WO2001005781A1

WO2001005781A1 - A comonomer, and a polymer stabilized with it during polymerization

Info

Publication number: WO2001005781A1
Application number: PCT/FI2000/000585
Authority: WO
Inventors: Markku Auer; Carl-Erik WILÉN; Juha STRANDÉN; Ari Rosling; Jan Näsman; Hendrik Luttikhedde
Original assignee: Valtion Teknillinen Tutkimuskeskus
Priority date: 1999-07-21
Filing date: 2000-06-28
Publication date: 2001-01-25
Also published as: NO20020288D0; AU5830200A; KR20020031389A; JP2003505382A; NO20020288L; CA2379845A1; EP1196405A1; FI991634A

Abstract

The invention concerns an E-vitamin derivative or a compound analogous with it, having formula (I), where X is an oxygen or sulfur atom, p is an integer 0 or 1, and R3 - R11 are identical or different groups selected from hydrogen, C1-6alkyl or α-alkene having formula (II), where n, m and o are integers 0 - 4 independent of each other and R1 and R2 are identical or different groups selected from hydrogen or C1-6alkyl or C1-6alkene, which may be substituted with an aromatic ring, or R7 and R8 are together an oxygen atom and/or R4 and R5 and/or R10 and R11 form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, C1-6alkyl or α-alkene. The invention also concerns the use of a derivative consistent with formula (I) as a stabilizing comonomer, and a stabilized copolymer and a method for the production of a stabilized copolymer.

Description

A CO ONOMER, AND A POLYMER STABILIZED WITH IT DURING POLYMERIZATION

The present invention relates to an E-vitamin derivative or a compound analogous with it as defined in the preamble of claim 1, to a method for the production of the aforesaid derivative, to its use as defined in claim 16, to a stabilized copolymer as defined in the preamble of claim 17 and to a method for the production of a stabilized copolymer as defined in the preamble of claim 24.

In prior art, specification FI 92212 presents a method for the production of a stable α-olefin polymer using a Ziegler-Natta type catalyst in which the α-olefin reacts with a complex comprising a metal of group I -IV of the periodic system and an α-alkenyl substituted stabilizer co-ordinated to it with a het- eroatom as a ligand. The catalyst is attached to a magnesium carrier, and a chain of at least 5 carbons is needed between the stabilizer residue of the stabi- lizer ligand and the polymerizing functional unsatu- rated bond.

Further, specification DE 1947590 describes how a component containing a hydrocarbon based, steri- cally protected hydroxyl group and linked to an α- vinyl group situated at a distance of at least two carbon atoms is copolymerized in the polymerization conditions of olefins in the presence of an old- generation Ziegler-Natta catalyst. The problem is a low polymerization activity. A generally known practice is to polymerize polyolefins using Ziegler-Natta type catalysts. The catalyst consists of a metalorganic compound in which the procatalyst is typically an at least partially reduced compound of a transition metal of group IV, V, VI or VII, usually a compound of e.g. titan or zirconium, while the cocatalyst is an organometallic compound of an alkali metal, alkaline earth metal, zinc or aluminum, e.g. triethylaluminum and diethylmagne- sium. An example of such a catalyst is a combination of titan chloride and triethylaluminum. The activity increases considerably when the above-mentioned compo- nents are attached to a fixed carrier; e.g. MgCl₂. Ziegler-Natta catalysts are characterized by an ability to give the polymer the particle form of the catalyst during polymerization, thus producing polymer particles of 0.2 - 5 mm. The polymer particle thus produced is porous, and without an additive increasing the stability, it is chemically dissolved during use.

A known practice is to use a stabilizer having a large molar mass, e.g. derivatives of tert -butyl phenol and pentaerythritol , as an additive. Another known practice is to use polymer-based and oligomeric molecules. A limitation is, however, a lower solubility in polymer. Substituted phenols and aromatic amines are widely used antioxidants . Usually the polymer product obtained after the polymerization reaction is melted in a so-called extruder stage, and additives improving stability are added to the molten product, whereupon the product is granulated.

Further, the use of so-called metallocene catalysts is known in industry. Such catalysts have been used since the early 1990' s in polymerization processes beside or instead of Ziegler-Natta catalysts. Metallocene catalysts are based on a so-called sandwich structure, in which a metallic center, e.g. zirconium, is placed between two cyclopentadienyl rings (bischloro-zirconocene) , and on derivatives of that structure. Metallocene catalysts have in some cases increased the polymerization activity even with comonomers that have previously been difficult to co- polymerize. Therefore, metallocenes are increasingly used in various industrial applications.

A problem with previously known methods is that the stabilizing additive is added to the product at the extruder stage, which is why it has not been possible to utilize a catalyst producing a particle product and a polymerization process because of the stability problem. A further problem is that the additives in the polymer product vanish during use. One of the reasons for this is that the additives improving stability drift to the surface of the product, with the result that the stabilizing effect is diminished and disappears with time and that the additives may get into contact e.g. with foodstuffs. In addition, it has been established that some additives have estrogenic effects. The loss of additives in the product may also be partly due to evaporation taking place during proc- essing or dissolution occurring during washing.

Another problem is irregular distribution of additives in the polymer product. Irregular distribution may result e.g. from an incompatibility of the stabilizers with paraffin-type hydrocarbon-based poly- mers due to a high polarity. In addition, the amount of stabilizer added to polyolefins has to be limited because of the tendency of the stabilizers to crystallize .

Further problems are a poor product yield and an atacticity of the product in polymerization carried out using a Ziegler-Natta catalyst .

The object of the invention is to eliminate the problems referred to above and to disclose a new usable comonomer having a stabilizing effect. A fur- ther object of the invention is to disclose a copolymer stabilized during polymerization.

