KR20070098278A - omega;-ALKENYL ALUMINUM COMPOUND AND METHOD FOR PREPARING THEREOF - Google Patents

Abstract

A Ћ-alkenyl aluminum compound as co-catalyst is provided to increase physical properties including impact strength and tension strength and possibility of high density polyethylene without addition of comonomer. A Ћ-alkenyl aluminum compound represented by the formula(1) of AlR^1R^2_2 is provided, wherein R^1 is C4-C20 alkenyl and R^2 is hydrogen or C1-C8 alkyl group optionally substituted by halogen atom. The Ћ-alkenyl aluminum compound is prepared by reacting optionally substituted C4-C20 aliphatic alpha, Ћ-diene or cycloaliphatic diene and organic aluminum compound represented by the formula(2) of AlR^2_2X at 40-100 deg. C for 3-4 hours, wherein R^2 is C2-C10 alkyl group, and X is hydrogen or halogen atom.

Description

ω-alkenyl aluminum compound and method for preparing the same

1 is a ¹³ C NMR spectrum of a high density polyethylene prepared in Examples using the ω-alkenylaluminum compound of the present invention.

The present invention relates to a compound which can be used as a promoter in a method for producing high density polyethylene by polymerizing an ethylene monomer using a magnesium-supported Ziegler-Natta catalyst and a method for producing the same.

High-density polyethylene (HDPE) is composed of only carbon and hydrogen, and its components are simple. Due to the high molecular weight obtained by the conventional advanced catalyst technology, the mechanical and chemical properties of the final product are excellent. In order to control various physical properties of high density polyethylene, a second comonomer is added to ethylene during polymerization to supplement the properties required in the HDPE manufacturing process or the final product.

The method for producing such a high density polyethylene is to copolymerize ethylene and an alpha -olefin having a minor carbon number of 4 or more as a minor component using a general Ziegler-Natta catalyst. However, commercially available magnesium-supported Ziegler-Natta catalysts have a low comonomer conversion for α-olefins having 4 or more carbon atoms, and the comonomers remain in a substrate such as hexane, thus producing products of different grades as in a continuous process. There is a problem of falling cost and efficiency.

The present inventors have conducted research to solve the above problems of the prior art, and as a result, have developed a promoter capable of improving the physical properties and processability of the conventional high density polyethylene.

Accordingly, an object of the present invention is to provide a cocatalyst that can dramatically increase the impact strength and tensile strength without adding a comonomer to improve the conventional physical properties and processability in the production of high density polyethylene.

Another object of the present invention is to provide a method for producing the cocatalyst.

In order to achieve the above object of the present invention, the present invention provides a ω-alkenylaluminum compound of formula 1:

[Formula 1]

AlR ¹ R ² ₂

In Chemical Formula 1,

R ¹ is alkenyl having 4 to 20 carbon atoms, R ² is the same or different, hydrogen or an alkyl group having 1 to 8 carbon atoms having no substituent or substituted with a halogen element.

In order to achieve the above another object of the present invention, the present invention comprises the step of reacting a substituted or unsubstituted aliphatic α, ω-diene or cycloaliphatic diene having 4 to 20 carbon atoms of the main chain and the organoaluminum compound of formula (2) Provided is a method for preparing the ω-alkenylaluminum compound of Formula 1.

[Formula 2]

AlR ² ₂ X

In the above formula, R ² is the same or different and is an alkyl group having 2 to 10 carbon atoms, and X is hydrogen or a halogen atom.

In the method of the present invention, the diene and the organoaluminum compound of Formula 2 may be reacted in a molar ratio of 10: 1 to 20: 1.

In the method of the present invention, the diene and the organoaluminum compound of Chemical Formula 2 may be reacted at a temperature of 40 to 100 ° C. for 3 to 4 hours.

In the method of the present invention, the diene and the organoaluminum compound of Formula 2 may be reacted, and then the unreacted diene may be separated by vacuum extraction.

