CS212324B2 - Method of making the block ethylene and propylene copolymeres - Google Patents

Abstract

PURPOSE:To prepare the title copolymer having high impact strength, rigidity and heat resistance, by polymerizing propylene in the presence of titanium trichloride and an organo-aluminum compound, and then carrying out the random copolymerization of propylene and ethylene in the presence of the above polymer. CONSTITUTION:Propylene (which may contain a small amount of ehylene) is polymerized in liquid state, in the absence of an inert solvent, and then randomly copolymerized with propylene and ethylene in liquid propylene or in gaseous phase. The polymerization is carried out in the presence of a catalyst system comprising (A) a solid TiCl3 catalyst obtained by reducing TiCl4 with an organo-aluminum compound, and activating the product, (B) an organo-aluminum compound of formula (R is 1-8C straight chain alkyl, etc.; Y is halogen, etc.; l is 2-3), and if necessary, (C) an agent for improving the stereoregularity. The weight ratio of the polymer to the TiCl3 catalyst is >=8000/1.

Description

The present invention relates to a process for the production of propylene-ethylene block copolymers, and to a process for the production of propylene-ethylene copolymers by improved performance using high performance mixed catalyst systems.

Since the inventions of Ziegleren and Natta stereoregular catalysts, crystalline polyolefins have been manufactured industrially. Particular attention has been drawn to crystalline polypropylene as a mini-resin with high rigidity and heat resistance. However, since crystalline polypropylene is brittle at low temperatures, it is not suitable for applications in which the material must have high impact toughness at low temperatures. To overcome this disadvantage, extensive research will be undertaken to improve polyolefin preparation methods.

Among the processes developed hitherto, processes for block polymerization of propylene with clear olefins, in particular ethylene, are known. Japanese Patent Applications Nos. 13,049/68 and 26,113/72 and Japanese Patent Applications published unexamined 6. 120986/74, 135 987/76 and 3,684/77 propose block copolymerization processes in which propylene alone is polymerized in the first stage. in liquefied propylene in the absence of an inert solvent and then, in the second stage, ethylene and propylene are irregularly copolymerized in the liquefied monomer or gaseous monomer in the second step! or the ethylene itself is polymerized in the gas phase.

When conventional copolymerization systems are used in the block copolymerization of propylene and ethylene, which essentially consist of a solid titanium tetrachloride catalyst (such as titanium tetrachloride obtained by reducing aluminum chloride or hydrogen or the titanium tetrachloride co-crystallization products). % of aluminum and aluminum chloride) and, on the other hand, of the organolithium compound, a large amount remains in the polymer product particles. The amount of polymer produced, based on the gram of solid titanium tetrachloride catalyst, is small. When molding such a polymer product into products, the polymer turns yellow and thus reduces its commercial value.

In addition, the polymer particles are usually blended in the melt with ingredients, pelletized and re-formed from the melt in various forming machines. In this melting process, very often polymer degradation occurs, resulting in a deterioration of the chemical properties. In addition, the degradation of ultraviolet light by light is so pronounced that it is difficult to use these molded articles for extended periods of time. Using the above-mentioned conventional catalytic systems, it is therefore necessary to undergo the polymer preparation to undergo a subsequent treatment such as, for example, extraction of catalyst residues, etc., as is required for polymerization in an inert solvent. The subsequent processing of the polymer cumulates the production.

In addition, since the low molecular weight and low crystalline wettable products are more soluble in the inert solvents commonly used in polymerization than in the liquefied monomer, when the block copolymerization of propylene and ethylene is carried out in the absence of inert solvent, the polymer particles contain substantially more As a result, using the conventional catalysts, the properties of propylene polymers, i.e., stiffness and heat resistance, are compromised, and such shaped articles are used in those applications where these physical properties are desired. , is difficult.

Low-molecular and low-salinity polymer fractions accumulate in large quantities on the surface of the polymer particles. This increases the cohesion between the particles and creates problems with the agglomeration of the polymer, reducing the heat transfer from the polymerization vessel caused by the deposition of the polymer on the inner walls of the undersized vessel. In addition, there are often clogging of the piping, hoppers for the powdered product. and forces during delivery of the polymer slurry or powder product.

In carrying out the polymer in the gas phase as suggested in the published. Japanese Patent Application Nos. 597/66 and 13,962/72, and Japanese publication no. No. 145,589 / 76, etc., is operated in a fluidized bed reactor, optionally mixed, and monomer is used as fluidizing gas. This removes the polymerization heat and prevents the polymer particles from melting or melting.

In the case of polymers having high coalescence, very high levels of fluidized gas need to be used for their fluidization, or the fluidized bed needs to be vigorously agitated. This results in difficulties in uniformly dissipating heat and agglomerating the polymer and melting it. This threatens - the entire production.

The large amount of low-molecular and low-crystalline polymers contained in the polymer particles causes the οΗβΓβΚΟ, θιτΊοΙ.when the polypropylene's soft properties, i.e., its stiffness and thermal stability, to deteriorate considerably. Therefore, in block copolymerization of propylene and ethylene in the sub-base in the absence of an inert solvent in the liquefied monomer or in the gas phase, catalyst systems must be used which reduce the formation of these low-molecular and low-crystalline polymers, if they cannot be avoided at all, and .

When the polymerization is carried out in the gas phase, it is effective to circulate the monomer gas, but if the polymer particles produced have a wide size distribution and if a considerable amount of fines is present, these fines are escaped and a great deal of effort is required; use expensive devices to separate these fine particles. Otherwise, these particles could clog the heat exchanger or circulating compressor. For this reason, the particle size of the polymer product should be as narrow as possible.

In carrying out the process for the production of the ethylene-propylene block copolymers according to the invention, it is therefore important to use catalytic systems which, as far as practicable, do not form isolated and low-molecular-weight polymers, or If they form in smaller or larger amounts, they polyolyte particles with a lower cohesive and narrower particle size distribution.

In carrying out the polymerization in a manner similar to that of the invention, in the absence of an inert solvent, but using known catalyst systems, the above-mentioned difficulties arise because the polymeric particles contain a low molecular weight polymer and a low molecular weight polymer. Japanese Published Patent Application No. 20,501/64 and Japanese Patent Application Published without Prophet No. 1046/71, etc., propose methods for producing titanium trichloride-based systems which impart small, finely divided polymer particles with a narrow size distribution. Particles in which titanium tetrachloride is reduced with an organoaluminum compound and the product is then further heat treated.

