WO2001081292A1 - Derives de diester phtalique et donneurs d'electrons - Google Patents
Derives de diester phtalique et donneurs d'electrons Download PDFInfo
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- WO2001081292A1 WO2001081292A1 PCT/JP2001/003460 JP0103460W WO0181292A1 WO 2001081292 A1 WO2001081292 A1 WO 2001081292A1 JP 0103460 W JP0103460 W JP 0103460W WO 0181292 A1 WO0181292 A1 WO 0181292A1
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- butyl
- phthalate
- tert
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- polymerization
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic acid esters
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- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Definitions
- the present invention relates to an electron donor for a catalyst for polymerization of olefins, a plasticizer for resins such as vinyl chloride, a novel diester derivative of phthalate which can be used as an intermediate compound of various compounds, and an active ingredient containing the same.
- the present invention relates to an electron donor used for a catalyst for polymerization of olefins. Background art
- phthalic acid diesters have been widely used as plasticizers for vinyl chloride, and getyl phthalate, dibutyl phthalate, and diisooctyl phthalate are typical.
- a propylene-based olefin is subjected to a polymerization reaction in the presence of a solid catalyst component containing magnesium and titanium as main components, the above-mentioned olefins are used to improve the stereoregularity and polymerization activity of the produced polymer.
- Many proposals have been made to use specific phthalate esters as electron donors (internal electron donors) contained in solid catalyst components.
- 1-2006 discloses a solid catalyst component for the polymerization of olefins containing alkoxymagnesium, titanium tetrachloride and dibutyl phthalate. Polymerization of propylene in the presence of this solid catalyst component is disclosed. As a result, a stereoregular polymer is obtained in high yield, and the effect is somewhat improved.
- polymers obtained using the above-mentioned catalysts are used for various applications such as containers and films, in addition to molded products such as automobiles and home electric appliances. These are formed by melting polymer powder produced by polymerization and molding by various molding machines. In particular, when manufacturing large molded products by injection molding, etc., the fluidity (melt flow rate) of the molten polymer ) May be required, and much research has been done to increase the melt flow rate of the polymer.
- Melt flow rate is highly dependent on the molecular weight of the polymer.
- hydrogen as a molecular weight regulator for the resulting polymer in the polymerization of olefins.
- a large amount of hydrogen is usually added, but the pressure resistance of the reactor is limited due to its safety.
- the partial pressure of the monomer to be polymerized must be reduced, and in this case, the productivity is reduced.
- the use of a large amount of hydrogen causes a cost problem.
- an object of the present invention is to provide a catalyst capable of obtaining a highly stereoregular polymer with extremely high activity or yield, and a high response to hydrogen.
- a novel phthalic acid diester derivative that exhibits excellent usefulness as a catalyst, especially a catalyst for the polymerization of olefins such as propylene or ethylene, and a catalyst for the polymerization of olefins containing this as an active ingredient
- olefins such as propylene or ethylene
- the present inventors have conducted intensive studies on a catalyst for polymerization of olefins in order to solve the problems left in the prior art, and as a result, have found that an electron donor which is one of the components forming the catalyst.
- the present inventors have found a novel phthalic acid diester derivative that can be used for the above-mentioned method and that can act very effectively, and confirmed the effects thereof, thereby completing the present invention.
- the phthalic acid diester derivative according to the present invention for achieving the above object has the following general formula (1):
- R 1 represents an alkyl group having 1 to 8 carbon atoms or a halogen atom
- R 2 and R 3 represent an alkyl group having 1 to 12 carbon atoms, and even if R 2 and R 3 are the same
- the number n of the substituent R 1 is 1 or 2, and when n is 2, R 1 may be the same or different.
- the electron donor used as a catalyst for polymerization of olefins according to the present invention is characterized by containing a phthalic acid diester derivative represented by the general formula (1) as an active ingredient.
- a phthalic acid diester derivative represented by the general formula (1) as the alkyl group having 1 to 8 carbon atoms for R 1 , specifically, a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, isoptinole group, tert-butynole group, n-pentynole group, isopentyl group, neopentynole group, n-hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2 , 2-dimethylpentyl, isooctyl, and 2,2-dimethylhexyl.
- the halogen atom of R 1 is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- Preferred groups for R 1 are a methyl group, an ethyl group, a tert-butyl group, a chlorine atom, a fluorine atom, and a bromine atom, and particularly preferably a methyl group, a t.rt-butyl group, a chlorine atom, a fluorine atom, and It is a bromine atom.
