JPH0335322B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a propylene random copolymer that has excellent transparency, low surface tackiness, and low odor. The applicant has already produced a low-crystalline propylene random copolymer with excellent properties using a titanium catalyst component containing magnesium, titanium, and a halogen as essential components, and a catalyst system that requires the use of an electron donor. A method to do this has been proposed in Japanese Patent Application Laid-Open Nos. 53-79984 and 1987-104686. In subsequent studies, we found that benefits such as increased catalytic activity and longer catalyst life could be obtained by adopting a combination formulation of a specific electron donor that was not specifically disclosed in the prior application in the catalyst system. At the same time, it has been found that it is possible to produce a propylene random copolymer that has even better transparency, has a further reduced tendency to stick to the surface, and has less odor. Therefore, the present invention
The present invention relates to an improved method for producing propylene random copolymers. More specifically, the present invention provides a highly active titanium catalyst component comprising (A) magnesium, titanium, halogen, and an electron donor as essential components, wherein the electron donor comprises (a) a polyhydric carboxylic acid ester and (b) )RCOOR′, whose hydrocarbon group R,
a titanium catalyst component which is an ester selected from the group consisting of monocarboxylic acid esters in which at least one R' is a branched or ring-containing chain group; (B) an organoaluminum compound catalyst component; and (C) Si Propylene and α-olefin having 4 or more carbon atoms are randomly copolymerized in the presence of a catalyst formed from an organosilicon compound catalyst component having a -O-C bond or a sterically hindered amine catalyst component, and the propylene content is 40%. The present invention relates to a method for producing a propylene random copolymer, which comprises producing a random copolymer having a crystallinity of 40% by weight or less and a crystallinity of 40% by weight or less. The titanium catalyst component (A) used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen, and a specific electron donor described below as essential components.
This titanium catalyst component (A) contains magnesium halide with lower crystallinity than commercially available magnesium halides, and usually has a specific surface area of about 3 m ² /g.
As mentioned above, it is preferably about 40 to about 1000 m ² /g, more preferably about 80 to about 800 m ² /g, and its composition does not substantially change by washing with hexane at room temperature. In the titanium catalyst component (A), the halogen/titanium (atomic ratio) is about 5 to about
200, especially about 5 to about 100, electron donor/titanium (molar ratio) about 0.1 to about 10, especially about 0.2 to about 6, magnesium/titanium (atomic ratio) about 2 to about 100, especially about 4 to about
A value of about 50 is preferable. Component (A) may also contain other electron donors, metals, elements, functional groups, etc. It may also contain organic or inorganic diluents such as silicon compounds, aluminum compounds, polyolefins, etc. Such a titanium catalyst component (A) can be obtained, for example, by mutual contact of a magnesium compound (or magnesium metal), an electron donor and a titanium compound, but optionally with other reactants, such as silicon, Compounds such as phosphorus aluminum can further be used. As a method for producing such a titanium catalyst component (A), for example, JP-A-50-108385 and JP-A-50-126590 are used.
No. 51-20297, No. 51-28189, No. 51-
No. 64586, No. 51-92885, No. 51-136625, No. 52
-87489, 52-100596, 52-147688,
No. 52-104593, No. 53-2580, No. 53-40093,
No. 53-43094, No. 55-135102, No. 55-135103
No. 56-811, No. 56-11908, No. 56-18606
It can be manufactured according to the method disclosed in No. Some examples of methods for producing these titanium catalyst components (A) will be briefly described below. (1) A magnesium compound or a complex compound of a magnesium compound and an electron donor,
Grinding or not, with or without grinding aids, pretreated with electron donors and/or reaction aids such as organoaluminum compounds or halogen-containing silicon compounds, in the presence or absence of grinding aids, etc. The solid obtained is reacted with a titanium compound that forms a liquid phase under reaction conditions. However, the above electron donor is used at least once. (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 precipitate a solid titanium complex. (3) React the material obtained in (2) with a titanium compound. (4) React the material obtained in (1) or (2) with an electron donor and a titanium compound. (5) A magnesium compound or a complex compound of a magnesium compound and an electron donor,
Grinding in the presence or absence of grinding aids etc. and in the presence of titanium compounds, pre-treated with electron donors and/or reaction aids such as organoaluminum compounds and halogen-containing silicon compounds; The solid obtained without this is treated with a halogen or a halogen compound or an aromatic hydrocarbon. However, the above electron donor is used at least once. (6) Treating the compounds obtained in (1) to (4) above with a halogen, a halogen compound, or an aromatic hydrocarbon. Among these preparation methods, in catalyst preparation,
Preferably, liquid titanium halide is used, or a halogenated hydrocarbon is used after or during use of a titanium compound. One of the electron donors that can be a component of the highly active titanium catalyst component (A) of the present invention is an ester of polyhydric carboxylic acid. Suitable esters of these polycarboxylic acids are:

