric alcohols, or unsaturated polyamines, such as
2-butenediol-1,4, 2-cyclo hexenediol-1,4,1,6-hexenediamine,
2-hydroxymethy I-l-propen-3-ol, and other unsaturated alcohols and
amines as listed above The preparation of this type ofunsaturated
siliconcontaining polymer is illustrated below.
UNSATURATED SILICON-CONTAINING POLYMER 300 parts of
dicarboxyphenyldimethylsilane and 176 parts of 2-butene-diol-1,4 were
mixed and heated at 1350 C for 4 hours and at 160 C for 2 hours The

resulting polyester was a soft thermoplastic solid.
Other preferred silicon-containing polymers are those obtained by
reacting an unsaturated polybasic acid -with a silane-alcohol reaction
product as described in U S Patent Specification No 2,628,215
Unsaturated polycarboxylic acids that may be used for this pur-pose
are: maleic acid, fumaric acid, aconitic acid, 2-butenedioic acid, and
others described hereinabove A preparation of unsaturated
silicon-containing polymers of this type is illustrated in Examples 2
and 3 of the above-noted U.S Patent Specification No 2,628,215.
Preferred phosphorus-containing polymers are those obtained by
reacting a phosphoruscontaining polybasic acid, such as phosphorus OH
O OH / 1 i/ acids R-P, phosphonic acids R-P OH OH OH and phosphorous
acid P-OH wherein R is an OH oroganic radical, with unsaturated
polyalcohols or poly-amines Examples of such polybasic acids are:
benzenephosphonic acid, benzenethiophosphonic acid,
cyclohexanephosphonic acid, propanephosphonic acid,
2,3,4trimethylpentanephosphonic acid, and 2phenylethanephosphonic acid
The unsaturated alcohols and amines used in preparing these polymers
may be any of those described above.
These polymers may be prepared by the abovedescribed methods of
preparing polyesters.
The preparation of an unsaturated polymer containing phosphorus is
illustrated below.
UNTSATURATED PHOSPHORUS-CONTAINING 80 POLYMER 12.7 parts of
benzenephosphonic acid and about 20 parts of 2-cyclo-hexenediol-1,4
were slowly heated to 200 C and held there for 3 hours A slow stream
of pure nitrogen was 85 used to sweep out water of reaction At the end
of the reaction period, the product was distilled under vacuum to
remove all volatiles.
On cooling a hard clear paic coloured polyester was obtained having a
Durrans' melting ft) point over 100 C and being soluble in a mixture
of toluene and tetrahydrofuran.
Other preferred phosphorus-containing polymers are those obtained by
reacting an unsaturated phosphorus-containing acid, such as 3 95
octenephosphonic acid, 3-butenephosphorus acid and
3-cyclohexenephosphonic acid, with polyhydric alcohols as described
above.
The unsaturated polymers used in the preparation of the novel
epoxidized products pre 100 ferably have molecular weights between
about 2000 and 5000 but those between 5000 to 50000 _ ave also proved
ve-y valuable.
The epoxidation of the unsaturated polymeric products is accomplished
by treating the 105 polymers with an epoxidizing agent Organic
peracids, such as performic, peracetic, perbenzoic acid and

monoperphthalic acid, are preferred agents for this reaction.
The amount of the epoxidizing agent 110 employed will vary over a
considerable range depending on the type of product desired In
general, at least one mole of the oxidizing agent, such as perbenzoic
acid should be employed, for every unsaturated group to be 115
epoxidized In some cases, it is rather difficult to effect the
epoxidation of all of the unsaturated bonds and if a completely
epoxidized product is required, additional 786,116 786,116 7
epoxidizing agent and/or longer reaction period may be required.
It is preferred to carry out the epoxidation reaction in a suitable
mutual solvent for the reactants and product Chloroform is an
especially useful solvent for the purpose, but other materials, such
as ethyl ether, dichloromethane, benzene and ethyl acetate may used.
The temperature employed during the epoxidation may vary over a
considerable range depending upon the type of reactants and oxidizing
agents selected It is generally desirable to maintain the temperature
between -20 to about 80 C Atmospheric, superatmospheric, or
sub-atmospheric pressures may be employed as desired.
The epoxidized polymeric products of the present invention will vary
in physical form depending upon the nature of the basic polymeric
material In most cases, the resulting product will be viscous liquids
to semi-solids.
The products will posses a plurality of active epoxy groups and in
some cases may contain unreacted unsaturated linkages In this latter
case, the products may be further reacted through the epoxy groups
and/or unsaturated linkages.
The presence of the plurality of epoxy groups along the chain in
combination with the presence of the other features, such as the
presence of oxygen, sulphur, nitrogen, phosphorus or silicon endows
the products with many new and unobvious properties The new products,
for example, have improved compatibility with oils and resins are are
more easily cured through the epoxy groups The products of the present
invention are thus ideally suited for preparing improved surface
coating compositions of the air-drying or baking type In utilizing the
products in this application, it is generally desirable to combine the
epoxidized polymeric product with the epoxy curing agent and, if
desired, solvents or other film-forming materials, and then applying
the resulting mixture to the surface to be coated The coatings
prepared in this manner may be allowed to set to a hard finish or heat
may be applied to hasten the cure.
The products of the present invention also have good adhesive
properties and are of great value in the preparation of adhesive and
impregnating compositions In utilizing the products for these
applications, it is generally desirable to combine the epoxidized

polymeric product with a suitable solvent or diluent, such as benzene,
toluene, propionitrile, crotonitrile and benzonitrile and a curing
agent, so as to form a spreadable fluid and homogeneous mixture, and
then applying the resulting mixture to the desired surface Adhesive
compositions prepared in this manner are suitable for uniting various
surfaces, such as, for example, wood to wood, wood to metal, metal to
metal, rubber to metal or any combination thereof After the
application has been made, the adhesive may be allowed to set at room
temperature or heat may be applied to hasten the cure.
The products of the present invention also find use in the preparation
of pottings and they may be cured to form hard castings These 7 L 1
products are generally prepared by mixing the epoxidized polymeric
products with the curing agent and then adding this mixture to the
desired mould or casting containing electrical wires or apparatus and
then allowing the mis 75 ture to stand After a short period, the
mixture sets up to form the desired hard flexible casting Heat may
also be applied.
The curing of the epoxidized products of the present invention in the
above-noted appli g;o cations may be accomplished by the addition of
epoxy curing agents These agents include Friedel-Crafts catalysts,
such as aluminium chloride, aluminium bromide, zinc chloride, boron
trifluoride, silicon tetrachloride, stannic 85 chloride, stannic
bromide, titanium tetrachloride; amines, such as ethylene diamine,
2,4,6-tri(dimethylaminomethyl)phenol, amine aldehyde resins, amide
aldehyde resins, dialdehydes, polybasic acids such as organic and 90
mineral acids, and their anhydrides and polymercaptans These agents
are preferably employed in amounts varying from about 01 % to 5 % by
weight of the material being polymerized In many cases, the
polymerization 95 may be effected by merely adding the agents, but in
some cases it may be necessary to heat to a temperature varying
preferably from about 300 C to 800 C.
The epoxidized products of the present in 100 vention may be used in
the above application by themselves or may be used in combination with
other epoxy-containing materials Such epoxy materials include
epichlorohydrin, glycidol, butadiene dioxide, diglycidyl ether, 105
allyl glycidyl ether, glycidyl ethers of polyhydric phenols such as
those obtained by react.
ing epichlorohdyrin with polyhydric phenols as bisphenol-A, and
resorcinol, glycidyl ethers of polyhydric alcohols, such as those
obtained 110 by reacting epichlorohydrin with glycerol, sorbitol and
hexanetriol, and dehydrochlorinating the resulting product, and
glycidyl esters, such as diglycidyl phthalate, diglycidyl adipate and
diglycidyl succinate These dissimilar materials 115 are preferably
employed in amounts varying from about 2 % to 90 % by weight of the

