NL8001389A - PROCESS FOR THE COPOLYMERIZATION OF ETHENE AND MULTIPLE UNSATURATED HYDROCARBONS. - Google Patents

Description

803080 / vdveken '*' *

Applicant * ANIC S.p.A. in Palermo, Italy.

Short designation} Process for the polymerization of ethylene and simple unsaturated hydrocarbons · 5

The invention relates to an improved, high-yield process for the preparation of copolymers from ethylene or ethylene exclusively mixed with one or more α-olefins, and a compound containing two or more unsaturated or unsaturated olefin bonds, of which a catalyst system is used consisting of 1) an organic metal compound with a Group III metal of the Periodic Table and 2) a compound prepared by reacting magnesium or manganese metal vapors with a titanium compound and a halogen-providing compound

The products resulting from the copolymerization of ethylene only and the polyunsaturated compound are crystalline polymers ·

A number of methods are known for the preparation of crystalline copolymers by polymerizing ethylene with a conjugated or non-conjugated polyolefin, in particular butadiene and ethylidene norbornene (see, for example, Dutch patent applications No. 75 * 09283, 7707832 and Dutch patent 158,512.

These processes employ coordinated vanadium-based anionic catalysts which, while yielding high polymerization yields, have catalytic activity such that the copolymer must be more cumbersome to clean from the transition metal residue, including the oxidation stability of the copolymer and an undesired color arises. Further reference is made to Dutch patent application 77 * 01005 which relates to a catalyst composition which is particularly effective in the polymerization and copolymerization of mono-α-olefins and which is prepared by reaction of an organometallic compound of a Group III metal of the Periodic Table, with a composition prepared by 1) diluting or subliming magnesium under vacuum and 2) condensing this vapor in a condensed phase consisting of titanium tetrahalide and a halogen-supplying compound * 39 The same patent expires on da the activity of the fiflft 13 89-2 catalyst composition in the homo- and copolymerization of α-olefins is very high when such an amount of magnesium metal is evaporated that the atomic ratio of Mg to Ti in the condensed phase is much more than 0, 5, while a compound is present which is capable of supplying halogen to the amount of magnesium metal above the atomic ratio of Mg to Ti of 0.5 with respect to the complex MgX2 · 2TiX2 (X-halogen). In this way, again MgX0 is formed which reacts with the stoichiometric complex to form a new and more effective titanium-containing complex. It has now been found that by changing the conditions under which magnesium evaporates and by choosing reactants and reaction conditions is ethylene by itself or mixed with other α-olefins with a compound containing one or more unsaturated olefin bonds to form highly crystalline polymers in those cases where only ethylene is used. In addition to magnesium, manganese can also be used for the preparation of the catalyst composition.

The activity of the catalyst system described above is such that an amount of 50 kg or more of copolymer is prepared per g of titanium. The catalyst composition is prepared by evaporation of magnesium or manganese in the metallic state or in the form of one of the alloys and condensation of the vapor in a cold solution prepared by dissolving a titanium compound and a halogen compound in an inert diluent. .

Metal (m) can also be used in powder form or in the form of granules or clumps and is preferably evaporated under vacuum by sublimation, at magnesium at a pressure of between 2 and 10 Torr and a temperature depending on the pressure between 650 and 300 ° C.

For manganese conditions are more extreme, namely 50 800-1100 ° C at 10 "1 to 10 ~ 4 Torr.

When operating at higher temperatures, the metal can be evaporated from the molten state even at atmospheric pressure.

The solution in which the vapor condenses is stirred at a low temperature, which depending on the solvent can be -120 to 0 ° C, in general -80 to -20 ° C. The use of an inert i 1 ... _ - 80 0 1 3 89 1 * * -3- diluent, which is chosen from low volatility low freezing point hydrocarbon solvents (eg n-heptane, n-octane, toluene etc <>) is not strictly necessary since the reaction is even in the pure titanium compound and halogen-containing compound can be carried out *

Titanium tetrachloride is a liquid titanium compound which lends itself to this purpose while alkyl halides are suitable as halogen compounds in which they form excess reaction medium # 10 Examples of alkyl halides are 1-chlorobutane, 1-chlorhexane and 1-bromhexane, although secondary or tertiary alkyl halides and aryl or alkylaryl halides are also reactive.

Of the inorganic halides, SnCl 2 is preferred,

SbCl5, (JeCl ^ and POCl ^.

