JPH0455207B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for directly producing a wax-like polymer of α-olefin having 3 or more carbon atoms by low polymerization of α-olefin having 3 or more carbon atoms. A method for producing a wax-like polymer by homopolymerization of ethylene or copolymerization of ethylene and a small amount of α-olefin having 3 or more carbon atoms using a Ziegler type catalyst has already been proposed (for example, Japanese Patent Publication No. 40594/1983). issue). However, α with 3 or more carbon atoms
-α- with 3 or more carbon atoms by polymerization of olefin
There is still no known method for directly producing wax-like polymers of olefins. The reason for this is that when producing α-olefin polymers using many catalyst systems applicable to the production of high molecular weight polymers of α-olefins, the amount of molecular weight modifiers such as hydrogen used during polymerization is simply increased. This is because, even if a low molecular weight polymer can be produced by simply using the method, only an oily or rubbery polymer different from a crystalline polymer which is a waxy substance can be obtained. Therefore, in the past, wax-like substances of α-olefins having 3 or more carbon atoms, such as polypropylene waxes having a small molecular weight, hardness, and high melting point, have been produced by producing high-molecular-weight crystalline polypropylene. could only be produced by pyrolysis at high temperatures (eg British Patent No. 852431). However, this type of thermal decomposition method not only has the drawback that the operation is complicated, but also the polypropylene wax produced has many double bonds and has problems with thermal stability.Furthermore, the wax is already colored at the time of production. It has many technical challenges, including difficulties that are often encountered in the field. The present inventors have developed a method for directly producing an α-olefin polymer wax with a lower double bond content by polymerizing α-olefin, which does not require thermal decomposition operations as in the prior art. I've been doing research to find out. As a result, using a catalyst consisting of a specific combination of catalyst components, a crystalline polymer with an intrinsic viscosity (measured in decalin at 135°C) of 0.03 to 0.8 dl/g under hydrogen/alpha-olefin (partial pressure ratio) conditions was obtained. It has been discovered that a wax-like polymer of α-olefin having 3 or more carbon atoms can be directly produced. According to the research of the present inventors, the following (A) a highly active titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, (B) an organoaluminum compound catalyst component, and (C) Si-O- Using a catalyst formed from an organosilicon compound catalyst component having a C bond or a Si-N-C bond, a sterically hindered amine catalyst component, or an ester catalyst component of phosphorous acid and a C2 _{- C4} alcohol, hydrogen/α - Polymerizing α-olefin having 3 or more carbon atoms in the coexistence of hydrogen such that the olefin (partial pressure ratio) is 1 or more,
Intrinsic viscosity (measured in decalin at 135℃) is 0.03~
It has been found that by producing a crystalline polymer of 0.8 dl/g, it is possible to directly produce a polyolefin wax with excellent properties, overcoming many of the technical problems associated with the thermal decomposition method. Accordingly, an object of the present invention is to provide a method for polymerizing α-olefins having 3 or more carbon atoms to directly produce waxes of α-olefins having 3 or more carbon atoms having excellent properties. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The highly active solid titanium catalyst component (A) used in the present invention contains magnesium, titanium, halogen, and an electron donor as essential components. Here, the magnesium/titanium (atomic ratio) is preferably about 2 to about 100, more preferably about 4 to about 70,
The halogen/titanium (atomic ratio) is preferably about 4 to about 100, more preferably about 6 to about 40, and the electron donor/titanium (molar ratio) is preferably about 0.2.
