KR20020031389A - A comonomer, and a polymer stabilized with it during polymerization - Google Patents

Abstract

The present invention relates to an E-vitamin derivative having the general formula (I) or a compound similar thereto.

<Formula I>

{Wherein

X is oxygen or sulfur atom,

p is an integer of 0 or 1,

R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II)

<Formula II>

(Wherein, n, m and o are independently an integer from 0 to 4 with each other, R ₁ and R ₂ are the same selected from C _1-6 alkyl or C _1-6 alkenyl which may be substituted with hydrogen, or an aromatic ring Or other terms)

Or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ and / or R ₁₀ and R ₁₁ together with the carbon atom to which they are attached, are selected from hydrogen, C _1-6 alkyl or α-alkene Forms a benzene ring which may be substituted with a selected group}

The present invention also relates to the use and stabilization copolymers of the derivatives having the general formula (I) as stabilizing comonomers and to methods of preparing such stabilizing copolymers.

Description

A comonomer, and a polymer stabilized with it during polymerization

In the prior art, Finland Patent FI 92212 discloses reacting an α-olefin with a complex comprising an α-alkenyl substitution stabilizer coordinated to this metal by a hetero atom as a group I-IV metal and ligand of the periodic table. Disclosed is a method for producing a stable α-olefin polymer using a Ziegler-Natta catalyst comprising. The catalyst is attached to the magnesium carrier, and a chain of five or more carbons is required between the stabilizer residue of the stabilizer ligand and the unsaturated bond that performs the polymerization.

German patent DE 1947590 also discloses olefin polymerization in the presence of a conventional Ziegler-Natta catalyst in which a component bound to an α-vinyl group based on hydrocarbons and having stereoscopically protected hydroxyl groups located at two or more carbon atom distances is present. It is disclosed how to copolymerize under conditions.

It is generally known practice to polymerize polyolefins using Ziegler-Natta catalysts. This catalyst consists of an organometallic compound, the procatalyst is usually at least partly reduced compounds of transition metals of group IV, V, VI or VII, typically compounds of eg titanium or zirconium, and the cocatalyst is Organometallic compounds of alkali metals, alkaline earth metals, zinc or aluminum, for example triethylaluminum and diethylmagnesium. An example of such a catalyst is a combination of titanium chloride and triethylaluminum. When the components are attached to a fixed carrier (eg MgCl ₂ ), the activity is greatly increased. Ziegler-Natta catalysts are characterized by being able to allow the polymer to take the form of particles of the catalyst during polymerization, thus producing polymer particles of 0.2 to 5 mm. The polymer particles thus prepared are porous bodies and can be chemically dissolved in use, even without additives that enhance stability.

It is known to use high molecular weight stabilizers such as tert-butylphenol and pentaerythritol derivatives as additives. Processes based on polymers and using oligomeric molecules are also known. However, they are limited in their low solubility in polymers. Substituted phenols and aromatic amines are widely used as antioxidants. Typically the polymer product obtained after the polymerization reaction is melted in a so-called extrusion step and the product is granulated by adding an additive which improves stability to the molten product.

In addition, methods of using so-called metallocene catalysts are known in the art. These catalysts have been added to Ziegler-Natta catalysts since the early 1990s, or have been used instead in polymerization processes. Metallocene catalysts are based on so-called sandwich structures (bischloro-zirconocenes) in which a central metal such as zirconium is disposed between two cyclopentadienyl rings and derivatives of this structure. Metallocene catalysts have increased the polymerization activity in some cases even for comonomers, which have previously been difficult to copolymerize.

A problem with conventionally known methods is the need to add stabilizing additives to the product at the extruder stage, which makes stability a problem and makes it impossible to use catalysts and polymerization processes to produce particle products.

Another problem is that the additives in the polymer product dissipate during use. One of the causes is that as the additive that improves stability moves to the product surface, over time the stabilizing effect decreases or disappears and the additives come into contact with food, for example. In addition, some additives have been found to have environmental hormone action. The loss of additives in the product is due in part to the dissolution that occurs during evaporation or washing that occurs during the process.

Another problem is the irregular distribution of additives in the polymer product. Irregular distribution may be due to, for example, incompatibility of the paraffinic hydrocarbon based polymer and stabilizer due to high polarity. In addition, since the stabilizer tends to crystallize, the amount of stabilizer added to the polyolefin should be limited.

Another problem is poor production yield and the hybridization of the product in polymerizations carried out using Ziegler-Natta catalysts.

The present invention relates to E-vitamin derivatives or similar compounds as defined at the outset of claim 1, to methods of making such derivatives, their use as defined in claim 16, stabilized air as defined at the outset of claim 17 And to a process for preparing the stabilized copolymer as defined at the beginning of claim 24.

1 shows the results of a mass spectrum analysis of the comonomer 5-hydroxy-4,6,7-trimethyl-3- (hex-5-enyl) -benzofuran according to the present invention.

Figure 2 shows the results of NMR spectrum analysis of the comonomer 5-hydroxy-4,6,7-trimethyl-3- (hex-5-enyl) -benzofuran according to the present invention.

