JPH01297408A - Production of propylene-based elastomer - Google Patents

Abstract

PURPOSE:To efficiently obtain a propylene-based elastomer having practicable tensile strength even in an unvulcanized state, sufficient flexibility and low- temperature characteristics with hardly any surface tackiness at a low cost by using an improved Ziegler-based catalyst. CONSTITUTION:A catalyst system consisting of (A) a solid component consisting essentially of Mg, Ti and a halogen atom and an electron donor, (B) an alkoxy group-containing aromatic compound expressed by the formula [R<1> is 1-20C alkyl; R<2> is 1-10C hydrocarbon, OH or nitro; m is 1-6; n is 0-(6-m)] and (C) an organoaluminum compound is used to polymerize 20-95wt.% propylene homopolymer or a copolymer of propylene and a 4-30C alpha-olefin and 80-5wt.% copolymer of ethylene and propylene by a multistage polymerization method.

Description

DETAILED DESCRIPTION OF THE INVENTION C. Industrial Application Field The present invention relates to an improvement in a method for producing a propylene elastomer. More specifically, the present invention uses an improved Ziegler-based catalyst and uses a multi-stage polymerization method to achieve practical tensile strength even in an unvulcanized state, low surface tackiness, and low-temperature properties. The present invention relates to a method for efficiently producing a propylene elastomer with good properties at low cost.

εPrior art] Thermoplastic elastomers have traditionally been used as energy-saving and resource-saving elastomers, especially as substitutes for vulcanized rubber, such as automobile parts, industrial machinery parts, electronic/electrical parts,
Widely used as building materials.

By the way, olefinic thermoplastic elastomer (TO
P) is usually produced by a method of kneading polypropylene and ethylene-propylene-diene rubber (EPDM) in the presence of peroxide (Japanese Patent Laid-Open No. 61-2177).
Publication No. 47). However, this method has the disadvantage that the operation is complicated and the manufacturing cost is inevitably increased.

On the other hand, various attempts have been made to reduce costs by producing high molecular weight polymers having mechanical properties similar to TOpl in the polymerization step.

For example, propylene-hexene copolymer (JP-A-49-5
3983, JP 62-19444), elastic polypropylene (JP 61-179247)
etc. have been proposed. However, all of these high molecular weight polymers have the drawback of insufficient low temperature properties.

Furthermore, the propylene/ethylene-propylene two-stage polymerization method is well known as a method for improving the low-temperature properties of polypropylene (Japanese Unexamined Patent Publication No. 57-50804). It is difficult to produce a vulcanized rubber-like polymer that has both high tensile strength.

[Problems to be Solved by the Invention] Under these circumstances, the present invention has a practical tensile strength even in an unvulcanized state, sufficient flexibility and low-temperature properties, and The purpose of this invention is to provide a method for efficiently producing a propylene elastomer with low surface tackiness at low cost.

C Means for Solving Problem 1 As a result of intensive research to achieve the above object, the present inventors achieved the object by employing a multi-stage polymerization method using a specific catalyst system. The present invention was completed based on this finding.

That is, the present invention uses a multistage polymerization method using a catalyst,
(a) Propylene homopolymer or propylene and carbon number 4
20-95% by weight of copolymer with ~30 a-olefins
and (b) copolymer of ethylene and propylene 80-5
% by weight, the catalyst is (a) a solid component containing magnesium, titanium, a halogen atom, and an electron donor as essential components, and (b) a general formula (in which R1 is an alkyl group having 1 to 20 carbon atoms, R2 is a hydrocarbon group, hydroxyl group, or nitro group having 1 to 10 carbon atoms, m is an integer of 1 to 6, and n is an integer of 0 to (6-m). an alkoxy group-containing aromatic compound, and (c)
A catalyst system consisting of a combination with an organoaluminum compound, or (A) the solid component (a) and (b) an aromatic compound containing an alkoxy group are reacted in the presence or absence of (c) an organoaluminum compound. The present invention provides a method for producing a propylene elastomer characterized by using a catalyst system comprising a combination of the obtained solid catalyst component and (B) an organoaluminum compound.