When these catalysts are used to produce ethylene-propylene block copolymers in an analogous manner to the process of the present invention, the polymers produced have a narrow particle size distribution but contain large amounts of low molecular weight and low crystalline polymer byproducts which greatly increase cohesion between polymer particles. In addition, the polymerization activity of the catalysts and their stereoregativity are unsatisfactory. It has hitherto been very difficult to produce block copolymers of propylene and ethylene under stable conditions.

It has now been developed, in the framework of extensive research to overcome the above-mentioned problems, an economical and stable process for the production of propylene-ethylene block copolymers with improved properties, which is not complicated by the above difficulties.

Thus, the present invention relates to a process for the production of propylene-ethylene block copolymers having improved properties using a specific catalyst system.

The improvements brought by the method of the invention include the following aspects:

The polymer produced is obtained in the form of particles with a narrow size distribution.

Propylene / ethylene block copolymers contain small amounts of catalyst residues, so that they do not tend to stain and degrade.

During production . Propylene / ethylene block copolymers are used in a more efficient catalyst system that prevents the cohesive and agglomeration of the polymer product particles.

The further advantages of the invention are apparent from the following description.

SUMMARY OF THE INVENTION The present invention provides a process for the production of propylene-ethylene block copolymers in which, in a first step, polymerization of propylene alone or with a smaller amount of ethylene is initiated, substantially in the absence of an inert solvent. and thereafter propylene and ethylene are copolymerized in an expensive step in a monomm ™ liquefied or vapor-phase environment, or ethylene itself is vapor-phase polymerized, and characterized in that the catalyst system used in the block copolymerization is:

A, a solid titanium tetrachloride catalyst obtained by reducing the titanium tetrachloride with an organohinite compound and following activation,

B. an organo-affinity compound of the general formula wherein is

R is a straight-chain or branched-chain alkyl group; 1 to 8 carbon atoms, Y is halogen or hydrogen or alkoxy and q is greater than or equal to 2 and less than or equal to 3, and optionally

C. an electron donor, wherein the catalyst A is used to obtain at least 8000 g of block copolymers per 1 g of solid catalyst.

Examples of solid titanium dioxide catalysts used as component A of the catalyst system include:

What is claimed is: 1. A solid titanium tetrachloride catalyst, obtained by reacting products a), b) or c), defined below, with a halogen or a halogen-ether compound.

a) Reduced product obtained by reduction of organotaluminum chloride with a compound of formula

R? ^1x 3-n where represents

R 'is a straight or branched chain alkyl, alicyclic or aryl group, each containing up to 18 carbon atoms,

X * - halogen or hydrogen; and.

q a number greater than or equal to 1 or equal to 3.

b) heat treating the solid obtained by heating and reduced product), optionally in the presence ^of the ^causes of the inert organic ^{¹H KEH} the extended Oust ^EDL and ^{p, p} te lot about 50 to 120 ° C.

c) The reaction product obtained by further reacting the reduced product a) with an aluminum compound of the general formula wherein

R 'is a straight or branched chain alkyl, alicyclic or aryl group, each containing up to 18 carbon atoms,

X is a halogen atom and represents a number greater than or equal to 1 and less than 1.5.

2. The solid-Loir Icatalyzá titanium trichloride product obtained by reacting a ') or b') ^of defined longer, Etterem ^An SLE uj ^{d s} c ^s a ^s reacting this twisted firmly ^Star substances clůoridem titanium.

a ') ^{R d} in ^the alkylated ^p ro ^d uct ztetaný re c ^ ^d ukcí organoaluminum chloride tetanteitete reciprocally ^ Nou formula wherein

R, X * and n are as defined above.

b ') heat treating the solid obtained by heating and reduced product ") or ^p and the ^{DE argue} omnosti iner ^ o ^p ou extended ^Inhalants and at ²⁰ and ^from the temperature ^{of 100} ° C.

3. The titanium tetrachloride solid catalyst obtained by the reaction of the above defined titanium tetrachloride catalyst 2. with a mixture of a halogen or a halogen compound with an ether.

4. A solid titanium tetrachloride catalyst, obtained by reducing organotumium tetrachloride with a compound of the formula:

R, X and n are as hereinbefore defined, by reaction of the reduced product with an ether compound and then reacting the solid compound, treated with ether and aluminum compound of the formula wherein ^{R, χ} and ^£ naj ^s meaning given above, optionally followed by reacting the thus obtained solid an ether or a mixture of a halogen or a halogen compound with an ether.

Of these catalysts, catalysts 1 and 2 are preferred.

The solid catalysts based on titanium tetrachloride used as components A. of the catalyst system, and examples thereof are given in paragraphs 1 to 4, are proposed, for example, in U.S. patent application δ. No. 831,630, filed Sep. 9, 1977, British Patent No. 1,391,067, Japanese Patent Application Published Unexamined. 16 298/76 etc., and as regards the preparation of these substances, reference is made to these publications.

As examples of organoaluminum compounds of the general formula wherein

R ', X' and n are as defined above, including methylaluminium dichloride, ethylaluminium dichloride, n-propylaluminium dichloride, ethylaluminium sesquichloride, dimethylaluminium chloride, diethylaluminium chloride, di-n-propylaluminium chloride, trimethylaluminium, triethylaluminium, triethylaluminium, triethylaluminium, , diethylaluminum bromide, diethylaluminum iodide, etc. Of these, diethylaluminum chloride and ethylaluminum sesquichloride are particularly preferred.

In the reduction of titanium tetrachloride with an organoaluminium compound of the formula R 1, AlX 3 - _n in the preparation of 1 to 4, the molar ratio of organoaluminum compound to titanium tetrachloride is usually about 0.1 to 2, preferably 0.3 to 1.5. The reduction is usually carried out at about -70 to ⁶⁰ ° ^ preferentially ^BC - ^{20 and 30} ° С ^ ^t and ^p Rednose them ^straight in the presence of an inert hydrocarbon solvent the like aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon such as pentane, hexane, heptane, benzene, tolue-. nu, xylene, etc.

The ether compounds used in the preparation of catalysts 1 to 4 are those of the formula ^{R, -O-Rg} , where each of the symbols is used

R1 and ^R2, which are the same or different, represent a straight or branched chain alkyl group containing from 1 to 8 carbon atoms.

Suitable examples include: diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-isoaixyl ether, dineopentylether, di-n-hexyl ether, methyl-n-butyl ether, methylisoamyl ether, ethyl isobutyl ether, etc. these ethers are obtained with particularly good results using di-n-butyl ether and di-isoamyl ether.

