Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
  • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
  • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
  • C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
  • C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
  • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
  • C07D335/12—Thioxanthenes
  • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
  • C07D335/16—Oxygen atoms, e.g. thioxanthones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1545—Six-membered rings

Definitions

• 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.
• specification FI 92212 presents a method for the production of a stable ⁇ -olefin polymer using a Ziegler-Natta type catalyst in which the ⁇ -olefin reacts with a complex comprising a metal of group I -IV of the periodic system and an ⁇ -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.
• specification DE 1947590 describes how a component containing a hydrocarbon based, steri- cally protected hydroxyl group and linked to an ⁇ - 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. MgCl 2 .
• 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 .
• additives improving stability are added to the molten product, whereupon the product is granulated.
• metallocene catalysts are 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.
• 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.
• 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 .
• 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) :
• R 3 - R u are identical or different groups selected from hydrogen, d- 6 alkyl or ⁇ - alkene having the formula (II)
• Ri and R 2 are identical or different groups selected from hydrogen or C ⁇ _ 6 alkyl or C ⁇ _ 6 alkene, which may be substituted with an aromatic ring, e.g. a styrene derivative or R 7 and R 8 are together an oxygen atom and/or R 4 and R 5 and/or R ⁇ 0 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 ⁇ - 6 alkyl or ⁇ -alkene.
• an aromatic ring e.g. a styrene derivative or R 7 and R 8 are together an oxygen atom and/or R 4 and R 5 and/or R ⁇ 0 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 ⁇ - 6 alkyl or ⁇ -alkene.
• C ⁇ - 6 alkyl or C ⁇ _ 6 alkene means a branched or non-branched hydrocarbon chain containing 1 - 6 carbon atoms .
• the derivative has the formula (III)
• R 3 - Ru are identical or different groups selected from hydrogen, C ⁇ _ 6 alkyl or ⁇ -alkene having the formula (II) .
• the derivative has the formula (V)
• R 3 - Ru are identical or different groups selected from hydrogen, C ⁇ _ 6 alkyl or ⁇ -alkene having the formula (II) , or R 7 and R 8 are together an oxygen atom and/or R 4 and R 5 and/or R ⁇ 0 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 1-6 alkyl or ⁇ -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 ⁇ - 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.
• E-vitamin derivatives according to the invention is formed by compounds consistent with formula (III) or (IV), where one the 2-position groups R 3 and R 4 or 3 -position groups R 5 and R 6 is hydrogen or C ⁇ - e alkyl and the other an ⁇ -alkene consistent with formula (II) , R 7 - Ru are hydrogens or C ⁇ _ 6 alkyls and the sum of integers m, n and o is 1 - 12 and Ri and R 2 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 R 3 and R 4 or of the heterocycle 3 -position groups R 5 and R s is a hydrogen or Ci-galkyl while the other is an ⁇ -alkene consis- tent with formula (II) , where n + m + o is an integer 1 - 6 and Ri and R 2 are hydrogens and R 9 - Ru are C ⁇ _ 6 alkyls.
• the derivative is a compound consistent with formula (III) , where X is oxygen, one of groups R 3 and R 4 is a methyl group and the other is an ⁇ -alkene consistent with formula (II) , where n + m + o equals 1 or 2 and R x and R 2 are hydrogens, R 5 - R 8 are hydrogens and R 9 - Ru are methyls.
• R 3 or R 4 may alternatively be a hydrogen instead of a methyl group.
• the derivative is a compound consistent with formula (IV) , where X is oxygen, R x - R 4 are hydrogens, one of groups R 5 and R 6 is an ⁇ -alkene consistent with formula (II) , where n + m + o equals 4, and R 9 - Ru are methyl groups.
• E-vitamin derivatives consist of compounds consis- tent with formula (III) or (IV) where one of groups R 9 - Ru in 5 , 7 and 8 -position (formula III) or 4 , 6 and 7-position (formula IV) in the heterocycle is an ⁇ - alkene consistent with formula (II) and two of the groups are hydrogens or C ⁇ -6 alkyls, and the sum of the integers m, n and o is in the range of 1 - 12 and Ri and R 2 are as specified above.
• a preferred group of compounds according to the invention consists of compounds (III) or (IV) in which R 9 in 5-position (formula III) or 4-position in the heterocycle is an ⁇ -alkene consistent with formula
• n is 0 or 1
• m is 0 or 1 and o is 1 - 4
• Ri and R 2 are hydrogens or C ⁇ _ e alkyls.
• R 10 and Ru are hydrogens or C ⁇ _ 6 alkyls.
• X is oxygen
• R x - R and R ⁇ 0 - Ru are methyls
• R 5 - R 8 are hydrogens
• R 9 is an ⁇ -alkene consistent with formula (II) where n is 0, m is 1 and o is 3.