The present invention will be explained in detail below.

In the method of the present invention, as a catalyst, (1) (a) a solid component containing magnesium, titanium, a halogen atom, and an electron donor as essential components; an alkyl group, R2 is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group, m is an integer of 1 to 6, and n is an integer of 0 to (6-m). group compound and (c)
a catalyst system consisting of a combination with an organoaluminum compound, or (ii) (A) the above (i) solid component and (b) an alkoxy group-containing aromatic compound in the presence or absence of (c) an organoaluminum compound; A catalyst system consisting of a combination of a solid catalyst component obtained by reacting with (B) and an organoaluminum compound is used.

First, to explain the catalyst system (i) above, (a)
The solid component contains magnesium, titanium, a halogen atom, and an electron donor as essential components, and can be prepared by bringing a magnesium compound, a titanium compound, and an electron donor into contact.

Examples of the magnesium compound include magnesium sybaride, magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, alkylmagnesium, and alkylmagnesium halide. , or a reaction product of an organomagnesium compound with an electron donor, halosilane, alkoxysilane, silanol, aluminum compound, etc. Among these, magnesium halide, alkoxymagnesium, alkylmagnesium, and alkylmagnesium halide are preferable. It is. Further, these magnesium compounds may be used alone or in combination of two or more.

Further, examples of the titanium compound include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-
Tetraalkoxytitanium such as butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium, tetrahalogenated titanium such as TrC14, TiBr, Ti14, (CHso)TiC et al., (CzHsO)TiC
fh, (C3H70)T t CQs, (n -C,H
sO)T i CQs, (C2H5O)T i B r
Trihalogenated alkoxytitanium such as 3, (CHsO)2T f Ch, (C2H50), Ti
CQt, (C5Hto)2Ti Cii4, (n −
C4HsO)2T I CQt, (CzHsO)2T
Dihalogenated alkoxytitanium such as i B rz, (CHsO)sT f C1, (CzH*0 )3T
s Cus(C3H70)3T i CIL, (n
Examples include monohalogenated alkoxytitanium such as -C4HsO)3T i Cft, and among these, highly halogen-containing titanium compounds, particularly titanium tetrachloride, are preferred. These titanium compounds may be used alone or in combination of two or more.

Furthermore, organic compounds containing oxygen, nitrogen, phosphorus, sulfur, etc. can be used as the electron donor.

Examples of such electron donors include esters, thioesters, amines, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides, aldehydes, and organic Examples include acids.

Specifically, dimethyl phthalate, diethyl phthalate, diethyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methylpropyl heptathalate, methylisobutyl heptathalate, ethylpropyl phthalate,
Ethyl isobutyl 7-thaleate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl propyl terephthalate, methyl isobutyl terephthalate,
Ethylpropyl tere7thaleate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, diethyl isophthalate, diisobutyl iso7tate, methyl ethyl iso 7 tallate, methylpropyl isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate Aromatic dicarboxylic acid diesters such as 7-talate, ethyl isobutyl iso-7-talate and propyl isobutyl isophthalate, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl acetate, ethyl valerate, Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoate phenyl acid, benzyl benzoate, ethyl toluate, amyl toluate, ethyl anisate, ethyl ethoxybenzoate, p
- Monoesters such as ethyl butoxybenzoate, ethyl 0-chlorobenzoate and ethyl naphthoate, esters having 2 to 18 carbon atoms such as T-valerolactone, coumarin, 7-thallide, ethylene carbonate, benzoic acid, p-oxy Organic acids such as benzoic acid, acid anhydrides such as succinic anhydride, benzoic anhydride, 0-)ruyl anhydride, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, etc. having 3 to 1 carbon atoms
5 ketones, aldehydes with 2 to 15 carbon atoms such as acetaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthylaldehyde, acids with 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluyl chloride, anisyl chloride, etc. Halides, ethers with 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether, acetic acid amide, benzoic acid amide, toluic acid amide, etc. , amines such as tributylamine, N,N'-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine, and nitriles such as acetonitrile, benzonitrile, and tolnitrile. .

