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Title:
A COMONOMER, AND A POLYMER STABILIZED WITH IT DURING POLYMERIZATION
Document Type and Number:
WIPO Patent Application WO/2001/005781
Kind Code:
A1
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 R¿3? - R¿11? are identical or different groups selected from hydrogen, C¿1-6?alkyl or $g(a)-alkene having formula (II), where n, m and o are integers 0 - 4 independent of each other and R¿1? and R¿2? are identical or different groups selected from hydrogen or C¿1-6?alkyl or C¿1-6?alkene, which may be substituted with an aromatic ring, or R¿7? and R¿8? are together an oxygen atom and/or R¿4? and R¿5? and/or R¿10? and R¿11? form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, C¿1-6?alkyl or $g(a)-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.

Inventors:
AUER MARKKU (FI)
WILEN CARL-ERIK (FI)
STRANDEN JUHA (FI)
ROSLING ARI (FI)
NAESMAN JAN (FI)
LUTTIKHEDDE HENDRIK (FI)
Application Number:
PCT/FI2000/000585
Publication Date:
January 25, 2001
Filing Date:
June 28, 2000
Export Citation:
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Assignee:
VALTION TEKNILLINEN (FI)
AUER MARKKU (FI)
WILEN CARL ERIK (FI)
STRANDEN JUHA (FI)
ROSLING ARI (FI)
NAESMAN JAN (FI)
LUTTIKHEDDE HENDRIK (FI)
International Classes:
C07D307/78; C07D307/79; C07D311/72; C07D335/16; C08F2/44; C08F4/64; C08F210/00; C08F210/06; C08F212/08; C08F224/00; C08F228/06; C08K5/1545; (IPC1-7): C07D311/72; C07D307/79; C07D335/16; C08F2/44; C08F210/00; C08K5/1545; C08K5/45
Domestic Patent References:
WO1993010175A11993-05-27
WO1995027744A11995-10-19
WO1997049738A11997-12-31
Foreign References:
GB2224028A1990-04-25
EP0392389A21990-10-17
EP0878502A21998-11-18
DE19747600A11999-01-14
EP0695733A11996-02-07
Other References:
J. GREEN ET AL.: "Bond stabilisation in tocopherols. Part 1. The claisen rearrangement of alkyl tocopheryl ethers", J. CHEM. SOC. (C), vol. 6, 1966, pages 1422 - 1427, XP002933684
D. MCHALE ET AL.: "Bond stabilisation in tocopherols. Part II.1. Claisen rearrangement of but-2-enyl tocopheryl ethers", J. CHEM. SOC. (C), vol. 6, 1966, pages 1427 - 1431, XP002933685
DATABASE CA [online] CHEMICAL ABSTRACTS; FUJIREBIO: "Preparation of benzofuran derivatives", XP002950699, accession no. STN Database accession no. 119:139070
DATABASE CA [online] CHEMICAL ABSTRACTS,; NOVAK LAJOS ET AL.: "One-pot route to vinyl-2,3-dihydrobenzofurans", XP002950700, accession no. STN Database accession no. 120:191445
DATABASE CA [online] EISAI CO. LTD.: "Preparation of chroman derivatives", XP002954901, accession no. STN Database accession no. 113:58940
MAKOTO MATSUI ET AL.: "Aluminium chloride-tetraalkylammonium halide complex as a novel catalyst in friedel-crafts alkylation. Direct construction of the chroman structure from 1,3-diene", BULL. CHEM. SOC. JPN., vol. 68, no. 9, 1995, pages 2663 - 2668, XP000961205
DAVID E. NICHOLS ET AL.: "2,3-Dihydrobenzofuran analogues of hallucinogenic phenethylamines", J. MED. CHEM., vol. 34, no. 1, 1991, pages 276 - 281, XP000961189
YOSHIJI FUJITA ET AL.: "Friedel-crafts reaction of 3,6-dihydro-4-methyl-2H-pyran with phenols. A convenient synthesis of a key intermediate of alpha-tocopherol", CHEMISTRY LETTERS, vol. 9, 1985, pages 1399 - 1400, XP002955303
DATABASE CA ON STN CHEMICAL ABSTRACTS SERVICE (COLUMBUS, OHIO, USA); YAMAMOTO, Y. ET AL.: "New vitamin E compound discovered in fish eggs (2)", XP002955304
DATABASE CA ON STN CHEMICAL ABSTRACTS SERVICE (COLUMBUS, OHIO, USA); FUJIREBIO INC.: "Preparation of propenylhydroquinone and propenylbenzoquinone derivatives", XP002955305
Attorney, Agent or Firm:
PAPULA OY (P.O. Box 981 Helsinki, FI)
Download PDF:
Claims:
CLAIMS
1. Evitamin derivative or a compound analo gous with it, having the formula (I) where X is an oxygen or sulfur atom, p is an integer 0 or 1, and R3R1l are identical or different groups selected from hydrogen, C16alkyl or aalkene having the formula (II) (CH2) n_ (CR1R2) m_ (CH2) O_CH=CH2 (II) where n, m and o are integers 04 independ ent of each other and Ri and R2 are identical or dif ferent groups selected from hydrogen or C16alkyl or Ci 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 Rlo and Rll form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, C16alkyl or aalkene.
2. Derivative as defined in claim 1, c h a r a c t e r i z e d in that it has the formula (III) where X is an oxygen or sulfur atom and R3 R1l are identical or different groups selected from hy drogen, C16alkyl or aalkene having the formula (II).