In the method of the present invention, the diene is 1,3-butadiene, 1,4-pentadiene, 1-acetoxy-1,3-butadiene, 1,3-butadiene dioxide, cis, cis-1,5- Cyclooctadiene, trans, trans-1,4-diphenyl-1,3-butadiene, 1,3-hexadiene, 3-methyl-1,2-butadiene, trans-2-methyl-1,3-pentadiene , Hexachloro-1,3-butadiene, dicyclopentadiene, 1,9-decadiene, 2-methyl-1,4-pentadiene, bicyclo (2,2,1) hepta-2,5-diene, 1,4-cyclohexadiene, 2,4-dimethyl-1,3-pentadiene, butadiene monooxide, 1,5-hexadiene, 1,4-hexadiene, 1,7-octadiene bicyclo (2, 2,1) hepta-2,5-diene, cis-1,3-pentadiene, trans-1,3-pentadiene, 1,4-pentadiene, 1,2,3,4,5-pentamethylcyclo Pentadiene, 2,3-dimethyl-1,3-butadiene, 1,5-cyclooctadiene, bicyclo (4,3,0) nona-3,6-diene, 1,3-cycloheptadiene, 1, 1,4,4-tetraphenyl-1,3-butadiene, 1,2-butadiene, 5,5-dimeth Oxy-1,2,3,4-tetrachlorocyclo-pentadiene, trans-1-methoxy-3- (trimethylsiloxy), 1,2,3,4,5-pentamethylcyclopentadiene, 1- Methoxy-1,4-cyclohexadiene, 1-methoxy-1,3-cyclohexadiene, 1- (trimethylsiloxy) -1,3-butadiene, 1,5-cyclooctadiene, 3,3, 6,6-tetramethoxy-1,4-cyclohexadiene, 1,6-heptadiene, 1,8-nonadiene, 1-methyl-1,4-cyclohexadiene, 3-methyl-1,4- Any one selected from the group consisting of pentadiene, cis, cis-1,3-cyclooctadiene, 2,3-dimethoxy-1,3-butadiene, and trans-2-methyl-1,3-pentadiene Can be.

According to the ω-alkenylaluminum compound of the present invention and a method for producing the same, it is possible to obtain a high-density polyethylene that is significantly improved in impact strength and tensile strength without changing the conventional high-density polyethylene manufacturing process.

Hereinafter, the present invention will be described in detail.

One aspect of the invention relates to the ω-alkenylaluminum compound of formula 1:

[Formula 1]

AlR ¹ R ² ₂

In Chemical Formula 1,

R ¹ is alkenyl having 4 to 20 carbon atoms, R ² is the same or different, hydrogen or an alkyl group having 1 to 8 carbon atoms having no substituent or substituted with a halogen element.

The ω-alkenylaluminum compound of Chemical Formula 1 according to the present invention can be used as a co-catalyst in a method for producing high density polyethylene by polymerizing an ethylene monomer using a magnesium-supported Ziegler-Natta catalyst.

The ω-alkenylaluminum compound of Formula 1 not only acts as a promoter for activating the magnesium-supported Ziegler-Natta catalyst, but also serves to provide a comonomer for ethylene, thereby dramatically improving the physical region of the high density polyethylene. That is, when the conventional comonomer is added separately, the conversion rate of the comonomer is low, so that high density polyethylene production cost is high. However, by using the ω-alkenylaluminum compound according to the present invention, a high density of high strength is achieved even in a small amount corresponding to the catalytic amount. Polyethylene can be obtained. This effect is that the ω-alkenylaluminum compound activates the main catalyst as a co-catalyst, and the ethylene monomer reacts at the active point. At this time, since the double bond is present in the alkenylaluminum compound, the monomer is grown at the stage of growth of the main chain. It is thought that this is because it is inserted into the catalytic active point prior to phosphorus ethylene and serves as a tie-molecule that connects each crystal structure without being included in the crystal region forming the density of polyethylene.

Another aspect of the present invention is the ω-alkenyl of the formula (1) comprising the step of reacting a substituted or unsubstituted aliphatic α, ω-diene or cycloaliphatic diene having 4 to 20 carbon atoms in the main chain and the organoaluminum compound of formula (2) It relates to a process for preparing an aluminum compound:

[Formula 2]

AlR ² ₂ X

In the above formula, R ² is the same or different and is an alkyl group having 2 to 10 carbon atoms, and X is hydrogen or a halogen atom.

