JPS6395214A - Production of propylene based block copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer, having excellent heat-sealability as well as transparency and useful as packaging films, etc., by suspension polymerizing propylene, ethylene and alpha-olefin in the presence of a specific highly active and stereoregular catalyst and forming a low crystalline copolymer by a vapor- phase polymerization method. CONSTITUTION:A 2-10C alpha-olefin is prepolymerized in the presence of a catalyst consisting of a titanium catalyst component, consisting essentially of Mg, Ti, a halogen and electron donor and having 5-200mu average particle size and <2.1 geometric standard deviation value of a particle size distribution, organometallic compound catalyst component of a group I-III metal of the periodic table and an electron donor catalyst component. (A) Propylene, (B) ethylene and (C) a 4-20C alpha-olefin are suspension polymerized in liquid propylene solvent and the unreacted substances are flashed to afford the aimed copolymer consisting of 86-97mol% component (A), 0.5-6mol% component (B) and 2-13mol% component (C). The components (A) and (C) are then copolymerized under condition so that the reaction system may form the vapor phase to produce a low crystalline copolymer containing 10-90mol% component (A) and 10-90mol% component (C). Thereby the aimed copolymer is obtained.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing a propylene block copolymer. More specifically, the present invention is directed to films that have excellent heat-sealability, heat-sealability, transparency, and anti-blocking properties, and have low hydrocarbon soluble content, particularly for packaging films such as packing films, for example, food packaging films. This invention relates to a method for producing a propylene block copolymer suitable for. [Prior art J Polypropylene has excellent physical properties and is used for legal purposes. For example, it is widely used in the field of packaging films, but in this type of use it is In order to improve heat sealability at high temperatures, it is common to copolymerize ethylene in an amount of about 1 to 5% by weight and provide a propylene-ethylene copolymer. Polypropylene film modified as described above has the advantage of better transparency and scratch resistance than low-density polyethylene film, which is also used as a packaging film, but it also has poor heat sealability at low temperatures. Inferior. In order to further improve heat-sealability, there is a method of increasing the amount of ethylene copolymerized, but in this case, the proportion of soluble copolymer that is of no use value increases, and the yield of the desired copolymer decreases. There is a disadvantage that the value decreases. Moreover, in slurry polymerization, the properties of the slurry during polymerization deteriorate, and the polymerization may even become difficult. In order to avoid such disadvantages, a method of copolymerizing propylene with ethylene and α-olefin having 4 or more carbon atoms using a conventional titanium trichloride catalyst was proposed in JP-A-49-1999.
No. 35487, JP-A-51-79195, JP-A-52
It has been proposed in various publications such as No.-16588. According to these proposals, it can be said that the production rate of solvent-soluble polymers is reduced compared to the case of binary copolymerization of propylene and ethylene, but compared to the case of homopolymerization of propylene. , -In addition, the production ratio of solvent-soluble polymers is large, and (in ethylene and or α-
As the amount of copolymerized olefin increases, this tendency becomes even more pronounced. The present inventors have discovered a specific solid titanium catalyst component, an organometallic compound catalyst component, and an organometallic compound catalyst component that produce approximately the same proportion of solvent-soluble polymers during propylene homopolymerization as compared to the titanium trichloride catalyst proposed above. When a carrier catalyst formed from an electron donor catalyst component is used in the copolymerization of propylene, ethylene, and an α-olefin having 4 or more carbon atoms, an unexpected result is obtained compared to the case of using the titanium trichloride catalyst in the proposal. It was found that the amount of soluble polymer can be further reduced, and extremely excellent results can be obtained in terms of the yield of the target copolymer and the catalyst efficiency, and the method was proposed in JP-A-54-26891. Although a significant improvement was observed through the use of the catalyst specifically disclosed in this publication, when attempting to produce a copolymer with a considerably high ethylene content, it is necessary to Problems remained, such as the deterioration making it difficult to carry out further polymerization and the solid polymer not being obtained at a sufficiently high yield. If it is not possible to increase the ethylene content to obtain a copolymer with a low melting point, the only way is to increase the content of α-olefin having 4 or more carbon atoms.
Since the α-olefin has a smaller effect of lowering the breath and the rate of copolymerization is also slow, it was not advisable to increase the content of the α-olefin more than necessary. Furthermore, the present inventors disclosed in JP-A No. 59-47210 that a copolymer of propylene, ethylene, and α-olefin having 4 or more carbon atoms, which is suitable for use as a film with excellent heat-sealing property, was replaced with an unfavorable soluble copolymer. We have proposed a method that can obtain high yields while reducing the amount of by-products. However, the copolymers obtained by this method do not necessarily have sufficient heat sealability, heat sealability, transparency, and blocking resistance, and the hydrocarbon soluble content is not sufficiently low. The propylene copolymers in the prior art described above are obtained by random copolymers. On the other hand, α-olefin copolymers obtained by block copolymerization rather than random copolymers are also known. JP-A-58-162620 discloses an α-olefin block copolymer which is obtained by block copolymerization of a-shaped fins and has excellent heat-sealability, transparency, and anti-blocking properties. However, this olefin block copolymer does not have heat-sealing properties, blocking resistance, and heat-sealing resistance over time comparable to the polyolefin composition disclosed in Japanese Patent Publication No. 57-24375. [Problem to be Solved by the Invention 1 Therefore, the present invention provides a propylene-based block copolymer with excellent heat sealability, transparency, and blocking resistance, and a low hydrocarbon soluble content, which is a propylene-based block copolymer that is presently known A propylene-based block copolymer with better heat-sealability, blocking resistance, and heat-seal aging resistance than other propylene-based random copolymer compositions (blended products) has been produced. The aim is to provide this without any additional benefits. Means for Solving Problem E 1 The above object is achieved according to the present invention by (A) containing magnesium, titanium, halogen and an electron donor as essential components and having an average particle size of about 5 to about 2;
A highly active and highly stereoregular titanium catalyst component with a geometric standard deviation value of particle size distribution of less than 2.1 at 00μ, an organometallic compound catalyst component of a metal from Group 1 to Group 3 of the periodic table, and (0 electron The titanium catalyst component (A
) In the presence of an α-olefin prepolymerization catalyst obtained by prepolymerizing α-olefins having 2 to 10 carbon atoms in a range of 1 to 2000 g per gram, propylene, ethylene, and A step of copolymerizing α-olefin No. 20 in suspension polymerization step [A] using liquid propylene as a solvent, and then vaporization by flashing the liquid unreacted raw material in the polymerization reaction mixture obtained in the 1aPA polymerization step. The repeating unit derived from propylene (a
) is 86 to 97 mol%, 0.5 to 6 mol% of the repeating unit (b) derived from ethylene, and 2 to 13 mol% of the repeating unit (C) derived from α-olefin having 4 to 20 carbon atoms. %, and the molar ratio c
/(b+c) in the range of 0.3 to 0.9 A flash step (
2)), and further by copolymerizing propylene and an α-olefin having 4 to 20 carbon atoms in the presence of the propylene-based random copolymer and under conditions where the reaction system forms a gas phase; Repeating unit derived from propylene (d
) is in the range of 10 to 90 mol% and the repeating unit (e) derived from an α-olefin having 4 to 20 carbon atoms is in the range of 10 to 90 mol%. The above object is achieved by a method for producing a propylene-based block copolymer characterized by combining the phase polymerization step [c]. The present invention will be explained in detail below. First, the catalyst used in the present invention will be explained. The highly active and highly stereoregular solid titanium catalyst component (A) used in the present invention contains magnesium, titanium, halogen, and an electron donor as essential components, and the magnesium/titanium (atomic ratio) is less than 1. Larger and preferably 2
50 to 50, particularly preferably 6 to 30, halogen/titanium (atomic ratio) preferably 4 to 100, particularly preferably 6 to 40, electron donor/titanium (molar ratio) preferably 0.1 to 10, especially It is preferably in the range of 0.2 to 6. The specific surface area is preferably 3 cm2/g or more, more preferably about 40 cm2/g or more, and even more preferably 100 m2/g to 800 m2.