^R ESPONDING The osmolality of the ether with ^p-Nou Eq ^{Adi during} warm-I as ^{well as} 0 and ^{from 130} ° C, ^eg e ^d in ^{preference, and} even 20 to 100 ° C. Reactions ^{i t} s ^p Leh molar Omer et erov ^{h E l and} amine compound act ^to cl ^ ny orHu t ^ a ^^ him contained in the solid used in the range of about 0.1 to 3, preferably about 0.5 to 1 , 5 ·

As examples of aluminum compounds of the general formula

R "AIX - _n L 3 p wherein ^R, X and £ have a ^h ora above can be mentioned the following: methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminiumdichlorid, n-butylaluminiumdichlorid, n-hexylaluminiumdichlorid, n oktylaluminiumdicHorid, fenylaluminiumdichlorid, o-tolylaluminium dichloride, ethylaluminium dibromide, phenylaluminium dibromide, methylaluminium diiodide, etc. Of these, particularly preferred are ethylaluminium dichloride. The above aluminum compounds can be used either singly or in the form of mixed systems of two or more of these compounds.

The reaction of aluminum composite ECN ^{b eh} of formula R * Alx ^{p j p} _ ^p with Eq ^Adi te ^p s ^p ture of about 200 ° C, ^{d Pla} SAFETY ^E and ^also from 50 to 120 ° C. When it reatai t ^{s p} is the molar Omer compounds ^y of aluminum to chloride titanitému contained in the used solid, preferably about 0.1 to 5 ·

As the halogen or halogen compounds, which are used not reacting mixtures of halogen compounds and ether compounds in the manufacture of the above mentioned catalyst components 1, 3 and 4, the ^p ou ^running in ^{Ales p} he ^{n e substance, b} sahuj ^{I C, the} HA ^l o ^g en is selected from the group consisting of

(a) Cl £, Br ₂ or

b) interhalogen compounds of formula (xx ') and wherein each of s ^y mbol

X and X ', which are different, represent chlorine, bromine or iodine and are a number from 1 to 3,

c) halogenated hydrocarbon compounds of the general formula

R ₃ -X where

R3 is a straight or branched chain alkyl, alicyclic or aryl group, each of which contains from 3 to 18 carbon atoms, and

d) halogenated methylderivatives of the general formula wherein represents

X is halogen and q is 0, 12 or 3.

Examples of interhalogen compounds b) include bromide, iodine chloride, iodotri trichloride, iodine bromide, etc.

Examples of halogenated hydrocarbons c) include compounds such as straight or branched chain alkyl halides, alicyclic halides, aromatic halides, and aralkyl halides, etc. Of these, straight or branched chain alkyl halides give the best results, in particular primary and secondary halides. Particularly preferred is n-butyl iodide.

Examples of halogenated hydrocarbon compounds d) include carbon tetrachloride, chloroform, methylene chloride, tetrabromomethane, bromoform, methylene bromide, and mixtures thereof. Carbon tetrachloride is particularly preferred.

Of the above halogen-containing substances, iodine provides the best results.

Reakce'směsi halogen or halogen-containing compound and the ether compound is carried out at about Ote te ^pl. 0 to ¹⁵⁰ DEG C., ^with preference ⁴⁰ to ¹⁰⁰ ° C. MoMrd ^p Omer ether ^Star composites to titanitému trichloride contained in the solid is about 0.001 to about 5, preferably about 0.005 to 3.0, and the molar ratio of halogen or halogen compound to titanitému chloride is about 0.001 to 2.0, preferably about 0.005 to 1.0.

The reaction with titanium tetrachloride in the preparation of catalyst 2 is transferred at a temperature of about ^{0 Z 100} ° C, preferably ^of about ²⁰ and ⁸⁰ ° C. ^M ol ^{a ry p} Omer Florida titanitému the titanium trichloride contained in the solid is from about 0.2 to about 15, preferably about 0.5 to 5. The titanium tetrachloride is preferably used as such or in solution in an inert hydrocarbon solvent a titanium tetrachloride concentration of at least 10% by weight.

Each of the above reactions is usually carried out for about 5 minutes to 5 hours, and is preferably carried out in the presence of an inert hydrocarbon solvent such as hexane, heptane, octane, benzene, toluene, xylene, and the like. reaction or polymerization preferably after isolation, ie after separation, washing and drying.

Examples of inert hydrocarbon solvents useful as washing agents include hexane, heptane, octane, benzene, toluene, xylene and the like.

As examples of the organoaluminium compounds used according to the invention as catalyst component B of the general formula wherein

R, Y and a are as defined above, such as dimethylaluminum chloride, diethylaluminum chloride, di-isobutylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, trimethylaluminum, triethyl aluminum, diethylaluminum hydride, diethylaluminiumimethoxide, etc. Most preferred.

When an electron donor, i.e. component (c), is used to improve stereoregularity, these are known compounds such as amines, ethers, esters, sulfur derivatives, halogens, benzene, azulene, etc., organic and inorganic nitrogen and phosphorus compounds, etc. As examples include triethylamine, tri-n-butylamine, diethyl ether, ethyl vinyl ether, methyl acrylate, methyl methacrylate, ethyl benzoate, ethyl p-anisate, methyl n-butyrate, gamma-butyrolactone, epsilon-caprblactone, di-n-butylsulfide, thiophenol benzoyl chloride; methyl p-methylbenzoate, tri-n-butylphosphite, triphenylphosphite, tri-n-butylphosphine, triphenylphosphine, tri-n-butylphosphate, hexamethylphosphoric triamide, etc.

Of the catalyst components, i.e. the amount of solid catalyst based on activated titenitého chloride (component A), organic aluminum compound (component B) and the enhancer eroregu ^{l t} r ^and the (C) is not limited zvlOto ^s. UCE n ^{l E} was used in ^runs C ^á motorního ratio (A) from about 0.1 to 10, preferably about 0.5 to 5, and component B is preferably used in a polymerization vessel in an amount of 0.05 to 50 mmoles, preferably 0.1 to 20 mmol, based on mol of monomer. The B / A molar ratio is about 1 to 500, preferably about 1 to 100.

The order of addition of the catalyst components to the polymerization reactor is not limited, but when they come into direct contact of components A and C at high concentrations in the absence of component B, the activity of the catalyst system is sometimes reduced. If there is such a concern, the order of addition of the individual components should be considered.

In the production of block copolymers of propylene and ethylene, difficulties due to the presence of catalytic residues in the polymer can be avoided even without routine catalyst removal (extraction) by adjusting the polymer yield per gram of solid titanium tetrachloride catalyst to at least 8,000 g. It is almost impossible to achieve a polymer yield of more than 8,000 g of polymer per gram of titanium tetrachloride catalyst, since these catalysts have low activity. In those cases where such catalyst activity can be achieved, the activity of the catalyst is reduced for a long time, so that said activity is equally unattainable from a practical point of view.

