US3684782A

US3684782A - Manufactured shaped articles of unsaturated olefinic copolymers

Info

Publication number: US3684782A
Application number: US759197A
Authority: US
Inventors: Paolo Longi; Alberto Valvassori; Francesco Greco; Ermanno Bernasconi
Original assignee: Individual
Current assignee: Individual
Priority date: 1967-09-12
Filing date: 1968-09-11
Publication date: 1972-08-15
Anticipated expiration: 1989-08-15
Also published as: NL6812748A; DE1795317C3; GB1243013A; CH525258A; DE1795317A1; FR1579426A; BE720742A; DE1795317B2; SU457225A3; ES358022A1

Abstract

The invention provides manufactured shaped articles, more particularly elastic films and fibers, having excellent characteristics. The articles are transformation products of certain terpolymers of ethylene, propylene, and hydrocarbon monomers containing at least two double bonds, which terpolymers contain, by mols, 70-85 percent ethylene, 15-30 percent propylene, and 0.05-3 percent of the polyene, have a molecular weight above 20,000, and are amorphous in the relaxed state but crystallize under stretching, more particularly after vulcanization.

Description

United States Patent Longiet a].

[54] MANUFACTURED SHAPED ARTICLES 0F UNSATURATED OLEFINIC COPOLYMERS Montello, Caronno Varesino, all of Italy [22] Filed: Sept. 11, I968 [21] Appl. No.: 759,197

[301 Foreign Application Priority Data Sept. 13, 1967 Italy ..20358 N67 [52] US. Cl ..260/80.78, 252/288, 252/290 R, 260/795 R [51] Int. Cl. ..C08f 15/40 [58] Field of Search ..260/80.78, 878, 88.2 P; 264/288, 289, 290 R, 210 R [56] References Cited I UNITED STATES PATENTS 3,378,606 4/1968 Kontos ..260/878 3,000,866 9/ 1961 Tarney ..260/80.5 3,162,620 12/ 1964 Gladding ..260/80.5 3,225,019 12/ 1965 Leonard ..260/88.2 3,300,459 l/ 1967 Natta ..260/88.2

1151 3,684,782 1 Aug. 15,1972

3,106,442 10/1963 Compostella ..18/48 3,509,116 4/1970 Cote ..260/88.2 3,592,881 7/1971 Ostapchenko ..260/897' FOREIGN PATENTS OR APPLICATIONS 957,070 5/ 1964 Great Britain OTHER PUBLICATIONS Copolymerization edited by George E. Ham Interscience Publishers, Div. of John Wiley & Sons, New York, pages 234-240.

Primary Examiner-Joseph L. Schofer Assistant ExaminerRoger S. Benjamin Attorney-Patricia Q. Peake and Stevens, Davis, Miller & Mosher [57] ABSTRACT The invention provides manufactured shaped articles, more particularly elastic films and fiibers, having excellent characteristics. The articles are transformation products of certain terpolymezrs of ethylene, propylene, and hydrocarbon monomers containing at least two double bonds, which terpolymers contain, by mols, 70-85 percent ethylene, 15-30 percent propylene, and 005-3 percent of the polyene, have a molecular weight above 20,000, and are amorphous in the relaxed state but crystallize under stretching, more particularly after vulcanization.

10 Claims, No Drawings MANUFACTURED SHAPED ARTICLES OF UNSATURATED OLEFINIC COPOLYMERS THE PRIOR ART Amorphous, vulcanizable terpolymers of ethylene, higher alpha-olefins and hydrocarbon polyenes, i.e., hydrocarbon monomers containing at least two double bonds are known in the art. In general, such terpolymers are amorphous and have mechanical properties comparable to those of an elastomer.

THE PRESENT INVENTION In accordance with this invention, there are provided shaped manufactured articles, including elastic films and fibers, having outstanding characteristics and combining high elasticity with markedly good resistance to mechanical stress, which articles are transformation products of certain specific terpolymers of ethylene, propylene, and hydrocarbon monomers containing at least two double bonds and which, while being amorphous in the relaxed state and at low elongations, are capable of being stretched strongly, before and more particularly after vulcanization, of crystallizing under the strong stretching, and of acquiring in the stretched state '(and only in such state) very high mechanical resistance to tensile stress.

