Process for producing catalyst for α-olefin polymerization and process for producing α-olefin polyme

专利摘要:
The present invention includes the steps of contacting each other with a solid catalyst component (1) containing Ti, Mg and a halogen as an essential component, an organoaluminum compound (2) and a compound (3) having a -COCOC- bonding group in the ring-closure structure. providing a process for preparing the α-olefin polymer, comprising homopolymerizing or copolymerizing the α-olefin in the presence of a process for producing the catalyst for α-olefin polymerization and a catalyst for the α-olefin polymerization prepared by the method. do.
公开号:KR20030061318A
申请号:KR10-2003-0001295
申请日:2003-01-09
公开日:2003-07-18
发明作者:구마모토신이치
申请人:스미또모 가가꾸 고교 가부시끼가이샤；
IPC主号:

专利说明:

Process for producing catalyst for α-olefin polymerization and process for producing α-olefin polymer {Process for producing catalyst for α-olefin polymerization and process for producing α-olefin polymer}
[1] The present invention relates to a process for producing a catalyst for α-olefin polymerization and a process for producing an α-olefin polymer.
[2] Supported solid catalyst component (1) obtained by supporting a tetravalent titanium halide compound on magnesium halide as described in JP-A-57-63310, 58-83006 and 61-78803, organoaluminum It is known to obtain high stereoregular polymers by polymerizing α-olefins in the presence of a catalyst comprising a mixture consisting of a compound (cocatalyst) (2) and an organosilicon compound (third component) (3).
[3] Further, as described in Japanese Laid-Open Patent Publication No. 7-216017, a step of (i) obtaining a solid product by reducing a titanium compound with an organic magnesium compound in the presence of an organosilicon compound and an ester compound, wherein the solid product is an ester compound (Ii) treating the treated product with a mixture of ether compound and titanium tetrachloride or a mixture of ether compound, titanium tetrachloride and ester compound to obtain the desired solid catalyst component containing a trivalent titanium compound ( α in the presence of a catalyst comprising a mixture comprising a solid catalyst component (1), an organoaluminum compound (cocatalyst) (2) and an organosilicon compound (third component) (3) obtained according to a process comprising iii) It is also known to obtain high stereoregular polymers by polymerizing olefins.
[4] Further, as described in Japanese Patent Laid-Open No. 10-212319, the step of (i) obtaining a solid product by reducing a titanium compound with an organic magnesium compound in the presence of an organosilicon compound and an ester compound, yielding the solid product with an ether compound (Ii) treating the treated product with a mixture of titanium tetrachloride, (iii) further treating the treated product with an organic acid halide compound and thereby treating the treated product with a mixture of ether compounds and titanium tetrachloride or ether compounds, titanium tetrachloride and esters. Solid catalyst component (1), organoaluminum compound (cocatalyst) obtained according to a process comprising the step (iv) of further treatment with a mixture of compounds to obtain the desired solid catalyst component containing a trivalent titanium compound ( Α-olefin in the presence of a catalyst comprising a mixture of 2) and an organosilicon compound (third component) (3) By sum it is also known that how to obtain a stereoregular polymer.
[5] According to the method described above, high-stereoregular polymers can be prepared through an extrusion-free / de-liming process. However, there is a further need to improve the quality of high stereoregular polymers.
[6] It is an object of the present invention to provide a process for preparing a polymerization catalyst suitable for obtaining a high quality α-olefin polymer and a process for producing such α-olefin polymer.
[7] The present invention includes the steps of contacting each other with a solid catalyst component (1) containing Ti, Mg and a halogen as an essential component, an organoaluminum compound (2) and a compound (3) having a -COCOC- bonding group in the ring-closure structure. and a method for producing a catalyst for α-olefin polymerization.
[8] The present invention also provides a solid catalyst component (1) containing Ti, Mg and halogen as essential components, an organoaluminum compound (2), a compound having a -COCOC- bonding group (3) and an alkoxy silicone compound (4) in contact with each other. It provides a method for producing a catalyst for α-olefin polymerization, comprising the step of.
[9] The present invention also provides solid catalyst component (1), organoaluminum compound (2), compound (3) having -COCOC- bonding group and 1,3-diether compound (4) containing Ti, Mg and halogen as essential components. It provides a method for producing a catalyst for α-olefin polymerization, comprising the step of contacting each other).
[10] The present invention also provides a solid catalyst component (1), an organoaluminum compound (2), a compound having a -COCOC- bonding group (3) and a piperidine compound (4) containing Ti, Mg and halogen as essential components. It provides a method for producing a catalyst for α-olefin polymerization, comprising the step of contacting.
[11] The present invention further provides a method for producing an α-olefin polymer, comprising the step of homopolymerizing or copolymerizing α-olefin in the presence of a catalyst for α-olefin polymerization, wherein the catalyst is a catalyst for α-olefin polymerization. It is obtained according to any of the above methods in the preparation.
[12] As used herein, a compound having a -COCOC- binding group in the ring-closure structure is a compound used as an external donor. As such compounds, The compound of is illustrated. In the formula, R ² to R ⁷ are independently of each other a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a hydrocarbyloxy group of 1 to 20 carbon atoms, R ¹ and R ⁸ are independently a hydrocarbon group of 1 to 20 carbon atoms Or a hydrocarbyloxy group having 1 to 20 carbon atoms, wherein two groups represented by R ¹ and R ⁸ are bonded to each other, or the left end of a carbon atom to which R ¹ is bonded and the right end of a carbon atom to which R ⁸ is bonded Is directly bonded (in the latter case, R ¹ and R ⁸ are absent).
[13] Examples of R ² to R ⁷ include hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl group, n-pentyl group, i- Pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, i-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, i-decyl group , Phenyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, tert-butoxy group, n-pentoxy group, i -Pentoxy group, neopentoxy group, n-hexoxy group and i-hexoxy group.
[14] Examples of preferred compounds of the above formula include 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2,4-dimethyl-1,3-dioxolane, 2-methoxy-1,3-dioxolane, 4-methoxy-1,3-dioxolane, 2,2-dimethoxy-1,3-dioxolane , 1,3-dioxane, 2-methyl-1,3-dioxane, 4-methyl-1,3-dioxane, 2,2-dimethyl-1,3-dioxane, 2,4-dimethyl-1 , 3-dioxane, 2-methoxy-1,3-dioxane, 4-methoxy-1,3-dioxane, 2,2-dimethoxy-1,3-dioxane, 2,4-dimethoxy -1,3-dioxane, 1,3-dioxepan, 2-methyl-1,3-dioxepan, 4-methyl-1,3-dioxepan, 5-methyl-1,3-dioxepan, 2, 4-dimethyl-1,3-dioxepan, 2,5-dimethyl-1,3-dioxepan, 2-methoxy-1,3-dioxepan, 4-methoxy-1,3-dioxepan, 5- Methoxy-1,3-dioxepan and s-trioxane. Of these, 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepan or s-trioxane are particularly preferable.
[15] Compounds having a -COCOC- binding group used in the present invention are compounds used as so-called external donors. As such a compound, a compound of the above formula is exemplified. In the formula, R ¹ to R ⁸ are each independently a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a hydrocarbyloxy group of 1 to 20 carbon atoms. R ¹ to all the groups of R ⁸ may be bonded may be bonded to each other, R ¹ to R ⁸ are bonded three carbon atoms jungdu dog directly to each other. For example, the right end of the central carbon atom bonded to R ⁴ and the carbon atom bonded to R ⁶ may be directly bonded to each other. In this case, R ⁴ and R ⁶ are not present. Examples of R ¹ to R ⁸ are similar to those exemplified for R ² to R ⁷ above.
[16] Examples of compounds in which any combination of R ¹ to R ⁸ herein does not have a bond include dimethylacetal, diethylacetal, propylenealdehyde, dimethylacetal, n-octylaldehyde, dimethylacetal, benzaldehyde, dimethylacetal, 2,2 Dimethoxypropane, 3,3-dimethoxyhexane and 2,6-dimethyl-4,4-dimethoxyheptane.
[17] Examples of compounds in which any groups of R ¹ to R ⁸ are bonded to each other or examples of compounds in which two or three carbon atoms having a bond with R ¹ to R ⁸ are directly bonded to each other also include -COCOC- in the ring-closure structure thereof. Each compound exemplified above as a compound having a bonding group, 1,1-dimethoxycyclopentane, 1,1-dimethoxycyclohexane, 1,1-diethoxycyclopentane, 1,1-diethoxycyclohexane, 2 -Methoxytrimethylene oxide, 2-ethoxytrimethylene oxide, 2,4-dimethoxytrimethylene oxide, 2,4-diethoxytrimethylene oxide, 2-methoxytetrahydrofuran, 2-ethoxytetrahydrofuran , 2,5-dimethoxytetrahydrofuran, 2,5-diethoxytetrahydrofuran, 2-methoxytetrahydropyran, 2-ethoxytetrahydropyran, 2,6-dimethoxytetrahydropyran and 2,6 Diethoxytetrahydropyran There is this. Among them, a compound in which R ¹ and R ⁸ are bonded to each other or R ¹ and R ⁸ do not exist and two carbons bonded to each of R ¹ and R ⁸ are directly bonded to each other, that is, a -COCOC- bond in a ring-closure structure. Preference is given to compounds having groups. Especially preferred are 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepan or s-trioxane.
[18] Preferred examples of the alkoxy silicon compound used in the present invention are compounds of the formula R ³ _r Si (OR 4) _4-r . In the formula, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a hetero atom-containing substituent, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, r is a number satisfying 0 ≦ r <4, and all R ³ and R ⁴ are the same as or different from each other.
