FI92212C - Process for producing an oxide resistant and stable olefin copolymer - Google Patents

Description

92212

Process for the preparation of an oxygen-resistant and stable olefin copolymer - Process for the preparation of an oxygen-stable and stable olefin copolymer 5

The invention relates to a process for the preparation of a stable α-olefin copolymer, in which an α-olefin is reacted with a complex comprising a metal belonging to a group I-IV of the Periodic Table and an α-alkenyl substituent coordinated thereto by a heteroatom, is a procatalyst based on a titanium compound and a cocatalyst based on an organometallic compound.

The Ziegler-Natta catalyst system, which consists of the so-called Ziegler-Natta catalyst system, is commonly used for the polymerization of olefins. procatalyst and cocatalyst. The procatalyst is based on a transition metal compound of Groups IVA-VIII of the Periodic Table of the Elements and the cocatalyst is based on an organometallic compound of a metal of Groups IA-III (B) of the Periodic Table of the Elements (groups designated according to Hubbard.

25 L. Rompp, 8th ed., P. 3051).

In general, the transition metals of the procatalyst are e.g. titanium, vanadium and zirconium. The procatalysts may then be based on titanium chloride, TiCl4, which, when used in combination with triethylaluminum, forms a conventional type of catalyst. The yield of the polymer formed, and in particular its stereospecificity, can be increased by using an electron donor as a third component. In this type of silo with catalyst systems, the activity level is about 1-2 kg of polypropylene / g of catalyst.

Today, stereoselective and high-yield procatalysts of the 5 Ziegler-Natta catalyst system are prepared by depositing a transition metal compound and a potential donor on solid magnesium compound supports. It has been calculated that the number of active centers for procatalysts of this type is twice the number of procatalysts compared to procatalysts lacking a support. By modifying the support in various ways, the activity of the catalyst can be further improved. Thus, the activity of the new procatalysts has been brought up to a level of 30 g polymer / g catalyst.

High yield catalysts are also characterized by their ability to impart to the resulting polymer the particulate form of the original catalyst, which is repeated in polymer particles of 0.2-5 mm in diameter. However, the resulting polymer particles are porous and therefore easily oxidized. Without stability-enhancing additives, such a product decomposes chemically in use. It is therefore common practice to melt the polymer obtained from the reactor, to which stabilizers are added, after which the product is granulated.

Melt blending with stabilizers after polymer preparation and subsequent granulation could be eliminated if stabilization were performed during the polymerization step. In that case, the polymerization product would be ready for further processing as such. Due to the stabilization problems 30, a process for the production of a particulate product has not been fully utilized for polymer products.

Stabilizers and other additives may migrate to the surface of the products during use, thereby reducing the stabilizing effect. The causes of additive losses may be evaporation during melting, loss during the washing phase and loss of polar additive components.

II

3,921 2 migration and uneven distribution of stabilizer additives in the polymer matrix. The latter is often due to incompatibility with paraffin-type hydrocarbon-based polymers due to the high polarity of the stabilizers. In particular, amine stabilizers, such as paraphenylenediamide derivatives, tend to separate from the polyolefin matrix. The amount of stabilizer in polyolefins in addition to the dough is limited because the additive tends to crystallize.

10

It is prior art to use high molecular weight stabilizers such as tertiary butylphenol and pentaerythritol derivatives as additives. Another known way is to use polymer-based oligomeric molecules. However, the limitation of the dough operation is at the same time the reduced solubility of the additive in the polymer. The prior art is also a process in which a hydrocarbon-based sterically protected hydroxyl group-containing component additionally attached to a α-vinyl group at a distance of at least two atoms can be copolymerized under normal olefin polymerization conditions. Accordingly, DE 1 947 590 discloses a process for preparing a copolymer in which an α-olefin is reacted with an ethylenically unsaturated metal phenoxide 25 in the presence of a catalyst formed by a titanium or vanadium halide compound and an organoaluminum or organozinc compound. Organometallic compounds can be omitted if the metal phenoxide has a metal-carbon bond.

