DE2830160A1 - FRACTIONABLE ELASTIC POLYPROPYLENE AND THE METHOD FOR MANUFACTURING IT - Google Patents

Description

The invention relates to elastic polypropylene.

Both crystalline and amorphous polypropylenes are known. An at least predominantly isotactic or syndiotactic structure is generally assumed for crystalline polypropylene and an at least predominantly atactic structure is generally assumed for amorphous polypropylene. US Patents 3,112,300 and 3,112,301 (Natta et al.) Describe isotactic or predominantly

gend isotactic polypropylene. The structural formulas for isotactic and syndiotactic polypropylene are given in U.S. Patent 3,511,824. "Atactic ¹¹ polypropylene is defined as polypropylene in which the methyl group substituents are randomly arranged above and below the main chain of atoms when the latter are all in the same plane.

Most of the commercial types of propylene are highly crystalline and are known to be used in manufacturing used by plastic products. Amorphous polypropylenes are also commercially available and generally rubbery materials of low strength. The amorphous polypropylenes are usually less than that Fraction present in predominantly isotactic polypropylene and can be easily extracted. she are usually used in adhesives.

Rubbery polypropylenes are also known. According to the publications, these products are obtained directly by conventional polymerization using special catalysts, by repeated extractions of conventional polypropylene, by chemical treatment of crystalline polypropylene and by multistage

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Polymerization process produced. Representative rubbery polypropylenes are described in U.S. Patents 3,329,741, 3,175,999, 3,511,824, and 3,784,502. However, these polypropylenes have not found widespread use in products in which an elastic Polymer is required.

There is therefore a need for a polypropylene that has practical elastic properties and as a direct reaction product can be produced by a practical method.

The invention relates to a fractionable, elastic polypropylene which has an inherent viscosity of 1.5 to 9, no yield strength, a tensile set of not more than 150% and about 10 to 80% by weight of a fraction which is soluble in diethyl ether and which has an inherent viscosity of more than 1.50, has an isotactic crystalline polypropylene content of about 0.5 to 5% by weight and has birefringence, when a film formed from the fraction is placed under crossed Nicoic prisms in a polarizing microscope viewed at about 25 ° C or stretched between crossed polarizing films at 25 ° C.

The invention also includes the diethyl ether soluble polypropylene itself.

According to one embodiment, the invention is directed to an elastic, fractionable product in which the "whole polymer", i.e. the direct reaction product itself without separation of any polypropylene components, is elastic and has properties similar to vulcanized rubber. This result is carried out without the polymerisation (sequential polymerisation) carried out under continuously changing conditions achieved at which the reaction conditions or proportions of the monomers during the polymerization

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can be changed to form alternating "blocks" in the polymer structure.

By "fractionable" is meant that the product is not homogeneous and thus consists essentially of two or more fractions obtained by extraction are easily separable with solvents such as diethyl ether and hexane. So all the polymers exist in the essentially from about 10 to 80 wt .-% (preferably 40 to 75 wt .-%) of a soluble in diethyl ether Fraction and varying proportions of other fractions, typically about 10 to 35% by weight of one Fraction that is soluble in boiling hexane but insoluble in boiling diethyl ether, and about 10 to 55% of a fraction that is insoluble in boiling hexane.

The fraction soluble in diethyl ether itself represents a further embodiment of the invention.

The "diethyl ether soluble" or "ether soluble" portion in that used here for a polypropylene Meaning is determined in boiling diethyl ether according to the method described below under "Methods of analysis" is described.

The measure of elasticity used to characterize the polypropylenes according to the invention is the "tensile set", which is defined as the elongation left in a specimen produced by pressing, after being stretched at a rate of 51 cm / minute to 300% elongation at 22 to 24 ° C and then allowed to recover at the same rate immediately thereafter until the Voltage of the sample is 0. The tensile set is expressed as a percentage of the original length or the The distance between the marks on the mounting clamps. All the polymers and the

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Additional, in diethyl ether soluble polypropylenes according to the invention have a tensile set of not more than 150%, preferably not more than 100%. Some samples have a tensile set of 75% Or less·

All of the polymers according to the invention have no yield point. The term used here "Yield strength" means that in the test carried out to break at 51 cm / minute at 25 ° C according to ASTM D 412 no elongation value occurs at which the tension required to further increase the elongation (Force) decreases.

All tensile strength and stress-strain measurements mentioned in this description including the examples are used on straight or dumbbell-shaped test specimens 6.4 mm wide and 0.45 to 2.0 mm thick Samples made according to ASTM Method D 412 with the exception that if average values are given, two Samples of the product are tested.

The figure shows a stress-strain curve (hysteresis curve) of a typical polymer according to of the invention (polymer according to Example 1) compared to a largely isotactic polypropylene of the prior art (Pro-fax 6523 ", manufacturer Hercules, Inc., isotactic content 94%). The according to The polymer produced in Example 1 has a tensile set of 93% at an elongation rate of 51 cm / minute and relaxation at the same speed. The polymer shows no yield point. The isotactic polypropylene has a tensile set of 300% (i.e. it shows no recovery) and shows a yield point at about 15% elongation at an elongation rate of 0.5 cm / minute and a relaxation rate of 51 cm / minute.

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All of the polymers according to the invention have one Inherent Viscosity from 1.5 to 9, preferably from 3 to 8. The fraction soluble in diethyl ether has a Inherent Viscosity greater than 1.5, preferably greater than 2.5. The inherent viscosity mentioned here is measured in decahydronaphthalene at 135 ° C using the method described below under "Analysis methods" is described. It is expressed in dl / g. The polypropylenes according to the invention become with increasing Content of ether-soluble fraction and increasing inherent viscosity of this fraction increasingly elastic. Birefringence is clearly visible when one is pressed by pressing a sample of the ether-soluble fraction between Slide formed slide under crossed Nicols Prisms in a heatable polarizing microscope at about 25 ° C is viewed. When the temperature is increased, the birefringence disappears in the region of the melting point of the film. Birefringence is also present clearly visible when a film formed from the ether-soluble fraction between crossed polarizing flat materials is pressed or stretched at a temperature of about 25 ° C.

All of the polymers have an isotactic content of 55% or less, preferably from about 25 to 45%.

The "isotactic fraction" is the fraction of the polymerized To understand propylene units, which are present in chain sections in which five successive polymerized propylene units are the same have steric configuration. So has a polypropylene, in which 45% of the polymerized propylene units in increments of five or more consecutive polymerized propylene units are present, all of which have the same steric configuration, an isotactic proportion of 45%. The one given here

13 isotactic component can be directly

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table resonance (NMR) can be measured according to known methods. A suitable example of these methods will be described below under "Methods of Analysis". For a given isotactic fraction, the polymers are highly elastic according to the invention, as shown by its tensile set and the lack of yield strength.

All of the polymers also contain a proportion of syndiotactic polypropylene. Under "syndiotactic Part "is to be understood as the part of the polymerized propylene in which the methyl groups alternate above and below the level of the main chain. The proportion of syndiotactic polypropylene

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can also be measured directly by 13 C-NMR.

All the polymers have a tensile strength in

2 Range from about 2.76 to 17.24 N / mm, determined according to the ASTM Method D 412. The ether-soluble fractions have

ρ tensile strengths of about 0.69 to 4.14 N / mm.

Each entire polymer has a major melting point between about 135 and 155 ° C, determined according to the method described below under "Methods of Analysis".

The fractions of the new elastic polypropylenes which are soluble in diethyl ether have properties which distinguish them from the fractions of the known polypropylenes extracted with solvent. For example, they have relatively wide molecular weight distributions, recognizable by the relatively high values of the ratio M / M, where M _{w is} the weight average molecular weight and M is the number average molecular weight (see Billmeyer in "Textbook of Polymer Science", pages 6-7, Interscience / Wiley 1962).