[19] Examples of R ³ as a hydrocarbon group in the above formula include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group, branched alkyl groups such as isopropyl group, secondary-butyl Groups, tert-butyl groups and tert-amyl groups, cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, cycloalkenyl groups such as cyclopentenyl groups and aryl groups such as , Phenyl group and tolyl group. In the above formulae, an example of R ⁴ as a hydrocarbon group is the same group as these groups.
[20] Examples of the hetero atom in R ³ as the hetero atom-containing substituent in the above formula include an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom. Examples of hetero atom-containing substituents include dimethylamino group, methylethylamino group, diethylamino group, ethyl-n-propylamino group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, Piperidinyl groups, perhydroindolyl groups, perhydroisoindolyl groups, perhydroquinolyl groups, perhydroisoquinolyl groups, perhydrocarbazolyl groups, perhydroacridinyl groups, furyl groups, pyranyl groups, Perhydrofuryl groups and thienyl groups. Among these, it is preferable that the hetero atom is a substituent capable of directly bonding to the silicon atom in the alkoxy silicon compound.
[21] Preferred alkoxy silicone compounds are alkoxy silicone compounds having at least one R ³ in which the carbon atom directly bonded to the silicon atom in the above formula is a tertiary or quaternary carbon atom. Examples of preferred alkoxy silicone compounds include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, 3 Tert-butyl-n-propyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxy Methoxysilane, tert-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutyl Isobutyldimethoxysilane, cyclobutyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl tert-butyldimethoxysilane Dicyclohexyldimethoxysilane, Cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclo Hexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, di Isopropyl diethoxysilane, diisobutyl diethoxysilane, di-tert-butyl diethoxysilane, tert-butyl methyl diethoxysilane, tert-butyl ethyl diethoxysilane, tert-butyl- n-propyl die Methoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane, tert-amyl- n-butyl diethoxysilane, dicyclo Pentyl diethoxysilane, dicyclohexyl diethoxysilane, cyclohexyl methyl diethoxysilane, cyclohexyl ethyl diethoxysilane, diphenyl diethoxysilane, phenylmethyl diethoxysilane, 2-norbornane methyl dimethoxysilane, bis (per Hydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (per Hydroisoquinolino) methyldimethoxysilane, (perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) ethyldimethoxysilane, (perhydroquinolino) (n-propyl) dimethoxysilane, (per Hydroisoquinolino) (n-propyl) dimethoxysilane, (perhydroquinolino) (tert-butyl) dimethoxysilane and (perhydroisoquinolino) (tert-butyl) dimethoxysilane.
[22] Piperidine compounds as used in the present invention means compounds having a piperidine structure herein. As the compound, Compounds of can be exemplified. In the formula, R ¹ to R ¹¹ are each independently a hydrogen atom, a straight chain, branched or alicyclic alkyl group having 1 to 20 carbon atoms.
[23] Examples of such compounds include 1-methylpiperidine, 1-ethylpiperidine, 1-n-propylpiperidine, 1-isopropylpiperidine, 2-methylpiperidine, 2-ethylpiperidine, 2-n-propylpiperidine, 2-isopropylpiperidine, 3-methylpiperidine, 3-ethylpiperidine, 3-n-propylpiperidine, 3-isopropylpiperidine, 4- Methylpiperidine, 4-ethylpiperidine, 4-n-propylpiperidine, 4-isopropylpiperidine, 1,2-dimethylpiperidine, 1,3-dimethylpiperidine, 1,4 -Dimethylpiperidine, 2,3-dimethylpiperidine, 2,3-diethylpiperidine, 2,4-dimethylpiperidine, 2,4-diethylpiperidine, 2,5-dimethylpipe Ferridine, 2,5-diethylpiperidine, 2,6-dimethylpiperidine, 2,6-diethylpiperidine, 2,6-n-propylpiperidine, 2,6-diisopropyl Piperidine, 2,4,6-trimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetraethylpiperidine and mixtures of two or more thereof . Of these, 2,6-dimethylpiperidine or 2,2,6,6-tetramethylpiperidine is preferred.
[24] Solid catalyst components used in the present invention may be those known in the art. Examples of solid catalyst components include Japanese Patent Publication No. 46-34092, Japanese Patent Publication No. 47-41676, Japanese Patent Publication 55-23561, Japanese Patent Publication 57-24361, Japanese Patent Publication 52-39431 Japanese Patent Publication No. 52-36786, Japanese Patent Publication No. 1-28049, Japanese Patent Publication No. 3-43283, Japanese Patent Application Publication No. 4-80044, Japanese Patent Application Publication No. 55-52309, Japanese Laid-Open Patent Publication Japanese Patent Application Laid-Open No. 58-21405, Japanese Patent Application Laid-Open No. 61-181807, Japanese Patent Application Laid-Open No. 63-142008, Japanese Patent Application Laid-Open No. 5-339319, Japanese Patent Application Laid-Open No. 54-148093 Patent Publication No. 4-227604, Japanese Patent Application Laid-Open No. 6-2933, Japanese Patent Application Laid-Open No. 64-6006, Japanese Patent Application Laid-Open No. 6-179720, Japanese Patent Publication No. 7-116252, Japanese Patent Application Publication Japanese Patent Laid-Open No. 8-134124, Japanese Laid-Open Patent Publication No. 9-31119, Japanese Laid-Open Patent Publication No. 11-228628, Japanese Laid-Open Patent Publication No. 11-80234 and Japanese Laid Open Patent Publication It is those described in Patent Application No. 11-322833 call.
[25] Preferred solid catalyst components are those which further comprise Ti, Mg and halogen atoms as well as electron donors. As the electron donor, organic acid esters or ethers described below are preferable.
[26] Methods (1) to (5) are exemplified below as a method for producing the solid catalyst component. Among these, the method (5) is preferable.
[27] Method (1) comprising contacting a magnesium halide compound and a titanium compound with each other.
[28] Method (2) comprising contacting a magnesium halide compound, an electron donor and a titanium compound with each other.
[29] Method (3): dissolving a magnesium halide compound and a titanium compound in an electron donating solvent (i) and then impregnating the solution with a carrier material (ii).
[30] Method (4) comprising contacting a dialkoxy magnesium compound, a halogenated titanium compound and an electron donor with each other.
[31] Method (5) comprising contacting a solid component containing a magnesium atom, a titanium atom and a hydrocarbyloxy group with a halogen compound, an electron donor and / or an organic acid halide.
[32] The above solid component is a solid component containing at least one of magnesium atom, titanium atom and hydrocarbyloxy group. The content of hydrocarbyloxy groups in the solid component is preferably at least 20% by weight, more preferably at least 25% by weight, with the amount of the solid component being 100% by weight.
[33] Preferred solid components are those obtained by reducing the titanium compound of formula 1 to an organic magnesium compound in the presence of an organosilicon compound having a Si—O bond. In this case, it is preferable that the ester compound coexist as an optional component from the viewpoint of improving the polymerization activity and stereoregular polymerization capacity of the obtained polymerization catalyst. In formula 1, a is 1 to 20, preferably 1 ≦ a ≦ 5, more preferably 1, 2 or 4, R ² is a hydrocarbon group having 1 to 20 carbon atoms, and X ² is a halogen atom or 1 carbon atom. Hydrocarbyloxy group of 20, wherein all X ² may be the same or different from each other.
[34]
[35] Examples of such organosilicon compounds include compounds of the formulas Si (OR ¹⁰ ) _t R ¹¹ _4-t , R ¹² (R ¹³ ₂ SiO) _u SiR ¹⁴ ₃ and (R ¹⁵ ₂ SiO) _v . In these formulae, R ¹⁰ is a hydrocarbon group of 1 to 20 carbon atoms, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are independently of each other a hydrocarbon group or hydrogen atom of 1 to 20 carbon atoms, and t is 0 < t is a number satisfying 4, u is an integer of 1 to 1000, and v is an integer of 2 to 1000.
[36] Specific examples of the organosilicon compound include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetra-i-propoxysilane, di- i-propoxy-di-i-propylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyl Oxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenyl polysiloxane, methylhydropolysiloxane And phenylhydropolysiloxanes.
[37] Among the compounds of the three formulas described above, an alkoxysilane compound of the formula Si (OR ¹⁰ ) _t R ¹¹ _4-t is preferred, where t is preferably a number satisfying 1 ≦ t ≦ 4. Among these, the tetraalkoxysilane compound whose t = 4 is especially preferable, and tetraethoxysilane is the most preferable.
[38] Examples of R ² in formula 1 include alkyl groups, for example methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, amyl group, i-amyl group, hexyl group, heptyl group , Octyl group, decyl group and dodecyl group, aryl group such as phenyl group, cresyl group, xylyl group and naphthyl group, cycloalkyl group such as cyclohexyl group and cyclopentyl group, allyl Groups such as propenyl groups, and aralkyl groups such as benzyl groups. Among these, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable, and a linear alkyl group having 2 to 18 carbon atoms is particularly preferable.
[39] As the halogen atom represented by X ² in Chemical Formula 1, a chlorine atom, a bromine atom and an iodine atom are exemplified. Of these, chlorine atoms are particularly preferred. As a hydrocarbyloxy group having 1 to 20 carbon atoms represented as X ² , a hydrocarbyloxy group having the same group as R ² described above is exemplified. Especially preferred as X ² is an alkoxy group having a straight alkyl group having 2 to 18 carbon atoms.
[40] Examples of the titanium compound of Formula 1 include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxycitane, tetra-iso-propoxytitanium, tetra-n-butoxytitanium, tetra-iso-butoxytitanium n-butoxytitanium trichloride, di-n-butoxytitanium dichloride, tri-n-butoxytitanium chloride, di-n-tetraisopropylpolytitanate (a mixture of compounds in which a is 2 to 10), Tetra-n-butylpolytitanate (mixture of compounds in which a is 2 to 10), tetra-n-hexylpolytitanate (mixture of compounds in which a is 2 to 10), tetra-n-octylpolytitanate (a Mixtures of compounds having 2 to 10), condensates of tetraalkoxytatan obtained by reacting tetraalkoxytitanium with a small amount of water and mixtures of two or more of these compounds. Among these, tetra-n-butoxy titanium, tetra-n-butyl titanium dimer or tetra-n-butyl titanium tetramer is particularly preferable.