According to this prior art, the polymerization activity by polymerization has been so low that the process has been divided into laboratory curiosity. Namely, the polymerizations have been carried out with an old-fashioned catalyst based on titanium trichloride or titanium tetrachloride and alkylaluminum compounds.

Subsequently, olefin polymerization catalyst technology has advanced to the current level, where a gram of catalyst 4 92212 is capable of polymerizing even the above x 30 kg of α-olefin. Copolymerization of the polar components with these high yield catalysts has not been known on an industrial scale due to the tendency of these components to form a catalyst with active centers of compounds that inhibit polymerization. Thus, polar components such as alcohol, water and acetone have been used to interrupt the polymerization when the desired molecular weight is reached. Another obstacle is apparently that the sterically large stabilizer monomer is unable to approach the active centers on the surface of the support in the polymerization.

It is an object of the present invention to provide a process for preparing a stable α-olefin copolymer in the highest possible yield. A closer effort is to copolymerize α-olefin with a monomer-type stabilizer using a new type of high yield Ziegler-Natta catalyst system. The plan is then to produce stabilized polymer particles of suitable size directly from the polymerization step. A key object is also to provide a usable copolymer whose stabilizer component remains evenly distributed in the polymer product without separation into a separate phase. 25

The above objects have now been achieved by a new process for the preparation of a stable α-olefin copolymer, which is mainly characterized by what is stated in the characterizing part of claim 1.

30

In the process, an α-olefin is reacted with a complex that encapsulates a metal of Groups I-IV of the Periodic Table and an α-alkenyl-substituted stabilizer 35 coordinated thereto as a ligand with a heteroatom, wherein the glass is a titanium compound-based procatalyst and an organometallic compound. The invention is based on the fact that when a titanium compound supported on a magnesium compound is used as the procatalyst.

II

5,92212, the α-alkenyl-substituted stabilizer ligand of the complex is a compound of the following formula (I)

CH2 = CH- (CH2) R1

wherein R is a stabilizer residue containing heteroatoms and n is an integer from 5 to 15. Thus, the invention is based on the fact that when using a support-based procatalyst, there must be a chain of at least 5 carbon atoms between the stabilizer residue and the polymerization functional unsaturation.

The support component of the procatalyst based on the magnesium compound can be any hydroxy-, alkoxy- and / or halogen-containing magnesium compound, such as Mg (OH) Cl,

Mg (OH) 2, Mg (OR) 2 or MgCl2. Of these, magnesium dichloride MgCl2 is particularly preferred.

The supported titanium compound may be, for example, titanium alkoxide, titanium alkoxy halide or titanium halide. A particularly preferred titanium compound is titanium tetrachloride TiCl4.

The amine or phenol string can be used as the α-alkenyl-substituted stabilizer ligand of the coraplex of formula I used as a comonomer. Examples of amines include alkylpiperidines, phenylnaphthylamines, substituted diphenylamines and paraphenylenediamide derivatives. Phenols include substituted phenols and phenylalkanes. Of the sulphides, mention may be made of phenyl sulphides - and of phosphites, for example, tris- (p) -onylphenyl or phenyl phosphite.

It is preferred to use an α-alkenyl-substituted stabilizer ligand of formula I wherein R is 92212 6 - ^ OV-OH 11 and / or 5

- / N-H III

Of the 4-alkyl-2,6-dertert-butylphenols of formula I / II, mention may be made of 4- (hept-6-enyl) -2,6-dertert-butylphenol, 4- (non-8-enyl ) -2,6-di-tert-butylphenol, 4- (undec-10-enyl) -2,6-di-tert-butylphenol and 4- (dodec-11-enyl) -2,6-di-tert-butylphenol.

Of the 4-alkyl-2,2,6,6-tetramethylpiperidines of the formula I / III, mention may be made of 4- (hept-6-enyl) -2,2,6,6-tetramethylpiperidine, 4- (non-8-enyl ) -2,2,6,6-tetramethylpiperidine, 4- (undec-10-enyl) -2,2,6,6-tetramethylpiperidine and 4- (dodec-11-enyl) -2.2, 6,6-tetramethyl-20 piperidine.