The ratio M / M is used here as a dispersity

w η

draws. It is determined by gel permeation chromatography (GPC).

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The fractions soluble in diethyl ether also have a relatively high inherent viscosity in comparison to the inherent viscosity of the corresponding whole polymers. The ratio of inherent viscosity the ether-soluble fraction of the inherent viscosity of the entire polymer is usually in Range from 0.5 to 0.9.

In addition, the fractions soluble in diethyl ether have isotactic crystalline proportions of about 0.5 to 5% by weight. The birefringence gives a good indication of the crystalline portion. The crystalline part is due to the heat of fusion (Ah ₄ ;) and

13 13

C-NMR detected and determined. The C-NMR data a

show that the crystallinity of these fractions is isotactic. The methods for determining the above The properties mentioned are described below under "Analysis methods".

The above description of the properties of the ether-soluble fractions applies in particular to the ether-soluble fractions of whole polymers, which from the polymerization mixture by methods in which the polymer is not hot melted or extruded will have been isolated. In general, these show whole polymers isolated from the reaction mixture a higher proportion of components that can be extracted with ether, namely about 30 to 80%, than after melting, Extrusion or other processing methods. The reduction is due to an interaction the ether-soluble fraction with the more crystalline components in the product.

The high molecular weight component, which is soluble in diethyl ether, is the key factor in the elastic properties contributes to the polymers according to the invention. The polymers differ in this respect of the known polymers in which the elastomeric

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Properties limited to the fraction soluble in hexane are. The ether-soluble fraction of the polymers according to the invention is extremely elastic, but has in generally low tensile strength. It can be used with polypropylenes of higher crystallinity (i.e. those with a higher isotactic content) can be combined to create elastomeric materials with greatly improved tensile strength to manufacture. It is believed that the isotactic units in polypropylene with higher Crystallinity with the isotactic units in the ether-soluble component cocrystallize, whereby a cross-linked elastomeric network is formed.

The polypropylenes according to the invention can be prepared by polymerizing propylene in the presence of a catalyst which is the reaction product of an organometallic compound with a partially hydrated surface of a metal oxide such as AlpO ₃ , TiOp, SiOp and MgO or their physical mixtures. The organometallic compounds have the formula (RCHp) .M, in which M stands for Ti, Zr or Hf, R for aryl, aralkyl, t-alkyl (eg trialkylmethyl) or trialkylsilyl and the RCHp group is not attached to the carbon atom in the β-position contains hydrogen bonded to M. The above-mentioned alkyl radicals can contain 1 to 12 carbon atoms.

In general, the two catalyst components are reacted in a ratio of 0.01 to 1.0 mmol of the organometallic compound per gram of metal oxide. Preference is given to catalysts which are produced by reacting organozirconium compounds (RCHp) ₄ Zr, in particular tetraneophylzirconium (TNZ), with hydroxylated aluminum oxide (Al ₂ O ₃ ) in a ratio of about 0.1 to 1.0 mmol of organozirconium compound per gram of aluminum oxide Catalysts and their preparation are described in US Pat. No. 3,932,307. That

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283016Q

Hydroxylated alumina is preferably made by mixing vapor phase alumina with humidity equilibrate and thereby humidity Can be adsorbed, whereupon the mixture is heated in flowing nitrogen at about 120 to 500 ° C for 1 minute to 10 hours.

Suitable catalysts also include the reaction product other aforementioned organometallic compounds with the aforementioned metal oxides. These catalysts are used in the same manner as the preferred "neophyl zirconium aluminate-on-alumina" catalyst mentioned above manufactured. Examples of representative organometallic compounds are tetraneopentyl zirconium, tetrabenzyl titanium, tetrabenzyl zirconium, Tetraneonentylhafnium, Tetrabenzylhafnium, Tetrakis (trimethylsilylmethyl) zirconium, tetraneophyltitanium and tetraneonentyltitanium.

Catalysts which are produced by hydrogenation are also suitable of the above-mentioned reaction products of the organometallic compound and the metal oxide according to the in in U.S. Patent 3,950,269.

During the polymerization process, the catalyst, which is normally in the form of a suspension in a hydrocarbon, e.g., cyclohexane, is used (about 25 to 50 ml of hydrocarbon per gram of metal oxide) with Brought into contact propylene in liquid form, or the propylene can be in a suitable solvent, e.g. hexane or cyclohexane. Regardless of which of these media is used, the Catalyst can also be prepared by placing the components in the presence of the monomer or monomers be merged. Liquid propylene is preferably used as the reaction medium. The reaction is here a slurry of polypropylene is formed in the liquid monomer. Usually the catalyst

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in an amount of 1 g atom of zirconium, hafnium or titanium in the catalyst per 200,000 to 2,000,0OO g Propylene present.

The reaction can be carried out at normal pressure or at elevated pressure of up to 345 bar. You can work in batches as well as continuously. The reaction time in the batch reaction is usually about 10 minutes to 1 hour. The reaction temperatures are in the range of about 0 ⁰ C to 175 ° C, preferably in the range of 25 ° to 100 ⁰ C.

It has been found that by the presence of water . _The substance in the reaction medium not only reduces the inherent viscosity of the polymers according to the invention, but also increases the proportion of the fraction soluble in diethyl ether. The polypropylenes according to the invention are therefore usually made in the presence of hydrogen gas. For example, a hydrogen partial pressure of 20 is with catalysts of Neophylzirkoniumaluminat on alumina at 50 ⁰ C, obtained about 1.38 bar (20 psi) a product infrequent

■ at least 3556 ether-soluble fraction with an inherent viscosity of at least 1.50, usually 2 or more, j

■ contains. As the amount of hydrogen increases, the proportion of ether-soluble fraction generally increases without

! 25 substantial lowering of the inherent viscosity of this j

j group. !

• The ratio of zirconium to metal oxide in the catalyst system affects the proportion of those obtained both in the presence and in the absence of hydrogen ether-soluble fraction. For example, neophyl zirconium aluminate-on-aluminum oxide is used as catalyst oxide of about 0.6 mmol of tetraneophylzirconium nro g of aluminum oxide normally obtained a polymer that is about

Contains 30% by weight of the ether-soluble fraction. With As the ratio of zirconium to aluminum oxide decreases, the proportion of the ether-soluble fraction increases.

The inherent viscosity of the entire polymer and the ether-soluble fraction can also be adjusted by the reaction temperature. As the reaction temperature increases, the inherent viscosity decreases and the proportion of the ether-soluble fraction increases, especially at temperatures above about 50 ^° C.

The tensile set of the entire polymer is with increasing proportion and increasing inherent viscosity of the ether-soluble fraction generally lower. The polymers have particularly low elongation residues,

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when the inherent viscosity of the ether-soluble fraction is 2.5 or more. Process for the production of such Polymers are described in the examples.

The order in which propylene, hydrogen and the catalyst are introduced into the reaction zone usually has no major effect, but it has been found that when the metal is hafnium, the proportion of ether-soluble polymer becomes higher when the catalyst is at least about Leave in contact with hydrogen for 5 minutes before introducing the propylene.

After excess propylene has been blown off, the polypropylene can be isolated by conventional methods will. If liquid propylene is used as the reaction medium, any unreacted propylene and volatile solvent that was part of the catalyst slurry by kneading on the hot roller mixer, can be removed by extraction-extrusion or steam stripping. As an alternative that can Product mixture also by adding a liquid carbon-hydrogen, e.g. cyclohexane, swollen to a gel and the polypropylene by adding a liquid such as Acetone is precipitated and converted to a filterable solid, whereupon it is filtered off. If as Reaction medium a liquid, e.g. Cyclohexane, is used, the polypropylene can be precipitated with Acetone and subsequent filtration can be isolated in the manner described above.