The terpolymers which are the source of the present elastic transformation products, more particularly elastic fibers and films, contain, by mols, 70-85 percent ethylene, 15-30 percent propylene, and 005-3 percent of the polyene.

These products show, particularly after vulcanization, elongations at break of 300 to 3,000 percent tensile strength of 30 to 500 kg/cm, and elastic recoveries of 85 to 100 percent.

These terpolymers are produced by copolymerizing ethylene, propylene, and the polyenes in contact with a catalyst prepared from a. vanadium compounds such as vanadium tetrachloride, vanadium oxychloride, vanadium triacetylacetonate, vanadium alkoxychloride, vanadium alcoholates, vanadium or vanadyl salts of carboxylic acids, vanadyl acetylacetonate; and

b. organometallic aluminum compounds, particularly alkyl aluminum compounds such as triethyl aluminum, tri-isobutyl aluminum, tri-hexyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, aluminum ethyl sesqui-chloride, ethyl aluminum dichloride, diethyl aluminum monoalcoholate, and alkoxyethyl aluminum chloride.

In practice, the catalyst-forming components (a) and (b) are selected to result in a halogen-containing catalyst, i.e., at least one of the components selected contains halogen.

The copolymerization is carried out in the absence of air and moisture, generally by using hydrocarbons as the inert liquid reaction medium, for instance, n-heptane, cyclohexane, benzene, toluene or liquid propylene, and by operating at temperatures from -l to +1 00 C, preferably from -40 to +30 C.

Ethylene and propylene may be used in gaseous mixture in the desired ratio or may be introduced into the reactor separately (ethylene in the gaseous state and propylene in the liquid state), the unsaturated termonomer is more conveniently introduced in solution in a hydrocarbon solvent.

. For instance, when a diethyl aluminum chloride/vanadium triacetylacetonate catalytic system is used it is possible to obtain terpolymers the propylene and ethylene contents of which are within the limits specified above, by feeding the two gaseous monomers at a temperature of 20 C in a molar ratio propylene/ethylene of from 2.5 to 0.6.

The termonomer may be a linear or cyclic hydrocarbon containing at least two double bonds only one 'of which is susceptible of polymerizing in the presence of catalysts of the type recited above, while the others are capable of entering into crosslinking reactions as discussed infra.

Typical examples of the termonomers are a. aliphatic, non-conjugated polyenes including hexadiene- 1 ,4,5 ,7-dimethyloctadiene-1 ,6 decatriene- 1,4,9;

(b) alkenylcycloalkenes such as: 4-vinyl-cyclohexene-l 3(2-butenyl) cyclobutene;

(c) non-conjugated monocyclic dienes such as: cyclooctadiene-l ,5, cyclopentadienel ,4;

(d) polycyclic endomethylene polyenes including dicyclopentadiene, 5-butenyl-norbomene-2,S- isopropenylnorbomene-2, 5-ethylidenenorbomene-2;

(e) polycyclic polyenes with condensed rings, in which each pair of condensed rings has two carbon atoms in common such as, for instance: 4,9,7,8- tetrahydroindene, 6-methyl-4,9,7,8-tetrahydroindene, 5,6-dimethyl-4,9,7,8-tetrahydroindene;

(f) poly-alkenylcycloalkanes such as: divinylcyclobutane and trivinylcyclohexane.

The terpolymers used always have a molecular weight higher than 20,000, proved by an intrinsic viscosity greater than 0.5 in tetrahydronaphthalene at 1 35 C.

Molecular weight regulating agents, for instance hydrogen, diethyl zinc, diethyl cadmium and, in general, organometallic compounds of zinc and cadmium, halogenated hydrocarbons, diolefins with cumulated double bonds such as alllene, or acetylene hydrocarbons, may be present during the copolymerization, in order to insure that the terpolymer has a suitable degree of polymerization.