3. Derivative as defined in claim 1, c h a r a c t e r i z e d in that it has the formula (V) where R3R11 are identical or different groups selected from hydrogen, C16alkyl or aalkene having the formula (II), or R7 and R8 are together an oxygen atom and/or R4 and Rs and/or Rlo and Rll form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, C16alkyl or aalkene.
4. Derivative as defined in claim 1 or 2, c h a r a c t e r i z e d in that one of groups R3 and R4 or one of groups Rs and R6 is hydrogen or a Cl6alkyle and the other an aalkene consistent with formula (II) and R7Rll are hydrogens or C16alkyls.
5. Derivative as defined in any one of claims 1,2 or 4, c h a r a c t e r i z e d in that m + n + o is an integer 16, and R1 and R2 are hydrogens.
6. Derivative as defined in claim 1,2 or 4 5, c h a r a c t e r i z e d 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 aalkene consistent with formula (II), where n + m + o equals 1 or 2 and Riruz and RsRg are hydrogens and Regroll are methyl groups.
7. Derivative as defined in claim 1,2 or 4 5, c h a r a c t e r i z e d in that it has formula (IV), where X is oxygen, R1R4 are hydrogens, one of groups R5 and R6 is an aalkene consistent with formula (II), where n + m + o equals 4, and RgRll are methyl groups.
8. Derivative as defined in claim 1 or 2, c h a r a c t e r i z e d in that one of groups Regroll is an aalkene consistent with formula (II) and two of the groups are hydrogens or C16alkyls, and RsRg are hydrogens or Cl6alkyls.
9. Derivative as defined in any one of claims 1,2 or 8, c h a r a c t e r i z e d in that Rlo and Rll are homogenous or C16alkyls, Rg is an aalkene consis tent with formula (II), where n is 0 or 1, m is 0 or 1 and o is an integer 14 and R1R2 are hydrogens or C16alkyls.
10. Derivative as defined in any one of claims 1,2 or 89, c h a r a c t e r i z e d in that it has formula (III), X is oxygen, RlR4 and RloRll are methyl groups, R5R8 are hydrogens and Rg is an aalkene 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 89, c h a r a c t e r i z e d in that it has formula (III), X is oxygen, R3R4 and RloRll are methyl groups, R5R8 are hydrogens and Rg is an aalkene consistent with formula (II), where m is 0 and o + n equals 1.
12. derivative as defined in claim 1 or 3, c h a r a c t e r i z e d in that one of groups R9Rll is an aalkene consistent with formula (II) and the other groups are hydrogens or C16alkyls, and R3R8 are hydrogens or C16alkyls or R7 and R8 are together an oxygen atom and/or R4 and Rs form a benzene ring to gether with the carbon atoms to which they are bonded.
13. Derivative as defined in any one of claims 1,3 or 12, characterized. in that Rlo is an aalkene consistent with formula (II) where n is 0 or 1, m is 0 or 1 and o is an integer 14 and Ri and R2 are methyl groups, R9 is a C16alkyl, Rll 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 113, c h a r a c t e r i z e d in that it is 6 hydroxy2,5,7,8tetramethyl2 (but3enyl)chromane, 6hydroxy2,5,7,8tetramethyl2 (prop2enyl) chromane, 6hydroxy2,2,7,8tetramethyl5 (1, 1 dimethylhex5enyl)chromane, 6hydroxy2,2,7,8 tetramethyl5 (prop2enyl)chromane, 5hydroxy4,6,7 trimethyl3 (hex5enyl)benzofurane or a hydroxythi oxanthone derivative.
15. Method for producing an Evitamin deriva tive or a compound analogous with it, which has the formula (I), c h a r a c t e r i z e d 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 aalkylene is added to the fused heterocyclic derivative thus formed.
16. Use of an Evitamin derivative as defined in claim 1 or a compound analogous with it as a stabi lizing comonomer for the production of stabilized co polymer.
17. Stabilized copolymer, comprising at least one monomer variety, which is an olefin and/or a cy clic and/or aromatic compound containing an aalkene chain, and a stabilizing comonomer, c h a r a c t e r i z e d in that the comonomer is an Evitamin deriva tive 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 R3Rll are identical or different groups selected from hydrogen, C16alkyl or aalkene having the formula (II) (CH2) n(CRlR2) m(cH2) ocH=cH2 (II) where n, m and o are integers 04 independ ent of each other and Ri and R2 are identical or dif ferent groups selected from hydrogen or C16alkyl or Ci 6alkene, which may be substituted with an aromatic ring, or R7 and Ra are together an oxygen atom and/or R4 and R5 and/or Rlo and Rll form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, C16alkyl or aalkene.