As already mentioned, the isolation method can influence the amount of the fraction which is soluble in diethyl ether and which is found in the polymer obtained.

The polypropylenes according to the invention are formed in good yield, especially when neophyl zirconium aluminum-on-aluminum oxide catalysts are used. The yields range from about 30,000 to

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1,000,000 g polymer / g atom zirconium and amount usually at least about 200,000 grams of polymer per gram atom of zirconium.

The ether-soluble fraction according to the invention is separated off by extraction with boiling diethyl ether.

The polypropylenes according to the invention include copolymers derived from other oc-olefins than propylene derived units in small amounts of, for example, up to about 10% of the total polymer contain. These α-olefins can be produced by copolymerization can be incorporated into the polymers without changing the essential properties described here. Representative of such cc-01efine are ethylene, 1-butene, 1-pentene and 1-hexene.

All of the polymers according to the invention and the ether-soluble fractions can be highly isotactic Polypropylene in proportions that are in a wide range from, for example, 2 to 98 wt .-% vary, mixed, whereby mixtures with advantageous properties are obtained. Mixtures that are about Contain 60 to 95% by weight of polypropylene according to the invention and 40 to 5% by weight of highly isotactic polypropylene, generally have elastomeric properties. That used highly isotactic polypropylene has an isotactic content of at least about 85%. Several polypropylenes of this type are commercially available, for example the product "Pro-fax 6523" already mentioned.

The polypropylenes according to the invention can be processed in the same way as conventional elastomers. If desired, the product can be made with additives such as Carbon black, mineral fillers, oils and pigments are compounded. The polypropylenes are excellent general-purpose thermoplastic elastomers with properties which they are suitable for use in foils (including

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heat-shrinkable films), filaments, fibers and films with elastomeric properties and for lamination of materials, overmoulding of wires and cables, in hot melt adhesives and injection molded parts, pressed parts or Make extrusion parts such as pneumatic tires and tubes suitable

Oriented products such as uniaxially oriented tapes and uniaxially or biaxially oriented films can also can be prepared from the whole polymers and from the elastomeric mixtures mentioned above. the uniaxially oriented films show excellent elastic recovery after subsequent stretching. the Biaxially oriented films are particularly advantageous for packaging purposes because they have the property of being low Shrink tension, which is desirable in heat-shrink packs, with a high degree of extensibility, which is achieved during wrapping under stretching and stretching is desired, combine. Biaxially oriented films can be produced using known methods, for example, where the film is stretched in two directions at the same time (usually 400 to 700%), and then gradually releasing the tension. The slide can be used during the - be heated to about 125 ° C during stretching. In this case it is cooled while it is still under tension.

In order to achieve high flexibility, the addition of extractable plasticizers is not necessary in the case of the polymers according to the invention. They are therefore particularly suitable for extruded tubes that are used in contact with liquids such as milk, blood and parenteral fluids. These hoses can be produced by known methods, for example extrusion as a melt at temperatures between about 200 ° and 250 ° C. in an extruder which is provided with a polyethylene screw and a hose injection mold. The hose is placed in a water-filled vacuum

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chamber extruded to cool the product and its Maintain dimensions. Normally the whole polymers or elastomeric mixtures are made from whole polymers with highly isotactic polypropylene are used for this purpose.

Products of the type mentioned above can be obtained directly from the entire polymerizate and frequently from the in Diethyl ether-soluble fraction according to the invention and from mixtures of these polymers with a high degree isotactic polypropylene. In certain applications, the polymers can have a thermal and mechanical treatment, such as the application of shear forces, for use in products containing lower molecular weights and narrower molecular weight distributions require to be subjected. A particularly important advantage of the invention is that that it enables elastomeric polypropylene to be made directly, so that it is not necessary to put it in his Separate components that are to be used in the manufacture of such products.

Analytical methods

The solubility in the solvents mentioned here is determined as follows:

The solvent is heated to the boil in a round-bottomed glass flask. The vapors rise up through the outer zone of a vertical cylindrical chamber and are cooled in a reflux condenser. The condensate drips into an extraction thimble made of fiber material or glass, which is provided with a glass frit disc in the bottom and is suspended in the middle of the vertical cylinder. The thimble contains a sample (1 to 2 grams) of the polypropylene having an average particle size no greater than about 3.2 mm. The outer wall of the extraction thimble is surrounded by the hot solvent vapors and is ^{heated by these 1} , so that the actual extraction takes place

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or is carried out in the vicinity of the boiling point of the solvent. The extraction continues, until the loss during an overnight extraction (at least 15 hours) is no more than Is 0.01 g. The entire extraction is carried out in a nitrogen atmosphere and in solvent vapors. The extracted part of the sample is the soluble part.

The inherent viscosity is determined as follows:

At 25 ° C, 0.0275 g of the polypropylene sample is dissolved in 50 ml of decahydronaphthalene, the 0.1 g / l BHT (2,6-di-t-butyl-4-methylphenol) contains, the polypropylene concentration 0.05% (w / v) at 135 ° C amounts to. At this temperature the sample is dissolved under nitrogen while using a magnetic stirrer Is stirred for 2 hours. The solution is poured through a filter rod into a Cannon-Ubbelohde viscometer, whereupon the outflow time at 135 ° C. is measured in comparison with the outflow time of the solvent alone.

T
Viscosity (^,. | = ° -—

T = outflow time of the solution
T _Q = outflow time of the solvent C = concentration
(0.05 g / dl)

The content of isotactic polymer! In the sense used here, it is determined by 13 C-NMR spectra as follows:

The 13 C-NMR spectra are recorded at 137 ° C. with one at 22.63 MHz according to the Fourier transform mode of action working spectrometer "Bruker WH-90" added. For typical determinations, 10,000 scans are made. The high frequency pulse will be like this

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set so that there is a tilt angle of 60 °. The samples are available as solutions of 0.2 g of polymer in a mixture of 1 ml of o-dichlorobenzene and 1 ml of dideuterotetrachlorathane, the 0.05% (w / v) BHT contains as a stabilizer and tetramethylsilane as a reference,

13 used. Determined with the aid of 13 C-NMR spectra Isotactic polymer content! is the area of the mmmm pentad peak at about 21.7 ppm divided by the

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total area of the C-methyl resonances (see Zambelli and coworkers, Macromolecules 6 (1973) 925). The syndiotactic structure content is determined in the same way from the peak at about 20.2 ppm.

Crystallinity by ¹³ C-NMR spectra

13 When a polypropylene sample is analyzed by 13 C-NMR in as described above and then re-examined after cooling the solution to ambient temperature there may be a decrease in the height and area of the nunmm pentad peak when crystallization some sufficiently long isotactic sequences occur.

This difference is a measure of the ¹³ C "rigidity" of the polymer and corresponds to the isotactic pentads that have been immobilized.

The observed percentage of isotactic pentads in the hot and cool polymer solutions can be

13 are designated by H and C, respectively. The percentage of C rigidity can then from the equation

¹³ C rigidity in% = HC (lOO-H)

100-C

be calculated. (The term (100-H) / (100-C) is used to denote the absolute values of the non-isotactic Bringing pentads of H and C to the same level.)

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The percent C-isotactic rigidity is correlated to the crystallinity measured by differential scanning calorimetry (see below). the

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C-isotactic crystallinity in % can be determined by the

the following equation can be calculated:

¹³ C-isotactic crystallinity = 0.625 χ (% ¹³ C-isotactic rigidity)

The factor 0.625 is the slope of a straight line that is obtained when 2 / ih ^ (see below) in dependence

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dependence of the C-isotactic rigidity in% for a number of polypropylenes including the product "Pro-fax 6523" is displayed graphically.