[41] By organo magnesium compound is meant any organo magnesium compound having a magnesium-carbon bond. Of these, Grignard compound or dihydrocarbyl magnesium of formula R ¹⁶ MgX ⁵ and formula R ¹⁷ R ¹⁸ Mg is particularly preferred. In the formula, Mg is a magnesium atom, each of R ¹⁶ , R ¹⁷ and R ¹⁸ is a hydrocarbon group having 1 to 20 carbon atoms, R ¹⁷ and R ¹⁸ may be the same or different from each other, and X ⁵ is a halogen atom.
[42] Specific examples of R ¹⁶ to R ¹⁸ include alkyl, aryl, aralkyl, alkenyl groups such as methyl, ethyl, propyl, i-propyl, butyl, secondary-butyl, tert-butyl , i-amyl, hexyl, octyl, 2-ethylhexyl, phenyl and benzyl groups. In the formation of their ether solutions, the use of Grignard compounds is particularly preferred in view of the catalyst performance obtained.
[43] It is possible to use organo magnesium compounds in admixture with organometallic compounds to form hydrocarbon soluble complexes. Examples of organometallic compounds include compounds of Li, Be, B, Al and Zn.
[44] As the above ester compound, mono-carboxylic acid esters and poly-carboxylic acid esters are exemplified. As these compounds, for example, saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters and aromatic carboxylic acid esters are listed.
[45] Specific examples of ester compounds include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl varate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl Benzoate, methyl toluate, ethyl toluate, ethyl aniseate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, Dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-i-propyl phthalate, di-n-butyl phthalate, di-i-butyl phthalate, di -n-octyl phthalate and diphenyl phthalate. Of these, unsaturated aliphatic carboxylic acid esters such as methacrylic acid ester and maleic acid ester, and aromatic carboxylic acid esters such as phthalic acid ester are preferred. Dialkyl phthalates are particularly preferred.
[46] Titanium compounds, organosilicon compounds and ester compounds are used after being dissolved or diluted in a suitable solvent. Examples of solvents include aliphatic hydrocarbons such as hexane, heptane, octane and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin and ether compounds, For example, diethyl ether, dibutyl ether, di-i-amyl ether and tetrahydrofuran.
[47] The temperature of the reduction reaction is usually -50 to 70 ° C, preferably -30 to 50 ° C, particularly preferably -25 to 35 ° C. The time required for the reduction reaction is not particularly limited and is usually about 30 minutes to about 6 hours. After the reaction is carried out at this temperature, it is possible to further carry out the post-reaction at a temperature of 20 to 120 ° C.
[48] These compounds used in the reduction reaction can be used together with a porous carrier, for example an inorganic oxide or an inorganic polymer, so that the obtained solid product is impregnated into the porous carrier. The porous carrier may be conventional. Examples of porous carriers include porous inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ and ZrO ₂ and organic porous polymers such as polystyrene, styrene-divinylbenzene copolymers, styrene-ethylene Glycol-methyl dimethacrylate copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylo Nitrile, acrylonitrile-divinylbenzene copolymer, polyvinylchloride, polyethylene and polypropylene. Among these, organic porous polymers are preferable, and styrene-divinylbenzene copolymer or acrylonitrile-divinylbenzene copolymer is particularly preferable.
[49] The pore capacity of the porous carrier having a pore radius of 200 to 2000 mm 3 is preferably 0.3 cc / g or more, more preferably 0.4 cc / g or more, and the pore capacity of the pore capacity when the pore radius is 35 to 75000 mm 3 is determined. The proportion is at least 35%, more preferably at least 40%. If the pore capacity is less than 0.3 cc / g or the ratio is less than 35%, the solid product cannot be effectively impregnated into the porous carrier.
[50] The organosilicon compound is usually 1 to 500, preferably 1 to 300, particularly preferably 3 to 100 in terms of atomic ratio, Si / Ti, that is, the ratio of silicon atoms in the organosilicon compound to titanium atoms in the titanium compound used. It is used in the amount of.
[51] The organic magnesium compound is converted in terms of its atomic ratio, (Ti + Si) / Mg, that is, the ratio of titanium atoms in the used titanium compound to silicon atoms in the organic magnesium compound and silicon atoms in the used organosilicon compound. It is usually used in an amount of 0.1 to 10, preferably 0.2 to 5.0, particularly preferably 0.5 to 2.0.
[52] Each titanium compound, organosilicon compound and organo magnesium compound is usually 1 to 51, preferably 2 to 2, in terms of atomic ratio, Mg / Ti, i.e., the ratio of magnesium atoms in the obtained solid catalyst component to titanium atoms herein. 31, particularly preferably in an amount from 4 to 26.
[53] The ester compound (optional component) is usually 0.5 to 100, preferably 1 to 60, particularly preferably 2, in terms of molar ratio, ester compound / Ti, i.e., ratio of used ester compound to tartan atoms in the used titanium compound. To an amount from 30 to 30.
[54] The solid product obtained by the reduction reaction is usually separated by solid-liquid separation and washed several times with inert hydrocarbon solvents such as hexane, heptane and toluene.
[55] The solid component comprises trivalent titanium atoms, magnesium atoms and hydrocarbyloxy groups and generally exhibits an amorphous state or a very weak crystalline state. In view of catalyst performance, amorphous solid components are particularly preferred.
[56] As used herein, a halogen compound having a halogenation ability means any compound capable of replacing a hydrocarbyloxy group in a solid component with its halogen atom. Among these, halogen compounds of group 4 elements, halogen compounds of group 13 elements, or halogen compounds of group 14 elements are preferable.
[57] As the halogen compound of the Group 4 element, a compound of the formula M (OR ⁹ ) _b X ⁴ _4-b is preferable. In this formula, M is a Group 4 element, R ⁹ is a hydrocarbon group of 1 to 20 carbon atoms, X ⁴ is a halogen atom, b is 0 ≦ b <4, preferably 0 ≦ b ≦ 2, particularly preferably Is a number satisfying b = 0. Examples of M include Ti, Zr and Hf, with Ti being preferred.
[58] Examples of R ⁹ include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group , Hexyl group, heptyl group, octyl group, decyl group and dodecyl group, aryl group such as phenyl group, cresyl group, xylyl group and naphthyl group, allyl group such as propenyl group, And aralkyl groups such as benzyl groups. Among these, an alkyl group having 2 to 18 carbon atoms or an aral group having 6 to 18 carbon atoms is preferable, and a linear alkyl group having 2 to 18 carbon atoms is particularly preferable. The halogen compound of the Group 4 element may be a compound having two or more OR ⁹ groups different from each other.
[59] As X ⁴ in the above formula, chlorine atom, bromine atom and iodine atom are exemplified. Of these, chlorine atoms are particularly preferred.
[60] Specific examples of the halogen compound of the above formula include titanium tetrahalide, such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide, alkoxide trihalide, such as methoxy titanium trichloride, ethoxy titanium trichloride, butoxy trichloride Titanium, phenoxytitanium trichloride and ethoxytitanium tribromide, dihalogenated dialkoxytitanium such as dimethoxytitanium dichloride, diethoxychloride dichloride, dibutoxytitanium dichloride, diphenoxytitaric dichloride and dibromide Diethoxytitanium and compounds obtained by modifying “titanium” in the formula above with zirconium or hafnium. Of these compounds, titanium tetrachloride is most preferred.
[61] As the halogen compound of the Group 13 element or the halogen compound of the Group 14 element, a compound of the formula MR _ma X _a is preferable. In the above formula, M is a Group 13 element or Group 14 element, R is a hydrocarbon group of 1 to 20 carbon atoms, X is a halogen atom, for example F, Cl, Br and I, of which Cl is preferred. m is the valence of M (e.g., when M is Si, m is 4) and a is 0 <a ≤ m (e.g. when M is Si, a is preferably 3 or 4 It is a number to satisfy).
[62] Examples of the Group 13 elements include B, Al, Ga, In, and Tl. Among these, B or Al is preferable, and Al is more preferable. C, Si, Ge, Sn and Pb are exemplified as a Group 14 element. Among these, Si, Ge or Sn is preferable.
[63] As R in the above formula, an alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, Octyl group, decyl group and dodecyl group, aryl group such as phenyl group, tolyl group, cresyl group, xylyl group and naphthyl group, cycloalkyl group such as cyclohexyl group and cyclopentyl group , Allyl groups such as propenyl groups, and aralkyl groups such as benzyl groups. Of these, alkyl groups or aryl groups are preferred, and methyl groups, ethyl groups, n-propyl groups, phenyl groups or p-tolyl groups are particularly preferred.
[64] As a Group 13 halogen compound, boron trichloride, boron methyldichloride, boron ethyldichloride, boron phenyldichloride, boron cyclohexyldichloride, dimethyl boron chloride, methylethylborate, aluminum trichloride, aluminum methyldichloride, ethyldichloride Aluminum, Phenyldichloride, Aluminum Cyclohexyl Chloride, Aluminum Dimethyl Chloride, Diethyl Aluminum Chloride, Methyl Ethyl Chloride, Ethyl Aluminum Sesquichloride, Gallium Chloride, Gallium Dichloride, Gallium Trichloride, Gallium Methyl Chloride, Ethyl Dichloride Gallium Chloride, Phenyl Dichloride, Gallium Cyclohexyl Dichloride, Gallium Dimethyl Chloride, Gallium Methylethyl Chloride, Indium Chloride, Indium Trichloride, Methyl Indium Dichloride, Phenyl Indium Chloride, Dimethyl Indium Chloride, Thallium Chloride, Thallium Chloride, Dichloride Methyl thallium dichloride, phenyl thallium dichloride, dimethyl thallium chloride and chlorides in the compounds as fluoride, brominated or iodide It is formed by the compounds and the like.