The E-vitamin derivative or the compound analogous with it, its production method and the stabilized copolymer and its production method according to the invention are characterized by what is presented in the claims . The E-vitamin derivative of the invention or the compound analogous with it, i.e. a compound having a corresponding structure, has the following formula (I) :

where X is an oxygen or sulfur atom, p is an integer = 0 or 1 , and R₃ - R_u are identical or different groups selected from hydrogen, d-₆alkyl or α- alkene having the formula (II)

- (CH₂)_n- (CRιR₂)_m- (CH₂)₀-CH=CH₂ (ID

where n, m and o are integers 0 - 4 independent of each other and Ri and R₂ are identical or different groups selected from hydrogen or Cι_₆alkyl or Cι_ ₆alkene, which may be substituted with an aromatic ring, e.g. a styrene derivative or R₇ and R₈ are together an oxygen atom and/or R₄ and R₅ and/or Rι₀ and Ru form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, Cι-₆alkyl or α-alkene.

Cι-₆alkyl or Cι_₆alkene means a branched or non-branched hydrocarbon chain containing 1 - 6 carbon atoms . In an embodiment of the invention, the derivative has the formula (III)

or the formula (IV)

where X is an oxygen or sulfur atom and R₃ - Ru are identical or different groups selected from hydrogen, C_ι_₆alkyl or α-alkene having the formula (II) .

In an embodiment of the invention, the derivative has the formula (V)

where R₃ - Ru are identical or different groups selected from hydrogen, C_ι_₆alkyl or α-alkene having the formula (II) , or R₇ and R₈ are together an oxygen atom and/or R₄ and R₅ and/or Rι₀ and Ru form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, C_1-6alkyl or α-alkene.

The E-vitamin derivative of the invention or the compound analogous with it preferably has a struc- ture containing at least one fused benzene ring and a ring containing a heteroatom, and an α- chain linked with them. The heteroatom, such as an oxygen or sulfur atom, and the hydroxy group are preferably bonded to opposite sides of the benzene ring of the heterocycle, with the result that an effect stabilizing the compound is produced.

One group of E-vitamin derivatives according to the invention is formed by compounds consistent with formula (III) or (IV), where one the 2-position groups R₃ and R₄ or 3 -position groups R₅ and R₆ is hydrogen or Cι-_ealkyl and the other an α-alkene consistent with formula (II) , R₇ - Ru are hydrogens or Cι_ ₆alkyls and the sum of integers m, n and o is 1 - 12 and Ri and R₂ are as specified above. A preferred group of compounds according to the invention are compounds (III) or (IV) in which one of the heterocycle 2-position groups R₃ and R₄ or of the heterocycle 3 -position groups R₅ and R_s is a hydrogen or Ci-galkyl while the other is an α-alkene consis- tent with formula (II) , where n + m + o is an integer 1 - 6 and Ri and R₂ are hydrogens and R₉ - Ru are Cι_ ₆alkyls. In an embodiment, the derivative is a compound consistent with formula (III) , where X is oxygen, one of groups R₃ and R₄ is a methyl group and the other is an α-alkene consistent with formula (II) , where n + m + o equals 1 or 2 and R_x and R₂ are hydrogens, R₅ - R₈ are hydrogens and R₉ - Ru are methyls. R₃ or R₄ may alternatively be a hydrogen instead of a methyl group. In an embodiment, the derivative is a compound consistent with formula (IV) , where X is oxygen, R_x - R₄ are hydrogens, one of groups R₅ and R₆ is an α-alkene consistent with formula (II) , where n + m + o equals 4, and R₉ - Ru are methyl groups.

Another group of E-vitamin derivatives according to the invention consists of compounds consis- tent with formula (III) or (IV) where one of groups R₉ - Ru in 5 , 7 and 8 -position (formula III) or 4 , 6 and 7-position (formula IV) in the heterocycle is an α- alkene consistent with formula (II) and two of the groups are hydrogens or Cι_-6alkyls, and the sum of the integers m, n and o is in the range of 1 - 12 and Ri and R₂ are as specified above.

A preferred group of compounds according to the invention consists of compounds (III) or (IV) in which R₉ in 5-position (formula III) or 4-position in the heterocycle is an α-alkene consistent with formula

(II) where the integer n is 0 or 1, m is 0 or 1 and o is 1 - 4 and Ri and R₂ are hydrogens or Cι__ealkyls. R₁₀ and Ru are hydrogens or Cι_₆alkyls. In a preferred case, in a derivative consistent with formula (III) , X is oxygen, R_x - R and Rι₀ - Ru are methyls, R₅ - R₈ are hydrogens and R₉ is an α-alkene consistent with formula (II) where n is 0, m is 1 and o is 3. In an embodiment, the derivative is a compound consistent with formula (III) where X is oxygen, R₃ - R₄ and R₁₀ - Ru are methyl groups, R₅ - R₈ are hydrogens and R₉ is an α-alkene consistent with formula (II) where m is 0 and n + o is 1.