18. 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) ortheformula(IV) R 9 rus Ru. Ro _ X R3 R11 where X is an oxygen or sulfur atom and R3 R1l are identical or different groups selected from hy drogen, C16alkyl or aalkene having the formula (II).
19. 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 (V) where R3R1l are identical or different groups selected from hydrogen, Cl6alkyl or aalkene having the formula (II), or R7 and R8 are together an oxygen atom and/or R4 and R5 and/or Rlo and Rll form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, Cl6alkyl or aalkene.
20. Stabilized copolymer as defined in any one of claims 1719, c h a r a c t e r i z e d in that the olefin is ethylene, propylene, butylene and/or pentene.
21. Stabilized copolymer as defined in any one of claims 1720, c h a r a c t e r i z e d in that the the aromatic compound is styrene.
22. Stabilized copolymer as defined in any one of claims 1721, c h a r a c t e r i z e d in that the copolymer consists of one olefin or styrene mono mer and comonomer consistent with formula (III), (IV) or (V).
23. Stabilized copolymer as defined in any one of claims 1722, c h a r a c t e r i z e d 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 aalkene chain, and a stabilizing co monomer are copolymerized in the presence of a cata lyst by a polymerization technique known in itself, c h a r a c t e r i z e d in that the comonomer used is an Evitamin 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 R3R1l are identical or different groups selected from 44eeE4 hydrogen, C16alkyl or a alkene having the formula (II) (CH2) n (CR1R2) m (CH2) oCH=CH2 (II) where n, m and o are integers 04 independ ent of each other and R1 and R2 are identical or dif ferent groups selected from hydrogen or C16alkyl or Ci 6alkene, which may be substituted with an aromatic ring, or R7 and R8 are together an oxygen atom and/or R4 and Rs and/or Rlo and Rll form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, C16alkyl or aalkene.
25. Method as defined in claim 24, c h a r a c t e r i z e d 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, c h a r a c t e r i z e d in that the copolymerization is performed using a metallocene catalyst or its deriva tive.
27. Method as defined in any one of claims 24 26, c h a r a c t e r i z e d in that the catalyst used in copolymerization contains a scyclopentadienyl transition metal compound and an alumoxane compound.
28. Method as defined in any one of claims 24 27, c h a r a c t e r i z e d in that the catalyst used in copolymerization contains a scyclopentadienyl transition metal compound and a compound containing boron.
29. Method as defined in any one of claims 24 28, c h a r a c t e r i z e d in that the comonomer has been complexed to the catalyst.
30. Method as defined in any one of claims 24 29, c h a r a c t e r i z e d in that the olefin is ethylen, propylene, butylene and/or pentene.
31. Method as defined in any one of claims 24 30, c h a r a c t e r i z e d in that the aromatic compound is styrene.
32. Method as defined in any one of claims 24 31, c h a r a c t e r i z e d in that the amount of monomer and stabilizing comonomer supplied into the process is exactly defined.
Description:
A COMONOMER, 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 pro- duction of the aforesaid derivative, to its use as de- fined in claim 16, to a stabilized copolymer as de- fined 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 a-olefin poly- mer using a Ziegler-Natta type catalyst in which the a-olefin reacts with a complex comprising a metal of group I-IV of the periodic system and an a-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 a- 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 re- duced compound of a transition metal of group IV, V, VI or VII, usually a compound of e. g. titan or zirco- nium, while the cocatalyst is an organometallic com- pound 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 abil- ity to give the polymer the particle form of the cata- lyst 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 hav- ing 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 solubil- ity in polymer. Substituted phenols and aromatic amines are widely used antioxidants. Usually the poly- mer 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 cata- lysts. 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 rea- sons for this is that the additives improving stabil- ity drift to the surface of the product, with the re- sult 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 distribu- tion 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 crystal- lize.

