NO119132B - - Google Patents

Description

Process for the selective polymerization of alpha-olefins into crystalline or amorphous polymers.

The invention relates to a new method for the selective polymerization of unsaturated coal water substances into crystalline or amorphous polymers or mixtures with predominant proportions of crystalline or amorphous polymers. The invention relates in particular to the selective polymerization of alpha-olefins of the general formula

where R means a saturated aliphatic, alicyclic or an aromatic residue, alone or in mixtures with each other or with mixtures of small amounts of other monomeric polymerisable substances. Norwegian patent no. 95095 describes new essentially linear head-tail polymers of unsaturated coal water substances and a method for producing these polymers. As is clear from this patent, mixtures of linear head-tail polymers with branches are obtained below, which are essentially no longer than R, and which contain the amorphous and crystalline polymers in varying proportions. Depending on their steric structure and their molecular weight, these polymers exhibit very different properties. The amorphous polymers have viscoelastic properties, which lie between the properties of a high-viscosity liquid and of a non-vulcanized

crystallisable elastomer, while the solid, highly crystalline polymers can be oriented

when stretched and forms high-quality fibres.

The obtained mixtures of linear polymers of amorphous or crystalline nature with branches no longer than CH3 are unique in their kind. Both types of polymers are, as the infrared spectrum shows, linear. Thus, e.g. polypropylenes, which are produced according to the invention, both of the crystalline and also of the amorphous type, similar infrared spectra, which are completely different from the infrared spectrum of known polypropylenes, and which contain branches, which are longer than CH .(. Before the claim, there was only one known example of a vinyl polymer, which existed both in amorphous and crystalline form, and these were the polyvinyl ethers described by Schildknecht and co-workers (Ind. Eng. Chem, Volume 40

(1948), page 2104 and volume 41 (1949), page

1998 and 2098). These polyvinyl ethers are obviously completely different from the polymerization products according to the present invention.

In order to more easily imagine the steric conditions, one can produce main chains of carbon atoms on a flat surface in a zigzag shape. Then, for each R group bound to an asymmetric carbon atom, two different orientations must be assumed, depending on whether the R group lies above or below the plane. When all R groups are on the same side of the plane, and the asymmetric carbon atoms in the main chain thus at least for long stretches of the molecule have the same steric configuration, then you get extremely regularly structured polyolefins with a great tendency to crystallization. This assumption was substantiated by X-ray analysis. Such regularly structured polymers, which can be obtained in crystalline form, are referred to as "isotactic polymers".

When directly opposite this the asymmetric carbon atoms of the two steric configurations, i.e. the 1-configuration and the d-configuration, are distributed statistically along the main carbon f of the chain, as is generally the case with all previously known vinyl polymers, and when the substituent R is much larger than the hydrogen atom, then the polymers are amorphous and cannot be crystallized. Such polymers are termed "non-isotactic polymers".

The production of the chains on a plan was stated only to clarify the matter. In reality, in the case of the isotactic polymers, the main chains do not exhibit a planar, but a helical structure, in which the course or progress of the spirals corresponds to a specific number of carbon atoms, usually three. In such cases, all bonds between the R group and the main chain have the same bending angle just opposite the vertical planes to the axis of the helices.

The polymers with isotactic chains show a tendency to crystallization at an already relatively low molecular weight, e.g. of 1,000 or higher. In addition to this crystallization ability, isotactic polyolefins also exhibit a higher density, a higher softening and melting point and a lower solubility compared to non-isotactic products of the same molecular weight. The melting point of the crystalline polymers generally falls with the length of the linear R groups. When these R groups, i.e. the side chains, get a considerable length compared to the distance for the carbon atoms in the main chain, and when they possess a great mobility, they prevent the formation of crystals. Directly opposite this, polymers with a static distribution of the orientation of the side chains in relation to the main chain are always amorphous products.

The crystalline and amorphous polymers of the unsaturated coal water substances described in this way are obtained according to patent no. 95,095 by a polymerization of monomers, in which catalysts are used, which are obtained from a compound of the metals from the subgroup of the periodic system 4— 6. group, including thorium and uranium, at. reaction with an organic compound of the metals from the 2nd or 3rd group of the periodic system, and which, at least on the surface, contains bonds between alkyl groups and polyvalent metals. The catalytic compounds of metals from subgroup 4-6 of the periodic table. group are compounds of the heavy metals titanium, zirconium, hafnium, thorium, vanadium, tantalum, niobium, chromium, molybdenum, tungsten and uranium, which occur with several values.

The organic compounds of metals from the 2nd and 3rd groups of the periodic system include compounds of beryllium, magnesium, zinc, cadmium and other metals from the second group, as well as compounds of aluminum and other metals from the 3rd group of the periodic system. These metals are bound to the same or different alkyl or alkoxy residues or halogen atoms.

Special active catalysts are prepared according to patent no. 95,095 in the presence of the free unsaturated coal water substances, and the preparation is generally carried out in the presence of solvents.

Until now, it was not known to conduct the described polymerization process in such a way that either predominantly or exclusively polyolefins are formed with a regular sequence of CH2 groups and CHR groups in long straight chains, in which the asymmetric carbon atoms in the main chain in the least for long stretches of the molecule have the same steric configuration (polymers of isotactic structure) with a great tendency to crystallization or predominantly or exclusively amorphous olefin polymers are produced, where the asymmetric carbon atoms in the two steric configurations have a static distribution along the main chain (polymers of non-isotactic structure).

It now turned out that one can direct the polymerization of alpha-olefins selectively predominantly or exclusively to polymers of isotactic structure or predominantly or exclusively to polymers of non-isotactic structure, or to mixtures of both polymer types in a desired ratio by setting of the following physical and possibly chemical factors:

Physical factors.

1) The aggregate state of the catalyst, in particular the aggregate state of the heavy metal compounds, which are used for production. 2) The catalyst's degree of dispersity in the solvent during the polymerization.

These factors are decisive for the progress of the polymerization.

Chemical factors.

3) The value of the heavy metal in the heavy metal compound used for the production of the catalyst. 4) The nature of the substituents, which are bound to the heavy metal. 5) The nature of the substituents of the metal-organic compounds.

These factors are certainly of importance, as they can influence or even determine the physical factors.

Depending on the choice of one or more of these factors, the polymerization proceeds either in the direction of the production of polymers with an isotactic structure or in the direction of the production of non-isotactic polymers.

For the production of polyolefins of predominantly or exclusively crystalline nature and isotactic structure, solid, preferably crystalline catalysts must be used and for their production solid, preferably crystalline heavy metal compounds. For example, one will start from solid, crystallized titanium dichloride or titanium trichloride and direct the production of the catalysts in such a way that it consists of solid parts, which at least on the surface contain bonds to the organometallic compounds. The reaction must be conducted in such a way that the original crystal structure of the heavy metal compounds is destroyed as little as possible.

On the other hand, for the production of polyolefins of predominantly or exclusively amorphous nature and non-isotactic structure, liquid or dissolved catalysts are used, and in accordance with this, their production is either based on similarly liquid or dissolved heavy metal compounds from the subgroup of 4-6 . group or when using solid heavy metal compounds as starting material, it is ensured that they dissolve during the production of the catalyst. For example, the starting point is liquid titanium tetrachloride, ensuring that the reduction takes place under such circumstances that nothing or only the smallest possible amount of crystalline parts is formed.

Furthermore, the catalyst's dispersion

degree of importance for the course of the polymerization. It turned out that with coarsely dispersed catalysts you get polyolefins of predominantly or exclusively crystalline nature and isotactic structure, and with highly dispersed catalysts you get polyolefins of predominantly or exclusively amorphous nature and non-isotactic structure.

It also turned out that catalysts of the kind described in patent no. 95,095 can be divided into fractions, of which the fractions which contain the coarser dispersed or more crystalline particles as catalysts for the polymerization of unsaturated coal water substances predominantly or exclusively leads to isotactic and crystalline polymers, while the fractions, which contain the finer dispersed and smaller crystalline particles during the polymerization of unsaturated coal water substances predominantly or exclusively give amorphous, non-crystallizable polymers of non-isotactic structure.

The dispersity of the catalysts can be reduced in the usual way for the production of crystalline, isotactic polymers, e.g. by separating the finer dispersed parts by filtration, decantation, sedimentation, centrifugation, flotation or other methods and only using them, e.g. remaining coarser disperse parts on the filter.

On the other hand, for the production of polyolefins of predominantly or exclusively amorphous nature and non-isotactic structure, catalysts can be used, the dispersion of which is increased by dividing the catalyst obtained by filtration, decantation, sedimentation, centrifugation, flotation or other methods into coarse and fine parts, and only the fine particles are used for the polymerization.

While an unfractionated catalyst according to patent no. 95,095 gives an indiscriminate mixture of amorphous and crystalline polymers, according to the invention, by fractionating the catalyst, e.g. by filtering the solution, which contains the catalyst, through filter plates with relatively small pores, obtain two different fractions of which the filter residue is suitable for the production of polymers of predominantly crystalline nature and isotactic structure, and the filtrate is suitable for the production of polymers of predominantly or exclusively amorphous nature and not isotactic structure. Appropriate filters are used for this purpose, e.g. porous glass or ceramic plates, which have pores from 5-15 microns.