The catalyst systems used according to the invention have a considerably higher efficiency compared to conventional catalyst systems used in block copolymerizations. They can achieve an activity of at least 8,000 g of polymer per gram of titanium tetrachloride solid catalyst in a very short time.

If it is convenient to remove traces of catalyst residues that are contained in the polymer, a simple procedure can be used. For example, these traces of catalyst residues can be easily removed by a simple procedure described in Japanese Patent Application Laid-open No. 21 285/78 by contacting a powdered polymer with an epoxide or a mixed gas of an epoxy-alcohol mixture. and water.

In the production of propylene and ethylene block copolymers using the catalyst system of the invention, the formation of low molecular weight and low crystalline polymer is avoided, and therefore the cohesion between the polymer particles is low. As a result, problems such as reducing the heat transfer efficiency due to polymer agglomeration, polymer deposition on the inner walls of the polymerization vessel during polymerization, blockage of the pipeline, hopper, or silo to the pulverulent polymer during transportation of the polymer slurry or pulverulent polymer are avoided. Block copolymers of propylene and ethylene with excellent balance of impact strength and heat resistance are obtained.

Since the propylene-ethylene block copolymers obtained according to the invention have a very narrow particle size distribution, the fine particle escape of the gas-phase reactor in a fluidized bed or stirred fluidized bed reactor does not cause difficulty, thus allowing continuous operation. Since difficulties such as polymer agglomeration in the polymerization zone, increasing agitation force, polymer deposition on reactor internal walls, etc., due to powder cohesion, are eliminated, mixing, heat dissipation, fluidization, etc. in the polymerization vessel are very easy. Another characteristic advantage inherent in the catalyst systems used in the present invention is the very high polymerization activity compared to conventional catalyst systems used in block copolymerization.

The polymerization according to the invention is carried out in two stages in the presence of the above catalyst system and essentially in the absence of an inert solvent. In some cases, it may be desirable to disperse the catalyst in a small amount of inert solvent, but the amount of solvent is negligible compared to the amount of polymerized monomer. In the first step, polymerization of propylene alone or a mixture thereof with a small amount of ethylene in the liquefied propylene is initiated. The polymerization is carried out in liquefied propylene or in the gas phase such that the ethylene content of the polymer produced in the first stage is not more than about 4% by weight.

Thus, crystalline polypropylene is produced which amounts to about 60 to 95% by weight of the final block copolymer. When propylene alone is polymerized in the first stage, polymers with a well-balanced heat resistance and heat resistance are obtained after the second stage of polymerization. In order to obtain a product with improved gloss, impact strength and improved cloud formation properties under impact stress, and if it can be tolerated that this improvement is achieved at the expense of stiffness, a first stage of copolymerization can be carried out in the presence of small amounts of ethylene.

In the second stage of copolymerization, the irregular copolymerization of propylene and ethylene in the liquefied propylene or gas phase or the polymerization of ethylene in the gas phase itself is carried out so that the ethylene content of the polymer block produced in the second stage is 10% or more. Thus, a block of ethylene-propylene copolymer or homopolymeric ethylene block is produced which is 5 to 40% by weight of the resulting block copolymer.

Examples of practical methods for carrying out block copolymerization of propylene and ethylene include:

1. Both stages of polymerization are carried out still in the liquid monomer.

2. First-digested ^s potymerace initiates in from ^{the p} and ^L n ^{e d} m monomer in polymerization, pol ^{y p} okračuje in liquid monomer or in gas phase, and then the second stage is done in gas phase.

3. Both stages of polymerization are still carried out in the gas phase.

The inventive method can be applied when věech these processes and in all cases fully in its ^pl atnuje účtoek.

When polymerization is conducted in a liquefied monomer, operated at a temperature of about 0 to ⁹⁰ DEG C. ^EXAMPLE E ^D nose ^t them ⁴⁰ and ⁸⁰ ° ^, and under ^{pressure, wherein} the monomer pMtomen in ^the apaln the ^E form, preferably under superatmospheric pressure about 1.5 to 4 MPa. When polymerization is conducted in gas phase working ^{at t} e ^pl of ^{I p} o ^d a point M ^of the KNU ^T i ^poly Mern ^¹H o ^ odlukti ^par e ^d in preference ^of pM te ^p ture of 4 ° to ¹⁰ Q C and at a pressure of about atmospheric pressure to about 6.0 MPa, preferably at a pressure of about 0.5 to 5 MPa.

Although known molecular weight regulators such as hydrogen etc. are preferably added in both stages of polymerization in order to control the processability of the polymer, however, ethylene polymerization or irregular copolymerization of ethylene and propylene can be carried out in the absence of such molecular weight regulators.

The polymerization may be carried out batchwise using one or more polymerization reactors or continuously using two or more polymerization reactors. Conventional tank reactors, loop-wound reactors are suitable for conducting liquefied monomer polymerization, and mixed-bed, fluid-bed or stirred-bed fluidized bed reactors are suitable for gas-phase polymerization.

The invention is illustrated in more detail in the following examples, but is not limited thereto. The results of the examples are summarized in Tables 1 and 2. Physical property values are measured according to the following methods:

Melt Flow Index: ASTM D 1238-57T

Vicat softening temperature: ASTM D 1525

Brittle temperature: ASTM D 746

Flexural strength: ASTM D 747-58T

Izod impact strength: at ²⁰ and - ²⁰ ° C ^ASTM D ²⁵⁶

The ethylene content of the resulting polymer is calculated from the infrared spectrum. Limit vistozí-rs ^whose number [η] in tetraline was пгёН at ¹ 35 ° C. ^K o ^h eze PR ^and SKU is calculated ^and the shear stress when a vertical stress obtained when · shear test carried out in one direction extrapolates to zero. According to the findings of the invention, powder processing becomes very difficult when the powder cohesion exceeds 2 g / cm @ 2. The amount of polymer in grams, based on gram of titanium tetrachloride solid catalyst (g of polymer / g of TiCl4 solid catalyst), is referred to as catalyst activity.