Figure 3 shows the results of mass spectra analysis of comonomer 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman according to the present invention.

4 shows the results of NMR spectral analysis of comonomer 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman according to the present invention.

It is an object of the present invention to disclose useful novel comonomers which eliminate the above mentioned problems and have a stabilizing effect. Another object of the present invention is to disclose a copolymer stabilized during polymerization.

E-vitamin derivatives or similar compounds thereof, methods of preparation thereof, and comonomers stabilized according to the invention and methods of preparation thereof have the features set forth in the claims.

E-vitamin derivatives of the present invention or similar compounds, ie compounds having the corresponding structure, have the formula (I).

Where

X is oxygen or sulfur atom,

p is an integer of 0 or 1,

R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II)

Wherein n, m and o are each independently an integer from 0 to 4, and R ₁ and R ₂ are hydrogen or C _1-6 alkyl or C _1-6 which may be substituted with an aromatic ring (styrene derivative) Same or different term selected from alkenes)

Or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ and / or R ₁₀ and R ₁₁ together with the carbon atom to which they are attached, are selected from hydrogen, C _1-6 alkyl or α-alkene To form a benzene ring which may be substituted with a selected group.

C _1-6 alkyl or C _1-6 alkene means a branched or unbranched hydrocarbon chain having 1 to 6 carbon atoms.

According to one embodiment of the invention, the derivative has the formula (III) or (IV).

Where

X is oxygen or sulfur atom,

R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II) above.

According to one embodiment of the invention, the derivative has the formula (V)

Where

R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II) above,

Or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ and / or R ₁₀ and R ₁₁ together with the carbon atom to which they are attached, are selected from hydrogen, C _1-6 alkyl or α-alkene To form a benzene ring which may be substituted with a selected group.

The E-vitamin derivatives of the present invention or similar compounds are preferably structures having one or more fused benzene rings and rings containing heteroatoms, and α chains linked to these rings. It is preferable that a hetero atom such as an oxygen or sulfur atom and a hydroxy group are bonded to the opposite side of the benzene ring of the heterocycle, and as a result, a stabilizing effect of the compound can be obtained.

In the group of E-vitamin derivatives according to the present invention, in the above formula (III) or (IV), one of the R ₃ and R ₄ groups in the 2-position or the R ₅ and R ₆ groups in the 3-position is hydrogen or C _1-6 Alkyl, another is α-alkene having formula (II) above, R ₇ -R ₁₁ is hydrogen or C _1-6 alkyl, the sum of the integers m, n and o is 1-12, R ₁ and R ₂ consists of a compound as defined above.

Preferred E-vitamin derivatives according to the present invention are those in which the R ₃ and R ₄ groups in the heterocycle 2-position or the R ₅ and R ₆ groups in the heterocycle 3-position are hydrogen or C _Α -alkene having _1-6 alkyl, the other of which has formula (II), wherein the sum of the integers m, n and o is 1-6, R ₁ and R ₂ are hydrogen, R ₉ -R ₁₁ is C _1-6 alkyl. In one embodiment, the derivative is an α-alkene in formula (III) wherein X is oxygen, one of the groups R ₃ and R ₄ is a methyl group and the other is the formula (II) wherein the integers m, n And o is 1 or 2, R ₁ and R ₂ are hydrogen, R ₅ -R ₈ is hydrogen, and R ₉ -R ₁₁ is methyl. R ₃ or R ₄ may alternatively be hydrogen instead of methyl. In one embodiment, the derivative is an α-alkene in formula (IV) wherein X is oxygen, R ₁ -R ₄ is hydrogen, and one of R ₅ and R ₆ groups has formula (II), wherein m, n, and o are 4 and R <_9> -R <_11> is a methyl group.

Another group of E-vitamin derivatives according to the invention is in the above formula (III) or (IV), R ₉ -in positions 5, 7 and 8 (Formula III) or 4, 6 and 7 (Formula IV) of the heterocycle. One of R ₁₁ groups is an α-alkene having the formula (II) wherein the sum of the integers m, n and o is 1 to 12, R ₁ and R ₂ are as defined above and the other two groups are hydrogen or C _It consists of a compound which is _1-6 alkyl.

Preferred compounds according to the invention are α-alkenes in the above formula (III) or (IV), wherein 5-position (Formula III) or 4-position R ₉ of the heterocycle has the formula (II), m being 0 or 1 And n is 0 or 1, o is an integer from 1 to 4, and R ₁ and R ₂ are hydrogen or C _1-6 alkyl. R ₁₀ and R ₁₁ are hydrogen or C _1-6 alkyl. Preference is given to the above formula (III) in which X is oxygen, R ₁ -R ₄ and R ₁₀ -R ₁₁ are methyl, R ₅ -R ₈ is hydrogen, and R ₉ is of formula (II) Alkene wherein m is 1, n is 0 and o is 3; In one embodiment, the derivative is a compound of formula (III) wherein X is oxygen, R ₃ -R ₄ and R ₁₀ -R ₁₁ are methyl groups, R ₅ -R ₈ is hydrogen, and R ₉ is formula (II) Is an a-alkene having m) wherein m is 0 and the sum of n and o is 1.