At the end of the polymerization, the terpolymer is purified and isolated by treating the reaction mass with methanol containing 5 percent of concentrated l-lCl, separating the methanol phase containing the catalyst decomposition products, washing the residual heptane phase repeatedly with methanol and, finally, precipitating the terpolymer with acetone and drying the precipitate at C at reduced pressure. In these operations, methanol may be replaced by water, and instead of precipitating the terpolymer with acetone, it may be stripped of the polymerization solvent.

The terpolymers prepared as described and having the characteristics stated are linear, free of crosslinks and completely soluble in boiling heptane, xylene and tetralin. The terpolymers can be crosslinked by the following processes:

1. vulcanization with sulfur according to known techniques, with or without the use of fillers; atms.

2. crosslinking with sulfur chlorides used either in the gaseous state or dissolved in aliphatic, aromatic or halogenated hydrocarbons, ethers, etc., at temperatures from 0 to 200 C, preferably from 0 to 150 C, and by operating at positive pressures of the reactants comprised between 0.1 and atoms (or concentrations comprised between 0.1 and 100 percent, preferably between 1 and 50 percent). The duration of the treatment is generally from 1 to 600 minutes. This crosslinking treatment may be carried out in the presence of sulfur and fillers such as zinc oxide, silica, kaolin, etc., if necesi;

3. crosslinking achieved by adding to the terpolymer unsaturated monomers containing one or more double bonds (for example: styrene, divinylbenzene, diolefins, etc.) resulting in the copolymerization thereof with the unsaturated units present in the terpolymer by means of initiators of the radical type such as, for instance: azobisisobutyronitrile, dibenzyl peroxide, dicumylperoxide, etc., if necessary, in the presence of fillers or of preformed unsaturated polymers such as: styrene/vinylcyclohexene copolymer, styrene/butadiene copolymer, etc. This crosslinking process is preferably carried out at temperatures comprised between 50 and 150 C;

4. vulcanization according to process (1), but with the addition of radical type initiators of the kind mentioned in (3), for facilitating the crosslinking. Such a process is preferably performed at temperatures from to 150 C;

5. crosslinking by using more than one of the processes herein set forth.

The crosslinking treatment modifies certain physical and mechanical characteristics of the terpolymer, including the tensile strength, elongation at break, and elastic recovery.

The transformation of these specific terpolymers into the shaped articles which are the object of this invention, in particular the transformation into fibers, can be effected before or during the crosslinking. Thus, the transformation into fibers can be achieved by the spinning of a molten mass, or of solutions, of the terpolymer.

The transformation products are unique in having properties which resemble those of rubbers and, at the same time, the properties of similar shaped articles of other materials not normally classified as elastomers. For instance, the fibers have properties like those of rubbers and at the same time are like conventional fibers and useful for like purposes. Since crosslinked products are easily obtained, it is possible to obtain elastic fibers, elastic films and, in general, manufactured shaped articles which meet the special requirements of being both highly elastic and resistant to mechanical stress.

The following examples are given to illustrate the invention without limiting the scope thereof.

EXAMPLE 1 A. terpolymer containing, by mols, 77.5 percent ethylene, 22.3 percent propylene and 0.2 percent methyltetrahydroindene, as determined by examination of the IR absorption spectrum, was prepared as follows:

The apparatus used consisted of a four-necked cylinder of 3,000 cc capacity, provided with a mechanical stirrer, a thermometer, and a tube for feeding in the gases.

Into this apparatus there were introduced, in a nitrogen atmosphere, 1,500 cc anhydrous n-heptane, 0.65 g of diethylaluminum chloride and 1.5 cc of methyltetrahydroindene. The whole was then cooled down to 20 C and a gaseous mixture of propylene and ethylene was fed in at respective flow rates of 360 and 240 liters/hour.