- R 2 and R 3 are methyl, ethyl, n-propyl, isopropyl, n-butynole, isoptinole, tert-butyl, n-pentyl, isopentinole, neopentynole, n-hexyl, Isohexyl, 2,2-dimethylbutyl, 2,2-dimethylpentyl, or isooctyl, 2,2-dimethylhexyl, n-nonyl, isononyl, n-decyl, isodecyl , N- is a dodecyl group.
- an ethyl / butyl group, n -butyl group, isobutyl group, tert-butyl group, neopentyl group, isohexyl group and isooctyl group are preferred, and an ethyl group, n-butyl group, neopentyl group and isohexyl group are preferred.
- the groups are particularly preferred.
- the number n of the substituent R 1 is 1 or 2, and when n is 2, R 1 may be the same or different.
- R 1 When n is 1, R 1 is replaced with a hydrogen atom at the 3-, 4-, or 5-position of the phthalic acid diester derivative of the general formula (1), and when n is 2, R 1 is Substitutes hydrogen atoms at the 4- and 5-positions. .
- n is S 1 or 2
- R 1 is an alkyl group having 1 to 5 carbon atoms or a halogen atom
- R 2 and R 3 are alkyl groups having 4 to 8 carbon atoms having a tertiary carbon. Compounds are preferred.
- n is 1 or 2
- R 1 is an alkyl group having 1 to 5 carbon atoms or a halogen atom
- R 2 and R 3 are carbon atoms having a tertiary carbon.
- particularly preferred compounds are dineopentyl 4-methylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentylolene 4-phthylphthalate, dineopentylone 4,5-gethinolephthalenolate, and dineopentyl 4-promophthalate. , 3-Denopentyl phthalolelophthalate, 4-tert-butyl phthalate / dineopentyl oleate / le.
- n 2
- one of R 1 is a halogen atom
- the other is an alkyl group having 1 to 8 carbon atoms
- R 2 and R 3 If at least one is an alkyl group having 1 to 12 carbon atoms other than an alkyl group having 4 to 8 carbon atoms having a tertiary carbon, 4-methyl-5- Jethyl chlorophthalate, 4-Methyl-5-bromoethyl phthalate, 4-Ethinole-5-chloromouth phthalenolate, 4-Ethynolee 5-Brethyl phthalate, 4-Methyl-5-chlorophthalate di-n-butyl, 4-Methinole 5-Promophthalenoleic acid di-n-butyl, 4-ethynole-5-chloro mouth phthalenoleic acid n-butyl / le, 4-ethylinole-5-bromophthalenoic acid di-n-butyn
- R 2 and R 3 When only one of the groups is an alkyl group having 4 to 8 carbon atoms having a tertiary carbon, a specific compound is 3-ethylethyl phthalate-tert-butyl, 4-methylethyl phthalate-tert-butyl, 3-ethyl phthalate Tert-butyl ethynole-tert-butyl, tert-butyl 4-ethyl phthalate, tert-butyl 4,5-dimethynolephthalanolate tert-butyl, tert-butyl 4,5-ethyl phthalenolate tert-butyl, 4-methyl-15 —Ethylphthalic acid tert-butyl, 4-ethyl-5-methylethyl phthalate-tert-butynole, 4-methylinole-5-chloroethynyl phthalinoleate tert-butylin
- n is 1 or 2
- R 1 is an alkyl group having 6 to 8 carbon atoms
- both R 2 and R 3 have 4 to 8 carbon atoms having a tertiary carbon.
- the compound is an alkyl group of the formula: di-tert-butyl 4-n-hexylphthalate, di-tert-butyl 4-isohexylphthalate, 4- (2,2-dimethylbutyl) phthalic acid Di-tert-butynole, 4- (2,2-dimethinolepentyl) phthalenolate di-tert-butynole, iso-otatinolephthalenolate di-tert-butinole, 4-n-hexinole-5-cyclobutanephthalate Di-tert-butynole, 4-n-hexynole-5-bromophthalenoleic acid di-tert-butylinole, 4-isohexynole-5 monoch
- Preferred compounds among these compounds are getyl 4-methyl phthalate, di-n-butyl 4-methyl phthalate, diisobutyl 4-methyl phthalate, diisohexyl 4-methyl phthalate, diisooctynole 4-methyl phthalate, and getyl 4-ethyl phthalate Di-n-butyl 4-ethyl phthalate, di-isobutyl 4-ethyl phthalate, di-hexyl 4-ethyl phthalate, di-octyl 4-ethyl phthalate, di-n-butyl 4-tert-butyl phthalate, di-n-butyl 4-tert-butylinolephthalate, 4-tert-butylphthalenolate diisobutyl, 4-tert-butyl diisohexyl / phthalate, 4-tert-butyl / diisooctyl phthalate / dimethyl phthalate, 4,5-di
- n is 1 or 2
- R 1 is a halogen atom
- at least one of R 2 and R 3 has 1 to 1 carbon atoms other than a C 4 to C 8 alkyl group having a tertiary carbon.