material being polymerized.
The epoxidized products of the present invention also find application
as intermediates 120 in the preparation of other valuable chemical
products As they possess epoxy groups, they may be hydrated to form
glycols, or may be reacted with monofunctional agents, such as
monocarboxylic acids to produce derivatives 125 which are valuable as
plasticizers, lubricating oils and drying oils Such acids may be
exemplified by acetic, butyric, caproic capric, stearic, palmitic,
lauric, myristic, benzoic acid, isopropylbenzoic acid, toluic acid,
acids derived 130 786,116 786,116 from drying and semi-drying oils as
acids derived from linseed, soyabean, perilla, oiticica, tung, walnut,
dehydrated castor oil, as well as resin acids, such as abietic acid.
To illustrate the manner in which 'he present invention may be carried
out, the following examples are given Unless otherwise specified,
parts described in the examples are parts by weight EXAMPLE i parts of
Polyester B as described above were added to 100 parts of chloroform
500 parts of 10 % perbenzoic acid solution were added to the mixture
and the mixture and the mixture allowed to stand at room temperature.
The product was then washed with dilute sodium carbonate solution and
filtered The chloroform was then stripped off and the product
concentrated to a viscous liquid having a high epoxy value.
A xylene solution of the above epoxidized product ( 40 %t O solids)
containing S parts of diethylene triamine was spread on steel panels
and heated to 60 C for 30 minutes The resulting film is very hard and
mar resistant.
About 100 parts of the above-described epoxidized alkyd resin were
combined with 10 parts of phthalic anhydride and 5 parts of ethylene
diamine and the mixture heated to 600 C The resulting mixture sets up
in a short time to hard clear casting.
The above-described epoxidized alkyd resin also reacts with 25 %O by
weight of soyabean oil fatty acids to form a thick oil which dries in
the presence of O 5 % cobalt drier to form hard solvent resistant
films.
EXAMPLE II
360 parts of the above described Polyester A were dissolved in 300
parts of benzene, 16 parts of sodium acetate added and then 208 parts
of a 27 % peracetic acid solution slowly added The mixture was allowed
to viarn to 23 C and then let stand overnight The product was water
washed and the volatile components were stripped off at 1000 C ( 1 mm)
to yield a viscous liquid epoxidized product having a molecular weight
of about 21000, Iodine No 34 and an epoxy value of 0 092 eq/100 g.
A xylene solution of the above epoxidized product containing 5 parts
of 2,4,6-tri(dimethylaminomethyl)phenol was spread on steel panels and
heated to 70 ' C The resulting films were very hard and mar resistant.

About 50 parts of the above-described epoxidized product was combined
with 50 parts of 2,2-bis( 2,3-epoxypropoxyphenyl) propane and 5 parts
of 2,4,6-trildimethylaminometihyl) phenol and the mixture heated to
600 C In a short period the mixture set up to a hard flexible casting.
EXAMPLE III
700 parts of the above-described Polyamide A were combined with 2000
parts of chloroform 700 parts of a 27 % 1 o peracetic acid solution
were then added to the mixture and tu mixture allowed to stand at 0 to
10 C for 10 hours The product was then washed with ice water, cold 20
% sodium hydroxide and more ice water Chloroform was then taken off to
form a solid resin having a high epoxy value.
A xylene solution of the above-described epoxidized polyamide
containing S parts of diethylene triamine was spread on steel panels
and heated to 60 C for 30 minutes The resulting film was very hard and
mar resistant.
parts of the above-described epoxidized polyamide vias then mixed with
60 parts of 2,2-bis( 2,3-epoxypropoxyphenyi) propane and the mixture
diluted with acetonitrile to form a spreadable paste This mixture
acted as an adhesive to bond steel and aluminium surfaces EXAMPLE IV
700 parts of the above-described Polycarbamate A were combined with
1000 parts of 85 chloroform 700 parts of a 27 % 3 i O peracetic acid
solution were then added to the mixture and the mixture allowed to
stand at O C to 10 C overnight The products was then washed with ice
water, cold 20 % O sodium hydroxide 90 and then more ice water
Chloroform was then taken oil and the product concentrated to form a
resinous product.
parts of the above-described epoxidized polycarbanmate was mixed with
60 parts of 95 2,2-bis( 2,3-epoxypropoxyphenyl) propane and the
mixture diluted with acetonitrile to form a spreadable paste This
mixture acted as an adhesive to bond steel and aluminium surfaces.
A xylene solution of the above-described 100 epoxidized polycarbamate
containing 5 parts of diethylene triamine was spread on steel panels
and heated to 60 ' C for 30 minutes The resulting film had good
adhesion and was hard and flexible 105 Epoxidized products having
related properties may be obtained by replacing polycarbamate in the
above-described procedure with equivalent amounts of Polycarbamate B.
EXAMPLE V
500 parts of a polyester of 4,4 '-thiodibutanol and maleic acid
prepared as shown above was combined with 200 parts of benzene and 8
parts of sodium acetate and the mixture cooled to 6 to 9 ' C 400 parts
of 40 % O peracetic acid solution were then added thereto over 30
minutes The mixture was allowed to warm to 20 ' C over a period of 4
hours and washed with water The mixture was then distilled to remove
the benzene The resulting product was a light pale coloured resin

having a high epoxy value and having some of the thio-linkages
converted to sulphone groups.
A xylene solution of the above epoxidized product was combined with 5
parts of diethylene triamine and the mixture spread out at least one
of the following elements: oxygen, 65 nitrogen, silicon, phosphorus
and sulphur, present in at least two different locations in the said
chain, is reacted with an epaxidizing agent in an amount sufficient to
convert at least twi of the unsaturated carbon-to-carbon linkages 70
per molecule to epoxy groups.
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* GB786117 (A)
Description: GB786117 (A) ? 1957-11-13
Improved process and nutrient medium for producing penicillin
Date of Application and filing Complete Specification: Sept 1, 1955.
786,117 No 25176/55.
0 q a 01 Application made in India on Sept 14, 1954.
Complete Specification Published: Nov 13, 1957.