As the E-vitamin derivative having the above formula (III), for example, 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman, 6-hydroxy -2,5,7,8-tetramethyl-2- (prop-2-enyl) -chroman, 6-hydroxy-2,2,7,8-tetramethyl-5- (1,1-dimethyl -Hex-5-enyl) -chroman and 6-hydroxy-2,2,7,8-tetramethyl-5- (prop-2-enyl) -chromen. E-vitamin derivatives having the above formula (IV) include, for example, 5-hydroxy-4,6,7-trimethyl-3- (hex-5-enyl) -benzofuran.

In one embodiment of the invention, the compound analogous to the E-vitamin derivative is in the above formula (IV) wherein one of the R ₉ -R ₁₁ groups is an α-alkene having the formula (II) and the other is hydrogen or C _1-6 alkyl and R ₃ -R ₈ is hydrogen or C _1-6 alkyl. Or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ together with the carbon atom to which they are attached form a benzene ring. In a preferred embodiment, R ₁₀ is an α-alkene of formula (II) wherein n is 0 or 1, m is 0 or 1, o is 1 to 4, R ₁ and R ₂ are methyl groups, R ₉ is C _1-6 alkyl, R ₁₁ is hydrogen, R ₇ and R ₈ together are oxygen atoms, and R ₄ and R ₅ together with the carbon atom to which they are attached form a benzene ring. Examples of the compound represented by the above formula (V) include thioxanthone derivatives such as hydroxythioxanthone derivatives.

The derivatives according to the invention may of course have all kinds of structures corresponding to the above structures, for example the following structural formulas.

E-vitamin derivatives having the formula (I) or compounds similar thereto are prepared using suitable organic chemical synthesis.

E-vitamin derivatives or similar compounds (I) of the present invention are, for example,

A) Hydroquinone derivatives can be prepared by reaction with a suitable tertiary unsaturated alcohol or thiol.

In method A), the compound having the formula (I) is a hydroquinone derivative such as mono-, di- or trialkyl hydroquinone, for example dimethyl or trimethyl hydroquinone, such as alkadienol, for example It can be prepared directly by reacting 2,7-octadiene-1-ol or 3-methyl-1,6-heptadiene-3-ol or thiol in a suitable solvent. Alternatively, according to method A), in a first step, the hydroquinone derivative is converted to 2-alkyl-alka-1, x-dien-3-ol (eg, 3-methylhept-1,6-diene-3-ol) or In a suitable solvent with a suitable unsaturated alcohol such as 3-alkyl-x-halogen-alk-1-en-3-ol (eg, 3-methyl-5-chlor-pent-1-en-3-ol), or thiol Reaction in the presence of a suitable catalyst can produce intermediate products containing (halogen-alkyl) groups or corresponding groups. In a second step, a hydrogen halide or a corresponding compound is separated from a halogen alkyl group or an equivalent group in the intermediate product in the presence of alkali to prepare a compound having formula (I). Suitable catalysts are, for example, metal halides such as aluminum chloride, zinc chloride. Suitable solvents are, for example, acids such as formic acid, sulfuric acid or equivalents, tetrahydrofuran (THF), and dichloromethane. Suitable alkalis are, for example, 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU).

E-vitamin derivatives or compounds similar thereto (I) provided by the present invention are, for example,

B) The hydroquinone derivative can be prepared by reacting with a suitable unsaturated alcohol or thiol and adding α-alkene to the fused heterocyclic derivative thus formed.

In a first step of method B), hydroquinone derivatives such as mono-, di- or trialkylhydroquinones are replaced with a suitable tertiary unsaturated alcohol such as 3-alkyl-alk-1-en-3-ol, for example 3- The fused heterocyclic derivatives can be prepared by reacting methyl-but-1-en-3-ol or thiol with a suitable catalyst in the presence of a suitable catalyst. Suitable catalysts are, for example, metal halides such as aluminum chloride and zinc chloride. Suitable solvents are, for example, tetrahydrofuran (THF), dichloromethane and acids such as formic acid. In a second step of the process, α-alkene having formula (II) is added to the heterocyclic derivative under acidic conditions.

E-vitamin derivatives or similar compounds of the invention are preferred for use as stabilizing comonomers, i.e. stabilizers, in copolymerization to prepare stabilized copolymers. The function of the stabilizer is to prevent and reduce the harmful action of the copolymer of heat, UV light, oxygen and / or ozone.

Stabilized copolymers consist of one or more monomers and stabilized comonomers. The monomers at issue here are cyclic and / or aromatic compounds with olefins and / or α-alkene chains. The olefin monomers can be, for example, ethylene, propylene, 1-butene, isobutene and / or 4-methyl-1-pentene, or the like or mixtures thereof. The aromatic compound may be styrene. Of course, the monomers can be of any type. Stabilizing comonomers are E-vitamin derivatives or similar compounds having the above formula (I), having a clear stabilizing action and capable of polymerizing under conventional polymerization conditions. Stabilizing comonomers can be, for example, derivatives of chromman-, benzofuran- or hydroxythioxanthones.

The comonomer, ie the stabilizer of the present invention, is preferably bound to the copolymer by an α-alkene chain.