E-vitamin derivatives consistent with formula

(III) include e.g. 6-hydroxy-2 , 5 , 7 , 8-tetramethyl-2- (but-3-enyl) -chromane, 6-hydroxy-2 , 5 , 7 , 8-tetramethyl-

2- (prop-2-enyl) -chromane, 6-hydroxy-2 ,2,7,8- tetramethyl-5- (1, 1-dimethyl -hex-5 -enyl) -chromane and 6-hydroxy-2 ,2,7, 8-tetramethyl-5- (prop-2 -enyl) - chromane. E-vitamin derivatives consistent with for- mula (IV) include e.g. 5-hydroxy-4 , 6 , 7-trimethyl-3- (hex-5-enyl) -benzofurane . In an embodiment of the invention, the compound analogous with the E-vitamin derivative is a compound consistent with formula (IV) in which one of groups R₉ - Ru is an α-alkene consistent with formula (II) and the other groups are hydrogens or Cι_₆alkyls and R₃ - R₈ are hydrogens or Ci-βalkyls. Alternatively, R₇ and R₈ are together an oxygen atom and/or R₄ and R₅, together with the carbon atoms to which they are bonded, form a benzene ring. In a preferred embodi- ment , Rio is an α-alkene consistent with formula (II) where n is 0 or 1, m is 0 or 1 and o is an integer 1 - 4 and R_x and R₂ are methyl groups, R₉ is a Cι_₆alkyl, Ru is a hydrogen, R₇ and R₈ are together an oxygen atom and R₄ and R₅, together with the carbon atoms to which they are bonded, form a benzene ring. A compound consistent with formula (V) may be e.g. a thioxanthone derivative, such as a hydroxythioxanthone derivative.

The derivative according to the invention may naturally have any kind of structure corresponding to those described above, e.g.

An E-vitamin derivative consistent with formula (I) or a compound analogous with it is produced using suitable synthesizing methods of organic chemistry. The E-vitamin derivative of the invention or the compound (I) analogous with it can be produced e.g.

A) by allowing a hydroquinone derivative to react with a suitable tertiary unsaturated alcohol or thiol .

In method A) , a compound consistent with formula (I) can be produced directly by allowing a hydroquinone derivative, such as a mono-, di- or trialkyl- hydroquinone , e.g. dimethyl or trimethyl hydroquinone, to react with a suitable unsaturated alcohol, such as alka-dienol, e.g. 2 , 7-octadien-l-ol or 3 -methyl-1 , 6- heptadien-3-ol , or thiol in a suitable solvent. Optionally, according to method A) , in a first stage it is possible to prepare an intermediate product con- taining a (halogen-alkyl) group or a corresponding group by allowing a hydroquinone derivative to react with a suitable unsaturated alcohol, such as 2-alkyl- alka-1 ,x-dien-3 -ol , e.g. 3-methylhept-l , 6-dien-3-ol or 3-alkyl-x-halogen-alk-l-en-3-ol , e.g. 3-methyl-5- chlor-pent-l-en-3-ol , or thiol in the presence of a suitable catalyst in a suitable solvent . In a second stage, a compound consistent with formula (I) is prepared by splitting off a hydrogen halogenide or a corresponding compound from the halogen alkyl group or an equivalent group in the intermediate product in the presence of an alkali. A suitable catalyst is e.g. a metal halide, such as aluminum chloride and zinc chloride. Suitable solvents are e.g. acids, such as formic acid, sulfuric acid or equivalent, tetrahydrofurane (THF) and dichloromethane . A suitable alkali is e.g. 1, 8-diazabicyclo (5.4.0) undec-7-ene (DBU) .

An E-vitamin derivative or a compound (I) analogous with it as provided by the invention can be produced e.g. B) by allowing a hydroquinone derivative to react with a suitable unsaturated alcohol or thiol and adding an α-alkene to the fused heterocyclic derivative thus formed.

In a first step in method B) , a fused heterocyclic derivative can be produced by allowing a hydro- quinone derivative, such as mono-, di- or trialkylhy- droquinone, to react with a suitable tertiary unsaturated alcohol, such as 3-alkyl-alk-l-en-3-ol e.g. 3- methyl-but-l-en-3-ol or thiol, in the presence of a suitable catalyst in a suitable solvent. A suitable catalyst is e.g. a metallic halide, such as aluminum chloride and zinc chloride. Suitable solvents are e.g. tetrahydrofurane (THF) and dichloromethane and acids, e.g. formic acid. In a second step in the method, an α-alkene consistent with formula (II) is added to the heterocyclic derivative in acid conditions.

The E-vitamin derivative of the invention or a compound analogous with it is preferably used as a stabilizing comonomer, i.e. as a stabilizer, in co- polymerization to produce a stabilized copolymer. The function of the stabilizer is to prevent and reduce the harmful effects of heat, UV radiation, oxygen and/or ozone on the copolymer.

The stabilized copolymer consists of at least one monomer variety and a stabilizing comonomer. The monomer in question is an olefin and/or a cyclic and/or aromatic compound containing an α-alkene chain. The olefin monomer may be e.g. ethylene, propylene, 1- butene, isobutene and/or 4 -methyl-1-pentene or the like or a mixture of these. The aromatic compound may be styrene . Naturally, the monomer may be of any type.

The stabilizing comonomer is an E-vitamin derivative or a compound analogous with it which has the formula

(I) and which has a clearly stabilizing effect and which can be polymerized under normal polymerization conditions. The stabilizing comonomer may be e.g. a derivative of chromane-, benzofurane- or hydroxythi- oxanthone . The comonomer, i.e. stabilizer of the invention, is preferably bonded by its α-alkene chain to a copolymer.

In an embodiment of the invention, the co- polymer comprises one olefin or styrene monomer variety and an E-vitamin derivative according to the invention or a compound analogous with it having the formula (III) , (IV) or (V) .

The copolymer preferably belongs to so-called addition polymers. When an addition polymer is formed, no small -molecule side products are generated, i.e. the structural unit of the polymer has a ^• monomeric composition. Monomers may have a linear or a branched hydrocarbon chain, and they contain at least one dual bond enabling a polymerization reaction to take place.