[Formula] or

[Formula] (where R' is a substituted or unsubstituted hydrocarbon group,
R ² and R ⁵ 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. Also R ³ and R ⁴
may be connected to each other. Substituted hydrocarbon groups in R ¹ to ^{R 4} include those containing different atoms such as N, O, and S, such as C-O-C and COOR.
(Here R is a hydrocarbon group), COOH, OH, SO ₃ H,
It has groups such as -C-N-C- and _NH2 . ) can be exemplified. Particularly preferred among these are diesters of dicarboxylic acids in which at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms. Specific examples of preferable polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, dibutyl malonate, diethyl methylmalonate, diethyl ethylmalonate,
Diethyl isopropylmalonate, diethyl butylmalonate, diethyl phenylmalonate, diethylmalonate, diethyl allylmalonate, diethyl diisobutylmalonate, diethyl di-n-butylmalonate, dimethyl maleate, monooctyl maleate, dioctyl maleate, maleic acid Aliphatic compounds such as dibutyl, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, dibutyl itaconate, dioctyl citraconate, dimethyl citraconate, etc. Polycarboxylic acid ester; alicyclic polycarboxylic acid ester such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadixate; monoethyl phthalate, dimethyl phthalate, Methyl ethyl phthalate, monoisobutyl phthalate, mononormal butyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, ethyl normal butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-phthalate
Butyl, diisobutyl phthalate, di-n-phthalate
heptyl, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate,
Aromatic polycarboxylic acid esters such as triethyl trimellitate and dibutyl trimellitate; 3.
Examples include heterocyclic polycarboxylic acid esters such as 4-furandicarboxylic acid. Other examples of polyhydric carboxylic acid esters that can be supported in the titanium catalyst component include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate,
Di-n-octyl sebacate, di-2- sebacate
Examples include esters of long-chain dicarboxylic acids such as ethylhexyl. Among these polyfunctional esters, preferred are:
It has a skeleton of the general formula described above, and more preferably an ester of phthalic acid, maleic acid, substituted malonic acid, substituted succinic acid, 1,2-cyclohexanedicarboxylic acid, etc. and an alcohol having 2 or more carbon atoms, Particularly preferred is a diester of phthalic acid and an alcohol having 2 or more carbon atoms. Other electron donor components that can be supported on the titanium catalyst component include RCOOR' [R and R' are hydrocarbon groups that may have substituents, and at least one of them is a branched (fatty) It is a monocarboxylic acid ester represented by a cyclic group) or a ring-containing chain group. For example _, as R and/or R', ( _CH3 ) _2CH- , _C2H5CH ( _CH3 )-,
(CH ₃ ) ₂ CHCH ₂ −, (CH ₃ ) ₃ C−, C ₂ H ₅ CH (CH ₃ )
CH ₂ −,