- the compound is an alkyl group of 2
- the following compounds can be used: 3-ethylphenol phthalonophthalophthalate, 4-ethylethyl phthalate, 3-chloroethylenolate, 4-chloroethylenophthalate, 3-ethylethyl phthalate , 4-Jetyl bromophthalate, 3-Ethyl phthalate, 4-Ethyl phthalate, 4,5-Dichlorophthalic acid, 4,5-Diethyl phthalene phthalate, 4-Chloro-5-bromophthalene oleate Detinore, 3-n-Phinoolenophthalanole-n-Putinole, 4-N-Phenole
- preferred compounds are dimethyl ethyl 4-bromophthalate, di- n -butyl 4-bromophthalenolate, diisobutyl 4-bromophthalate, dimethyl ethyl 4-phthalate, di-n-butyl 4-chlorophthalate, and di-butyl 4-chlorophthalate.
- the phthalic acid diester derivative of the present invention is useful as an electron donor for catalysts for polymerization of various olefins. That is, it can be used as a homopolymerization or copolymerization electron donor such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-11-pentene and butylcyclohexane, and particularly homopolymerization of ethylene or propylene, or It is suitable as an electron donor for a catalyst for copolymerization of ethylene and propylene, and more preferably as an electron donor for a homopolymerization of propylene or a catalyst for copolymerization with ethylene.
- the phthalic acid diester derivative of the present invention can be prepared by various methods.
- ester synthesis is well known, and is described in detail, for example, in “Experimental Chemistry Course” (4th edition: Volume 22). Here are some examples.
- the most common ester synthesis method utilizes the dehydration reaction of carboxylic acid and alcohol. At this time, a mineral acid such as hydrochloric acid or sulfuric acid or a base such as triethylamine may be used as a catalyst.
- ester synthesis using a dehydrating agent is well known.
- dicyclohexyl carbodiimide trifluoroacetic anhydride is used as a dehydrating agent.
- a synthesis method using a carboxylic anhydride instead of carboxylic acid is known.
- a method of synthesizing from an acid halide is also known, and is often used particularly for esterification of a carboxylic acid having low reactivity due to steric hindrance or the like.
- an intermediate which is called a monoester or a half ester, is then esterified directly, or further via an acid halide.
- a method of synthesizing a gesture is also known. The synthesis method described here may be used, or another known method may be used.
- a specific method for synthesizing 4-neophthalic acid dineopentyl is to introduce 4-methylphthalic acid and neopentyl alcohol into a flask and reflux for 2 hours in the presence of sulfuric acid. After completion of the reaction, the mixture is cooled to room temperature, distilled water and ether are added, and the product is extracted into an ether layer. After repeating the washing operation of the ether layer by flushing, the aqueous layer is neutralized by adding an aqueous solution of sodium hydrogen carbonate. After adding saline and repeating the washing operation with distilled water, sodium sulfate is added to the ether layer, followed by filtration. After removing the ether contained in the obtained filtrate by vacuum distillation, vacuum distillation is performed again to obtain a yellow liquid. Cooling and recrystallization with ethanol are performed to obtain white crystals.
- the phthalic acid diester derivative according to the present invention is used as an electron donor, which is a component of a catalyst system for olebuin polymerization, the polymerization activity and the yield of a highly stereoregular polymer can be improved as compared with conventionally known high performance catalysts. In addition, the response to hydrogen is significantly improved.
- a flushing operation was performed by adding 15 Oml of a 5% aqueous sodium bicarbonate solution, and as a result, the aqueous layer showed a pH value of 7 to 8.
- the mixture was washed with 30 Oml of saturated saline, and further washed with 15 Oml of distilled water.