It is 7g. Usually, titanium compounds are not removed by simple means such as washing with hexane at room temperature. In addition to the above-mentioned essential components, it may contain other elements, metals, functional groups, etc., and may further be diluted with an organic or inorganic diluent. The solid titanium catalyst component (A) has an average particle size of 1 to 2.
00μ, preferably 3 to 100μ, particularly preferably 6 to 50μ, and the geometric standard difference in particle size distribution is 2.
less than 1, preferably 1.9 or less, more preferably 1.7
It is as follows. Here, the particle size distribution of the titanium catalyst component particles can be measured by a light transmission method. Specifically, the catalyst component is diluted in an inert solvent such as decalin to a concentration of around 0.01 to 0.5%,
The particle size distribution is determined by placing the sample in a measurement cell, shining a narrow light into the cell, and continuously measuring the intensity of the light passing through the liquid when the particles are in a settled state. Based on this particle size distribution, the standard deviation σ
g is determined from a lognormal distribution function. More specifically, it is 16wt% in terms of the average particle diameter (θ5°) and small particle size.
Vg is determined as the ratio (θ, ./θ16) of the particle diameter (θts). Note that the average particle diameter of the catalyst is expressed as a weight average diameter. The solid titanium catalyst component (A) has the ability to produce highly stereoregular polymers with high catalytic efficiency. For example, when propylene is homopolymerized under the same conditions, the isotuffity ( Polypropylene containing 92% or more, especially 96% or more (insoluble matter in boiling an-hebutane) of 3.00 og or more per mmol of Ti, especially s, o o 0
It has the ability to produce 10,000 g or more, more preferably 10,000 g or more. Preferably, the shape is spherical, ellipsoidal, or granular. By using a titanium catalyst component that satisfies these various requirements, a copolymer with a high ethylene content can be produced with good operability and high yield. A titanium catalyst component (
A) After forming a magnesium compound having an average particle size and particle size distribution, and more preferably a shape within the above-mentioned range, contacting is carried out. It can be obtained by a method of performing & embroidery, or a method of bringing a liquid magnesium compound and a liquid titanium compound into contact to form a solid catalyst having the particle properties as described above. Other such methods include a method in which a Mg compound, a Ti compound, and an electron donor are supported on the above-mentioned carrier having a uniform shape, or a method in which a finely powdered catalyst is granulated into the above-mentioned preferred shape. For example, JP-A-55-135102, JP-A-55-135102;
-135103, 56-811, 56-673
No. 11, Patent Application No. 56-181019, No. 61-211
It is disclosed in No. 09, etc. A few examples of these methods will be briefly described. (1) Average particle diameter is 5 to 2. A magnesium compound/electron donor complex having a geometric standard deviation of particle size distribution σg of less than 2.1 is pretreated with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound, or The reaction is carried out without pretreatment with a halogenated titanium compound, preferably titanium tetrachloride, which forms a liquid phase under the reaction conditions. (2) By reacting a liquid magnesium compound with no reducing ability and a liquid titanium compound in the presence of an electron donor, the average particle diameter is 5 to 200 μ and the geometric standard deviation σg of the particle size distribution is less than 2.1. The solid component of is precipitated. If necessary, it is further reacted with a liquid titanium compound, preferably titanium tetrachloride, or with an electron donor. In particular, in the present invention, when a magnesium compound or an electron donor complex precipitated as a spherical solid from a liquid is used in the method (1), or (2)
Good results can be obtained when the solid component is precipitated by the method described above under conditions such that spherical solids are precipitated. Magnesium compounds used in the preparation of the titanium catalyst component include magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, magnesium tubalide, Examples include organomagnesium compounds, reaction products of organomagnesium compounds and electron donors, halosilanes, alkoxysilanes, silyls, aluminum compounds, and the like. Of the titanium catalyst component mentioned above? The organoaluminum compound that may be used in olefin polymerization can be selected from the organoaluminum compounds that can be used in olefin polymerization described later. Furthermore, titanium catalyst component I! Halogen-containing silicon compounds that may be used in 4gl include:
Examples include silicon tetrahalides, silicon alkoxy halides, silicon alkyl halides, and halopolysiloxanes. Examples of titanium compounds used in the preparation of the titanium catalyst component include titanium halides, alkoxytitanium halides, 7-lyloxytitanium halides, alkoxytitaniums, allyloxytitaniums, and titanium tetrahalides, especially titanium tetrachloride. is preferred. Electron donors that can be used in the preparation of the titanium catalyst component include alkoxysilanes such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. Oxygen electron donors, nitrogen-containing electron donors such as ammonia, amines, nitriles, incyanates, etc. can be used. More specifically, those having 1 to 1 carbon atoms, such as methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylpencyl alcohol.
8 alcohols; phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones having 3 to 15 carbon atoms such as , acetophenone, and benzophenone; Ketones having 2 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde
to 15 aldehydes; methyl formate, methyl acetate,
Ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl nochloroacetate, methyl methacrylate, 1:l)/ethyl acid, cyclohexanecarboxylic acid Ethyl, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, ben'! Fl
l phenyl, benyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, dibutyl malonate, isopropyl diethyl malonate, n-butyl diethyl malonate, noethyl phenylmalonate, diethyl 2-7lyl malonate, is
o Butyl diethyl malonate, di-n-butyl diethyl malonate, di-n-butyl succinate, diethyl methyl succinate, dibutyl ethyl succinate, maleinlli! dibutyl maleate, monooctyl maleate, dioctyl maleate, butyl butyl maleate, butyl noethyl maleate, diisooctyl hexamalate, diethyl itaconate, din-butyl itaconate, dimethyl citraconate, 1.2- diethyl cyclohexanedicarboxylate,
di-2-ethylhexyl 1,2-cyclohexanenocarboxylate, trimethyl heptatarate, monoisobutyl heptatarate,
Noethyl 7talate, Ethyl n-butyl 7talate, Din-propyl 7talate, N-butyl 7talate, Wliso-butyl 7talate, Di-n-heptyl 7talate, 2-ethylhexyl 7talate, Di-n-octyl 7talate , cineobentyl heptalate, benzylbutyl heptalate, diphenyl heptalamate, di-1so-butyl naphthalene dicarboxylate, di-2 sebacate
- Organic acid esters with 2 to 30 carbon atoms such as ethylhexyl, γ-butyrolactone, δ-valerolactone, coumarin, 7-thallide, and ethylene carbonate; 2-carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride, etc. to 15 acid halide necks; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, isoamyl ether, tetrahydro-7rane, anisole, diphenyl ether; acetic acid amide, acetic acid amide, toluic acid Acid amide such as amide'M: Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyrinone, picoline, tetranotylmethylenecyamine, tetramethylethylenequamine; acetonitrile, benazonitrile , nitriles such as tolnitrile;
po such as trimethyl phosphite, triethyl phosphite, etc.