【formula】

【formula】

【formula】

【formula】

It may be a group such as [Formula]. If either R or R′ is a group as described above, the other may be a group as described above,
Alternatively, it may be another group, such as a linear or cyclic group. Specific examples of the above RCOOR' include various monoesters of carboxylic acids such as dimethyl acetic acid, trimethyl acetic acid, α-methyl butyric acid, β-methyl butyric acid, methacrylic acid, and benzoyl acetic acid, isopropanol,
Examples include various monocarboxylic acid esters of alcohols such as isobutyl alcohol, tert-butyl alcohol, and the like. Among these, those in which R is branched are particularly preferred, and those in which R' is also branched are more preferred. When supporting these electron donors, it is not necessarily necessary to use them as starting materials, but by using compounds that can be converted into these in the process of preparing the titanium catalyst component and converting them into these compounds at the stage of preparation. Good too. Electron donors other than the above (a) and (b) may coexist in the titanium catalyst component, but should be kept to a small amount since coexisting in too large a quantity will have sub-effects. In the present invention, the magnesium compound used to prepare the solid titanium catalyst component [A] is a magnesium compound that may or may not have reducing ability. Examples of the former include magnesium compounds with magnesium-carbon bonds and magnesium-hydrogen bonds, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, and propylmagnesium chloride. , butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, butylmagnesium hydride, and the like. These magnesium compounds can also be used in the form of complex compounds with organoaluminium, etc., and
It may be in a liquid state or a solid state. On the other hand, magnesium compounds without reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride,
Alkoxymagnesium halides such as ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride; allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n- Alkoxymagnesium such as octoxymagnesiummagnesium and 2-ethylhexoxymagnesium; allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate, etc. can be exemplified. Further, these magnesium compounds without reducing ability may be derived from the above-mentioned magnesium compounds having reducing ability, or may be derived during preparation of the catalyst component. For example, there is a method in which a magnesium compound having reducing ability is brought into contact with a compound such as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, or an alcohol to convert it into a magnesium compound having no reducing ability. Moreover, the magnesium compound may be a complex compound with other metals, a composite compound, or a mixture with other metal compounds. Furthermore, it may be a mixture of two or more of these compounds. Among these, preferred magnesium compounds are those without reducing ability, and particularly preferred are halogen-containing magnesium compounds, particularly magnesium chloride, alkoxymagnesium chloride, allyloxymagnesium chloride. In the present invention, there are various titanium compounds used for preparing the solid titanium catalyst component [A], but usually Ti(OR) _g X _4-g (R is a hydrocarbon group, X is a halogen, 0≦g≦4 ) is suitable. More specifically, _TiCl4 ,
Titanium tetrahalides such as _TiBr4 , _TiI4 ; Ti
( _OCH3 ) _Cl3 , Ti _{( OC2H5} ) _Cl3 , Ti(On− _{C4H9 )}
Trihalogenated alkoxytitanium such _{as Cl3} , Ti( _OC2H5 ) _Br3 , Ti( _Ois0C4H9 ) _{Br3 ; Ti}
(OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On−
_{Dihalogenated alkoxy} titanium such as _{C4H9 ) 2Cl2} , Ti( _OC2H5 ) _2Br2 ; Ti( _OCH3 ) _3Cl , _Ti
(OC ₂ H ₅ ) ₃ Cl, Ti (On−C ₄ H ₉ ) ₃ Cl, Ti
Monohalogenated trialkoxytitanium such as (OC ₂ H ₅ ) ₃ Br; Ti(OCH ₃ ) ₄ , Ti(OC ₂ H ₅ ) ₄ , Ti(On−
Examples include tetraalkoxytitanium such as C ₄ H ₉ ) ₄ . Preferred among these are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be used after being diluted with a hydrocarbon or halogenated hydrocarbon. In preparing the titanium catalyst component (A), a titanium compound, a magnesium compound, and (a), (b) to be supported,
(c) an electron donor selected from the above, and other reaction reagents that may be used as necessary, such as other electron donors such as alcohols, phenols, monocarboxylic acid esters, silicon compounds, aluminum compounds; The amount of electron donor to be supported varies depending on the preparation method and cannot be absolutely specified, but for example, about the amount of electron donor to be supported per 1 mole of magnesium compound.