The diene and the organoaluminum compound of Chemical Formula 2 may be reacted in a ratio of 10: 1 to 20: 1. Too much of the diene compound outside the above range may cause a cyclolation reaction. Too much of the diene compound may cause all of the alkyl groups to be substituted, thereby weakening the role of the promoter. At this time it may be reacted for 3 to 4 hours at a temperature of 40 to 100 ℃ and unreacted diene can be separated by vacuum extraction.

In preparing the ω-alkenylaluminum compound according to the present invention, the reaction between the organoaluminum compound and the diene is preferably performed in the absence of any medium, and is preferably 40 to 100 ° C, preferably 50 to 90 ° C, Is reacted for about 3 to 4 hours, preferably 2 to 3 hours at a temperature of 60 ~ 80 ℃. After the reaction time, the unreacted diene is preferably separated by vacuum extraction. In addition, in order to prevent the by-products caused by the abnormal reaction, it is preferable to block the reactor from the outside, and in some cases, it is preferable to react the reaction under nitrogen under normal pressure when using a glass-based reactor.

When the diene compound has a substituent, the substituent may be a halogen atom, an oxy group, an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkylsiloxy having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms.

Specific examples of the diene compound include 1,3-butadiene, 1,4-pentadiene, 1-acetoxy-1,3-butadiene, 1,3-butadiene dioxide, cis, cis-1,5-cyclooctadiene , Trans, trans-1,4-diphenyl-1,3-butadiene, 1,3-hexadiene, 3-methyl-1,2-butadiene, trans-2-methyl-1,3-pentadiene, hexachloro -1,3-butadiene, dicyclopentadiene, 1,9-decadiene, 2-methyl-1,4-pentadiene, bicyclo (2,2,1) hepta-2,5-diene, 1,4 -Cyclohexadiene, 2,4-dimethyl-1,3-pentadiene, butadiene monoxide, 1,5-hexadiene, 1,4-hexadiene, 1,7-octadiene bicyclo (2,2,1 ) Hepta-2,5-diene, cis-1,3-pentadiene, trans-1,3-pentadiene, 1,4-pentadiene, 1,2,3,4,5-pentamethylcyclopentadiene, 2,3-dimethyl-1,3-butadiene, 1,5-cyclooctadiene, bicyclo (4,3,0) nona-3,6-diene, 1,3-cycloheptadiene, 1,1,4 , 4-tetraphenyl-1,3-butadiene, 1,2-butadiene, 5,5-dimethock Ci-1,2,3,4-tetrachlorocyclo-pentadiene, trans-1-methoxy-3- (trimethylsiloxy), 1,2,3,4,5-pentamethylcyclopentadiene, 1- Methoxy-1,4-cyclohexadiene, 1-methoxy-1,3-cyclohexadiene, 1- (trimethylsiloxy) -1,3-butadiene, 1,5-cyclooctadiene, 3,3, 6,6-tetramethoxy-1,4-cyclohexadiene, 1,6-heptadiene, 1,8-nonadiene, 1-methyl-1,4-cyclohexadiene, 3-methyl-1,4- Any one selected from the group consisting of pentadiene, cis, cis-1,3-cyclooctadiene, 2,3-dimethoxy-1,3-butadiene, and trans-2-methyl-1,3-pentadiene Can be.

As described above, the ω-alkenylaluminum compound of Chemical Formula 1 according to the present invention may be used as a co-catalyst in a method of preparing high density polyethylene by polymerizing ethylene monomer using a magnesium-supported Ziegler-Natta catalyst. More specifically, the ω-alkenylaluminum of formula 1 according to the present invention is reacted with a magnesium-supported Ziegler-Natta catalyst, and then it is introduced into an ethylene polymerization reactor to prepare high density polyethylene.

The magnesium-supported Ziegler-Natta catalyst is generally used in the preparation of polyolefins, and is not particularly limited. The magnesium-supported Ziegler-Natta catalyst may be prepared by contacting a solid anhydrous magnesium support with a titanium compound represented by the following Chemical Formula 3 in a nonpolar solvent.