In one embodiment of the invention, the copolymer comprises one olefin or styrene monomer and an E-vitamin derivative according to the invention or a compound thereof having the above formulas (III), (IV) or (V).

It is preferable that a copolymer belongs to what is called an addition polymer. Low molecular by-products do not occur when forming the additive polymer. That is, the structural unit of a polymer consists of monomers. The monomer may have a linear or branched hydrocarbon chain and has one or more double bonds so that a polymerization reaction can occur.

In the copolymer, different kinds of monomers can be arranged in various ways, for example, in a regular manner, alternatingly, in segments or in such another way. The monomers can also be arranged in an irregular manner. The structure of the copolymer is preferably generally regular, such as isotactic or syndiotactic, which is typically seen when polymerizing monomers using a metallocene or Ziegler-Natta catalyst (stereospecific polymerization). . The structural properties of the product obtained by polymerization using a metallocene catalyst are of regular order. The crystallization properties of the polymer depend, among other things, on the regularity of the structure. However, the polymer may also have a hybrid array portion, or may be a fully hybrid array.

In the process of the invention for preparing stabilized copolymers, although not described in detail herein, single or multistage polymerizations per se known by the precipitation, solution or gas phase polymerization process of one or more monomers and stabilizing comonomers are used. The process copolymerizes in the presence of a catalyst.

According to one embodiment, the catalysts used for copolymerization are preferably liquid or solid metallocene catalysts or derivatives known per se, formed from derivatives of transition metals comprising lanthanides, for example. The most suitable transition metals for the preparation of catalysts are the transition metals belonging to groups 3 and 4 and the lanthanides having an oxidation value of +2, +3 or +4. The metallocene component has 1-3 anions or neutral groups with π-bonds. In order to enhance the activity of the catalyst, it is common to use a cocatalyst consisting mainly of methylalumoxane (MAO). More preferred is the use of, for example, boron containing compounds such as tri (hydrocarbyl) boron and halogenated derivatives thereof instead of MAO. The catalyst used may be, for example, tetraphenyl borate. In the copolymerization process of the present invention, for example, a metallocene catalyst of the type described in Finland Patent Application No. 941662 can be used. Of course, other catalysts used in the art may be used in this copolymerization method. The catalyst may comprise a solid carrier. The carrier may consist of any carrier material, which will not be described in detail herein.

In one embodiment of the present invention, the catalyst used for copolymerization contains a π-cyclopentadienyl transition metal compound and an alumoxane compound. In other embodiments, the catalyst contains a π-cyclopentadienyl transition metal compound and a boron containing compound.

In one embodiment, the stabilizing comonomers are chemically complexed with the catalyst by their heteroatoms, for example, bound by chemical bonding to the zirconium atoms of the catalyst. The comonomers may of course be used as such or may be used, for example, in admixture with other monomers in the polymerization solution during polymerization.

In the polymerization step, stabilizing comonomers and monomers, such as olefins and / or styrene monomers, are copolymerized, in which the comonomers of the invention are polymerized with substantially other monomers to bond chemically simultaneously to the copolymer. Will be. The monomer to be polymerized is bound to the active site, for example the Zr atom of the catalyst, to allow for faster polymerization. The polymer grows as the structural units of the copolymer increase. The copolymer contains several monomers in specific proportions.

The copolymer can be, for example, ethylene /-, propylene /-, butylene /-or styrene / E-vitamin derived copolymers. The copolymerization product may consist of two or more monomers. Different production methods and different monomer ratios can be used to control the properties of the copolymer.

The copolymers provided by the present invention can be used as such or in a mixture with other monomers. Copolymers stabilized with comonomers according to the invention can be used, for example, as fillers in the food industry.

E-vitamin derivatives or the like compounds of the present invention have the advantage that they can be polymerized in excellent yields under typical polymerization conditions, and have an excellent ability to inhibit oxidation and can be used as oxidation inhibitors in preparing polymers. In addition, the comonomers of the present invention, for example, improve the adhesion properties of the polymer to the filler.

The copolymers of the present invention have the advantage that the stabilizing comonomers, ie, stabilizers are chemically bonded to the polymer structure during polymerization, which means that the stabilizers are evenly distributed throughout the polymer, and the chemical bonds prevent the loss of the stabilizers in the product. Means. In other words, the stabilizer is prevented from escaping to the product surface during use. Therefore, stabilizers do not transfer to foods protected with plastics, for example, and therefore are not delivered to people.

The copolymerization method of the present invention has the advantage of using a metallocene catalyst. Under polymerization conditions, these catalysts are superior to other currently known catalysts. Using such metallocene catalysts it is possible to produce polymer products having a regular ordered structure and hence high melting points.

Another advantage provided by the copolymerization process according to the invention is that stabilization is carried out during the polymerization. In other words, since the stabilizer is added to the comonomer as an essential component during the polymerization to form the polymerization product, the product can be used directly for further processing, ie the product thus obtained does not need to be melted again or fed to the extruder. Thus, the cost of extruder input, which can reach tens of millions to even billions of FIM, is reduced. The invention will now be described with reference to the drawings and by way of detailed embodiment examples.