In addition to tetrachloride, the titanium compounds can also be used well in the other halides, including the trivalent halides, alcoholates, haloalcoholates, chelates and all organic metal derivatives. In practice, all titanium compounds can be used, the difference being only by the reaction-20. speed is determined

The ratio of M to Ti required for the preparation of highly active catalytic compositions is greater than 0.5, and in particular values of from 15 to 30 are preferred, with an even greater excess of M (Mg or Mn) does not yield any benefits. The amount of the halogen-providing compound used in the reaction depends on the amount of M, the ratio for mono-halogenated organic compounds ^ 2 and for inorganic compounds capable of producing more than one halogen atom per molecule. supply should be ^ 1. The reaction of the vaporous metal, the Ti compound and the halogen compound already takes place partly at the above low temperature. For the termination of the reaction, it must be left to stand for a long time (a few days) at ambient temperature or preferably to heat for a few hours (1 ~ 5 hours), depending on the temperature chosen therein (50-180 ° C).

The reaction proceeds faster with an inorganic halogen-supplying compound # 800 1 3 89 -4-.

The halogen-providing compound is not absolutely necessary in low-temperature solutions in which the metal vapors are condensed9, but may be added later before the solution is brought to a higher temperature to terminate the reaction,

The fine suspension prepared in this way is usually used directly as a catalyst for the polymerization to be described below, provided that no excess of one of the reactants or any reaction by-product interferes with the formation of the catalyst. The suspension may also be filtered and the solid re-suspend the substance in the most suitable dispersant »usually in the same agent in which the polymerization is carried out. The solid compound can also be dispersed on an inert solid support, for example, the polymer to be prepared · the other catalyst beet component consists of an organic metal compound of an element of the third group of the Periodic System,

Of these elements, aluminum is used in most cases for efficacy and convenience. Examples of these are the trialkyl and triaryl aluminum compounds such as Al (C2H ^) j # 11 (iC ^ H ^) ^ Al (G ^ H ^) ^, the alkyl aluminum hydrides, for example, Al (II) (iC ^ H ^) and the alkyl and aryl aluminum halides, for example, ΑΙ ^ Η, - ^ ΟΙ and il (C2, -) Cl2.

Preference is given to the trialkyl compounds which, however, are very effective even when mixed with halogen derivatives,

The molar ratio of organic metal compound to titanium compound must be more than 3 in order to obtain maximum specific activity.

For practical reasons, this ratio is kept very high, for example 100 and 500, because in the polymerization extremely small amounts of titanium compound are used. The copolymerization of the present invention is based on the copolymerization of ethylene with a conjugated or unconjugated polyolefin, using the above catalyst components in the presence of an inert diluent, at a "- ...... - -------- ----------- - ----- ------ - .......- ...... 1 800 1 3 89 - 5 - *> * temperature between 40 and 120 ° C and a reaction pressure from 1 to 20 kg / cm2 In batch testing, the reactants are fed into the reactor, the catalyst forming or contacting in the presence of the mixture of two monomers · 5 In practice, two methods can be employed, both of which are active the first method, the catalytic component containing titanium is added last whereas, according to the second method, the reaction between the two catalyst components added successively to the monomer mixture takes place separately. In the latter case, the duration of the pre-contact, although not critical, should not be too long, in particular if the ratio of Al to Ti is high »

As an inert diluent, it is preferred to use aliphatic hydrocarbons, although the presence of a diluent during the polymerization is not strictly necessary because in the gaseous state the catalyst can be dispersed in a small amount of low boiling solvent. to add.

The monomers selected for the copolymerization example are indicated below. The conditions heretofore mentioned are very general, and all kinds of ethylene copolymers can be prepared using the method of the present invention, starting from the precise data reported in the copolymers listed below. without departing from the scope of the invention. With regard to the required polymer, the most suitable reaction conditions can be selected,

The monomers are ethylene and a cyclic or acyclic hydrocarbon with more than one unsaturated bond which may be conjugated to the other. * Prototypes of such hydrocarbon groups which are preferred for their activity and low cost are 1.3- butadiene and 5-ethylidene ~ (2,2,1) -dicyclohepta-2-ene (ethylidene norbonene) »

The polymerization reactivity is lower than that of ethylene and therefore they are added in excess of 50 times or more in excess of the same 800 1 3 89-6 monomer required for the preparation of the copolymer.

This excess is used to recirculate the solution. In practice, only a few percent more ethylene comono-5 in the copolymer is sufficient (less than 10 mo, $).