Thus, in the process of the present invention for the preparation of a stable α-olefin, a complex obtained by coordinating a compound of formula I with an organometallic compound is used. Coordination is best accomplished with a compound of formula I wherein the heteroatom of the R group is a V or VI atom of the Periodic Table. The organometallic compound is based on a metal belonging to group I, II, III or IV of the Periodic Table and preferably on a halogen atom and / or a hydrocarbon group.

Most preferably, a complex obtained by coordinating a compound of formula I wherein the heteroatom of the group R is O, N, P or S with an organoaluminum compound is used. In some embodiments, the organoaluminum compound can act as both a complexing agent for a compound of Formula I and a cocatalyst for polymerization.

7 9221 2

The structural units of the polymer formed by the invention are -CH, -CH- according to the following formula

5 I IV

R 1 wherein R 1 is hydrogen or a hydrocarbon group of up to 10 carbon atoms, and what is new is that structural units of the following formula are included in the process according to the invention.

CH, -CH-

I V

15 (CH2) n

R

wherein R is a stabilizer residue contained in the heteroatom and 20 n is an integer between 15, preferably between 5-9. In the structural unit of the copolymer of formula V, it is preferred that R is an active residue of an amine stabilizer or a phenol stabilizer.

The group R of the structural unit of formula V is preferably

- (N-H III

30

If it is desired to synergistically combine the properties of the amine and phenolic stabilizers, it is advisable to include them both in the same α-olefin copolymer chain, whereby the group R of the repeating unit of formula V becomes

- ^ ~ H 111 ettå Η II

8,92212

It is also preferred that it contains 0.05 to 0.35% by weight of structural units of formula V.

The functional groups of the stabilizer comonomer are precomplexed before polymerization with a metal alkyl component. This applies in particular to amine- and phenol-type stabilizer monomers which contain a labile hydrogen atom. The stable stabilizer monomer is complexed with an organometallic compound (e.g. triethylaluminum, isobutylaluminum) 10 to give the following compounds OH 0A1 (C2H5) 2 A1 (C2H5) 3 -> + C2H6 (CH2) n (CH2) n 20 CH = CH2 CH = CH2 25 A1 (CH3) 3 + HN) - (CH2) nCH = CH2 -> (CH3) 3A1 <- NH4 ^ - (CH2) nCH = CH2

If the stabilizer monomers are not pre-complexed, the Ziegler-Natta catalyst is deactivated, as shown in Appendix 3.

35 Activity dependence so-called The length of the spacer group (= (-CH 2 -) n) is shown in Appendix 4. Accordingly, it is preferable to use a compound having a hydrocarbon chain length of 5 to 9 carbon atoms. 1 ll

The polymers produced by the process according to the invention can be used for the production of products either as such 922129 or mixed with other polymers. Due to their polymeric structure, the additives do not migrate to the surface of the product while the product is modified or stabilized as desired. The improvement of stability is shown in Examples 1-6. The compatibility of the polymers thus modified with other polymers, in particular polyolefins, is improved, as are the adhesion properties. In food applications, this can be avoided. migration of additives into food.

10

The functionality of the invention is illustrated by the following examples.

Example 1

The polymerizations were carried out in a stirred 1 L 15 steel reactor. The stabilizer monomer (preparation shown in Appendix 1), a stoichiometric amount of triethylaluminum and 0.4 L of heptane were charged to the reactor in the presence of nitrogen and stirred at 70 ° C for 60 minutes. Triethylaluminum and dimethoxydiphenylsilane 20 used as an external donor were then mixed in a nitrogen cabinet with 100 ml of heptane. Thereafter, about 40 mg of the fourth generation Ziegler-Natta catalyst was mixed with the cocatalyst-electron donor solution in a 100 ml steel vessel and the mixture was fed to the reactor under nitrogen pressure.

