Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Ethene-propene or ethene-propene-diene copolymers

Definitions

• 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.
• 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.
• 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
• 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.
• 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.
• hydrocarbons for instance, n-heptane, cyclohexane, benzene, toluene or liquid propylene
• 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.
• 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;
• alkenylcycloalkenes such as: 4-vinyl-cyclohexene-l 3(2-butenyl) cyclobutene;
• non-conjugated monocyclic dienes such as: cyclooctadiene-l ,5, cyclopentadienel ,4;
• polycyclic endomethylene polyenes including dicyclopentadiene, 5-butenyl-norbomene-2,S- isopropenylnorbomene-2, 5-ethylidenenorbomene-2;
• 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;
• 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.
• 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.
• 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:
• 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;
• 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;
• the crosslinking treatment modifies certain physical and mechanical characteristics of the terpolymer, including the tensile strength, elongation at break, and elastic recovery.
• 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.
• 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.
• 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.
• 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.
• 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.).
• 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:
• 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.
• 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.
• 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
• 7 cc of methyltetrahydroindene were used.
• Example '1 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.
• 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.
• Example 1 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.
• vanadium triacetylacetonate 0.1 g dissolved in 10 cc of toluene
• 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
• 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.
• 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.
• 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:
• Example 2 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.
• the vulcanized product was insoluble in all solvents
• 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:
• Example 2 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).
• 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.
• 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.
• 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.
• 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
• domethylenic polyenes polycyclic polyenes having condensed rings each pair of which has two carbon atoms in common, and polyalkenylcycloalkanes.
• 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.

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• Medicinal Chemistry (AREA)
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• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Citations (9)

• 1968
  • 1968-09-06 NL NL6812748A patent/NL6812748A/xx unknown
  • 1968-09-09 SU SU1269507A patent/SU457225A3/ru active
  • 1968-09-11 ES ES358022A patent/ES358022A1/es not_active Expired
  • 1968-09-11 US US759197A patent/US3684782A/en not_active Expired - Lifetime
  • 1968-09-11 DE DE1795317A patent/DE1795317C3/de not_active Expired
  • 1968-09-11 CH CH1354768A patent/CH525258A/de not_active IP Right Cessation
  • 1968-09-12 BE BE720742D patent/BE720742A/xx unknown
  • 1968-09-12 FR FR1579426D patent/FR1579426A/fr not_active Expired
  • 1968-09-12 GB GB43435/68A patent/GB1243013A/en not_active Expired

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