Example 1 Preparation of 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman

Preparation of 3-methylhept-1,6-dien-3-ol:

To 232 g (0.4 mol) of vinyl magnesium chloride in THF was added a solution of 35 g (0.36 mol) of 5-hexen-2-one in 150 mL of dry THF. The reaction mixture was stirred at room temperature for 20 hours and carefully poured into 450 mL of cold NH ₄ Cl saturated aqueous solution. The organic extract was concentrated, dissolved with dichloromethane, dried using Na ₂ SO ₄ and concentrated. The residue was distilled off to give 35.5 g (78%) of 3-methylhept-1,6-diene-3-ol (tp 45 ° C / 10 mmHg).

Preparation of 6-hydroxy-2,5,7,8-tetramethyl-2- (4-chloro-butyl) -chroman:

A suspension containing 20 g (0.150 mol) of anhydrous AlCl _{2 in} 200 mL of dichloromethane was stirred at 0 ° C. while simultaneously adding 25.8 g (0.42 mol) of CH ₃ NO ₂ under an argon protective layer. After the mixture was stirred at 0 ° C. for 10 minutes, 30.4 g (0.2 mol) of trimethyl-hydroquinone were added batchwise. The resulting brown suspension was cooled to −20 ° C. and a solution containing 3-methylhept-1,6-dien-3-ol in 750 ml of dichloromethane was added dropwise over 0.5 hour. The resulting mixture was slowly cooled to room temperature, stirred overnight and then poured into ice / water. The organic layer was collected, washed twice with NaHCO ₃ solution and concentrated. This gave 40 g of crude product containing trace impurities. Distillation of the crude product gave 15 g (25%) of 6-hydroxy-2,5,7,8-tetramethyl-2- (4-chlorobutyl) -chroman fraction in the form of a light brown liquid, mp X Crystallized overnight at &lt; RTI ID = 0.0 &gt; ¹ H NMR: 1.22 (s, 3H, CH ₃ -C (2)); 1.5 (d, 3H, -CHClCH ₃ ), 1.65 (m, 2H, ArCH ₂ -CH _2- ), 1.8 (m, 4H, -CH ₂ -CH _2- ), 2.1, 2.12, 2.15 (3s, 9H, ArCH ₃ ); 2.62 (t, 2H, CH ₂ Ar); 4.1 (m, 1H, CH) and 4.23 (s, 1H, OH). ¹³ C 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) -chroman

1,8-diazabicyclo (5.4.0) undec-7 in 14.8 g (0.05 mol) of 6-hydroxy-2,5,7,8-tetramethyl-2- (4-chlorobutyl) -chroman 36.3 g (0.24 mol) of ene (DBU) were added and the solution was heated to 100 ° C. and stirred for 20 h. The reaction mixture was then cooled to room temperature, poured into 350 ml of dichloromethane and washed several times with soft HCl. The organic layer was concentrated to give 10.2 g of crude product without DBU. In addition, this material was purified by distillation to give 5 g (38) of 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman (tp 154 DEG C / 1mmHg). %) Was obtained.

Example 2: Preparation of 5-hydroxy-4,6,7-trimethyl-3- (hex-5-enyl) -benzofuran

Trimethyl hydroquinone (23.7 g) and 2,7-octadiene-1-ol (19.7 g) were weighed and placed in a reaction vessel, and 50 ml of formic acid was added to the mixture. The temperature of the mixture was raised to the boiling point of formic acid and the reaction proceeded for 3 hours. The reaction mixture was poured into 150 mL of ice-water mixture and the organic phase was recovered with diethyl ether. After evaporating the organic solvent, 100 ml of methanol and 1 ml of hydrochloric acid were added to the residue. The reaction mixture was hydrolyzed at the boiling point of methanol for 30 minutes and the solvent was evaporated from the mixture. The mixture was dissolved in diethyl ether and the organic phase was washed twice with sodium bicarbonate and five times with distilled water. Diethyl ether was evaporated. At this time, the yield was 48.0 g. n-hexane was added to the mixture and stirred for 30 minutes at the boiling point of hexane, then the mixture was cooled to room temperature. The portion not dissolved in hexane consisted mainly of inert trimethyl hydroquinone and the product was separated from the mixture by filtration. The solid portion was dissolved in a small amount of ethanol, and a fixed amount of water was added to this solution to form a precipitate, followed by filtration to separate the product (7.5 g). Subsequently, the product was identified as 5-hydroxy-4,6,7-trimethyl-3- (hex-5-enyl) -benzofuran based on mass spectral analysis (FIG. 1) and NMR spectral analysis (FIG. 2). .

Example 3: Preparation of 6-hydroxy-2,2,7,8-tetramethyl-5- (1,1-dimethyl-hex-5-enyl) -chroman

Dimethyl hydroquinone and formic acid were mixed together and 3-methylbuten-3-ol was added to the reaction mixture in small portions for 1 hour. After the mixture was reacted for 2 hours at the boiling point of formic acid, an amount of ice-water mixture was added thereto to stop the reaction. The organic phase was recovered with 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 were added to the residue, and then the mixture was hydrolyzed for 30 minutes at the boiling point of methanol. Methanol was evaporated and the residue was dissolved in diethyl ether and washed twice with sodium bicarbonate and alternately with water five times. Diethyl ether was evaporated and the residue was distilled in vacuo. The intermediate product 6-hydroxy-2,2,7,8-tetramethyl-chroman (1.25 g) was recovered under conditions of a pressure of 0.2 mbar and a temperature of 110 to 120 ° C.