Index at acceptance:-Class 2 ( 3), AA( 1 B:2 C 1).
International Classification:-C 12 d.
Improved Process and Nutrient Medium for Producing Penicillin We,
STANDARD PHARMACEUTICAL WORKS LIMITED, an Indian Company, situated at
67, Dr Suresh Sarkar Road, Calcutta-14, West Bengal, India, do hereby
declare the invention, for which we pray that a patent may be granted
to us, and the method by which it is to be performed, to be
particularly described in and by the following statement:-
This invention relates to a new and useful process for the production
of penicillin, and to a nutrient medium for said process.
The earliest surface culture method in Czapek-Dox glucose medium for
the production of penicillin was abandoned and the submerged culture
method in liquid medium is now universally practised This consists of
growing any penicillin-producing strain of penicillium in a liquid
medium consisting principally of corn-steep liquor, glucose and
lactose Another liquid medium used in industry, though very sparingly,
consists principally of hydrolysed casein or peptone, wheat steep
liquor together with glucose as a readily assimilable sugar and
lactose as a slowly assimilable sugar But the use of a medium
consisting of 3 % to 6 % corn-steep liquor with lactose has been
favoured by large numbers of industrial concerns This medium is
especially advantageous to those industrial concerns which are
situated in countries where corn-steep liquor is available at a cheap
price and where the quality of corn-steep liquor suitable for
production of penicillin can be ascertained in advance, as all batches
of corn-steep liquor, even when manufactured by the same concern, do
not give the same yield of penicillin.
As corn-steep liquor is not produced in many countries, the
practicability of commercial production of penicillin in corn-steep
liquor medium is possible only by importing corn-steep liquor from
abroad The medium consisting of corn-steep liquor has the disadvantage
of excessive foam formation, and tends to increase the p H of the
medium durlPrice 3/6 l ing fermentation to above 8, when it interferes
with obtaining higher penicillin yield.
Accordingly the present invention is directed mainly to solving the
problem of replacing the use of corn-steep liquor alto 50 gether by
the use of an equally efficient but cheaper material After a large
number of experiments, it has been found by us that high yields of
penicillin can be obtained in submerged culture with adequate aeration
55 and agitation of any penicillin-producing strain of penicillium by
the use of a nutrient medium containing mustard oil cake or sesame oil
cake or groundnut oil cake, either individually or in any combination
of them, 60 maintained at a p H between 6 3 and 7 6 dur.

ing fermentation, the said medium further containing, as a source of
carbon and energy, a disaccharide, such as lactose We have further
discovered that mustard oil cake or 65 sesame oil cake or groundnut
oil cake can also be used in combination with starchbearing or
protein-bearing materials, such as certain other types of vegetable
oil cakes such as soyabean meal, or cotton seed meal 70 It has been
observed that certain constituents of musitard oil cake, sesame oil
cake or groundnut oil cake, not only favour high yield of total
penicillin, but also that the penicillin obtained consists principally
of 75 penicillin ' G '-the most widely used crystalline form of
penicillin With the addition of a precursor, such as phenylacetic acid
or a salt thereof or phenylacetamide, the percentage of penicillin 'G'
yield in our oil cake 80 medium ranges between 85 %-98 % O X This is
of great importance from the point of view of economic production of
penicillin 'G'.
The yield of penicillin in our oil cake medium is further stimulated
by the addition of small 85 quantities of the following salts, viz:
Sodium or Potassium Nitrate, Potassium or Sodium Di-Hydrogen
Phosphate, Magnesium Sulphate, and Calcium Carbonate.
The expression " oil cake " is used herein 90 786,117 to refer to the
solid mass or residue left after extracting most of the oil from
groundnuts or from seeds of cotton, hemp, mustard, flax, sesame,
soyabeans or like materials.
The following are the advantages of our oil cake medium: ( 1) In our
medium only 2 % to 4 %,'O of oil cake is necessary, while in
conventional media the amount of corn-steep liquor necessary is as
high as 6 %.
( 2) The p H of our medium during fermentation is automatically
controlled It does not go above 7 6.
( 3) Very little foam is formed and consequently very little anti-foam
agent is necessary.
( 4) The price of the mustard oil cake or sesame oil cake or groundnut
oil cake is much less than that of corn-steep liquor.
( 5) The yield of penicillin in oil cake medium is as high as 1500
units per c c of medium after 52 to 96 hours of fermentation.
( 6) Yields containing a high percentage of penicillin 'G' are
obtained even without a precursor such as phenyl-acetic acid or a salt
thereof or phenylacetamide, though with the addition of such a
precursor the yield of penicillin 'G' is further enhanced.
According to this invention, a process for producing penicillin
comprises cultivating a penicillin-producing micro-organism such as
Penicillium notatuni or Penicilljiun Chtrvsogenuin under submerged
conditions in contact with an aqueous nutrient medium, characterised
in that the said medium contains mustard oil cake or sesame oil cake

or groundnut oil cake, either individually or in any combination,
maintained at a p H between 6 3 and 7 6 during fermentation and
further contains as a source of carbon and energy, a disaccharide such
as lactose.
The invention further provides a nutrient medium for cultivating a
penicillin-producing micro-organism containing mustard oil cake or
sesame oil cake or groundnut oil cake, either individually or in any
combination, and a disaccharide such as lactose.
The invention further provides penicillin when produced by the process
hereinbefore described.
The nutrient medium may contain, in addition to above oil cakes,
starch-bearing or protein-bearing materials such as other types of oil
cakes, for example, Soyabean meal and Cotton seed meal either
individually or in combination.
It is to be noted that the said oil cakes should be incorporated in an
amount of 2 % to 4 ' by weight of the total nutrient medium For
satisfactory yield, the fermentation is carried on for a period of 52
to 96 hours depending upon the nature of the particular oil cakes
employed It has been found that the growth of penicillin is greatly
enhanced if the p H is maintained within the range of 6 3 to 7 6 For
supplying oxygen, filtered bacteria-free air in adequate quantities
under pressure of 10 to 16 lb per sq in.
may be passed through the medium under mechanical agitation, e g, by
rotating pro 70 pellors within the fermentation vat Practically any
type of mild or stainless steel vat havine aeration and agitation
devices can be used The degrees of aeration and agitation are widely
variable 75 In carrying out this invention, the aqueous nutrient
medium should be sterilised prior to being inoculated with any strain
of penicillin-producing penicillium.
The following is illustrative of possible 80 combinations of the oil
cakes used in our aqueous nutrient medium:(I) Mustard oil cake, or (
2) Sesame oil cake, or ( 3) Groundnut oil cake 85 or ( 4) Mustard oil
cake and Sesame oil cake, or ( 5) Mustard oil cake and Groundnut oil
cake, or ( 6) Sesame oil cake and Groundnut oil 90 cake, or ( 7)
Mustard oil cake and Soyabean meal, or ( 8) Mustard oil cake and
Cotton seed meal, 95 or ( 9) Sesame oil cake and Soyabean meal, or (
10) Sesame oil cake and Cotton seed meal, or ( 11) Groundnut oil cake
and Soyabean meal, 100 or ( 12) Groundnut oil cake and Cotton seed
meal.
In order that the invention can be fully understood, it will now be
described with the help of the following examples It should 105 be
understood that the following detailed examples are not to be
considered restrictive and that variations thereof are within the
broad scope of the invention claimed.