0.05 to about 5 moles, 0.05 to about 5 moles of titanium compound
The proportion can be about 500 moles. In the present invention, titanium catalyst components such as those described above are used.
Olefin polymerization or copolymerization is carried out using a combination catalyst of (A), an organoaluminum compound catalyst component (B), and an organosilicon compound catalyst component or sterically hindered amine catalyst component (C) to be described later. The above component (B) includes (i) at least 1 in the molecule;
Organoaluminum compounds having 1 ^to 15 _Al -carbon bonds, such as those with the general formula R ¹ _n Al (OR ^{2 )} _o H _p 4 hydrocarbon groups which may be the same or different from each other. X is halogen, m is 0<m≦3, 0≦n<3, p is 0≦p<
3. q is a number of 0≦q<3, and m+n
+p+q=3); (ii) Group metals represented by the general formula M ¹ AlR ¹ ₄ (where M ¹ is Li, Na, K, and R ¹ is the same as above); Examples include complex alkylated products of aluminum and aluminum. Examples of the organoaluminum compounds that belong to (i) above include the following. General formula R ¹ _n Al(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 _n AlX _{3- n} (Here, R ¹ is the same as above. X is halogen, m
is preferably 0<m<3. ), general formula R ¹ _n AlH _3-n (where R ¹ is the same as above. m is preferably 2
≦m<3. ), general formula R ¹ _n Al (OR ² ) _o X _q (where R ¹ and R ² are the same as above. ,
Examples include those represented by m+n+q=3. Among the aluminum compounds belonging to (i), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum,
In addition to trialkenylaluminums such as triisoprenylaluminum, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide, and alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, R ¹ ₂ . Partially alkoxylated alkylaluminum, dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminium bromide, ethylaluminum sesquichloride, butylaluminum, with an average composition expressed as ₅ Al(OR ² ) _0.5 , etc. Partially halogenated alkyl aluminum, diethylaluminum hydride such as sesquichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide, alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide etc. , dialkyl aluminum hydride such as dibutyl aluminum hydride, ethyl aluminum dihydride,
Partially hydrogenated alkyl aluminums such as alkyl aluminum dihydrides such as propyl aluminum dihydride, partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide It is. Compounds belonging to (ii) above include LiAl
Examples include (C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ . Further, as a compound similar to (i), it may be an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl(C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl
( _C4H9 ) _{2 ,} Examples include: Among these, it is particularly preferable to use trialkylaluminum and the above-mentioned alkyl aluminum in which two or more aluminums are combined. The organosilicon compound catalyst component (C) having a Si--O--C bond used in the present invention is, for example, an alkoxysilane, an aryloxysilane, or the like. Examples of such include the formula R _o Si (OR ¹ ) _4-o (where 0≦n≦3, R is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, aminoalkyl group, etc., or halogen, R ¹
is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxyalkyl group, provided that n R, (4-n)
The ^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. In addition, as another example, a compound having no Si-O-C bond and a compound having an O-C bond may be reacted in advance or reacted at the polymerization site to form an Si-O-C bond.
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-chloropropyltriethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriethoxysilane Isopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxysilane, dimethyltetraethoxysilane Examples include siloxane and phenyldiethoxydiethylaminosilane. Among these, particularly preferred are methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, ethyl silicate, These are those represented by the formula R _o Si (OR ¹ ) _4-o such as diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenylmethoxysilane. Component (C) can also be used in the form of an adduct with other compounds. In addition, examples of sterically hindered amine catalyst components include:

[Formula] [In the formula, R ² is a hydrocarbon group, preferably a substituted or unsubstituted alkylene group, and preferably the alkylene group is an alkylene group having 2 or 3 carbon atoms. When it is a substituted alkylene group, the substituent is
For example, it is a hydrocarbon group such as an alkyl group, an acyloxy group, an alkoxy group, etc. ^R3 , ^R4 , ^R5 ,
R ⁶ is hydrogen or a hydrocarbon group which may have a substituent, at least one of R ³ and R ⁴ and at least one of R ⁵ and R ⁶ is a hydrocarbon group, and R ³ and R ⁴ or R ⁵ and R ⁶ may be linked to each other to form a ring, for example a carbocycle or a heterocycle. Preferably all of R ³ , R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups. Further, when one of R ³ and R ⁴ and/or R ⁵ and R ⁶ is hydrogen, the other is preferably a secondary or tertiary hydrocarbon group. R ⁷ is hydrogen or a hydrocarbon group. A heterocyclic compound having a skeleton or general formula [In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are hydrocarbon groups that may have a substituent, and R ¹¹ and R ¹² or R ¹³
R ¹⁴ may be connected to each other to form a ring. Further, either R ¹¹ or R ¹² and either R ¹³ and R ¹⁴ may be connected to form a ring.
R ¹⁵ is hydrogen or a hydrocarbon group. ] It is a substituted methylene diamine compound having a skeleton shown in the following. Specifically, for example, the heterocyclic compound has the general formula