After about half an hour, 20 cc of a heptane solution containing 0.06 g of VOCl was added. After 10 minutes the polymerization was stopped, the reaction product was treated in a separator funnel with about 1 liter of methanol containing 5 percent of l-lCl and the heptane phase was then separated from the methanol phase; the heptane phase was repeatedly washed with further methanol (non-acid) and, finally, the dissolved polymer was precipitated by pouring the heptane phase into about 3 liters of acetone.

After drying at C at a reduced pressure, 30 g of a white polymer were obtained, which hadthe aspect of an unvulcanized rubber, and the intrinsic viscosity [1;] of which determined in tetrahydronaphthalene at C, was 3.5 dl/g.

Under X-ray analysis the crude polymer appeared to be completely amorphous.

A sample of the crude terpolymer (10 g) was transformed into a thin plate by press-molding it at C, and vulcanized by maintaining the plate, for 4-5 hours at room temperature and at a reduced pressure, in a glass vessel containing, in a separate pot, 20-30 cc of sulfur monochloride. After this treatment, the product was insoluble in all solvents and examination of the IR absorption spectrum showed the disappearance of the band at 12.67; characteristic of the double bond of methyltetrahydroindene. The Lassaigne test for sulfur was definitely positive.

The press molded and crosslinked plate, elongated to 600 percent of its initial length and subjected to X-ray examination, showed the presence of crystallinity bands of the polyethylene type. Mechanical and dynamic properties of the plate, determined according to ASTM test D 412-64 T (Die D), are reported in Table 1.

Another sample of the crude terpolymer (20 g) was transformed into fibers by dissolving it in 120 cc of toluene, in a Werner mixer. The solution was let stand for 3 days in order to remove air bubbles and then was extruded in a dry-spinning apparatus (type of spinneret: 8/0.4 X 1 mm; pressure 6 kg/cm; winding up speed 4 m/min.).

The fibers were crosslinked by the treatment applied to the press-molded plate and as described above. The fibers were found to have the following properties:

Tenacity in g/d 0.2

elongation in percent 1000 elastic recovery at 100 percent of elongation= 98 percent Tenacity and elongation of such fibers were determined according to ASTM test D 2563/67 T; elastic recovery was determined according to the method of Susich and Backer, described in Textile Research J., 21, 482(1951).

EXAMPLE 2 A terpolymer containing, by mols, 82.7 percent ethylene, 17.1 percent propylene and 0.2 percent methyltetrahydroindene, as determined by examination of the IR absorption spectrum, was prepared by the process described in Example 1, with the differences that vanadium triacetylacetonate (0.15 g dissolved in 20 cc of toluene) was used as one catalystforming component, instead of VOCl the propylene and ethylene flow rates were, respectively, 330 and 270 liters/hour, and 6 cc of methyltetrahydroindene were used.

After being stretched 500 percent of its initial length,

the cross linked product was found to be crystalline by X-ray analysis.

EXAMPLE 3 A terpolymer containing, by mols, 81.1 percent ethylene, 18.3 percent propylene, and 0.6 percent methyltetrahydroindene was prepared by the procedure described in Example 1, except that the organometallic aluminum compound used was ethyl aluminum sesquichloride (0.8 g); the propylene and ethylene flow rates were, respectively, 400 and 800 liters/hour; and 7 cc of methyltetrahydroindene were used.

Seven minutes after the polymerization started it was stopped and, proceeding as in Example '1, 36 g of terpolymer were isolated. It had an intrinsic viscosity of 4.85 dl/g, and appeared completely amorphous on X- ray examination.

A sample of the crude terpolymer was transformed into a thin film during vulcanization of the terpolymer using the following recipe:

terpolymer 100.0 Ultrasil VN 3 (SiO, of high purity) 10.0 Vulcafor MBT (mercaptobenzothiazol): 0.5 Eveite MS (tetramethylthiourammonosulfide) 1.5 Sulfur 1.0 Zinc oxide 5.0

The resulting film of the vulcanized terpolymer was insoluble in all solvents, even at the boiling point. Some properties are shown in Table 1. Elongation at break and tensile strength were determined according to ASTM test D 882-64 T (method A); elastic recovery was determined according to ASTM test D 412-64 T (Die D). When the film was stretched to 400 percent of its initial length and subjected to X-ray examination it was found to be crystalline.