25 ·· The fourth generation Ziegler-Natta catalyst refers to a catalyst system with a procatalyst (e.g. Ti content 1.5-6%, Mg content 8-30%, Cl content 35-70%, donor compound content 0, 5-15%, specific surface area = 150-250 m2 / g) is formed by depositing a transition metal compound (e.g. TiCl4) and an internal donor on a solid magnesium compound support (e.g. MgCl2) · A cocatalyst is formed in a periodic table of elements in a group of elements. -III (B) from an organometallic compound 35 (e.g. A1 (C2H5) 3). The third part of the catalyst system is an external donor (e.g. dimethoxydiphenylsilane). Such a 10,92212 fourth generation Ziegler-Natta catalyst is more stereoselective and has a higher yield than previous generation catalysts. Lisfix only for the four-generation Ziegler-Natta catalyst is characterized by a controlled morphology (the ability to give the resulting polymer the particulate form of the original catalyst.

Hydrogen was fed to the reactor and the polymerization was started with hydrogen sulfide propylene until the desired partial pressure was reached. The molar ratio of aluminum alkyl (triethylaluminum) to dimethoxydiphenylsilane was determined to be 15. The molar ratio of aluminum to titanium cisphilf catalyst stirrer was determined to be 200. The stirrer speed was 500 rpm.

15

The polymerizations were stopped after 3 hours with lisfifimal-ethanol and hydrochloric acid (the piperidine monomer was used in the polymerization, the polymer was dissolved in ethanol and ammonia solution). The polymer was filtered and dried at 50 ° C and weighed. The isotacticity index was determined by heptane extraction. After the copolymer was extracted in either boiling n-heptane for 3 hours in a tax Soxhlet apparatus for 15 hours, the phenolic stabilizer in the copolymer was analyzed by UV spectrophotometer.

25

Copolymerizations of propylene and 4- (hept-6-enyl) -2,6-di-tert-butylphenol were performed by changing the vfile concentration ratio of the monomers (the comonomer content can be adjusted to the desired level). The results are presented in Annex 30 5.

The resulting copolymer products consisted of spherical particles. The oxidation resistance of the polymers was tested by Differential Scanning Calorimetry (= DSC) by placing 35 polymer samples in an oxygen atmosphere, and the polymer was polymerized at a rate of 10 ° C per minute. The state in which oxidation began (0ΙΤ = oxidation induction temperature) was recorded. Copolymer oxygen

II

92212 11 was compared to pure polypropylene (No. 4), commercial polypropylene (No. 5) and polypropylene to which 0.75% by weight of Irganox 1010 stabilizer was added in an extruder (No. 6). Both commercial and polypropylene, to which Irganox 1010 stabilizer had been added, lost stability in the stabilizer extraction step. In contrast, the extracted copolymers still had almost as much stability as the unextracted commercial polypropylene.

10

An aging test was also performed in an oven at 110 ° C, after which the formation of the 1708 cm-1 absorption peak was periodically examined by infrared spectrophotometry (IR). This absorption peak can be combined with the formation of polymer oxidation products (ketones, aldehydes, etc.). Unstabilized polypropylene oxidizes under these conditions in 6 hours. In contrast, the extracted copolymers do not oxidize until after about 12 days.

20 Example 2

The dependence of the activity on the length of the spacer group (-CH2-) was investigated by polyxnering the following functional monomers, the preparation of which is shown in Appendix 1 (Appendix 4) 4- (butyl-3-enyl) -2,6-ditert-butylphenol ( Comparative Example) 4- (pent-4-enyl) -2,6-di-tert-butylphenol 4- (hex-5-enyl) -2,6-di-tert-butylphenol 4- (hept-6-enyl) - 2,6-dertert-butylphenol 4- (non-8-enyl) -2,6-ditert-butylphenol 4- (undec-10-enyl) -2,6-dertert-butylphenol ·. 4- (dodec-11-enyl) -2,6-ditert-butylphenol with propylene. The polymerization conditions were similar to those in Example 1, except that the partial pressure of propylene was 4 bar, the partial pressure of hydrogen was 0.1 bar, the reactor was 2 l and the amount of heptane was 1 l. The copolymers contained 0.05 to 0.15% by weight of stabilizer. The results for polymerone activity are shown in Appendix 4 to 92212 12. Accordingly, it is preferable to use a compound having a hydrocarbon chain length of 5 to 9 carbon atoms.

