* GB786114 (A)

Description: GB786114 (A) ? 1957-11-13

Improvements in or relating to method of making a split metal sleeve and theresulting 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).

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p

* GB786115 (A)

Description: GB786115 (A) ? 1957-11-13

Improvements relating to vehicle wheels, more especially for use on vehiclesusuallyoperating on soft, easily penetrable ground

Description of GB786115 (A)

PATENT SPECIFICATION 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. COMPLETE SPECIFICATION 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.

* Sitemap * Accessibility * Legal notice * Terms of use

* Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p

* GB786116 (A)

Description: GB786116 (A) ? 1957-11-13

A process for preparing epoxidized condensation polymers and the resultingproducts

Description of GB786116 (A)

A high quality text as facsimile in your desired language may be available amongst the following family members:

BE540982 (A) CH341647 (A) FR1136342 (A) NL103509 (C) BE540982 (A) CH341647 (A) FR1136342 (A) NL103509 (C) less Translate this text into Tooltip

[84][(1)__Select language] Translate this text into

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.

PATENT SPECIFICATION 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(A X), 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. COMPLETE SPECIFICATION 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.

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p

* GB786117 (A)

Description: GB786117 (A) ? 1957-11-13

Improved process and nutrient medium for producing penicillin

Description of GB786117 (A) Translate this text into Tooltip

[75][(1)__Select language] Translate this text into

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.

PATENT SPECIFICATION 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. COMPLETE SPECIFICATION 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 A fermentation nutrient medium was prepared, having the same 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 the medium maintained a p H between 7 1 and 7 5 with continuous aeration and agitation After complete fermentation, a sample of the culture filtrate was assayed to contain 1395 Oxford units per c c. EXAMPLE 4 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 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 a period of 73 hours under submerged conditions During fermentation the medium maintained a 70 p H between 7 2 and 7 6 with continuous aeration and agitation After complete fermentation, a sample of the culture filtrate was assayed to contain 1410 Oxford units per c c. EXAMPLE 6 75 A fermentation nutrient medium was prepared, having the same 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 effected according to the method of Example 1. 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 the medium maintained a p H between 7 2 and 7 6 with continuous aeration and agitation After complete fermentation, a sample of the culture filtrate 90 was assayed to contain 1430 Oxford units per c c. EXAMPLE 7 A fermentation nutrient medium was prepared, having the same 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 fermentation was continued at a temperature of 230 C to 270 C for a period of 76 hours under submerged conditions During fermentation the medium maintained a 105 p H between 7 3 and 7 6 with continuous aeration and agitation After complete fermentation, a sample of the culture filtrate was assayed to contain 1390 Oxford units per c c 110 EXAMPLE 8 A fermentation nutrient medium was prepared, having the same 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 A fermentation nutrient medium was prepared, having the same 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 A fermentation nutrient medium was prepared, having the same 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 medium maintained a p H between 7 2 and 7 6 with continuous aeration and agitation After complete fermentation, a sample of the culture filtrate was assayed to contain 1395 Oxford units per c c. 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. The fermentation was continued at a temperature of 230 C to 270 C for a period of 76 hours under submerged conditions During fermentation the medium maintained a p H between 7 1 and 7 5 with continuous aeration and agitation After complete fermentation, a sample of the culture filtrate was assayed to contain 1390 O:,ford units per c c. EXAMPLE 12 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 20 ' to 4 ' of a mixture of groundnut 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 23-C to 27 ^C for a period of hours under submerged conditions During fermentation the medium maintained a p H between 7 2 and 7 5 with continuous aeration and agitation After complete fermentation, a sample of the culture filtrate was assayed to contain 1440 Oxford units per c c. 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

* Sitemap * Accessibility * Legal notice * Terms of use * Last updated: 08.04.2015 * Worldwide Database * 5.8.23.4; 93p

* GB786118 (A)

Description: GB786118 (A) ? 1957-11-13

Improvements in or relating to resinous compositions

Description of GB786118 (A)

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 Translate this text into Tooltip

[80][(1)__Select language] Translate this text into

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.

COMPLETE SPECIFICATION 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 Into a 3-necked flask equipped with stirrer, thermometer, and reflux condenser with attached Dean-Stark tube is placed carbic an- hydride (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 been collected in the Dean-Stark trap. The reaction mixture is then 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 Into a 3-necked flask equipped with stirrer, thermometer, and reflux 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 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), 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 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), 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 been collected in the Dean-Stark trap. The reaction mixture is then 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 ,tem- perature 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; 119 grams) and 2.6 grams of anhydrous sodium acetate. The temperature 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; 119 grams) and 2.8 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 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 is maintained at 3540 C. during the entire addition time of four hours 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 <img class="EMIRef" id="026598833-00060001" /> 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: <img class="EMIRef" id="026598833-00060002" /> wherein R and RI are independently selected from the group consisting of aliphatic hydro.