EXAMPLE 4 A terpolymer containing by mols, 82.9 percent ethylene, 16.8 percent propylene, and 0.3 percent methyltetrahydroindene, determined from the 1R absorption spectrum was prepared by the process of Example 1, except that VOCl was used as the vanadium compound (0.1 g in 10 cc of toluene) and the propylene and ethylene flow rates were, respectively, 250 and 350 liters/ hour. Ten minutes after polymerization started it was interrupted and, proceeding as in the foregoing examples, 18 g of the terpolymer were recovered. It had an intrinsic viscosity of 2.57 dl/g determined as mentioned hereinabove, and X-ray examination showed it to be amorphous.

A sample of the crude terpolymer was transformed into a plate by press-molding as in Example 1, and then vulcanized as described in that Example. Properties of the shaped article of the vulcanized terpolymer, determined according to ASTM test D 412-64 T (Die D), are recorded in Table 1. When the plate was stretched 600 percent of its initial length'and subjected to X-ray examination, it was found to be crystalline.

EXAMPLE 5 A terpolymer containing, by mols, 78 percent ethylene, 21.4 percent propylene, and 0.6 percent methyltetrahydroindene, determined from the 1R absorption spectrum, was prepared by the procedure of Example 1, except that 10 cc of methyltetrahydroindene were used, and 0.6 cc of a solution containing 0.1 mols of Zn (0 1 1 in 100 cc heptane were added, and the propylene and ethylene flow rates were, respectively, 340 and 260 liters/hour. Fifteen minutes after the polymerization started, it was interrupted and proceeding as in Example 1, 28 g of the terpolymer were recovered. It had an intrinsic viscosity of 2.7 dl/g.

A sample of the terpolymer was vulcanized with sulphur at 150 C for 80 minutes, by adopting the recipe described in Example 3. Properties of the vulcanized product, determined according to ASTM test D 41264 T (Die D) are listed in Table 1. When this product was stretched to 600 percent of its initial length, it was crystalline by X-ray analysis.

EXAMPLE 6 A terpolymer containing, by mols and on basis of the IR absorption spectrum examination, 78.8 percent ethylene, 20.4 percent propylene, and 0.8 percent 5 ,7- dimethyloctadiene-l,6 was prepared by the procedure of Example 1, except that vanadium triacetylacetonate (0.1 g dissolved in 10 cc of toluene) was used as the vanadium-containing component of the catalyst, 30 cc of 5,7-dimethyloctadiene-l ,6 was used as the termonomer, and the propylene and ethylene flow rates were, respectively, 400 and 500 liters/hour. After 20 minutes of polymerization, 20 g of the terpolymer were recovered. It had an intrinsic viscosity of 1.3 dl/g determined as in Example 1 and the other examples herein, and on X-ray examination was found to be amorphous.

A sample of the terpolymer was vulcanized with sulfur at 150 C for minutes, by adopting the recipe described in Example 3.

Table 1 shows properties of the vulcanized terpolymer determined according to ASTM test D 412-64 EXAMPLE 7 A terpolymer containing, by mols, and as determined by examination of the IR absorption spectrum, 78.2 percent ethylene, 20.6 percent propylene and 1.2 percent 4-vinylcyc1ohexene-l, was prepared according to the procedure of Example 6. The difi'erences were that vanadium triacetylacetonate (0.05 g dissolved in 10 cc toluene) was used as the vanadium-containing catalystforming component and 80 cc of 4-vinylcyclohexene-l were used as termonomer. 20.5 g'of the terpolymer were obtained. It had an intrinsic viscosity of 4.0 dl/g and was amorphous on X-ray examination.