[65] Specific examples of the halogen compound of group 14 element group include tetrachloromethane, trichloromethane, dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloro ethane, tetrachloro silane, trichloro silane, methyltrichloro silane, ethyltrichloro silane, n-propyltrichloro silane, n-butyltrichloro silane, phenyltrichloro silane, benzyl Trichloro silane, p-tolyltrichloro silane, cyclohexyltrichloro silane, dichloro silane, methyldichloro silane, ethyldichloro silane, dimethyldichloro silane, diphenyldichloro silane, methylethyldichloro silane, monochloro silane, trimethylchloro silane, Triphenylchlorosilane, tetrachloride germane, trichloride germane, methyl trichloride germane, ethyl trichloride germane, phenyl trichloride germane, dichloride germane, dimethyl Germanic chloride, Diethyldichloride Germanic, Diphenyldichloride Germanic, Germanic Monochloride, Trimethyl Germanic, Germanic Triethyl chloride, Germanic Tri-n-butyl Chloride, Tin Tetrachloride, Tin Methyl Trichloride, n-butyl Trichloride, Dimethyl dichloride, di-n-butyl dichloride, di-i-butyl dichloride, diphenyl dichloride, tin divinyl dichloride, methyl trichloride, tin phenyl trichloride, lead dichloride, lead methyl chloride And lead phenyl chloride, and compounds in which the chlorinated compounds in the named compounds are replaced with fluoride, brominated and iodide, respectively.
[66] As the halogen compound, titanium chloride, methyldichloride, aluminum dichloride, tetrachloro silane, phenyltrichloro silane, methyltrichloro silane, ethyl trichloro silane, n-propyltrichloro silane or tin chloride are polymerization activities. It is especially preferable at the point of view. The compounds may be used in a mixture of two or more of these.
[67] When electron donors are used in the present invention, a polymerization catalyst can be obtained which produces higher stereoregular polymers.
[68] Examples of electron donors include oxygen-containing electron donor compounds such as ethers, ketones, aldehydes, carboxylic acids, organic acid esters, inorganic acid esters, organic amides, inorganic acid amides, and acid anhydrides and nitrogen-containing electron donor compounds such as alumina, Amines, nitriles and isocyanates. Of these, organic acid esters, organic acid ethers or mixtures thereof are preferred, and carboxylic acid esters, carboxylic acid ethers or mixtures thereof are more preferred.
[69] As the carboxylic ester, for example, mono-carboxylic acid ester and poly-carboxylic acid ester are listed. More specifically, saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters and aromatic carboxylic acid esters are listed.
[70] Specific examples of carboxylic esters include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl Toluate, Ethyl Toluate, Ethyl Aniate, Diethyl Succinate, Dibutyl Succinate, Diethyl Malonate, Dibutyl Malonate, Dimethyl Maleate, Dibutyl Maleate, Diethyl Itaconate, Dibutyl Itaco Nate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-i-propyl phthalate, di-n-butyl phthalate, di-i-butyl phthalate, di-n-octyl Phthalates and diphenyl phthalates. Of these, carboxylic acid esters, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters and aromatic carboxylic acid esters such as benzoic acid esters and phthalic acid esters are preferred. Aromatic polycarboxylic acid esters are particularly preferred, and dialkyl phthalates are most preferred.
[71] Preferred examples of esters include Dialkyl ethers, diethers and mixtures of two or more thereof. In the formula, R ⁵ to R ⁸ are independently of each other a straight alkyl group, branched alkyl group, alicyclic group, aryl group or aralkyl group having 1 to 20 carbon atoms, but R ⁶ and R ⁷ may be independently a hydrogen atom have.
[72] Preferred examples of ethers include dimethyl ether, diethyl ether, di-n-butyl ether, methyl ethyl ether, methyl-n-butyl ether, methyl cyclohexyl ether, 2,2-di-i-butyl-1,3-dime Oxypropane, 2-i-propyl-2-i-pentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-i-propyl-2- 3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-di-i-propyl-1,3-dimethoxypropane, 2-i-propyl-2-cyclohexylmethyl-1,3-dimethic Oxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-i-propyl-2-i-butyl-1,3-dimethoxypropane, 2,2-di-i-propyl-1 , 3-dimethoxypropane, 2,2-di-propyl-1,3-dimethoxypropane, 2-i-propyl-2-cyclohexyl-1,3-dimethoxypropane, 2-i-propyl-2- Cyclopentyl-1,3-dimethoxypropane, 2,2-di-cyclopentyl-1,3-dimethoxypropane and 2-heptyl-2-pentyl-1,3-dimethoxypropane, and mixtures of two or more thereof Have All.
[73] As ethers, dialkyl ethers are particularly preferred, and di-n-butyl ether is most preferred. Hereinafter, di-n-butyl ether is referred to briefly as dibutyl ether or butyl ether.
[74] The 1,3-diether compound used in the present invention means a compound having a 1,3-dialkoxypropane structure in the present specification. Examples of the compound may include R ⁵ to R ⁸ independently of each other, an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms, or R ⁶ and R ⁷ may independently represent a hydrogen atom. Compound.
[75] Specific examples of the compound include 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-iso Propyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2 Isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane and these There are two or more mixtures. Among them, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane or 2,2-dicyclohexyl-1,3-dimethoxypropane This is preferable.
[76] As the organic acid halide used in the present invention, a monocarboxylic acid halide or a polycarboxylic acid halide is preferable. Examples of the organic acid halides include aliphatic carboxylic acid halides, alicyclic carboxylic acid halides, and aromatic carboxylic acid halides. Specific examples thereof include acetyl chloride, propionic acid chloride, butyric acid chloride, valeric acid chloride, acrylic acid chloride, methacrylic acid chloride, benzoic acid chloride, toluic acid chloride, aniseic acid chloride, succinic acid chloride, malonic acid chloride, maleic acid chloride, itaconic acid chloride And phthalic acid chlorides. Of these, aromatic carboxylic acid chlorides such as benzoic acid chloride, toluic acid chloride and phthalic acid chloride are preferred. Aromatic dicarboxylic acid dichlorides are more preferred, and phthalic acid chlorides are particularly preferred.
[77] Contacting in the method (5) is usually carried out in an inert gas, for example nitrogen and argon atmosphere. Examples of contact methods are as follows.
[78] Method (1): A method comprising contacting a solid component by adding a halogen compound and an electron donor, wherein the order of addition is limited.
[79] Method (2): A method comprising adding a halogen compound and an organic acid halide to contact a solid component, wherein the order of addition is limited.
[80] Method (3): a method comprising contacting a solid component by adding a mixture of a halogen compound, an electron donor and an organic acid halide.
[81] Method (4): A method comprising contacting a solid component by adding a mixture of a halogen compound and an electron donor and an organic acid halide, wherein the order of addition is limited.
[82] Method (5) comprising: (i) applying and contacting an electron donor to a solid component followed by (ii) contacting a halogen compound thereto.
[83] Method (6): a method comprising the steps of (i) contacting and applying an electron donor to a solid component followed by (ii) contacting a halogen compound with an electron donor thereto, wherein the order of addition is limited.
[84] Method (7) comprising: (i) adding and contacting an electron donor to a solid component followed by (ii) contacting a mixture of a halogen compound and an electron donor thereto.
[85] Method (8): a method comprising contacting a halogen compound by adding a solid component and an electron donor, wherein the order of addition is limited.
[86] Method (9): A method comprising contacting a halogen compound by adding a solid component and an organic acid halide, wherein the order of addition is limited.
[87] Method (10): A method comprising contacting a halogen compound with the addition of a solid component, an electron donor and an organic acid halide, wherein the order of addition is limited.
[88] As a contacting method, for example, after completing any of the above methods, the method (1) comprising the step of further treating with a halogen compound one or more times and after completing any of the above methods, the halogen compound and the electron donor Further provided is a method (2) comprising the step of further treating at least once with a mixture of.
[89] Among these aforementioned methods, method (2); Method (4); After completion of method (4), preference is given to methods and methods (7) comprising the step of further contacting one or more times with a mixture of halogen compounds and electron donors. Of these four methods, the latter three methods are more preferred. (I) contacting a solid component with a mixture of a halogen compound and an ether and an organic acid halide in this order, followed by contacting a mixture of a halogen compound, a carboxylic ester and an ether with the contact (ii) and a mixture of the halogen compound and an ether (1) comprising contacting the solid component with a carboxylic acid ester (i) by contacting at least one additional time with a step (i), followed by contacting with a mixture of a halogen compound, a carboxylic ester and an ether Particular preference is given to a process (2) comprising the step (ii) and (iii) further one or more contact treatments with a mixture of halogen compounds and ethers.
[90] The method of contacting is not limited. For example, mechanical grinding methods and slurry methods using devices such as ball mills are presented. The mechanical grinding method is undesirable from an industrial point of view because the obtained solid catalyst component contains a large amount of fine powder and consequently widens its particle size distribution. Therefore, a method of contacting it in the presence of a diluent is preferred. The solid catalyst component obtained according to the above-mentioned contact method can be used as it is. However, it is preferable to remove the unnecessary components in the component by washing the obtained component with a diluent that is inert to the component to be treated.