- the ether layer (upper layer) was transferred to an Erlenmeyer flask, and dehydrated using anhydrous sodium sulfate. Ether was removed by distillation under reduced pressure, and distillation under reduced pressure was performed. At a top temperature of about 190 ° C, a yellow viscous liquid, 13.Og, was obtained.
- MS used a measuring device Finigan Mat (GC-MS)
- 1 H-NMR used a measuring device JEOL GSX270
- the measuring solvent was CDC13.
- Raman spectroscopy was performed using a measuring device JEOL RFT800.
- a flushing operation was performed by adding 25 Oml of a 5% aqueous sodium hydrogen carbonate solution, and as a result, the pH value of the aqueous layer was 7 to 8.
- the mixture was washed with 30 Oml of a saturated saline solution, and further washed with 15 Oml of distilled water.
- the ether layer (upper layer) was transferred to an Erlenmeyer flask, and dehydrated using anhydrous sodium sulfate. Ether was removed by distillation under reduced pressure, and distillation was performed under reduced pressure. At a top temperature of about 170 ° C, 61.9 g of a pale yellow viscous liquid was obtained.
- the H value of the aqueous layer was 7 to 8.
- the plate was washed with 150 ml of a saturated saline solution, and further washed with 150 ml of distilled water.
- the ether layer (upper layer) was transferred to an Erlenmeyer flask, and dehydrated using anhydrous sodium sulfate. Ether was removed by distillation under reduced pressure, and distillation under reduced pressure was performed. At a top temperature of about 150 ⁇ , 15.3 g of a yellow viscous liquid was obtained.
- the operation of removing the aqueous layer was repeated three times.
- a flushing operation was performed with 20 Oml of a 5% aqueous solution of sodium hydrogencarbonate, and the DH value of the aqueous layer was 7 to 8 as a result.
- the mixture was washed with 20 Oml of saturated saline, and further washed with 150 ml of distilled water.
- the ether layer (upper layer) was transferred to a triangular flask, and dehydrated using anhydrous sodium sulfate. Ether was removed by vacuum distillation, and vacuum distillation was further performed.
- the reaction mixture was washed three times with 10 Oml of toluene at 90 ° C, freshly added with 2 Oml of titanium tetrachloride and 8 Oml of toluene, heated to 110 ° C, and reacted with stirring for 1 hour. .
- the solid was washed seven times with 10-Oml of n-heptane at 40 ° C to obtain a solid catalyst component.
- the solid-liquid in the solid catalyst component was separated by filtration and dried, and the titanium content in the solid was measured to be 3.7% by weight.
- the weight (a) of the obtained polymer was 270.9 g, and when this polymer was extracted with boiling n-heptane for 6 hours, the polymer (b) insoluble in n-heptane was 26 It was 3.0 g, and the ratio of boiling n-heptane insolubles (hereinafter abbreviated as HI) in the polymer was 97.5% by weight.
- Used solid The polymerization activity per solid catalyst component was 60, 100 gZg.
- the value of the melt index (melt flow rate) of the polymer (a) (hereinafter abbreviated as MI) (measurement method conforms to ASTM D 1238, JIS K 7210) was 19 g / 10 min. .
- Example 2 To the suspension, instead of a solution of 3.5 g of dyneopentyl 4-methylphthalate dissolved in 3.5 ml of toluene, instead of a solution of 3.5 g of dyneopentyl 4-methylphthalate in 3.5 ml of toluene, dineopentyl 4-bromophthalate obtained in Example 2 was added.
- a solid catalyst component was prepared in the same manner as in Example 6 except that a solution in which 4.2 mg was dissolved was used, and further, a polymerization catalyst was formed and polymerization was performed.
- the titanium content in the obtained solid catalyst component was 2.9% by weight
- the polymerization activity per solid catalyst component was 60,800 gZg
- HI was 97.1% by weight
- Ml was 25 g / l Omin.
- Example 3 To the suspension, instead of a solution of 3.5 g of dyneopentyl 4-methylphthalate dissolved in 3.5 ml of toluene, instead of a solution of 3.5 g of toluene in 4.7 ml of toluene, the 3-fluorophthalic acid obtained in Example 3 was added.
- a solid catalyst component was prepared in the same manner as in Example 6 except that a solution in which 3.6 mg of dineopentyl was dissolved was used, and further, a polymerization catalyst was formed and polymerization was performed.
- the titanium content of the solid catalyst component content in the 3.2 wt%, polymerization activity 58 per solid catalyst component, OO 0 g / g, HI is 96.9 wt 0/0, MI is 1 8 gZ l 0 min.