A sample of the terpolymer was vulcanized with sulfur at 150 C for 80 minutes, by adopting the recipe described in Example 3. The vulcanized terpolymer had mechanical and dynamic properties, determined according to ASTM test D 412-64 T (Die D), as reported in Table l. The product, after being stretched 400 percent of its initial length, was foundto be crystalline by X-ray examination.

EXAMPLE 8 20 g of the terpolymer prepared as shown in Example l'were mixed in a roll mixer at 40 C with 4 g of zinc oxide and 0.6 g of elementary sulfur. The mixture was transformed into a thin plate of 0.5 mm thickness by press-molding at 200 C, and then subjected to the crosslinking treatment described in Example 1. The mechanical and dynamic properties of the plate of vulcanized terpolymer, determined according to ASTM test D 412-64 T (Die D), are given in Table 1.

EXAMPLE 9 A terpolymer containing, by mols, 81 percent ethylene, 18 percent propylene and 1 percent S-ethylidenenorbomene-Z, as determined by examination of the IR absorption spectrum, was prepared as follows:

Into the apparatus described in Example 1, in a nitrogen atmosphere, there were introduced 2000 cc anhydrous n-heptane, 1.75 g of diethyl aluminum chloride, 0.065 g of Zn (C l-l and 2 cc of 5-ethylidenenorbomene-Z. The whole was then cooled down to 20 C and a gaseous mixture of propylene and ethylene was fed in at respectively flow rates of 370 and 530 liters/hour.

After about half an hours, 20 cc of a toluene solution containing 0.007 g of vanadium triacetylacetonate were added. During the polymerization, 4 cc of S-ethylidenenorbomene-2 were gradually added (0.5 cc every 2 minutes). After 18 minutes the polymerization was stopped and, proceeding as described in Example 1, 35 g of terpolymer were isolated. It had an intrinsic viscosity of 1.2 dl/g and on X-ray examination appeared to be completely amorphous.

A sample of the terpolymer was vulcanized with sulfur at 170 C for minutes, by adopting the following recipe:

terpolymer 100 S.W.C. (4,4'-thio-bis-(6-t-buty1,

Z-methylphenol) 0.2 Ultrasil VN 2 (SiO, of high purity) 10.0

Vulcafor MBT (mercap eiiz othiazol) ZDC (Zinc diethyldithiocarbamate) Tio,

4 Sulfur 1.5

The vulcanized product was insoluble in all solvents,

even at the boiling point. Some properties, determined according to ASTM test D 412-64 T (Die D), are shown in Table 1. When this product was stretched to 450 percent of its initial length and subjected to X-ray examination, it was found to be crystalline.

EXAMPLE 10 A terpolymer containing, by mols, 82.8 percent ethylene, 15.1 percent propylene and 2.1 percent 5- ethylidenenorbornene-2, as determined by examination of the IR absorption spectrum, was prepared as follows:

Into the apparatus described in Example 1, in a nitrogen atmosphere, there were introduced 2,000 cc anhydrous n-heptane, 1.75 g of diethylaluminum chloride, 0.13 g of Zn (C 11 and 4 cc of S-ethylidenenorbomene-2. The whole was then cooled down to 20 C and gaseous propylene and ethylene were fed in at the same flow rate (450 liters/hour). After about half an hour, 30 cc of a toluene solution containing 0.027 g of vanadyl acetylacetonate were added. During the polymerization, 6 cc of S-ethylidenenorbornene-Z were gradually added (0.5 co every 5 minutes).

After 65 minutes the polymerization was stopped and, proceeding as in Example 1, 42 g of terpolymer were isolated. It had an intrinsic viscosity of 2.3 dl/g and on X-ray examination appear to be completely amorphous.

A sample of the terpolymer was vulcanized as described in Example 9. Some properties of the vulcanized product, determined according to ASTM test D 412-64 T (Die D) are set forth in Table 1. After being stretched SOO-percent of its initial length, the vul- The transformation products of the specific vulcanized terpolymers which are provided by this invention, and more specifically the elastic fibers and films, have elongations at break in excess of 300 percent; tensile strengths in excess of 30 kg/cm; and elastic recoveries at 100 percent elongation of at least percent; detemiined in accordance with the standard ASTM tests.