The melting points mentioned here are the upper (major) melting points as determined by differential scanning calorimetry (dsc). A sample of 10 to 20 mg is heated at a rate of 20 ° C / minute from -40 ° to 200 ⁰ C, at a rate of 5 ° C / min. cooled from 200 ° to -40 ° C and heated at a rate of 10 ° C / minute again from -40 ° to 200 ⁰ C. The upper melting point is taken from the heat flow / temperature curve obtained during reheating. It is the temperature at the main endothermic peak on this curve. The melting points of the ether-soluble fractions are determined on the first heating. All of the ether-soluble fractions mentioned in the following examples had comparable thermal histories (70 ° C./4 hours for the removal of volatile constituents and subsequent storage at room temperature). For further details of the methods, reference is made to "Newer Methods of Polymer Characterization" by Ke, page 350 (Interscience 1964).

Crystallinity from the heat of fusion

The heat of fusion, Ah, is calculated from the area enclosed by the dsc melting peak. The "start temperature ¹¹ " and "end temperature", ie the lower and upper limits, which are to be used for the calculation of the area

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determining the turning part of the curve are chosen visually as deviations of the curve from the baseline. The equation Ah _f = area / Km is used. Herein, K is a calibration constant believed to be independent of temperature and determined using indium, which has a known heat of transition, while m is the mass of the sample. The values are given in calories / g. (See Ke (loc.cit.), Pp. 357-359).

The weight fraction of crystalline polymer X can be determined from the equation Ah, = X Ah , in which Ah ^ is the heat of fusion per g of polymer and Ah is the heat of fusion per g of pure crystal. (See Mark and Tobolsky "Polymer Science and Materials", page 180 (Interscience / Wiley 1971)). An Ah value of 50 cal / q has been suggested for polypropylene. X, expressed in%, corresponds to Ah _f / 50 χ 100 or 2Ah _f .

Birefringence is a well-known optical phenomenon resulting from differences in the index of refraction for light that has been polarized to correspond to differences in polarizability in different directions in an anisotropic material. It can be observed in the smallest detail under a polarizing microscope or, more simply, as a multicolored spectral image when a film is stretched between two crossed polarizing layers and viewed through the layers. Both methods were used in the experiments described in the following examples. See, for example, Battista "Fundamentals of High Polymers", pp. 97-98 (Reinhold 1958); Seymor "Introduction of Polymer Chemistry", pages 284-285 (McGraw-Hill 1971) and Tanford "Physical Chemistry of Macromolecules", pages 116-118 (Wiley 1961).

The invention is further illustrated by the following examples. In these examples, the amounts given relate to in parts and percentages by weight,

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unless otherwise stated.

In all of the experiments described in the examples, care was taken to keep oxygen and water off the polymerization and all stages preceding it were excluded. All materials used exhibited high purity. The catalyst slurries were made under nitrogen. Likewise, all transfers and decantations were carried out under nitrogen performed.

Unless otherwise stated, the aluminum oxide serving as a carrier was produced in each experiment by leaving the vapor phase aluminum oxide to equilibrate with atmospheric humidity, then ^{heating the product obtained for 4 hours at 400 °} C. in flowing nitrogen and then cooling it under nitrogen.

example 1

A 1 liter autoclave made of stainless steel, which is provided with a stirrer, is ^{heated for 2 hours at 150 °} C. while it is evacuated. The vacuum connection is shut off and nitrogen is forced into the autoclave up to a pressure of 20.7 bar (300 psi), the system being allowed to cool to room temperature.

A catalyst slurry is prepared by Ig aluminum oxide (AlpOO in 40 ml cyclohexane 14 hours stirred, a solution of 0.36 mmol of tetraneophylzirconium in 2.0 ml of toluene is added and the mixture is stirred for a further hour. The slurry is with a syringe into a 75 ml stainless steel cylinder designed in such a way that that its contents under nitrogen pressure in the for polymerization used autoclave can be injected.

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450 ml of cyclohexane are put through a layer of acidic Woelm aluminum oxide in a glass vessel and then under Nitrogen pressure introduced into the autoclave, which has been let down to normal pressure and with nitrogen is rinsed. The autoclave is evacuated for 1 minute to a pressure of about 66.5 mbar and with 126 g of propylene while stirring at 500 rpm (pressure 6.2 bar (90 psi) at 22 ° C). Hydrogen will up to a total pressure of 7.93 bar (115 psi) (partial pressure of hydrogen 1.72 bar = 25 psi) pressed on. The solution is heated to 50 ° C and the catalyst slurry is injected, followed by the temperature rises to 70 ° C within about 5 minutes. The system will then start from the time it is Reached 50 ° C, held at 50 to 52 ° C for one hour (total pressure 6.7 to 13.8 bar = 97-200 psi), whereupon the autoclave is blown off, cooled and opened. The obtained viscous mixture becomes approximately equal in three Divide parts and stir each part in a mixer with about 700 ml of acetone. The here formed Solids are filtered off, combined and stirred in a mixer with about 700 ml of acetone, which is 0.3 g Tetrakis / methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl ) propionafc7-methane as an antioxidant ("Irganox 1010") contains. After filtration, drying in air and drying in a vacuum oven at 70-80 ° C. for 4 hours 102.4 g of polypropylene are obtained as a crumb-like solid. A film pressed at 225 ° C is not sticky and moderately strong, stretchy and elastic. The polymer has an inherent viscosity of 5.5 and

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an isotactic structure content of 37% determined by 13 C-NMR analysis. Its melting point is 151 ⁰ C.

The product contains 46.5% of a solution in diethyl ether Fraction having an inherent viscosity of 3.1

Has. Birefringence is clearly visible when a film formed from this fraction is stretched between crossed polarizing layers at room temperature. The ratio of the inherent viscosity of the ether-soluble fraction to the inherent viscosity of the entire polymer is 0.56. No reduction in the syndiotactic pentads can be observed in the 13 C-NMR spectrum. An isotactic crystallinity of 2%

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is determined by 13 C-NMR analysis. A melting point of 58 ° C. and an Ah _f value of 1.6 cal / g (0.0067 J) are observed. The dispersity is 7.6. Birefringence is also clearly visible when a film is viewed under crossed Nikolian prisms in a heatable polarizing microscope at about 25 ° C. When the temperature is increased at 10 ° C / minute, the birefringence disappears at about 78 ° C.

A 0.76 mm thick sheet of the entire polymer becomes made by hot pressing a sample of the product at 180 ° C. When sampling this slide at 51 cm / minute stretched and immediately relaxed to zero tension at the same speed, they show one average tensile set of 93%. Another sample of this film shows in the stress-elongation test a tensile strength at break of

6.66 N / mm ² (966 psi) at 620% elongation. A yield point is not observed in these determinations.

Example 2

A 1 liter stainless steel autoclave equipped with a stirrer is heated at 150 ° C. for 2 hours while it is evacuated. The vacuum connection is shut off and propylene is forced onto the autoclave to a pressure of 3.45 bar (50 psi), whereupon the system is allowed to cool to room temperature.

A slurry of a benzyl hafnium aluminate catalyst

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tors on luminiumoxyd ^A is prepared by adding 1 g of alumina, a solution of 0.29 mmol Tetrabenzyl- hafnium in 3.0 ml of toluene and 4O ml of cyclohexane are stirred 17 hours.

The autoclave is blown off to remove excess propylene, 1 minute to about 66.5 mbar (50 mm Hg) evacuated and cooled in ice / methanol. The stirrer is switched on and operated at 200 rpm, whereupon 168 g of propylene are added to the autoclave.