Examples include compounds having a -c bond; alkoxysilanes such as ethyl silicate and nophenyldimethoxysilane; and the like. These electron donors are
Two or more types can be used. The electron donor preferably contained in the titanium catalyst component (A) is an ester of an organic or inorganic acid, an alkoxy(
aryloxy) silane compounds, ethers, ketones, tertiary amines, acid halides, and acid anhydrides, and organic acid esters and alkoxy (
(aryloxy)silane compounds are preferred, and among them, esters of aromatic monocarboxylic acids and alcohols of I to 8, malonic acid, substituted malonic acid, substituted succinic acid, maleic acid, substituted maleic acid, and 1,2-cyclohexanenocarboxylic acid. Acids, esters of docarboxylic acids such as heptatalic acid and alcohols having 2 or more carbon atoms are particularly preferred. Of course, these electron donors do not necessarily need to be used as raw materials in the preparation of the titanium catalyst, and other electron donors such as They may be used as compounds that can be converted into electron donors and converted into these electron donors during the catalyst preparation process. The titanium catalyst component obtained by the methods exemplified above can be purified by thoroughly washing with a liquid inert hydrocarbon after the reaction is completed. Inert liquid hydrocarbons used for this purpose include n-pentane, impentane, n-
Aliphatic hydrocarbons such as hexane, isohexane, 1-hebutane, n-octane, isooctane, n-decane, n-dodecane, kerosene, liquid paraffin; fats such as cyclopenkune, methylcyclopenkune, cyclohexane, methylcyclohexane Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, and cymen;
Examples include halogenated hydrocarbons such as rubenzene and nochloroethane, and mixtures thereof. Preferred organometallic compound catalyst components (B) used in the present invention are organoaluminum compounds, and compounds having at least one Al-carbon bond in the molecule can be used, such as (i) General formula R2Al(OR2)nHp
Xq (where R1 and R2 are usually 1 to 1 carbon atoms
The hydrocarbon groups contain 5, preferably 1 to 4 hydrocarbon groups and may be the same or different from each other. X is a halogen, the theory is 0 -≦3, n is O≦n<3, p is 0≦p<3, q is a number of 0≦q<3, and -10n0p10q= 3), an organoaluminum compound represented by Gi) the general formula MIAj! Examples include complex alkylated products of Group 1 metals represented by Rs (where M+ is Li%Na% and R' is the same as above) and aluminum. Examples of the organoaluminum compounds belonging to (i) above include the following. General formula R'AIt(OR”)
3-ta (where R1 and R2 are the same as above. Ugly is preferably a number of 1.5≦logical≦3), general formula R
'AlX2- (where R1 is the same as above,
^A I Hz -va (where RI is the same as above,
Crane is preferably 2≦-ku3), general formula R111
Aj! (OR2) nXq (where R' and R2 are the same as above. can be exemplified. Among the aluminum compounds belonging to (i), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminium, trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide, butylaluminum butoxide, etc. In addition to fulkylaluminum sesquialkoxides such as , ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, Rm, 5Ajl (OR”
) partially alkoxylated alkylaluminums having an average composition represented by o, s, etc., noalkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, noethylaluminum bromide, ethylaluminum sesquichloride,
Partially halogenated alkyls such as alkylaluminum sesquihalides like bunalluminum sesquichloride, ethylaluminum sesquipromide, alkylaluminum cybarides like ethylaluminum chloride, propylaluminum dichloride, butylaluminum nobromide, etc. Aluminum, partially hydrogenated alkylaluminum, such as diflukylaluminum hydride such as diethylaluminum hydride, butylaluminum hydride, flukylaluminum rhamnohydride such as ethylaluminum rhamnohydride, probylaluminum rhamnohydride, ethylaluminum Partially alkoxylated and halogenated alkylaluminiums such as ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide. In addition, as a compound similar to (i),
Examples of such compounds include (CzHs)iAIOAj (
CzHs)z, (CJshA I OA 1 (C4H
I)2, (C2LhAINAl(C2H5)2Cs
Examples include Hs. As a compound belonging to the above Gi), LiA l (C2H5) LiAj! (C?H1
9) 4 etc. can be exemplified. Among these, it is particularly preferable to use trialkylaluminum or a mixture of trialkylaluminum and alkyl aluminum halide or aluminum halide. , ethers, ketone M tolyls, phosphines, stibines, arsines, phosphoramides, esters, thioethers, thousand onysters, Pi! anhydrides,
These include acid halides, aldehydes, Alfray) M, alkoxysilanes, organic acids, and amides and salts of metals belonging to Groups 1 to M4 of the periodic table. Salts can also be formed in situ by reaction with an organic acid and the organometallic compound used as catalyst component (B). Specific examples of these include, for example, titanium catalyst component (8)
The electron donor contained in can be selected from those exemplified above. Good results are obtained when using organic acid esters, alkoxy(71J-roxy)silane compounds, ethers, ketones, acid anhydrides, amines, and the like. In particular, when the electron donor in the titanium catalyst component (A) is a monocarboxylic acid ester, the electron donor as component (0) is preferably an alkyl ester of an aromatic carboxylic acid. When the electron donor in (A) is an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms as exemplified above as a preferable example, the general formula Rn5
i(OR'L-n (wherein, R and R1 are hydrocarbon groups, 0≦
It is preferable to use an alkoxy(aryloxy)silane compound represented by n<4) or an amine with large steric hindrance as component (C). Specific examples of the alkoxy(aryloxy)silane compounds include trimethylmethoxysilane, trimethylmethoxysilane, dimethylsimethoxysilane, nomethylnoethoxysilane, noisoprobylcymethoxysilane, t-butylmethyldimethoxysilane, t- Butylmethylnoethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane,
Phenylmethyldimethoxysilane diphenyldimethoxysilane, bis0-)lylcimethoxysilane, bism-)
Rilkumethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisdithylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, dithyltrimethoxysilane, dicytrimethoxysilane Ethoxysilane, vinyltritoxysilane, methyltrimethoxysilane, n”fa pyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, γ
-Chlorpropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, L-butyltriethoxysilane, n-
Butyltriethoxysilane, 180-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltriptoxysilane, cyclohexyltriethoxysilane, cyclohexyltriethoxysilane Silane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane,
2-norbornanemethyldime)4 disilane, ethyl silicate, butyl thiate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetophethoxydisilane ethyltriethoxysilane, n-
Propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, nophenyldimethoxysilane, phenylmethyldimethoxysilane, bis9-)lylvmethoxysilane, p-tolylmethyl Dimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl 7naldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenylthiethoxysilane, ethyl silicate, and the like are preferred. Further, as the amine with large steric hindrance, 2. 2,6.6-Titramethylpiperidine, 2,2,5. Particularly preferred are 5-tetramethylpyrrolidine, derivatives thereof, and tetramethylmethylenediamine. Among these compounds, alkoxy(aryloxy)silane compounds are particularly preferred as the electron donor used as the catalyst component (C). In the prepolymerization in the present invention, the above catalyst components (
A), it is preferable to use a catalyst system in which, in addition to the organometallic compound (A), the electron donor catalyst component (0) also coexists, in which case the titanium catalyst component (A) contains 0.