Example 3 The polymerizations were carried out as batch polymerizations by feeding 1.4 mol / l of propylene, 0.5 l of heptane and 0.3 mol / l of phenol monomer (except for 4- (pent-4-enyl)) into a 1 l steel reactor. -2,6-ditert-butylphenol fed 0.15 mol / l). Otherwise, the polymerization conditions 10 were similar to Example 1.

The copolymers contain 0.15-0.350% by weight of stabilizer. The results for the stability of the copolymers are shown in Table 1.

15

table 1

No Time to start oxidation by _IR method_ 20

Pure polypropylene <1/2 day

Spacer n = 2> 12

Spacer n = 3> 12

Spacer n = 4> 12 25 Spacer n = 5> 12 ··; Spacer n = 7> 12

Spacer n = 9> 12

Spacer n = 10> 12 30

Example 4

The polymerization conditions were similar to Example 1, the pressure was 0.3 bar to allow spectroscopic examination of the polymer. (Spectroscopic methods 35 require a concentration of at least 1% by weight. A concentration of 0.01% by weight is sufficient for stabilization.) 4- (Hept-6-enyl) -2,6-ditert-butylpheno- was used as the functional monomer; . (0.15 mol / L) and 4- (hex-5-enyl) -2,2,6,6-tetra-13,92212 methylpiperidine (0.15 mol / L, preparation shown in Appendix 2). The polymer yield was 0.13 kg / g of catalyst, under the corresponding polyxerification conditions the homopolymerization activity of propylene was 0.15 kg / g of catalyst. Terpolymer 5 has an isotacticity index of 97% and an oxidation time by DSC of 210 ° C. The terpolymer product obtained is pure white and consists of spherical particles. (M „10'3 = 45,

Mw 10’3 = 221 and PD = 4.9) 10 Example 5 (Comparative Example)

The polymerization conditions were similar to those in Example 4. 4- (Hex-5-enyl) -2,2,6,6-tetramethylpiperidine (prepared according to Annex 2) (0.3 mol / l) was used as the functional comonomer. The polymer yield was 0.16 kg / g of catalyst. The product obtained was pure white and spherical, with an isotacticity index of 96% and an oxidation time by DSC of 210 ° C. (M '10'3 = 52, Mw 10'3 = 265 and PD = 5.1)

Example 6 4- (Hept-6-enyl) -2,6-ditert-butylphenol (0.17 mol) was homopolymerized under the conditions of Example 1. The polymer yield was 1.1 kg / g of catalyst (2.4 g of polymer). The polymerization time was 18 hours. The product was relatively spherical. In a calorimeter at 320 ° C, the product did not decompose in the presence of oxygen.

25 t »· 92212 1) NaH 1) Mg H0jCH2VO-CH2 ^ 0 C ,, CH2,3-OH --CHCH2.3-O-CH2 ^ 0> g)> c /) <CH3

BrCH2 ^ CH3

DMF I rM

H-C-1 J <CH3 (I) 3 CH, (") 1-LC | °" 3

3 H

1) soci2

Y

,, mr -— ^ SA “, ·

H 3 H H

(V) (, V) (III) 1) CH2 = CH-CH2MgBr ^ (ch2) 4-ch = ch2-► H3C ^ vJ <CH3 »J? CH3

3 H

(VI)

Figure 1.4- (Hex-5-enyl) -2,2,6,6-tetramethylpiperidine.

ii 92212 I) 0.83 moles of sodium hydride was dissolved in ether to which 0.66 moles of Cl- (CH2) 3-OH was added in half an hour, after which 0.73 moles of benzyl bromide were added to the mixture at 5 drops per second. After 2 hours, the mixture was cooled to 0 ° C, after which dimethylformamide (100 ml) was carefully added to the mixture. The mixture was allowed to react for 10 hours, after which the product was distilled (b.p. 115 ° C / 10 mmHg, yield 87%).