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 copoly- mer stabilized during polymerization.

The E-vitamin derivative or the compound analogous with it, its production method and the sta- bilized copolymer and its production method according to the invention are characterized by what is pre- sented 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-R1l are identical or differ- ent groups selected from hydrogen, C16alkyl or a- alkene having the formula (II) -(CH2) n-(CRlR2) m-(CH2) o-cH=cH2 (II) where n, m and o are integers 0-4 independ- ent of each other and Ri and R2 are identical or dif- ferent groups selected from hydrogen or C16alkyl or Ci- 6alkene, which may be substituted with an aromatic ring, e. g. a styrene derivative or R7 and Ra are together an oxygen atom and/or R4 and Rs and/or Rlo and Rll form together with the carbon atoms to which they are bonded a benzene ring, which may be substituted with groups selected from hydrogen, Cl6alkyl or a-alkene.

Cl6alkyl or C16alkene means a branched or non-branched hydrocarbon chain containing 1-6 carbon atoms.

In an embodiment of the invention, the de- rivative has the formula (III)

<BR> <BR> (III) or the formula (IV) (IV) where X is an oxygen or sulfur atom and R3- RI, are identical or different groups selected from hy- drogen, C16alkyl or a-alkene having the formula (II).

In an embodiment of the invention, the de- rivative has the formula (V) <BR> <BR> (V) where R3-R1l are identical or different groups selected from hydrogen, C16alkyl or a-alkene having the formula (II), or R7 and R8 are together an oxygen atom and/or R4 and Rs and/or Rlo and Rll form together with the carbon atoms to which they are bonded a benzene

ring, which may be substituted with groups selected from hydrogen, C16alkyl or a-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 a-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 com- pound 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 Kg and R6 is hy- drogen or Cl-6alkyl and the other an a-alkene consis- tent with formula (II), R7-Rll are hydrogens or Cl 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 Rs and R6 is a hydro- gen or Cl6alkyl while the other is an a-alkene consis- tent with formula (II), where n + m + o is an integer 1-6 and Ri and R2 are hydrogens and Rg-Rll are Cl 6alkyls. In an embodiment, the derivative is a com- pound consistent with formula (III), where X is oxy- gen, one of groups R3 and R4 is a methyl group and the other is an a-alkene consistent with formula (II), where n + m + o equals 1 or 2 and Ri and R2 are hydro- gens, R5-R8 are hydrogens and Rg-Rll 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 oxy- gen, Rl-R4 are hydrogens, one of groups R5 and R6 is

an a-alkene consistent with formula (II), where n + m + o equals 4, and Rg-Rll are methyl groups.