Among these, esters, ethers, ketones and acid anhydrides are preferred, particularly di-n-butyl heptatalate,
Suitable examples include aromatic dicarboxylic acid diesters such as diisobutyl phthalate, and alkyl esters having 1 to 4 carbon atoms of aromatic monocarboxylic acids such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluidic acid. Aromatic dicarboxylic acid diesters are particularly preferred because they improve the catalytic activity and activity persistence as well as the stereoregularity of the resulting polymer.

The solid component (a) can be prepared by a known method (Japanese Unexamined Patent Publication No. 53-430
94, JP-A-55-135102, JP-A-55-135103, JP-A-56-18606), for example, (1) a magnesium compound or a complex compound of a magnesium compound and an electron donor. , a method of pulverizing in the presence of an electron donor and a grinding aid used as desired, and reacting with a titanium compound; (2) a method of reacting a liquid magnesium compound with no reducing ability and a liquid titanium compound; A method of precipitating a solid titanium complex by reacting in the presence of an electron donor, (3) (1) above.
or a method of reacting the product obtained in (2) with a titanium compound, (4) the product obtained in (1) or (2) above,
Furthermore, a method of reacting an electron donor and a titanium compound,
(5) A magnesium compound or a complex compound of a magnesium compound and an electron donor is ground in the presence of an electron donor, a titanium compound, and a grinding aid used as desired, and then treated with a halogen or a halogen compound. (6) A method in which the compounds obtained in (1) to (4) above are treated with a halogen or a halogen compound.

Furthermore, methods other than these (Japanese Unexamined Patent Publication No. 56-166205
No. 1, JP-A-57-63309, JP-A-57-
190004, JP-A-57-300407, JP-A-58-47003), the solid component (a) can also be prepared.

In addition, oxides of elements belonging to groups ■ to ■ of the periodic table, for example,
A composite oxide containing at least one oxide of an oxide such as silicon oxide, magnesium oxide, or aluminum oxide or an oxide of an element belonging to groups ■ to ■ of the periodic table, such as a solid material in which the magnesium compound is supported on silica alumina or the like. , an electron donor, and a titanium compound in a solvent at a concentration of 0 to 200
The solid component can be prepared by contacting for 2 minutes to 24 hours at a temperature in the range of 10 to 150°C.

In preparing the solid component, an organic solvent inert to the magnesium compound, electron donor and titanium compound, such as an aliphatic hydrocarbon such as hexane or heptane, or an aromatic hydrocarbon such as benzene or toluene, may be used as a solvent. , or a saturated or unsaturated aliphatic group having 1 to 12 carbon atoms,
Halogenated hydrocarbons, such as mono- and polyhalogen compounds of cycloaliphatic and aromatic hydrocarbons, and the like can be used.

Regarding the composition of the solid component (a) prepared in this way, the magnesium/titanium atomic ratio is usually 2 to 100.
The halogen/titanium atomic ratio is in the range of 5 to 200, and the electron donor/titanium molar ratio is in the range of 0.1 to 10.

The alkoxy group-containing aromatic compound of component (b) of the catalyst system (i) is a compound represented by the general formula (in the formula, R11R1, m and n have the same meanings as above), and such a compound as,
For example, m-methoxytoluene, 0-methoxyphenol, m-methoxyphenol, 2-methoxy-4-methylphenol, vinylanisole, p-(1-propenyl)anisole, p-allylanisole, l,3-bis(
p-methoxyphenyl)-1-pentene, 5-allyl-
Monoalkoxy compounds such as 2-methoxyphenol, 4-allyl-2-methoxyphenol, 4-hydroxy-3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole, nitrophenetole,
0-dimethoxybenzene, m-dimethoxybenzene, p
-dimethoxybenzene, 3,4-dimethoxytoluene,
2.6-Simethoxyphenol, 1-allyl-3,4-
Dialkoxy compounds such as dimethoxybenzene and 1.
3.5-trimethoxybenzene, 5-allyl-1,2,
3-trimethoxybenzene, 5-allyl-1,2,4-
trimethoxybenzene, 1,2.3-1-dimethoxy-
5-(1-propenyl)benzene, 1.2.4-trimethoxy-5-(1-propenyl)benzene, 1.2.3
-trimethoxybenzene, 1.2.4-trimethoxybenzene, and other trialkoxy compounds, among which dialkoxy compounds and trialkoxy compounds are preferred.