[91] Examples of diluents include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, cycloaliphatic hydrocarbons such as cyclohexane and cyclopentane, and halogenated hydrocarbons, For example, 1,2-dichloride and monobenzene benzene.
[92] The amount of diluent used per contact is usually 0.1 ml to 1000 ml, preferably 1 ml to 100 ml per gram of solid component. The amount of diluent used per wash is about the same as described above. Typically, 1 to 5 washes are performed per contact.
[93] The temperature at which contacting and washing is carried out is usually -50 to 150 ° C, preferably 0 to 140 ° C, more preferably 60 to 135 ° C. The contact time is not particularly limited and is preferably 0.5 to 8 hours, more preferably 1 to 6 hours. The washing time is also not particularly limited and is preferably 1 to 120 minutes, more preferably 2 to 60 minutes.
[94] The amount of halogen compound used is usually 0.5 to 1000 mmol, preferably 1 to 200 mmol, more preferably 2 to 100 mmol, per gram of solid component.
[95] Preference is given to using halogen compounds in mixtures with electron donors. In this case, the electron donor is used in an amount of usually 1 to 100 mol, preferably 1.5 to 75 mol, more preferably 2 to 50 mol per mol of the halogen compound.
[96] The amount of electron donor is usually from 0.01 to 100 mmol, preferably from 0.05 to 50 mmol, more preferably from 0.1 to 20 mmol per gram of solid component. If this amount exceeds 100 mmol, solid component particles may collapse.
[97] The organic acid halide is usually used in an amount of 0.1 to 100 mmol, preferably 0.3 to 50 mmol, more preferably 0.5 to 20 mmol, per 1 g of solid component, and usually 0.01 to 1.0 mol, preferably 0.03 to 0.5, per g of magnesium atom in solid component. It is used in the amount of. If the amount of the former exceeds 100 mmol or the amount of the latter exceeds 1.0 mol, the solid component particles may collapse.
[98] When two or more of the above compounds are used in one or more contacts, the amount described above for each compound is the amount per contact.
[99] When used for the polymerization, the solid catalyst component obtained can be mixed with an inert diluent to form a slurry or dried to obtain a flowable powder. As a drying method, there is illustrated how the volatiles are removed under reduced pressure and how the volatiles are removed under a stream of inert gas such as nitrogen and argon. The drying temperature is preferably 0 to 200 ° C, more preferably 50 to 100 ° C. The drying time is preferably 0.01 to 20 hours, more preferably 0.5 to 10 hours.
[100] As used herein, an organoaluminum compound means a compound having at least one Al-carbon bond. Typical examples thereof include compounds of the formulas R ¹⁹ _w AlY _3-w and R ²⁰ R ²¹ Al—O—AlR ²² R ²³ . In the formula, R ¹⁹ to R ²³ are independently of each other a hydrocarbon group having 1 to 20 carbon atoms, Y is a halogen atom, a hydrogen atom or an alkoxy group, and w is a number satisfying 2 ≦ w ≦ 3.
[101] Specific examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, tri-i-butylaluminum and trihexylaluminum, dialkylaluminum hydrides such as diethylaluminum hydride and di-i- Butylaluminum hydride, dialkylaluminum halides such as diethylaluminum chloride, mixtures of trialkylaluminum and dialkylaluminum halides, such as mixtures of triethylaluminum and diethylaluminum chloride, and alkylalumoxanes, For example, tetraethyldialoxane and tetrabutyldialumoxane.
[102] Of these, trialkylaluminum, mixtures of trialkylaluminum and dialkylaluminum halides or alkylalumoxanes are preferred. Particular preference is given to triethylaluminum, tri-i-butylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or tetraethyldialumoxane.
[103] The α-olefin used in the present invention means an α-olefin having 3 or more carbon atoms. Examples thereof include straight chain mono-olefins such as propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1 and deken-1, branched mono-olefins such as 3-methyl Butene-1,3-methylpentene-1 and 4-methylpentene-1, vinylcyclohexane and mixtures of two or more thereof.
[104] Of these, homopolymerization of propylene or butene-1 or copolymerization of mixed olefin-containing propylene or butene-1 is preferred as the main component, and homopolymerization of propylene or copolymerization of mixed olefin-containing propylene is particularly preferred as the main component. When copolymerizing, (1) it is possible to use a mixture of two or more olefins selected from the group consisting of ethylene and the above-described α-olefins, or a polyunsaturated bond-containing compound such as conjugated dienes and non-conjugated dienes with the above olefins. , (2) it is possible to carry out hetero-block copolymerization via two or more stages of polymerization.
[105] The catalyst for α-olefin polymerization used in the present invention can be obtained by contacting the solid catalyst component, the organoaluminum compound and the external donor described above with each other. The method of contacting it is not limited as long as a catalyst for polymerization can be obtained. For example, a method of contacting these three components by themselves with each other (1), a method of diluting each of these three components with a solvent, and then contacting each other (2) and these three components separately in the polymerization vessel After feeding, a method (3) of contacting each other in a polymerization vessel is presented. It is preferable to feed each component to the polymerization vessel under conditions containing no water at all using an inert gas such as nitrogen or argon. It is possible to contact two or three of these three mixtures in advance and feed the contacted mixture to the polymerization vessel.
[106] In the process for producing the α-olefin polymer of the present invention, the catalyst can be used on its own (hereinafter, polymerization is referred to as "main polymerization"). In addition, the prepolymerized polymerization catalyst obtained by the prepolymerization of the catalyst can be used for the main polymerization.
[107] The prepolymerized polymerization catalyst can usually be obtained by polymerizing (ie, prepolymerizing) a small amount of olefins in the presence of the solid catalyst component and the organoaluminum compound described above. As a prepolymerization method, it is preferable to carry out a slurry polymerization method in which an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene and toluene is used as the solvent. . The solvent may be partially or wholly replaced by liquefied olefins.
[108] The amount of the organoaluminum compound used for the prepolymerization is usually 0.5 to 700 mol, preferably 0.8 to 500 mol, particularly preferably 1 to 200 mol, per mol of the titanium atoms contained in the solid catalyst component.
[109] The amount of prepolymerized olefin is usually from 0.01 to 1000 g, preferably from 0.05 to 500 g, particularly preferably from 0.1 to 200 g per gram of solid catalyst component.
[110] The slurry concentration of the above-mentioned slurry polymerization method is preferably 1 to 500 g / l of solid catalyst component, particularly preferably 3 to 300 g / l of solid catalyst component. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. The partial pressure of olefins in the gas phase of the prepolymerization is preferably 0.01 to 20 kg / cm ² , particularly preferably 0.1 to 10 kg / cm ² . However, the partial pressure is limited to olefins present as a liquid at the temperature of the prepolymerization. The prepolymerization time is not particularly limited and is usually 2 minutes to 15 hours.
[111] A method for supplying a solid catalyst component, an organoaluminum compound and an olefin to a prepolymerization vessel, comprising the step (1) of supplying a solid catalyst component and an organoaluminum compound and then supplying an olefin and a solid catalyst component and an olefin After feeding, a method (2) is illustrated which comprises feeding an organoaluminum compound. A method of supplying olefins to a polymerization vessel, the method comprising the step of continuously supplying olefins to maintain the pressure in the polymerization vessel at a predetermined pressure and a method comprising simultaneously supplying a predetermined total amount of olefins. (2) is illustrated. In order to control the molecular weight of the olefin polymer obtained by prepolymerization, a chain transfer agent such as hydrogen can be used.
[112] In some cases, such external donors (ie external donors) may be used for prepolymerization. The amount of external donor used for the prepolymerization is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 100 mol per mol of the titanium atom contained in the solid catalyst component, and usually 0.003 to 5 mol per mol of the organoaluminum compound, It is preferably 0.005 to 3 mol, particularly preferably 0.01 to 2 mol.
[113] In prepolymerization, the method of supplying the external donor to the prepolymerization vessel is not particularly limited. As such a method, there is illustrated a method (1) comprising feeding only an external donor and a method (2) comprising feeding a contact product between the external donor and the organoaluminum compound. The olefins used for the prepolymerization may be essentially the same or different from the olefins used for the main polymerization.
[114] A process for the main polymerization comprising the step of polymerizing an olefin in the presence of a catalyst obtained by contacting a solid catalyst component, an organoaluminum compound and an external donor with each other (1), polymerizing the olefin in the presence of a prepolymerized catalyst Illustrative is a method (2) comprising the step of polymerizing and polymerizing the olefin in the presence of a prepolymerized catalyst, the contact product between the organoaluminum compound and the external donor.