The molecular weight of the copolymer can be controlled by adding hydrogen and by changing the reaction conditions. The eopolymers prepared according to the process of the present invention have properties which depend on the composition. The ethylene butadiene copolymers contain trans-unsaturated bonds, while the cis- and vinyl-unsaturated bonds are wholly or almost entirely absent, as evidenced by the 1,4-transaddition of the butadiene units. The ethylene-butadiene copolymers rich in ethylene are characterized by a density of 0.940 to 0.960, a melting point of about 130 ° C and a distribution of the unsaturated bonds as seen in the enclosed ^ C-IMR spectrum (with respect to to a copolymer containing 12.3 ntol (butadiene), which contains three peaks attributed to the different structures of the butadiene units along the polymer chain (peaks belonging to the methylene groups in butadiene at α 32.6, b 32, 7 and c (32.9 ppm). It should be noted here that the analogous prepared copolymers in the C-NME spectrum show only two of the three peaks. It is known that crystalline poly-α-olefins, for example polyethylene, isotonic polypropylene, isotetic polybutene, etc. have been commercially available for some time. These poly-α-olefins consist of hay polymers and copolymers containing small amounts of a second α-olefin to solve certain technical difficulties,

The amount of the second olefin is usually so low that the crystallinity of the homopolymer is not reduced too much, while certain important mechanical properties such as modulus, maximum tensile strength, etc., are determined by the high crystallinity.

In the case of eopolymers of ethylene and butadiene, by combining the units of both kinds in one crystal, crystalline polymers can be obtained from the entire composition range from pure polyethylene to pure transpolybutadiene. Therefore, in this case, the restriction applicable to the copolymers of mono-α-olefins does not apply, in which, to maintain a very high crystallinity, the olefin may only occur in very small amounts in the copolymer. A very great advantage of the copolymers prepared by the present process is that they contain unsaturated bonds (in the main chain itself, such as with butadiene, or in the side groups, such as with ethylidene norbornene).

With these unsaturated bonds the copolymer can be easily cross-linked (with sulfur or the like), further improving the technical properties, such as heat resistance, impact strength or resistance to substances that cause hairline cracks.

The unsaturated bonds also allow for certain transformations that would otherwise be difficult or completely impossible, such as foaming and the "vein effect of plate heat" formation.

Example I.

The titanium-containing catalyst component 20 is prepared in a horizontal 1 liter rotating glass vessel in which an aluminum crucible which is electrically heated with a tungsten wire is placed in the center.

240 ml of n-heptane and 0.2 ml of iCl 2 are placed in the vessel and 0.9 g of magnesium chips in the crucible and the solution is cooled to 25 DEG-70 DEG.

After a vacuum has been applied in the rotating device (IQ- * 5 'Toarr), the crucible is heated by connecting such high electrical voltage to the wire ends that the wire becomes red hot.

The evaporation of Mg results in the formation of a brown suspension, to which 8.2 ml of n-butyl chloride (1-chlorobutane) is added after the vacuum has been released by supplying nitrogen.

The suspension is heated at 80 ° C for 5 hours using a reflux condenser.

35 C © polymerization.

11 ”·" "*" * ——- 80 0 1 3 89 - 8 -

A vacuum is applied in a stainless steel autoclave with a volume of 5 liters, equipped with a mechanical stirrer and an adjustable electric heating, and a solution is prepared consisting of: 5 anhydrous n-heptane 2200 ml butadiene 200 g

Al (02H ^) 5 15 mmol, which is added by suction

The temperature of the autoclave is first brought to "JQ ° 0 10" and then hydrogen and ethylene are added with a partial pressure of 3.5 "and 4.5 kg / cm 2, respectively.

10 ml of the above-prepared heptane suspension containing 0.075 mmol of titanium, under ethylene pressure, is added to a 100 ml steel bottle fitted with a supply and discharge shut-off valve. # 15 Then 50 ml of a heptane solution containing 7.5 mmol are added. Al (C_Hc) C1_ contains d 0 d during the first 5 min * of the reaction.

add the mixture in the autoclave using a piston pump

The ethylene is immediately absorbed and the feed is continued without interruption to keep the original pressure constant at a temperature of 70 ° C.