These alkoxy group-containing aromatic compounds may be used alone or in combination of two or more.

The organoaluminum compound of component (c) has the general formula % formula % ([) (in the formula, R3 is an alkyl group having 1 to 10 carbon atoms, X is a halogen atom such as chlorine or bromine, and p is 1 to 3) can be used. Examples of such aluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, and trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, and diisobutylaluminum monochloride. , dialkyl aluminum monohalides such as dioctyl aluminum monochloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, and the like can be suitably used. One type of these aluminum compounds may be used, or two or more types may be used in combination.

Regarding the usage amount of each component constituting the (i) catalyst system,
(a) Component usually has a reaction volume of 12 in terms of titanium atoms.
The molar ratio of component (b) to the titanium atoms in component (a) is usually 0, O1 to 5001, preferably 1 to 3.
00 is used. This amount is 0.01
If it is less than 500, the physical properties of the produced polymer may deteriorate, and if it exceeds 500, the catalyst activity tends to decrease.

In addition, component (iii) has an aluminum/titanium atomic ratio of
The amount used is usually 1 to 3,000, preferably 40 to 800. If this amount exceeds the above range, the catalyst activity may become insufficient.

Next, to explain the catalyst system (ii) above, the solid catalyst component (A) in the catalyst system combines the solid component (a) and the alkoxy group-containing aromatic compound (b). ) can be prepared by reacting in the presence or absence of an organoaluminum compound. A hydrocarbon solvent is usually used for this preparation. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, and saturated or unsaturated aliphatics having 1 to 12 carbon atoms.
Mention may be made of halogenated hydrocarbons such as mono- and polyhalogen compounds of alicyclic and aromatic hydrocarbons. These solvents may be used alone or in combination of two or more.

In the absence of an organoaluminum compound, the component (a) and (
When preparing the solid catalyst component (A) by reacting component (b) with component (b), the alkoxy group-containing compound of component (b) is
The molar ratio to titanium atoms in the component is usually 0.1 to 2.
00, preferably 1 to 50, and the concentration is usually 0.0 L to 10 mmof
l/A, preferably in the range of 0.1 to 2 mmol/l.

If the molar ratio to titanium atoms is outside the above range, it will be difficult to obtain a catalyst with the desired activity. Moreover, the concentration is 0.
If it is less than 01 mmoα/α, the volumetric efficiency is low and it is not practical, and if it exceeds 10 mmoα/α, overreaction is likely to occur and the catalytic activity may decrease.

In addition, the reaction temperature is usually 0 to 150°C, preferably 10°C.
The temperature is selected within the range of ~50°C. If this temperature is less than 0°C, the reaction will not proceed sufficiently and it will be difficult to obtain the desired activity, and if it exceeds 150'O, side reactions will occur and the activity will tend to decrease. Furthermore, the reaction time is temperature dependent - cannot be determined approximately, but is usually 1
minutes to 20 hours, preferably 10 to 60 minutes.

When the reaction is carried out in the presence of the organoaluminum compound of component (c), the concentration of the aluminum compound is usually 0.
05~100mmof! /II, preferably 1-10m
It is selected within the range of mol/ffi. This concentration is 0.05
If it is less than mm o t/E, the effect of carrying out the reaction in the presence of the organoaluminum compound will not be sufficiently exhibited,
If it exceeds 100 mm o (t/l), (a) reduction of titanium in the solid component may proceed, leading to a decrease in catalytic activity.