[115] The amount of the organoaluminum compound used for the main polymerization is usually 1 to 1000 mol, particularly preferably 5 to 600 mol, per 1 mol of titanium atoms contained in the solid catalyst component.
[116] The amount of the external donor used for the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, particularly preferably 0.5 to 800 mol, per mol of the organoaluminum compound, usually 0.001 to 5 mol, per mol of the titanium atom contained in the solid catalyst component. It is preferably 0.005 to 3 mol, particularly preferably 0.01 to 1 mol.
[117] In the case of the main polymerization, the polymerization temperature is usually -30 to 300 ° C, preferably 20 to 180 ° C. The polymerization pressure is not particularly limited, and from an industrial or economic point of view, it is generally from atmospheric pressure to 100 kg / cm ² , preferably from about 2 to about 50 kg / cm ² . The polymerization mode can be batch or continuous. As the polymerization method, a slurry polymerization method using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane and octane, a solution polymerization method using the solvent, an olefin present as a liquid at a polymerization temperature The bulk polymerization method and gas phase polymerization method using the as a medium are illustrated. In the main polymerization, a chain transfer agent such as hydrogen may be used to control the molecular weight of the obtained olefin polymer.
[118] Example
[119] The present invention will be described in detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples.
[120] Various physical properties of the polymer are measured as follows.
[121] 1. 20 ° C xylene soluble part (CXS value (% by weight))
[122] CXS dissolves 1 g of polymer in 200 ml of heated xylene to obtain a solution (1), slowly cooling the solution to 50 ° C (2), and cooling the solution to 20 ° C by impregnating the cooled solution with ice water under stirring. (3) to precipitate the polymer by continuously cooling at 20 ° C. for 3 hours (4), to separate the precipitated polymer by filtration to obtain a filtrate (5) and to obtain a polymer which is 20 ° C. xylene solubles in the filtrate. Is measured according to step (6) to obtain the weight (Wg) thereof.
[123] The value calculated as 100 x W is CXS (% by weight). The smaller the CXS value, the higher the high stereoregularity of the polymer.
[124] 2. Intrinsic viscosity ([η])
[125] The intrinsic viscosity of the polymer is measured in a tetralin solvent at 135 ° C. using an Ubbellohde viscometer.
[126] 3. Bulk Density (g / ml)
[127] The bulk density of the polymer is measured according to JIS K-6721 (1996).
[128] 4. Composition Analysis
[129] (1) titanium atomic content
[130] The content of titanium atoms in the solid sample is determined by (i) decomposing the solid sample into dilute sulfuric acid (i), adding an excess aqueous hydrogen peroxide solution to obtain a liquid sample (ii), and double the characteristic absorption of 410 nm of the liquid sample. Beam spectrophotometer, type U-2001 [manufacturer; Hitachi, Ltd] and (iv) to obtain the titanium atomic content from the characteristic absorption of 410 nm obtained and the calibration curve otherwise prepared (iv).
[131] (2) containing alkoxy groups
[132] The content of alkoxy groups in the solid sample is determined by (i) decomposing the solid sample with water to obtain a liquid sample, and (ii) determining the content of alcohol corresponding to the alkoxy group in the liquid sample according to gas chromatography internal standard method. And converting the obtained alcohol content into an alkoxy group content (iii).
[133] (3) carboxylic acid ester content
[134] The content of the carboxylic acid ester in the solid sample is determined by (i) decomposing the solid sample with water to obtain a liquid sample, extracting the soluble components in the liquid sample with an unsaturated hydrocarbon solvent to obtain an extract (ii) and gas chromatography inside It is measured according to the method comprising the step (iii) of measuring the content of the carboxylic acid ester in the liquid sample according to the standard method.
[135] Example 1
[136] (1) Synthesis of Solid Catalyst Components
[137] Into a flask equipped with a stirrer purged with nitrogen, 3.99 g of anhydrous magnesium chloride, 17.8 ml of decane and 19.8 ml of 2-ethylhexanol were introduced, and then the mixture was stirred at 135 ° C. for 2 hours to obtain a uniform solution. In addition, 1.30 g of 2,2-diisobutyl-1,3-dimethoxypropane was added thereto, and the mixture was stirred at 135 ° C. for 1 hour, and then cooled to ambient temperature.
[138] Meanwhile, 100 ml of titanium tetrachloride was introduced into a flask equipped with a stirrer purified by nitrogen, and then cooled to -20 ° C. The solution is added dropwise over 1 hour so that the internal temperature does not exceed 15 ° C., after which the temperature is raised to 110 ° C. over 5 hours. Then, 1.92 g of 2,2-diisobutyl-1,3-dimethoxypropane are added thereto and the mixture is stirred at 110 ° C. for 2 hours. The resulting slurry is filtered and the solid is washed 10 times each with 30 ml of decane at 110 ° C., further three times each with 30 ml of hexane at ambient temperature and then dried to obtain a solid catalyst component. The content of titanium atoms in the solid catalyst component is 2.14 wt%.
[139] (2) Polymerization of propylene
[140] A stainless steel autoclave having an internal volume of 3 L was purified with argon, 2.6 mmol of triethylaluminum, 0.26 mmol of 1,3-dioxolane and 8.00 mg of the solid catalyst component synthesized in (1) were introduced thereto, and hydrogen was This is applied in an amount corresponding to a partial pressure of 0.033 MPa. 780 g of liquefied propylene are then introduced thereto. The temperature of the autoclave was raised to 80 ° C. and polymerization continued at 80 ° C. for 1 hour. After completion of the polymerization, the unreacted monomers are removed. 176 g of polypropylene powder are obtained by drying the resulting polymer under reduced pressure.
[141] The yield of polypropylene per gram of solid catalyst component (hereinafter abbreviated as "PP / cat") is 22000 g / g, and the CXS, [η] and bulk densities of the polymers are 2.4 wt%, 1.56 dl / g and 0.378 g, respectively. / ml.
[142] Comparative Example 1
[143] (1) Polymerization of propylene
[144] Example 1 (2) is repeated except that 1,3-dioxolane is not used and 10.3 mg of solid catalyst component is introduced.
[145] PP / cat is 26900 g / g, CXS is 3.5% by weight, higher than the value obtained in Example 1 using 1,3-dioxolane (2.4% by weight), [η] and bulk density are respectively 1.59 dl / g and 0.370 g / ml.
[146] Example 2
[147] (1) Synthesis of Solid Components
[148] Into a reactor equipped with a stirrer purged with nitrogen, 14.5 kg of diisobutyl phthalate, 670 L of hexane, 349 kg of tetraethoxysilane and 38 kg of tetrabutoxytitanium are introduced and the mixture is stirred. 890 L of dibutyl ether solution (concentration: 2.1 mol / L) of butylmagnesium chloride was then added dropwise to the stirred mixture over 5 hours while maintaining the temperature of the reactor at 8 ° C. After completion of the dropping, the mixture was stirred at 20 ° C. for 1 hour, then filtered and the solid product obtained was washed three times with 1100 L of toluene each at ambient temperature. To the washed solid product, toluene is added to a total volume of 843 liters to obtain a slurry.
[149] (2) Synthesis of Solid Catalyst Components
[150] To the slurry obtained in the above (1), 441 L of toluene is added and the mixture is stirred at 105 DEG C for 1 hour. To this was added 200 L of toluene and 222 kg of diisobutyl phthalate and the mixture was stirred at 95 ° C. for 30 minutes. Thereafter, the mixture is filtered and the solid obtained is washed twice with 1100 L of toluene each time. To the washed solid, toluene is added to a total volume of 843 liters to obtain a slurry. Then 19.0 kg dibutyl ether, 15.0 kg diisobutyl phthalate and 737 kg titanium tetrachloride are added thereto and the mixture is stirred at 105 ° C. for 3 hours. Thereafter, the mixture is filtered and the washing is repeated three times with 1100 L of toluene at 95 ° C., and toluene is added thereto so that the total volume is 843 L to obtain a slurry. Then 19.0 kg dibutyl ether and 368 kg titanium tetrachloride are added thereto and the mixture is stirred at 105 ° C. for 1 hour. Thereafter, the mixture is filtered and the solid obtained is washed four times each with 1100 L of toluene at 95 ° C., three times each with 1000 L of hexane at ambient temperature, and then dried to obtain a solid catalyst component.
[151] The solid catalyst component contains 2.0 weight percent titanium atom, 10.5 weight percent phthalic ester, 0.6 weight percent ethoxy group and 0.2 weight percent butoxy group.
[152] (3) Polymerization of propylene
[153] A stainless steel autoclave with an internal volume of 0.1 L was clarified with argon and 0.57 mmol of triethylaluminum, 0.057 mmol of 1,3-dioxolane and 3.65 mg of the solid catalyst component synthesized in (2) were introduced thereto. Then 40 g of liquefied propylene are introduced thereto. The temperature of the autoclave was raised to 60 ° C. and polymerization continued at 60 ° C. for 1 hour. After completion of the polymerization, the unreacted monomers are removed. 17.3 g of polypropylene powder is obtained by drying the resulting polymer under reduced pressure. PP / cat and CXS are 4700 g / g and 17.9 wt%, respectively.
[154] Comparative Example 2
[155] (1) Polymerization of propylene
[156] Example 2 (3) is repeated except that 1,3-dioxolane is not used and 2.13 mg of solid catalyst component is introduced.
[157] PP / cat is 6300 g / g and CXS is 28.9 weight% higher than the value obtained in Example 2 using 1,3-dioxolane (17.9 weight%).
[158] Example 3
[159] (1) Polymerization of propylene