EXAMPLE 1 110
A fermentation nutrient medium of the following composition was
prepared: Mustard oil cake 2 to 4 Sodium Nitrate 0 3 113 Potassium
Di-Hydrogen Phosphate 0 05 Magnesium Sulphate 0 0125 Lactose 3 O
Phenyl Acetic Acid O 2 Calcium Carbonate 55 120 Tap Water to make up
to 100 c c.
litres of the above medium was sterilised at a pressure of 15 lb lsq
in for 30 minutes The medium was then inoculated with 0 5-i litre of
vegetable growth of Peni 125 cillillu 1 im Notatiniii or Penicillium
Chi yvsolenurn and the fermentation was continued at a temperature of
23-C to 27 C for a period of 65 hours under submerged conditions.
During the fermentation the medium main 130 786,117 tained a p H
between 7 and 7 6 with continuous aeration and agitation After
complete fermentation, a sample of the culture filtrate was assayed to
contain 1400 Oxford units per c c.
EXAMPLE 2
A fermentation nutrient medium was prepared, having the same
composition as that of Example 1 except that said 2 % to 4 % of
mustard oil cake was replaced by 2 % to 40 % of sesame oil cake, and 0
2 % phenylacetic acid was replaced by 0 2 %' phenylacetamide.
Sterilisation and inoculation were effected according to the method of
Example 1.
The fermentation was continued at a temperature of 23 o C to 27}C for
a period of 68 hours under submerged conditions During fermentation,
the medium maintained a p H between 7 1 and 7 6 with continuous
aeration and agitation After complete fermentation, a sample of the
culture filtrate was assayed to contain 1450 Oxford units per c c.
EXAMPLE 3
composition as that of Example 1 except that said 2 % to 40/% O of
mustard oil cake was replaced by 20 ' to 4 % of groundnut oil cake
Sterilisation and inoculation were effected according to the method of
Example 1.
The fermentation was continued at a temperature of 230 C to 27 'C for
a period of 63 hours under submerged conditions During fermentation
EXAMPLE 4
composition as that of Example 1 except that said 2 % to 4 ' of
mustard oil cake was replaced by 2 % to 4 % of a mixture of mustard
oil cake and sesame oil cake Sterilisation and inoculation were
effected according to the method of Example 1 The fermentation was

continued at a temperature of 230 C to 27 o C for a period of 72 hours
under submerged conditions During fermentation the medium maintained
a' p H between 7 and 7 6 with continuous aeration and agitation After
complete fermentation, a sample of the culture filtrate was assayed to
contain 1425 Oxford units per c c.
EXAMPLE 5
A fermentation nutrient medium was prepared having the same
composition as that of Example 1 except that said 2 % to 4 % of
mustard oil cake was replaced by 2 % to 4 % of a mixture of mustard
oil cake and groundnut oil cake Sterilisation and inoculation were
effected according to the method of Example 1.
The fermentation was continued at a temperature of 230 C to 270 C for
the medium maintained a 70 p H between 7 2 and 7 6 with continuous
EXAMPLE 6 75
composition as that of Example 1 except that said 2 % to 4 %,0 of
mustard oil cake was replaced by 20 % O to 4 ,' of a mixture of sesame
oil cake and ground 80 nut oil cake Sterilisation and inoculation were
The fermentation was continued at a temperature of 23 CC to 27 'C for
a period of 85 64 hours under submerged conditions During fermentation
culture filtrate 90 was assayed to contain 1430 Oxford units per c c.
EXAMPLE 7
composition as that 95 of Example 1 except that said 2 % to 4 % of
mustard oil cake was replaced by 2 %o to 4 % of a mixture of mustard
oil cake and soyabean meal Sterilisation and inoculation were effected
according to the method of Ex 100 ample 1.
the medium maintained a 105 p H between 7 3 and 7 6 with continuous
culture filtrate was assayed to contain 1390 Oxford units per c c 110
EXAMPLE 8
composition as that of Example 1 except that said 2 % to 4 % O of
mustard oil cake was replaced by 2 % to 4 % 115 of a mixture of
mustard oil cake and cotton seed meal Sterilisation and inoculation
were effected according to the method of Example 1.

The fermentation was continued at a tem 120 perature of 23 CC to 270 C
for a period of 71 hours under submerged conditions During
fermentation the medium maintained a p H between 7 and 7 6 with
continuous aeration and agitation After complete fermen 125 tation, a
sample of the culture filtrate was assayed to contain 1420 Oxford
units per c c.
EXAMPLE 9
composition as that 130 4 786,117 of Example 1 except that said 2 %'
to 4 , of mustard oil cake was replaced by 2 'er to 4 , of a mixture
of sesame oil cake and soyabean meal Sterilisation and inoculation
were effected according to the method of Example 1.
The fermentation was continued at a temperature of 23 YC to 27-C for a
period of 69 hours under submerged conditions During fermentation the
medium maintained a p H between 7 1 and 7 6 with continuous aeration
and agitation After complete fermentation, a sample of the culture
filtrate was assayed to contain 1425 Oxford units per c c.
EXAMPLE 10
composition as that of Example 1 except that said 2 % to 49 of mustard
oil cake was replaced by 2 '0 to 4 '.
of a mixture of sesame oil cake and cotton seed meal Sterilisation and
inoculation were effected according to the method of Example 1.
The fermentation was continued at a temperature of 230 C to 27 TC for
a period of hours under submerged conditions During fermentation the
EXAMPLE 11
A fermentation nutrient niedium was prepared, having the same
composition as that of Example 1 except that said 2, to 4 ',', of
mustard oil cake was replaced by 2 %' to 400 of a mixture of groundnut
oil cake and soyabean meal Sterilisation and inoculation were effected
according to the method of Example 1.
culture filtrate was assayed to contain 1390 O:,ford units per c c.
EXAMPLE 12
composition as that of Example 1 except that said 2 % to 4 ', of
mustard oil cake was replaced by 20 ' to 4 ' of a mixture of groundnut
oil cake and cotton seed meal Sterilisation and inoculation were