In this way, the solid catalyst component (A) is prepared.

Examples of the organoaluminum compound as the component (B) in the catalyst system (ii) include the organoaluminum compounds exemplified as the component (c).

Regarding the usage amount of each component in the (i) catalyst system, (
The solid catalyst component of component A) is usually 0.0005 to 1 mmofl/per reaction volume 1a in terms of titanium atoms.
The organoaluminum compound of (B) ff usually has an aluminum/titanium atomic ratio of 1 to 3000. Preferably, an amount in the range of 40 to 800 is used. If this atomic ratio exceeds the above range, the catalyst activity will be insufficient.

In the method of the present invention, the catalyst system is used to produce (a) a propylene homopolymer or a copolymer of propylene and an a-olefin having 4 to 30 carbon atoms by a multistage polymerization method.
A propylene-based elastomer comprising 5% by weight and (b) 80 to 5% by weight of a copolymer of ethylene and propylene is produced.

The propylene homopolymer or copolymer of propylene and α-olefin as component (a) usually has an intrinsic viscosity of 0.5.
~6.0dl/y, preferably 1.0-3.0dQ/y
It is a low crystalline polymer in the range of .

When component (a) is a copolymer of propylene and σ-olefin, the content of α-olefin units in the copolymer is 0.1 to 30 mol%, preferably 1 to 10 mol%. It is desirable that it be within the range.

The α-olefins include those having 4 to 30 carbon atoms;
For example, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, tetradecene-1, octadecene-1,4
-methylpentene-1,4-methylhexene-1,4,
4-dimethylpentene-1 and the like can be used.

One type of these σ-olefins may be used, or two or more types may be used in combination.

The copolymer of ethylene and propylene as component (b) usually has an intrinsic viscosity in the range of 0.5 to 8.0 dfl/y, preferably 1.0 to 5.0 dl/g, and contains ethylene units. The content of is 10 to 60 mol%, preferably 20
Preferably, the content is in the range of 40 mol %.

The content of the propylene homopolymer or copolymer of propylene and α-olefin as component (a) and the copolymer of ethylene and propylene as component (b) in the propylene elastomer is 20 to 95% by weight, respectively. % and 80-5% by weight, preferably 60-92% and 40% by weight
It is necessary that the content be in the range of ~8% by weight, and if the content deviates from this range, it will be difficult to obtain an elastomer with desired physical properties.

The polymerization order and the number of polymerization stages in the multistage polymerization method of the present invention are not particularly limited and can be arbitrarily selected. For example, when producing an elastomer consisting of 60% by weight of component (a) and 40% by weight of component (b), the propylene homopolymer or copolymer of propylene and α-olefin as component (a) is and 50% by weight each in the third stage.
and 10% by weight, and the copolymer of ethylene and propylene as component (b) may be polymerized at io weight% and 30% by weight in the second stage and the fourth stage, respectively. However, in the case of gas phase polymerization, it is preferable to polymerize in the order of component (b) and component (a). Polymerization methods include suspension polymerization,
Either solution polymerization or gas phase polymerization is possible, and either continuous polymerization or discontinuous polymerization can be used.

(a) Component propylene homopolymer or propylene and a
- When producing a copolymer with an olefin, the polymerization temperature is usually selected in the range of θ to 200°C, preferably 60 to 100°C, and the olefin pressure is usually selected in the range of 1 to 50 kg/cra. When copolymerizing propylene and α-olefin, propylene and α-olefin are mixed so that the content of α-olefin units in the copolymer is 0.1 to 30 mol%, preferably 1 to 10 mol%. It is desirable to adjust the concentration ratio between

On the other hand, when producing a copolymer of ethylene and propylene as component (b), the ethylene/propylene gas ratio is usually 0.01 to 10.0. Preferably in the range of 0.2 to 1.0, the polymerization temperature is usually O to 200'O, preferably 40
~80℃ range, olefin pressure is usually 1~50 kg
/ cm”.