The speed of the stirrer is increased to 500 rpm and the system is heated to 25 ° C. (pressure 10.7 bar = 155 psi), whereupon hydrogen up to a hydrogen partial pressure 1.72 bar = 25 psi (total pressure 12.4 bar = 180 psi). The catalyst slurry is then injected as in Example 1. The system will be up within 35 minutes Heated to 75 ° C and then held for one hour at 72-77 ° C under the autogenous pressure (27.6 to 30 bar = 400 to 435 psi), whereupon the autoclave is blown off and cooled.

The product is stirred with 300 ml of cyclohexane in a mixer and thereby converted into a gel. Then 1 l of acetone is added, the mixture is stirred for about 1 minute and the product is filtered off. It is filtered off in a mixer with 1 l of fresh acetone containing 0.3 g of the antioxidant "Irganox 1010", dried in the air and then dried in a vacuum oven for 4 hours at 70 to 80 ^° C., with 40.9 g solid polypropylene are obtained. The product has an inherent

13 Viscosity of 8.2 and one determined by 13 C-NMR analysis Isotactic polymer content! of 45%. The melting point is 154 ° C.

After extraction with diethyl ether the product contains an ether-soluble fraction which makes up 39.1% of the total polymer and has an inherent viscosity of 4.7.

8Ö9884 / 0968

The ratio of the inherent viscosity of the ether-soluble fraction to the inherent viscosity of the entire polymer is 0.57. Birefringence is clearly visible when a film formed from this fraction is crossed between polarizing layers is stretched at room temperature. An isotactic crystallinity of 1%

13th
is determined by 13 C-NMR analysis. A melting point of 57 ° C and an Ah _f - ^v alue of 1.5 cal / g (0.00625 J / g)

are found. A reduction in the syndiotactic

13th
Pentads in the C. NMR spectrum are not observed. The dispersity is 5.1. Birefringence is also clearly visible when a film is viewed under crossed Nikol's prisms in a heatable polarization microscope at about 25 ^{° C.} When the temperature is increased by 10 ° C / minute, the birefringence disappears at around 98 ° C.

A 0.45 mm thick sheet of the entire polymer is produced by hot-pressing a sample of the product at 180.degree manufactured. When samples of this film are stretched at a speed of 51 cm / minute and immediately are then relaxed to zero voltage at the same speed, they show an average Tensile set of 106%. Other samples of this film show up to in the stress-elongation test an average tensile strength at break

2
Break of 15.72 N / mm (2280 psi) at 510% elongation. A yield point is not observed in these determinations.

Example 3

A 1 liter autoclave made of stainless steel and equipped with a stirrer Steel is heated at 150 ° C for 2 hours while evacuating. The vacuum connection is shut off, whereupon propylene is injected to a pressure of 3.45 bar (50 psi). The system then becomes the Leave to cool to room temperature.

909604/0968

A catalyst slurry is prepared by 1.0 g of aluminum oxide, a solution of 0.3 mmol of tetraneopentyl zirconium in 4.0 ml of toluene and 40 ml of cyclohexane are stirred for 16 hours.

The autoclave is let down to remove excess propylene, evacuated to about 66.7 mbar for about 1 minute and cooled in ice. Stirring is then started at 200 rpm and the autoclave is charged with 168 g of propylene. The stirring speed is increased to 500 rpm, the system is heated to 27 ° C (pressure 11.4 bar = 165 psi) and hydrogen is injected up to a partial pressure of 1.72 bar = 25 psi (total pressure 13.1 bar - 190 psi) . The catalyst slurry is then injected in the manner described in Example 1. The system is heated to 50 ° C. in the course of 16 minutes and then kept under autogenous pressure (18.62 to 20.69 bar = 270-300 psi) for 1 hour at 50 to 54 ° C., after which the autoclave is blown off and cooled.

The product is converted into a gel by stirring it with 400 ml of cyclohexane in a mixer. To Addition of 1 l of acetone, the mixture is stirred for about 1 minute and the product is then filtered off. It will be in a mixer with 1 l of fresh acetone containing 0.3 g of the antioxidant "Irganox 1010", stirred, filtered off and air-dried in a vacuum oven at 70-80 ° C. for 4 hours to give 81.7 g of solid polypropylene which has an inherent viscosity of 5.4, an isotactic polymer content of 40% (determined by 13 C-NMR analysis) and has a melting point of 150 ° C.

After extraction with diethyl ether, the product contains an ether-soluble fraction which makes up 50.8% of the total polymer and has an inherent viscosity of 4.8. The ratio of the inherent viscosity to the ether-soluble

305884/0968

_3o- 283Q16Q

The inherent viscosity fraction of the entire polymer is 0.89. Birefringence is clearly visible when a film made from this fraction is stretched between crossed polarizing layers at room temperature. A melting point of 73 ° C and an Ah _f value of 0.0054 J / g (1.3 cal / g) are observed. The dispersity is 4.6.

A 0.73 mm thick sheet of the whole polymer is produced by hot pressing a sample of the product at 180 ⁰ C. When samples of this film are stretched at 51 cm / minute and then tensioned at the same speed to zero tension, they show an average tensile set of 54%. Other samples of this film show an average tensile strength in the stress-elongation test up to breakage.

2 strength at break of 10.34 N / mm (1500 psi) 730% elongation. A yield point is not observed in these determinations.

Example 4
A. Preparation of the polymer

A slurry of 19 g activated alumina in 487 ml of cyclohexane is placed in a dry glass bottle under nitrogen. A solution of 4.8 mmol Tetraneophylzirconium in 24 ml of toluene is added with stirring. The bottle is closed and the catalyst is on slurry stirred overnight with a magnetic stirrer.

A dry 19 l reactor is flushed with propylene, to displace the nitrogen, and then charged with 3300 g of propylene. After heating to 25 ° C, the Pressing hydrogen increases the reactor pressure by 6.2 bar (90 psi) and the catalyst slurry is stirred in the manner described in Example 1 injected at 500 rpm. When adding the catalyst

809884/0968

the reactor temperature rises to 35 ° C. The reactor temperature is increased to 40 ° C. by heating. The reactor temperature is 40 to 64 ° C and the pressure 16.2 to 22.41 bar during the reaction time of 1 hour (235-325 psi). During the course of the reaction, the temperature is raised by venting gas from the reactor kept within the stated range. Hydrogen is used to replace the hydrogen lost by blowing off pushed down.

The polypropylene formed is rolled on the two-roll mixer at temperatures of up to 120 ° C in order to achieve the Remove solvent. At the same time stabilizers are added (0.2% of the condensation product of 3 moles of 3-methyl-6-t-butylphenol with 1 mole of crotonaldehyde ("Topanol CA") and 0.5% dilauryl thiodipropionate ("Cyanox LTDP"). Stabilized polypropylene weighing 1948 g is obtained. The product is 5 minutes Kneaded on a two-roll mixer at 180 ° C to remove traces of solvent. Its inherent viscosity is 3.3, the content of isotactic polymer ^ 36% and the melting point 146 ° C.

Extraction of a 200 g sample with boiling diethyl ether shows that the product contains an ether-soluble fraction which makes up 66% of the total polymer and has an inherent viscosity of 1.9. The ratio of the inherent viscosity of the ether-soluble fraction to the inherent viscosity of the entire polymer is 0.58. Birefringence is clearly visible when a film made from this fraction is stretched between crossed polarizing layers at room temperature. An isotactic crystallinity of 3% is determined by ¹³ C-NMR analysis. A melting point of 57 ° C and an Ah _f value of 0.0067 J / g (1.6 cal / g) are found. A reduction in the size of the syndiotactic pentads in the ¹³ C-NMR spectrum is not observed. The dispersity

8Ö988W0988

283016Q

is 10.6. Birefringence is also clearly visible when one is from the ether-soluble fraction produced film under crossed Nikolschen prisms in a heatable polarizing microscope at about 25 ° C is observed. When the temperature is increased by 10 ° C / minute, the birefringence disappears at about 59 ° C.