- the results of these polymerizations are listed in Table 4.
- Example 9 (Hydrogen change test using the solid catalyst component of Example 6)
- Example 10 (Hydrogen change test using the solid catalyst component of Example 6)
- Example 11 Hydrophilicity change test using the solid catalyst component of Example 6
- Example 1 2 (Hydrogen change test using the solid catalyst component of Example 7)
- the experiment was performed in the same manner as in the polymerization of Example 7, except that 2.0 liters of hydrogen gas was charged instead of 2.0 liters of hydrogen gas during the polymerization.
- the polymerization activity per solid catalyst component was 50,100 g / g
- H I was 97.7% by weight
- M I was 9.5 g / 1 Omin.
- Table 4 shows the results of these polymerizations.
- Example 13 Hydrophilicity change test using the solid catalyst component of Example 7
- Example 14 (Hydrogen change test using the solid catalyst component of Example 7)
- a solid catalyst component was prepared in the same manner as in Example 6, except that 3.3 g of di-n-pentyl phthalate was used instead of 3.5 g of dineopentyl 4-methylphthalate. Polymerization was performed. As a result, the titanium content in the solid catalyst component was 2.6% by weight, the polymerization activity per solid catalyst component was 46,400 g / g, HI was 97.9% by weight, and MI was 10 g Z 1 Omin. The results of these polymerizations are listed in Table 4.
- a solid catalyst component was prepared in the same manner as in Example 6, except that 2.9 ml of di-n-butyl phthalate was used instead of 3.5 g of dineopentyl 4-methylphthalate, and further, formation of a polymerization catalyst and polymerization.
- the titanium content of the solid catalytic component is 3.0 wt%
- the polymerization activity per solid catalyst component 4 2, 4 0.0 g Roh g, HI 9 8.7 wt 0/0, MI is It was 6.6 g / 1 Omin. Table 4 shows the results of these polymerizations.
- a flushing operation was performed by adding 25% of a 5% aqueous sodium hydrogen carbonate solution, and as a result, the pH value of the aqueous layer was 7 to 8.
- the mixture was washed with 30 Oml of a saturated saline solution, and further washed with 15 Oml of distilled water.
- the ether layer (upper layer) was transferred to an Erlenmeyer flask, and dehydrated using anhydrous sodium sulfate. Ether was removed by distillation under reduced pressure, and distillation was performed under reduced pressure. Top temperature reaches approx. 170 ° C As a result, 61.9 g of a pale yellow viscous liquid was obtained.
- a flushing operation was performed by adding 200 ml of a 5% aqueous sodium hydrogen carbonate solution, and as a result, the pH value of the aqueous layer was 7 to 8.
- the resultant was washed with 20 Oml of saturated saline and further washed with 15 Oml of distilled water.
- the ether layer (upper layer) was transferred to an Erlenmeyer flask, and dehydrated using anhydrous sodium sulfate.
- Ether was removed by distillation under reduced pressure, and distillation was performed under reduced pressure.
- 20.5 g (yield 43.3%) of a yellow viscous liquid was obtained.
- the yellow liquid was di-n-butyl 4-tert-butylphthalate.
- Tables 1-3 The analytical values are shown in Tables 1-3.
- a flushing operation was performed by adding 20 Oml of a 5% aqueous sodium hydrogen carbonate solution, and as a result, the pH value of the aqueous layer was 7 to 8.
- the substrate was washed with 20 Oml of saturated saline, and further washed with 15 Oml of distilled water.
- the ether layer (upper layer) was transferred to an Erlenmeyer flask, and dehydrated using sodium sulfate anhydride. The ether was removed by vacuum distillation, and vacuum distillation was further performed. At a top temperature of about 170 ° C, 12.5 g (yield 37.5%) of a yellow viscous liquid was obtained. As a result of identification of this yellow liquid by the same analyzers as described above, it was confirmed that the yellow liquid was getyl 4-methylphthalate.
- the analytical values are shown in Tables 1-3.
- a flushing operation was performed by adding 20 Oml of a 5% aqueous sodium hydrogen carbonate solution, and as a result, the pH value of the aqueous layer was 7 to 8. After removing the aqueous layer, the mixture was washed with 20 Oml of saturated saline, and further washed with 15 Oml of distilled water. After removing the aqueous layer, the ether layer (upper layer) was transferred to an Erlenmeyer flask, and dehydrated using anhydrous sodium sulfate. The ether was removed by distillation under reduced pressure, and distillation was performed under reduced pressure.