The fermentation was continued at a temperature of 23-C to 27 ^C for a
period of hours under submerged conditions During fermentation the
In Specification No 613,469 there is 70 claimed a method of producing
a streptomycin-like antibiotic substance which comprises growing the
organism Actinoniiyces griseus in or on a liquid nutrient medium whose
substantially sole source of nitrogen 75 ous and growth-promoting
substances is a member of the group consisting of the meals, flours,
meal-infusions and flour-infusions of beans, peanuts, cotton seed and
linseed.
Further, in Specification No 700 316 there 80
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* GB786118 (A)
Description: GB786118 (A) ? 1957-11-13
Improvements in or relating to resinous compositions
A high quality text as facsimile in your desired language may be available
amongst the following family members:
FR1136434 (A) NL102358 (C)
FR1136434 (A) NL102358 (C) less

Improvements minor relating to Resinous Compositions.
We, VELSICOL CHEMICAL CORPORATION, a corporation organised under the
laws of the
State of Illinois, United States of America, of 330, East Grand
Avenue, City of Chicago,
State of Illinois, United States of America, do hereby declare the
invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly
described in and by the following statement:
This invention relates to novel stabilized and plasticized polymeric
products containing epoxides of organic acid esters.
More Especifiaally, the present invention provides a new plasticized
and stabilized resinous composition comprising a chlorine containing
vinyl polymer in combination with esters of 5,6-epoxybicyclo [2.2.1]
heptane-2,3-dkar- boxylic acid having the structure
<img class="EMIRef" id="026598833-00010001" />
wherein R and R1 are independently selected from the group of
aliphatic hydrocarbon radicals containing up to 12 carbon atoms.
The compound illustrated above as an ester- epoxide of the acid which
has been termed in the literature as carbic acid (the word " Carbic"
is a Registered Trade Mark). Carbic anhydride which can be readily
hydrolyzed to carbic acid is the Diels-Alder adducit of
cyclopentadiene and maleic-anhydride. For the purposes ob brevity the
above esters will hereinafter be referred to as carbic ester epoxides.
While ordinarily those resins which contain vinyl chloride as a
constituent element of the polymer are compounded with an individual
stabilizer and plasticizer, it would be desirable to both stabilize
and plasticize these resins by the addition of only a single compound.
The products of the present invention accomplish this desirable end,
and in a single compound incorporate the properties of both an
excellent plasticizer and an eEcient- stabilizer for resins based on
or containing vinyl chloride as a constituent element.
Aside from the unusual combination of both stabilizing and
plasticizing properties, these individual properties are in themselves
interesting.
As a stabilizer alone the present compositions are especially
valuable. The compounds prevent degradation of vinyl chloride polymers

by heat and light, when used in small concentrations, more efficiently
than do other commercial stabilizers. The present carbic ester
epoxides are noteworthy in other respects, namely, that unlike many
other materials used for stabilizers, the present composition contains
no metallic salts such as lead, cadmium, tin, barium, and the like.
The absence of these metal saSts reduces the toxic hazards ordinarily
associated with these materials. In addition, the present compositions
are colorless as are the films and other products of polyvinyl
chloride containing them. Accordingly, the present compositions are
eminently suitable in preparing stabilized films land other products
where transparency and light color are at a premium. The above
properties suggest the utility of the present compositions in the
preparation of transparent stabilized films for food packaging where
requirements as to toxicity are most stringent. While the present
composition can be used as a stabilizer alone, it may be desirous in
certain applications to secure a synergystic effect by the addition of
metal salts or soaps, which may be done with out decreasing the
valuable attributes of the present composition, and even in some cases
showing a substantial increase in stabilization over either of the
components used alone. The comparative low cost of the carbic ester
epoxides is an important economic factor iri their use to augment or
replace many stabilizer systems now in use.
As a plasticizer alone, the products of the present invention have
properties equal or superior to materials heretofore conventionally
employed as plasticizers, such as dioctyl phthalate, diisoctyl
phthalate, dibutyl and dioctyl sebecate, tricresyl phosphate, dibutyl
phthalate, didecyl adipate, glycerol monolaureate, polymerized fatty
acid esters, low order polyesters, halogenated fatty acid esters, and
the like. As was previously discussed, the present compositions
contain no elements other than carbon, hydrogen, and oxygen, and
thereby present little toxic or irritant hazard when incorporated into
products as a plasticizer. They are compatible with polyvinyl chloride
resins in amounts in excess of 100 parts per hundred parts of resin,
by weight, or about the same range of compatibility as dioctyl
phthalate in most cases. The above figure may vary either slightly up
or slightly down, depending upon the constituents of the vinyl resin
and the physical condition of the polymer (e.g., particle size).
The carbic ester epoxides are colorless, odorless, and compatible with
other commercial plasticizers and diluents which might be used in
vinyl resin processing, permitting the outstanding properties of the
present plasticizer- stabilizer to be realized when incorporated with
vinyl resins and other plasticizers.
As may be readily understood, the lamount of carbic ester epoxide
necessary to stabilize vinyl resins containing chlorine is of a rather

low order, being from about 2 to 10 parts per hundred parts of resin,
with about 3 Ito 5 parts per hundred parts of resin being a preferred
range. When used to plasticize vinyl chloride resins, the amount of
plasticizer may be as high as 100 parts per hundred parts of resin.
For purposes of plasticization it is preferred to have at least 10
parts, and as high as 65 parts of carbic ester epoxide per 100 parts
of resin is generally adequate. When using carbic ester epoxide as a
plasticizer, no additional stabilizer need be added since the maternal
simultaneously performs both functions. Use of the carbic ester
epoxide in amounts over about 10!% does not necessarily result in a
more stable product than one ,containing 10% or less of the present
products. It is further evident that when the present material is used
in conjunction with other stabilizers or plasticizers, a smaller
amount will be needed than if used alone.
The present epoxy compounds !are useful as plasticizers in polyvinyl
chloride resins and copolymers prepared from vinyl chloride when
compounded as plastisols, organosols, emulsions, latices, or
hydrosols, or when used for calendering, extrusion, injection molding,
solvent spreading, and solution casting. The plasticizer-stabilizer
material of the present invention can be incorporated into the resin
by the use of standard equipment known in the field such as Day
mixers, pony mixers, 2 roller rubber mills, ink mills, knife blenders,
banbury mixers, or plasticators.
When plastisol or organisol formulations are desired, the percentage
by weight of plasticizers is quite high, while in calendered sheet or
extrusion it will be correspondingly lower.
The carbic ester epoxides of the present invention can be prepared
from carbic acid esters. For example, commercially available alcohols
up to 12 carbon atoms are esterified with carbic acid using
conventional procedures.
These alcohols are exemplified by methyl, ethyl, isopropyl, propyl,
butyl, isobutyl, isoamyl, amyl, hexyl, octyl, iso-octyl, nonyl, decyl,
dodecyl alcohol, and ithe like.
The esterification procedure can be carried out in the alcohol as
solvent or additional inert solvents can be used. If desired, acid
catalyst can be used to promote the rate of esterification. Azectropic
distillation in a high boiling solvent is one method commonly used to
prepare esters of this type.
When esters of carbic acid are prepared wherein Ithe alcohol contains
five or more carbon atoms, purification and isolation by vacuum
distillation is not a preferred procedure since decomposition may
occur at the higher temperatures required for distillation and the
yield of product is correspondingly decreased. An alternative
procedure which avoids possibility of decomposition is to employ a