II) 0.28 mol. the product (point I) was added to magnesium flakes (0.34 moles) in ether. Thereafter, 2,2,6,6-tetramethyl-piperidone (0.19 mol) was added to the mixture. The mixture was allowed to react for 12 hours, after which water and hydrochloric acid were added until the pH of the mixture was 3. The product was extracted with ether and the aqueous phase was basified with ammonia solution, after which the product was distilled (b.p. 156 ° C / 1 mmHg, yield 62%).

III) The product (0.066 mol) (point II) was dissolved in 100 ml of ether to which hydrochloric acid was added until the pH of the mixture was 2.5. The ether was evaporated on an evaporator and the salt was dissolved in chloroform (100 ml). To this mixture was added thionyl chloride (138.5 g) and the temperature of the mixture was raised to 60 ° C. The mixture was allowed to react at this temperature for 10 hours, after which the excess thionyl chloride was evaporated on a evaporator. To the product was added 50 ml of water and the solution was basified with sodium hydroxide. The mixture was then extracted with ether. The product was distilled (b.p. 130 ° C / 1 mmHg, 74% yield).

IV) The product (0.0435 moles) (point III) was dissolved in ethanol (150 ml) to which hydrochloric acid was added until the pH was 2. Then a platinum oxide catalyst (0.85 g) was added to the mixture. The reactor vessel was evacuated, after which hydrogen was added to the reactor until the pressure was 2 bar. After completion of the hydrogenation reaction, ethanol was evaporated 24 hours later. The product was dissolved in water and basified with sodium hydroxide, after which the product was extracted with ether. The product formed was crystallide (yield 97%); : V) The product (0.042 moles) (point IV) was added to 60% HBr (29.6 g) and the patient was raised to 110 ° C for three hours. Thereafter, the temperature was lowered to 70 ° C, where the mixture was allowed to react for 16 hours. The product was basified with sodium hydroxide. The product was distilled (b.p. 98 ° C / 2mmHg, 41% yield).

VI) CH 2 = CH-CH 2 -Br (0.017 moles) was added to magnesium flakes (0.017 moles) in ether. The product (0.00574 moles) was then added to the mixture (λ7). The product was extracted with ether and the aqueous phase was basified with ammonia solution, after which the product 4- (hex-5-enyl) -2,2,6,6-tetramethylpiperidine was distilled off (b.p. 95 ° C / 2 mmHg, yield 60%).

16 9221 2

OH OH

Paraformaldehyde HCl (g) CH 2 Cl 2 + CH2 = CH- (CH2) -MgBr n-1

OH

vv <o -—1 (CH2) -ch = ch2 n n = 2,3 ....., 10

Preparation of various bromoalkenes:

HMPA

1) Br- (CH2) -Br -> ► CH2 = CH- (CH2) -Br n + 1 T = 195C n-1 n = 3,4,5 (Ni) 2) CH2 = CH-CH2-MgBr + Br- (CH2) -Br -> - CH2 = CH- (CH2) -Br n-2 n-1 n = 6,7,8 pBr3 3) CH2 = CH- (CH2) -OH -W CH2 = CH- (CH2) -Br2 2 n-1 ^ n · 1 n = 9.10

Figure 2. Preparation of different α-alkenylphenols.