- a flushing operation was performed by adding 20 ° C. of a 5 ° / 0 aqueous sodium hydrogen carbonate solution, and as a result, the pH value of the aqueous layer was 7 to 8.
- the mixture was washed with 20 Oml of saturated saline, and further washed with 15 Oml of distilled water.
- the ether layer (upper layer) was transferred to an Erlenmeyer flask, and dehydrated using anhydrous sodium sulfate. The ether was removed by distillation under reduced pressure, and distillation was performed under reduced pressure.
- a flushing operation was performed by adding 20 Oml of a 5% aqueous sodium hydrogen carbonate solution, and as a result, the pH value of the aqueous layer was 7 to 8.
- the mixture was washed with 20 Oml of saturated saline, and further washed with 15 Oml of distilled water.
- the ether layer (upper layer) was transferred to an Erlenmeyer flask, and dehydrated using anhydrous sodium sulfate. Ether was removed by distillation under reduced pressure, and distillation under reduced pressure was performed. At a top temperature of about 170 ° C, 35.5 g (yield 42.1%) of a yellow viscous liquid was obtained.
- 4-bromophthalate was identified. It was confirmed to be disohexyl luate.
- the analytical values are shown in Tables 1-3.
- the plate was washed three times with 100 ml of toluene at 90 ° C, and 20 ml of titanium tetrachloride and 80 ml of toluene were newly added, and the temperature was raised to 110 ° C for 1 hour.
- the reaction was carried out with stirring.
- the solid was washed seven times with 100 ml of n-heptane at 40 ° C to obtain a solid catalyst component.
- the solid-liquid in the solid catalyst component was separated, and the titanium content in the solid content was measured to be 3.2% by weight.
- Example 23 Same as Example 23 except that 3.7 g of 4-tert-butynolephthalic acid di-n-butynole obtained in Example 17 was used instead of 3.2 g of di-n-butyl 4-methylphthalate Then, a solid component was prepared, and a polymerization catalyst was formed and polymerization was performed. As a result, the titanium content in the obtained solid catalyst component was 3.3% by weight. Table 5 shows the polymerization results.
- a solid component was prepared in the same manner as in Example 23 except that 2.5 g of 4-methyl phthalate getyl obtained in Example 18 was used instead of 3.2 g of di-n-butyl 4-methylphthalate. Further, a polymerization catalyst was formed and polymerization was performed. As a result, the titanium content in the obtained solid catalyst component was 3.1% by weight. Table 5 shows the polymerization results.
- Example 26
- a solid was obtained in the same manner as in Example 23 except that 3.0 g of 4-ethyl tert-butyl phthalate obtained in Example 19 was used instead of 3.2 g of di-n-butyl 4-methylphthalate.
- the components were prepared, and a polymerization catalyst was formed and polymerization was performed. As a result, the titanium content in the obtained solid catalyst component was 3.4% by weight. Table 5 shows the polymerization results.
- a solid component was prepared in the same manner as in Example 23, and at the time of formation of the polymerization catalyst, dicyclopentyl dimethoxysilane (DCM) was used as an organosilicon compound instead of 0.113 mmol of hexylmethyldimethoxysilane (CMDMS).
- PDMS hexylmethyldimethoxysilane
- a solid component was prepared in the same manner as in Example 23, and when forming a polymerization catalyst, diisopropyldimethoxysilane (CMDMS) instead of 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) was used as an organic silicon conjugate.
- CDMS diisopropyldimethoxysilane
- DIP DMS DIP DMS
- a solid component was prepared in the same manner as in Comparative Example 2, and at the time of formation of the polymerization catalyst, dicyclopentyl dimethoxysilane (DCPD MS) was used as an organosilicon compound instead of 0.1 mmol of hexylmethyldimethoxysilane (CMDMS).
- DCPD MS dicyclopentyl dimethoxysilane
- CDMMS hexylmethyldimethoxysilane
- a polymerization catalyst was formed and polymerization was carried out in the same manner as in Comparative Example 1 except that 13 mmol was used. Table 5 shows the polymerization results.
- a polymer component was prepared in the same manner as in Comparative Example 2, and an organic cake was formed during the formation of the polymerization catalyst.
- a polymerization catalyst was formed and polymerization was carried out in the same manner as in Comparative Example 1 except that 0.13 mmol of diisopropyldimethoxysilane (DIP DMS) was used instead of 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) as the elemental compound.