In each of the above polymerizations, the reaction time was 5 minutes to 1
About 0 hours is sufficient, and the molecular weight of the polymer can be adjusted by known means, for example, by adjusting the hydrogen concentration in the polymerization vessel.

In the present invention, post-treatment after polymerization can be carried out by conventional methods. That is, in the gas phase polymerization method, after polymerization, a nitrogen stream or the like may be passed through the polymer powder drawn out from the polymerization vessel in order to remove olefins and the like contained therein. Further, if desired, it may be pelletized using an extruder, and at that time, a small amount of water, alcohol, etc. may be added to completely deactivate the catalyst.

In addition, in the bulk polymerization method, after the monomer is completely separated from the polymer extracted from the polymerization vessel after polymerization,
Can be pelletized.

Next, different examples of embodiments of the present invention are shown in flowcharts in FIGS. 1 and 2.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

Example 1 (1) Preparation of solid component (a) Purified hebutane 20 mnsM9 (OEt) was placed in a glass Mitsuro flask with an internal volume of 500 m1 that was sufficiently purged with nitrogen!
Add 1.2 g of di-n-butyl 49 and 7-talate, keep the inside of the system at 90°C, and stir TiC1,4! After dropping a, add T i C1! 111 ml+ of a was added, the temperature was raised to 110°C, the mixture was reacted for 2 hours, and then purified at 80°C was washed with butane. Next, T i CL 115! was applied to the obtained solid phase part. Add a, 110
The reaction was continued for an additional 2 hours at °C. After the reaction, the product was washed several times with 100 mA of purified butane to remove the solid component (a).
Toshi l;.

(2J ethylene-propylene/propylene two-stage polymerization 2a
n-heptane 1 in a stainless steel pressure autoclave.
．． 2L AIIE t, 3mmo! and 1-allyl-3
,4-dimethoxybenzene (ADMB) 0.08mmo
n was added, and the internal temperature was maintained at 50°C.

Next, ethylene (flow rate 2.51/m1n) and propylene (flow rate 7.5n/rnin) were supplied, and the internal pressure was reduced to 3 kg.
/ crtr'' and flowing gas for 15 minutes, the n-hebutane slurry containing solid component 18 and shoulder 9 obtained in (1) was added, and copolymerization of ethylene and propylene was carried out at 50°C for 10 minutes. The reaction was carried out (-stage polymerization). After the reaction was completed, the system was lightly purged and replaced with argon several times, then propylene was supplied to a pressure of 8 kg/cra2, and propylene was polymerized at 70°C for 40 minutes. (second stage polymerization).The results are shown in Table 1.

The physical properties in the table are values for a sample (thickness: 3 m) obtained by kneading at 195° C. for 2 minutes using a Laboplasto Mill with an internal volume of 30 cc, and then press-molding at 200° C. Physical property measurements were performed in accordance with JISK-6301.

Examples 2 to 5 Example 1 except that the polymerization time was changed in Example 1.
Polymerization was carried out in the same manner. The results are shown in Table 1.

Comparative Example 1 In Example 1, diphenyldimethoxysilane (DMDP) having stereoregular effect was used instead of ADMB.
S) Polymerization was carried out in the same manner as in Example 1, except that 0.08 mmoQ was used. The results are shown in Table 1.

Example 6 Polymerization was carried out in the same manner as in Example 1, except that the flow rates of ethylene and propylene in the −th stage were changed. The results are shown in Table 1.

Example 7 In Example 1, hexene-1100 was used in the second stage polymerization.
Polymerization was carried out in the same manner as in Example 1, except that mmall was added. The results are shown in Table 1.

Example 8.9 Polymerization was carried out in the same manner as in Example 7, except that the a-olefin shown in Table 1 was used instead of hexene-1. The results are shown in Table 1.