In the copolymer, different monomer varieties may be arranged in different ways, e.g. in a regular fashion, such as alternately, as a segment or in other ways like this. The monomers may also be arranged in an irregular fashion. The structure of the copolymer is preferably mainly regular, such as isotactic or syndiotactic, as is typically the case when monomers are polymerized using metallocene or Ziegler-Natta catalysts (stereospecific polymerization) . A feature characteristic of especially products obtained via polymerization using metallocene catalysts is a syndiotactic form. The crystallizing properties of the polymer depend on the regularity of the structure, among other things. However, the polymer may also contain atactic parts or it may completely atactic.

In the method of the invention for the production of a stabilized copolymer, at least one monomer variety and a stabilizing comonomer are copolymer- ized in the presence of a catalyst in a single-stage or multi-stage polymerization process known in itself, using e.g. precipitation, solution or gas phase polymerization, which will not be described here in detail. According to an embodiment, the catalyst used in copolymerization is preferably e.g. a liquid or solid metallocene catalyst or its derivative known in itself, which is formed from derivatives of transition metals, including lanthanides . Among the best transition metals for the production of catalysts are transition metals belonging to groups 3 and 4, and lanthanides whose oxidation number is +2, +3 or +4. The metallocene components contain 1 - 3 anionic or neu- tral groups having a π-bond. To improve the activity of the catalyst, a cocatalyst, which often consists of methylalumoxane (MAO) , is generally used. More preferably, MAO can be replaced e.g. with compounds containing boron, e.g. tri (hydrocarbyl) boron and its halogenated derivatives. The cocatalyst used may be e.g. tetraphenyl borate . In the copolymerization method of the invention, it is possible to use e.g. a metallocene catalyst of the type described in patent application FI 941662. Naturally, in the copolymeriza- tion method in question, it is also possible to use other catalysts used in this field. The catalyst may comprise a solid carrier. The carrier may consist of any carrier material, which will not be described here in detail. In an embodiment of the invention, the catalyst used in copolymerization contains a π-cyclo- pentadienyl transition metal compound and an alumoxane compound. In an alternative embodiment, the catalyst contains a π-cyclo-pentadienyl transition metal com- pound and a compound containing boron.

In an embodiment, the stabilizing comonomer is chemically complexed e.g. by its heteroatom to the catalyst, being bound via a chemical bond e.g. to a Zr atom of the catalyst. The comonomer may naturally also be used as such or mixed with other monomers e.g. in the polymerization solution during polymerization. At the polymerization stage, the stabilizing comonomer and the monomers, e.g. olefin and/or styrene monomers, are copolymerized, in which process the comonomer of the invention is polymerized substantially along with other monomers, being simultaneously chemically bound to the copolymer. The monomer to be polymerized is bound to an active point, e.g. a Zr atom in the catalyst, causing faster polymerization. The polymer grows as the structural units of the copolymer are increasing. The copolymer contains different monomers in certain proportions.

The copolymer may be e.g. an ethylene/-, pro- pylene/-, butylene/- or styrene/E-vitamin derivative- copolymer. The copolymerization product may naturally consist of more than two monomer varieties. Using different production methods and proportions of different monomers, it is possible to adjust the properties of the copolymer.

Copolymers as provided by the invention can be used either as such or in a mixture with other polymers. A copolymer stabilized with a comonomer according to the invention can be used e.g. as packing material in the foodstuff industry.

The E-vitamin derivative of the invention or the compound analogous with it has the advantage that it is able to polymerize in typical polymerization conditions with a good yield and that it has a good ability to inhibit oxidation, allowing it to be used as an oxidation inhibitor in polymer production. Fur- thermore, the comonomer improves the adhesion properties of polymers e.g. with respect to fillers.

The copolymer of the invention has the advantage that the stabilizing comonomer, i.e. stabilizer, is chemically bonded to the polymer structure during polymerization, which means that it is uniformly distributed in the entire polymer and the chemical bonds prevent the loss of stabilizer in the product, in other words, they prevent the stabilizer from drifting toward the surface of the product during use. Thus, the stabilizer will not drift e.g. to a foodstuff protected with plastic and is therefore not transferred to people.

The copolymerization method of the invention has the advantage that it allows the use of a metallocene catalyst. In polymerization conditions, such a catalyst works better than other catalysts known at present. When the metallocene catalyst in question is used, a polymer product having a syndiotactic structure and therefore a higher melting point can be manufactured.

A further advantage provided by copolymeriza- tion according to the invention is that stabilization is performed during polymerization, in other words, the stabilizer is added as a comonomer to the polymerization product essentially during polymerization, so that the product is directly ready for further processing, in other words, the product thus obtained need not be melted again and fed into an extruder. Thus, a saving is also made in the investment costs of the extruder, which may amount to several tens of millions, even over a hundred million FIM. In the following, the invention will be described by the aid of a detailed examples of its embodiments with reference to the drawings, wherein

Fig. 1 presents the results of a mass spec- trometry analysis of a comonomer according to the in- vention, 5-hydroxy-4 , 6 , 7-triτnethyl-3- (hex-5-enyl) - benzofurane,

Fig. 2 presents the results of an NMR- spectrometry analysis of a comonomer according to the invention, 5-hydroxy-4 , 6 , 7-trimethyl-3 - (hex-5-enyl) - benzofurane,

Fig. 3 presents the results of a mass spec- trometry analysis of a comonomer according to the in- vention, 6-hydroxy-2 ,5,7, 8-tetramethyl-2- (but-3 -enyl) - chromane , and

Fig. 4 presents the results of an NMR- spectrometry analysis of a comonomer according to the invention, 6-hydroxy-2 ,5,7, 8-tetramethyl-2- (but-3- enyl ) -chromane .

Example 1; preparation of 6-hydroxy-2 , 5 , 7 , 8- tetramethyl-2- (but-3-enyl) -chromane.