[160] A stainless steel autoclave having an internal volume of 3 L was purified with argon, 2.6 mmol of triethylaluminum, 0.26 mmol of 1,3-dioxolane, 0.26 mmol of cyclohexylethyldimethoxysilane, and the solid synthesized in (2) of Example 2. 6.13 mg of catalyst component are introduced here. Hydrogen is then added thereto in an amount corresponding to a partial pressure of 0.033 MPa. Also 780 g of liquefied propylene are introduced thereto. The temperature of the autoclave was raised to 80 ° C. and polymerization continued at 80 ° C. for 1 hour. After completion of the polymerization, the unreacted monomers are removed. 186 g of polypropylene powder are obtained by drying the resulting polymer under reduced pressure. PP / cat, CXS, [η] and bulk density are 30300 g / g, 0.69 wt%, 2.14 dl / g and 0.392 g / ml, respectively.
[161] Example 4
[162] (1) Polymerization of propylene
[163] Example 1 (1) is repeated except that 0.13 mmol of 1,3-dioxolane and 6.6 mg of solid catalyst component are introduced.
[164] PP / cat, CXS, [η] and bulk density are 30200 g / g, 0.79 wt%, 2.07 dl / g and 0.397 g / ml, respectively.
[165] Example 5
[166] (1) Polymerization of propylene
[167] Example 1 (1) is repeated except that 1,3-dioxolane is changed to 1,3-dioxane and 8.37 mg of solid catalyst component is introduced.
[168] PP / cat, CXS, [eta] and bulk density are 30900 g / g, 0.80 wt%, 2.30 dl / g and 0.388 g / ml, respectively.
[169] Example 6
[170] (1) Polymerization of propylene
[171] Example 1 (1) is repeated except that 1,3-dioxolane is changed to 2-methyl-1,3-dioxolane and 8.88 mg of solid catalyst component is introduced.
[172] PP / cat, CXS, [eta] and bulk density are 29200 g / g, 0.76 wt%, 2.19 dl / g and 0.390 g / ml, respectively.
[173] Example 7
[174] (1) Polymerization of propylene
[175] Example 1 (1) is repeated except that 1,3-dioxolane is changed to 3,3-dimethoxyhexane and 6.82 mg of solid catalyst component is introduced.
[176] PP / cat, CXS, [η] and bulk density are 26500 g / g, 0.95 wt.%, 2.21 dl / g and 0.394 g / ml, respectively.
[177] Comparative Example 3
[178] (1) Polymerization of propylene
[179] Example 1 (1) is repeated except that 1,3-dioxolane is not used and 5.26 mg of solid catalyst component is introduced.
[180] PP / cat is 37100 g / g and CXS is 1.1% by weight, higher than the value obtained in Example 3 using 1,3-dioxolane (0.69% by weight).
[181] [eta] and bulk density are 2.12 dl / g and 0.399 g / ml, respectively.
[182] Example 8
[183] (1) Polymerization of propylene
[184] Example 1 (1) is repeated except that cyclohexylethyldimethoxysilane is changed to t-butyl-n-propyldimethoxysilane and 6.10 mg of solid catalyst component is introduced.
[185] PP / cat, CXS, [eta] and bulk density are 33900 g / g, 0.60 wt%, 2.97 dl / g and 0.394 g / ml, respectively.
[186] Comparative Example 4
[187] (1) Polymerization of propylene
[188] Example 1 (1) is repeated except that 1,3-dioxolane is not used and 7.96 mg of solid catalyst component is introduced.
[189] PP / cat is 40700 g / g and CXS is 0.82% by weight, higher than the value obtained in Example 8 using 1,3-dioxolane (0.60% by weight). [eta] and bulk density are 3.23 dl / g and 0.396 g / ml, respectively.
[190] Example 9
[191] (1) Polymerization of propylene
[192] (1) of Example 3, except changing cyclohexylethyldimethoxysilane to bisperhydroisoquinolinodimethoxysilane, introducing 6.48 mg of solid catalyst component, and changing the partial pressure of hydrogen to 0.20 MPa Repeat.
[193] PP / cat, CXS, [η] and bulk density are 19300 g / g, 0.89 wt%, 1.73 dl / g and 0.394 g / ml, respectively.
[194] Comparative Example 5
[195] (1) Polymerization of propylene
[196] Example 1 (1) is repeated except that 1,3-dioxolane is not used and 5.80 mg of solid catalyst component is introduced.
[197] PP / cat is 32800 g / g and CXS is 1.3% by weight, higher than the value (0.89% by weight) obtained in Example 9 using 1,3-dioxolane. [eta] and bulk density are 1.57 dl / g and 0.395 g / ml, respectively.
[198] Example 10
[199] (1) Synthesis of Solid Catalyst Components
[200] A 100 ml volumetric flask, dropping funnel and thermometer equipped with a stirrer are purged with nitrogen. Toluene slurry obtained in the same manner as in Example 2 (1) was introduced thereto in an amount of 8 g in terms of solids, and then toluene was removed so that the slurry volume was 26.5 ml.
[201] The slurry is maintained at about 40 ° C. and a mixture of 16.0 ml of titanium tetrachloride and 0.8 ml of dibutyl ether is added thereto. In addition, a mixture of 2.4 ml of phthalic acid chloride and 2.4 ml of toluene was added dropwise thereto for 7.5 minutes, and after completion of the dropping, the resulting mixture was stirred at 115 ° C. for 3 hours.
[202] The reaction mixture is solid-liquid separated at 115 ° C. and the solid obtained is washed three times with 40 ml of toluene at 115 ° C. each. Toluene is added to the washed solid to produce 26.5 ml of toluene slurry, which is then heated to 105 ° C.
[203] A mixture of 0.8 ml dibutyl ether and 16 ml titanium tetrachloride is added thereto and the mixture is stirred at 105 ° C. for 1 hour. After complete stirring, the mixture is solid-liquid separated at 105 ° C. and the solid obtained is washed twice with 40 ml of toluene at 105 ° C., respectively.
[204] Toluene was added to the washed solid to form 26.5 ml of toluene slurry, which was then heated to 105 ° C. A mixture of 0.8 ml dibutyl ether and 16 ml titanium tetrachloride is added thereto and the mixture is stirred at 105 ° C. for 1 hour. After complete stirring, the mixture is solid-liquid separated at 105 ° C. and the solid obtained is washed twice with 40 ml of toluene at 105 ° C., respectively.
[205] Toluene was added to the washed solid to form 26.5 ml of toluene slurry, which was then heated to 105 ° C. A mixture of 0.8 ml dibutyl ether and 16 ml titanium tetrachloride is added thereto and the mixture is stirred at 105 ° C. for 1 hour. After complete stirring, the mixture is solid-liquid separated at 105 ° C. and the solid obtained is washed three times with 40 ml of toluene at 105 ° C., respectively. 7.80 g of solid catalyst component is obtained by drying the washed solid under reduced pressure.
[206] The solid catalyst component contains 2.34 wt% titanium atoms, 14.06 wt% phthalic esters, 0.04 wt% ethoxy groups and 0.08 wt% butoxy groups.
[207] (2) Polymerization of propylene
[208] Same as Example (1) except that the cyclohexylethyldimethoxysilane was changed to dicyclopentyldimethoxysilane and the solid catalyst component was changed to 6.43 mg of the solid catalyst component synthesized in the above (1). The polymerization is carried out.
[209] PP / cat, CXS, [η] and bulk density are 39300 g / g, 0.19 wt%, 3.04 dl / g and 0.411 g / ml, respectively.
[210] Example 11
[211] (1) Polymerization of propylene
[212] Example 1 (1) is repeated except that the solid catalyst component is changed to 9.73 mg of the solid catalyst component synthesized in Example (1).
[213] PP / cat, CXS, [eta] and bulk density are 19300 g / g, 1.6 wt%, 1.65 dl / g and 0.385 g / ml, respectively.
[214] Comparative Example 6
[215] (1) Polymerization of propylene
[216] Example 1 (1) is repeated except that 1,3-dioxolane is not used and 7.53 mg of solid catalyst component is introduced.
[217] PP / cat is 26800 g / g and CXS is 1.9% by weight, higher than the value (1.6% by weight) obtained in Example 11 using 1,3-dioxolane. [eta] and bulk density are 1.60 dl / g and 0.383 g / ml, respectively.
[218] Example 12
[219] (1) Polymerization of propylene
[220] A 3 liter stainless steel autoclave was clarified with argon, 2.6 mmol of triethylaluminum, 0.26 mmol of 1,3-dioxolane, 0.26 mmol of 2,2-diisobutyl-1,3-dimethoxypropane and Example 2 16.92 mg of the solid catalyst component synthesized in (2) of was introduced thereto. Hydrogen is then added thereto in an amount corresponding to a partial pressure of 0.033 MPa. Also 780 g of liquefied propylene are introduced thereto. The temperature of the autoclave was raised to 80 ° C. and polymerization continued at 80 ° C. for 1 hour. After completion of the polymerization, the unreacted monomers are removed. 170 g of polypropylene powder is obtained by drying the resulting polymer under reduced pressure.
[221] The PP / cat, CXS, [η] and bulk densities of this polymer are 10000 g / g, 1.2 wt%, 1.55 dl / g and 0.370 g / ml, respectively.
[222] Comparative Example 7
[223] (1) Polymerization of propylene
[224] Example 12 is repeated except without using 1,3-dioxolane and introducing 8.64 mg of solid catalyst component.
[225] PP / cat is 17900 g / g and CXS is 1.5% by weight, higher than the value obtained in Example 12 using 1,3-dioxolane (1.2% by weight). [eta] and bulk density are 1.65 dl / g and 0.393 g / ml, respectively.
[226] Example 13
[227] (1) Polymerization of propylene
[228] A stainless steel autoclave with a volume of 0.1 L was purified with argon, 0.57 mmol of triethylaluminum, 0.057 mmol of 1,3-dioxolane, 2,2,6,6-tetramethylpiperidine and (2 3.9 mg of the solid catalyst component synthesized in) is introduced here. Then 40 g of liquefied propylene are introduced thereto. The temperature of the autoclave is then raised to 60 ° C. and polymerization continues at 60 ° C. for 1 hour. After completion of the polymerization, the unreacted monomers are removed. 24.8 g of polypropylene powder are obtained by drying the resulting polymer under reduced pressure. PP / cat and CXS are 6400 g / g and 3.8% by weight, respectively.
[229] Example 14
[230] (1) Polymerization of propylene
[231] Example 13 is repeated except that 0.114 mmol of 1,3-dioxolane is used and 5.3 mg of solid catalyst component is used. PP / cat and CXS are 5100 g / g and 3.1 wt%, respectively.
[232] Example 15
[233] (1) Polymerization of propylene
[234] Example 13 is repeated except that 1,3-dioxolane is changed to 0.057 mmol of 1,3-dioxane and 3.5 mg of solid catalyst component is introduced. PP / cat and CXS are 6200 g / g and 4.3% by weight, respectively.
[235] Comparative Example 8
[236] (1) Polymerization of propylene
[237] Example 13 is repeated except that 4.0 mg of solid catalyst component is introduced without 1,3-dioxolane and the polymerization time is changed to 42 minutes.
[238] PP / cat is 9600 g / g and CXS is 5.7% by weight, higher than the figure (3.8% by weight) obtained in Example 13 using 1,3-dioxolane.
[239] The present invention provides a process for producing a polymerization catalyst suitable for obtaining a high quality α-olefin polymer and a process for producing such α-olefin polymer.

