SE449616B - SET TO COPOLYMERIZE ONE AND ONE OR MULTIPLE MULTI-SATURED CALVET AND CATALYTIC SYSTEM FOR IMPLEMENTATION OF THE SET - Google Patents

Description

10 15 20 25 30 35 449 616 In this way, further formation of MgX2 is obtained, which works with the stoichiometric complex so that one gets a new and more active complex containing titanium.

It has now been shown that by modify the conditions of the magnesium evaporation and by selection of reagents and reaction conditions can copolymerize ethylene, either as such or in admixture with other alpha-olefins, with one or more polyunsaturated hydrocarbons containing conjugated or non-conjugated double bonds, so as to obtain highly crystalline poly- more if only ethylene is used. In addition to magnesium can also manganese be used for the preparation of the catalytic component.

The activity of the catalytic described above the system is such that one gets an amount of copolymers per gram titanium of 50 kg or more. The catalytic system is consists of two components. One catalytic component is prepared by evaporating magnesium or manganese, either as pure metal or in the form of an alloy down there, and condenses the steam into a cold solution prepared by dissolving a titanium compound and a halogen donor in an inert solution medium.

The metal (M) can be used in powder form, in the form of granules or in lumps and preferably evaporated below vacuum during sublimation. For magnesium, the temperature varies turn for a pressure of between 2 and 10-4 of the pressure between about 650 and 30,000.

Dry as a function Manganese requires harsher conditions, namely 800-100 ° C -1o'4 If the work is carried out at a higher temperature, the pine evaporates from the molten state even at moss paint pressure. l for 10- Dry.

The solution into which the vapor is condensed is kept stirring at low temperature. Depending on which solvent used, this may be in the range -l20 to OOC and usually between -80 and -ZOOC.

The use of an inert solvent, selected from low volatile hydrocarbon solvents with low freezing point (e.g. pelvis n-heptane, n-octane, toluene etc.L is not strictly necessary invariably, in that the reaction can even be carried out l0 l5 20 25 30 35 449 616 within the titanium compound and the halogenated compound in their pure state.

Titanium tetrachloride is a liquid titanium compound that is suitable for this purpose and alkyl halides are suitable as halogenated compounds, their saturated excess forms the reaction medium.

Examples of alkyl halides that can be used are 1-chloro- butane, l-chlorhexane and l-bromohexane, but secondary or tertiary alkyl halides and aryl or alkaryl halides are also reactive. Of the inorganic halides, SnCl4, SbCl5, GeCl4 and POCl3 proved to be most suitable.

Of useful titanium compounds, in addition to tetrachloride, other halides, including the trivalent halides, alcohols holtates, haloalcoholates, chelates and all organometallics derivatives proved to be suitable. In practice, one can use then any titanium compound, making the difference them between only is the speed of the reaction.

The M / Ti ratio that must be achieved for extremely active catalytic compositions exceed 0.5 and is especially more than 4. Suitable value for this ratio is between 15 and 30 and a further Excess M (Mg or Mn) does not bring any benefits. Multi- the hakgemkmenn fl e compounds in the reaction are regulated with taking into account the amount M, in relation to which it should have a ratio of more than 2 with monohalogenated organic compounds and more than 1 in the case of inorganic compounds which can give more than one halogen atom per molecule- The reaction between The M-vapor, the Ti compound and the halogenated compound already occurs at the above-mentioned low temperature. For full- the boarding of the reaction takes either a long time (a few days) standing at ambient temperature or, which is to pull, heating for a few hours (1-5 h) depending on the selected temperature (50-180 ° C). The reaction proceeds faster when the halogen donor is Inorganic.

Halogmukmaunn is not strictly necessary in the wide low temperature solution in which the metal vapor condenses seras. It can be added later, but before the solution temperature is increased to complete the reaction.

The fine, in the manner described above 449 616 lO 15 20 25 30 35 the pension is usually used directly as a catalytic component for the polymerization described in more detail below, sat that neither excess of any of the reagents nor by-products of the reaction form significantly disturbing agents in the formation of the catalyst. Alternatively can the suspension is filtered and the solid is resuspended their in the dispersant considered most suitable, usually that in which the polymerization is carried out. It is also possible dispersing the solid compound on an inert solid carriers, which are formed, for example, from polymers of the same type as the one to be produced.