After 3 hours, it appears that ethylene is still absorbed in approximately the same amounts as initially. However, the test is interrupted and the suspension is removed from the autoclave and filtered. 258 g of dry polymer with a melt flow index 2 of 49.5 are obtained. a butadiene unit content (mol) of 3.3 $ and a melting point (T ^), according to the differential heat analysis, of 131 ° C. The white solid polymer that closely resembles polyethylene is mixed per 100 g of polymer with the following compounds * 30 zinc oxide 5 g stearic acid 1 g 2,2'-methylene-bis (4-methyl-terbutylphenol) (Ae0,2246) 1 g H-oxydiethylbenzothioazole-2-sulfenamide (HOBS special) 1.5 g dibenzothiazyldisulfide (Vulkacit DM) 0, 5 g 35 sulfur 3 g eo 0 1 3 89 - 9 -

The mixture JO is treated min * at 180 ° C in a press and a product is obtained which contains 40% residue after extraction with boiling xylene (the polymer itself is completely soluble) *

Example II *

The mixture is run at 85 ° C according to the procedure of example I

test by autoclave *

In this case, the partial pressure of ethylene and hydrogen is 5 and 3 kg / cm2, respectively, while 250 g of butadiene are fed *

All other quantities are the same as in Example 10 I.

After a polymerization lasting three hours, 250 g of dry polymer are obtained with the following properties: butadiene units - 3.3 $ (mol), SVIg 0.84, SVI21 21 / ^^ 2 16 "32.5» melting point «129 ° C» impact strength 13.7 kg / cm2 * 15 In the crosslinking according to example I, the product has an impact strength of 50.4 kg / cm20 Example III *

The device and according to the method of the previous examples a polymerization test is carried out using the following components: n-heptane I84O ml butadiene 102 g A1 (G_HC) Z 17.6 mmol O) H2 3.5 kg / cm2 25 ethylene 5.0 "

Ti complex (see Example I) 0.06 mmol ».

The temperature in the autoclave during the gas supply and the polymerization is kept constant at 85 [deg.] C., replenishing the consumed ethylene. The test is interrupted for 30 hours, the product is filtered, dried and 285 g are obtained.

The analysis shows the following results: butadiene units: 1.5 $ (mol), SVI - 0.99 f / 10 min », SVI21 $ - 27.4, Tm (DSC) -133 ° C * 35 Example IV »800 1 3 89 —10 -

A solution prepared from 400 ml of n-heptane and 40 ml of bicyclo (2,2,1) -5-ethylidene-2-heptene (ethylidene norbornene) is sucked into a stainless steel autoclave of the type described in Example I, but with a volume of 2 liters. The temperature of the autoclave is controlled at 850C and ethylene and hydrogen are introduced with a partial pressure of 5 and 3 kg / cm 2, respectively.

The catalyst consisting of a suspension in heptane of the product, which is obtained by reaction of 5 mmole Al (1C2) ^ and 0.012 mmole titanium in the form described in Example 1, is run for 10-160 min, at ambient temperature, using of a steel bottle and nitrogen overpressure,

The test lasts 1 hour, replenishing the spent ethylene to keep the partial pressure constant.

The solid product obtained after filtration of the suspension and drying weighs 35 8 and has the following properties: 3.3 wt.% Ethylidene norbornene, SVI-3.4 g / 10 min., SVI-3 (20 min. / 33, $ 0.9633 g / cm.

Example 7,

The titanium-containing catalyst component 20 is prepared in the manner described in Example 1, starting from the following components, 1-chloro-acetane 120 ml

TiCl0.088 ml manganese metal 1.3 g.

The solution is cooled to -50 ° C and a vacuum -4 of 10 Torr is applied, after which the manganese is evaporated and condensed. A dense dark brown suspension is formed, which is heated at 100 ° C for 1 hour *

Chemical analysis shows that the homogenized suspension contains 5.10 mmol / l Ti, 186.2 mmol / l Mn, and 390 mmol / l Cl.

The copolymerization of butadiene and ethylene is carried out with the apparatus described in Example I,

The solution introduced into the reactor is prepared from: 35 n-heptane 2200 ml 800 1 3 89; - 11 - butadiene 250 g ll (ieC ^ H ^) ^ 22.5 mmol, ia Setting the temperature at 85 ° C, the autoclave is brought to a pressure of 5 kg / cm2 of hydrogen and 5 kg / ca2 of ethylene. 15 ml of the suspension containing the titanium complex prepared in the manner described above are added. Then ethylene is introduced for 5 hours to keep the pressure constant at the original value of 10 kg / cm 2 at 85 ° C, then the test is interrupted, the product is filtered and dried. 200 g of polymer with the following properties are obtained 1, 4 trans-butadiene units 5> 15 ° C (mol), SVI 2 - 0.05 g / 10 min ,,

Tm (DSC) - 152 ° C / n7 (in decalin at 105 ° C) l 1.75.