Preparation of 3-methylhept-l , 6-dien-3 -ol : To 232 g (0.4 mol) of vinyl magnesium chloride in THF was added a solution consisting of 35 g (0.36 mol) of 5-hexene-2-one in 150 ml of anhydrous THF. The reaction mixture was stirred for 20 h at room temperature, whereupon it was cautiously poured into 450 ml of cold, saturated, aqueous NH₄CL solution. The organic extract was concentrated and diffused with di- chloromethane, dried using Na₂S0 and concentrated. The residue was distilled, and the yield obtained was 35.5 g (78%) 3-methylhept-l, 6-dien-3-ol; t.p. 45 °C/10 mmHg . Preparation of 6-hydroxy-2 , 5 , 7 , 8-tetramethyl- 2 - (4-chloro-butyl) -chromane :

A suspension containing 20 g (0.150 mol) anhydrous AlCl₃ in 200 ml of dichloromethane was stirred at 0 °C while at the same time adding 25.8 g (0.42 mol) of CH₃N0₂ under a protective layer of argon. After the mixture had been stirred for 10 min at 0°C, 30.4 g (0.2 mol) of trimethyl -hydroquinone was added in batches. The brown suspension obtained as a result was cooled to -20 °C and a solution consisting of 3- methylhept-1 , 6-dien-3-ol in 750 ml of dichloromethane was added drop by drop during 0.5 h. The mixture thus produced was allowed to cool down slowly to room temperature, and it was stirred overnight, whereupon it was poured on ice/water. The organic layer was collected, washed twice using a NaHC0₃ solution and concentrated. The yield thus obtained was 40 g of a raw product containing insignificant impurities. The raw product was distilled, and the yield thus produced was 15 g (25 %) of 6-hydroxy-2 , 5 , 7 , 8 -tetramethyl-2 - (4 - chlorobutyl) -chromane fraction in the form of a light brown liquid, t.p. 180 °C/l mmHg, which was crystallized overnight in a cooler mp X °C. ¹H NMR: 1.22 (s, 3H, CH₃-C(2))_; 1.5 (d, 3H, -CHC1CH₃) 1.65 (m, 2H, ArCH₂- CH₂-) 1.8 (m, 4H, -CH₂-CH₂-) 2.1, 2.12, 2.15 (3S, 9H,

ArCH₃) ; 2.62 (t, 2H, CH₂Ar) ; 4.1 (m, 1H, CH) and 4.23

(s, 1H, OH) . ¹³C NMR: 11.3, 11.8, 12.2, 20.7, 23.6,

25.2, 31.3, 34.4, 36.7, 59.1, 73.9, 117.1, 118.5,

121.1, 122.5, 144.7 and 145.2.

Preparation of 6-hydroxy-2 , 5 , 7 , 8-tetramethyl- 2- (but-3 -enyl) -chromane:

To 14.8 g (0.05 mol) of 6-hydroxy-2 , 5 , 7 , 8- tetramethyl-2- (4 -chlorobutyl) -chromane was added 36.3 g (0.24 mol) of 1 , 8-diazabicyclo (5.4.0) undec-7-ene (DBU) and the solution was heated to 120 °C and stirred for 20 h. After that, the reaction mixture was allowed to cool down to room temperature, poured into 350 ml of dichloromethane and washed repeatedly using diluted HCl . The organic layer was concentrated, and the yield thus obtained was 10.2 g of raw product that was free of DBU. In addition, the material was purified by distilling, and the result thus obtained was 5g (38 %) of 6-hydroxy-2, 5, 7, 8-tetramethyl-2- (but-3- enyl) -chromane; t.p. 154 °C/lmmHg.

Example 2; preparation of 5-hydroxy-4 , 6 , 7-trimethyl-3- (hex-5-enyl) -benzofurane :

HO-CH₂-CH=CH-(CH₂)₃-CH=CH₂

HCOOH

Trimethyl hydroquinone (23.7 g) and 2,7- octadien-1-ol (19.7 g) were weighed and put into a reaction vessel and 50 ml of formic acid was added into the mixture. The temperature of the mixture was raised to the boiling point of formic acid, and the reaction was allowed to continue for three hours. The reaction mixture was poured into 150 ml of ice-water mixture, and the organic phase was recovered in diethyl ether. The organic solvent was evaporated, whereupon 100 ml of methanol and 1 ml of hydrochloric acid was added to the residue. The reaction mixture was hydrolyzed at the boiling point of methanol for 30 min, whereupon the solvent was evaporated from the mixture. The mix- ture was dissolved in diethyl ether, and the organic phase was washed twice using sodium hydrogen carbonate and five times using distilled water. The diethyl ether was evaporated. At this point, the yield was 48.0 g. n-hexane was added to the mixture, which was then stirred for 30 min at the boiling point of hex- ane, whereupon the mixture was allowed to cool down to room temperature. The portion not dissolved in hexane, mainly consisting of inert trimethyl hydroquinone and the product, was separated from the mixture by filtering. The solid portion was dissolved in a small amount of ethanol and precipitated by adding some water into the solution, whereupon the product (7.5 g) was separated by filtering. After that, based on mass spectrometry (Fig. 1) and NMR spectrometry (Fig. 2) analyses, the product was identified as 5-hydroxy-4 , 6 , 7- trimethyl-3- (hex-5 -enyl) -benzofurane.