The second catalytic component consists, of an organometallic compound of a Group III element in the periodic table. Of these elements, aluminum is most often used. minimum due to its efficiency and suitability in rich.

Examples of compounds are trialkyl and triarylaluminum. nium, for example Al (C 2 H 5) 3, Al (1-C 3 H 7) 3, Al (C 6 H 5) 3, alkyl- aluminum hydrides, for example Al (H) (1-C 3 H 7) 2, and alkyl- and arylaluminum halides, for example Al (C 2 H 5) 2 Cl and Al (C2H5) Cl2.

The trialkyl derivatives are preferred, but they are also very effective in admixture with the halogenated derivatives.

Molar ratio of organometallic compound to titanium compound must exceed 3 in order to achieve maximum specific activity. For practical reasons, this relationship is very high, for example between 100 and 500, taking into account to the fact that extremely small amounts of titanium compounds is used in the polymerization. As previously mentioned is the copolymerization process of the present invention based on copolymerization of ethylene with one or more polyunsaturated hydrocarbons, said catalysts the components are used in the presence of an inert solution at a temperature between 40 and 12000 and one working pressure of between 100 and 2000 kPa.

In batch tests, the reagents have been fed into the reactor in such a way that the catalyst is either formed in presence of the mixture of the two monomers or comes into con- pace with it. f; 10 15 20 25 30 449 616 In practice, you can apply two working methods, which both are effective. As the titanium content is first added, holding the catalytic component last, while in other led the reaction between the catalytic components, which should be added to the monomer mixture successively, is carried out separate. In the latter case, there is a pre-contact time, which, although not critical, should not be for long, especially if using high Al / Ti ratios. the.

Aliphatic hydrocarbons are preferably used as ingrta solvents. However, solvents not strictly necessary during the polymerization stage, as it is possible to work in the gas phase by introducing the catalyst dispersed in a small amount at low temperature lucky boiling solvent.

The monomers selected for exemplification of the polymerization process are those listed therein following. The conditions described above are completely nerella and all types of ethylene copolymers can be prepared in accordance with the procedure of the present invention on the basis of the detailed teachings set out in the the preparation of the copolymers discussed below, without therefore being beyond the scope of the invention.

The person skilled in the art can easily choose the most suitable working conditions. with regard to the polymer to be produced.

The monomers are ethylene on the one hand and a cyclic acyclic hydrocarbon containing more than one unsaturated binder which may be conjugated, on the other hand. Prototypes of these classes of hydrocarbons, which are preferred with regard to to the reactivity and low cost, is 1,3-butadiene and 5-Ethylidene- (2,2,2) -dicyclohepta-2-ene (ethylidene norbornene) These have a smaller reactivity during polymerization than ethylene, why they are added in excess (50 times or more) over the amount of the same monomer required to one must] get the copolymer. This surplus is utilized through that its solution is recycled. The practical useful the ethylene comonomer in the copolymer is only a few percent (less than 10 mol%).

The molecular weight of the copolymer can be controlled by .m 10 15 20 449 616 6 hydrogen supply, in combination with varying the reaction conditions.

The compositions of the present invention The polymers have properties that vary with their composition. setting. The ethylene-butadiene copolymers contain trans- unsaturated bonds, while cis and vinyl unsaturated bonds does not occur at all or practically does not occur at all, as shown by 1,4-addition of the butadiene units.

The ethylene-butadiene copolymers with a lot of ethylene have densities between 0.940 and 0.960, melting points around 130 ° C and a distribution of unsaturated bonds resulting from of the attached 13 C-NMR spectrum (for a copolymer more containing 2.3 mol% butadiene), showing 3 peaks which can be attributed to various designed butadiene units with the polymer chain (the peaks attributable to methylenes in tadiene at a = 32.6, b = 32.7 and c = 32.9 ppm). It must mentioned that analogous copolymers prepared in a known manner has only two of these three peaks in the 13 C-NMR spectrum. The It is known that crystalline poly-alpha-olefins, for example poly- ethylene, isotactic polypropylene, isotactic polybutene, etc., have been in the trade for some time.

These poly-alpha-olefins consist of either homo- polymers or copolymers with small amounts of a second alpha-olefin for solving certain technical problems. The amount of the other olefin is normally so low that it does not too much reduces the crystallinity with respect to homogeneity polymer, since certain important mechanical properties, such as as module, yield strength, etc., are associated with the high crystallinity.