Table I shows the results of the polymerization using titanium tetrachloride or vanadium tetrachloride and aluminum triethyl produced catalysts, which on one occasion were used unfractionated, but on the other occasion were fractionated by filtration into the coarsely dispersed residue and the finely dispersed filtrate. The table shows that while the unfractionated catalyst gives a propylene polymer, which consists of 47.8 per cent of crystalline parts, the fractionation results in a residue on the one hand, which leads to a polymer with a higher content (approx. 54 per cent) of crystalline polymers, while on the other hand the filtrate gives a completely amorphous polymer.

Table I.

Percentage of crystalline polymers in polyolefins obtained by polymerization of olefins in the presence of unfractionated or fractionated catalysts, which were obtained from heavy metal tetrachlorides and aluminum triethyl.

When the filter residue is resuspended in an inert liquid and filtered, you get a filtration residue, which upon polymerization yields a product with a higher content of crystalline proportions and a filtrate, which upon polymerization yields a polymer with smaller proportions of crystalline products.

A further way to produce a catalyst of high dispersity consists in suspending the catalyst produced in the usual way in a solvent for the olefin, which is to be polymerised, in such a way that a cloudy suspension is formed. From this, the coarser dispersed part of the solid catalyst is separated by means of mechanical or physical methods, and this can be used for the production of crystalline polymers. The remaining suspension, which now only contains colloidal particles, is suitable for the production of amorphous, non-isotactic polymers.

A further important rule of thumb to influence the polymerization in the direction of crystalline polymers is that where an insoluble heavy metal compound is used as a starting material for the production of the catalyst, in which the heavy metal exists in a lower value than the maximum value that the heavy metal can have according to its position in the Periodic Table.

On the other hand, the quantity of the amorphous polymers in the polymerization products is increased when a heavy metal compound is used for the production of the catalyst, in which the heavy metal has a higher value, in particular maximum value, which accrues to it according to its position in the periodic table.

In the production of the polymerization catalyst using a titanium compound of a lower value, one starts, for example, from solid, powdered, micro-crystalline titanium dichloride or titanium trichloride, suspends it in a carbon hydrogen and adds a metal alkyl compound, such as triethylaluminum or diethylaluminum, after which the mixture is heated to 50-90° C. If we proceed here from titanium trichloride, then the reaction mixture retains the same violet color as the titanium trichloride itself. A catalyst is obtained, which leads the polymerization of unsaturated coal water substances essentially in the direction of the formation of polymerization products of a crystalline nature. The proportion of the isotactic polymers in the product obtained is generally the higher the purer the titanium trichloride, which was used for the preparation of the catalyst, i.e. the lower its content of titanium tetrachloride and of its oxidation or hydration by-products.

Instead of titanium trichloride, in the example described, one can also proceed from titanium dichloride, which is just as well suited for the production of catalysts for a process which essentially leads to crystalline polymerization products of alpha-olefins.

Titanium tribromide, on the other hand, despite its lower value and its crystalline aggregate state, gives larger amounts of non-isotactic polymers than titanium trichloride. This leads back to the fact that titanium tribromide is fairly soluble in the coal hydrogen used. When it therefore reacts with the organometallic compound, at least part of it dissolves in the coal-hydrogen, and the catalyst formed by the reaction of the dissolved titanium tribromide with the metal alkyl does not differ significantly from the catalysts which are produced from high-quality liquid or soluble halides.

On the other hand, if you start from heavy metal compounds in which the heavy metal has a higher value, especially its maximum value, e.g. based on liquid titanium tetrachloride, even in the presence of dispersants a smaller proportion of isotactic polymers is obtained in the polymerization product. When crystalline and isotactic proportions are also contained in the polymer, this can be explained by assuming that the black solid precipitate, which is formed by the reaction of titanium tetrachloride with the organometallic compound, contains a titanium compound of lower value, which is at least partly exhibits a crystalline structure.

Titanium tetrabromide behaves in a similar way to titanium tetrachloride, in that it partly gives amorphous and partly crystalline polymers. The relatively high melting point of titanium tetrabromide does not apply here, as titanium tetrabromide dissolves completely in the solvent used under the reaction conditions. These conditions are confirmed by a study of table II, which shows the influence of the halogen, which is bound in the heavy metal compound, during which the halogen is bound to the heavy metal in a lower, as well as in a higher value. The table reproduces the proportion of crystalline polymers in the polymerization of propylene with catalysts, which is obtained by reacting aluminum triethyl in a titanium trihalide or tetrahalide.

It appears from this that in the case of bro- | the amide and the iodide as a heavy metal compound', the change in valence from 4-3 does not increase the crystallinity of the polymerization product, because in these cases the degree of dispersity of the catalyst in the reaction medium is of decisive importance. Thus, the catalyst obtained from titanium triiodide gives smaller amounts of crystalline polymers than the catalyst from titanium tetraiodide, as the catalyst obtained from titanium triiodide is more finely distributed in the reaction medium than the catalyst obtained from titanium triiodide. In the case of titanium tribromide and titanium tetrabromide, the different factors will keep each other in equilibrium, which is why the proportion of crystalline substance in the polymerization product is the same in both cases. In the same way, the ratio between amorphous, non-crystalline parts in the polymerizate formed can be influenced in favor of the latter by using compounds of other heavy metals from subgroups 4-6 of the periodic table. group of a lower dignity than the metal maximum, as a result of its position in the periodic table can be possessed by. This is the case with compounds of the metals zirconium, hafnium, thorium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and uranium, for example when using solid, crystalline vanadium trichloride, zirconium trichloride or chromium trichloride.

On the other hand, predominantly or exclusively amorphous polymerization products are obtained when, in the production of the catalysts as heavy metal compounds of the mentioned metals, those of higher, especially of the maximum value, for example vanadium tetrachloride or vanadium oxytrichloride, zirconium tetrachloride or chromium oxydichloride are used. These conditions can be deduced from Tables III and IV, which show the influence of the preparation of catalysts of heavy metal halides of different valence, and aluminum triethyl on the percentage crystallinity of the polymers obtained from propylene (Table III) and butene-1, (Table IV).

The preferred embodiment of the invention for the production of catalysts, which are suitable for the formation of essentially crystalline polymers, and which consists in using a solid, crystalline lower-valued heavy metal compound as starting material, has numerous advantages over other methods for the production of these catalysts, e.g. the possibility of using smaller amounts of organometallic compounds for activation of the catalyst surface.

According to patent no. 95,095, a ratio of 1:12 mol aluminum compound to 1 mol titanium compound can be used. Also in the table of the description, when using titanium tetrachloride or correspondingly higher valuable compounds of other heavy metals, a molar ratio between the heavy metal compound and the aluminum alkyl compound of the order of 1:2.5 to 1:10 is used, while in the case of the titanium trichloride and correspondingly lower valuable heavy metal compounds other molar ratio of 1:2 or lower. This can be explained on the basis of the following hypothesis regarding the reaction mechanism in the preparation of the catalyst and in the polymerization of the unsaturated coal water substances with the catalyst.

According to the preferred embodiment according to the invention, the organometallic compound such as aluminum triethyl is dissolved in the unsaturated coal hydrogen, which is to be polymerized, and the heavy metal compound, e.g. the solid, crystalline titanium trichloride or the liquid titanium tetrachloride is reacted in the presence of the olefin with the organometallic compound. Depending on the heavy metal compound used, one of the following reactions takes place below:

It is already clear from this course of reaction that the need for aluminum alkyl in the second case, i.e. when a heavy metal of a higher value is used, is twice as great as in the first-mentioned case, i.e. when a heavy metal of a lower value is used. In practice, the consumption of organometallic compound is even less, since when using the solid titanium trichloride, the reaction is limited to the surface of the titanium trichloride crystals.

A further advantage consists in the fact that the turnover according to equation (a) only requires one work step. If, on the contrary, a catalyst is obtained for the polymerization of olefins into crystalline polymers according to equation (b), then the obtained reaction product must be mechanically fractionated to separate the solid, at least partially crystalline part of the obtained catalyst from the highly dispersed micellar or dissolved part, because only the solid, preferably crystalline fraction is suitable for the formation of predominantly or exclusively crystalline polymers.

On the other hand, mixtures of amorphous and crystalline polymers of the unsaturated coal water substances are obtained in the presence of the unfractionated catalysts, which are obtained from preferably soluble or liquid heavy metal compounds, such as titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride and the like. In the reaction of such heavy metal compounds with the organometallic compounds, a change in the value of the heavy metal compounds takes place. In the case of titanium tetrachloride, this value change takes place according to the following equations:

Equations (c) and (d) proceed rapidly under strong gas evolution, during which the titanium trichloride, which is formed, or an even lower valuable product cannot occur in crystalline form. All methods for producing the catalysts, by which the formation of well-crystallising reaction products is prevented, lead to catalysts which favor the formation of amorphous polymers.

Furthermore, the substituents on the heavy metal are important for the course of the polymerization. Both the chemical nature of the anions and also their molecular size exert an influence on the polymerization, whereby the proportion of amorphous polymers rises with the size of the anion, which is bound to the heavy metal.