6-hydroxy-2,2,7,8-tetramethylchroman and 7-methyl-1,6-octadiene were mixed together. The reaction solution was heated and an acid catalyst was added. The mixture was reacted for 24 hours, and the product 6-hydroxy-2,2,7,8-tetramethyl-5- (1,1-dimethyl-hex-5-enyl) -chromman was separated by a conventional method. And purified by distillation.

Example 4: Preparation of 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman

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 placed in a 50 ml reaction vessel. The temperature was raised to the boiling point of formic acid and at this temperature, the reaction was allowed to proceed for 2 hours and 50 minutes. The mixture was poured into an ice-water mixture to stop the reaction and the organic phase was recovered and washed in a conventional manner. The part not dissolved in hexane was first separated from the product, and the product was dissolved in ethanol, treated with water to form a precipitate, and then washed with hexane and diethyl ether. Yield was 1.3 g. Mass spectral analysis (FIG. 3) and NMR spectral analysis (FIG. 4) confirmed that the product was 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman. .

Example 5: Preparation of 6-hydroxy-2,2,7,8-tetramethyl-5- (prop-2-enyl) -chroman

Dimethyl hydroquinone and formic acid were mixed together and 3-methylbuten-3-ol was added to the reaction mixture in small portions for 1 hour. After the mixture was reacted for 2 hours at the boiling point of formic acid, an amount of ice-water mixture was added thereto to stop the reaction. The organic phase was recovered with 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 were added to the residue, and then the mixture was hydrolyzed for 30 minutes at the boiling point of methanol. Methanol was evaporated and the residue was dissolved in diethyl ether and washed twice with sodium bicarbonate and alternately with water five times. Diethyl ether was evaporated and the residue was distilled in vacuo. The intermediate product 6-hydroxy-2,2,7,8-tetramethyl-chroman (1.25 g) was recovered under conditions of a pressure of 0.2 mbar and a temperature of 110 to 120 ° C.

The intermediate product (0.5 g) was dissolved in 10 ml of acetone. K ₂ CO ₃ (0.37 g) was added slowly, the mixture was stirred for 30 minutes, and then C ₃ H ₅ Br (0.33 g) was added slowly. A reflux condenser was used during the reaction. The mixture was heated for 48 hours to give only the final product 6-hydroxy-2,2,7,8-tetramethyl-5- (prop-2-enyl) -chrome. The product was separated from the mixture by column chromatography.

Example 6 Preparation of Hydroxythioxanthones

6-tert-butyl- (2-1,1-dimethylhept-6-enyl))-phenol, which may be prepared by a process according to International Patent Application No. PCT / FI95 / 00196 From thiosalicylic acid in a manner known per se.

Example 7: Copolymerization

The polymerization test was carried out in an experiment on the copolymerization of 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman and propylene in the presence of a metallocene catalyst. Metallocene catalysts consisted of π-cyclo-pentadienyl transition metals and alumoxanes.

Treatment of the? -Cyclo-pentadienyl transition metal with alumoxane as well as comonomers was carried out in a nitrogen cabinet containing up to 2 ppm oxygen and up to 5 ppm nitrogen. The polymerization was carried out in an autoclave equipped with a turbine mixer. Reaction temperature was adjusted to the precision of 0.3 degreeC.

The dry autoclave was emptied and washed with water. This process was repeated three times. The first batch of distilled toluene was fed to the reactor using high pressure nitrogen. 5 mg of Ansa metallocene catalyst was dissolved in a second batch of MAO / toluene solution and left to react for 5 minutes at room temperature to preactivate.

The catalyst / activator mixture was fed to the reactor. Propylene monomer was added to initiate prepolymerization. After 3 minutes, the comonomer diluted with toluene was added using propylene gas until the propylene partial pressure reached 2 bar. Polymerization activity was determined by continuously adding gaseous propylene and measuring propylene consumption while keeping the total pressure in the reactor constant. After 30 minutes, the propylene feed was stopped and the polymerization was stopped by adding 100 ml of methanol. The polyolefin was filtered off and the product, ie the copolymer, was treated with 1% methanol / HCl solution to remove catalyst residues. The product was washed twice with ethanol, dried under vacuum at 50 ° C. and weighed. The amount of the obtained copolymer was 3 g. After diffusion of the copolymer using a Soxhlet apparatus, the concentration of bound stabilizer was determined. The results of the polymerization are shown in Table 1.

In Table 1, it can be seen that the OIT temperature increases as the content of the comonomer increases, which indicates the effect of the stabilizer. It can also be seen from Table 1 that the crystallization of the product decreases with higher copolymer content levels, indicating that the comonomer is chemically bound to the rest of the polymer.