Preferably, it ranges from about 10 to about 10, more preferably from about 0.4 to about 6. Also, its specific surface area is
Preferably 3 m ² /g or more, more preferably about 40
m ² /g or more, more preferably 100m ² /g or more
It is 800m ² /g. Such a solid titanium catalyst component (A) usually does not eliminate titanium compounds by simple means such as washing with hexane at room temperature. Regardless of the raw material magnesium compound used for catalyst preparation, the x-ray spectrum may be amorphous with respect to the magnesium compound, or may be amorphous compared to that of a normal commercially available magnesium dihalide. and is preferably in a highly amorphous state. The solid titanium catalyst component (A) preferably has an average particle size of about 1 to about 200μ, more preferably about 5 to about 100μ, particularly preferably about 8 to about 50μ, and has a geometric standard of particle size distribution. Deviation σg is preferably less than 2.1, more preferably 1.95
It is better if it is below. Here, the particle size distribution of the titanium catalyst component (A) can be determined by a light transmission method. Specifically, the catalyst component is diluted to a concentration of around 0.01 to 0.5% in an inert solvent such as decalin, placed in a measurement cell, and the cell is illuminated with a narrow light, passing through the liquid in a sedimented state with particles. The particle size distribution is determined by continuously measuring the intensity of the light emitted. Based on this particle size distribution, the standard deviation σg is determined from a lognormal distribution function. The average particle diameter of the catalyst can be expressed as a weight average diameter, and the particle size distribution can be calculated by sieving within a range of 10 to 20% of the weight average particle diameter. If particles whose average particle size is too small than the above range are used, the amount of soluble polymer may increase during polymer aggregation or slurry polymerization, resulting in a decrease in yield, which is undesirable. If a particle size larger than the above range is used, it will be difficult to perform homogeneous polymerization, and the amount of ultra-low molecular weight polymer produced will increase, which may cause the product to become sticky. It is preferable to adopt the average particle diameter as exemplified above. Furthermore, if a particle size distribution having a geometric standard deviation σg larger than the above is used, the uniformity of polymerization is impaired and the same drawbacks as mentioned above are likely to occur, which is not preferable. As mentioned above, it is preferable to adopt σg of less than 2.1, since this may cause a substantial disadvantage. As the titanium catalyst component (A), it is preferable to use a titanium catalyst component (A) having a regular shape such as a sphere, an ellipsoid, a flake, or a granule. The highly active solid titanium catalyst component (A) may contain other elements, metals, functional groups, etc. in addition to the above-mentioned essential components. Furthermore, it may be diluted with an inorganic or organic diluent. It is also preferable that the titanium catalyst component (A) has a high performance capable of producing about 1000 g or more of polyolefin wax per 1 mmol of titanium. A solid titanium catalyst component (A) that satisfies all of these favorable conditions can be prepared, for example, by a method of preparing a catalyst using a magnesium compound having an average particle size and particle size distribution within the above range, or by a method of preparing a catalyst using a magnesium compound having an average particle size and a particle size distribution within the above range, or by preparing a catalyst using a liquid magnesium compound and a liquid magnesium compound. By contacting a titanium compound,
It can be provided by a method of adjusting the average particle size and particle size distribution at the time of catalyst preparation. The method itself is known. For example, JP-A-55-135102, JP-A-55-135103, JP-A-56
-811, Japanese Patent Application No. 56-181019, and the like. Several aspects of these methods are briefly discussed below. (1) A magnesium compound/electron donor complex with an average particle diameter of about 1 to about 200μ and a geometric standard deviation of particle size distribution σg of less than 2.1 is used as an electron donor and/or
Or an embodiment in which the reaction is carried out with a halogenated titanium compound, preferably titanium tetrachloride, which forms a liquid phase under the reaction conditions, with or without pretreatment with a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. (2) A liquid magnesium compound that does not have reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to form particles with an average particle size of about 1 to about
An embodiment in which a solid component having a diameter of 200μ and a geometric standard deviation of particle size distribution σg of less than 2.1 is precipitated, and, if necessary, is further reacted with a liquid titanium compound, preferably titanium tetrachloride, or with an electron donor. Examples of magnesium compounds used in the preparation of the solid titanium catalyst component (A) include magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium produced by various methods. , alkoxymagnesium halide, allyloxymagnesium halide, magnesium dihalide, organomagnesium compounds, and reactants of organomagnesium compounds with electron donors, halosilanes, alkoxysilanes, silanols, and aluminum compounds. The organoaluminum compound that may be used in the preparation of the titanium catalyst component (A) can be appropriately selected from organoaluminum compounds that can be used in the olefin polymerization described below.