In copolymers of ethylene and butadiene, the feasibility of devices of the two kinds in the same crystal that one can obtain substantially crystalline polymers throughout the composition range from pure polyethylene to pure -polybutadiene. Thus, in this case, it does not exist limitation, which exists in the case of copolymers of mono- -alpha-olefins, in which an olefin must be present in a myc- small amount in the copolymer to the crystallinity must be able to be kept at a high level. An extremely important part with copolymers prepared according to the present invention 10 15 20 25 30 35 449 616 invention is because they contain unsaturated bonds (either in the main chain, as in the case of butadiene, or in side groups, as in the case of ethylidene norbornene).

By means of these unsaturated bonds, the copolymer can easily crosslinked (with sulfur or other reagents) for surface further improvement of its technical characteristics, such as heat resistance, impact resistance or resilience against agents, which cause the appearance of tensile cracking.

The unsaturated bonds also allow certain trans- formations, which would otherwise be difficult to carry out impossible, such as foaming and thermoforming sheets.

Example 1 The titanium-containing catalytic component is produced placed in a horizontally arranged, rotating glass bottle on l l, at the center of which an electrically heated by means of tungsten wire aluminum crucible is placed. 240 ml of n-heptane and 0.2 ml of TiCl4 were placed in carbon and 0.9 g of magnesium turnings were placed in the crucible. a kyiaes to -70 ° C. 10-3 Torr), the crucible was heated to red heat.

Solution- After placing the flask under vacuum, Vaporization of Mg led to the formation of a brown suspension, to which n-butyl chloride (1-chlorobutane, 8.2 ml) was then added in vacuo abolished by the addition of nitrogen.

The suspension was then heated to BOOC for 3 hours using a reflux condenser.

Co-polymerization A stainless steel autoclave with a volume of 5 l and equipped equipped with a mechanical stirrer and regulated heat supply, under vacuum and a solution consisting of the following was asked: anhydrous n-heptane 2200 ml butadiene 200 g Al (C2H5) 3 15 mmol was added under suction.

The temperature of the autoclave was regulated at 70oC before hydrogen and ethylene were added at partial pressures of 350 and 450 kPa. 10 ml of the preparation according to the previous description the heptane suspension, containing 0.075 mmol of titanium lO l5 25 30 35 449 616 the autoclave was charged with an overpressure of ethylene using use of a 100 ml steel container with inlet and outlet valves.

A heptane solution (50 mL) of Al (C 2 H 5) Cl 2 (7.5 mmol) was then added during the first five minutes of reaction. to the mixture already present in the autoclave using a piston pump. One could observe an immediate absorption of ethylene, which was continuously fed to in such a way that the initial pressure was kept constant, early as the temperature was maintained at 70 ° C.

After 3 hours it was found that ethylene was still absorbed was prepared with an intensity approximately equal to the initial intensity. However, the test was interrupted, and the suspension in the autoclave was drained and filtered.

388 g of dry polymer with an MFI2.16 were obtained 49.5, a butadiene unit content (mol) of 3.3% and a melting point Tm, determined by differential thermal analysis, at 13 ° C. The polymer, which was a white solid which very similar to a polyethylene, was mixed with the following g, per 1000 g of polymer: zinc oxide stearic acid 2,2'-methylene-bis (4-methyl-terbutylphenol) (A.o.22'46) 1 N-oxidethylethylbenzothiazole-2-sulfenamide (NOBS special) dibenzothiazyl disulfide (Vulkacite DM) sulfur The mixture was treated in a press at 180 ° C below 30 minutes, giving a product which gave 40% residue extraction with boiling xylols (the polymer as such was completely soluble).

Excmvel 2 A test was performed at 85 ° C using autoclave and method according to Example 1.

In this case, the partial pressures of the etcn were hydrogen 500 and 300 kPa and 250 g of butadiene were introduced, respectively.

All other quantities were the same as in Example 1.

After 3 hours of polymerization, 250 g of dry copolymer were obtained. U » 10 ' 20 30 449 616 butadiene units = 3.3% (mol), new: 16 = 0.84, Mrizllö / nrI2, l6 = 32.5, melting point 1z9 ° c, impact strength 1370 kPa. more with the following features: After crosslinking as described in Example 1, had the product has an impact strength of 5040 kPa.