Example VI,

The titanium-containing catalyst component 15 is prepared in the apparatus described in Example I from n-otane 300 ml (PiCl4 0.187 ml

SnCl. 8 ml 4

Mg metal 1.2 g.

---------------- n 20 The magnesium is evaporated at 5 »10 Torr and condensed in the solution having a temperature of about -50 ° C,

The resulting suspension is brought to ambient temperature. After 24 hours, the solution above the decanted solid is free from titanium, while the homogenized suspension is 6.32 mmol / l Ti, 187 mmol / l Mg, 207 mmol / l Sn and 863 mmol / l Cl.

Copolymerization.

The test is carried out with the autoclave described in Example I at 25 ° C using the same procedure and the same components as in Example V, with the exception of the titanium-containing catalyst component, which in this case consists of 11.85 ml of the the above suspension exists. The polymer obtained weighs 180 g and has the following properties: SVI2 ^ - 0.1 g / 10 min., T α 131 ° C (DSC), butadiene units * 3 »34 $ (mol), 8 0 0 1 3 89

Claims (7)

6. Process according to claims 1 to 5, characterized in that the preparation reaction of component 1) of the catalyst system is terminated at a temperature of 20-180 ° C. 7 * Process according to one or more of the preceding Claims characterized in that the titanium compound in the catalyst system preferably consists of a halide, alcoholate, haloalcoholate or organometal derivative of trivalent or tetravalent titanium * 80 0 1 3 89 - 13- 8. Process according to one or more of the preceding conolusu.es, characterized in that the halogen-providing compound consists of an organic or inorganic halide * 9. Process according to claims 1-8, characterized in that the organic halogen-supplying compound preferably consists of chloroalkane, bromoalkene, chlorarene or bromarene. 10 * -¾ Process according to claims 1-9 », characterized in that the molar ratio of organic halogen-providing compound to evaporated metal is equal to or greater than 2. 10 11 * Process according to claims 1-8, characterized in that that the organic halogen-supplying compound preferably consists of SnCl, SbCl, GeCl. or PQC1Z. 4 4 4 3 12 * Process according to claims 1-11, characterized in that the molar ratio of inorganic halogen-supplying compound to evaporated metal is equal to or greater than 1 * 15 * Follow the process »claims 1 to 12, characterized in that component 1) of the catalyst system is prepared by reacting the evaporated metal with the titanium compound at a metal to titanium ratio of four or more, preferably 15-30> 20. highly crystalline copolymers according to the process described in claims 1 to 13, characterized in that ethylene is reacted with a polyolefin containing unsaturated optionally conjugated bonds, 15 * Process for the copolymerization of ethylene with an equivalent polyolefin containing conjugated double bonds according to claims 1-14, characterized in that the polymerization reaction is carried out in the presence of an inert solvent * 16 * Process according to claims 1 4 and 15, characterized in that the inert solvent is the same used for the preparation of component 1) of the catalyst system according to claims 1-13 * 17 · Process according to claims 14-16, characterized in that the polymerization reaction is carried out at a temperature of 40-120 ° C * 35 18 «Process according to claims 14-17» with the I "* 800 1 3 89 -14 characterized in that the polymerization reaction is carried out at a pressure of from 1 to 20 atmospheres. * The process according to claim 14, characterized in that the ethylene and polyolefin introduced into the catalyst system are gaseous and that no solvents are present. 20th Process according to claim 19, characterized in that the reaction is carried out after the catalyst composition has been applied to an inert support. 21. Process according to claims 9-20, characterized in that the reaction is carried out at a pressure of 1-30 atmospheres. 22. Process according to claims 9-21, characterized in that the reaction is carried out at a temperature between ambient temperature and a temperature slightly below the melting point of the copolymer. 23 * Process according to one or more of the preceding claims, characterized in that the polyolefin is 1,3-butadiene. A method according to one or more of the preceding claims, characterized in that the polyolefin is ethylidene phenomenon (5-ethylidene (2,2,1) -bicyclohepta-2-ene). Crystalline copolymers with ethylene and polyolefin containing optionally conjugated unsaturated bonds, prepared according to the preceding conelusion with a reactive unsaturated bond in the linear macromolecule. - 13 26 · An ethylene-butadiene copolymer with a "C-IMMR-spatrum 25 with three peaks at 32.6, 32.7 and 32.9 PP" relating to the methylene groups in the butadiene units. 800 1 3 89 "II. _