- DIP DMS diisopropyldimethoxysilane
- CDMS cyclohexylmethyldimethoxysilane
- the mixture was washed three times with 100 Oml of toluene at 90 ° C, freshly added 20 ml of titanium tetrachloride and 8 Oml of toluene, heated to 110 ° C, and reacted with stirring for 1 hour I let it.
- the solid was washed seven times with 100 ml of n-heptane at 40 ° C to obtain a solid catalyst component.
- the solid-liquid in the solid catalyst component was separated and the titanium content in the solid was measured. %.
- Example 2 Same as Example 1 except that 3.9 g of di-n-butyl 4-bromophthalate was replaced by 3.2 g of di-n-butyl phthalate obtained in Example 20 Then, a solid component was prepared, and a polymerization catalyst was formed and polymerization was further performed. As a result, the titanium content in the obtained solid catalyst component was 3.3% by weight. Table 6 shows the polymerization results.
- Example 21 Same as Example 1 except that 3.8 g of di-n-butyl 4,5-dichlorophthalate obtained in Example 21 was used instead of 3.9 g of di-n-butyl bromophthalate Then, a solid component was prepared, and a polymerization catalyst was formed and polymerization was performed. The titanium content in the resulting solid catalyst component was 3.0% by weight. Table 6 shows the polymerization results.
- Solid component was obtained in the same manner as in Example 1 except that 4.5 g of diisohexyl 4-bromophthalate obtained in Example 22 was used instead of 3.9 g of di-n-butyl 4-bromophthalate.
- 4.5 g of diisohexyl 4-bromophthalate obtained in Example 22 was used instead of 3.9 g of di-n-butyl 4-bromophthalate.
- a polymerization catalyst was formed and polymerization was further performed.
- the titanium content in the solid catalyst component was 2.9% by weight. Table 6 shows the polymerization results.
- a solid component was prepared in the same manner as in Example 29, and when forming the polymerization catalyst, dicyclopentyldimethoxysilane (DCPDMS) was used as the organosilicon compound instead of 0.13 mmol of hexylmethyldimethoxysilane (CMDMS).
- DCPDMS dicyclopentyldimethoxysilane
- CDMMS hexylmethyldimethoxysilane
- a polymerization catalyst was formed in the same manner as in Example 6 except that 0.13 mmol was used. And polymerized. Table 6 shows the polymerization results.
- a solid component was prepared in the same manner as in Example 29, and 'during the formation of the polymerization catalyst, diisopropyldimethoxysilane was used instead of 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) as an organosilicon conjugate.
- DI ⁇ DMS cyclohexylmethyldimethoxysilane
- Example 29 49, 800 98.5 CMDMS Example 30 47, 200 98. 2 15 CMDMS Example 3 143, 900 9 7.92 1 CMDMS Example 32 49, 400 98.01 8 CMDMS Example 33 54, 400 99.0 7.5 DCPDMS Example 34 53 3, 500 98.8 1 12 DIPDMS From Tables 4, 5 and 6, the phthalic acid diester derivative of the present invention was used as an electron donor. It can be seen that by polymerizing the olefins using the contained catalyst, an olefin polymer can be obtained in an extremely high yield. Further, it can be seen that the Example has a higher Ml value and an excellent hydrogen response compared to the Comparative Example having the same amount of hydrogen.
- the phthalic acid diester derivative according to the present invention when used as an electron donor, which is one component of a catalyst for polymerization of olefins, the phthalic acid diester derivative has higher polymerization activity and higher stereoregularity than conventionally known high-performance catalysts. Extremely high yield of reactive polymer and response to hydrogen. Therefore, general-purpose polyolefins can be provided at low cost, and are expected to be useful in the production of highly functional copolymers of olefins.