[Formula] or

[Formula] [In the formula, R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as above. R ⁷ is hydrogen or a substituent such as a hydrocarbon group, metal, or alkyl metal; R ¹⁰ is hydrogen or a hydrocarbon group such as an alkyl group, acyloxy group, or alkoxy group; 0
≦n≦3, 0≦m≦2, and n or m
R ¹⁰ may be the same or different. ] Examples include compounds having the following skeleton. More specifically,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

2,6-substituted piperidines such as [Formula],

【formula】

【formula】

【formula】

【formula】

【formula】

Examples include 2,5-substituted pyrrolidines such as [Formula]. Further, specific examples of the substituted methylene diamine compound include N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetraethylmethylenediamine, 1,3-dibenzylimidazo Examples include lysine and 1,3-dibenzyl-2-phenylimidazolidine. In the present invention, propylene and an α-olefin having 4 or more carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, 4 - Random copolymerization with methyl-1-pentene, a mixture thereof, etc., with a propylene content of 40 to 90 mol%, preferably 50 to 90 mol%.
A random copolymer is produced with a crystallinity of 88 mol % and a crystallinity (according to X-rays) of less than 40% by weight, preferably from 0 to 35% by weight. During the copolymerization, ethylene may be present in a small amount, but the amount should be suppressed so that the ethylene content in the copolymer is 6 mol % or less. Also, preferable random copolymers are:
The intrinsic viscosity [η] measured in decalin at 135℃ is
0.5 to 6.0d/g, especially 1.0 to 5.0d/g
in the range of g. The melting point based on DSC (differential scanning calorimeter) is preferably 135°C or lower, particularly 130°C or lower. In addition, the content insoluble in boiling n-heptane is 5.0% by weight or less, and the content soluble in boiling methyl acetate is 20% by weight.
Preferably, it is less than % by weight. In order to obtain a random copolymer with such properties, it is preferable to adopt a method in which propylene and α-olefin having a carbon number of 4 or more are supplied in fixed amounts to the polymerization system to carry out continuous copolymerization. Of course, batch or semi-continuous copolymerization methods may also be employed. The propylene content ratio, crystallinity, etc. can be adjusted by adjusting the propylene supply ratio, uniformity of polymerization, etc. In addition, the above-mentioned intrinsic viscosity is determined by the molecular weight regulator,
For example, it can be arbitrarily adjusted by changing the amount of hydrogen used. The polymerization can be carried out in the liquid phase or in the gas phase, but it is preferable to carry out the polymerization in the liquid phase. When carrying out liquid phase polymerization, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may also be used as the reaction medium. The amount of catalyst used is approximately 0.0001 to approximately 1.0 mmol of component (A) in terms of titanium atoms per reaction volume, (B)
The components are adjusted such that the metal atoms in component (B) are about 1 to about 2000 moles, preferably about 5 to about 500 moles, per 1 mole of titanium atoms in component (A), and (C)
The components are 0.001 to about 10 moles of Si atoms or N atoms in component (C) per 1 mole of metal atoms in component (B),
The amount is preferably about 0.01 to about 2 mol, particularly preferably about 0.05 to about 1 mol. These catalyst components (A), (B), and (C) may be brought into contact during polymerization, or may be brought into contact before polymerization. In contacting before polymerization, only two arbitrary components may be freely selected and brought into contact, or two or three components may be brought into contact with a part of each component.
Furthermore, each component may be brought into contact with each other before polymerization under an inert gas atmosphere or under an olefin atmosphere. The supply ratio of propylene and α-olefin having 4 or more carbon atoms varies depending on the composition of the desired random copolymer and polymerization conditions, such as polymerization temperature and polymerization pressure, but generally propylene/α-olefin ( molar ratio) is in the range of about 85/15 to 10/90. The copolymerization temperature of the olefin is preferably about 20 to about 200°C, more preferably about 50 to about 180°C.
The pressure is preferably from normal pressure to about 100 kg/cm ² , preferably from about 2 to about 50 kg/cm ² . Furthermore, polymerization was carried out under two different reaction conditions.