Example 1

1. Catalyst synthesis

a) Into a 200 1 autoclave equipped with a stirrer was charged with 45.5 1 of hexane and 11.8 1 ^titanium tetrachloride tan ^ičitéh OA rozWk: at ^d ržuje heat ^at a ^{d d} -W about -5 ° C. К extended ^ ^k u for m ^s c n ^{e hook} pivoted ^{to the BC} and AC ^h m ^s and ^d C ^{h 0} min 13 La ^{- 'p} Rik ^{in the AP} and thaw ^{for 43 h} Exan 2 ^{1 9.4 1} e ^{di methyl} and ^{l and} chlorides and umi.n. During this ob ^{d y} is a temperature in a car ^monastery vu u ^d R ^z is made between. -10 and -5 ° C. Rea ^CZK the mites ^for at ^d R ^z U is ¹ 5 m ^and the nut ^at that ^p lot ^of - ¹⁰ to 0 ° C and the ^p, and ^k is a temperature in a ^P Ru ^run at a ^d N ^{e H} o ^di n ^y raised to 65 Deň: 32 ° C. Rea ^{at the} CN mites ^{s to} 2 ^h of ^di n ^y MIC ^{ha at 65} ° C. Pa ^for from ^{the s} and ^p aln phase of ^dd EL ^{I P} evný product, which was washed six times with 50 1 of hexane.

b) the hexane is removed from EVN ^{eh P} o ^p ro ^d u ^k and the ^TA's. ZIS ^to Aný ^{characterized} dried ^p ro ^d u ^KT en sus ^{p d} U is in 92 1 of hexane to which was added 19,6 1 diisoamyl ether. The suspension was stirred for 1 ^d it yne ^at 35 ° C, solid ^p ro ^d u ^k t is the ^DDE l ^s of ^k and ^p, and ^adhered on ^{the phage} and honor-carboxylate diameter ^of 1 us ^{is 50 hex} nu.

To the ether treated product is added ^; 60 1 of a solution of titanium tetrachloride in hexane at concentration of ^{0% and} 4 of ^b jemovýc ^h and the suspension 2 in his ^d u ^{d y} R ^z U is for m ^s c ^hook n ^s at 70 ° C. ^p and ^{k p} and ^k and n ^{a l} phase was removed and washed ten times 50 1 of hexane. The solid was collected from hexane and dried. The solid product thus obtained is referred to as a titanium tetrachloride I solid catalyst.

2. Block copolymerization of propylene and ethylene

The block copolymerization is carried out in two stages.

To a 200 L autoclave equipped with a stirrer was added 1.9 g of solid titanium tetrachloride catalyst I and 20 g of diethylaluminum chloride. In the first step slur ^j E 150 1 Ex ^APA linseed ^pollen-ene and ^p o ^{ly and} measuring the ^beta of ^the RAC ^{at a} pot ^ ^ ⁷⁰ ° C ^to about ^d u ^{d LeVeLs} Community produced polymer reached 17.0 kg . During the polymerization, hydrogen is added to the mixture in a conventional manner to control the molecular weight.

At the end of the first stage, a small sample of the polymer is taken to measure the limit viscosity number [η] of the polymer produced. The polymerization time in the first stage is 2.5 h.

^{In the} second growth ^p n ^{I p p p y} rav ^of pulsation at ⁵⁰ ° C UV Zanca ^ADETO e ^thy only and ^p Rovai ^DI random copolymerization of ethylene and propylene in the presence of hydrogen, until it produces the second stage 4.5 kg of polymer . During the polymerization, the concentration of ethylene in the gas phase in the autoclave is 8.9 to 11.3% mel, the mean concentration of ethylene in the gas phase being 10.2%. The polymerization time in the second stage is 1.9 h.

At the end of the second stage, a polymer slurry was introduced into a 200 L autoclave from the top of the polymerization vessel. 100 L of liquefied propylene is introduced from the bottom to wash out the soluble catalyst and soluble by-products and the polymer is removed from the bottom. The washed polymer is dried to a white powdered polymer. The polymer obtained is then pelletized by adding 0.1% by weight of 2,6-di-tert-butyl-p-cresol and 0.1% by weight of calcium stearate.

The structure and physical properties of the polymer obtained are shown in Tables 1 and 2.

Example 2

The procedure of Example 1 is repeated except that 3.9 ml of methyl methacrylate is added as the third component together with the polymerization catalyst. The average concentration of ethylene in the gas phase in the second stage is 9.8 mol%. The polymerization time in the first stage is 3.1 and in the second stage 2.3 h.

The structure and physical properties of the polymer obtained are shown in Tables 1 and 2.

Comparative Example 1

The procedure described in Example 1 was repeated except that 6.7 g of TiCl 4 AA was used in place of the solid titanium tetrachloride catalyst I. The average concentration of ethylene in the gas phase in the second stage is 10.0 mol%. The polymerization time in the first stage is 2.1 h and in the second stage 1.6 h.

Although the obtained polymer is treated in the same manner as in Example 1, it contains a large amount of catalyst residues and turns yellow during pelletization. For this reason, the polymer is subsequently treated with an alcohol and heptane mixture to decompose and extract the catalyst residues. The polymer is then dried, 0.1 wt. 2,6-di-tert-butyl-p-cresol and 0.1 wt.% Calcium stearate and pelletized.

^{BC d} eve measurement ^poly AERNI sus ^{s p} oc Enzo ^cyclo nu ^d is ^{difficult, E, P} he ^dž VA ^of the ^p uc ^AV pipe after discharging from the autoclave. The polymerization temperature is very unstable due to the difficulty of heat transfer ^4. The polymer is deposited on the inner walls of the autoclave during polymerization.

The structure and physical properties of the polymer obtained are shown in Tables 1 and 2.

Example 3

Synthesis of catalyst

a) In a 1 1 autoclave, the atmosphere is displaced with argon, and the autoclave was introduced 200 ml ^H Exan and 5 ⁰ ml ^id for chlorine dioxide ^eh o. ^The SNI ^KL mites characterized by ^{d k? f P} s U is -5 ° C. К this solution was added dropwise a solution of 58 ml diethylaluminum chloride in 150 ml of dry hexane to and ^would reek, Melting ^{No. h} on it through the system at ^d r ela ^F to - ³ ° C. ^P at the ^d th ^e ce ^Leh amount of ^{s from the} STA in the mine waste ^{30 tp} edges ^c U is ^{T PL} e OTA ^EI increased to ⁷⁰ ° C and a mixture ^of a still ^{larger-ALS d d} Michio inu.

The mixture was allowed to stand and then the reducing product was separated into a liquid and washed with 200 ml of hexane.

b) 70 g of the reduction product is treated with n-decane to form a suspension having a concentration of about ^{2 g /} m ^{l p} SUS was heated Enns ^R IV ^and 2 ^h in the ^{y d} to 14 ^0C. After that one of the ^p racování are ^p ernatant separated and the solid was washed twice with 200 ml of hexane. A titanium tetrachloride product is obtained, hereinafter referred to as titanium tetrachloride product A.