．． The electron donor catalyst component ranges from 1 to 30 mol, preferably 0, 5 to 10 mol, more preferably 1 to 5 mol (0 is preferred, and the prepolymerization is carried out in an inert hydrocarbon solvent). Alternatively, an α-olefin having 2 to 10 carbon atoms is prepolymerized using a liquid monomer as a solvent or without using a solvent, but prepolymerization in an inert hydrocarbon solvent or in a liquid monomer is particularly preferable. The polymerization amount in the prepolymerization is 1 to 2000g per 1g of titanium catalyst component, preferably 3 to 1000g, and more preferably 10 to 500g.Increasing the prepolymerization amount more than necessary impedes the improvement of heat sealability. Not preferred. Inert hydrocarbon solvents used for prepolymerization include propane, butane, n-pentane, iso-pentane, n-
Aliphatic hydrocarbons such as hexane, inhexane, n-hebutane, n-octane, isooctane, n-7'cane, n-dodecane, kerosene, aliphatic compounds such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane Examples include hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as methylene chloride, ethyl chloride, ethylene chloride, and chlorobenzene. Among them, aliphatic hydrocarbons, especially carbon Aliphatic hydrocarbons having numbers 4 to 10 are preferred. In prepolymerization, when inert F8A or liquid monomer is used, 0.001 to 500 mmol, especially 0.005 to 1() in terms of titanium atom (titanium catalyst component information) per solvent 11. It is preferable that the amount is 0 mmol, and the organic aluminum compound (B) is Aj! /Ti (atomic ratio) is 0.5 to 1000, preferably 1.0 to 200. More preferably, it is used in a ratio of 2.0 to 5o. The α-olefins used in the pre-4a polymerization include ethylene, propylene, 1-1f', 1-pentene, and 4-olefin.
7thyl-1-pentene, 3-methyl-1-heptene, 1
-Hebutene, 1-octene, 1-decene, etc. with 10 carbon atoms
The following α-olefins are preferable, and those having 3 to 6 carbon atoms are more preferable, and propylene is preferable. Copolymerization of more than one species may be used. The polymerization temperature in the prepolymerization stage varies depending on the α-olefin used and the am of the inert solvent and cannot be unconditionally defined, but it is generally -40 to 80°C, preferably -20 to 40°C. °C, more preferably about -10 to 30 °C 0 For example, -4 when the α-olefin is propylene
0 to 70℃, -40 to 40 for 1-butene
"C14-methyl-1-pentene and 3-methyl-1-
In the case of pentene, a temperature of about -40 to 70°C is appropriate. Hydrogen can coexist in the pre-(0'm) polymerization. In the suspension polymerization step of the present invention [A-J, propylene, ethylene, and R1k atoms of 4 to 4 are used as catalysts. 20 α-olefins are copolymerized.α-olefins having 4 to 20 carbon atoms are copolymerized.
Examples of olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-
Methyl-1-pentene, 1-heptene, 1-octene,
1-thecene, 1-dodecene, 1-tetofdecene, 1-
Examples include octadecene. Among these, α-olefins having 4 to 10 carbon atoms are preferred;
A-shaped fins having 4 to 6 carbon atoms are particularly preferred. In the suspension polymerization step of the present invention, propylene, which is used as a monomer for copolymerization, is used as the reaction medium. In the suspension polymerization step [A1, the catalyst component (A) is about 0.0001 to about 1 titanium atom per liquid phase 11.
mmol, the catalyst component (It) is about 0.001 to about 100 mmol in terms of the metal atom, the catalyst component (C)
from about 0.001 to about 100 mmol, respectively.
11/ The amount of the metal atom in the catalyst component (B) should be about 1 to about 1000 moles, preferably about 1 to about 300 moles, per 1 mole of titanium atoms in the catalyst component (A). , catalyst component (0) is the catalyst component (1
1) Sum of metal atoms from Groups 1 to 3 of the periodic table 1
Usually 0.01 to 10 mol, more preferably 0.1 to 5.0 mol, particularly preferably 0.2 mol per atom.
to 2.0. The polymerization temperature can be from room temperature to about 90° C., preferably from about 50° C. to about 80° C. 1. The polymerization pressure is not particularly limited, but
A range from atmospheric pressure to about 50 kg/cm", preferably from atmospheric pressure to 40 kg/cm" can be adopted. During polymerization, hydrogen can be used as a molecular weight regulator for the desired copolymer. In the flash step E port 1 of the present invention, a liquid unreacted raw material, that is, unreacted propylene, and a carbon atom number of 4 to 20 are extracted from the suspension polymerization reaction product obtained in the L suspension polymerization step of the α-olefin is removed by flashing. The flash step is carried out at a temperature of 20 to 200°C, preferably 4°C.
0 to 150°C, more preferably 50 to 100°C
Beat for 1 minute to 3 hours, preferably 5 minutes to 2 hours, more preferably 10 minutes to 1 hour. The flash step can be carried out in a conventional manner. In the method of the present invention, the crystalline polypropylene-based random copolymer obtained by the suspension polymerization step (1), followed by the flash step (1), has an ar1 return unit (propylene component) derived from propylene (a ) is 86 to 97 mol%, preferably 88 to 96 mol%, more preferably 89 to 95 mol%, and the repeating unit derived from ethylene (ethylene component) is 0.5 to 6 mol%, preferably 1 to 6 mol%. 5 mol%, more preferably 1.5 to 4 mol% and a repeating unit derived from a-shaped fins having 4 to 20 carbon atoms (α-olefin component) (
C) is in the range from 2 to 13 mol%, preferably from 3 to 11 mol%, more preferably from 4 to 9 mol%, particularly preferably from 4 to 7 mol%, and the molar ratio c/(b
A crystalline propylene random copolymer having +c) in the range of 0.3 to 0.9, preferably 0.4 to 0.8, more preferably 0.5 to 0.8 is produced. In order to produce such a propylene-based random copolymer, although it differs slightly depending on the polymerization conditions and the type of α-olefin, the feed rate of the raw material in the suspension polymerization step [A. is 75 to 95 mol%, more preferably 80 to 92 mol%
, ethylene 0.1 to 5 mol%, preferably 0.2 to 4 mol%, more preferably 0.3 to 3 mol%,
α-olefin 4 to 4 having 4 to 20 carbon atoms
The content may be 0 mol%, preferably 8 to 30 mol%, more preferably 12 to 25 mol%. In the method of the present invention, the temperature of the crystalline propylene random copolymer obtained in the flash step [a] at 135°C.