Furthermore, examples of halogen-containing silicon compounds that may be used in preparing the titanium catalyst component (A) include silicon tetrahalides, silicon alkoxy halides, silicon alkyl halides, and halopolysiloxanes. The titanium compound (C) used in the preparation of the titanium catalyst component (A) has the formula Ti(OR) _g x _4-g (R is a hydrocarbon group, e.g. a _C1 - _C12 alkyl group, a _C6 -C A tetravalent titanium compound represented by ₂₀ aryl groups, x is a halogen, and 0≦g≦4 is preferred. More specifically, titanium tetrahalides such as _TiCl4 , _{TiBr4 , TiI4} ; Ti( _OCH3 ) _Cl3 , Ti( _OC2H5 ) _Cl3 , Ti
Trihalogenated alkoxy (or _aryloxy ) titanium such _as (On _-C4H9 ) _Cl3 , Ti( _{OC2H5 ) Br3} , Ti( _OC6H5 ) _Cl3 ; Ti
(OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On−
_{Dihalogenated dialkoxy (or aryloxy) titanium such as C4H9)2Cl2 , Ti ( OC6H5} ) _{2Cl2 ,} Ti( _{OCH3 ) 3Cl} ,
Monohalogenated trialkoxy (or aryloxytitanium) such as Ti(OC ₂ H ₅ ) ₃ Cl, Ti(On−C ₄ H ₉ ) ₃ Cl, Ti(OC ₆ H ₅ ) ₃ Cl; Ti(OC ₄ H Examples include tetraalkoxytitanium (or _{tetraaryloxytitanium} ) such as ₉ ) ₄ , Ti( _OC6H5 ) ₄ , and mixtures thereof. Preferred are halogen-containing titanium compounds, which are formed in situ by the combination of halogen-free titanium compounds, such as tetraalkoxy (or aryloxy) titanium, and a halogenating agent, such as silicon tetrachloride. can be used. As titanium compounds it is also possible to use titanium trihalides such as titanium trichloride. Among these, titanium tetrachloride is particularly preferred. In addition, examples of electron donors that can be used in the production of titanium catalyst component (A) include alcohols, phenols, ketones, aldehydes, carboxylates, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. Examples include oxygen-containing electron donors, ammonia, amines, nitriles, and nitrogen-containing electron donors such as isocyanates. Examples of such electron donors include methanol, ethanol, propanol, pentanol,
Alcohols with 1 to 18 carbon atoms such as hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propulphenol, nonylphenol , C6 to C20 phenols which may have a lower alkyl group such as cumylphenol and naphthol; acetone,
Methyl ethyl ketone, methyl isobutyl ketone,
Carbon number 8 such as acetophenone and benzophenone
Ketones having 2 to 15 carbon atoms; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate,
Ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, dibutyl maleate, diethyl butylmalonate, diethyl dibutylmalonate, diethyl 1,2-cyclohexanecarboxylate, Di-2-ethylhexyl 1,2-cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, toluic acid Ethyl, amyl toluate, ethyl ethylbenzoate, methyl anisate,
Organic acid esters having 2 to 30 carbon atoms, such as ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; Ethyl acid, butyl silicate, vinyltriethoxysilane,
Alkoxysilane (or allyloxysilane) such as phenyltriethoxysilane and diphenylmethoxysilane; carbon number 2 to 15 such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisyl chloride, phthalic acid dichloride, etc.
Acid halides; ethers with 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, and ethylene glycol monobutyl ether; acetic acid amide, benzoic acid amide, toluic acid Acid amides such as amides; acid anhydrides such as benzoic anhydride and phthalic anhydride; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; Nitriles such as acetonitrile, benzonitrile, trinitrile, etc. can be mentioned. Two or more of these electron donors can be used in combination. The halogen atom constituting the titanium catalyst component (A) is fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred. Electron donors preferably contained in the solid titanium catalyst component (A) include active hydrogen such as esters of organic or inorganic acids, alkoxysilanes, ethers, ketones, tertiary amines, acid halides, and acid anhydrides. In particular, organic acid esters,
or alkoxysilane (or allyloxysilane),
Among them, polyvalent esters of aliphatic or aliphatic polycarboxylic acids, esters of aromatic carboxylic acids, and alkoxysilanes (or allyloxysilanes) having two or more alkoxy groups (or allyloxy groups) are preferable, especially those of the following formula:

[Formula] or

[Formula] or

[Formula] or

[Formula] (where R ¹ is a substituted or unsubstituted hydrocarbon group, R ² ,
R ⁵ and R ⁶ are hydrogen or substituted or unsubstituted hydrocarbon groups,
R ³ and R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. Furthermore, R ³ and R ⁴ may be connected to each other. The hydrocarbon group substituted here includes those containing different atoms such as N, O, and S, such as C-O-C, COOR, COOH,
It has groups such as OH, _SO3H , -C-N-C-, and _NH2 . ) is preferable. The above hydrocarbon group is a C ₁ -C ₂₀ hydrocarbon group,
Examples include methyl, ethyl, propyl, butyl, octyl, vinyl, and ethylene groups. For example, specific examples of preferable esters having the above-mentioned skeleton include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, α-
Diisobutyl methylglutarate, diethyl methylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate, diethyl butylmalonate,
Diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monoisooctyl maleate, diisooctyl maleate,
Aliphatic polycarboxylic acids such as di-n-butyl maleate, diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisooctyl citraconate, etc. ester, 1,2-
Alicyclic polycarboxylic acid esters such as diethyl cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadixate, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate , diethyl phthalate, ethyl isobutyl phthalate, di-n-phthalate
Propyl, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl phthalate Aromatic polycarboxylic acid esters such as butyl, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate,
Heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid, benzoylethyl salicylate, 1,2-diacetoxybenzene, 1-methyl-2,3-diacetoxybenzene, 2,3-diacetoxynaphthalene etc. can be mentioned. The organoaluminum compound catalyst component (B) used in the present invention has at least 1
Compounds with Al-carbon bonds are available,
For example, () general formula R ¹ _n Al (OR ² ) _o H _p X _q (where
R ¹ and R ² are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, e.g.