molecular still where lower temperalures can be used and the product
is purified by mean-free-path distillation. The molecular still is
also used to advantage in the distillation and purification of the
epoxide.
The esters and epoxides can also be purifled by chemical means For
example, the reaction mixture containing acid, alcohol, diester,
half-ester, and solvent and acid catalyst can he treated with an
aqueous NaHCO, solution to remove unreacted dicarboxylic acid,
half-ester, and acid catalyst. The reaction mixture is then washed
with water, dried, treated with activated charcoal, and the solvent,
together with any remaining alcohol removed by distillation, vacuum
distillation, or steam distillation.
The esters so prepared can be epoxidized across the double bond in the
5,6-positions of the bicycle heptene ring. This epoxidation can be
carried in a solvent by the use of an organic per-acid such as
peracetic acid, perbenzoic acid, or perphthalic acid.
When using peracetic acid a preferred solvent is acetic acid. Other
solvents can be utilized. When peroxidation of the ester is complete,
which is determined by measuring the extent of utilization of pemacid
reagent by known iodometric titration means, the reaction mixture b
washed with water, aqueous
NaHCO, solution, and again with water.
These reagents are suitably divided to obtain the most rapid effect.
The product is then stripped of solvent and excess moisture and
treated with activated charcoal at from about 50 to 1000 C. for from 2
to 6 hours to improve color. It may be desirable to distill the
organic acid solvent from rthe reaction mixture before washing to
lower losses in the washing operation, but this procedure may be
adjusted for the most convenient process.
The following examples I [to VI illustrate the preparation of carbate
esters.
EXAMPLE I.
Preparation of Dibutyl Carbate
Into a 3-necked flask equipped with stirrer, thermometer, and reflux
condenser with attached Dean-Stark tube, is placed carbic anhydride (2
moles; 164 grams), butyl alcohol (5 moles; 370 grams), 250 ml. of
toluene, and 8 grams of p-toluene sulfuric acid. The contents of the
flask are heated at reflux until the theoretical amount of water has
been collected in the Dean-Stark trap. The reaction mixture is then
washed three times with 9 of its volume of water, three times with -t
of irs volume with 5% aqueous NaOH solution, and again with water. The
excess alcohol and toluene solvent are removed by distillation under
vacuum. The ester is further purified with activated charcoal at 80 to
100 C. for 4 hours and the ester recovered by filtration.

The product boils at 127 'to 129 C. at 1 mm.
of Hg. pressure and has refractive index nD2 1,4721 and density
d4201.044 to 1.045.
EXAMPLE II
Preplaration of Di(n-amyl) Carbate
condenser with attached Dean-Stark tube is placed carbic anhydride
(2 moles; 164 grams), n-amyl alcohol (5 moles; 441 grams), 250 ml. of
toluene, and 8 grams of p-toluene sulfonic acid. The contents of the
flask ;are heated at reflux until the theoretical amount of water has
washed 3 times with t its volume of water, 3 times with 9 its volume
of 51 /, aqueous NaOH solution, and again washed with water las above.
The excess alcohol and toluene are removed by distillation under
vacuum. The ester is further purified by treatment with activated
charcoal at 80 to 100"
C. for four hours and recovered by filtration.
The product boils at 142 to 145 C. at 1 mm. of Hg. pressure with
refractive index nD2 1.4714 to 1.4719 and density d4201.025 to 1.028.
EXAMPLE III
Preparation of Di-(2-ethylhexyl) Carbate
condenser with attached Dean-Stark tube is placed carbic acid
anhydride (2 moles; 164 grams), 2ethylhexyl alcohol (5 moles; 650
grams), 250 ml. of toluene, and 8 grams of p-tolueae sulfonic acid The
contents of the flask are heated at reflux until the theoretical
amount t,f water has been collected in the Dean-Stark rap. The
reaction mixture is then washed 3 times with a its volume of water, 3
times with Q its volume of 5% aqueous NaOH solution, and again washed
with water as above. Tfi excess alcohol and toluene are removed by
distillation under vacuum. The ester is further purified by treatment
with activated charcoal at 80 to 100" C. for four hours and recovered
by filtration. The product boils at 144 to 1480 C. at 0.1 mm. of Hg.
pressure with refractive index nD2 1.4709 Ito 1.4713 and density
d4200.992 to 0.995.
EXAMPLE IV
Preparation of Dodecyl Carbate
moles; 164 grams), decyl alcohol (5 moles; 791 grams), 250 ml. of
toluene, and 8 grams of p-toluene sulfuric acid.
The contents of the flask are heated lat reflux until the theoretical
amount of water has been collected in the Dean-Stark trap. The
reaction mixture is then washed three times with 31 of its volume of