It is also possible to divide the process into more than one stage. According to the present invention, since the catalytic activity is high and the activity decreases little with the passage of polymerization time, the copolymer yield per unit catalyst can be extremely high. In addition, the resulting copolymer has excellent uniformity and has a very low content of low-molecular-weight byproducts, so when it is formed into a film, etc., it has good transparency, almost no stickiness, and the film has no odor. Few. In addition, high heat-sealing strength can be obtained even when the film is subjected to corona treatment or left under high temperatures. The random copolymer obtained by the present invention is particularly useful for film applications or as a modifier for thermoplastic resins such as polypropylene. Next, it will be explained in detail using examples. Example 1 (Catalyst synthesis) After sufficiently purging an autoclave with an internal volume of 3 with _N2 , 1.5 g of refined kerosene, 75 g of commercially available MgCl ₂ , 109 g of ethanol, and 10 g of Emazol 320 (manufactured by Kao Atlas Co., Ltd., sorbitan distearate) were added. The system was heated to 125°C with stirring at 600 rpm for 20 min.
Stir for a minute. The system internal pressure was set to 10Kg/cm ² (G) with N ₂ ,
A SUS tube with an inner diameter of 3 mm that was directly connected to an autoclave and kept at 125°C was opened, and the liquid was transferred to a 5-glass flask (equipped with a stirrer) filled with refined kerosene 3 that had been cooled to -15°C in advance. The amount of liquid transferred was 1, and the required time was about 20 seconds. The produced solid was collected by filtration and thoroughly washed with hexane. Microscopic observation revealed that the solid was perfectly spherical and had a particle size of 5 to 30 microns. Put 1.5 TiCl ₄ into the glass flask from step 3, and add 75 g of the above solid suspended in 150 ml of refined kerosene to the glass flask for 20 minutes with stirring.
After addition at 120°C, 12.9 ml of diisobutyl phthalate was added and the system was heated to 120°C. After stirring for 1 hour,
Stirring was stopped, the supernatant was removed by decantation, 1.5 ml of TiCl ₄ was added, and the mixture was stirred at 130° C. for 2 hours. The solid portion collected by heating was thoroughly washed with hot kerosene and hexane to obtain a titanium composite. The composite contains Ti2.3wt% on an atomic basis,
Contains Cl63.0wt%, Mg20.0wt% and diisobutyl phthalate 9.9wt%. (Polymerization) An autoclave with an internal volume of 17 was sufficiently replaced with propylene. 50 moles of propylene, 33 moles of 1-butene, and 7N hydrogen were introduced into the system. 3 mmol of triethylaluminum, 0.3 mmol of diphenyldimethoxysilane, and 0.03 mg of the Ti catalyst component (calculated as Ti atoms) were added at 70° C. and stirred for 1 hour. After 1 hour, a small amount of methanol was added to the system and the pressure was removed to obtain a polymer. The polymer yield is
It weighed 912g. According to the analysis, the propylene content is
The melting point according to DSC was 126°C, the melting index measured at 230°C was 3.8 g/10', and the odor level of the polymer was A according to a sensory test. In addition, after aging a 1 mm thick sheet made from this copolymer according to JIS K6758 at 80°C for 24 hours, the surface tackiness was checked, but no tackiness was found. Odor level A: No odor B: Almost no odor C: Slight odor D: Smell E: Strong odor Examples 2 to 5 In Example 1, the amount of propylene/1-butene added, the polymerization temperature, and the time of polymerization were Table 1 shows the results obtained by changing the type and amount of the organometallic compound and the type and amount of the electron donor. Example 6 (Catalyst synthesis) 210 mmol of commercially available magnesium chloride, 30 mmol of titanium tetrachloride, and 30 mmol of diethyl 2-allylmalonate were placed in a nitrogen atmosphere in an internal volume containing 2.8 kg of stainless steel (SUS-32) balls with a diameter of 15 mm. 800ml, inner diameter 100mm stainless steel (SUS
-32) is charged into a ball mill container, and the impact acceleration
Contact with 7G for 24 hours. 10g of the obtained pulverized material,
Suspended in 100 ml of ethylene dichloride at 80°C.
The mixture was stirred for 2 hours. The solid portion was collected by filtration. The solid part was analyzed to contain 1.8% by weight of titanium, 59% by weight of chlorine, 20% by weight of magnesium, and 2-
Contains 22.7% by weight of diethyl allylmalonate. Add 100 ml of fully purified hexane into a 200 ml flask. After the system was sufficiently purged with nitrogen, 60 mmol of triethylaluminum, 30 mmol of phenyltriethoxysilane, and 1.5 mg of the above Ti catalyst component were added in terms of Ti atoms. 20℃
After stirring for 2 hours, the solid portion was washed with sufficiently purified hexane. The solids portion contains 1.6% by weight titanium, 56.0% by weight chlorine, 18.0% by weight magnesium, 0.8% by weight aluminum and 2.5% by weight silicon. (Polymerization) In Example 1, propylene and 1-hexene were used instead of propylene and 1-butene, and the amounts were changed to 43 mol and 43 mol, respectively, and polymerization was carried out under the conditions shown in Table 1 using the Ti catalyst component described above. I went there. Examples 7, 8, 9 (Catalyst synthesis) In the catalyst synthesis of Example 6, 30 mmol of diethyl 2-allylmalonate was added to di-maleate, respectively.
The catalyst was synthesized in the same manner except that 30 mmol of -butyl, 42 mmol of isobutyl pivalate, and 30 mmol of diethyl 1,2-cyclohexanecarboxylate were used. (Polymerization) Under the conditions shown in Table 1, propylene/1-butene copolymerization was carried out in the same manner as in Example 1.