Example 3 A polymerization test was performed using of the same apparatus and method as in the previous example using use of the following reagents: n-heptane 1840 ml butadiene 102 g Al (C 2 H 5) 3 17.6 mmol H2 350 kPa ethylene 500 kPa Ti complex (see Example 1) 0.06 mmol Auiokiaven was kept at 85 ° C both during gastiiiförsein and the underpolymerization, during which the ethylene is precipitated used.

After 4 hours, the sample was stopped and the product was filtered off. was dried and dried to give 285 g. ” Analysis gave the following results: butadiene units 1.5% (moi), NFI2, 16 = 0.99 g / 10 min, MFI21.6 = 27.4, Tm (DSC) = 133 ° C.

Example1'4 A solution prepared from 400 ml of n-heptane and 40 ml Bicyclo (2,2,1) -5-ethylidene-2-heptene (ethylidene norbornene) into a stainless steel autoclave of the same type as in example l, but with space 2 l. The autoclave temperature control at 85 ° C and ethylene and hydrogen were added at partial pressures of 500 and 300 kPa, respectively.

The catalyst, consisting of heptane suspension of it product obtained by reaction of 5 mmol of Al (i-C4H9) 3 with 0.012 mmol of titanium in the manner described in Example l for 60 minutes at ambient temperature was introduced using of a steel container and overpressure by means of nitrogen.

The test lasted for 1 hour, during which time the spent ethylene was set so that its partial pressure was kept constant.

It after filtering the suspension and drying the solid product obtained from the filtrate weighed 35 g. 10 20 25 30 35 10 4119 6'l6 It had the following properties: 3.3% ethylidene born (weight), MFI2 16 = 3.4 g / 10 min, MFI26 = 33, . 'I' i I 620 „ln = 0.9e33 g / cm °.

Example 5 The titanium-containing catalytic component is produced was prepared in a similar manner to that described in Example 1, but starting from the following reagents: 1-chloroctane 120 ml TiCl4 0.088 ml manganese metal 1.5 g The solution was cooled to -SOOC and placed under a vacuum. kuum of 10_4 Torr, after which the manganese was evaporated and condensed serades. A dark brown suspension was obtained, which was then heated to 100 ° C for 1 hour.

Chemical analysis showed that the homogenized suspension the ion contained 5.10 mmol / l Ti, 186.2 mmol / l Mn, 390.0 mmol / l l Cl.

Copolymerization A copolymerization test between butadiene and ethylene was carried out using the apparatus described in empel l.

The solution fed to the reactor was prepared from: n-heptane 2200 ml butaaieñ 250 g Al (i.C4H9) 3 22.5 mmol After adjusting the temperature to 85 ° C was set autoclave under pressure with 300 kPa hydrogen and 5 kPa ethylene. 15 cm3 of the titanium complex containing suspension The preparation, prepared as described above, is hereby completed ter. Additional ethylene was added over 3 hours to keep the pressure at initial value, which was 1000 kPa at 8500, after which the sample was stopped and the product was filtered off and dried. kades. 200 g of polymer were obtained with the following properties: 1,4-trans-butadiene units = 5.15% (mol), MFI2'1 = 0.05 g / io min, rm (Dsc) = 132 ° c, [n] (in alkaline at los c) = 1.75.

Example 6 The titanium-containing catalytic component is produced was placed in an apparatus analogous to that described in Example -.-._-, lr fl n- 10 20 449 616 ll pel l av: n-octane 300 ml Tiçlq 0.187 ml SnCl4 8 ml Mg-metal 1.2 g The magnesite evaporated at 5.10 ° C. was introduced into the solution, which was kept at about -50 ° C, after which The temperature of the resulting suspension was increased to about yield temperature. After 24 hours it was set aside material decanted the above solution free from while the homogenized suspension contained 6.32 mmol / l Ti, l87 mmol / l Mg, 207 mmol / l Sn and 863 mmol / l Cl.