water, three times with 9 of its volume with 5.% aqueous NaOH
solution, and again with water. The excess alcohol and toluene solvent
are removed by distillation under vacuum. The ester is further
purified with activated charcoal at 80 to 100" C.
for four hours and the ester recovered by filtration. The product
boils at 168 to 174"
C. at 0.1 mm of Hg. pressure and has refractive index no2"1.4709 to
1.4711 and density d,200.978 to 0.981.
EXAMPLE V
Preparation of Dilauryl Garbate
moles; 164 grams), lauryl alcohol (5 moles; 931 grams), 250 ml. of
toluene, and 8 gnams. of p-toluene sulfuric acid. The contents of the
flask were heated at reflux until the theoretical amount of water had
washed three times with t of its volume of water, three times with t
of its volume with 5i% aqueous NaOH solution, and lagain with water.
The excess alcohol and toluene solvent are removed by distillation
under vacuum. The ester is further purified with activated charcoal at
80 Ito 100" C. for 4 hours and the ester recovered by filtration.
The product boils at 175 to 182" C. at 0.01 mm. of Hg. pressure and
has refractive index ran2"1.4703 to 1.4706 and density do200.975 to
0.979.
EXAMPLE VI
Preparation of Dihexyl Carbate
Into a 3-necked flask equipped with stirrer.
thermometer, and reflux condenser with attached Dean-Stark tube, is
placed carbic anhydride (2 moles; 164 grams), hexyl alcohol (5 moles;
510 grams), 250 ml. of toluene, and 8 grams of p-toluene sulfuric
acid. The con tents of the flask were heated at reflux until the
theoretical amount of water had been colbathed in the Dean-Stark trap.
The reaction mixture is then washed three times with -t- of its volume
of water, three times with - of its volume with 5% aqueous NaOH
solution, and again with water. The excess alcohol and toluene solvent
are removed by distillation under vacuum. The ester is further
purified with activated charcoal at 80 to 100 C. for 4 hours and the
ester recovered by filtration.
The product boils at 156 to 1600 C. at 1 mm. of Hg. pressure and has
refractive index nD2 1.4712 to 1.4716 and density d;201.011 to 1.014.
The six examples heretofore illustrated all represent preparation of
symmetrical esters of carbic acid, namely, esters wherein both
carboxyl groups in the molecule are esterified with the same alcohol.
Mixed esters of carbic acid, namely, esters wherein each carboxyl

group in the molecule is esterified with a different alcohol, and
epoxides of such mixed esters are also readily preparable from carbic
anhydride and comi3l- nations of the various alcohols previously
described. Simple mixing of the anhydride and a slight molar excess of
desired alcohol accompanied with gentle heating results in the
formation of the half-ester. Excess alcohol reactant is stripped from
the reaction mixture and the residual half-ester is further treated
with a stoichiometric, or slightly in excess thereof, quantity of a
different alcohol by refluxing in toluene or a similar inert solvent
in the presence of an acid catalyst such as benzene sulfuric acid.
Total reaction time is determined by measuring the water formed during
reaction and recovered by azeotropic distillation in a Dean-Stark
trap. The mixed ester so prepared is purified in the same manner as
are the symmetrical esters and the procedure for epoxidation is
likewise the same.
The following Examples VII through XIII illustrate methods of
epoxidizing the esters of carbic acid to produce carbic ester
epoxides.
EXAMPLE VII
Dibutyl Carbate Epoxide
To 682 grams (2.32 moles) of dibutyl carbate was slowly added with
cooling and vigorous stirring, a solution of 550 grams (2.90 moles) of
40% peracetic acid and 10.1 grams of anhydrous sodium acetate. The
temperature was maintained at 3540" C. during the entire addition time
of 'about four hours and two hours subsequent stirring. The reaction
mixture was poured into water and the product extracted with ether.
The ether extracts were washed with water, dried over anhydrous sodium
sulfate, and the ether solvent removed by distillation under vacuum.
The crude product (647 grams) was purified by distillation in a
Claisen-Head flask. The product was recovered as the fraction boiling
159158- C. at 1.0 mm. of mercury pressure with refractive index
nD201.4775 to 1.4780 and a density of d,"1.110 to 1.112.
It was also found that the above epoxide composition is readily
purified by means of a molecular still.
EXAMPLE VIII
Preparation of Diamyl Carbate Epoxide
To diamyl carbate (0.5 moles; 222 grams) was slowly added with cooling
and stirring, a solution of 40..?,o' peracetic acid (0.625 moles;
119 grams) and 2.6 grams of anhydrous sodium acetate. The temperature
is maintained at 3540 C. during the entire addition time of four hours
and during two hours subsequent stirring. When reaction is complete as
determined by peracid utilization, acetic acid and water are removed
by distillation under vacuum maintaining the ,temperature below
about 40 C. The crude product remaining as residue is washed three

times with 1 its volume of 5 % aqueous
NaHCO, solution and again with water as before. The ester epoxide is
dried over anhydrous NaeSO4. The product is then treated with
activated charcoal for about four hours at 500 C. and recovered by
filtration. The product boils at 172 to 174" C. at 1 mm. Hg.
pressure and has refractive index nD2 1.4773 to 1.4776 and density of
d;2 1.092 to 1.095.
EXAMPLE IX
Preparation of Dihexyl Carbate Epoxide
To dihexyl carbate (0.5 moles; 236 grams) was slowly added with
cooling and stirring, a solution of 401% peracetic acid (0.62 moles;
is maintained at 35-400 C. during the entire added tion time of four
hours and during two hours subsequent stirring. When reaction is
complete as determined by peracid utilization, acetic acid and water
are removed by distillation under vacuum maintaining the temperature
below about 40 C. The crude product remaining as residue is washed
three times with Q its volume of water, three times with 1/3 its
volume of aqueous NaHCO3 solution, and again with water as before. The
ester epoxide is dried over anhydrous Na2SO4. The product is then
treated with activated charcoal for about four hours at 50G C. and
recovered by filtration. The product boils at 185 to 1880 C. at 1 mm.
Hg. pressure and has refractive index nD201.4769 to 1.4774 and density
of d12 1.080 to 1.083.
EXAMPLE X
Preparation of Didecyl Carbate Epoxide
To didecyl carbate (0.5 moles; 292 grams) was slowly added with
cooling and stirring, a solution of 40 /0 peracetic acid (0.62 moles;
and during two hours subsequent stirring. When reaction is complete as
determined by peracid utilization, acetic acid and water are removed
by distillation under vacuum maintaining the temperature below about
40 C. The crude product remaining as residue is washed three times
with A its volume of water, three times with A its volume of 5iP/o
aqueous NaHCO3 solution and again with water as before. The ester
epoxide is dried over anhydrous Na5SO4. The product is then treated
with activated charcoal for about four hours at 50 C. and recovered by
filtration. The product boils at 170 to 177
C. at 0.01 mm. Hg. pressure and has refracrivet index riD201.4763 to
1.4767 and density of d4201.051 to 1.055.
EXAMPLE XI
Preparation of Di(2-ethylhexyl) Carbate
Epoxide