Example 3 ; preparation of 6 -hydroxy-2 , 2 , 7 , tetramethyl - 5 - ( 1 , l -dimethyl -hex- 5 -enyl ) - chromane

Dimethyl hydroquinone and formic acid were mixed together, and 3-methylbuten-3 -ol was added little by little into the reaction mixture during one hour. The mixture was allowed to react for 2 h at the boiling point of formic acid, whereupon the reaction was interrupted by adding some ice-water mixture into it . The organic phase was recovered in diethyl ether and washed several times with water. The organic phase was evaporated, and 75 ml of methanol and 1 ml of concentrated hydrochloric acid was added into the residue, whereupon the mixture has hydrolyzed for half an hour at the boiling point of methanol . The methanol was evaporated, and the residue was dissolved in diethyl ether, which was washed alternately twice with sodium hydrogen carbonate and five times with water. The diethyl ether was evaporated and the residue was distilled in a vacuum. The intermediate product (1.25 g) , 6-hydroxy-2 , 2 , 7 , 8-tetramethyl-chromane, was recovered in conditions as follows: p = 0.2 mbar and T = 110 - 120 °C.

6-hydroxy-2 , 2 , 7 , 8-tetramethylchromane and 7- methyl-1 , 6-octadiene were mixed together. The reaction solution was heated, whereupon an acid catalyzer was added into it . The mixture was allowed to react during 24 hours, and the product, 6-hydroxy-2 , 2 , 7 , 8- tetramethyl-5- (1 , 1 -dimethyl-hex-5 -enyl) -chromane, was separated by the conventional method and purified by distilling.

Example 4; preparation of 6-hydroxy-2 , 5, 7 , tetramethyl-2- (but-3 -enyl) -chromane

HCOOH

1.02 g of trimethyl hydroquinone, 0.844 g of

3-hydroxy-3 -methyl -1 , 6-heptadiene and 10 ml of formic acid (98 %) were added into a 50-ml reaction vessel. The temperature was increased to the boiling point of formic acid, at which temperature the reaction was al- lowed to continue for 2 h 50 min. The reaction was interrupted by pouring the mixture into an ice-water mixture, whereupon the organic phase was recovered and washed in the conventional manner. From the product were first separated the portions not dissolved in hexane, whereupon the product was dissolved in etha- nol , precipitated with water and washed using hexane and diethyl ether. The yield was 1.3 g. The product was identified via mass spectrometry (Fig. 3) and NMR spectrometry (Fig. 4) analyses as 6-hydroxy-2 , 5 , 7, 8- tetramethyl-2- (but-3 -enyl) -chromane. Example 5; preparation of 6-hydroxy-2 , 2 , 7 , 8- tetramethyl-5- (prop-2-enyl) -chromane

Dimethyl hydroquinone and formic acid were mixed together, and 3 -methylbuten-3 -ol was added little by little into the reaction mixture during one hour. The mixture was allowed to react for 2 h at the boiling point of formic acid, whereupon the reaction was interrupted by adding some ice-water mixture into the mixture. The organic phase was recovered in diethyl ether and washed several times with water. The organic phase was evaporated and 75 ml of methanol and 1 ml of concentrated hydrochloric acid was added into the residue, whereupon the mixture was hydrolyzed for half an hour at the boiling point of methanol. The methanol was evaporated, and the residue was dissolved in diethyl ether, which was washed alternately twice with sodium hydrogen carbonate and five times with water. The diethyl ether was evaporated, and the residue was distilled in vacuum. The intermediate product (1.25 g) , 6-hydroxy-2 , 2 , 7 , 8-tetramethyl-chromane, was recovered under the following conditions: p = 0.2 mbar and T = 110 - 120 °C.

The intermediate product (0.5 g) was dissolved in 10 ml of acetone. K₂C0₃ (0.37 g) was added gradually and the mixture was stirred for 30 min, whereupon C₃H₅Br (0.33 g) was added gradually. A reflux condenser was used during the reaction. The final product, 6-hydroxy-2 ,2,7, 8-tetramethyl-5- (prop-2- enyl) -chromane, was obtained by heating the mixture for 48 h. The product was separated from the mixture via column chromatography .

Example 6; Preparation of hydroxythioxanthone

A hydroxythioxanthone derivative was prepared from 6-tert-butyl- (2- (1 , l-dimethylhept-6-enyl) ) - phenol, which can be produced e.g. by a method according to patent PCT/FI95/00196, and from thiosalicylic acid in a manner known in itself.

Example 7; copolymerization A polymerization test was carried out to experiment on copolymerization of 6-hydroxy-2 , 5 , 7 , 8- tetramethyl-2- (but-3 -enyl) -chromane and propylene in the presence of a metallocene catalyst . The metallo- cene catalyst consisted of π-cyclo-pentadienyl transition metal and alumoxane .

The treatment of the π-cyclo-pentadienyl transition metal and alumoxane as well as the comonomer was performed in a nitrogen cabinet containing un- der 2 ppm oxygen and under 5 ppm water. The polymerization was carried out in an autoclave equipped with a turbine mixer. The reaction temperature was adjusted with an accuracy of 0.3 °C.

The dry autoclave was evacuated and rinsed with water. This was repeated three times. A first batch of distilled toluene was fed into the reactor by using nitrogen over-pressure. 5 mg of ansa metallocene catalyst was dissolved in a second batch of MAO/toluene solution and pre-activated by letting them interact with each other at room temperature for 5 min.

The catalyst/activator mixture was fed into the reactor. Pre-polymerization was started by adding a propylene monomer. After 3 min., a comonomer diluted with toluene was added using propylene gas, until the partial pressure of propylene reached 2 bar. The polymerization activity was monitored by measuring the propylene consumption while maintaining a constant total pressure in the reactor by continuously adding gaseous propylene. After 30 min, polymerization was interrupted by stopping the supply of propylene and adding 100 ml of methanol. Polyolefin was filtered and the catalyst residue was removed by treating the product, i.e. the copolymer, with a 1-% methanol/HCl solu- tion. The product was washed twice with ethanol, dried in vacuum at a temperature of 50 °C and weighed. The amount of copolymer obtained was 3 g. The copolymer was diffused using a Soxhlet device before determining the concentration of bonded stabilizer. The results of the polymerization this means that are presented in Table 1.