17 9221 2 1) 2.49 moles of paraformaldehyde was dissolved in 450 ml of benzene and the mixture was heated to 50 ° C. Gaseous hydrochloric acid was introduced into the mixture so that the solution was always saturated. To this mixture was added 2,6-di-tert-butyl-enol dissolved in 80 ml of benzene. Thereafter, the reaction was allowed to proceed for 8 hours while the solution remained saturated. Water and hydrochloric acid were then added to the product. The product was extracted with ether to give 4-chloromethyl-2,6-di-tert-butylphenol (85% yield). 1 2) Preparation of 4- (butyl-3-enyl) -2,6-di-tert-butylphenol. Allyl bromide (1.66 moles) was added to magnesium flakes (1.66 moles) in ether. The product (0.51 moles) was then added to the mixture (step 1). The mixture was allowed to react for 12 hours, after which water and NH 4 Cl were added. The product was extracted with ether, after which the product was distilled (110 ° C / 1.5 mmHg, yield 44%) 3) Preparation of 4- (pent-4-enyl) -2,6-ditert-butylphenol. The temperature of Br- (CH2) 4-Br was raised to 195 ° C, after which 250 ml of hexamethylphosphoric triamide (= HMPA) was added to form CH2 = CH-CH2-CH2-Br (b.p. 98 ° C / 760mmHg, yield 46%). . 2 CH 2 = CH-CH 2 -CH 2 -Br (133 g) was added to magnesium flakes in ether. The product (0.30 moles) was then added to the mixture (step 1). The mixture was allowed to react for 12 hours, after which water and NH 4 Cl were added. The product was extracted with ether, after which the product was distilled (124 ° C / 1.5 mmHg, yield 37%) 4) Preparation of 4- (hex-5-enyl) -2,6-ditert-butylphenol. Same procedure as in 3, except that Br- (CH2) s-Br was used instead of Br- (CH2) 4-Br. The product was distilled (b.p. 138 ° C / 1.5 mmHg, 45% yield).

5) Preparation of 4- (hept-6-enyl) -2,6-ditert-butylphenol. Same procedure as in 3, except that Br- (CH2) 6-Br was used instead of Br- (CH2) 4-Br. The product was distilled (b.p. 151 ° C / 1.5 mmHg, 41% yield).

6) Preparation of 4- (non-8-enyl) -2,6-ditert-butylphenol. Allyl bromide (1 mole) was added to magnesium flakes (1 mole) in ether. The mixture was then cooled to 0 ° C, followed by the addition of 7-bromo-1-heptane and 1 g of Ni catalyst (bis (triphenylphosphinenickel (II) chloride)) and the mixture was allowed to react for 12 hours, after which water and hydrochloric acid were added. moles, yield 26%) 8-bromo-1-octene was added to the magnesium flakes in ether, followed by the addition of (0.086 moles) of product (item: 1) and the reaction was allowed to react for 12 hours, after which water and NH 4 Cl were added. ° C / 2mmHg, yield 52%).

7) Preparation of 4- (undec-10-enyl) -2,6-ditert-butylphenol. (1.09 moles) 9-Deken-1-ol was added 24.6 g of pyridine and 300 ml of dichloromethane. The mixture was cooled to -35 ° C, after which 0.4γ3 was added (0.45 moles). The mixture was allowed to react for 4 hours, after which the product 9-bromo-decene was distilled off (b.p. 168 ° C / 10 mmHg, yield 45.8%).

T. L. Patton, J. T. Horeczy, and D. E. Delson, (Esso), U.S. 3,477,991, (1969).

2 G. A. Kraus and K. Lardberge, Synthesis, no. 10, p. 885, (19S4).

, β 92212 9-Bromo-decene (0.5 moles) was added to the magnesium flakes (0.5 moles) in ether, followed by the addition of product (0.17 moles) to the mixture (step 1). The mixture was allowed to react for 12 hours, after which water and NH 4 Cl were added. The product was distilled (b.p. 180 ° C / 2mmHg, 47% yield).

8) Preparation of 4- (dodec-11-enyl) -2,6-di-tert-butylphenol. The same preparation as in step 7, except that 10-undeken-1-ol was used instead of 9-Deken-1-ol. The product was distilled (b.p. 188 ° C / 1.5 mmHg, 45% yield).