Another group of E-vitamin derivatives ac- cording to the invention consists of compounds consis- tent with formula (III) or (IV) where one of groups Rg -Rll in 5,7 and 8-position (formula III) or 4,6 and 7-position (formula IV) in the heterocycle is an a- alkene consistent with formula (II) and two of the groups are hydrogens or Cl6alkyls, and the sum of the integers m, n and o is in the range of 1-12 and R and R2 are as specified above.

A preferred group of compounds according to the invention consists of compounds (III) or (IV) in which Rg in 5-position (formula III) or 4-position in the heterocycle is an a-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 C16alkyls. Rlo and RI, are hydrogens or Cl6alkyls. In a preferred case, in a derivative consistent with formula (III), X is oxygen, Rl-R4 and Rlo-Rll are methyls, R5-R8 are hydrogens and Rg is an a-alkene consistent with for- mula (II) where n is 0, m is 1 and o is 3. In an em- bodiment, the derivative is a compound consistent with formula (III) where X is oxygen, R3-R4 and Rlo-Rll are methyl groups, R5-R8 are hydrogens and Rg is an a-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 com- pound analogous with the E-vitamin derivative is a compound consistent with formula (IV) in which one of groups Rg-Rn is an a-alkene consistent with formula (II) and the other groups are hydrogens or C16alkyls and R3-R8 are hydrogens or C16alkyls. 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, Rlo is an a-alkene consistent with formula (II) where n is 0 or 1, m is 0 or 1 and o is an integer 1- 4 and Rl and R2 are methyl groups, Rg is a C16alkyl, Rll is a hydrogen, R7 and Rg 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 con- sistent 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 for- mula (I) or a compound analogous with it is produced using suitable synthesizing methods of organic chemis- try.

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 for- mula (I) can be produced directly by allowing a hydro- quinone 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-1-ol or 3-methyl-1,6- heptadien-3-ol, or thiol in a suitable solvent. Op- tionally, 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-l, x-dien-3-ol, e. g. 3-methylhept-1,6-dien-3-ol or 3-alkyl-x-halogen-alk-1-en-3-ol, e. g. 3-methyl-5- chlor-pent-1-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 pre- pared by splitting off a hydrogen halogenide or a cor- responding 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 chlo- ride. 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 a-alkene to the fused heterocyclic deriva- tive thus formed.

In a first step in method B), a fused hetero- cyclic derivative can be produced by allowing a hydro- quinone derivative, such as mono-, di-or trialkylhy- droquinone, to react with a suitable tertiary unsatu- rated alcohol, such as 3-alkyl-alk-1-en-3-ol e. g. 3- methyl-but-1-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 a-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 a-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 inven- tion, is preferably bonded by its a-alkene chain to a copolymer.

In an embodiment of the invention, the co- polymer comprises one olefin or styrene monomer vari- ety and an E-vitamin derivative according to the in- vention 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 po- lymerization using metallocene catalysts is a syndio- tactic form. The crystallizing properties of the poly- mer 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 pro- duction of a stabilized copolymer, at least one mono- mer 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 polym- erization, 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 transi- tion metals for the production of catalysts are tran- sition metals belonging to groups 3 and 4, and lan- thanides whose oxidation number is +2, +3 or +4. The metallocene components contain 1-3 anionic or neu- tral groups having a a-bond. To improve the activity of the catalyst, a cocatalyst, which often consists of methylalumoxane (MAO), is generally used. More pref- erably, MAO can be replaced e. g. with compounds con- taining 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 cata- lyst used in copolymerization contains a s-cyclo- pentadienyl transition metal compound and an alumoxane compound. In an alternative embodiment, the catalyst contains a s-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 co- monomer of the invention is polymerized substantially along with other monomers, being simultaneously chemi- cally bound to the copolymer. The monomer to be polym- erized is bound to an active point, e. g. a Zr atom in the catalyst, causing faster polymerization. The poly- mer 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 dif- ferent 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 ac- cording 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 proper- ties of polymers e. g. with respect to fillers.