[Formula 3]

Ti (OR ³ ) _ℓ X _4-ℓ

In Chemical Formula 3,

R ³ is the same or different and is an alkyl group having 1 to 10 carbon atoms, X is a halogen element, and 1 is an integer of 0 to 4;

At this time, magnesium halide may be used as the magnesium carrier, and magnesium halides such as magnesium chloride, magnesium iodide, magnesium fluoride or magnesium bromide; Alkylmagnesium halides such as methyl magnesium halide, ethyl magnesium halide, propyl magnesium halide, butyl magnesium halide, isobutyl magnesium halide, hexyl magnesium halide or amyl magnesium halide and the like; Alkoxymagnesium halides such as methoxy magnesium halide, ethoxy magnesium halide, isopropoxy magnesium halide, butoxy magnesium halide or octoxy magnesium halide; An aryloxymagnesium halide such as phenoxy magnesium halide or methylphenoxy magnesium halide is exemplified. Mixtures of two or more of the magnesium halides may also be used. In addition, the magnesium halide is effective even when used in the form of a complex with another metal.

The solvent used in the preparation of the catalyst is a nonpolar solvent, and even if it is polar, it can also be used provided that it does not involve chemical reaction with the compounds and reactants used in the synthesis of the catalyst.

In addition, the compounds used in the preparation of the catalysts should be substances that are soluble in liquids or nonpolar solvents, at least partially soluble and liquid at the temperatures used for preparing the catalysts. Preferred examples of the nonpolar solvent are isobutane, pentane, hexane, n-heptane, octane, nonane, decane and isomers thereof, and alicyclic compounds such as cyclohexane, and aromatic compounds such as benzene, toluene and ethylbenzene can also be used. have. The most commonly used nonpolar solvent is hexane. Nonpolar solvents should be purified and used in a suitable manner to remove substances that affect catalytic activity, such as water, oxygen, and polar compounds.

In Formula 3, R ³ is preferably an alkyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms, preferably X is Br, Cl, and more preferably Cl. L is an integer of 0-4. Most preferred titanium compounds of formula (3) are titanium tetrachloride or chlorinated titanium oxide.

The titanium compound may be added to the slurry by itself, but is preferably added in a dissolved state in a suitable solvent such as a nonpolar solvent to form a slurry of the support. The particle size of the solid anhydrous magnesium support is 0.1 to 200㎛, preferably 10 to 150㎛ can be used. The shape of the carrier is in the form of spherical fine particles, preferably anhydrous magnesium chloride having a water content of less than 1.0%.

 The amount of the titanium compound represented by Formula 3 is used in an amount of 1: 1 to 20, preferably 1: 1 to 10, in molar ratio with respect to the anhydrous magnesium carrier.

In the contact reaction between the magnesium-supported Ziegler-Natta catalyst and ω-alkenyl aluminum prepared in the same manner as described above, the titanium solid complex is dried on the support containing magnesium at no substrate. Drying temperature is 30-100 degreeC, Preferably it is 50-80 degreeC. The drying time is preferably at least 1 hour and preferably 1 to 3 hours. Further vacuum drying is performed here. Vacuum drying time is at least 1 hour. Ω-alkenylaluminum is added to the dried solid complex catalyst. In this case, the molar ratio of titanium in the aluminum / solid complex is 20: 1 to 40: 1, and the reaction is preferably performed at a contact reaction temperature of 60 to 90 ° C for about 1 hour.

The catalyst prepared above is placed in an ethylene polymerization reactor, and then 30 to 50 psi of hydrogen is injected, the temperature of the reactor is maintained at 80 to 85 ° C., and the ethylene pressure is adjusted to 115 to 120 psi to prepare high density polyethylene.

The present invention will be described in more detail with reference to the following examples. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Example

The organic reagents and solvents needed for catalyst preparation and polymerization were purified by standard methods from Aldrich, and hydrogen and ethylene were used after passing through a water and oxygen filtration device. Air was used at all stages of catalyst preparation and polymerization. It proceeded by blocking the contact with water.

Apparent density was measured using an apparent tester (Apparent Density Tester 1132, manufactured by APT Institute fr Prftechnik) by the method defined in DIN 53466 and ISO R 60.

The melt index (MI) of the polymer was measured by ASTM D-1238 (conditions E, F, 190 ° C), and the value measured by condition E was I ₂ and the value measured by condition F was I ₂₁ . Notation.