A 0.78 mm thick film of the entire polymer shows an average tensile set of 85%. Their average tensile strength at break is 6,34 N / mm ² (920 psi) b
is not observed.

2
6.34 N / mm (920 psi) at 725% elongation. A yield point

A 2.0 mm thick film of the same polymer is used uniaxial under ASTM conditions at 23 ° C at 51 cm / minute stretched to 700% and relaxed at the same speed to zero tension. The received Sample is 330% of its original length. This gives a draw ratio of 2.3. The stretched one Sample shows a tensile strength at break of

15.21 N / mm ² (2206 psi) at 180% elongation at 51 cm / minute. She immediately recovers completely from this stretch, a sign of very high elasticity. A yield point is not observed.

B. Production and testing of foils

Films of different thickness are prepared from the product according to Part A was prepared by pressing at 225 ° C and rapidly quenching in water at 5 to 10 ⁰ C. The elasticity behavior is measured by stretching recovery tests. Here, 56 to 11 microns thick stretched film at 100%, 200% and 300% of their original length, is removed and then the stress and the films are left an hour of relaxation. The degree of recovery of the samples is measured. The results are given in the following table.

The % recovery is defined as

. (Length at maximum stretch - Lrings of relaxation) (length at maximum stretch - original length)

Stretching recovery

100% 92%

200% 91%

300% 88.5%

A heat shrinkable film is made by biaxial orientation manufactured. A 0.76 mm thick film is heated for 2 minutes at 125 ° C., at the same time in vertical directions Directions at 125 ° C and a stretch rate of 10,000% / minute stretched four times, 5 minutes at the stretching temperature of 125 ° C annealed, cooled and removed from the clamping device, whereupon it is contracts to (3.75 x). The shrinkage of the film is then measured at various temperatures. the Results are given in the table below.

Shrinkage
temperature shrinkage O, 165 shrinkage stress 24 psi 75 ° C 9% O, 24 N / mm = 35 psi 100 ⁰ C 26% O, 386 N / mm ² = 56 psi 125 ° C 54% N / mm ² =

• ASTM D-2838-69

Example 5

A 0.00125 molar solution of tetraneophylzirconium in cyclohexane is prepared. A suspension of a active supported catalyst of neophyl zirconium aluminate on aluminum oxide is continuously produced by the 0.00125 molar solution of tetraneophylzirconium in an amount of 294 cm / hour and a suspension of 0.0374 g of aluminum oxide per ml of mineral oil in an amount of 1.4 g of AlpOg / hour in a stirrer autoclave made of stainless steel with a capacity of 961 cm, where they are inserted with 161 ml

Hexane kept at 51 ° C. The aluminum oxide is produced by drying in flowing nitrogen at 1000 ° C for 6 hours and partial rewetting by contact with a Atmosphere of 50% relative humidity at 23 ° C for 16 hours and subsequent renewed drying through Heat at 400 ° C for 4 hours in flowing nitrogen. After a holding time of about 117 minutes, during which the reactions between tetraneophylzirconium and activated aluminum oxide are formed Drained of neophyl zirconium aluminate, the catalyst suspension is continuously with the same Rate introduced into a 253 cm stainless steel autoclave and placed therein at 158 ml / hour Diluted cyclohexane. After a residence time of 25 minutes in the autoclave, the diluted catalyst suspension is used continuously into a 253 ml polymerization vessel maintained at 127.6 bar and 85 ° C. and provided with a stirrer made of stainless steel, where it merges with propylene. The propylene is in introduced in an amount of 386 g / hour in a cyclohexane stream which in an amount of 592 ml / hour. fed will. An additional stream of 250 ml cyclohexane / hour. is introduced as a rinse for the stirrer.

The product stream is withdrawn at the same rate as the total input, so that the nominal residence time in the reactor is about 7.4 minutes. The product mix is introduced into a chamber where the catalyst is removed by adding a 0.00836 molar solution of isopropanol in cyclohexane at a rate of 523 ml / hour. is deactivated.

The polypropylene solution is continuously fed through a regulated pressure reducing valve into one kept at 50 ° C Product template peeled off. The polymer product is isolated by treatment with acetone. The precipitated polymer is in a Waring mixer in the presence of

809884/0968

Crushed acetone. The ^ olympic crumbs are in a Hood in the air and then dried in a warm roller mixer. 12 g of product are formed every hour.

The product has an inherent viscosity of 3.0, an isotactic polymer content of 44% and a melting point of 150 ^° C.

A 0.76 mm thick sheet of the entire polymer is produced by hot-pressing a sample of the product at 180.degree manufactured. When samples of this film are stretched at 51 cm / minute and immediately thereafter at the same speed are relieved until the stress is zero, they show an average residual elongation of 89%. Another sample of this film shows a tensile strength in the stress-elongation test until it breaks at break of 10.4 N / mm (1506 psi) at 780% elongation. There is no yield point in these provisions observed.

The entire polymer is extracted with boiling diethyl ether. The fraction insoluble in ether then becomes extracted with boiling hexane. The following results are obtained:

fraction % Of the whole
Polymers 2.4 Isotak
tables
Structure, Enamel
Point,
⁰ C Ether-soluble 47 3.8 14th 56 Hexane soluble 23 3.3 47 111 Insoluble in hexane 30th 3.0 65 155 Whole polymer 44 150

Birefringence is clearly visible when a film made from the ether-soluble fraction is between crossed polarizing layers is stretched at room temperature. An isotactic crystallinity of 1%

8Ö9884 / Ö968

is determined by 13 C-NMR analysis and an Ah _f value

of 0.011 J / g (2.7 cal / g) was observed. A diminutive

13 tion of the syndiotactic pentad is not observed in the 13 C-NMR spectrum. The dispersity is 7.6. Birefringence is also clearly visible when a film is placed under crossed Nikolsch prisms in one heated polarizing microscope is viewed at about 25 ° C. When the temperature increases at 10 ° / minute the birefringence disappears at about 60 ° C. The ratio of the Inherent Viscosity to the ether-soluble The inherent viscosity fraction of the entire polymer is 0.80.

Example 6 A. Preparation of the polymer

A 3.8 l stainless steel autoclave equipped with a stirrer Steel is heated at 150 ° C for 2 hours while evacuating. The vacuum connection is shut off, Propylene pushed up to a pressure of 3.4 bar (50 psi) and the system of cooling on Leave room temperature.

t-ine catalyst slurry is made by 5.7 g of aluminum oxide and 188 ml of cyclohexane are stirred for 18 hours, a solution of 1.43 mmol of tetraneophylzirconium in 7.2 ml of toluene is added and the mixture is stirred for a further 1.5 hours.

Autoclave is vented, evacuated mbar to remove excess propylene to remove about 1 minute to about 66.66 and cooled to below 0 ⁰ C. Stirring is then started at 500 rpm and the autoclave is charged with 795 g of propylene. The system is heated to 25 ° C. (pressure 8.96 bar = 130 psi) and hydrogen is injected into the autoclave up to a hydrogen partial pressure of 2.07 bar (30 psi). The internal pressure continues to rise to 12.8 bar (185 psi). The catalyst

009884/0968

Slurry is injected in the manner described in Example 1. The system is heated to 35 ° C. over a period of 14 minutes and then kept under autogenous pressure (16.9 to 19.3 bar = 245 to 280 psi) for 1 hour at 35 to 51 ° C., whereupon the autoclave is depressurized and cooled. The product is added to 1 l of cyclohexane and the mixture is left to stand overnight. After adding 1 l of acetone, the mixture is stirred in a mixer and the product is filtered off. This treatment with acetone is repeated. Finally, the product with 1 l of fresh acetone, which contains 1.5 g of "Irganox 1010" antioxidant, is placed in a mixer. The mixture is stirred overnight. The solid is filtered off, air-dried and dried in a vacuum oven for 4 hours at 70 to 80 ^° C., 247.3 g of solid polypropylene being obtained. The product has an inherent viscosity of 5.4, an isotactic polymer content of 36% and a melting point of 144 ° C.