II

„922Ί 2 j p · ν> |! ": - g o * P * EC“ Qj o t- '5. <u h-> - r-r in to So c: r 3 -i rr ui - ·

rr - 'CT O

o to ω „° rt« rt l /> ° ^ X ΙΛ § c <-i - 3 ^ 5 -

Ο I—> -> - · - I— *> - · - OOqoTC

** ~ v --- h- Ό> __ in

O Ln Ln ui t_n i_n i_n p. Ο O

1Λ O ro - B h- p · - Ο <Λ rj <X> X 3

X

P- <Π) NJ 3

. LO

C

(/ 5

CD

to

X

o 3 Ό - Ϊ O £ U ^ CD (/ H Μ I CT £ O O OOO-fc * u H * z.

w 5 3 J— 'rq O O OOOO OP * g o C / l γϊ P- D ri-

P- D O

& rr 3

^ rr C

P- O C

Π CL

j— · CD

. D

<ω x c rr

C

(/ 5 Ό

O

Ό CO - <Ο Ο 3

h- Cj CD

* <3 - ‘w ^ ^ s ** Γ-r - cd fsj ο η- a u XO (/>

'* to O

ώ 2 r-τ- & h- * <rr rr P-

Ci 20 922'12

Appendix 4. Dependence of activity on spacer group length (see Example 2) spacer Propylene Stab. Yield n moles / 1 10'3 Poly kg / g moles / 1 catalyst 4- (bytyl-3-enyl) -2,6-ditert-butylphenol 2 1.5 7.5 1.0 1.5 15 0.8 4 - (pent-4-enyl) -2,6-ditert-butylphenol 3 η 1.5 7.5 1.5 1.5 15 1.3 4- (hex-5-enyl) -2,6-ditert-butylphenol 4 1 .5 7.5 2.4 - "- 1.5 15 2.1 4- (hept-6-enyl) -2,6-ditert-butylphenol 5 1.5 7.5 2.8 1.5 15 2.5 4- (non-8-enyl) -2,6-di-tert-butylphenol 7 1.5 7.5 2.9 4- (undec-10-enyl) -2,6-di-tert-butylphenol 9 1 .5 7.5 3.2 1.5 1.5 2.8 4- (dodec-11-enyl) -2,6-ditert-butylphenol 10 1.5 7.5 2.7 .1.5 15 2.1

Propylene only 1.5 - 2.4

Polymerization conditions, see Example 2. Comparative Example 11 92212 T3

r-> C C C C

CJ O O O

o c c c c c c c c

• Η -Η O Ή O - <- <O * H O

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Claims (7)

A process for producing a stable α-olefin copolymer in which an α-olefin is reacted with a complex comprising a metal from any of groups I-IV of the periodic system and a heteroatom containing a ligand coordinated orkenyl substituted stabilizer, wherein a procatalyst based on a titanium compound and a cocatalyst based on an organometallic compound are characterized by the procatalyst being a titanium compound on a carrier of a magnesium compound. 92212 to the α-alkenyl-substituted stabilizer ligand is constituted by a compound of the formula (I) CH 2 = CH - (CH 2) n R (I) 5 R , preferably between 5 and 9. 10 Process according to claim 1, characterized in that the procatalyst is made up of magnesium chloride, MgCl2, on which titanium chloride, TiCl4, is deposited. 3. A process according to claim 1 or 2, characterized in that a complex is obtained obtained by co-ordinating a compound of formula (I) with an organometallic compound based on a metal of group I, II, III or IV. in the periodic table, as well as a halogen atom and / or a hydrocarbon group. 20 4. A process according to claim 3, characterized in that a complex is used which is obtained by co-ordinating a wastewater of formula (I) with an organoaluminum wastewater. A method according to claim 4, characterized in that; A compound of formula (I) is used, where R is - 0 / H (11) 6. Process according to claim 4, characterized in that a sheep compound of formula (I) is used, where R is 35 / - (N-H (III) 92212 Process according to claim 4, characterized in that compounds of formula (I) are used, where R is both γΛ - (N-H (III) 'Ή