When titanium compounds are used as starting materials, which, in addition to or instead of halogen atoms, contain lyophilic groups or groups that interfere with crystallization, e.g. alkoxy groups or hydroxyl groups, as compounds of the general formula

Ti(OR)nCl4_n

where n means a number from 1-4, then with an increasing number of the lyophilic or crystallization-disturbing groups during the reaction with organometallic compounds catalysts are produced, which have a less regular structure, and a higher degree of dispersity, and therefore lead to the formation of non-isotactic amorphous polymers . This appears from table V, which reproduces the crystallinity proportions of the polymerization product, which was obtained by the polymerization of propylene in the presence of catalysts, which were produced from titanium compounds of different value and different bonding with aluminum triethyl.

The table shows that by using the titanium dichloride, which exhibits both the lowest value and which is also solid and crystalline, a product with the highest crystallinity is obtained. With titanium trichloride, approximately the same results are obtained. With increasing value, change in the aggregate state to liquid, and replacement of the halogen atoms with alkoxy or hydroxyl groups, the proportion of crystalline parts falls and the proportion of amorphous parts rises in the polymer. With ortho-titanic acid or tetraalkyl titanates exclusively amorphous products are obtained.

The formation of amorphous polymerization products can be further favored by using organic compounds of the metals from the 2nd or 3rd group of the periodic table in the production of the polymerization catalysts, e.g. aluminum alkyl compounds, in which the alkyl groups have stronger lyophilic properties. The presence of such groups favors the degree of dispersity of the catalyst obtained. Micellar colloidal dispersions of the catalyst in the solvent are obtained. Suitable lyophilic groups for this purpose are likewise alkoxy groups, further alkyl residues with relatively long chains of carbon atoms. Such alkyl residues must have more than 4, preferably 6-16 carbon atoms.

Tables VI and VII show the influence of the lyophilic groups in the organometallic component of the catalyst for the formation of crystalline and amorphous polymers in the polymerization of propylene (Table VI) and butene-1 (Table VII).

The percentage of crystalline products is also indicated in these tables.

Table VI shows that the proportion of amorphous polymers increases with the number of carbon atoms in the alkyl group in the aluminum tri-alkyl; while with aluminum triethyl the highest proportions of crystalline polymers are obtained, these proportions decrease with increasing alkyl size. When using the aluminum alkylene with alkyl groups of considerable length and correspondingly highly lyophilic properties, the reaction with heavy metal compounds does not form precipitates, but colloidal solutions. Of these dispersions, the finely dispersed catalysts cannot be separated by mechanical precautions, such as filtration and the like.

Table VI also shows that the formation of non-crystalline catalysts and their degree of dispersity can also be favored by the use of heavy metal compounds, which exhibit alkoxy groups of considerable length. Thus, dibutoxycytethane dichloride even with aluminum triethyl leads to the formation of a catalyst, which predominantly gives amorphous polymers of unsaturated coal water substances.

Table VII shows that the same, although also weakened regularities, which could be observed in Table VI in the polymerization of polypropylene also exist in the polymerization of higher alpha olefins, such as butene-1. It is particularly noteworthy that the formation of crystalline polybutenes is particularly favored by the production of the catalysts from an organometallic compound containing butyl groups, so that with aluminum tributyl a polybutene with an even higher degree of crystallinity is obtained than with aluminum triethyl.

Finally, the significance of the heavy metal's dignity is also apparent from tables VI and VII.

Furthermore, table VIII shows that the effects of the length of the alkyl chain in the organoaluminum compound, which appear in table VI, also exist with heavy metal compounds other than titanium compounds. This table shows the percentage degree of crystallinity of polymers produced from propylene, respectively butene-1 and catalysts produced from titanium, zirconium and vanadium tetrachloride or vanadium and chromium trichloride and the aluminum alkylene of different chain lengths.

Finally, the polymerization is directed towards the production of polyolefins predominantly or exclusively of an amorphous nature by using organometallic compounds which, in addition to alkyl groups, contain halogen atoms. This is evident from Table IX, in which the results of the polymerization of propylene with respect to the percentage of crystalline substances using catalysts which were prepared from titanium trichloride or titanium tetrachloride and various organometallic compounds are reproduced.

The effect of the nature and preparation of the catalyst on the polymerization can be explained as follows: In the reaction of a solid heavy metal compound with organometallic precursors, at least superficial bonds are formed between the heavy metal and the alkylene in the organometallic compounds. The first adsorbed monomeric olefin penetrates the surface of the catalyst, i.e. on the heavy metal side, into the alkyl chain, whereby the alkyl chain grows. The paraffinic chain formed is less strongly adsorbed on the surface of the catalyst than the monomeric olefin, and has a tendency to dissolve from the surface of the catalyst. In the same way, another and further molecules of the monomer are adsorbed by the catalyst surface, and incorporated into the metal alkyl chain. If the second and further adsorbed molecules of the monomer are oriented in the same way as the first molecule of the monomer, a polymerization product of regular structure and a great tendency to crystallization is obtained. This is the case when the catalyst itself is solid and crystalline, and exhibits a regular surface, as is the case with catalysts obtained by reacting titanium trichloride with aluminum triethyl. If the second and further molecules of the monomer are not oriented, then an amorphous, non-crystallizable polymerization product is obtained. Due to its amorphous structure, the surface of the catalyst cannot exert any orienting effect, e.g. when the catalyst is present in micellar dispersion in a solvent, and thus the molecules of the monomer do not provide any "orientation surface".

Example 1.

Into a 2150 ccm autoclave filled with nitrogen, introduce two steel balls, a glass ampoule, which contains 7.2 g of crystallized titanium dichlord and the solution of 11.4 g of Al-tri-ethyl in 500 ccm of n-heptane. The temperature is increased to 82° C, and at this temperature the autoclave is set in motion, and this causes the glass ampoule to burst.

The autoclave is kept moving for 10 hours at 80-85° C. The gases are then released

out, and the non-polymerized propylene

is intercepted. Methanol is now introduced into the autoclave. The white, powdery polymer is then drained and treated in the usual manner with acid to remove the inorganic compounds present. There are available

115 g of a white, powdery polymer, which corresponds to an 82 percent conversion of the added propylene.

The polymer is then separated into fractions

using hot solvents.

The oily products of lower molecular weight, which correspond to 5.8 per cent of the total

extracted polymer is removed by extraction with hot acetone. By means of the subsequent treatment with hot ether, 8.3 percent of the polymer is brought into solution. This fraction consists of X-ray amorphous polypropylene, which exhibits an intrinsic viscosity of 0.47 measured in tetralin solution at 135° C.

With the help of hot n-heptane, a further fraction is obtained, which corresponds to 10.4 per cent of the total amount of polymer, and which exhibits an intrinsic viscosity of 0.57. This fraction is radiographically more than 50 percent crystalline.

The reaction residue, which corresponds to 75 per cent of the total amount of polymer, consists of an X-ray highly crystalline polypropylene with an intrinsic viscosity of 1.86.

The raw polymer obtained therefore had a crystallinity of at least 80 per cent.

Example 2.

In a 435 ccm autoclave, glass ampoules with 2 gr. TiCl;! in 30 cc of n-heptane and a 1 inch steel ball to break the ampoules to pieces at the moment polymerization begins. A solution of 5.7 gr is then introduced into the autoclave in a nitrogen atmosphere. triethylaluminum in 60 ccm n-heptane, and the autoclave is heated to 70° C. Then introduce 103 gr. liquid propylene, and immediately afterwards the autoclave is set in motion to break apart the ampoules, which contain TiCL. A slight rise in temperature is noted, while the pressure slowly but steadily drops. After 6 hours, during which the temperature has remained between 80-90° C, and when you no longer notice any pressure increase, 50 ccm of methanol is pumped into the autoclave to split the catalyst, and the remaining gases containing 10 NI (Normal liter) are removed . A solid, compact mass is discharged from the autoclave, which is first cleaned in the manner described in example 1 with methanol and then with concentrated HC1, the mass being swollen with boiling toluene. The mass is then coagulated with methanol, filtered, washed with methanol and dried in a vacuum in the heat.

The polymer obtained changes to 82 gr., which corresponds to a polymerization of 79.6 per cent, calculated on the propylene used, and the polymer consists of 85 per cent crystalline polypropylene, which can be separated from the non-crystalline products (15 per cent) by extraction with solvents.

, The amorphous part is completely insoluble in acetone. The largest part is soluble in the heat of ether, has a softening point of 100° C, an intrinsic viscosity of 0.685 and a molecular weight of approx. 18,000. The heptane-insoluble, crystalline part has a softening point of 165° C, an intrinsic viscosity of 2.39 and a molecular weight of approx. 120,000.

Example 3.

In a 500 ccm autoclave, provided with a mantle for heating by means of circulating oil and a thermostat for temperature regulation to 1° C, introduce in a nitrogen atmosphere 0.98 gr. TiCls and 220 ccm of anhydrous n-heptane. The autoclave is then evacuated, and the solvent is saturated with the (98.5 per cent) propylene at a pressure of 1000 mm Hg above atmospheric pressure, while at the same time the internal temperature of the autoclave is brought up to 70° C. The autoclave is kept at 70° C in motion for 90 min. After this time, the solution of 1 ccm of triethylaluminum in 30 ccm of n-heptane is added under propylene pressure.