Samgolxmerisation The test was performed in the auto described in Example 1. at the SSOC using the same method and the same reaction agents as in Example 5, with the exception of the titanium the catalytic component, which this time consisted of 11, 85 ml of the above suspension. The polymer weighed = 0.1 g / 10 min, Tm = 13 ° C (DSC), butadiene units = 3.34% (mol). 180 g and had the following properties: MFI

Claims (23)

449 616 12 PATENT REQUIREMENTS A method of copolymerizing ethylene and one or more polyunsaturated hydrocarbons containing conjugated or non-conjugated double bonds, characterized in that the ethylene and the polyunsaturated hydrocarbon are copolymerized at a temperature between ambient temperature and a temperature slightly below the melting point of the copolymer, at a pressure between 100 and 3000 kPa in the presence of a catalytic system, comprising (1) a component prepared by evaporation of magnesium at a temperature of 300-650 ° C or prepared by evaporation of manganese at a temperature of BUÛ-HÛÛOC and by reacting the magnesium vapor or manganese vapor with a titanium compound and a halogen donor, optionally in an inert solvent, and (Z) an organometallic compound of aluminum or other Group III element of the Periodic Table. 2. A process according to claim 1, characterized in that the copolymerization is carried out in the presence of an inert solvent. 3. A process according to claim 2, characterized in that the inert solvent is the same as the solvent used to prepare component (1) of the catalytic system. 4. A method according to claim 1, characterized in that the ethylene and the polyunsaturated hydrocarbon are reacted in a gaseous state and in the absence of solvent. 5. A method according to any one of the preceding claims, characterized in that the catalytic system is deposited on an inert support. 6. A method according to any one of the preceding claims, characterized in that the copolymerization is carried out at a pressure of 100-2000 kPa. 7. A method according to any one of the preceding claims, characterized in that the copolymerization is carried out at a temperature of 40-120 ° C. 8. A process according to any one of the preceding claims, characterized in that the polyunsaturated hydrocarbon is β-butadiene. 9. A method according to any one of claims 1-7, characterized in that the polyunsaturated hydrocarbon is ethylidenebornene: i.e. (5-ethylidene (2,2,1) -bicyclohepta-2-ene). Catalytic system for carrying out copolymerization of ethylene and at least one polyunsaturated hydrocarbon containing conjugated or non-conjugated double bonds, characterized in that it comprises a component prepared by evaporation of magnesium at a temperature W of 300-650 ° C or prepared by evaporating manganese at a temperature of 800-1100 ° C and by reacting the magnesium manganese or manganese with a lithium compound and a halogen donor, optionally in an inert solvent, and (2) an organometallic compound of aluminum or another element of group III of the periodic table. ll. System according to claim 10, characterized in that component (1) has been prepared by evaporation of magnesium or manganese or an alloy thereof and by condensing the steam in a diluent containing the titanium compound and optionally the halogen donor. System according to claim 10 or 11, characterized in that component (1) has been prepared by sublimation of magnesium under vacuum between 2 and 10-4 Torr. 13. A system according to claim 10 or 11, characterized in that component (1) has been prepared by sublimation of manganese under vacuum between 10-1 and 10 -4 System according to any one of claims 10-13, characterized in that Torr. that the component (1) has been prepared by condensing the metal vapor in an inert solvent selected from aliphatic and aromatic hydrocarbons, at a temperature maintained between -IZÛÜC and DUC. A system according to any one of claims 11 to 11, characterized in that the component (1) has been prepared by completing the reaction in the preparation at a temperature of 20 to 180 ° C. A system according to any one of claims 10-15, characterized in that component (1) has been prepared by using a halogenicl, an alcoholate, haloalcoholate or organometallic derivative of trivalent or tetravalent titanium as the titanium compound. 17. A system according to any one of claims 10-16, characterized in that component (1) has been prepared by using an organic or inorganic halide as a halogen donor. l8. System according to claim 17, characterized in that component (1) has been prepared by using chloroalkane, bromomalkane, chlorinator or bromine. A system according to claim 17 or 18, characterized in that component (1) has been prepared by a reaction in which the molar ratio of the organic halogen donor and the vaporized metal is equal to or greater than 2: 1. 449 616 11+ A system according to claim 17, characterized in that the catalytic system has been prepared using SnCla, SbClw G fi cla and / or POCIB as halogen donor. Zl. System according to claim 20, characterized in that component (1) has been produced by a reaction in which the molar ratio of the inorganic halogen donor and the metal vapor is equal to or greater than 1: 1. System according to any one of claims 10-21, characterized in that component (1) has been prepared by reaction between the metal vapor and the titanium compound in a metal / titanium ratio equal to or greater than 4: 1. 23. A system according to claim 22, characterized in that the component (1) has been prepared by reacting the metal vapor and the titanium compound in a metal / titanium ratio of 15: 1 to} Ü: 1. H §I f »