Extraction with boiling diethyl ether shows that the product contains an ether-soluble fraction which is 74.5% of the total polymer and has an inherent viscosity of 4.6. The part which is insoluble in diethyl ether the polymer is extracted with boiling hexane, a hexane-soluble fraction making up 11.4% of the total polymer and has an inherent viscosity of 4.6. The fraction insoluble in hexane makes up 14.1% of the total polymer and has an inherent viscosity of 6.1.

When a film made from the ether-soluble fraction is placed between crossed polarizing layers When stretching at room temperature, birefringence is clearly visible. An isotactic crystallinity of

13th
1% is determined by 13 C-NMR analysis. A melting point of 60 ⁰ C and an Ah _f * r value of 0.0063 J / g (1.5 cal / g)

809884/0968

are observed. A reduction in the syndiotak-

table pentad is not found in the 13 C-NMR spectrum. The dispersity is 6.2. The ratio of the inherent viscosity of the ether-soluble fraction to the Inherent viscosity of the entire polymer is 0.85, birefringence is also clearly visible when a film viewed under crossed Nikolsch prisms in a heatable polarizing microscope at about 25 ° C will. When the temperature is increased at 10 ° C / minute, the birefringence disappears at around 88 ° C.

A 0.78 mm thick sheet of the entire polymer is produced by hot-pressing a sample of the product at 180.degree manufactured. When samples of this film are stretched at 51 cm / minute to 300% elongation and immediately with the same Speed are relieved to zero tension, they show an average residual elongation of 41%. Other samples of this film show at Stress-elongation test up to breakage a through-

2 Average tensile strength at break of 6.1 N / mm (884 psi) at 725% elongation. A yield point is not observed in these determinations.

B. Preparation and properties of mixtures

Len 1) ether-soluble fraction plus isotactic polypropylene

Part of the ether-soluble fraction obtained according to Part A is mixed by kneading on the roller mixer 0.5% "Cyanox LTDP" dilauryl thiodipropionate and 0.25% of the condensation product of 3 moles of 3-methyl-6-t-butylphenol stabilized with 1 mole of crotonaldehyde ("Topanol CA") as stabilizers. Samples of the stabilized, ether-soluble polymer are mixed with various amounts of isotactic polypropylene ("Pro-fax 6523", Content of isotactic polymer 94%, melting point 166 ° C) on the roller mixer for 5 minutes at 180 ° C

$ 09384/0368

mixes. Foils with a thickness of about 0.76 mm are produced by pressing at 180 ° C. for the determination of the remaining elongation in the manner described in Example 1 is stretched to 300% and relieved and then with Stretched 51 cm / minute to break. The following results are obtained:

Isotak
table
Polypro
pylen
"Pro-fax
6523 " Elongation
rest,% Tensile strength
at the
fracture
N / mm ² (psi) (568) fracture
strain
% Stretching
, border 0 26th 3.92 (370) > 1000 no 5 26th 2.55 (940) 910 no 15th 39 6.48 (1400) 980 no 25th 68 9.65 (1720) 860 no 33 110 11.86 (1660) 730 no 40 128 11, Λ5 (1860) 540 no 50 207 12.82 640 Yes (at 12%
Strain) 2) Whole Polymer plus isotactic polypropylene

The prepared according to Part A, with 0.5% dilaurylthio

dipropionate (Cyanox LTDP) and 0.25% of the condensation ' Stabilizing product of 3 moles of 3-methyl-6-t-butylphenol with 1 mole of crotonaldehyde (Topanol CA) as in Part B 1 te whole polymer is kneaded with isotactic polypropylene "Pro-fax 6523" on the roller mixer at 180 ° C, a mixture containing 20% of the isotactic polypropylene "Pro-fax" is obtained. Two rehearsals' a 0.74 mm thick film, which has been pressed at 180 ° C, have an average elongation residue of 68%. Another sample has tensile strength

2
at break of 13.8 N / mm (2000 psi) at 780% elongation. Two samples of a film from a 33% of the isotactic polypropylene "Pro-fax" containing mixture of the same

8Ö3884 / Ö968

Chen polymers have an average elongation residue; of 12R%. The other two samples have a thorough

2 Average tensile strength at break of 15.8 N / mm (2272 psi) at 680% elongation. No yield point is found for any mixture.

3) Ether-soluble fraction plus hexane-insoluble fraction

A mixture containing the ether-soluble fraction and the hexane-insoluble fraction of the produced according T _e il A whole polymer which 33% of the hexane-insoluble fraction, is described by kneading the polymers at 150 ° C according to the in part B 1 and B 2 Methods made. A 0.79 mm thick film is pressed at 180 ° C. Two samples have an average elongation set of 52% and no yield strength. Two other samples have an average tensile strength at break of 8 _r 71 N / min ^ (1263 psi) at 760% elongation.

Example 7

This example illustrates the decrease in the level of the ether-soluble fraction and the lowering the inherent viscosity of this fraction when an elastomeric polypropylene according to the invention on the Roller mixer is kneaded.

A 1 1 autoclave made of stainless steel, which contains 500 ml of cyclohexane, is 10 Mi- ', provided with a stirrer. Nuts heated at 150 ° C. The cyclohexane is removed at 90.degree. C. under vacuum and the autoclave is flushed with nitrogen at 150.degree. C. for 4 hours. While rinsing continues, a slurry of 1.0 g of alumina in 40 ml of cyclohexane is introduced. After forcing in hydrogen (8 cm at 34.5 bar = 500 psi), the autoclave is cooled to 8 ° C., whereupon 200 g of propylene are added from a weighed gas bottle. The autoclave is heated to 20 ° C and a solution of 0.5 mmol

8098S4 / 0968

Tetraneophylzirconium in 5 ml of toluene was introduced under nitrogen pressure in the manner described in Example 1 while stirring the system at 500 rpm. The temperature rises immediately to 24 ° C and in about 15 minutes to 28 ° C and has dropped to 23 ° C after an hour when excess propylene is vented. The gel obtained is cut into pieces and ^{heated at 70 °} C. under vacuum in order to remove all volatile constituents. This gives 55.5 g of elastomeric polypropylene.

At this point the product has an inherent viscosity of 8.2, an isotactic polymer content of 25% and a melting point of 144 ° C. It contains 57% of a fraction soluble in diethyl ether, which has an inherent viscosity of 6.4, a dispersity of 13.9, a melting point of 51 ° C and a Δΐι, - value of 0.0067 J / g (1, 6 cal / g). Birefringence is clearly visible when a film made of the ether-soluble fraction ¹ under crossed Nikol's prisms is considered in a heatable polarizing microscope at about 25 ° C. If the temperature with! When increasing 10 ° C / minute, the birefringence disappears at around 85 ° C.