Copolymerization Results of 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman and propylene inspection Stabilizer Zr (micromol / ℓ) Al (mmol / l) Stabilizer / Zr (mol / mol) Stabilizer / Al (mol / mol) T _M (℃) Crystallinity (%) Product (kg / mol Zr h atm) OIT One - 42 126 - - 128.4 73.4 5644 210 2 + 44 132 120 0.040 129.1 69.7 3984 229 3 + 44 132 120 0.040 131.0 64.6 3590 230 4 + 44 132 265 0.086 127.2 56.0 2510 244 5 + 44 132 356 0.120 129.0 58.2 2943 248

The E-vitamin derivatives or similar compounds of the present invention are suitable for use in various applications, for example in the preparation of all kinds of copolymers. In addition, the copolymer of the present invention is suitable for use in various applications for any purpose.

Embodiments of the invention are not limited to the examples set forth above, but may vary within the scope of the following claims.

Claims (32)

E-vitamin derivatives having the formula (I): <Formula I> {Wherein X is oxygen or sulfur atom, p is an integer of 0 or 1, R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II) <Formula II> (Wherein, n, m and o are independently an integer from 0 to 4 with each other, R ₁ and R ₂ are the same selected from C _1-6 alkyl or C _1-6 alkenyl which may be substituted with hydrogen, or an aromatic ring Or other terms) Or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ and / or R ₁₀ and R ₁₁ together with the carbon atom to which they are attached, are selected from hydrogen, C _1-6 alkyl or α-alkene Forms a benzene ring which may be substituted with a selected group} The derivative according to claim 1, which has the formula (III) or (IV). <Formula III> <Formula IV> (Wherein X is oxygen or sulfur atom, R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II) above) The derivative according to claim 1, which has the formula (V). <Formula V> (Wherein R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II) above, Or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ and / or R ₁₀ and R ₁₁ together with the carbon atom to which they are attached, are selected from hydrogen, C _1-6 alkyl or α-alkene Forms a benzene ring which may be substituted with a selected group) The α-alkene according to claim 1 or 2, wherein one of the R ₃ and R ₄ groups or one of the R ₅ and R ₆ groups is hydrogen or C _1-6 alkyl and the other is an a-alkene having the formula (II) And R ₇ -R ₁₁ is hydrogen or C _1-6 alkyl. The derivative according to any one of claims 1, 2 or 4, wherein the sum of m, n and o is 1 to 6 and R ₁ and R ₂ are hydrogen. The compound according to any one of claims 1 to 7, wherein in formula (III), X is oxygen, one of R ₃ and R ₄ groups is a methyl group, and the other is Α-alkenes having the formula (II), wherein the sum of the integers m, n and o is 1 or 2, R ₁ and R ₂ and R ₅ -R ₈ are hydrogen, and R ₉ -R ₁₁ is a methyl group Derivatives. The compound of any one of claims 1, 2 or 4, wherein in formula (IV), X is oxygen, R ₁ -R ₄ is hydrogen, and one of the groups R ₅ and R ₆ is The α-alkene having (II), wherein the sum of the integers m, n and o is 4, and R ₉ -R ₁₁ are methyl groups. A compound according to claim 1 or 2, wherein one of the R ₉ -R ₁₁ groups is an α-alkene having the above formula (II), the other two groups are hydrogen or C _1-6 alkyl, and R ₃ -R ₈ is Hydrogen or C _1-6 . The α-alkene of claim 1, 2 or 8, wherein R ₁₀ and R ₁₁ are hydrogen or C _1-6 , and R ₉ is an α-alkene having the formula (II), wherein m is 0. 10. Or 1, n is 0 or 1, o is 1 to 4, and R ₁ and R ₂ are hydrogen or C _1-6 alkyl. 10. The compound of any one of claims 1, 2 or 8 to 9, wherein in formula (III), X is oxygen, R ₁ -R ₄ and R ₁₀ -R ₁₁ are methyl groups, and R _5- R ₈ is hydrogen and R ₉ is an α-alkene having the formula (II), wherein m is 1, n is 0 and o is 3. 10. The compound of any one of claims 1, 2 or 8 to 9, wherein in formula (III), X is oxygen, R ₃ -R ₄ and R ₁₀ -R ₁₁ are methyl groups, and R ₅ -R ₈ is hydrogen and R ₉ is an α-alkene having the formula (II) wherein the integer m is 0 and the sum of n and o is 1. The compound according to claim 1 or 3, wherein one of the R ₉ -R ₁₁ groups is an α-alkene having the formula (II), the other groups are hydrogen or C _1-6 alkyl, and R ₃ -R ₈ is hydrogen Or C _1-6 alkyl, or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ together with the carbon atom to which they are attached form a benzene ring. 13. The compound of any one of claims 1, 3 or 12, wherein R ₁₀ is an α-alkene having the formula (II), wherein n is 0 or 1, m is 0 or 1, and o is 1 An integer from 4 to 4, R ₁ and R ₂ are methyl groups, R ₉ is C _1-6 alkyl, R ₁₁ is hydrogen, R ₇ and R ₈ together are oxygen atoms, and R ₄ and R ₅ are bonded to them And a benzene ring together with the carbon atom. 14. A compound according to any one of claims 1 to 13, wherein 6-hydroxy-2,5,7,8-tetramethyl-2- (but-3-enyl) -chroman, 6-hydroxy-2, 5,7,8-tetramethyl-2- (prop-2-enyl) -chroman, 6-hydroxy-2,2,7,8-tetramethyl-5- (1,1-dimethyl-hex- 