Gaseous propylene is continuously supplied there at a constant overpressure of 1000 mm Hg over the course of 4 hours. The polymerization rate after approx. 2 hours after the introduction of triethylaluminum corresponds to an absorption of 11.5 gr. propylene per hour and per Gr. TiCLj.

After the above-mentioned time, the reaction product is exhausted and purified. In this way, you get 42 gr. polypropylene with approx. 80 percent crystalline polymer. in Example 4:

In the apparatus described above, 0.05 gr. is introduced into a nitrogen atmosphere. TiCl3 and a solution of 3.25 gr. triethyl aluminum in 250 ccm n-heptane. The autoclave is kept in motion for 4 hours at a temperature of 70° C. The nitrogen is then removed, and propylene is introduced there, the solvent being saturated at a constant overpressure of 1000 mm Hg. It is kept in motion for 4 hours, maintaining a continuous supply of propylene at the aforementioned pressure. It is established that after 10 hours the polymerization rate corresponds to an absorption of 11.4 gr. propylene per hour and per Gr. TiCl3. The amount and nature of the polymer obtained corresponds to what is indicated in this regard in example 3.

Example 5:

In a 435 ccm shaking autoclave, introduce two stainless steel balls and a glass ampoule, which contains 1.85 gr. (0.012 mol) titanium trichloride. A solution of 3.9 gr is then added in a nitrogen atmosphere. tripropylaluminium in 100 ccm heptane. The autoclave is heated to 73° C, and at this temperature 90 gr. propylene. The movement of the autoclave is then started immediately, causing the ampoule to burst. The autoclave is kept in motion for approximately 10 hours at a temperature between 70-75° C. After this time, the reaction product is drained, which turns out to be a solid, very compact and solvent-moistened mass. The product is cleaned using hydrochloric acid leaching in the manner described in examples 1 and 2.

You get 72 gr. solid, white polypropylene, which is fractionated with solvents during heat extraction. The acetone extract corresponds to 3.5 percent of the polymer obtained, and consists of oily products with a low molecular weight.

The ether extract corresponds to 13.3 per cent of the product obtained, and consists of amorphous, solid polypropylene with an intrinsic viscosity of 0.725 (determined in tetralin at 135° C), which corresponds to a molar weight of approx. 20,000. The heptane extract corresponds to 11.4 per cent of the product obtained, and consists of polypropylene with an intrinsic viscosity of 0.9, which corresponds to a molecular weight of approx. 28,000. This fraction appears radiographically to consist of more than 50 percent crystalline polypropylene.

The extraction residue corresponds to 71.8 per cent of the product obtained, and consists of highly crystalline polypropylene, which has an intrinsic viscosity of 3.08, which corresponds to a molecular weight of approx. 180,000. The raw polypropylene obtained therefore exhibits a crystalline polypropylene content of at least 77.5 per cent.

Example 6.

In a 2080 ccm autoclave introduce 3.7 gr.

The resulting polymer has a crystallinity of around 60 per cent.

Example 7.

In a 435 ccm autoclave, introduce two steel balls, a glass ampoule, which contains 1.85 gr. TiCl;! and in nitrogen atmosphere a solution of 7.05 gr. (0.025 mol) of trihexylaluminum in 100 ccm of heptane. It is heated to 85° C, and 92 gr. propylene, immediately setting the autoclave in motion. The temperature is maintained for about 10 hours between 95 and 100° C, and after this time the reaction product is removed and purified in the usual way. You get 83 gr. polypropylene, which is fractionated in the heat during extraction with solvents. The acetone extract corresponds to 11.8 percent of the polymer obtained, and consists of oily polymers with a low molecular weight. The ether extract corresponds to 15 per cent of the polymer obtained, and consists of solid, amorphous polypropylene with an intrinsic viscosity of 0.57.

The heptane extract corresponds to 19.2 percent of the polymer obtained, and has an intrinsic viscosity of 0.8 (in tetralin solution at 135° C). According to X-ray testing, this fraction contains more than 50 percent crystalline polymer.

The extraction residue corresponds to 54 per cent of the polymer obtained, and consists of highly crystalline polypropylene with an intrinsic viscosity of 2.07.

The total product obtained thus has a crystalline polypropylene content of at least 64 per cent.

titanium trichloride and a solution of 99 gr. tri-n-butyl aluminum in 250 ccm heptane. You then add 220 gr. of a propylene-propane mixture with a content of 92 percent propylene, and heats the autoclave while stirring to 90° C. At this temperature, a rapid pressure drop occurs. The autoclave is kept in motion for 5 hours, the polymerization product is then withdrawn, and one obtains

190 gr. polypropylene, which by extraction with hot solvents is divided into the following fractions:

In Example 8.

In a 1100 ccm autoclave, 1.85 gr of nitrogen is introduced into the atmosphere. TiCl.j and a solution of 17.5 gr. of a trialkyl aluminum with an average molecular weight of trihexadecyl aluminum in 100 ccm of n-heptane. Then add 130 gr. of a propylene-propane mixture, which contains 91 percent propylene. It is heated to 90° C, and kept at this temperature for approx. 10 hours. After purification, 115.2 gr is obtained. polypropylene, which is fractionated by extraction with solvents in the heat.

The acetone extract makes up 11.4 per cent of the polymer obtained, and consists of oily products with a lower molecular weight. The ether extract makes up 19.5 per cent of the polymer obtained, and consists of solid, amorphous polypropylene with an intrinsic viscosity of 0.66 (in tetralin solution at 135° C). The heptane extract makes up 20 per cent of the polymer obtained, and consists of approx. 50 percent of crystalline polypropylene. This fraction shows a limiting viscosity of 0.80. The extraction residue makes up 49.1 per cent of the polymer obtained, and consists of X-ray highly crystalline polypropylene with an intrinsic viscosity of 3.15. The resulting polymer has a crystalline polypropylene content of approximately 59 percent.

Example 9.

A solution of 10 g is introduced into a 1100 ccm autoclave. Al(n-C4H9)3 in 150 ccm n-heptane, and then add 200 gr. of a propylene-propane mixture with a content of 92 percent propylene. The autoclave is heated to 73° C, and a solution of 3.8 gr is introduced there. TiCl4 in 20 ccm n-heptane. The temperature thereby rises spontaneously to 95° C, while the pressure drops rapidly.

The autoclave is kept approx. 4 hours of wood

temperatures between 80 and 90° C in motion. Methanol is now added to the autoclave. With normal cleaning, you get 80 gr.

white, solid polypropylene, which is then separated into fractions by hot solvent.

The following results are obtained during the fractionation:

The raw polymer therefore has a crystallinity of approx. 30 percent

Example 10:

In an evacuated, dried, stainless steel autoclave with a content of 2150 ccm, a solution in 500 ccm of n-heptane of 28.2 (equal to 1/10 mol) of a trialkylaluminum with an average molecular weight, which corresponds to trihexylaluminum, is filled. 28.5 gr is then added. liquid propylene, and then the autoclave is set in motion. The autoclave is then heated, and at a temperature of 80° C, a solution of 3.8 gr is added. TiCl4 in 40 ccm of heptane. This is followed by a spontaneous rise in temperature, which in a few minutes reaches 120° C, and then slowly drops again. As soon as the temperature has again dropped to 80° C, a further 3.8 gr is added. TiCl„ dissolved in 40 ccm of n-heptane, whereupon a further rise in temperature occurs, although it is lower than the first. The autoclave is left in motion for another two hours, the gaseous products are released, and finally approx. 100 ccm of methanol, to dissolve the polymerization catalyst. The residual gases originating from the dissolution of the catalyst are led out, and in the autoclave there is a solid, viscous mass, which is emptied out, and is purified by treatment in the heat with ether and hydrochloric acid, so that the inorganic substances present on the filter, which originate from the manufacture of the catalyst is removed. The solvent-swollen polymer is then coagulated with methanol, filtered and washed with methanol. The solid mass remaining on the filter is then dried at reduced pressure and at temperatures below 100°C.

Of the 253 gr. produced polymer,

which corresponds to a change of 87 per cent of the propylene used, 73.8 per cent is formed by an amorphous polymer, which in the heat is largely soluble in ethyl ether, and has the same properties as a non-vulcanized elastomer. The part soluble in ether, and removed in the heat with acetone, leaves behind a residue upon extraction, which has a softening point of 75° C, an intrinsic viscosity of 0.33 (determined in tetralin solution at 135° C) and a molecular weight of approx. 7,000. The other 26.2 percent consists of crystalline polypropylene, is for the most part insoluble in hot n-heptane, and has a softening point of 150° C, an intrinsic viscosity of 1.28 and a molecular weight of about 50,000.

Example 11.