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01922006A EP1188739B1 (en) | 2000-04-24 | 2001-04-23 | Phthalic diester derivatives and electron donors |
KR1020017016511A KR20020022717A (ko) | 2000-04-24 | 2001-04-23 | 프탈산디에스테르 유도체 및 전자 공여체 |
DE60135285T DE60135285D1 (de) | 2000-04-24 | 2001-04-23 | Diester-derivate der phthalsäure und elektronendonatoren |
US09/926,802 US6670497B2 (en) | 2000-04-24 | 2001-04-23 | Phthalic diester derivatives and electron donors |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000-122506 | 2000-04-24 | ||
JP2000122506A JP2001302593A (ja) | 2000-04-24 | 2000-04-24 | フタル酸ジエステル誘導体および電子供与体 |
JP2000261620A JP4712171B2 (ja) | 2000-08-30 | 2000-08-30 | オレフィン類重合用固体触媒成分および触媒並びに電子供与体 |
JP2000-261620 | 2000-08-30 | ||
JP2000298766A JP4738583B2 (ja) | 2000-09-29 | 2000-09-29 | オレフィン類重合用固体触媒成分および触媒 |
JP2000-298766 | 2000-09-29 |
Publications (1)
Publication Number | Publication Date |
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WO2001081292A1 true WO2001081292A1 (fr) | 2001-11-01 |
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/003460 WO2001081292A1 (fr) | 2000-04-24 | 2001-04-23 | Derives de diester phtalique et donneurs d'electrons |
Country Status (7)
Country | Link |
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US (1) | US6670497B2 (ja) |
EP (1) | EP1188739B1 (ja) |
KR (1) | KR20020022717A (ja) |
AT (1) | ATE404525T1 (ja) |
DE (1) | DE60135285D1 (ja) |
ES (1) | ES2310547T3 (ja) |
WO (1) | WO2001081292A1 (ja) |
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GB1422834A (en) * | 1972-11-17 | 1976-01-28 | Bayer Ag | Recrystallisation-resistant copper phthalocyanine pigments |
EP0045976A2 (en) * | 1980-08-13 | 1982-02-17 | Montedison S.p.A. | Components and catalysts for the polymerization of olefins |
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EP0363922A2 (en) * | 1988-10-11 | 1990-04-18 | Changchun Institute Of Applied Chemistry | The process for the preparation of 3,3',4,4'-biphenyltetracarboxylic acid and its derivatives |
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FI88047C (fi) * | 1991-05-09 | 1993-03-25 | Neste Oy | Pao tvenne elektrondonorer baserad katalysator foer polymerisation av olefiner |
TW412546B (en) * | 1994-05-19 | 2000-11-21 | Mitsui Petrochemical Ind | Solid titanium catalyst component for olefin polymerization, process for preparation of the same, olefin polymerization catalyst and process for olefin polymerization |
-
2001
- 2001-04-23 ES ES01922006T patent/ES2310547T3/es not_active Expired - Lifetime
- 2001-04-23 US US09/926,802 patent/US6670497B2/en not_active Expired - Lifetime
- 2001-04-23 EP EP01922006A patent/EP1188739B1/en not_active Expired - Lifetime
- 2001-04-23 AT AT01922006T patent/ATE404525T1/de not_active IP Right Cessation
- 2001-04-23 DE DE60135285T patent/DE60135285D1/de not_active Expired - Fee Related
- 2001-04-23 WO PCT/JP2001/003460 patent/WO2001081292A1/ja active IP Right Grant
- 2001-04-23 KR KR1020017016511A patent/KR20020022717A/ko not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1422834A (en) * | 1972-11-17 | 1976-01-28 | Bayer Ag | Recrystallisation-resistant copper phthalocyanine pigments |
EP0045976A2 (en) * | 1980-08-13 | 1982-02-17 | Montedison S.p.A. | Components and catalysts for the polymerization of olefins |
JPS62148450A (ja) * | 1985-12-24 | 1987-07-02 | Kawasaki Kasei Chem Ltd | 置換フタル酸化合物の製造法 |
JPS6372649A (ja) * | 1986-09-16 | 1988-04-02 | Hitachi Ltd | 3,3′,4,4′−ビフエニルテトラカルボン酸の製造方法 |
EP0363922A2 (en) * | 1988-10-11 | 1990-04-18 | Changchun Institute Of Applied Chemistry | The process for the preparation of 3,3',4,4'-biphenyltetracarboxylic acid and its derivatives |
Also Published As
Publication number | Publication date |
---|---|
DE60135285D1 (de) | 2008-09-25 |
EP1188739B1 (en) | 2008-08-13 |
US6670497B2 (en) | 2003-12-30 |
EP1188739A1 (en) | 2002-03-20 |
KR20020022717A (ko) | 2002-03-27 |
EP1188739A4 (en) | 2004-06-30 |
ATE404525T1 (de) | 2008-08-15 |
US20030036594A1 (en) | 2003-02-20 |
ES2310547T3 (es) | 2009-01-16 |
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