Then, 53 g -of the product are 10 minutes at 180 ⁰ C and 0.265 g of dilauryl thiodipropionate ( "Cyanox LTDP") and j 0.132 g of the condensation product of 3 moles of _3-methyl-6: t-butyl phenol with 1 mole of crotonaldehyde ( "Topanol CA ") '■

kneaded as antioxidants. The rolled product has ^: an inherent viscosity of 7.5 and contains 22% ether4 soluble fraction, which has an inherent viscosity of 9.1,; has a dispersity of 3.6, a melting point of 49 ° C and an Ah _f value of 0.0071 J / g (1.7 cal / g). A 1.9 to 2.0 mm thick plate of the rolled product is pressed at 180 ⁰ C. When samples of this plate are stretched to 300% elongation at 51 cm / minute and

809884/0968

are immediately afterwards relieved to zero voltage at the same speed they have an average residual elongation of 39%. Other samples of this plate show in the stress-strain test to break an average

2 tensile strength at break of 10.34 N / mm (1500 psi) at 910% elongation. A yield point is not observed in these determinations.

Example 8

A slurry of 2 g of aluminum oxide in 80 ml of cyclohexane is introduced into the autoclave described in Example 7, which had been pretreated in the manner described there. The autoclave is closed and pressed with ethylene to a total pressure of 4.48 bar (65 psi). The total pressure is then brought to 6.21 bar (90 psi) with hydrogen and the vessel sealed, whereupon 168 grams of propylene are introduced. While the system is stirred at 500 rpm, the temperature is increased to 50 ° C., whereupon 4 ml of a solution of 0.4 mmol of tetraneophylzirconium in toluene is forced in with nitrogen. An immediate temperature rise to 95 ° C takes place. The polymerization is allowed to take place for one hour. During this time the temperature gradually falls to 54 ° C. The excess propylene is blown off at the polymerization temperature and the product is freed from volatile substances by purging with nitrogen and evacuation at 70 ° C./0.27 mbar. This gives 146 g of an elastomeric propylene / ethylene copolymer which contains 6 mol% (4% by weight) of units derived from ethylene. After isolation, the copolymer has a Inherent Viscosity of 5.9, a Atherlöslichkeit of 64%, a melting point of 142 ⁰ C and a glass transition temperature (T) of -21 ° C. The ether-soluble fraction has an inherent viscosity of 3.35. 143 g of the product

809884/0968

Dukts are 10 minutes at 150 ° C with 0.72 g of dilauryl thiodipropionate (Cyanox LTDP) and 0.36 g of the condensation product of 3 moles of 3-methyl-6-t-butylphenol with
1 mol of crotonaldehyde (Topanol CA) rolled on the vial mixer. A 2 mm thick plate of the rolled product is gepre at 150 ⁰ C, SST. When samples of this plate are stretched to 300% elongation at 51 cm / minute and immediately relieved of stress at the same speed to zero tension, they show an average residual elongation of 87%. Other samples of this plate

show in the stress-elongation test until they break

2
an average tensile strength of 4.83 N / mm

(700 psi) at 900% elongation. A yield point is not observed in these determinations.

The content of polymerized ethylene was through

13th

C-NMR analysis determined (see Tanaka and Hatada,

J. Polym. Sci., Polym. Chem. Ed. 11 (1973) 2057. Die
Freezing temperature T was au
see Ke (loc.cit., page 350)

Glass transition temperature T was determined from the dsc curve;

BO 9 8 "

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Claims (21)

FROM KREISLER SCHÖNWALD MEYER EISHOLD FUES FROM KREISLER KELLER SELTING PATENTANWÄLTE Dr.-Ing. von Kreisler + 1973 Dr.-Ing. K. Schönwald, Cologne Dr.-Ing. Th. Meyer, Cologne Dr.-Ing. K. W. Eishold, Bad Soden Dr. J. F. Fues, Cologne Dipl.-Chem. Alek von Kreisler, Cologne Dipl.-Chem. Carola Keller, Cologne Dipl.-Ing. G. Selting, Cologne 5 KÖLN 1 J3EICHMANNHAUS am haupioaiinhof AvK / Ax Fractionable elastic polypropylene and process for its production Patent claims 1) Fractionable elastic polypropylene, which has an inherent viscosity of 1.5 to 9, has no yield point, a residual elongation of no more than 150% and contains 10 to 80% by weight of a fraction soluble in diethyl ether which is an inherent Viscosity of more than 1.50, an isotactic crystalline polymer content of about 0.5 to 5% by weight and has birefringence when a film made from the fraction is crossed Nicoic prisms are viewed in a polarizing microscope at about 25 ° C. 2) Fractional elastic polypropylene, which has an inherent viscosity of 1.5 to 9, has no yield point, a residual elongation of no more than 150% and contains 30 to 80% by weight of a fraction soluble in diethyl ether which is an inherent Viscosity of more than 1.50, an isotactic crystalline polymer content of about 0.5 to 5% by weight and has birefringence if 809884/09 & 8 Telephone:! 0221! 23 «41-4 · Telex: 888 2307 dopa d · Telcjrcri" n: Dompalonl Cologne a film made from the fraction under crossed Nicoic prisms in a polarizing microscope is considered at about 25 ° C. 3) polypropylene according to claim 1 or 2, characterized in that it has a residual elongation of not more than 100% has. 4) polypropylene according to claim 1 or 2, characterized in that it has an inherent viscosity of 2 to β Has. 5) polypropylene according to claim 1, characterized in that it is 40 to 75 wt .-% of the ether-soluble fraction contains. 6) polypropylene according to claim 1, characterized in that it has an inherent viscosity of 3 to 8 and one Elongation residue of not more than 100% and about 40 to 75% by weight of a fraction soluble in diethyl ether with an inherent viscosity greater than 2.5. 7) Polypropylene soluble in diethyl ether, characterized in that that it has an inherent viscosity greater than 1.50 and an isotactic crystalline content Polymer of about 0.5 to 5 wt .-% and has birefringence if one made therefrom Slide is viewed under crossed Nicoische prisms in a polarizing microscope at about 25 ° C. ; 8) polypropylene according to claim 7, characterized in that j that it has an inherent viscosity greater than 2.5. J 9) Polypropylene, consisting essentially of one Mixture of about 5 to 95 parts by weight of polypropylene according to claim 1 and about 95 to 5 parts by weight of high grade isotactic polypropylene. 809884/0968 10) Polypropylene, consisting essentially of a mixture of about 2 to 9 8 parts by weight of polypropylene according to claim 7 and about 98 to 2 parts by weight of highly isotactic polypropylene. 11) Polypropylene, consisting essentially of a mixture of about 60 to 95 parts by weight of polypropylene according to claim 1 and about 5 to 40 parts by weight of highly isotactic polypropylene. 12) polypropylene according to claim 1 in the form of a film. 13) polypropylene film according to claim 12, characterized in that the film is oriented. 14) Polypropylene according to claim 1 or 11 in the form of a film. 15) polypropylene film according to claim 14, characterized in that that the film is oriented. 16) polypronylene according to claim 1 in the form of an extruded Hose. 17) polypropylene according to claim 10 or 11 in the form of a extruded hose. 18) polypropylene according to claim 1, characterized in that that there are 10 mol% of other polymerized-monoolefin _ contains units. 19)] Process for the production of elastic polypropylene, characterized in that propylene is mixed with a catalyst which is the reaction product of a metal oxide and an organometallic compound of the formula (RCH ₂ J ₄ M, where M is Zr, Ti or Hf, R is an aryl radical, aralkyl radical, tertiary alkyl radical or a trialkylsilyl radical, said alkyl radicals containing 1 to 12 carbon atoms and in the group of the formula RCH ₂ no hydrogen atom is bonded to the carbon atom in β-position to M, or by hydrogenation of the Brings the above-mentioned catalyst prepared products in contact, the reaction being carried out in the presence of hydrogen. 803884/0968 20) Method according to claim 19, characterized in that M stands for Zr. 21) Method according to claim 19, characterized in that that one uses neophyl zirconium aluminate on aluminum oxide as a catalyst. 809884/0968