Into a 2150 ccm autoclave, working as in example 10, 70.2 gr. of a trialkyl aluminum with an average molecular weight, corresponding to the molecular weight of trihexadecyl, in 500 ccm of heptane, and 350 gr. liquid propylene. The autoclave is heated with stirring to 67° C; a solution of 3.8 gr is then introduced under nitrogen pressure. titanium tetrachloride in 40 ccm of heptane. The temperature rises to 110° C. When the temperature has again dropped to 100° C, another solution of 3.8 gr is introduced. titanium tetrachloride in 40 ccm of heptane. 5 hours after the beginning of the polymerization, 100 ccm of methanol are filled into the autoclave, and the remaining gases are released. The catalyst is removed as in example 10, and after purification 338.7 gr. solid polymer, which makes up 96.5 per cent of the propylene used. The raw product consists for the most part (83.8 per cent) of an amorphous polymer, and only 16.2 per cent crystalline, of the remaining polymer with the help of subsequent extractions with acetone, ether and n-heptane-separable polypropylene.

The amorphous part, which is insoluble in acetone and soluble in ether, has a softening point of 70° C, an intrinsic viscosity of 0.5 and a molecular weight of approx. 11,000. The crystalline, n-heptane-insoluble part has a softening point of approx. 150° C, an intrinsic viscosity of 1.09 and a molecular weight of approx. 37,000.

Example 12.

Into a 2150 ccm autoclave are introduced 3 steel balls and a glass ampoule, which has been remelted by a flame, and which contains 9 gr. dichlorodibutoxytitanium (TiCL/CX^H,,);,). A solution of 11.4 gr is pressed into the autoclave in a nitrogen atmosphere. triethyl aluminum in 500 ccm heptane. It is heated to 80° C, 275 gr is added. liquid propylene, and the autoclave is immediately set in motion. The movement is continued at a temperature between 90 and 100° C.

After about 10 hours, counted from the beginning of the polymerization, methanol is pumped into the autoclave, and the unreacted gases are released. The reaction product is extracted from the autoclave, which is a solid, viscous, brown-green colored mass, which is cleaned in the usual way. After purification, 54.2 grams of polymer is isolated, which corresponds to a 20 percent polymerization of the propylene used. More than half (64.9 per cent) of the polymer obtained consists of amorphous polypropylene, which for the most part is soluble in ethyl ether in the heat. The residue (35.1 per cent) consists of crystalline polypropylene, which can be separated from the amorphous part by means of subsequent extractions with a solvent.

Examples 13 and 14.

In an autoclave with an approximate 2-litre capacity, a solution of 11.4 gr is filled in a nitrogen atmosphere. triethyl aluminum in 500 ccm heptane and 190 gr. propylene. It is heated to 64° C, and at this temperature, under pressure, a solution of 0.03 mol of titanium tributylate monochloride in 50 ccm of pentane is added. The autoclave remains for approximately 8 hours at a temperature of 80 to 85° C in motion. After this time, the reaction product is exhausted, which after cleaning and drying consists of 8 gr. firm, rubbery, approx. 10% crystalline polypropylene containing polymer.

When you proceed in the same way, as described above, and also use titanium tetrabutylate, you get 5.4 gr. low molecular weight propylene polymer, containing only traces of crystalline polypropylene.

Example 15.

In a 2150 ccm autoclave filled with nitrogen, introduce 11.4 gr. Al(C2H-)3 dissolved in 200 ccm of heptane and 200 gr. propylene. It is heated with stirring to 81° C, and then a solution of 0.5 gr is introduced. titanium tetra-isopropylate in the autoclave, which is then kept in motion for approximately 15 hours at temperatures between 90 and 100° C. The reaction product is purified in the usual way, and one obtains 6 gr. polymer. These 6 gr. is divided by extraction with hot solvent into fractions in the usual way, and the following results are obtained:

The resulting polymer therefore has a crystallinity of 4 percent.

Example 16.

In a 435 ccm autoclave filled with nitrogen, a glass ampoule is introduced, which contains

holds 0.7 gr. Ti(OH)4 and a solution of 5.7 gr. A1(C2H,)3 in 150 ccm n-heptane. You then add 100 gr. of a propylene-propane mixture with a content of 90% propylene, and heats the autoclave to 90° C. At this temperature, the autoclave is set in motion,

and thereby the glass ampoule shatters. After 12 hours, the polymerization product is exhausted

tet, and the polymer is coagulated by adding methanol and acetone.

You get 2 gr. solid polymer and 35 gr. semi-solid and oily products with lower molecular weight.

The solid products show a crystallinity of approx.

50 percent

Example 17.

In a 2150 ccm autoclave, introduce 3 stainless steel balls and a glass ampoule, which contains 3.5 gr. titanium trichloride. A solution of 11.4 gr is then filled into the autoclave in an N2 atmosphere. triethyl aluminum in 500 ccm heptane. It is heated to 70° C, and 202 gr. butene, which is made from butyl alcohol and which contains 70 percent butene-1 and 30 percent butene-2. The autoclave is kept at a temperature of 70 to 80°C for 20 hours with stirring. Methanol is then pumped into the autoclave, and the unreacted gases are removed.

A very viscous mass is removed from the autoclave, which completely coagulates when additional methanol is added, and is cleaned in the usual way. You get 29 gr. white, solid polymer, which is fractionated in the heat by extraction with solvents. 65 per cent of the product obtained consists of crystalline polybutene with a molecular weight of over 30,000. The remaining part consists of a completely amorphous product, which possesses the same properties as a non-vulcanized elastomer.

When repeating the experiment using a TiCl4-trihexadecyl aluminum-

mixture as a catalyst, then a viscous product is obtained, which is liquid, as in the previous case with TiCl3, and practically completely consists of amorphous polybutene.

Example 18.

In a 435 ccm autoclave introduce 1.85 gr.

TiCl3, a solution of 3.9 gr. tripropyl aluminum in 100 ccm heptane and 85 gr. 1-butene. The polymerization is carried out at temperatures between 90 and 95° C. You get 60.5 gr. polybutene, which is divided into fractions in the usual way.

The crystalline fraction insoluble in hot ether makes up approx. 75 per cent of the total product.

Example 19.

In an oscillating 1100 ccm autoclave, introduce into a glass ampoule 6.5 gr. TiCl3 and 2 steel balls. The autoclave is filled with nitrogen, and a solution of 19.8 gr. Al(n-C;H9)3 in 500 ccm n-heptane. Heat to 85° C, and then add 115 gr. butene-1 (Phillips, absolutely pure), and sets the autoclave in motion to break the glass ampoule. The temperature rises rapidly to 95° C. The autoclave is kept moving for 4 hours, and then the polymerization product is removed and cleaned in the usual way. You get 109 gr. white, solid polybutylene with a fibrous appearance, which can be separated into the following fractions by extraction with hot solvents:

Example 20. In a 435 ccm autoclave a solution of 8 gr. aluminum tripropyl in 90 ccm n-heptane and 47 gr. butene-1 (Phillips, absolutely pure). The autoclave is heated to 65° C, and a solution of 3.8 gr is introduced there. titanium tetrachloride in 30 ccm of n-heptane under nitrogen pressure. The temperature rises spontaneously to approx. 75° C. The autoclave is then kept in motion for approximately 5 hours at temperatures between 75 and 85° C. After purification in the usual way, 22 gr. white, solid polybutylene. This is separated into the following fractions by extraction with hot solvents:

Example 21. of 7.6 gr. TiCl4 in 50 ccm n-heptane. Tempera-, i au r tt h the trip rises quickly to approx. 10° C while the pressure t 4^ , 5^*i^,2t,™ . decreases. The autoclave is maintained at temperatures

A solution of 19.8 gr.

Al(n-C4Hfl)3 in 450 ccm n-heptane. After addition, the polymerization product gives, after the process of 80 gr. butene-1 (Philips, absolute equal purification 44.2 gr. polybutene, which separates in pure) the autoclave is heated to 85° C, and for the following fractions during extraction at this temperature, a solution of hot solvents is added:

Example 22.

In a 2150 ccm autoclave, introduce 3 steel balls and an ampoule, which contains 8 gr.

titanium trichloride, and then under nitrogen

a solution of 12 gr. aluminum diethyl monochloride in 500 ccm n-heptane. One heats up to 76° C, and introduces 365 gr. technical propylene (85 percent propylene). Soon

then the autoclave is brought into swinging motion, which results in the ampoule, which

contains TiCl:3 breaks down. One holds

the autoclave at a temperature of 80 to 90°

C in motion, and reaches no pressure relief

more is felt, the gases are emitted. Since man

proceed as in example 2, you get 235 gr.

polymer, which corresponds to a conversion of 75 percent, considering the propylene used.

The obtained product consists for the most part

(84 per cent) of crystalline polypropylene, and

can be separated from the non-crystalline products by extraction with solvents.

Example 23.

In a 2080 ccm stainless steel autoclave is introduced

3 stainless steel balls and a glass ampoule, which

contains 7 gr. TiCl8. Then one is added

solution of 1.6 gr. (0.013mol) Al(C2H3)2C1

in 500 ccm of heptane. One heats the auto-

the clave to 70° C, and at this temperature inject 350 gr. propylene. The autoclave is then set in motion, whereby the ampoule

breaks. It lasts for about 10

hours at a temperature between 80 and 85° C, the autoclave in motion, while a persistent drop in pressure can be observed. After this time, the autoclave is emptied, whereby 10 NI of propylene is collected.