These R ¹ and R ² may be the same or different from each other in an alkyl group, aryl group, alkenyl group, cycloalkyl group, etc. X is halogen, m
is 0<m≦3, n is 0≦n<3, p is 0≦p<
3. q is a number of 0≦q<3, and m+n
+p+q=3), an organoaluminum compound represented by the general formula M ¹ AlR ¹ ₄ (where M ¹ is
Examples include complex alkylated products of Group 1 metals represented by Li, Na, and K (where R ¹ is the same as above) and aluminum. The organoaluminum compound belonging to the above () is, for example, R ¹ mAl(OR ² ) _3-n (where R ¹ and R ² are the same as above. m is preferably a number of 1.5≦m≦3). ), general formula R ¹ mAlX _3-n (where R ¹ is the same as above, X is halogen, m is preferably 0<m<3), general formula R ¹ mAlH _3-n (where R ¹ is the same as above. m is preferably 2≦
m<3. ), general formula R ¹ mAl(OR ² )nXq (where R ¹ and R ² are the same as above, X is halogen, 0<m≦3, 0≦n<3, 0≦q<3,
+n+q=3). In aluminum compounds belonging to (),
More specifically, trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisobrenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquiethoxide, butylaluminum Besides alkyl aluminum sesquialkoxides such as sesquibutoxide, R ¹ _2.5 Al (OR ² )
Partially alkoxylated aluminum alkyls having an average composition expressed _as alkyl aluminum sesquihalides such as bromide; partially halogenated alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc.; partially halogenated alkyl aluminum dihalides such as diethylaluminum hydride, dibutyl aluminum hydride, etc. Partially hydrogenated alkyl aluminums such as alkyl aluminum dihydrides such as dialkyl aluminum hydride, ethyl aluminum dihydride, propyl aluminum dihydride; partially hydrogenated alkylaluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide Examples include alkoxylated and halogenated alkyl aluminums. Examples of compounds belonging to the above () include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ . Further, as a compound similar to (), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl(C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl(C ₄ H ₉ ) ₂ ,

[Formula] etc. can be exemplified. Among these, it is particularly preferable to use trialkylaluminum and the above-mentioned alkyl aluminum in which two or more aluminums are combined. Si-O-C or Si- used in the present invention
Organosilicon compound catalyst component (C) having an N-C bond
Examples include alkoxysilane and aryloxysilane. As such an example, the formula RnSi(OR ¹ ) _4-o (where 0≦n≦3,
R is a hydrocarbon group, for example a C ₁ -C ₂₀ hydrocarbon group,
More specifically, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group, or a halogen,
R ¹ is a hydrocarbon group, for example a C ₁ -C ₂₀ hydrocarbon group,
More specifically, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxyalkyl group, etc. However, n R groups and (4-n) ^OR groups may be the same or different. . ) can be mentioned.
Other examples include siloxanes having ^one OR group and silyl esters of carboxylic acids. Other examples include compounds in which two or more silicon atoms are bonded to each other via oxygen or nitrogen atoms. The above organosilicon compounds can be produced by reacting a compound not having an Si-O-C bond with a compound having an O-C bond in advance or by reacting them at the polymerization site.
It may be used after being converted into a compound having an O-C bond. Examples of this include combinations of halogen-containing silane compounds or silicon hydrides that do not have Si-O-C bonds, and alkoxy group-containing aluminum compounds, alkoxy group-containing magnesium compounds, other metal alcoholates, alcohols, formic acid esters, ethylene oxides, etc. Examples include combination use. The organosilicon compound may also contain other metals (eg, aluminum, tin, etc.). More specifically, trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane , γ-chloropropyltrimethoxysilane, mekyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyl Triisopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxysilane, dimethyltetraethoxy Examples include disiloxane and phenyldiethoxydiethylaminosilane. Among these, particularly preferred are methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, ethyl silicate, Diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenylmethoxysilane, etc. are those represented by the above formula RnSi(OR ¹ ) _4-o . Sterically hindered amines include polyalkylpiperidines, polyalkylpyrrolidines, tetraalkylalkylene diamines, and the like. Component (C) can also be used in the form of an adduct with other compounds. In the present invention, an α-olefin having 3 or more carbon atoms is polymerized using a catalyst formed from the catalyst components (A), (B), and (C) described above, and the intrinsic viscosity (measured at 135°C in decalin) is A wax-like polymer is produced in the form of a crystalline polymer with a particle diameter of 0.03 to 0.8 dl/g. The α-olefins include propylene, 1-butene, 4
Examples include _C3 to _C10 α-olefins such as -methyl-1-pentene, 3-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, and 1-octene. These may be homopolymerized or the above α-olefins or the above α-olefins may be homopolymerized or
A waxy polymer can be produced by copolymerizing olefin with a small amount of ethylene. In the above copolymerization, one type of α-
It is preferable to carry out copolymerization such that the olefin content is at least 90 mol % or more, preferably 95 mol % or more. Particularly preferred are α-olefins having 3 to 6 carbon atoms, especially propylene. Catalyst components (A), (B), and (C) may be premixed prior to polymerization. When such premixing is performed, the catalyst components (A) and/or (B) may be mixed during polymerization.