Table 1 shows that the OIT temperature rises as the comonomer content increases, which is an indication of the effect of the stabilizer. Further, it can be seen from Table 1 that crystallization of the product decreases at higher copolymer content levels, indicating that the comonomer is chemically bonded to the rest of the polymer.

Table 1. The results of copolymerization of 6-hydroxy-2 ,5,7, 8 -tetramethyl-2- (but -3 -enyl) -chromane and propylene.

The E-vitamin derivative of the invention or the compound analogous with it is suited for use in different applications, e.g. for the manufacture of any kind of copolymer. Moreover, the copolymer of the invention is suited for use as different applications for any purpose . The embodiments of the invention are not restricted to the examples presented above; instead, they may be varied in the scope of the following claims .

Claims

1. E-vitamin derivative or a compound analogous with it, having the formula (I)

where X is an oxygen or sulfur atom, p is an integer 0 or 1 , and R₃ - Ru are identical or different groups selected from hydrogen, Cι-₆alkyl or α-alkene having the formula (II)

(CH₂) _a- (CRjRa) _m- (CH₂) ₀-CH=CH₂ (ID

where n, m and o are integers 0 - 4 independ- ent of each other and Ri and R₂ are identical or different groups selected from hydrogen or Cι_-6alkyl or Cι_ ₆alkene, which may be substituted with an aromatic ring, or R₇ and R₈ are together an oxygen atom and/or R₄ and R₅ and/or R₁₀ and Ru form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, Cι_₆alkyl or α-alkene.

2. Derivative as defined in claim 1, char - act er i z ed in that it has the formula (III)

where X is an oxygen or sulfur atom and R₃ - Ru are identical or different groups selected from hydrogen, Cι_₆alkyl or α-alkene having the formula (II) .

3. Derivative as defined in claim 1, char ac t e ri z ed in that it has the formula (V)

where R₃ - Ru are identical or different groups selected from hydrogen, Cι_-6alkyl or α-alkene having the formula (II) , or R₇ and R₈ are together an oxygen atom and/or R₄ and R₅ and/or R_i0 and Ru form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, C_halky1 or α-alkene.

4. Derivative as defined in claim 1 or 2 , charac t e ri zed in that one of groups R₃ and R₄ or one of groups R₅ and R₆ is hydrogen or a Cι-₆alkyle and the other an α-alkene consistent with formula (II) and R₇ - Ru are hydrogens or Cι_₆alkyls.

5. Derivative as defined in any one of claims 1, 2 or 4, charac t eri z ed in that m + n + o is an integer 1 - 6, and Ri and R₂ are hydrogens.

6. Derivative as defined in claim 1, 2 or 4 - 5, charac t e ri zed in that it has formula (III) , where X is oxygen, one of groups R₃ and R₄ is a methyl group and the other is an α-alkene consistent with formula (II) , where n + m + o equals 1 or 2 and Ri - R₂ and R₅ - R₈ are hydrogens and R₉ - Ru are methyl groups .

7. Derivative as defined in claim 1, 2 or 4 - 5, charac t eri zed in that it has formula (IV) , where X is oxygen, R_x - R₄ are hydrogens, one of groups R₅ and R_s is an α-alkene consistent with formula (II), where n + m + o equals 4, and R₉ - Ru are methyl groups .

8. Derivative as defined in claim 1 or 2 , charac t e ri zed in that one of groups R₉ - Ru is an α-alkene consistent with formula (II) and two of the groups are hydrogens or Cι_₆alkyls, and R₃ - R₈ are hydrogens or Cι_₆alkyls.

9. Derivative as defined in any one of claims 1, 2 or 8, charac t eri zed in that R_i0 and Ru are homogenous or Cι_-6alkyls, R₉ is an α-alkene consistent with formula (II) , where n is 0 or 1, m is 0 or 1 and o is an integer 1 - 4 and R_x - R₂ are hydrogens or Cι_₆alkyls . 10. Derivative as defined in any one of claims 1, 2 or 8 - 9, charac t eri z ed in that it has formula (III) , X is oxygen, R - R₄ and R₁₀ - Ru are methyl groups, R₅ - R₈ are hydrogens and R₉ is an α-alkene consistent with formula (II), where n is 0, m is 1 and o is 3.

11. Derivative as defined in any one of claims 1, 2 or 8 - 9, charact eri z ed in that it has formula (III) , X is oxygen, R₃ - R₄ and Rι₀ - Ru are methyl groups, R₅ - R₈ are hydrogens and R₉ is an α-alkene consistent with formula (II), where m is 0 and o + n equals 1.

12. derivative as defined in claim 1 or 3 , charac t eri zed in that one of groups R₉ - Ru is an α-alkene consistent with formula (II) and the other groups are hydrogens or Cι_-6alkyls, and R₃ - R₈ are hydrogens or Cι-₆alkyls or R₇ and R₈ are together an oxygen atom and/or R₄ and R₅ form a benzene ring together with the carbon atoms to which they are bonded.

13. Derivative as defined in any one of claims 1, 3 or 12, charact eri zed in that Rι₀ is an α-alkene consistent with formula (II) where n is 0 or 1, m is 0 or 1 and o is an integer 1 - 4 and R_x and R₂ are methyl groups, R₉ is a Cι-₆alkyl, Ru is a hydrogen, R₇ and R₈ are together an oxygen atom and R₄ and R₅, together with the carbon atoms to which they are bonded, form a benzene ring.