Example  One

(1) Preparation of magnesium-supported Ziegler-Natta catalyst

In a 2-liter Buchi reactor dried with nitrogen, 34 g of anhydrous magnesium chloride (more than 99% by weight, less than 1% water) were placed in the same reactor with 600 ml of purified hexane having a water content of less than 0.5 ppm. 200 ml of TiCl ₄ was slowly added to the solution at a speed of 200 rpm at a temperature of 35 ° C. for 1 hour, followed by further stirring for 1 hour. In this process, a solid material was formed, and the prepared solid material was precipitated, and then the liquid portion was removed, and washed several times with hexane until the titanium concentration of the washing liquid became 0.5 mmol or less. Purified hexane was added to bring the total volume to 1 liter to complete the final catalyst.

(2) Preparation of ω-octenyldiisobutyl aluminum compound

A 1 liter reactor with a magnetic bar was replaced with a nitrogen atmosphere, 500 ml of 1,7-octadiene was added, and 60 ml of diisoaluminum hydride was added thereto, and the temperature was raised to 80 ° C., followed by reaction for 2 hours. After the reaction, the solution was cooled to room temperature, and then unreacted 1,7-octadiene was removed using a vacuum.

(3) 7-octenyl diisobutylaluminum treatment of magnesium-supported Ziegler-Natta catalyst

0.7 g of the magnesium-supported Ziegler-Natta catalyst prepared in (1) in a slurry solution in n-hexane was put in a Schlenk flask containing 100 ml of magnetic bar, dried at 90 ° C., and vacuum-dried for about 1 hour. The 7-octenyldiisoaluminum obtained in 2) was added dropwise to the aluminum / titanium molar ratio of 20: 1, and then reacted at about 90 ° C. for 10 hours in a nitrogen atmosphere. Then 10 ml of n-hexane was added as a substrate.

(4) ethylene polymerization

A 20 liter CSTR reactor was subjected to alternating nitrogen and vacuum five times to make the interior of the reactor a nitrogen atmosphere. After injecting 15000 ml of n-hexane into the reactor, 1.16 mmol of the catalyst prepared in (3) was injected on a titanium atom basis, and about 2500 ml of hydrogen was injected. The temperature of the reactor was raised to 80 ° C. while the stirrer was rotated at 700 rpm and the ethylene pressure was adjusted to about 100 psi, followed by polymerization for 2 hours. After the polymerization was completed, the temperature of the reactor was lowered to room temperature, an excess methanol solution was added to the polymer, and the polymer was separated and collected, and dried in a vacuum oven at 60 ° C. for at least 6 hours to obtain a white powder polyethylene.

Figure 1 is a 125.65MHz ¹³ C NMR spectrum obtained for TiCl ₄ / Mg (OEt) ₂ -alkenyl Al-Et ₃ Al of the polyethylene prepared above, it can be seen that octenyl is present.

Comparative example  One

A 20 liter CSTR reactor was subjected to alternating nitrogen and vacuum five times to make the interior of the reactor a nitrogen atmosphere. After injecting 15000 ml of n-hexane into the reactor, 1.16 mmol of the catalyst was injected based on titanium atoms, and about 2500 ml of hydrogen was injected. While rotating the stirrer at 700 rpm, the temperature of the reactor was increased to 80 ° C., the ethylene pressure was adjusted to about 100 psi, and the polymerization was carried out by injecting butene into the comonomer at about 10% (about 10 psi) of ethylene partial pressure for 2 hours. Was carried out. After the polymerization was completed, the temperature of the reactor was lowered to room temperature, an excess methanol solution was added to the polymer, and the polymer was separated and collected, and dried in a vacuum oven at 60 ° C. for at least 6 hours to obtain an ethylene butylene copolymer of white powder.

The physical properties of the high density polyethylene prepared in Example 1 and Comparative Example 1 are shown in Table 1 below.

TABLE 1

Evaluation item unit Example 1 Comparative Example 1 density g / cm3 0.9591 0.9502 MI (2.16 / 5.0g) g / 10min 1.3 / 3.8 2.0 / 5.8 Melting point ℃ 133 131 Mn Mw PDI (Mw / Mn) g / mol 17,260 124,300 7.2 16,750 106,100 6.3 Yield strength educator Kg / cm2% 318> 1000 283> 1000 Izod impact strength 23 ℃ / -30 ℃ kg / cm2 65 (NB) / 59 (NB) 14/10 ESCR (F50) FNCT hr 5 8 13 10 Flexural modulus strength Kg / cm2 14000 277 11500 237 HDT ℃ 73.2 70.0 Shore d 61 58 Oxidation induction time (OIT) min 51 11

As can be seen in Table 1, the polyethylene produced by the method of the present invention can be seen that the strength is much superior to the polyethylene produced by the conventional method while maintaining the density.