and/or component (C) may be used again or may not be used. In the above premixing, a small amount of olefins may be present, and in this case, polymerization of the olefins occurs. Further, the liquid substance may be removed after premixing. Such premixing and prepolymerization are often effective in making subsequent polymerization operations more smooth, but when performing prepolymerization, the amount of prepolymerization should be about 1 to about 140 g per 1 mmol of titanium. , especially about 3 to about 30g
It is preferable to set it as approximately. The production of wax-like polymers consisting of crystalline polymers can be carried out under slurry polymerization or gas phase polymerization conditions. The polymerization temperature is preferably 20 to 150°C, more preferably 50 to 100°C.
If the polymerization temperature is lower than the above range, it is difficult to produce a wax-grade polymer with a molecular weight, and conversely, if the polymerization temperature is higher than the above range, it is difficult to produce a crystalline wax-like polymer that is hard and has a high melting point. Both cases are undesirable because it is difficult to The production of waxy polymers also requires the use of certain amounts of hydrogen. The amount should be greater than or equal to 1, preferably from about 3 to about 10, expressed as hydrogen/alpha-olefin (partial pressure ratio) in the polymerization system. When the waxy polymer is prepared by slurry polymerization, an inert hydrocarbon medium is preferably used and the concentration of alpha-olefin in the liquid phase is from about 1 to about 20% by volume, especially from about 1 to about 20% by volume. Preferably, the amount of the medium used is adjusted to 5% by volume. In slurry polymerization, it is also preferable to select conditions such that 80% by weight or more, particularly 90% by weight or more of the resulting polymer is insoluble in the polymerization medium. Examples of inert hydrocarbons that can be used for the above purpose include propane, butane, n-pentane, isopentane, n-hexane, n-heptane, n-
Aliphatic hydrocarbons such as octane, isooctane, n-decane, n-dodecane, kerosene, liquid paraffin; cyclopentane, methylcyclopentane,
Examples include alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; or mixtures thereof.
Among these, it is particularly preferable to use aliphatic hydrocarbons having 4 to 10 carbon atoms. In slurry polymerization, the slurry concentration is, for example, 40 to
Polymerization can be carried out while maintaining the amount within a range such as 400 g/. Waxy polymers can also be produced by gas phase polymerization or solution polymerization. Gas phase polymerization can be carried out using a fluidized bed, a stirred fluidized bed, or the like. The amount of each catalyst component to be used is preferably about 0.005 to about 0.5 mmol, more preferably about 0.001 to about 0.5 mmol per polymerization volume in terms of titanium atoms.
0.5 mmol, it is preferable to adjust component (B) such that the Al in component (B)/Ti in component (A) (atomic ratio) is about 1 to about 2000, preferably about 1 to about 500. . Further, it is preferable that component (C) has a Ti (molar ratio) of component (C)/component (A) of about 0.05 to about 200. When premixing each catalyst component or prepolymerizing olefin at the time of mixing, the amount of each catalyst component used includes the amount used at the time of premixing (or prepolymerization). Premixing (or prepolymerization) is usually carried out in an inert hydrocarbon medium, but the premix (or prepolymerization mixture) may be used as is for polymerization, or it may be used after separating and removing the inert hydrocarbon medium. If necessary, the polymer may be used for polymerization after further washing with an inert hydrocarbon. In the present invention, by the above operations, 135°C,
Intrinsic viscosity measured in decalin between 0.03 and 0.8
dl/g, preferably 0.05 to 0.6 dl/g, a polyolefin wax of α-olefin having 3 or more carbon atoms is produced. The limiting viscosity can be adjusted by adjusting the polymerization temperature and hydrogen partial pressure within the above-mentioned ranges. Thus, according to the present invention, the molecular weight distribution is narrow;
A hard and crystalline polyolefin wax with few double bonds can be easily obtained. Such polyolefin waxes, for example, have a crystallinity determined by X-ray diffraction of usually 40% by weight or more, preferably 50% by weight or more, an iodine value of 1g/100g wax or less,
Preferably 0.8g/100g wax or less, more preferably 0.6g/100g wax or less, molecular weight distribution
Mw/Mn is 6 or less, preferably 5 or less, more preferably 4 or less. For example, polypropylene wax usually has a melting point of 130 to 165.