14. Derivative as defined in any one of claims 1 - 13, charac t eri z ed in that it is 6- hydroxy-2 ,5,7, 8 -tetramethyl-2- (but -3 -enyl) -chromane, 6-hydroxy-2 ,5,7, 8 -tetramethyl-2- (prop-2 -enyl) - chromane, 6-hydroxy-2 , 2 , 7 , 8-tetramethyl-5- (1, 1- dimethyl-hex-5-enyl) -chromane, 6-hydroxy-2 ,2,7,8- tetramethyl-5- (pro -2 -enyl) -chromane, 5-hydroxy-4 ,6,7- trimethyl-3- (hex-5-enyl) -benzofurane or a hydroxythioxanthone derivative. 15. Method for producing an E-vitamin derivative or a compound analogous with it, which has the formula (I), charac t eri z ed in that (A) a hydroquinone derivative is allowed to react with a suitable unsaturated alcohol or thiol, or (B) a hydroquinone derivative is allowed to react with a suitable unsaturated alcohol or thiol and an α-alkylene is added to the fused heterocyclic derivative thus formed.

16. Use of an E-vitamin derivative as defined in claim 1 or a compound analogous with it as a stabilizing comonomer for the production of stabilized copolymer.

17. Stabilized copolymer, comprising at least one monomer variety, which is an olefin and/or a cyclic and/or aromatic compound containing an α-alkene chain, and a stabilizing comonomer, charact er i z ed in that the comonomer is an E-vitamin derivative or a compound analogous with it, which has the formula (I)

where X is an oxygen or sulfur atom, p is an integer 0 or 1 , and R₃ - Ru are identical or different groups selected from hydrogen, Cι_₆alkyl or α-alkene having the formula (II)

(CH₂)_n- (CRιR₂)_m- (CH₂)₀-CH=CH₂ III⁾

where n, m and o are integers 0 - 4 independent of each other and Ri and R₂ are identical or dif- ferent groups selected from hydrogen or Cι_₆alkyl or Cι_

₆alkene, which may be substituted with an aromatic ring, or R₇ and R₈ are together an oxygen atom and/or R₄ and R₅ and/or R_i0 and Ru form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, Cι_₆alkyl or α-alkene. Stabilized copolymer as defined in claim

17, c h a r a c t e r i z e d in that the comonomer has the formula (III)

or the formula

where X is an oxygen or sulfur atom and R₃ - Ru are identical or different groups selected from hydrogen, C_!_₆alkyl or α-alkene having the formula (II) .

19. Stabilized copolymer as defined in claim 17, charac t er i zed in that the comonomer has the formula (

where R₃ - Ru are identical or different groups selected from hydrogen, Cι-₆alkyl or α-alkene having the formula (II), or R₇ and R₈ are together an oxygen atom and/or R₄ and R₅ and/or R₁₀ and Ru form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, Cι_₆alkyl or α-alkene.

20. Stabilized copolymer as defined in any one of claims 17 - 19, charac t eri z ed in that the olefin is ethylene, propylene, butylene and/or pentene .

21. Stabilized copolymer as defined in any one of claims 17 - 20, charac t eri zed in that the the aromatic compound is styrene.

22. Stabilized copolymer as defined in any one of claims 17 - 21, characteri zed in that the copolymer consists of one olefin or styrene monomer and comonomer consistent with formula (III) , (IV) or (V) .

23. Stabilized copolymer as defined in any one of claims 17 - 22, charac t eri z ed in that the copolymer has a substantially regular structure.

24. Method for the production of stabilized copolymer, wherein at least one monomer variety, which is an olefin and/or a cyclic and/or aromatic compound containing an α-alkene chain, and a stabilizing comonomer are copolymerized in the presence of a catalyst by a polymerization technique known in itself, charac t eri zed in that the comonomer used is an E-vitamin derivative or a compound analogous with it, having the formula (I)

where X is an oxygen or sulfur atom, p is an integer 0 or 1 , and R₃ - Ru are identical or different groups selected from he—&e hydrogen, C_!-₆ lkyl or α- alkene having the formula (II) - (CH₂) _a- (CRιR₂)_m- (CH₂) ₀-CH=CH₂ (II)

where n, m and o are integers 0 - 4 independent of each other and Ri and R₂ are identical or dif- ferent groups selected from hydrogen or Cι_-6alkyl or Cι_ ₆alkene, which may be substituted with an aromatic ring, or R₇ and R₈ are together an oxygen atom and/or R₄ and R₅ and/or R₁₀ and Ru form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, Cι_₆alkyl or α-alkene.

25. Method as defined in claim 24, char a c t e ri zed in that the comonomer used is a co- monomer consistent with formula (III) , (IV) or (V) .

26. Method as defined in claim 24 or 25, charac t e ri zed in that the copolymerization is performed using a metallocene catalyst or its derivative . 27. Method as defined in any one of claims 24

- 26, charac t er i zed in that the catalyst used in copolymerization contains a π-cyclo-pentadienyl transition metal compound and an alumoxane compound.

28. Method as defined in any one of claims 24 - 27, charac t eri zed in that the catalyst used in copolymerization contains a π-cyclo-pentadienyl transition metal compound and a compound containing boron.

29. Method as defined in any one of claims 24 - 28, charac t eri zed in that the comonomer has been complexed to the catalyst .

30. Method as defined in any one of claims 24

29, charact er i ze d in that the olefin is ethylen, propylene, butylene and/or pentene. 31. Method as defined in any one of claims 24

30, charact e ri ze d in that the aromatic compound is styrene.

32. Method as defined in any one of claims 24 31, charac t eri zed in that the amount of monomer and stabilizing comonomer supplied into the process is exactly defined.