The solid polymer obtained, which is purified in the usual way, amounts to 315 gr. The acetone extract makes up 10.8 percent of the polymer obtained. The ether extract amounts to 16.2 percent and consists of solid, amorphous polypropylene with an intrinsic viscosity of 0.43. The heptane extract is 9.5 percent and consists of radiographically more than 50 percent crystalline polypropylene, which has an intrinsic viscosity of 0.955. The extraction residue makes up 63.4 per cent of the polymer obtained, and consists of highly crystalline polypropylene with an intrinsic viscosity of 2.05.

Example 24.

Into a 1100 ccm shaking autoclave, introduce two steel balls and a glass ampoule, which contains 1.85 gr. TiCl3. A solution of 4.95 gr is then added in a nitrogen atmosphere.

triisobutylaluminum in 100 ccm heptane.

The autoclave is heated to 85° C, and at this temperature 100 gr. propylene, after which the autoclave is immediately put into shaking mode. The autoclave is kept at temperatures between 70 and 75° C in motion for approximately 10 hours, whereby a significant pressure drop is noticed. In the same way as before, you get 65.6 gr. polypropylene, which is fractionated in the heat by extraction with solvents. Acetone extract makes up 5.1 percent of the polymer obtained. The ether extract makes up 27.4 per cent of the polymer obtained and consists of solid, amorphous polypropylene with an intrinsic viscosity of 0.895. The heptane extract makes up 14.9 per cent of the polymer obtained, consists of more than 50 per cent of crystalline polypropylene and shows a limit viscosity of 1.17 in tetralin solution at 135° C. The residue makes up 52.5 per cent, and consists of X-ray highly crystalline polypropylene, which exhibits a limiting viscosity of 2.56. The product obtained has a crystalline polypropylene content of at least 60 per cent.

Example 25.

In a 2150 ccm autoclave filled with nitrogen, a solution of 19.8 gr. Al(i-C4Hn)3 in 500 ccm n-heptane and 290 gr. propylene. It is heated to 66° C and then a solution of 7.6 g is added. TiCl4 in 80 ccm n-heptane. The temperature rises quickly to 95° C. The autoclave is kept in motion for approximately 7 hours at this temperature, the product is then removed and cleaned in the usual way. You get 215 gr. solid polymer, which is separated into the following fractions by hot solvent extraction:

The raw polymer therefore has a crystallinity of approx. 29 percent

Example 26.

You proceed as in example 10, but with a 435 ccm autoclave, in which you introduce 20 gr. (1/20 mole) of an aluminum dialkyl monochloride, with an average molecular weight corresponding to Aldidodecyl monochloride, in 75 ccm of anhydrous benzol, and 120 gr. liquid propylene. The autoclave is heated while shaking to 72° C, and a solution of 1.9 gr is injected under N2 pressure. titanium tetrachloride in 20 ccm of heptane. The temperature rises spontaneously a few degrees. Then inject another solution of 1.9 gr. titanium tetrachloride in 20 ccm of benzene. After approximately 10 hours from the beginning of the experiment, the catalyst is dissolved with methanol, and 68.5 g are obtained. solid polymer, which amounts to a turnover of 57 per cent of the propylene used. The polymerizate appears almost completely (over 90 per cent) to consist of an amorphous product. The acetone-insoluble and ether-soluble part of the amorphous polymer has a softening point of 55%, an intrinsic viscosity of 0.25 and a molecular weight of approximately 5,000.

Example 27.

In a 435 ccm autoclave, introduce in a nitrogen atmosphere 3.4 gr. titanium tribromide and a solution of 2.85 gr. triethyl aluminum in 100 ccm n-heptane. Then add 115 gr. of a propane-propylene mixture, which contains 91 percent propylene. The autoclave is heated to temperatures between 80 and 90° C, and kept in motion for approximately 10 hours. The polymerization product is purified as in the previous examples. You get 102 gr. solid polymer, which is fractionated by extraction in the heat with solvents.

The acetone extract makes up 10 per cent of the polymer obtained and consists of oily products with a low molecular weight. The ether extract makes up 36 percent and consists of a solid, X-ray amorphous polypropylene. The heptane extract makes up 20 per cent and consists of radiographically more than 50 per cent crystalline polypropylene. The extraction residue makes up 34 per cent of the polymer obtained, and consists of X-ray highly crystalline polypropylene.

The product obtained has a crystallinity of at least 44 percent.

Example 28.

In a 435 ccm autoclave introduce 5.15 gr.

TiJ3 and a resolution of 2.85 gr. Al(C2H5)!j in 100 ccm of heptane. You then add 130 gr. of a propylene-propane mixture with a content of 91 per cent propylene, and heats the autoclave to 85-90° C, and keeps it at this temperature for about 20 hours in motion.

The polymerization product consists of a semi-solid, sticky mass, which is cleaned with methanol and coagulated with methanol. You get 30 gr. solid, white polypropylene. By evaporation of the solvent used in the polymerization and purification steps, 54.3 gr. oily products with low molecular weight.

The 84.3 of the total product consists of 64.5 per cent of oily products.

The solid polymer is separated into fractions by extraction with hot solvents. This gives 10 percent of the collected polymer into crystalline polypropylene.

Example 29.

In a 435 ccm autoclave, introduce 2 steel balls and a glass ampoule, which contains 3.2 gr. (0.02 mol)VCl:! under nitrogen and the solution of 5.7 gr. triethyl aluminum in 100 ccm heptane. The autoclave is then heated to 81° C, and 98 gr. liquid pure propylene, after which the autoclave is set in an oscillating motion. The autoclave is kept for approximately 10 hours at a temperature between 81 and 90° C in motion, while a continuous and regular drop in pressure is noted. After the above-mentioned time, 50 ccm of methanol is pumped into the autoclave, and a total of 6 NI of gas is released. A solid polymer is taken out of the autoclave, which is first pulverized, then treated in the heat with ether and hydrochloric acid, and finally coagulated and filtered with methanol. As the ether in the heat is not observed to swell the divided polymerizate, it is necessary to resort to a further purification of the polymerizate itself, treating it in the heat with benzene (which swells it almost completely). The polymer is then coagulated with methanol and acetone, filtered, washed and dried in vacuum, whereby 64 gr. white, solid polymer.

The polymer obtained is fractionated as in the previous example. The acetone extract makes up 12.6 per cent of the polymer obtained, and consists of amorphous low molecular weight polymers. Ether extracts make up 21.4 per cent of the polymer obtained, and consist of amorphous polypropylene with an intrinsic viscosity of 0.55. The heptane extract makes up 24.1 per cent of the polymer obtained, and appears by X-ray testing to consist of more than 50 per cent crystalline polypropylene. This fraction has an intrinsic viscosity of 0.85, which corresponds to a molecular weight of approximately 20,000. The extraction residue consists of highly crystalline polypropylene with an intrinsic viscosity of 1.78, which corresponds to a molecular weight of approximately 80,000.

The raw polypropylene obtained therefore has a crystalline content of at least 54 per cent.

Example 30.

In a 2000 ccm autoclave, a solution of 11.4 gr is introduced in a nitrogen atmosphere. triethyl aluminum in 400 ccm n-heptane and 350 gr. of a mixture containing 82 percent propylene and 18 percent propane. The autoclave is heated while stirring to 80° C, and at this temperature a solution of 6.8 gr is injected. VOCI, in 100 ccm n-heptane. The temperature immediately rises to 87° C, while the pressure drops rapidly. After approximately 5 hours, methanol is pumped into the autoclave, and the polymerization product is emptied. It is purified from the inorganic products present by treatment in the heat with ether and hydrochloric acid and subsequent complete coagulation with methanol.

You get 172.5 gr. polypropylene, which makes up 60 percent of the propylene used. The polymer is then fractionated by extraction with solvents in the heat. The acetone extract makes up 29 per cent of the polymer obtained, and consists of amorphous polypropylene with a low molecular weight. The ether extract makes up 29.4 per cent and consists of amorphous polypropylene with an intrinsic viscosity of 0.52. The heptane extract with a crystallinity of approximately 50% exhibits an intrinsic viscosity of 1.15. The extraction residue consists of highly crystalline polypropylene and exhibits an intrinsic viscosity of 2.1.

The crude polymer thus obtained has a crystallinity of approximately 32.4 percent.

Example 31.

In a 435 ccm shaking autoclave made of stainless steel, 2 stainless steel balls and a glass ampoule, containing 3.25 gr. CrCl 2 (0.02 mol). A solution of 5.7 gr is then introduced into the closed autoclave under nitrogen. (0.05 mol) triethyl aluminum in 100 ccm n-heptane. The autoclave is heated during standstill to 80° C, then 115 gr. pure liquid propylene. Immediately afterwards, the autoclave is set in motion, which destroys the ampoule. The autoclave is then kept moving at a temperature between 80 and 110°C.