So far I looked at the center of the preferred embodiment for the present invention. Those skilled in the art will appreciate that the present invention can be implemented in a modified form without departing from the essential features of the present invention. Therefore, the disclosed embodiments should be considered in descriptive sense only and not for purposes of limitation. The scope of the present invention is shown not in the above description but in the claims, and all differences within the scope will be construed as being included in the present invention.

As described above, according to the present invention, by using the ω-alkenylaluminum promoter without adding a separate comonomer, the strength of the high density polyethylene can be remarkably improved, so that the high density polyethylene can be obtained advantageously in terms of cost and efficiency. have.

Claims (6)

Ω-alkenylaluminum compounds of formula 1: [Formula 1] AlR ¹ R ² ₂ In Chemical Formula 1, R ¹ is alkenyl having 4 to 20 carbon atoms, R ² is the same or different, hydrogen or an alkyl group having 1 to 8 carbon atoms having no substituent or substituted with a halogen element. A method for preparing the ω-alkenylaluminum compound of Chemical Formula 1, comprising reacting a substituted or unsubstituted aliphatic α, ω-diene or cycloaliphatic diene having 4 to 20 carbon atoms in a main chain with an organoaluminum compound of Formula 2: [Formula 2] AlR ² ₂ X In the above formula, R ² is the same or different and is an alkyl group having 2 to 10 carbon atoms, and X is hydrogen or a halogen atom. The method of claim 2, The diene and the organoaluminum compound represented by Chemical Formula 2 may be reacted at a molar ratio of 10: 1 to 20: 1. The method of claim 2, The diene and the organoaluminum compound of Formula 2 are reacted for 3 to 4 hours at a temperature of 40 to 100 ℃. The method of claim 2, Reacting the diene and the organoaluminum compound of Formula 2 and then separating the unreacted diene by vacuum extraction. The method of claim 2, The diene is 1,3-butadiene, 1,4-pentadiene, 1-acetoxy-1,3-butadiene, 1,3-butadiene dioxide, cis, cis-1,5-cyclooctadiene, trans, trans -1,4-diphenyl-1,3-butadiene, 1,3-hexadiene, 3-methyl-1,2-butadiene, trans-2-methyl-1,3-pentadiene, hexachloro-1,3 -Butadiene, dicyclopentadiene, 1,9-decadiene, 2-methyl-1,4-pentadiene, bicyclo (2,2,1) hepta-2,5-diene, 1,4-cyclohexadiene , 2,4-dimethyl-1,3-pentadiene, butadiene monoxide, 1,5-hexadiene, 1,4-hexadiene, 1,7-octadiene bicyclo (2,2,1) hepta-2 , 5-diene, cis-1,3-pentadiene, trans-1,3-pentadiene, 1,4-pentadiene, 1,2,3,4,5-pentamethylcyclopentadiene, 2,3 -Dimethyl-1,3-butadiene, 1,5-cyclooctadiene, bicyclo (4,3,0) nona-3,6-diene, 1,3-cycloheptadiene, 1,1,4,4- Tetraphenyl-1,3-butadiene, 1,2-butadiene, 5,5-dimethoxy-1,2,3,4-tetrachloro Ecyclo-pentadiene, trans-1-methoxy-3- (trimethylsiloxy), 1,2,3,4,5-pentamethylcyclopentadiene, 1-methoxy-1,4-cyclohexadiene, 1-methoxy-1,3-cyclohexadiene, 1- (trimethylsiloxy) -1,3-butadiene, 1,5-cyclooctadiene, 3,3,6,6-tetramethoxy-1,4 -Cyclohexadiene, 1,6-heptadiene, 1,8-nonadiene, 1-methyl-1,4-cyclohexadiene, 3-methyl-1,4-pentadiene, cis, cis-1,3- And cyclooctadiene, 2,3-dimethoxy-1,3-butadiene, and trans-2-methyl-1,3-pentadiene.

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