(c) 11.0 g of the titanium tetrachloride A product are suspended in 55 ml of toluene and iodine and diisoamyl ether are added in such quantities as to achieve a molar ratio of titanium tetrachloride A: iodine: diisoamyl ether product of 1.0: 0.1 : 1,0. The reaction mixture was reacted for ^{1 d} it yne at ⁸⁰ ° C and ZTA ^{Ka P} ev ⁿ g catalyst. ^Ba zi titanium trichloride.

This catalyst is hereinafter referred to as a solid chloride catalyst. titanium II.

Block copolymerization of propylene and ethylene

A 200 L autoclave equipped with a stirrer is evacuated and then propylene is pressurized to a pressure of about 10 psig (39,99 kPa) into the autoclave, and then the propylene pressure is reduced to -66.65 kPa. Both operations are repeated three times.

2.6 g of solid titanium tetrachloride II catalyst and 51 g of diethylaluminum chloride are then added.

In the first step was added 51 kg of liquefied propylene, and the polymerization in liquefied ^p ro ^py is not read ene ^P ro ^b ítet in ^{EXAMPLE I} Hydrogen tomnos pH 70 ° C. ^Where, on MMN ^also not ^{GP 31.7} ol ^y mer, a small sample of the polymer for determining intrinsic viscosity of the produced polymer and unreacted monomer in the autoclave is discharged to an overpressure of 0.2 MPa.

In the second stage, ethylene gas and propylene gas are introduced into the reactor and the excess pressure is increased to 10 bar. The polymerization is allowed to proceed in the gas phase in the presence of hydrogen at a temperature of ⁷⁰ ° C. B ^EH em ^p o ^ly polymerization, for the account of ^d defects ^of n ^{s p} ol ^y Psylla ^No n ^¹H on te ^pl and ODV ^Adi of ^the car ^to l ^VU mixture ^of-tight monomer gas r ^y c ^hl SADI it ^to an I ^{7 , 8} m ^ / h. -The n ^ply in exch Cart ^ te ^p la la oc ^{h d} s ^at 50 ° ^C and is closed again ^{Adi BC} es c ^and r ^{to the} ulačn ^I · ^P om resor SLP ^{d d} n ^s Wsti. auto ^monastery vu. ^W hen the amount of polymer reaches 6.5 kg, stopping supply of the mixed monomer gas and unreacted monomers are discharged from the autoclave. The ethylene concentration in the second stage autoclave is between 9.8 and 12.7 mol%, with an average ethylene concentration of 11.2 mol%.

The obtained polymer was converted into a 200 1 autoclave fitted with a stirrer, was added 19 ^{0 gp} ro ^py oxide and the mixture ^of the 3 ° min mtetá ^p s ⁶⁰ ° C and ^should Desa ^to tivoval ^y ZB ^ytky catalyst contained in the polymer. The polymer is then dried to a white powdered polymer. To the polymer was added 0.1% by weight of 2,6-di-tert-butyl l- ^{p y} -kresolu. and 0.1 wt% calcium stearate and the mixture is pelletized. The pellets show no undesirable coloring. The structure and physical properties of the polymer obtained are shown in Tables 1 and 2.

During this experiment, there were no problems with pipe blockage and the like, and when the interior of the autoclave was inspected after polymerization, neither wall deposits nor agglomerated polymer were found therein.

Comparative Example 2

The procedure of Example 3 was repeated except that 14.0 kg of polymer was produced in the first stage and 2.9 kg of polymer in the second stage. The ethylene concentration in the second stage is 10.0 to 12.7 mol%, with an average ethylene concentration of 11.3 mol%. The polymer obtained is treated with propylene oxide and pelletized as in Example 3. Although no blockage occurs during the experiment, the pellets obtained are colored yellow.

Example 4

The atmosphere in a 5 L autoclave equipped with a stirrer is completely expelled with nitrogen and 200 g of granulated sodium chloride is introduced into the autoclave as a catalyst dispersant. Then is added 0.105 g · solid catalyst based on titanium trichloride II and 1.6 g of diethylaluminum chloride and AE indicate hydrogen in an amount corresponding to a partial pressure ^{of 0.02} M and ^P ^. Tepteta uvni ^class car ^monastery vu increased ^to 7 ⁰ ° ^C, in which case ^p rop ^yl en ^Pr e ^ battery 3 MPa, and polymerization is continued in the gas phase of the pressure which keeps the dosing propylene. After 3 hours, propylene feed is stopped and unreacted propylene gas is vented until the overpressure inside the autoclave is 0.6 MPa. By calculating the mass balance from the amount of propylene introduced into the autoclave, it was found that up to this point 760 g of propylene homopolymer had been formed.

^{T h} e ^p lota about ^five increased ^{to 60} ° C and is given to ethylene-Len pressure UVN ^d ^ R ^k l · car ^VU 1 MPa. Irregular copolymerization of ethylene and propylene in the gas phase is carried out. The pressure of 10 bar is maintained by feeding ethylene and propylene. The ethylene concentration in the autoclave was kept constant at 35 mol%. After 1 hour the feed of propylene and ethylene is stopped, the unreacted monomers are drained and the catalyst is deactivated by addition of 20 ml of water-saturated propylene oxide. Then the polymer was added 800 ml of water to remove granules of sodium chloride, použitýc ^h for dis ^p er ^g c ^ip EVN ^Star it kata ^l yzátoru ^{and p} of ^poly mer is ^dfilt oestrus and ^y su ^{own PR} and ⁶ 0 C. . ^{Ka ne} with a white powdery polymer. The productivity of the solid titanium tetrachloride II catalyst is 8,083 g of polymer per gram of TiCl2. The ethylene content of the resulting polymer is 21% by weight. Cohesion UV pr ^ASK Ene ^{b y} ro ^P o ^h o ^l Ymer ^{1.58 g /} cm ^second К ^{p ras} was ^added at ^0, 1% of whom you weight of 2,6-di-tert-butyl-p-cresol and 0.1% by weight of calcium stearate and the white powdery polymer was processed by compression molding. The sheet produced by pressing has no undesirable coloring and processing does not cause any difficulties.

Comparative example

The example was repeated except that 0.351 g of TiCl4A was used in place of the solid titanium tetrachloride II catalyst. 806 g of a copolymer of propylene and ethylene are obtained. The productivity of this titanium tetrachloride is 2296 g of polymer per gram of TiCl4. The ethyl content of the resulting polymer is 19% by weight. The cohesiveness of the powder of the produced polymer is 3.35 ^grams / cm ² .