After 40 hours, counted from the beginning of the experiment, the unreacted propylene is exhausted. Solvents are removed from the product freed from the catalyst by washing out with methanol and hydrochloric acid by evaporation. By extraction with ether, 37 per cent of the polymer obtained is precipitated. The dissolved part appears quite amorphous. By subsequent extraction with boiling heptane, a fraction is obtained, which makes up 44 per cent of the polymer obtained. This fraction appears to be 50% crystalline and exhibits an intrinsic viscosity of 0.42. The extraction residue appears highly crystalline, and exhibits a limiting viscosity of 0.765. The product obtained thus appears to contain approximately 41 percent crystalline polypropylene.

Example 32.

In a 1100 ccm autoclave, 5.7 gr are introduced in a nitrogen atmosphere. triethyl aluminum in 200 ccm heptane and 172 gr. propylene. It is heated to 80° C, and at this temperature a solution of 0.75 gr is injected. chromyl chloride in 50 ccm heptane. It is kept in motion for approximately 20 hours, and after this time the product, which consists of small amounts of a propylene polymer with approximately 21% crystalline part, is emptied.

Example 33.

In a 435 ccm shaking autoclave, two steel balls, a glass ampoule, containing 2.36 gr. (0.012 mol) of zirconium trichloride, and a solution of 2.85 gr. triethyl aluminum in 100 ccm n-heptane. The autoclave is heated without stirring to 73° C, and at this temperature 70 gr. of a propylene-propane mixture, which contains 91 percent propylene. The autoclave is then immediately set in motion, whereby the ampoule is broken into pieces. The autoclave is kept moving for a few hours at 80° C. The polymer is cleaned as usual and fractionated in the heat with solvent.

By extraction in the heat with ether, approximately 30 per cent of the collected product, the amorphous polypropylene, is removed. The heptane extract makes up 10 per cent of the product obtained, and consists of a polypropylene with a crystallinity higher than 50 per cent. The extraction residue consists of highly crystalline polypropylene.

The product obtained therefore contains approximately 50 percent crystalline polypropylene.

Example 34.

In an oscillating 2080 ccm autoclave, a glass ampoule containing 9 gr. WC1(; and two steel balls. The autoclave is then filled with nitrogen, and a solution of 11.4 gr. gr. of a propylene-propane mixture with a content of 90% propylene. The autoclave is set in motion. After about 10 hours at 90 to 95° C, the polymerization product is discharged. It consists of a liquid brown mass. After washing with acid and evaporation of the solvent, 38 g of an oily product and 0.5 g of solid polymer are obtained.The solid product shows a crystallinity of approximately 50 per cent in X-ray examination.

Example 35.

In a 435 ccm autoclave, introduce two steel balls and a glass ampoule, which contains 3.2 gr. solid vanadium trichloride. Working according to the previous example, 5.7 gr is then introduced. (equal to 0.05 mol) aluminum triethyl, dissolved in 100 ccm heptane. The autoclave is heated to 83° C, and 110 gr. of a 70 percent 1-butene containing mixture of 1-butene and 2-butene; the autoclave is then set in motion, causing the ampoule to break. After approximately 10 hours of stirring at temperatures between 86 and 90° C, the autoclave is emptied, and the procedure is as in the previous examples.

You get 42 gr. of a solid, white fibrous mass, of which 21.5 gr., which constitutes 51.3 per cent, can be extracted with ether, and when tested with X-rays appears essentially amorphous. The extraction residue, which makes up 48.7 percent of the solid collected polymer, when tested with X-rays proves to be highly crystalline, and has a limiting viscosity of 1.1.

Example 36.

In a 2 liter autoclave, a solution of 11.4 gr is introduced in a nitrogen atmosphere. triethyl aluminum in 400 ccm heptane. Then add 220 gr. of a mixture containing 70 percent butene-1 and 30 percent butene-2. The autoclave is heated to 75° C, and at this temperature a solution of 7.7 gr is introduced under nitrogen pressure. vanadium tetrachloride in 100 ccm pentane. The autoclave is kept at temperatures between 75 and 80° C for approximately 10 hours with stirring. The polymer is then emptied and cleaned. 90.2 gr is obtained. polybutene, which is fractionated in the heat by extraction with acetone and ether.

The ether extraction residue makes up 27.8 percent of the polymer obtained, and consists of X-ray crystalline polybutene.

This fraction exhibits an intrinsic viscosity (determined in tetralin solution at 135° C) of 1.65.

Example 37.

In an autoclave with a volume of 2150 ccm, introduce two steel balls and an ampoule with 9.5 gr. (equivalent to 0.044 mol) ZrCl,. A solution consisting of 45 gr. (corresponding to 0.1 mol) of an aluminum trialkyl compound with a molecular weight, which corresponds to the average molecular weight of tridecyl aluminum, in 450 ccm of anhydrous benzene. The autoclave is heated, without stirring, to 82° C, after which 222 gr. propylene. Immediately afterwards, the autoclave is set in a swinging motion, whereby the ampoule breaks. This movement is continued for a duration of 14 hours at a temperature of 82 to 118° C, during which a continuous pressure drop is observed. After the expiry of the mentioned time period, 100 ccm of methanol is pumped in. The highly swollen reaction product with benzene is taken out of the autoclave. The product thus obtained contains a significant proportion of products with relatively low molecular weight, which turn out to be amorphous; the ether-insoluble part makes up 12 per cent of the total mass.

Example 38.

In a 1100 ccm autoclave filled with nitrogen, introduce 8 gr. Al(C;iH-).t dissolved in 200 ccm of heptane, and 200 gr. of a propylene-propane mixture with a content of 91 percent propylene. Heat to 82° C and then add 3.85 gr under nitrogen pressure. VC1,, dissolved in 50 ccm n-heptane. The temperature rises quickly to 100° C, whereby a pressure drop is established. The autoclave is kept for approximately 5 hours at temperatures between 90 and 100° C in motion.

The polymerization product is then emptied out. It consists of a compact, solid mass swollen with the help of a solvent. The product is purified by washing with solvents, which are acidified with hydrochloric acid, and then completely coagulated with methanol. You get 150.8 gr. solid, white polymer, which is separated into the following fractions by extraction with hot solvents:

The polymerization product therefore has a content of approx. 41 percent crystalline polymer.

Example 39.

In an autoclave with a volume of 435 ccm, two steel balls and an am

pool with 3.3 gr. (equivalent to 0.02 mol) CrCl.,. In the autoclave, a solution consisting of 22.5 gr. of an aluminum trialkyl compound with a molecular weight, which on average corresponds to the molecular weight of aluminum tridecyl, in 80 cc of anhydrous benzene. The autoclave is heated, without stirring, to 89° C, whereupon 100 gr. pro-

the arrow. Immediately afterwards, the stirrer is set in motion, whereupon the ampoule breaks. The stirring is continued for a duration of 14 hours while maintaining a temperature of 89 to 105° C. After the expiry of this time period, the process is as in example 35 with the purification and depletion of the polymerizate obtained. This polymer, which is richer in low molecular weight products, contains only 14 percent of a product, which is insoluble in ether and which is extractable with hot heptane. This last fraction turns out to be approx. 50% crystalline by X-ray test.

Example 40.

In a 2350 ccm autoclave, introduce two steel balls and an ampoule, which contains 7.8 gr. floating VC1,. Then a solution of 45 gr. trialkylaluminium, which has an average molecular weight, which corresponds to the molecular weight of tridecyl aluminium, in 500 ccm of n-heptane. It is heated to 87° C, and 260 gr. butene (which contains approx. 70 percent 1-butene). The autoclave is immediately set in motion and kept in motion for approximately 10 hours, whereby the internal temperature is maintained at 87° C.

When you work according to the previous examples, you get 113 gr. 1-butene polymer, which turns out to be practically amorphous. It contains less than 10 percent crystalline product.

In Example 41.

In a 2080 ccm autoclave filled with nitrogen, a solution of 17.5 gr.

Al(C|i;H.,.1).i in 200 ccm n-heptane. You then add 280 gr. of a propylene-propane mixture with a content of 91 percent propylene. Heat to 80° C and introduce under nitrogen pressure 2.2 gr. VOC1.,, dissolved in 50 ccm of heptane. The temperature rises rapidly to 90° C, while the pressure falls. The autoclave is kept in motion for approximately 5 hours, the product is then removed and cleaned in the usual way. After coagulation with a large amount of methanol, you get 90 gr. propyl-propylene, which is separated into the following fractions by extraction with hot solvents:

The resulting polymer thus had a crystallinity of approx. 15 percent

Example 42.