°C, preferably 140 to 160 °C, softening point (JIS K
2531) is usually 130 to 200℃, preferably 140℃
to 180°C, the penetration (JIS K 2530 penetration) is usually 5 or less, preferably 3 or less, and the density is 0.89 to 0.93 dl/g. Further, the isotacticity as measured by ¹³ C NMR is 90% or more, preferably 91% or more. In particular, for polypropylene waxes made of propylene homopolymer, this isotacticity is usually 92% or more, preferably 93%.
The above is shown. Polyolefin waxes obtained by thermal decomposition of high-molecular-weight polyolefins have a large amount of double bonds and are thermally unstable, and may also contain ultra-low-molecular-weight polyolefins that are liquid at room temperature. However, the polyolefin wax of the present invention does not have these drawbacks. do not have. That is, because it has excellent thermal stability and weather resistance, it exhibits excellent effects as a paint vehicle, a fluidity improver for various resins such as polyolefins and engineering plastics, and a roll release agent for heat-fixed toner. When the polyolefin wax is produced by slurry polymerization, the polyolefin wax insoluble in the polymerization medium can be separated from the polymerization medium by solid-liquid separation means such as filtration or centrifugation after the polymerization is completed. Solvent-soluble polymers can be recovered separately by distilling off the polymerization medium. Alternatively, the slurry after polymerization is once heated to dissolve the entire amount, and then the polymerization medium is removed to obtain a polyolefin wax containing a mixture of insoluble and soluble substances in the polymerization medium. be able to. A preferred method of this method is to carry out polymerization by flashing a solution in which all of the above amounts have been dissolved under vacuum, maintaining the solution under conditions of temperature and pressure sufficient to vaporize the entire amount of polymerization medium, and then applying vacuum. This method vaporizes the medium and collects the wax. Next, examples will be shown. Example 1 (1) Preparation of solid Ti catalyst component 4.8 kg of anhydrous magnesium chloride, 25.0 kg of decane, and 23.4 kg of 2-ethylhexy alcohol were heated at 130°C.
After heating the reaction for 2 hours to make a homogeneous solution, 11.1 kg of phthalic anhydride was added to this solution and heated at 130°C.
The mixture was further stirred and mixed for 1 hour to dissolve phthalic anhydride into the homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped into titanium tetrachloride 200 maintained at -20 DEG C. over 1 hour. After charging, the temperature of this mixed liquid was increased to 4.
The temperature was raised to 110°C over a period of time, and when it reached 110°C, 2.7 g of diisobutyl phthalate was added, and the mixture was kept at the same temperature for 2 hours with stirring. After 2 hours of reaction, the solid part was collected by heating and
Thoroughly wash with hexane at ℃ until the concentration of free titanium compound in the washing liquid becomes 0.1 mmol/or less. A solid Ti catalyst component was obtained by the above manufacturing method. (Prepolymerization) The obtained catalyst slurry is converted into Ti atoms and is 15
After resuspending in hexine to give a concentration of 150 mmol/triethylaluminum and further add diphenyldimethoxysilane to a concentration of 30 mmol/. Next, propylene was supplied at a rate of 3 g per 1 g of titanium catalyst component, and prepolymerization was carried out at a temperature of 30° C. or lower. The catalyst slurry that has undergone prepolymerization is
After leaving it to stand still and extracting the supernatant hexane, hexane is newly added and washing is carried out with stirring. This washing operation is repeated, and the washing is completed when the remaining amount of hexane present during prepolymerization becomes 10 vol % or less. (Polymerization) After charging 10 mmol of n-hexane and 20 mmol of triethylaluminum into a polymerization vessel having an internal volume of 35 mm, the temperature was raised to 80°C. Thereafter, propylene and hydrogen were added such that the gas composition was hydrogen/propylene (molar ratio) = 6.3. Polymerization was carried out at a pressure of 15 Kg/cm ² G and a temperature of 80° C. by adding 0.4 mmol of the Ti catalyst subjected to the above prepolymerization treatment. The polymerization pressure was maintained at 15 Kg/cm ² G by adding propylene gas. After the polymerization was completed, the hexane solvent was separated by filtration, and the resulting polymer was dried at 50°C under a nitrogen atmosphere. The polymer was in powder form and the yield was 2000 g. The intrinsic viscosity of the polymer (measured in decalin at 135°C) is
It was 0.20 dl/g. Melting point 151℃, Mw/Mn=
2.7, iodine value = 0.4g/100g wax, crystallinity 56%. Example 2 (Polymerization) In a polymerization vessel with an internal volume of 400, the above prepolymerized catalyst suspended in n-hexane and prepared at 1 mmol/hr was added, and triethylaluminum was added at 100 mmol/hr.