[Table] *Example 10 using 1-hexene (Catalyst synthesis) 0.11 mole of tetraethoxysilane was added dropwise to 0.1 mole of commercially available n-butylmagnesium chloride (n-butyl ether solvent) at room temperature under a nitrogen atmosphere.
Stirred at ℃ for 1 hour. The produced solid was collected by filtration and thoroughly washed with hexane. The solid was suspended in 30 ml of kerosene, 0.015 mol of diethyl phthalate was added dropwise, and the mixture was treated at 80° C. for 1 hour. Further, 200 ml of TiCl ₄ was added, and the mixture was treated at 120°C for 2 hours, the supernatant was removed by decantation, and 200 ml of TiCl ₄ was further added, and the mixture was treated at 120°C for 1 hour. After heating the resulting solid, it was thoroughly washed with hot n-decane and hexane. The Ti catalyst component contains 2.2% by weight of Ti, 63.0% by weight of Cl, 21.0% by weight of Mg, and 14.9% by weight of diethyl phthalate in terms of atoms. (Polymerization) In the polymerization of Example 1, the above Ti catalyst component was used and ethylene was added at a rate of 24 N/h for 1 hour. Polymer yield is 986
g, MI is 2.1 g/10', propylene content is 86.8 mol%, ethylene content is 1.8 mol%, 1-butene content
It was 11.4 mol%. The melting point was 123°C and the crystallinity was 27%. There was no tackiness of the press sheet, and there was no odor of the polymer. Example 11 (Catalyst synthesis) Commercially available magnesium chloride 95.3g, n-decane
488ml and 464.5ml of 2-ethylhexanol.
A heating reaction was carried out at 130° C. for 2 hours to form a homogeneous solution, and then 22.2 g of phthalic anhydride was added. This homogeneous solution was added dropwise to titanium tetrachloride 4 maintained at -20°C over 20 minutes with stirring, and then further stirred at -20°C for 1 hour.
Thereafter, the temperature was gradually raised to 120°C, after which 97.5 g of octyl phthalate was added, and the mixture was stirred at 120°C for 2 hours. Collect the solid part by filtration, and add it to 4
After stirring for 2 hours at 120° C., the solid material was collected by _filtration and thoroughly washed with purified hexane until no free titanium compounds were detected during the washing. The titanium catalyst component contains 2.0% by weight of Ti, 64.3% by weight of Cl, and 22.0% by weight of Mg in terms of atoms.
% by weight, containing 11.05% by weight of dioctyl phthalate. (Polymerization) Add 100 ml of sufficiently purified hexane into a 200 ml flask. After thoroughly purging the system with nitrogen, add 60 mmol of diethyl aluminum chloride, 2,
30 mmol of 2,6,6-tetramethylpiperidine and the above Ti catalyst component are converted into Ti atoms and are 1.5
mg - add atoms. After stirring at 20°C for 2 hours, the solid portion was washed with sufficiently purified hexane. The solid portion contains 1.8% by weight of titanium, 57.0% by weight of chlorine, 17.0% by weight of magnesium, 0.8% by weight of dioctyl phthalate,
Contains 18.5% by weight of 2,2,6,6-tetramethylpiperidine. (Polymerization) Triethylaluminum 1.5 under the conditions of Example 1
Polymerization was carried out with only millimoles added without addition of an electron donor. Polymer yield is 1100g, melting index
2.6, propylene content 87.6 mol%, crystallinity 31%,
The melting point was 129°C. The odor level of the polymer was A, and the press sheet had no tackiness. Example 12 A copolymerization reaction of propylene and 1-butene was continuously carried out using a 5-polymerization vessel (made of stainless steel) equipped with a stirrer. Continuously supply hexane 2.5/H,
Continuously drain the polymerization liquid so that the liquid volume in the polymerization vessel becomes 2.5. Ti catalyst component (from Example 1)
0.065 mmol/, triethylaluminum
3.25 mmol/diphenyldimethoxysilane
Each was continuously fed into the polymerization vessel at a rate of 0.325 mmol/each. Propylene in polymerization vessel
They were added at a ratio of 388 N/Hr and 1-butene at a ratio of 317 N/Hr, and polymerization was carried out at 70°C. The discharged polymerization liquid was poured into a large amount of methanol to recover the polymer. Propylene/1-butene copolymer: 172g/hour
obtained at a speed of According to analysis, propylene 1
-Butene copolymer has a propylene content of 72.4 mol%,
MI20.6, melting point was 110°C. Further, the press sheet had no tackiness, and the odor level of the polymer was A. After blending the polymer with a phenolic stabilizer, T
- It was formed into a die-cast film (50μ thick). (Film forming machine: manufactured by Thermoplastics Co., Ltd.). Layer two films together and heat at 85℃ and 90℃.
After heat-sealing with a seal bar width of 5 mm at a temperature of 100°C and 110°C and a pressure of 2 kg/cm ² for 1 second, it was allowed to cool. A 15 mm wide test piece was cut from this sample, and the strength was measured when the heat-sealed portion was peeled off at a crosshead speed of 200 mm/min. Table 2 shows the results. Further, the film was left at 40° C. for two weeks, then heat-sealed using the method described above, and the peel strength was measured. Table 2 shows the results.

[Table] From the results in this table, it can be seen that sufficient strength can be obtained even after the film has been left for a long time and is heat-sealed at a relatively low temperature.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing a method 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, wherein the electron donor comprises (a) a polyhydric carboxylic acid ester and (b) )RCOOR', in which at least one of the hydrocarbon groups R and R' is a branched or ring-containing chain group; propylene in the presence of a catalyst formed from a titanium catalyst component that is an ester, (B) an organoaluminum compound catalyst component, and (c) an organosilicon compound catalyst component having a Si-O-C bond or a sterically hindered amine catalyst component. and carbon number 4
A method for producing a propylene random copolymer, which comprises randomly copolymerizing the above α-olefins to produce a random copolymer having a propylene content of 40 to 90 mol% and a crystallinity of 40% by weight or less.