It will be appreciated that the catalyst systems used according to the invention have a higher polymerization activity and result in a powdered polymer whose particles have a lower cohesion.

Example 5

Preparation of Catalyst 1 (preparation of beta-type titanium tetrachloride)

Air in the reactor of 1 liter volume was displaced with argon, and the reactor - was charged with ²⁰⁰ ml suc ^HEH of hexane and ⁵⁰ m ^l chlorotrimethylsilane titaničitoho. ' The solution was maintained ^{at f} U is -5 ° C. To this solution was added dropwise a solution of 58 ml diethylaluminum chloride in 150 ml of dry hexane, and the ^ ^should te ^ ^p lota rea ntoo systomu maintained at - ³ ° C for not ^b te ^pl Oto yarn. Once ^P s ^be the marking of ^{Leh LeVeLs} Community, the mixture ^of the ^STE with ³⁰ mtout, mtohá ^p and the temperature increased ^{to 70} ° C and stirring was continued for another hour. The mixture was allowed to stand and then the beta-type titanium tetrachloride was separated from the liquid and washed three times with 200 ml of hexane.

Catalyst 2 Preparation (Lewis Handle Solid Preparation)

31.2 g of beta-type aluminum chloride prepared as described for the preparation of catalyst 1 are suspended in 106.0 ml of dry hexane and diamyl ether is added in a quantity such that 1.2 mol of diisoamyl ether is added to 1 mol of titanium tetrachloride. The mixture is then swirled ^at 40 ° C for ¹ hour. After ^the rea ci k ^p and ^l are ^p Nu erna ^t an ^t from the reaction mixture, and the treated solid is washed with 100 ml of hexane and dried.

Preparation of the catalyst

12.5 g solid obtained in the above Preparation of Catalyst 2 was added to a solution of 25.0 ml laluminiumd eth ^{y i} c ^h Lorido 3 ^7, 5 ^{g of} n-Delcan and the mixture ^of the 2 ^h of ^di n ^y zahMvá to 12 ° C * After the reaction, the supernatant is separated. The titanium tetrachloride is washed three times with 40 ml of hexane and dried. The titanium tetrachloride substance thus obtained contains 4.18% by weight of aluminum and in its X-ray diffraction diagram the maximum corresponding to the delta-type titanium tetrachloride is apparent.

Preparation of the catalyst

9.2 g of the titanium tetrachloride substance obtained according to Preparation of Catalyst 3 are suspended in 46.0 ml of hexane and thereto are added tetrachloromethane and diisoamyl ether in such a quantity as to obtain a molar ratio of titanium tetrachloride: tetrachloroethane:. isoamyletoer ^^ 3 ^ 5 and mix for 2 ^ ny for a ^HRI V ^{and 60} ° C. The supernatant was separated and the remaining solid was washed three times with 40 ml of hexane. A solid titanium tetrachloride catalyst is obtained. This catalyst is hereinafter referred to as the titanium trichloride III solid catalyst.

Block copolymerization of propylene and ethylene

A 200 L autoclave equipped with a stirrer is evacuated and then prop.ylene is pressurized into the autoclave to a pressure of 39.99 kPe and then the propylene pressure is reduced to a vacuum of -66.65 kPa. Both operations are opalkiaí three times.

2.6 g of solid chloride catalyst are then added. titanium (III) and 51 g of diethylaluminum chloride.

In the first stage is added 42.5 kg of liquefied propylene and liquefied polymerece oil ^p! Ene is allowed to talk in the presence of a ^thank at ⁷⁰ ° C. When ^{25.2 kg of} polymer was formed, a small sample of polymer was taken to determine the viscosity limit of the polymer produced and unreacted in the autoclave.

In the second stage, ethylene gas and propylene gas are introduced into the reactor and the overpressure is increased to 100 ° C. The polymerization is allowed to proceed in the gas phase in the presence of hydrogen at a temperature of ⁷⁰ ° C. Where, ^{on the} MNN Community vyroten ^ o ^ pol / mer Osáhne ^6.3 zasteví to ^d of ^d avka monornerního mixed gas and unreacted monomers from the autoclave, ethylene concentration in the autoclave in the second step is between 25.3 and 27.8% Mo, wherein the average concentration of ethylene is 26.9 mol%.

The obtained polymer was converted into a 200 1 autoclave fitted with a stirrer, ^{180 g of} the UA-propyleneoxy mixture was ^{stirred 30} min at ⁶⁰ ° C s to ^ saktivovaly ^{Excess amounts} of the catalyst contained in the polymer. The polymer is then dried to a white powdered polymer. 0.1% (w / w) 2,6-di-tert-butyl-β-quartzyl and 0.1% (w / w) calcium stearate are added to the polymer and the mixture is pelletized. The pellets showed no undesirable coloring. The structure and physical properties of the polymer obtained are shown in Tables 1 and 2.

During this experiment, there were no problems with pipe blockage, etc. and when the interior of the autoclave was inspected after polymerization, neither wall deposits nor agglomerated polymer were found therein. .

Comparative Example 4

The procedure of Example 5 is repeated except that 8.5 g of TiCl 3 is used instead of the solid titanium trichloride III catalyst. The ethylene concentration in the second stage is 25.4 to 27.6 mol% and the average concentration of ethylene in the gas phase is 26.6 mol%. The polymer is treated with propylene oxide as in Example 5 but still retains a large amount of catalyst and pellet residues during manufacture. Therefore, the polymer is subjected to treatment with 1% alcohol and heptane to decompose the catalyst and extract the catalyst residues. The polymer is then dried to a white powder. To the powder was added 0.1% hydrogen-2,6-di-butyl-β-quartz and 0.1% calcium stearate and the polymer was pelletized.

Temperature control problems occur during polymerization. When transporting the polymer after removal from the autoclave, the piping becomes clogged. Examination of the interior of the reactor after polymerization revealed that a large amount of polymer had deposited on the internal walls and on the agitator. The structure and physical properties of the obtained polymer are shown in Tables 1 and 2. It is understood that the copolymers of the invention have better heat resistance and flexural strength than the copolymers obtained according to the comparative examples.