The copolymer of the invention has the advan- tage that the stabilizing comonomer, i. e. stabilizer, is chemically bonded to the polymer structure during polymerization, which means that it is uniformly dis- tributed 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 pro- tected 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 metallo- cene 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 struc- ture and therefore a higher melting point can be manu- factured.

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 polym- erization 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 mil- lions, even over a hundred million FIM.

In the following, the invention will be de- scribed by the aid of a detailed examples of its em- bodiments 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-trimethyl-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. HCI (g)/ZnCI2 - /<+ or AIC13/CH3NO2 OH H DRU I +isomer H -11 "I * 0 0 Preparation of 3-methylhept-1,6-dien-3-ol: To 232 g (0.4 mol) of vinyl magnesium chlo- ride 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 Na2SO4 and concentrated. The residue was distilled, and the yield obtained was 35.5 g (78%) 3-methylhept-1,6-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) an- hydrous AlCl3 in 200 ml of dichloromethane was stirred at 0 °C while at the same time adding 25.8 g (0.42 mol) of CH3NO2 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 tem- perature, and it was stirred overnight, whereupon it was poured on ice/water. The organic layer was col- lected, washed twice using a NaHCO3 solution and con- centrated. 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/1 mmHg, which was crystal- lized overnight in a cooler mp X °C. 1H NMR: 1.22 (s, 3H, CH3-C (2)); 1.5 (d, 3H,-CHClCH3) 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 HC1. 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 puri- fied 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: Trimethyl hydroquinone (23.7 g) and 2,7- octadien-1-ol (19.7 g) were weighed and put into a re- action 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 filter- ing. 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 sepa- rated by filtering. After that, based on mass spec- trometry (Fig. 1) and NMR spectrometry (Fig. 2) analy- ses, the product was identified as 5-hydroxy-4,6,7- trimethyl-3- (hex-5-enyl)-benzofurane.

Example 3; preparation of 6-hydroxy-2,2,7,8- tetramethyl-5- (1, 1-dimethyl-hex-5-enyl)-chromane HO HCI (g)/ZnCl2 OH CH3 HO H ou H+/C=CH-(CH2)3-CH=CH2 HOo CH3 0 CH3(CH2< CH2=CH Dimethyl hydroquinone and formic acid were mixed together, and 3-methylbuten-3-ol was added lit- tle 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 con- centrated hydrochloric acid was added into the resi- due, 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 di- ethyl 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 recov- ered 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-2,5,7,8- tetramethyl-2- (but-3-enyl)-chromane HOCH=CH2 I HO-C-CH2-CH2-CH=CH2 HCOOH OHOH CH3 HO PO 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 in- terrupted 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 lit- tle 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 di- ethyl 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 wa- ter. 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 dis- solved in 10 ml of acetone. K2CO3 (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, 1-dimethylhept-6-enyl))- phenol, which can be produced e. g. by a method accord- ing 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 ex- periment 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 s-cyclo-pentadienyl transi- tion metal and alumoxane.

The treatment of the z-cyclo-pentadienyl transition metal and alumoxane as well as the comono- mer was performed in a nitrogen cabinet containing un- der 2 ppm oxygen and under 5 ppm water. The polymeri- zation 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 po- lymerization activity was monitored by measuring the propylene consumption while maintaining a constant to- tal 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 prod- uct, i. e. the copolymer, with a 1-% methanol/HC1 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 indi- cation 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. TestStabi-ZrAlStab Stab/TM Crys ProductOIT lizerpmol/lmmol/l/Zr Al °C % kg/mol Mol/Mol/Zrh Mol mol atm 1 42 126 128.473.4 5644 210 2+44 132 120 0. 040 129.169.7 3984 229 3 + 44 132 120 0. 040 131.064.6 3590 230 4 + 44 132 265 0. 086 127.256.0 2510 244 5+44132356 0. 120 129.058.2 2943 248 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 re- stricted to the examples presented above; instead, they may be varied in the scope of the following claims.