5-enyl) -chroman, 6-hydroxy-2,2,7,8-tetramethyl-5- (prop-2-enyl) -chroman, 5-hydroxy-4,6,7-trimethyl Derivatives characterized in that 3- (hex-5-enyl) -benzofuran or hydroxythioxanthone derivatives. A) reacting the hydroquinone derivative with a suitable unsaturated alcohol or thiol, or B) an E-vitamin derivative or the like having the above formula (I) characterized by reacting the hydroquinone derivative with a suitable unsaturated alcohol or thiol and adding α-alkylene to the fused heterocyclic derivative thus formed. Method of preparation. Use as a stabilizing comonomer for the preparation of a stabilizing copolymer of an E-vitamin derivative as defined in claim 1 or a compound thereof. A stabilizing copolymer comprising at least one monomer which is a cyclic and / or aromatic compound having an olefin and / or an α-alkene chain, and a stabilizing comonomer, wherein the comonomer is an E-vitamin derivative having the formula (I) Or a similar compound. <Formula I> {Wherein X is oxygen or sulfur atom, p is an integer of 0 or 1, R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II) <Formula II> (Wherein, n, m and o are independently an integer from 0 to 4 with each other, R ₁ and R ₂ are the same selected from C _1-6 alkyl or C _1-6 alkenyl which may be substituted with hydrogen, or an aromatic ring Or other terms) Or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ and / or R ₁₀ and R ₁₁ together with the carbon atom to which they are attached, are selected from hydrogen, C _1-6 alkyl or α-alkene Forms a benzene ring which may be substituted with a selected group} 18. The stabilized copolymer of claim 17 wherein the comonomer has the formula (III) or (IV). <Formula III> <Formula IV> (Wherein X is oxygen or sulfur atom, R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II) above) 18. The stabilized copolymer of claim 17 wherein the comonomer has the formula (V). <Formula V> (Wherein R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II) above, Or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ and / or R ₁₀ and R ₁₁ together with the carbon atom to which they are attached, are selected from hydrogen, C _1-6 alkyl or α-alkene Forms a benzene ring which may be substituted with a selected group) 20. The stabilized copolymer according to any one of claims 17 to 19, wherein the olefin is ethylene, propylene, butylene and / or pentene. The stabilizing copolymer according to any one of claims 17 to 20, wherein the aromatic compound is styrene. 22. Stabilization according to any one of claims 17 to 21, wherein the copolymer consists of one olefin or styrene monomer and a comonomer having the above formulas (III), (IV) or (V). Copolymer. 23. Stabilized copolymer according to any one of claims 17 to 22, wherein the copolymer has a substantially regular structure. Preparation of a stabilized copolymer comprising copolymerizing at least one monomer which is a cyclic and / or aromatic compound having an olefin and / or an α-alkene chain, and a stabilizing comonomer by a polymerization method known per se in the presence of a catalyst. The process according to claim 1, wherein the comonomer used is an E-vitamin derivative having the formula (I) or a compound thereof. <Formula I> {Wherein X is oxygen or sulfur atom, p is an integer of 0 or 1, R ₃ -R ₁₁ is the same or different group selected from hydrogen, C _1-6 alkyl or α-alkene having formula (II) <Formula II> (Wherein, n, m and o are independently an integer from 0 to 4 with each other, R ₁ and R ₂ are the same selected from C _1-6 alkyl or C _1-6 alkenyl which may be substituted with hydrogen, or an aromatic ring Or other terms) Or R ₇ and R ₈ together are an oxygen atom and / or R ₄ and R ₅ and / or R ₁₀ and R ₁₁ together with the carbon atom to which they are attached, are selected from hydrogen, C _1-6 alkyl or α-alkene Forms a benzene ring which may be substituted with a selected group} The method of claim 24, wherein the comonomer used has the formula (III), (IV) or (V). 26. The process according to claim 24 or 25, wherein the copolymerization is carried out using a metallocene catalyst or derivative thereof. 27. The process according to any one of claims 24 to 26, wherein the catalyst used for copolymerization comprises a -cyclo-pentadienyl transition metal compound and an alumoxane compound. 28. The process of any one of claims 24 to 27, wherein the catalyst used in the copolymerization comprises a π-cyclo-pentadienyl transition metal compound and a boron containing compound. 29. The method of any of claims 24 to 28, wherein the comonomer forms a catalyst complex. 30. The process according to any one of claims 24 to 29, wherein said olefin is ethylene, propylene, butylene and / or pentene. 31. The method according to any one of claims 24 to 30, wherein the aromatic compound is styrene. 32. The method according to any one of claims 24 to 31, wherein the amounts of monomers and stabilizing comonomers fed to the process are precisely defined.