Intrinsic viscosity measured in decalin of

The range is from 0.5 to 6 dl/g, preferably from 1 to 5 dl/g. The intrinsic viscosity of the crystalline propylene-based random copolymer can be determined by reducing the thickness of the heat-sealing layer of the polypropylene composite laminate laminated with the low-crystalline propylene-based random copolymer composition, and by reducing the thickness of the heat seal layer of the composite laminate. The above range is suitable from the viewpoint of heat-sealing strength and heat-sealable temperature by heat treatment. The melting point of the crystalline propylene random copolymer measured by a differential scanning calorimeter [Tml is 115°C to 1
The temperature range is 45°C, preferably 120°C to 140°C, more preferably 120°C to 135°C. The heat-sealing temperature and heat-sealing strength of the polypropylene composite laminate laminated with the low-crystalline propylene random copolymer composition, the blocking and scratch resistance of the polypropylene composite Mt laminate, the temperature that can be heat-sealed by heat treatment, etc. , the DSC melting point is preferably within the above range. Here, the DSC melting point is the thickness of 0 after 20 hours of molding.
, 1 m+* press sheet was measured from 0 to 200°C at an external temperature rate of 10°C/win, and the maximum endothermic peak was defined as T-. The crystallinity of the crystalline propylene random copolymer measured by X-ray diffraction is in the range of 30 to 60%, preferably 35 to 55%. The crystallinity of the crystalline propylene random copolymer is:
the heat-sealing temperature of the polypropylene composite laminate containing the low-crystalline propylene random copolymer composition;
The above range is suitable from the viewpoint of heat sealing strength, blocking property and scratch resistance of the polypropylene composite MI layer, heat sealing temperature during heat treatment, etc. Crystallinity is 1
It was determined by XM diffraction measurement of a pressed sheet with a diameter of 1.5aII6 formed by pressing at 80°C for 10 minutes and then at 25°C for 10 minutes. 25°C of the crystalline propylene random copolymer [I]
The amount [W+weight] soluble in n-decane in is determined by the general formula % (%) in relation to the melting point Tl11 of the copolymer, preferably the general formula 0.03 (165-Ts)≦W1≦0 .15 (165-
Tm) (here, T- is the numerical value of the melting point of the copolymer, excluding dimension), when the n-decane soluble content exceeds the above range, the low crystallinity propylene The blocking resistance of the polypropylene composite laminate formed by laminating the random copolymer composition begins to deteriorate. Here, 25 of the crystalline propylene random copolymer
The amount of soluble matter in n-decane solvent at ℃ is measured and determined by the following method. That is, 5 g of copolymer sample, 0.3 g of 2,6-diter
s-dimethyl-4-methylphenol and 500 theory 1
of n-decane and dissolve it on a 140°C oil bath. After dissolution, the mixture is allowed to cool naturally at room temperature for about 3 hours, and then cooled on a 25°C water bath for 12 hours. The n-decane solution containing the precipitated copolymer and dissolved polymer was subjected to Ir separation using a G-4 glass filter, and the Saito solution was dried at 10 mmHg and 150°C until it reached a constant weight, and dissolved in n-decane. Collect the polymer. The weight was measured, and the amount of the copolymer soluble in n-decane solvent at 25° C. was calculated and determined as a percentage of the weight of the sample copolymer. In the gas phase polymerization step [C1] of the present invention, propylene and the number of carbon atoms are Propylene and the α-olefin are copolymerized under conditions such that 4 to 10 α-olefins form a gas phase. 100 to 100,000 g, preferably 50 to 100,000 g per gram of the titanium catalyst component (A) of the catalyst prepolymerized with α-olefin.
0 to 501000 g, more preferably 1.000 g
A gas phase mixture of from 1 to 10,000 g of propylene and an α-olefin having 4 to 10 carbon atoms is copolymerized. In the gas phase polymerization step, it is necessary to copolymerize the monomers in the gas phase. The reason is as follows. In polymerization using a hydrocarbon solvent, the propylene/α-olefin random copolymer easily dissolves into the hydrocarbon solvent, making it difficult to maintain sufficient heat sealability and heat sealability of the resulting propylene block copolymer. Not only is it not possible to increase the viscosity of the hydrocarbon solvent, but the viscosity of the hydrocarbon solvent also increases, making it difficult to perform stable polymerization operations. As an a-shaped fin having 4 to 20 carbon atoms,
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, etc. having 18 or fewer carbon atoms is suitable, and the number of carbon atoms is 4
etc. 6 of 8 is particularly suitable. Copolymerization is carried out so that the amount is usually 100 times or more, preferably 500 times or more, and more preferably 1000 times or more the prepolymerized amount. In the serious gas phase polymerization step, the repeating unit (propylene component) (d) derived from propylene is 10 to 90 mol%, preferably 30 to 85 mol%, more preferably 50 to 80 mol%, derived from the α-olefin. A propylene/a-olefin random copolymer in which the repeating unit (α-olefin component) (e) is in the range of 10 to 90 mol%, preferably 15 to 70 mol%, more preferably 20 to 50 mol%. The proportion of the propylene/α-olefin random copolymer to be produced relative to the total polymer is 5 to 40% by weight, preferably 8 to 30% by weight, and more preferably 12 to 25% by weight. Here, the gas phase polymerization process [propylene α produced in C1]
- The α-olefin content [mol %] in the olefin copolymer is determined as follows. That is, the gas phase polymerization step [c]
The α-olefin content of the copolymer before entering into % by weight
, the number of carbon atoms in the copolymer after exiting the gas phase polymerization step is 4 to 20f) the Q-olefin content is 8%, the polymerization ratio in the gas phase polymerization step [C1 is W weight% and α- When the number of carbon atoms in the olefin is n, the tXα-olefin content [mol %] in the propylene/α-olefin copolymer produced in the gas phase polymerization step is expressed as follows. The polymerization temperature is 20 to 150 ℃ under the condition that the monomer is in the gas phase.