To di(2-ethylhexyl) carbate (0.5 moles; 266 grams) was slowly added
with cooling and stirring, a solution of 4Q% peracetic acid (0.62
moles; 119 grams) and 2.6 grams of anhydrous sodium acetate. The
temperature is maintained at 3540 C. during the entire addition time
of four hours and during Itwo hours subsequent stirring. When reaction
is complete as determined by peracid utilization, acetic acid and
water are removed by distillation under vacuum maintaining the
temperature below about 40 C. The crude product remaining as residue
is washed three times with W its volume of water, three times with A
its volume of 5i% aqueous NaHCO3 solution, and again with water as
before. The ester epoxide is dried over anhydrous NaSO4.
The product is then treated with activated charcoal for about four
hours at 50 C. and recovered by filtration. The product boils at 170
to 176 G at .1 mm. Hg. pressure and has refractive index nD2 1.4766 to
1.4770 and density of do2 1.060 to 1.062.
EXAMPLE XII
Preparation of Didodecyl Carbate Epoxide
To didoceyl carbate (0.5 moles; 320 gnams) was slowly added with
cooling and stirring, a solution of 40 /O peracetic acid (0.62 moles;
119 grams) and 2.6 grams of anhydrous sodium lactate. The temperature
is maintained at 3540 C. during the entire laddition time for four
hours and during two hours subsequent stirring. When reaction is
complete as determined by peracid utilization, acetic acid and water
are removed by distillation under vacuum maintaining the temperature
below about 40 C. The crude product remaining as residue is washed
three times with A its volume of water, three times with -3- its
volume of 5% aqueous NaHCO, solution, and again with water as before.
The epoxide is dried over anhydrous Na2SO4. The product is then
treated with activated charcoal for about four hours at 50 C. and
recovered by filtration. The product boils at 192 to 200 C. at 0.01
mm. Hg. pressure and has refractive index nD2 1.4760 to 1.4764 and
density of d42 1.046 to 1.050.
EXAMPLE XIII
Preparation of Diethyl Carbate Epoxide
To diethyl carbate (0.5 moles; 239 grams) was slowly added with
cooling and stirring, a solution of 40% peracetic acid (0.62 moles;
119 grams) and 2.6 grams of anhydrous sodium acetate The temperature
and during two hours subsequent stirring. When reaction is complete
ias determined by peracid utilization, acetic acid and water are
removed by distillation under vacuum maintaining the temperature below
about 40 C. The crude product remaining as residue is washed three
times with A its volume of water, three times with A its volume of 5,%
aqueous NaHCO3 solution, and again with water as before. The ester

epoxide is dried over anhydrous Na2SO4. The product is then treated
with activated charcoal for about four hours at 50 C. and recovered by
filtration. The product boils at 127 to 129
C. at 1 mm. Hg. pressure and has refractive index nD2 1.4814 to 1.4818
and density of d420l.175 to 1.178.
The foregoing carbate ester epoxides whose prepanation is illustrated
in the Examples VII through XIII have excellent properties as a
stabilizer-plasticizer for polyvinyl chloride resins as previously
described. The present compositions can be readily incorporated into
vinyl chloride resins to illustrate their unusual properties as
stabilizers. The following example will illustrate la standard
procedure for preparing a resin composition of the present invention
which can be casted.
EXAMPLE XIV
To 100 grams of vinyl chloride paste resin (Geon 121 the word "Geon"
is a registered
Trade Mark) was added 5 grams of dibutyl carbate epoxide as stabilizer
and 65 grams of diisoctyl phthalate ner color after stated periods of
even aging at 300 F.
Gardner Color
Time in Minutes
Stabilizer 105 260 315 380 410
A 4 5 5 5 5
B Colorless 4 5 18 -
C Colorless 3 6 10 12
Butyl Carbate
Epoxide Colorless 2 3 4 5
Control (None) 9 10 10 13
The stabilizers A, B, and C lare proprietary commercial epoxide type
stabilizers.
Dibutyl carbate epoxide and other carbate epoxides are excellent long
term polyvinyl chloride resin stabilizers. The initial color of resins
having the present materials incorporated is equal to most resins
containing stabilizers used commercially and superior to resins
containing the epoxy type stabilizer when used in equivalent
concentrations. In addition to good initial color, the long !term
stability of vinyl chloride resins is significantly better ithan other
stabilizers as evidenced by over-aging at 320 F. for seven hours.
Storage of cast vinyl resins containing dibutyl carbate epoxide caused
no detectable change in appearance and plasticizer migration was not
evident after several months. All other cast vinyl films containing as
little as 2,% of commercial epoxy type stabilizers showed evidence of
incompatibility and migration and spewing of the stabilizer.
Generally, the carbic ester epoxides described herein are superior

plasticizers and stabilizers for vinyl polymers containing chlorine.
Thus polyvinyl chloride, copolymers of vinyl chloride and vinyl
acetate, copolymers of vinyl chloride and vinyl ethers, copolymers of
vinyl chloride and vinylidene chloride, can be used with the present
carbic ester epoxides.
The present ;stabilizer plasticizers are effective for use in vinyl
polymers containing chlorine even when such polymers contain other
modifiers in the form of polymers.
Example XIV illustrates the use of one of the present carbic ester
epoxides in a vinyl polymer containing chlorine. Any other carbic
ester epoxide as herein contemplated can be incorporated into such
type polymer in the same fashion with effective land beneficial
results. Likewise, the plasticizer used in
Example XIV can be replaced in part or in its entirety with carbic
ester epoxides of the present class.
The mode of formulating vinyl polymers containing chlorine with
plasticizers and stabilizers is well known and is practiced daily in
the industry. The carbic ester epoxides herein described can be
formulated with chlorine containing vinyl polymers as stabilizer in
amounts up to about 10 parts per 100 parts polymers, or as
plasticizer-stabilizer in amounts up to about 100 parts per 100 parts
polymer by any of such well known methods and means
The present carbic ester epoxides are most often sufficient when used
alone as stabilizers or plasticizers. However, Xthey may be used in
combination with other stabilizers or plasticizers in the formulations
of vinyl polymers containing chlOrine!
What we claim is: -
1. A resinous composition comprising a chlorine containing vinyl
polymer and a compound of the formula
wherein R and Rl are independently selected from the group consisting
of aliphatic hydrocarbon radicals containing up to 12 carbon atoms.
2. A plasticized -and stabilized resinous composition according to
claim 1 containing up to about 100 parts of said compound per 100
parts of said polymer.
3. A ;plasticized and stabilized resinous composition according to
claim 1 or 2 containing from about 10 to 65 parts of said compound per
100 parts by weight of said polymer.
4. A stabilized resinous composition according to claim 1 containing
from about 2 to about 10 parts of said compound per 100 parts by
weight of said polymer.
5. A stabilized resinous composition according to claim 1 or 4
containing from about 3 to about 5 parts of said compound per 100
parts by weight of said polymer.

6. A resinous composition comprising a chlorine-containing vinyl
polymer and a compound of the structure set forth in claim 1, wherein
R and Rl each represent the -C4H radical.
7. A resinous composition comprising ra chlorine containing vinyl
polymer and up to about 65 parts per 100 parts of said polymer by
weight of a compound of the formula as set forth in claim 1, wherein R
and R1 each represent the -C8H17 radical.
8. A method of plasticizing and stabilizing a chlorine-containing
vinyl polymer which comprises incorporating therewith a stabilizing
and plasticizing amount of a compound having the formula:
wherein R and RI are independently selected from the group consisting
of aliphatic hydro.

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