Table 1

Ethylene content ⁽ % by weight) Viscosity limit number (r |) dl / g Catalyst activity ^gp ol ^y mer ^{/ g} HCl 4 first ^and cold en ^{p d} ruhý stu ^p en Example 1 4.2 1.77 3.18 1 1 300 Example 2 4.1 1.80 3.17 1 1 200 Comparative example 1 3.8 1, 76 3.03 3 200 Example 3 4.1 1.60 1, 80 12 200 Comparative example 2 4.2 1.62 1, 81 6 500 Example 5 9.6 1.76 2.99 12 100 Comparative example 4 9,5 1.76 2.96 3 700

Table 2

Flow index Vicatova Temperature Strength limit Impact resistance Koheze Color * melt temperature bend brittleness ževnatost powder softening Izod 0g / 10min) ( ⁰ C) (° C) (MPa) (kJ / m ² ) ^^ ^/ cm ²⁾

° C ^- 20 ° C

Example 1 2.8 76 -22 1 010 16.7 5.2 1.05 white Example 2 2.4 79 -23 1 069 14.7 5.0 0.95 white Comparative example 1 2,8 73 -21 892 17.7 5.8 3.76 yellow Example 3 7.5 77 -12 1 050 8.0 2.4 1.71 white Comparative example 2 7.3 75 -13 1 040 8.2 2.5 1.80 light yellow Example 5 2.5 69 -37 931 15.7 5.2 1.79 white Comparative example 4 2,4 65 -37 824 16.7 5.4 4.21 yellow

Note the color determined visually.

The invention has been illustrated in particular by the preceding examples. However, these examples are illustrative only and do not limit the scope of the invention in any way. The present invention is intended to include all modifications and changes within the spirit and scope of the skilled artisan.

SUBJECT OF THE INVENTION

Claims (7)

16 212324 Table 1 Ethylene Content Content Viscosity Limit Number (n) dl / g Catalyst activity first stage second stage g polymer / g TiCl 2 Example 1 4.2 1.77 3.18 1 1300 Example 2 4.1 1, 80 3 Comparative Example 1 3.8 1, 76 3.03 3 200 Example 3 4.1 1,60 1, 80 12 200 Comparative Example 2 4,2 1,62 1, 81 6,500 Example 5 9, 6 1,76 2,99 12 100 Comparative example 4 9,5 1,76 2,96 3 700 Table 2 Flow index Vicat Temperature Strength Strength Impact cohesive Color * melt temperature bending bending susceptibility of Izod softening powder (g / 10 min) (° C> (° C) (MPa) (kJ / m2) 20 ° C -20 ° C (g / cm 2) Example 1 2.8 76 -22 1 010 16.7 5.2 1.05 White Example 2 2.4 79 -23 1,069 14.7 5.0 0.95 White Comparative Example 1 2.8 73 -21 892 17.7 5.8 3.76 Yellow Example 3 7.5 77 -12 1,050 8.0 2.4 1.71 white Comparative Example 2 7.3 75 -13 1,040 8.2 2.5 1.80 Light Yellow Example 5 2.5 69 -37 931 15.7 5.2 1.79 white Comparative Example 4 2.4 65 -37 82 4 16,7 5,4 4,21 yellow Note: the color is determined visually. However, these examples are merely illustrative and are not intended to limit the scope of the invention in any way. All modifications and changes within the scope of the ordinary skill in the art are within the scope of the invention. OBJECT OF WINE LEZU A process for the production of block copolymers of propylene and ethylene, wherein polymerization of propylene itself or a mixture thereof with less ethylene is initiated in the first stage, essentially in the absence of an inert solvent, and then in the polymerization of the liquefied monomer or in the gas phase and then propylene and ethylene are copolymerized irregularly in the second stage in a liquefied monomer environment or in a gas phase, or the vapor phase ethylene itself is polymerized using a system comprising 17% by weight of a solid catalyst for the block copolymerization. a titanium trichloride base obtained by reduction of titanium tetrachloride with an organoaluminum compound and subsequent activation, B. an organoaluminum compound of formula V1X3-m wherein R is a straight or branched chain alkyl group having 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom or an alkoxy group and a number greater than or equal to 2 and less than or equal to 3, and optionally an electron donor. 14. The process of claim 1 wherein the solid catalyst A is a catalyst obtained by reacting components a), b) or c) wherein component a) is a reduced product obtained by reducing titanium tetrachloride with an organoaluminum compound of formula V1X3-n wherein R ' a straight or branched chain, alicyclic or aryl group, each of which contains up to 18 carbon atoms, X 'is a halogen atom or a hydrogen atom and an number greater than or equal to 1 and less than or equal to 3, component b) is a heat treated solid obtained by heating the reduced product a), optionally in the presence of an inert organic solvent, to a temperature of about 50 to 120 ° C, component c) is the reaction product obtained by further reacting the reduced product a) with the aluminum compound of the formula R p 1 X 3 -p wherein r is a straight or branched alkyl group, an alicyclic group or an aryl group each group contains up to 18 carbon atoms, X is a halogen atom and p is greater than or equal to 1 and less than 1.5, with a mixture of halogen or halogen and ether. 3. A process as claimed in claim 1, wherein the solid catalyst A is a catalyst obtained by reacting components a ') or b') wherein component a ') is a reduced product obtained by reducing titanium tetrachloride with an organoaluminum compound of formula R 1 X 1. 3-n wherein R 'is a straight or branched chain alkyl group, an alicyclic group or an aryl group, each of which contains up to 18 carbon atoms, 212324 18 X', a halogen atom or a hydrogen atom and a number greater than or equal to 1 and less, or equal to 3, and component b ') is a heat treated solid obtained by heating the reduced product a'), optionally in the presence of an inert solvent, at 20-100 ° C, with ether and subsequent reaction of the ether-treated solid with titanium tetrachloride. 4. A process as claimed in claim 3, wherein the solid catalyst is a catalyst according to claim 3, which is further reacted with a mixture of halogen or halogen and ether. 5. A process as claimed in claim 1, wherein the solid catalyst A is a catalyst obtained by reducing tlc chloride with an organometallic compound of the formula ## STR5 ## wherein R 'is a straight or branched chain alkyl group, an alicyclic group, or an aryl group, each containing up to 18 carbon atoms, X 'represents a halogen atom or a hydrogen atom and an integer greater than or equal to 1 and less than or equal to 3, by reacting the reduced product thus obtained with ether and then reacting the ether-treated solid compound with an aluminum compound of formula P 3 -p where R is "straight or branched chain alkyl group means an alicyclic group or an aryl group, each of these groups having up to 18 carbon atoms, X a halogen atom and a number greater than or equal to 1 and less than 1.5, followed by reaction of the thus obtained solid with ether or a mixture of halogen or halogen with ether. 6. Process according to claim 1, characterized in that component B is used in a concentration of 0.05 to 50 mmol per mole of monomer. 7. The process of claim 6 wherein the molar ratio of component B: A is 1: 1 to 500: 1. 8. The process of claim 1 wherein the molar ratio of component C: A is 0.1: 10.