mmol/hr, 5m of diphenyldimethoxysilane
mol/hr, n-hexane was continuously supplied at a rate of 40/hr. At the same time, propylene 4.5Kg/hr,
The gas composition is hydrogen/propylene (molar ratio)
= 7.0. Pressure 13Kg/ ^cm2G ,
Polymerization was carried out at a temperature of 80°C and an average residence time of 4 hours. The n-hexane slurry of the polymer was depressurized to atmospheric pressure to separate unreacted propylene and hydrogen, and the n-hexane was further separated in a decanter, followed by drying at 130°C in a _N2 stream using a fluidized bed dryer. I went there. The obtained polymer is in the form of a powder with good fluidity, and the polymerization activity is 4000g polymer/mmol.
It was Ti. The molecular weight was 0.30 dl/g in terms of intrinsic viscosity (measured in decalin at 135°C). Crystallinity
54%, melting point 155℃, Mw/Mn=2.3, iodine value 0.35
g/100g wax. Example 3 (Preparation of solid catalyst component (A)) After replacing a high-speed stirring device with an internal volume of 2 (Tokushu Kika Kogyo) with enough _N2 , 700 ml of refined kerosene was prepared on the market.
10 g of MgCl ₂ , 24.2 g of ethanol, and 3 g of Emazol 320 (manufactured by Kao Atlas Co., Ltd., sorbitan distearate) were added, and the temperature of the system was raised while stirring.
The mixture was stirred at 120° C. and 800 rpm for 30 minutes. Under high speed stirring,
Using a Teflon tube with an inner diameter of 5 mm, the liquid was transferred to a 2-glass flask (equipped with a stirrer) filled with refined kerosene 1 previously cooled to -10°C. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier. After 7.5 g of the carrier was suspended in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added and the system was heated to 120°C. After stirring and mixing at 120°C for 2 hours, the solid part was collected by filtration and heated again at 150°C.
The suspension was suspended in ml of titanium tetrachloride and stirred and mixed again at 130°C for 2 hours. Further, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component (A). The components are 2.3% by weight of titanium, 64.0% by weight of chlorine,
The magnesium content was 21.0% by weight. (Polymerization) (Preliminary polymerization) Preliminary polymerization was carried out according to the method described in Example 1. Purified hexane in an autoclave with an internal volume of 2
Pour 750ml into the tank and place it in a propylene atmosphere at room temperature.
2.51 mmol of triethylaluminum, 0.251 mmol of phenyltriethoxysilane, and 0.05 m of the prepolymerized solid Ti catalyst component in terms of titanium atoms.
mol was charged. After heating to 80℃, 6.3Kg/ with hydrogen
The pressure was applied to cm ² G, and the pressure was further increased to 7 kg/cm ² G using propylene, and polymerization was carried out for 2 hours. During polymerization, the temperature is
The temperature was maintained at 80°C, and the polymerization pressure was maintained at 7 kg/cm ² G by supplementing propylene. A solid powder was collected by filtration from the hexane slurry after the polymerization was completed, and the powder was dried. The polymerization results are shown in Table 1. Example 4 (Preparation of solid catalyst component (A)) 20 g of anhydrous magnesium chloride, 8.0 ml of diisobutyl phthalate, 3.3 ml of titanium tetrachloride, and silicone oil as a grinding aid (TSS-451, 20cs, manufactured by Shin-Etsu Chemical Co., Ltd.)
Internal volume 800 containing 2.8 kg of stainless steel (SUS-32) balls with a diameter of 15 mm and 3.0 ml in a nitrogen atmosphere.
ml, charged into a stainless steel (SUS-32) ball mill container with an inner diameter of 100 mm, and subjected to an impact acceleration of 7 G for 24
contact for an hour. 15g of the obtained co-pulverized material is 1,2
- Suspended in 150 ml of dichloroethane and heated to 80°C for 2 hours.
After contacting with stirring for a period of time, the solid portion is collected by filtration, thoroughly washed with purified hexane until no free 1,2-dichloroethane is detected in the washing liquid, and then dried to obtain catalyst component (A). The ingredients are 3.2% by weight of titanium and 60.0% by weight of chlorine magnesium.