• the derivative is a compound consistent with formula (III) where X is oxygen, R 3 - R 4 and R 10 - Ru are methyl groups, R 5 - R 8 are hydrogens and R 9 is an ⁇ -alkene consistent with formula (II) where m is 0 and n + o is 1.
• (III) include e.g. 6-hydroxy-2 , 5 , 7 , 8-tetramethyl-2- (but-3-enyl) -chromane, 6-hydroxy-2 , 5 , 7 , 8-tetramethyl-
• E-vitamin derivatives consistent with for- mula (IV) include e.g. 5-hydroxy-4 , 6 , 7-trimethyl-3- (hex-5-enyl) -benzofurane .
• the compound analogous with the E-vitamin derivative is a compound consistent with formula (IV) in which one of groups R 9 - Ru is an ⁇ -alkene consistent with formula (II) and the other groups are hydrogens or C ⁇ _ 6 alkyls and R 3 - R 8 are hydrogens or Ci- ⁇ alkyls.
• R 7 and R 8 are together an oxygen atom and/or R 4 and R 5 , together with the carbon atoms to which they are bonded, form a benzene ring.
• Rio is an ⁇ -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 R 2 are methyl groups, R 9 is a C ⁇ _ 6 alkyl, Ru is a hydrogen, R 7 and R 8 are together an oxygen atom and R 4 and R 5 , 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.
• 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 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.
• a hydroquinone derivative such as a mono-, di- or trialkyl- hydroquinone , e.g. dimethyl or trimethyl hydroquinone
• 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.
• 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 .
• 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
• 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 ⁇ -alkene to the fused heterocyclic derivative thus formed.
• 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.
• THF tetrahydrofurane
• dichloromethane acids
• 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.
• a stabilizing comonomer i.e. as a stabilizer
• 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 ⁇ -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 .
• 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
• 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 ⁇ -alkene chain to a copolymer.
• 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.
• 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.
• 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.
• 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 .
• transition metals belonging to groups 3 and 4 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 ⁇ -bond.
• 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 .
• the catalyst may comprise a solid carrier.
• the carrier may consist of any carrier material, which will not be described here in detail.
• the catalyst used in copolymerization contains a ⁇ -cyclo- pentadienyl transition metal compound and an alumoxane compound.
• the catalyst contains a ⁇ -cyclo-pentadienyl transition metal com- pound and a compound containing boron.
• 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.
• 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.
• 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.
• 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.
• Fig. 1 presents the results of a mass spec- trometry analysis of a comonomer according to the in- vention, 5-hydroxy-4 , 6 , 7-tri ⁇ nethyl-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.
• 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 NaHC0 3 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.
• 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.
• Example 3 preparation of 6 -hydroxy-2 , 2 , 7 , tetramethyl - 5 - ( 1 , l -dimethyl -hex- 5 -enyl ) - chromane
• 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.
• the intermediate product (0.5 g) was dissolved in 10 ml of acetone. K 2 C0 3 (0.37 g) was added gradually and the mixture was stirred for 30 min, whereupon C 3 H 5 Br (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 .
• 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 ⁇ -cyclo-pentadienyl transition metal and alumoxane .
• the treatment of the ⁇ -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.
• 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.
• 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 .

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• Polymers & Plastics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Pyrane Compounds (AREA)

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• 1999
  • 1999-07-21 FI FI991634A patent/FI991634A/sv unknown
• 2000
  • 2000-06-28 JP JP2001511440A patent/JP2003505382A/ja not_active Withdrawn
  • 2000-06-28 KR KR1020027000730A patent/KR20020031389A/ko not_active Application Discontinuation
  • 2000-06-28 EP EP00944066A patent/EP1196405A1/en not_active Withdrawn
  • 2000-06-28 AU AU58302/00A patent/AU5830200A/en not_active Abandoned
  • 2000-06-28 CA CA002379845A patent/CA2379845A1/en not_active Abandoned
  • 2000-06-28 WO PCT/FI2000/000585 patent/WO2001005781A1/en not_active Application Discontinuation
• 2002
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