°C, preferably 30 to 100 °C, more preferably 4
The polymerization pressure carried out at 0 to 80°C is not particularly limited as long as the monomer is in a gas phase at the working temperature, but it is 2 to 50 k.
g/am2, preferably 3 to 40 kg/cm2, more preferably 4 to 30 kg/cm''. In the gas phase polymerization step of the method of the present invention, some of the monomers such as propylene and α-olefin are This does not exclude polymerization conditions that cause liquefaction of the propylene-based block copolymer.
is usually 75 to 96 mol%, preferably 80 to 94 mol%, particularly preferably 84 to 92 mol%, and the repeating unit 0) derived from ethylene is usually 0.3 to 5 mol%, preferably 0.7 % to 4.5 mol %, particularly preferably 1 to 4 mol %, and repeating units derived from α-olefins having 4 to 20 carbon atoms (h
) is usually 4 to 20 mol%, preferably 5 to 1
5 mol %, particularly preferably in the range from F to 12 mol %. Further, the intrinsic viscosity of the propylene-based block copolymer obtained by the method of the present invention measured in decalin at 135°C [1] is usually in the range of 0.5 to 6 dl/g, preferably in the range of 1 to 5 dl/g. It is in. The crystallinity of the propylene block copolymer obtained by the method of the present invention, as measured by X#1 diffraction method, is usually in the range of 25 to 60%, preferably 30 to 55%, more preferably 35 to 50%. be. This property value is a measure of excellent tensile properties, and when combined with other property values, it is useful in providing the aforementioned random copolymer with excellent properties. The degree of crystallinity was determined by X-ray diffraction measurement of a 1.5-thick press sheet after 20 hours of molding a. In the propylene block copolymer obtained by the method of the present invention, the amount of soluble content in p-xylene solvent at 25°C is usually 30i'1ji1% or less, preferably 25% by weight or less. Also, n at 50°C
- The amount extracted into hexane solvent is usually 10% by weight or less, preferably 8% by weight or less, more preferably 671% by weight or less.
℃% or less. In the propylene-based block copolymer obtained by the method of the present invention, the amount of the copolymer composition soluble in p-xylene solvent at 25° C. is measured and determined by the following method. That is, 21 equipped with a stirring blade and a reflux condenser
Add 5 g of the copolymer sample and 12 g of p-xylene to a flask and hold under reflux of p-xylene for at least 2 hours to dissolve the sample in the p-xylene. Then under air cooling for 50 minutes
After cooling the contents to 25 °C, place the container in a cold water bath.
Rapidly cool to -30°C. Transfer the container to a constant temperature bath kept at 25°C and keep it in this state for 2 hours. A suspension of p-xylene containing the precipitated copolymer and dissolved polymer was filtered and separated using a G-4 glass filter, and the filtrate was dried at 150°C under a reduced pressure of about 10 mmHH until it reached a constant weight. Collect the polymer dissolved in xylene. Measure its weight,
The amount of the copolymer soluble in p-xylene solvent at 25° C. is calculated and determined as a percentage of the weight of the sample copolymer. In the propylene-based block copolymer obtained by the method of the present invention, the amount of the copolymer composition extracted into an n-hexane solvent at 50°C is measured and determined by the following method. That is, the copolymer sample and 12 n-hexane were added to a 21 flask equipped with a stirring blade and a reflux condenser, and the contents were heated to 50°C and kept at the same temperature for 2 hours. Next, this suspension was filtered and separated through a G-4 glass filter while it was still warm, and the furnace liquid was reduced to approximately 1011+o+I (H
Dry soot at 150℃ under reduced pressure until it reaches a constant weight! n at 50°C
- Collect the extracted polymer in hexane. The weight is measured, and the amount of the copolymer extracted into the n-hexane solvent at 50° C. is calculated and determined as a percentage of the weight of the sample copolymer. According to the present invention, a copolymer having physical properties essentially similar to polypropylene and having a low melting point of polypropylene can be produced in high yield.
It can be obtained in high yield and with reduced soluble copolymer abrasion. Furthermore, since the copolymer yield per titanium is large, the catalyst removal operation after polymerization can be omitted. The copolymer has excellent heat sealability, heat sealability, transparency, and blocking resistance.
Since the hydrocarbon soluble content is small, it is suitable for use in films, especially packaging films such as shrink films, such as food packaging films. Of course, it is also suitable for uses such as hollow bottles. A polypropylene composite laminate is formed by laminating the propylene block copolymer of the present invention on one or both surfaces of a substrate made of crystalline polypropylene. In addition to crystalline propylene homopolymer, the crystalline polypropylene serving as the base layer includes a crystalline propylene/α-olefin random copolymer whose main component is propylene, for example, an ethylene content of 0.1. A propylene phi ethylene random copolymer containing 0.1 to 5 mol% of propylene, 0.1 to 4 mol% of ethylene, and 0.1 to 4 mol% of 1-butene.
1 to 5 mol% propylene/ethylene/1-butene random copolymer, 1-butene content 0.1 to 5
Examples include propylene/1-butene random copolymer of mol%. 1 of the crystalline polypropylene
The intrinsic viscosity, measured in decalin at 35°C, is usually 1°5 to 4 dl/g, preferably 1.7 to 3.
5d1/g, and its crystallinity measured by X#X diffraction method is usually in the range of 50 to 70%, preferably in the range of 55 to 70%. The base material layer made of crystalline propylene may be in an unstretched state or in a pongee or two-wheel stretched state. The copolymer composition includes
In addition to the above polymer components, heat-resistant stabilizers, weather-resistant stabilizers, nucleating agents,
It is okay to add lubricants, slip agents, antistatic agents, antiblocking agents, antifogging agents, pigments, dyes, etc.
The blending ratio is appropriate within a range that does not impair the low-temperature heat-sealability and heat-seal strength of the polypropylene composite laminate. The following method can be exemplified as a method for producing a polypropylene composite laminate by laminating the propylene block copolymer of the present invention on one or both sides of the base material layer made of the crystalline polypropylene. (1) A method in which a base material made of crystalline polypropylene and the propylene-based block copolymer are laminated by coextrusion, and if necessary, longitudinal stretching and/or transverse stretching are performed separately or simultaneously. (2) When the propylene block copolymer is extruded in a molten state and laminated on the surface of a crystalline polypropylene base that has been unstretched, -axially stretched or biaxially stretched, and the base is in an unstretched state. is a method in which uniaxial stretching or biaxial stretching is further performed as necessary. In addition, when the base material is in the -#I stretched state, the method involves extruding and laminating in the same manner, and then further stretching in the same manner as the base material or in the cross direction, if necessary. (3) A method of laminating a film of the propylene block copolymer on the surface of a substrate made of crystalline polypropylene using an adhesive. The polypropylene composite laminate formed by laminating the propylene-based block copolymer of the present invention on one side or screen of a substrate made of crystalline propylene may have any shape, such as a laminated film, a laminated sheet, Examples include laminated packaging bags, MM containers, and other molded bodies that provide heat sealability. As is clear from the above-mentioned examples of the lamination method, the base material layer made of crystalline polypropylene constituting the propylene composite laminate can be in an unstretched state, a -axially stretched state, or a biaxially stretched state. The layer made of the propylene-based plastic copolymer may be either in an unstretched state, in a -axially stretched state, or in a biaxially stretched state. Further, the base material layer made of crystalline polypropylene and the layer made of the propylene block copolymer of the polypropylene composite laminate may be composed of any combination of the above states. The thickness of the base material layer made of crystalline polypropylene constituting the polypropylene composite laminate is arbitrary and not particularly limited, but the thickness of the heat seal layer made of the propylene block copolymer is generally (), 1 to 50μ,
It is preferably in the range of 0.5 to 30μ. When the polypropylene composite laminate is a composite unlaminated film or a composite laminate sheet, the thickness of the base layer made of crystalline polypropylene is in the range of 5 to 200 μm, preferably 10 to 70 μm, and the propylene block The thickness of the heat seal layer made of copolymer is usually 0°1 to 5°.