11.4 gr. triethylaluminum is dissolved in 50 ccm n-heptane, and added at 70" C and under mechanical stirring 7.6 gr.TiCl., in 20 ccm n-heptane. The reaction mixture is then filtered in a nitrogen atmosphere through a porous plate G4 (pore diameter 5 to 15 microns ), and the solid phase of the filter is used with a total of 120 ccm of a 2% aluminum triethyl-heptane solution. The solid phase is then suspended in 100 ccm of n-heptane, and introduced under a nitrogen atmosphere by mechanical stirring into a glass ampoule, which then 3 steel balls, the above-mentioned ampoule and a solution of

11.4 gr. aluminum triethyl in 400 ccm n-heptane. It is heated to 80° C and 295 gr is added. liquid propylene, and then the autoclave is immediately set in swinging motion. A temperature is maintained during stirring

of between 80 and 90° C, and no more

If there is some pressure drop, methanol is pumped into the autoclave and the gaseous products are emptied. The reaction product is extracted, an almost completely solid mass, which is purified in the usual way, following a treatment with boiling toluene and concentrated HCl. After precipitation and repeated washing with methanol, the mass is filtered and dried. You then get 111 gr. polymer, which corresponds to a turnover of 37.5 per cent of the propylene used. Of the polymerizate obtained, more than half (53.7 per cent) turns out to consist of crystalline polypropylene, which can be separated from the non-crystalline product by extraction with solvents.

Example 43.

In a 310 cc autoclave, 80 cc of the solution obtained by filtering the catalyst used in the previous example are introduced under nitrogen. It is heated to 80° C, 76 gr. liquid propylene and finally the autoclave is set in motion. After approximately 6 hours from the start of the polymerization, when no noticeable pressure drop is observed, methanol is pumped into the autoclave to remove catalysts, and the gaseous products are exhausted.

The reaction product is extracted from the open autoclave, which turns out to be a viscous, solid colorless liquid product; treatment with methanol gives a solid, rubbery product, which is treated in the usual way to be purified.

It turns out to be completely amorphous in X-ray testing.

Example 44.

To a resolution of 11.4 gr. triethylaluminum in 70 ccm of heptane is placed under stirring at a temperature of 70° C. a solution of 7.6 gr. titanium tetrachloride in 20 ccm of heptane. A black precipitate forms during simultaneous gas development. The precipitate is filtered under nitrogen on a porous plate (hole diameter 5 to 15 microns), and there washed repeatedly with heptane, which contains 2 percent triethylaluminum. The black precipitate is then suspended in 250 ccm of heptane, which contains 11.4 gr. triethylaluminium, and the suspension is siphoned off in a nitrogen atmosphere in a 1000 ccm three-necked flask fitted with a stirrer. Then heat to 65° C and add 150 gr. styrene. The mixture is kept under stirring for 2.5 hours at a temperature of 70 to 75° C. Then the resulting mixture is cooled, entirely in methanol, to dissolve the catalyst, and then treated with hydrochloric acid to dissolve the inorganic products present, in

The reaction mixture divides into two phases, of which the upper one consists of heptane, and which in the suspension contains the fluff-like, easily filterable polymer. This solid product, separated by filtration, is further purified by boiling with acetone, acidified with hydrochloric acid, filtration and washing out with acetone. In this operation, the polymer weight remains practically unchanged.

The polymer thus obtained appears

in X-ray testing to be highly crystalline and only melts above 210° C.

Example 45.

To 11.4 gr. triethylaluminium, dissolved in 70 ccm of N-heptane is placed at 70° C under mechanical stirring 7.3 gr. vanadium tetrachloride, dissolved in 20 ccm n-heptane. The reaction mixture, which consists of a liquid phase, which contains in suspension a brown precipitate, is then filtered in a nitrogen atmosphere through a porous plate with a pore cross section between 5 and 15 microns. The solid phase is then washed on the filter three times, each time with 30 cc of a solution of 1% triethylaluminum in n-heptane. The solid phase is then suspended in 250 ccm of n-heptane, and the suspension is siphoned off in a nitrogen atmosphere under mechanical stirring in a pre-aerated glass flask, equipped with a mechanical stirrer, dropping funnel and reflux condenser. In the flask, which is kept under a nitrogen atmosphere, say 11.4 gr. triethylaluminum. The mixture is brought to a temperature of 70° C, and while stirring, 150 gr. styrene. For 4 hours and with stirring, the temperature is kept between 70 and 75° C. After this time it is allowed to cool, the catalyst is dissolved with methanol and the reaction product is finally treated with hydrochloric acid. The liquid mass contains a solid, flake-like polymer in suspension, which is separated by filtration. The solid polymer consists of an acetone-soluble and an insoluble part. The insoluble part, which makes up 68 per cent of the total solid mass, is very crystalline. The part which is soluble in acetone turns out to be amorphous.

Example 46.

Into a 1000 ccm flask, the filtered solution, which was described in the previous example regarding the preparation of the catalyst, is introduced under nitrogen. Then 100 ccm of n-heptane is added, and it is heated to 80° C. Then, while stirring, 150 gr. styrene. For 4 hours and with stirring, the temperature is kept at between 70 and 75° C. After cooling, the reaction product is treated with methanol and hydrochloric acid. In this way, small amounts of polystyrene are precipitated from the methanolic D solution, which turns out to be completely amorphous. It shows that while the slightly dispersed catalyst, which can be separated by filtration, as indicated in example 45, gives a predominantly crystalline product, the dispersed part, which passes through the filter, on the other hand, gives a completely amorphous polymer.

Claims (15)

1. Process for the selective polymerization of alpha-olefins, in particular propylene, to linear head-tail polymers with a molecular weight above 1000, using catalysts obtained by reaction of compounds of metals from subgroups of the periodic system in group IV—VI, including thorium and uranium with metal alkyls, where the metals are from periodic table II. or III. group, in particular aluminum, magnesium, or zinc, whereby at least on the surface of the compound from IV-VI groups bonds are formed with alkyl groups, characterized in that in order to obtain poly-olefins with a regular sequence of CEL. groups, and CH.R groups in long, straight chains, in which the asymmetric carbon atoms of the main chain, at least for long stretches of the molecule, have the same steric configuration (polymers of isotactic structure), with a high tendency to crystallization, use solid crystalline and insoluble catalysts and resp. or use coarsely dispersed catalysts, and to obtain amorphous olefin polymers, in which the asymmetric carbon atoms - have a static distribution along the main chain (polymers of non-isotactic structure), use amorphous, liquid or dissolved catalysts and resp. or use highly dispersed catalysts. 2. Method as stated in claim 1, characterized in that the crystalline catalysts are produced from solid, coal-hydrogen insoluble, preferably crystalline compounds of metals from the subgroups in the IV-VI group of the periodic table. 3. Method as stated in claims 1-2, characterized in that the solid, preferably crystalline catalysts are produced from compounds of metals from subgroups IV.-VI of the periodic table. group that has a lower dignity than the highest dignity. 4. Method as stated in claims 1-2, characterized in that the solid, preferably crystalline catalysts are produced using organometallic compounds, which contain less than 5 carbon atoms in the alkyl. 5. Procedure as stated in the stand 1, characterized in that one who for bonding of a metal of the subgroups in the periodic system IV.-VI. group uses a halide preferably a chloride, of the trivalent titanium, zirconium, vanadium or chromium. 6. Method as stated in claim 1, characterized in that catalysts are used, whose dispersity compared to those produced in the usual way was reduced by separating out the finer dispersed parts, e.g. by filtration, decantation, sedimentation, centrifugation, filtration or other methods, and only use the coarser disperse parts remaining on the filter, whereby polymers with an isotactic structure are obtained. 7. Method as stated in claim 1, characterized in that the amorphous, liquid or dissolved catalysts are produced from compounds of metals in the subgroups of the periodic table IV.-VI. group, in their highest dignity. 8. Method as stated in claim 1, characterized in that the amorphous, liquid or dissolved catalysts are produced using compounds of metals from the subgroups of the periodic table IV.-VI. group, which contains lyophilic groups e.g. alkoxy groups. 9. Method as stated in claim 1, characterized in that the amorphous, liquid or dissolved catalysts are obtained from a compound of a metal from the subgroups of the periodic table IV.-VI. group, preferably of halides, oxyhalides or alkoxyhalides of titanium, zirconium, vanadium or chromium in a state of dignity of at least 4. 10. Method as stated in claim 1, characterized in that the amorphous, liquid or dissolved catalysts are produced using organometallic compounds, which contain alkyls with more than 4, preferably 6 to 16, carbon atoms. 11. Method as set forth in claim 1, characterized in that for the production of polyolefins with predominantly or exclusively amorphous nature and non-isotactic structure, an organometallic compound is used which, in addition to alkyl groups, contains halogen atoms. 12. Method as stated in claim 1, characterized in that the fine particles are used for the polymerization, whereby amorphous polymers are obtained. 13. Method as stated in claim 1 for the production of amorphous polymers, characterized in that a catalyst is used, which was obtained by suspending the catalyst produced in the usual way in a solvent for the olefin, which is to be polymerized, in such a way that a cloudy suspension is formed, from which the coarser-dispersed part of the solid catalyst is separated by means of a mechanical or physical method. 14. Method as stated in claim 1, characterized in that a highly dispersed catalyst is used, in the preparation of which one of the reaction components contains strongly lyophilic groups, which are suitable for favoring the dispersion of the catalyst in a micellar state in the solvent used. 15. Method as stated in claim 1 for the production of isotactic polymers, characterized in that less than 2.5 mol, preferably less than 1 mol, of the organic compound of metals from the periodic table II is used. or III. group, especially aluminum of 1 mol of the compound with a lower value than the maximum value of the metal from the subgroups of the periodic system IV.-VI. group.