These characteristics are possessed by the manufactured shaped articles, or transformation products, of the vulcanized terpolymers of ethylene, propylene and hydrocarbon monomers containing at least two double bonds, when the terpolymer contains 70-85 percent of ethylene, 15-30 percent of propylene, and 0.05-3 per cent of the hydrocarbon monomer, by mols, has a molecular weight in excess of 20,000, and, being 5 amorphous in the relaxed state, is capable of being stretched strongly in the vulcanized state and, after such stretching, by at least 200 percent of its initial length exhibits crystallinity on X-ray examination.

By transformation products as used herein are meant manufactured articles, such as elastic fibers, films, plates, and so on, obtained prior to or simultaneously with, vulcanization of the terpolymer.

Illustrations have been given of the preparation of the specific terpolymers having the required compositions and properties, and of the transformation thereof into manufactured shaped products prior to, or during, vulcanization of the terpolymer. It will be understood that some changes in details may be made inpracticing the invention. Therefore, we intend to include in the scope of the appended claims, all modifications and variations which will be obvious to those skilled in the art from the description and working examples contained herein.

What is claimed is 1. Elastic fibers and films which are transformation products of a normally amorphous, unsaturated, vulcanizable terpolymer of ethylene, propylene and a hydrocarbon monomer containing at least two double bonds and characterized in containing by mols 70-85 percent of ethylene, -30 percent of propylene, and 0.05 to 3 percent of the hydrocarbon monomer containing at least two double bonds, in having a high molecular weight in excess of 20,000, and in being prepared by introducing a mixture of ethylene, propylene and the hydrocarbon monomer containing at least two double bonds into a reactor and copolymerizing the mixture, all monomers of which are present in the reactor together throughout the copolymerization reaction, in contact with a halogen-containing catalyst obtained by mixing an organoaluminum compound with a hydrocarbon-soluble vanadium compound, said elastic fibers and films being obtained by shaping of said normally amorphous terpolymers prior to or dur- 45 ing vulcanization thereof and being thereafter stretched by at least 200 percent of their initial length to transform them into fibers and films which exhibit crystallinityin the stretched condition, and have elongations at break in excess of 300 percent; tensile strengths in excess of 30 kg/cm; and elastic recoveries at 100 percent elongation of at least percent, determined in accordance with standard ASTM tests.

domethylenic polyenes, polycyclic polyenes having condensed rings each pair of which has two carbon atoms in common, and polyalkenylcycloalkanes.

3. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and a non-conjugated aliphatic fifanufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and an alkenylcycloalkane.

5. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and a polycyclic endomethylenic polyene.

V 6. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and a polycyclic polyene containing condensed rings each pair of which has two carbon atoms in common.

7. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and polyalkenylcycloalkane.

8. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and methyltetrahydroindene.

9. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene and 5,7-dimethyloctadienel ,6.

10. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene and 4-vinylcyclohexane-l.

I l IR

Claims

2. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and hydrocarbon monomer selected from the group consisting of non-conjugated aliphatic polyenes, alkenylcycloalkenes, polycyclic endomethylenic polyenes, polycyclic polyenes having condensed rings each pair of which has two carbon atoms in common, and polyalkenylcycloalkanes.
3. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and a non-conjugated aliphatic polyene.
4. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and an alkenylcycloalkane.
5. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and a polycyclic endomethylenic polyene.
6. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and a polycyclic polyene containing condensed rings each pair of which has two carbon atoms in common.
7. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and polyalkenylcycloalkane.
8. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene, and methyltetrahydroindene.
9. Manufactured, elastic fibers and films according to clAim 1, obtained by shaping a terpolymer of ethylene, propylene and 5,7-dimethyloctadiene-1,6.
10. Manufactured, elastic fibers and films according to claim 1, obtained by shaping a terpolymer of ethylene, propylene and 4-vinylcyclohexane-1.