0μ, preferably in the range of 0.5 to 30μ. EXAMPLES The present invention will be specifically explained below with reference to Examples. [Measurement of blocking resistance and complete heat-sealing temperature of film 1 The method for determining the blocking resistance and complete heat-sealing temperature of the obtained copolymer is described below. film! On the excrement press board, place an aluminum sheet with a thickness of 0.1 strand, a polyester sheet (manufactured by Toshi Co., Ltd., trade name: Lumirror), and a polyimide resin sheet with a thickness of 50 μm cut out in the center into a 15 cm x 15 cm square ( DuPont, product name: Kapton) sheets were laid out in this order, and a 0.8 g sample was placed in the center (the cut-out part) (6) Then a Lumirror ■, an aluminum plate, and a press plate were further stacked in this order (Fig. (see 1)
. The sample sandwiched between the press plates was placed in a hot press at 200°C, and after preheating for about 5 minutes, the sample was depressurized (20 kg/cm"G) and kneaded to remove air bubbles inside the sample. Repeat the process 3 times 6 and finally 150 kl?/
Increase the pressure to cm2G and heat under pressure for 5 minutes. After depressurizing, take out the press plate from the press machine, transfer it to another press machine whose crimped part is kept at 30 ° C, pressurize and cool at 100 kg/as'' for 4 minutes, depressurize it, and take out the sample. Among the obtained films, a film with a uniform thickness of 50 to 70 μm is used as the film for the following measurement. Blocking resistance Two films cut into 6 x 10 cm sizes on the front and back are overlapped and this is stacked into two films with a uniform thickness. After sandwiching the film between sheets of paper, the film is further sandwiched between glass plates of approximately sII thickness and placed in a constant temperature bath at 60°C under a load of 7 kg for 2 days (aging).The film is removed from the constant temperature bath, cooled to room temperature, and then the two sheets are stacked together. After peeling off part of one edge of the film and inserting a Teflon rod here, clip the edge of the peeled film and fix it to the upper chuck of the tensile testing machine.At the same time, fix the Teflon rod to the lower chuck 4. The two films are separated through a tear rod (see Figure 2), which is fixed by pulling up the upper chuck at a rate of 10 centimeters per minute (see Figure 2). Measure using a machine.By dividing the stress value obtained by the width of the film used (6 cm), the blocking value (g/c++) of the film, which is a measure of blocking resistance, is determined.
seek. HEAT NUMBER/-2-2 C' 01 YO L RONY ≦ 2 and 1 NO L HEE - LINE The film prepared by the method described above is placed in a constant temperature bath at 50°C for 2 days (aging) , during aging, to prevent the films from touching each other,
Attach paper to both sides of the film. Cut the aged film described above into 15 mm 19 pieces, stack the two pieces together, and then add 0.1
Heat-seal by sandwiching two pieces of tear-on film with a thickness of 1 ml and heat-sealing, keeping the temperature at the bottom of the heat sealer hot plate constant at 70°C, and adjusting only the temperature at the top of the hot plate in 5°C increments. The pressure during heat sealing was 2 kg/e1 m2, the heat sealing time was 1 second, and the sealing width was 51III11 (therefore, the sealing area was 15 mm x 5 nm). The heat-sealing strength is determined by conducting a tensile test on the peel strength of the film heat-sealed at each of the above-mentioned heat-sealing temperatures at a tensile speed of 30 cm/min (see Figure L1). The peel strength at each heat sealing temperature in 5°C increments is determined by the method described above, and the plot of heat sealing temperature versus peel strength is connected by a curve. Based on this curve 800g715cm
The heat-sealing temperature at which <as degrees is defined as the complete heat-sealing temperature (see FIG. 4). Example 1 [Preparation of titanium catalyst component (A)] 714 g of anhydrous magnesium chloride, decane 3.72:1
Yo(/-2-ethylhexyl alcohol 3.51 to 1
After performing a heating reaction at 30°C for 2 hours to obtain a homogeneous solution, 167 g of anhydrous 7-talic acid was added to this solution, and stirring and mixing was performed at 130°C for an additional 1 hour to dissolve the anhydrous 7-talic acid in the homogeneous solution. . After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped into titanium tetrachloride maintained at -20°C over 1 hour. After charging, the temperature of this mixed liquid was raised to 110°C over 4 hours, and then the temperature was increased to 110°C.
When it reaches 7 tales) 0.4jt
1) and kept under stirring at the same temperature for 2 hours. After the completion of the 2-hour reaction, a solid portion is collected by hot filtration, and after resuspending this solid portion in 281 TiCL, a heating reaction is performed again at 110° C. for 2 hours. After the reaction was completed, the solid portion was collected again using hot TPS and heated to 110
Wash thoroughly with decane and hexane until no free titanium compound is detected in the washing solution. The titanium catalyst component synthesized by the above production method was dried using a dryer. The composition of the titanium catalyst component thus obtained was 2.3% by weight of titanium, 58.0% by weight of chlorine,
18.0% by weight of magnesium and 14.0% by weight of diisobutyl 7 clay. The titanium catalyst component was a granular catalyst with an average particle size of 18 μm and a geometric standard deviation (σg) of particle size distribution of 1.2. [Prepolymerization 1 In a nitrogen atmosphere with stirring charge of 21] Hexane 11, 5 mmol of triethylaluminum, 1 mmol of diphenylnomethoxylan, and 0.5 mmol of the titanium catalyst component were added to the RK reactor in terms of titanium atoms. After that, propylene was fed into the mixture at a rate of 11.1 N1/Hr for 5 hours. The temperature in this darkness was kept at 20°C. Five hours after the propylene feed was started, the propylene feed was stopped and nitrogen was fed instead to replace the inside of the reactor with nitrogen. Immediately after stopping stirring, the supernatant liquid was removed, and another 11 hours of purified hexane was added. After repeating this washing process three times, the slurry was re-slurried in hexane and transferred to a catalyst bottle for storage. The amount of prepolymerization was 98 g-)')'/g-catalyst. <Ratio) 7.5 kg of propylene, 2.3 kg of 1-butene, 38 N1 of ethylene, and 25 N1 of hydrogen were added to an autoclave having an internal volume of 50 A and replaced with propylene. Then, the temperature was raised to 50°C, 25 mmol of triethylaluminum, 25 mmol of diphenylcumethoxysilane, and 0.15 mmol of the prepolymerized titanium catalyst component were added, and polymerization was carried out at 60°C for 15 minutes. The internal pressure of the autoclave was 0.1 kg while maintaining the temperature at 50°C.