It was 17.0% by weight. (Polymerization) Propylene polymerization was performed by the method described in Example 3. The results are shown in Table 1. Example 5 (Preparation of solid catalyst component (A)) 20 g of anhydrous magnesium chloride, 8.0 ml of diisobutyl phthalate, and 3.0 ml of silicone oil (TSS-451, 20cs, manufactured by Shin-Etsu Chemical Co., Ltd.) as a grinding aid were added to a 15 mm diameter tube in a nitrogen atmosphere. A stainless steel (SUS-32) ball mill container with an internal volume of 800 ml and an inner diameter of 100 mm containing 2.8 kg of stainless steel (SUS-32) balls is charged, and the container is left in contact with the ball at an impact acceleration of 7 G for 24 hours.
15 g of the obtained co-pulverized material was suspended in 150 ml of titanium tetrachloride, and after contacting with stirring at 110°C for 2 hours, the solid part was collected by filtration, and free titanium compounds were detected in the washing liquid. The catalyst component (A) is obtained by thoroughly washing with purified hexane until completely free and drying. The components are 3.8% by weight of titanium, 59.0% by weight of chlorine,
The magnesium content was 16.0% by weight. (Polymerization) Propylene polymerization was performed using the method described in Example 3. The results are shown in Table 1. Examples 6, 7, and 8 Polymerization was carried out in accordance with Example 3, except that 0.251 mmol of phenyltriethoxysilane added during polymerization was changed to the compound shown in Table 1.

[Table] Example 9 Instead of propylene 4.5Kg/hr, propylene 4.4
Example 2 except using Kg and ethylene 0.1Kg/hr
Polymerization was carried out in the same manner as above, the polymer slurry was poured into 5 times the amount of methanol to recover the polymer, and the obtained polymer was dried at 100°C. The polymerization activity was 4200 g polymer/mmol Ti. The molecular weight was 0.28 dl/g in terms of intrinsic viscosity (measured in decalin at 135°C). Crystallinity 43%, melting point 138℃, Mw/Mn=3.7, iodine value 0.42g/100
The wax had an ethylene content of 3.5 mol%. Example 10 In a polymerization vessel with an internal volume of 35 m, 10 m of n-hexane, 0.5 m of liquid 1-butene, and 20 m of triethyl aluminum were added.
mol and 2 mmol of vinyltriethoxysilane were added, hydrogen was added to give a concentration of 15 kg/cm ² G, and the temperature was raised to 80°C. Polymerization was started by adding 0.5 mmol of the Ti catalyst component of Example 1, liquid 1-butene 3 was added over 3 hours, and polymerization was further continued for 1 hour. Polymerization was stopped by adding 0.5 ml of isobutanol, and the polymer was precipitated and separated by pouring into 50 ml of methanol, followed by drying at 50° C. in a nitrogen atmosphere. The yield of polymer is
It was 1600g. Intrinsic viscosity of polymer (135℃,
The value measured in decalin was 0.23 dl/g, the melting point after 1 hour of press molding was 108°C, Mw/Mn = 3.4, the iodine value was 0.3 g/100 g wax, and the crystallinity was 45%. Example 11 In a polymerization vessel with an internal volume of 35, 10 toluene, 0.5 4-methyl-1-pentene, 20 mmol of triethylaluminum, and 20 mmol of trimethylmethoxysilane were added.
and added hydrogen to 15Kg/cm ² G.
The temperature was raised to 80°C. 0.5m of Ti catalyst component of Example 1
mol was added to start polymerization, 4-methyl-1-pentene 3 was added over 3 hours, and polymerization was further continued for 1 hour. Polymerization was stopped by adding 0.5 ml of isobutanol, and the polymer was precipitated and separated by pouring into 50 ml of methanol, followed by drying at 50° C. in a nitrogen atmosphere.
The yield of polymer was 1500g. The intrinsic viscosity of the polymer (measured in decalin at 135°C) is
0.26 dll/g, melting point 230°C, Mw/Mn=3.6, iodine value=0.4 g/100 g wax, crystallinity 47%.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing the steps for preparing a catalyst used in the method of the present invention.

Claims (1)

[Scope of Claims] 1 (A) a highly active titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, (B) an organoaluminum compound catalyst component, and (C) having a Si-O-C bond. Using a catalyst formed from an organosilicon compound catalyst component, a sterically hindered amine catalyst component, or an ester catalyst component of phosphorous acid and a C ₂ to C ₄ alcohol, the hydrogen/α-olefin (partial pressure ratio) is 1 or more. α- with 3 or more carbon atoms in the coexistence of hydrogen such as
A method for producing a polyolefin wax, which comprises polymerizing an olefin to produce a crystalline polymer having an intrinsic viscosity (measured at 135°C in decalin) of 0.03 to 0.8 dl/g. 2. The method according to claim 1, characterized in that the production is carried out by slurry polymerization, and the concentration of the polymer in the polymerization system is 40 to 400 g/. 3. The method according to claim 2, wherein the polymer contains 80% by weight or more of solids that are insoluble in the polymerization medium.