Examples 10 to 12 Polymerization was carried out in the same manner as in Example 7, except that the amount of catalyst added and the polymerization time were changed. The results are shown in Table 1.

Comparative Example 2 In Example 10, DMDPS was used instead of ADMB.
Example 1O except that 0.08 mmol was used.
Polymerization was carried out in the same manner. The results are shown in Table 1.

Example 13 (1) Preparation of solid component (a)
75 all of purified hepatane, 75 mL of titanium tetrabutoxide, and 109 g of anhydrous magnesium chloride were added to flask No. 0, and flask No. 7 was heated to 90° C., and the magnesium chloride was completely dissolved over a period of 2 hours. Next, add 4 flasks.
After cooling to 0°C, 15 ml of methylhydrodiene polysiloxane was added to precipitate a magnesium chloride/titanium butoxide complex. After washing this with purified hebutane, 8.7 ml of silicon tetrachloride and 1.8 ml+ of diheptyl heptatalate were added thereto and held at 50°C for 2 hours. After washing with purified hebutane, further tetrachloride was added. 25 ml of titanium was added and held at 70° C. for 2 hours.

Next, this was washed with purified butane to obtain a solid component (a).

Polymerization was carried out in the same manner as in Example 10. The result is the first
Shown in the table.

Example 14 (1) Preparation of solid catalyst component (A) In a glass Schlenk tube with an internal volume of 500 rtrl that was sufficiently purged with nitrogen, 100 ml of purified hebutane 1°ADMBo,
2mmoffi and 0.59% of the solid component (a) obtained in (1) of Example 1 were added, and the mixture was stirred at 25°C for 15 minutes.

After the reaction was completed, the supernatant was removed, and 10% of butane was added to the purified product.
It was washed several times at 0 mA to obtain a solid catalyst component (A).

(2) Ethylene-propylene/propylene two-stage polymerization Example 1 was the same as Example 1 except that the solid catalyst component (A) prepared in (1) above was used instead of ADMB and solid component (A). Polymerization was carried out in the same manner. The results are shown in Table 1.

(Left below) [Effects of the Invention] According to the method of the present invention, by using an improved Ziegler catalyst, it has a practical tensile strength even in an unvulcanized state, and has sufficient flexibility and low-temperature properties. In addition, a propylene elastomer with low surface tackiness can be efficiently produced at low cost.

The propylene elastomer obtained by the method of the present invention is suitably used as a material for, for example, automobile parts, industrial machine parts, electronic/electrical parts, building materials, and the like.

[Brief explanation of the drawing]

1 and 2 are 70-charts of different examples of embodiments of the present invention, respectively. Patent applicant Idemitsu Petrochemical Co., Ltd.

Claims (1)

[Scope of Claims] 1. By a multistage polymerization method using a catalyst, (a) a propylene homopolymer or propylene with a carbon number of 4
20-95% by weight of copolymer with ~30 α-olefins
(b) In producing a propylene-based elastomer consisting of 80 to 5% by weight of a copolymer of ethylene and propylene, (a) magnesium, titanium, a halogen atom, and an electron donor are required components as the catalyst. (b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 is an alkyl group with 1 to 20 carbon atoms, R^2
is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group,
m is an integer of 1 to 6, n is an integer of 0 to (6-m)); and (c) an organoaluminum compound. Characteristic method for producing propylene-based elastomer. 2. In producing the propylene elastomer according to claim 1 by a multi-stage polymerization method using a catalyst, the catalyst includes (A) (a) a solid component containing magnesium, titanium, a halogen atom, and an electron donor as essential components; , (b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R^1 in the formula is an alkyl group having 1 to 20 carbon atoms, R^2
is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitro group,
m is an integer of 1 to 6, n is an integer of 0 to (6-m)) with an alkoxy group-containing aromatic compound represented by (c) in the presence or absence of an organic aluminum compound; A method for producing a propylene elastomer, which comprises using a catalyst system comprising a combination of the obtained solid catalyst component and (B) an organoaluminum compound.