权利要求:
Claims (19)
[1" claim-type="Currently amended] Α-, comprising contacting each other with the solid catalyst component (1) containing Ti, Mg and halogen as essential components, the organoaluminum compound (2) and the compound (3) having a -COCOC- bonding group in the ring-closure structure. Method for producing a catalyst for olefin polymerization.
[2" claim-type="Currently amended] The process for producing a catalyst for α-olefin polymerization according to claim 1, wherein the solid catalyst component further comprises an organic acid ester or ether.
[3" claim-type="Currently amended] 2. The solid catalyst component according to claim 1, wherein the solid catalyst component comprises a solid component (1) containing magnesium atoms, titanium atoms and hydrocarbyloxy groups, a halogen compound (2) having halogenation capability and an electron donor and / or organic acid halide (3). A process for producing a catalyst for α-olefin polymerization, which is prepared by a process comprising the step of contacting.
[4" claim-type="Currently amended] A method for producing an α-olefin polymer, comprising homopolymerizing or copolymerizing an α-olefin in the presence of a catalyst for α-olefin polymerization prepared by the method according to claim 1.
[5" claim-type="Currently amended] Contacting each other with the solid catalyst component (1) containing the Ti, Mg and halogen as essential components, the organoaluminum compound (2), the compound having a -COCOC- bonding group (3) and the alkoxy silicon compound (4) Method for producing a catalyst for α-olefin polymerization.
[6" claim-type="Currently amended] The method for producing a catalyst for α-olefin polymerization according to claim 5, wherein the compound having a -C-O-C-O-C- bonding group comprises a compound having a -C-O-C-O-C- bonding group in a ring-closure structure.
[7" claim-type="Currently amended] The process for producing a catalyst for α-olefin polymerization according to claim 5, wherein the solid catalyst component further comprises an organic acid ester or ether.
[8" claim-type="Currently amended] 6. The solid catalyst component according to claim 5, wherein the solid catalyst component comprises a solid component (1) containing magnesium atoms, titanium atoms and hydrocarbyloxy groups, a halogen compound (2) having halogenation capability and an electron donor and / or organic acid halide (3). A process for producing a catalyst for α-olefin polymerization, which is prepared by a process comprising the step of contacting.
[9" claim-type="Currently amended] A method for producing an α-olefin polymer, comprising homopolymerizing or copolymerizing an α-olefin in the presence of a catalyst for α-olefin polymerization prepared by the process according to claim 5.
[10" claim-type="Currently amended] Contacting each other with a solid catalyst component (1), an organoaluminum compound (2), a compound having a -COCOC- bonding group and a 1,3-diether compound (4) containing Ti, Mg and halogen as essential components Method for producing a catalyst for α-olefin polymerization, comprising the step of.
[11" claim-type="Currently amended] The method for producing a catalyst for α-olefin polymerization according to claim 10, wherein the compound having a -C-O-C-O-C- bonding group comprises a compound having a -C-O-C-O-C- bonding group in a ring-closure structure.
[12" claim-type="Currently amended] The process for producing a catalyst for α-olefin polymerization according to claim 10, wherein the solid catalyst component further comprises an organic acid ester or ether.
[13" claim-type="Currently amended] The solid catalyst component according to claim 10, wherein the solid catalyst component comprises a solid component (1) containing magnesium atoms, titanium atoms and hydrocarbyloxy groups, a halogen compound (2) having a halogenation capability and an electron donor and / or organic acid halide (3). A process for producing a catalyst for α-olefin polymerization, which is prepared by a process comprising the step of contacting.
[14" claim-type="Currently amended] A method for producing an α-olefin polymer, comprising homopolymerizing or copolymerizing α-olefin in the presence of a catalyst for α-olefin polymerization prepared by the method according to claim 10.
[15" claim-type="Currently amended] Contacting the solid catalyst component (1), organoaluminum compound (2), compound (3) having a -COCOC- bonding group and piperidine compound (4) with Ti, Mg and halogen as essential components, to each other The manufacturing method of the catalyst for alpha-olefin polymerization containing.
[16" claim-type="Currently amended] The method for producing a catalyst for α-olefin polymerization according to claim 15, wherein the compound having a -C-O-C-O-C- bonding group comprises a compound having a -C-O-C-O-C- bonding group in a ring-closure structure.
[17" claim-type="Currently amended] The process for producing a catalyst for α-olefin polymerization according to claim 15, wherein the solid catalyst component further comprises an organic acid ester or ether.
[18" claim-type="Currently amended] The solid catalyst component according to claim 15, wherein the solid catalyst component comprises a solid component (1) containing magnesium atoms, titanium atoms and hydrocarbyloxy groups, a halogen compound (2) having a halogenation capability and an electron donor and / or organic acid halide (3). A process for producing a catalyst for α-olefin polymerization, which is prepared by a process comprising the step of contacting.
[19" claim-type="Currently amended] A method for producing an α-olefin polymer, comprising homopolymerizing or copolymerizing α-olefin in the presence of a catalyst for α-olefin polymerization prepared by the method according to claim 15.

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同族专利:

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公开号 | 公开日

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DE10300262A1|2003-07-24|

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US20040092679A1|2004-05-13|

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CN1288174C|2006-12-06|

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CN1432583A|2003-07-30|

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US7049263B2|2006-05-23|

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US20030134992A1|2003-07-17|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2002-01-11|Priority to JP2002004401A

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2002-01-11|Priority to JPJP-P-2002-00004400

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2002-01-11|Priority to JPJP-P-2002-00004401

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2002-01-11|Priority to JP2002004400A

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2003-01-09|Application filed by 스미또모 가가꾸 고교 가부시끼가이샤

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2003-07-18|Publication of KR20030061318A

优先权:

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申请号 | 申请日 | 专利标题

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JP2002004401A|JP3941510B2|2002-01-11|2002-01-11|α-Olefin Polymerization Catalyst and Method for Producing α-Olefin Polymer|

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JPJP-P-2002-00004400|2002-01-11|

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JPJP-P-2002-00004401|2002-01-11|

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JP2002004400A|JP3941509B2|2002-01-11|2002-01-11|α-Olefin Polymerization Catalyst and Method for Producing α-Olefin Polymer|