/ C floor "G,!: The pressure was depressurized until the olefins in the autoclave were removed. (About 101 flats)
Then, 5Nl of hydrogen was added and further propylene/butene-
Gas phase polymerization was started by feeding a mixed gas with a molar ratio of 1 to 30/70 until the internal pressure of the autoclave reached 5.5 kg/cab"G. During the polymerization, the temperature was maintained at 50 °C and The pressure is 5,5
The propylene/gas butene mixture was replenished so that the amount was kg/c+o2G. ([C1 gas phase polymerization step)
After 90 minutes of polymerization, methanol was added to stop the polymerization. After depressurization, the produced polymer was collected and incubated overnight at 60°C for 30 minutes.
Drying was carried out under reduced pressure of 0.1 mHg. The yield of the obtained white powdery polymer was 3.2 kg, the apparent specific gravity was 0.34 H/1, the ethylene content was 2.3 mol%, 1.
-Butene content is 9.7 mol%, MF″R is 5,6 d
g/min, n-decane soluble portion amount is 19.3 weight fi%, 25
The amount of xylene soluble portion at ℃ is 24.3ffi amount%, 50℃
The amount of n-hexane extracted was 4.8 fflit%. Furthermore, the blocking property of the film produced by the method described above was 16 g/am. The complete heat seal temperature was 113°C. On the other hand, according to the analysis of each stage, the ethylene content of the copolymer after the [b]flash step was 2.8 mol%, and the butene-1 content was 5.8 mol%. Therefore, 1-butene/(1- The molar ratio of ethylene in butene was 0.67. *Ta,
[The polymerization ratio in the gas phase polymerization step (iii) was 23% by weight. Therefore, [1 in the copolymer produced in the gas phase polymerization step]
-Butene content was 24 mol%. Example 2 Polymerization was carried out according to the method of Example 1, except that the conditions during polymerization were changed to those shown in Table 1. The results are shown in Table 1. Examples 3, 4, 5 Polymerization was carried out according to the conditions in Table 1, replacing the di7-functional dilnomethoxysilane used as the electron donor in Example 1 with the compounds listed in Table 1. The results are shown in Table-2. Example-6 [Preparation of titanium catalyst component (A) 1] A high-speed stirring device (manufactured by Tokushu Kika Kogyo) with contents Mt21 was heated to sufficient N! After replacing, refined kerosene 700ml. Commercially available MgC1
□ 10 g of ethanol, 24.2 g of ethanol, and 3 g of Emazol 320 (trade name, manufactured by Kao Atlas Co., Ltd., Sorbitan Nosteare) were added, and the system was heated to a temperature of 120° C. and stirred at 800 rpm. High j! Refined kerosene 11, which had been cooled in advance to -10°C, was stirred using a Theaon tube with an inner diameter of 5IIl.
The liquid was transferred to a 211f glass 7 flask (equipped with a stirrer) filled with . The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier. After suspending 7.5 g of the carrier in 1501 titanium tetrachloride at room temperature, 4.5 ml of non-octyl 7-talate was added, and after stirring and mixing at 120°C for 2 hours, the solid portion was heated to tp3! !
i, suspended in 1501 titanium tetrachloride again, and stirred and mixed again at 130°C for 2 hours. A solid catalyst component [A] was obtained by washing with .The particle size of the catalyst was 64μ, and the geometric standard deviation value was 1.
It was 4. [Preliminary Polymerization 1 Performed in the same manner as in Example 1. Prepolymerization was 89 g-pp/g-catalyst. 1 Polymerization 1 Polymerization was carried out under the conditions shown in Table 1. The results are shown in Table 1. [Effect of the invention 1] According to the present invention, compared to currently known propylene-based random copolymers, it has excellent heat sealability, heat sealability, transparency, and blocking resistance, and has a low hydrocarbon soluble content. Less propylene block copolymer is obtained. Further, the propylene block copolymer of the present invention has heat sealability, blocking resistance, and heat seal aging resistance comparable to currently known polyolefin compositions. As mentioned above, the propylene block copolymer of the present invention has better heat sealability, blocking resistance, and better anti-blocking properties than currently known polyolefin compositions, even without forming the composition with other (co)polymers. Since it has heat-sealing resistance to aging, it is not necessary to form it into a composition, and the manufacturing cost can be lowered.

[Brief explanation of the drawing]

Fig. 1 shows a schematic cross-sectional view of the film 11111 method used in the test, tlS2 shows a schematic cross-sectional view of the method of measuring the blocking value of the film, and Fig. 3 shows a schematic cross-sectional view of the method of measuring the heat seal strength. Figure 4 shows the relationship between heat sealing temperature and peel strength. Patent applicant: Mitsui Petrochemical Industries, Ltd. Procedural amendment (0
Button December 9, 1986

Claims (1)

[Claims] (1) (A) Highly active and highly steric containing magnesium, titanium, halogen and electron donor as essential components, with an average particle size of about 5 to about 200μ and a geometric standard deviation value of particle size distribution of less than 2.1 in the presence of a catalyst formed from a regular titanium catalyst component, (B) an organometallic compound catalyst component of a metal from Group 1 to Group 3 of the periodic table, and (C) an electron donor catalyst component; (A
) In the presence of an α-olefin prepolymerization catalyst obtained by prepolymerizing α-olefins having 2 to 10 carbon atoms in the range of 1 to 2000 g per gram, [1] propylene, ethylene, and 4 carbon atoms. to 20 α-olefins are copolymerized in suspension polymerization step [a] using liquid propylene as a solvent, and then [2] flashing the liquid unreacted raw material in the polymerization reaction mixture obtained in the suspension polymerization step The repeating unit (a) derived from propylene is
86 to 97 mol%, 0.5 to 6 mol% of repeating units (b) derived from ethylene, and 2 to 13 mol% of repeating units (c) derived from α-olefin having 4 to 20 carbon atoms. and the molar ratio c/
A flash step (b) for producing a propylene random copolymer [I] in which (b+c) is in the range of 0.3 to 0.9, and further [3] in the presence of the propylene random copolymer [I]. , and by copolymerizing propylene and an α-olefin having 4 to 20 carbon atoms under conditions where the reaction system forms a gas phase, the repeating unit (d) derived from propylene is 10 to 90 mol% and A gas phase polymerization step [Ha ], A method for producing a propylene-based block copolymer, characterized by combining.