JPH04142310A - Rubberlike propylene copolymer - Google Patents

Abstract

PURPOSE:To provide a rubberlike propylene copolymer which has good elastic recovery at both ordinary and high temperatures and low surface tackiness by copolymerizing propylene with a 4-20C alpha-olefin in a specified molar ratio. CONSTITUTION:Propylene is mixed with a 4-20C alpha-olefin (e.g. butene-1) in such a molar ratio that the content of the 4-20C alpha-olefin is 0.1-15mol%, and the mixture is copolymerized in the presence of an olefin polymerization catalyst. In this way, a rubberlike propylene copolymer having an intrinsic viscosity of 1.5-10dl/g and a melting peak temperature (as determined by differential scanning calorimetry) of 100-155 deg.C, a residual elongation after 100% elongation of 40% or below and a boiling diethyl ether-soluble matter content of 30-75wt.% is produced. The obtained copolymer can be effectively used as a special rubber for modifying resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel rubbery propylene copolymer used as a special rubber for resin modification.

[Prior Art] In recent years, thermoplastic elastomers have attracted attention as new materials that fill the gap between rubber and plastic, and as energy-saving and resource-saving elastomers. In particular, as an alternative to vulcanized rubber, it is used in automobile parts such as bumpers and side moldings, industrial machinery parts, electrical parts, etc.
Widely used for civil engineering and building material sheets, retaining timbers, etc.

As such thermoplastic elastomers, partially crosslinked olefinic thermoplastic elastomers (TPO) are widely used because they have excellent mechanical properties as thermoplastic elastomers. However, in order to manufacture this TPO, it is generally necessary to perform complicated operations such as kneading polypropylene and ethylene-propylene-diene rubber (EPDM) in the presence of peroxide, and furthermore, the use of peroxide is required. Since this is necessary, the resulting TPO inevitably comes at a high cost.

Therefore, various attempts have been made to reduce costs by producing a polymer with mechanical properties similar to those of TPO in the polymerization step. 49-53983, Japanese Patent Publication No. 62-19444), elastic polypropylene (Japanese Unexamined Patent Publication No. 51-179247), etc. have been proposed. However, all of these polymers have the drawback of insufficient low temperature properties.

Furthermore, a propylene/ethylene-propylene two-stage polymerization method is well known for improving the low-temperature properties of polypropylene (for example, Japanese Patent Application Laid-Open No. 57-50804).
With this method, it is difficult to produce a polymer that has both flexibility and practical tensile strength.

On the other hand, polypropylene is industrially produced using Ziegler catalysts, or in this case, isotactic polypropylene is mainly produced with a crystalline structure of about 10 to 2.
15% atactic polypropylene pyrene is produced as a by-product. This atactic polypropylene has a number average molecular weight (
M,...) was low, around 10,000, and its practical value was poor.

In order to overcome the above-mentioned drawbacks, a rubbery lantam copolymer obtained by copolymerizing fluoropylene and 1-butene has been proposed (Japanese Patent Application Laid-Open No. 13479/1989).
Publication No. 5).

However, when producing this rubbery random copolymer,
It is necessary to add a large amount of 1-butene (approximately the same number of moles as propylene), which results in a disadvantage in that the crystallinity of the product decreases, resulting in lower thermal compression strain, melting point, and softening point. Furthermore, the use of a large amount of 1-butene inevitably increases the cost of the product.

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a rubbery propylene copolymer that exhibits excellent rubber properties with a good elastic recovery rate and has low surface tackiness.

Means and Effects for Solving the Problems In order to achieve the above objects, the present invention provides propylene and α having 4 to 20 carbon atoms.
- It is a copolymer with olefin, (A) α-olefin content of carbon a4-20 is 0, l
N13 mol%, (B) Intrinsic viscosity [η is 1.5 to 10 d! ;L/g, (
C) Melting peak temperature T determined by differential scanning calorimetry
(D) Residual elongation PS□ after 100% elongation. Provided is a rubbery propylene copolymer defined as having a boiling diethyl ether soluble portion of 0 to 40% (E) of 30 to 75% by weight.

The present invention will be explained in more detail below.

The rubbery propylene copolymer of the present invention is a copolymer of propylene and an α-olefin having 4 to 20 carbon atoms (hereinafter simply referred to as α-olefin).

In this case, there is no limitation on the type of α-olefin, such as butene-1, pentene-1, hexene-1, heptene-1, etc.
1, octene-1, nonene-1, decene-1, dodecene-1, tetradecene-1, octadecene-1,4-methylpentene-1,4-methylhexene-1,4,4-dimethylpentyne-1, etc. Butene-1 is particularly preferred. These α-olefins may be used alone or in combination of two or more.

Further, the properties of (A) to (E) of the copolymer of the present invention are as follows.

(An α-olefin content in the copolymer is 0.1 to 15 mol%, preferably 1 to 10 mol%.

If it is less than 0.1 mol %, the permanent elongation will be large and rubber-like properties will not be exhibited, and if it is more than 15 mol %, the breaking strength will be low and the surface will become sticky.

(B) Intrinsic viscosity [η] 1.5 to 10 d/g, preferably 1.8 to 6 d/g
It is.

If it is less than 1.5 dl/g, the surface will become sticky, and if it is more than 10 dl/g, the moldability will be poor.

(C) Melting peak temperature (T) determined by scanning calorimetry and quantity measurement method: 100 to 155°C, preferably 100 to 140°C.

If it is lower than 100°C, the thermal properties will be poor, and if it is higher than 155°C, the permanent elongation will be high.

(D) Residual elongation after 100% elongation (PS+oo) 40%
It is preferably 30% or less.

If it is higher than 40%, the elastic recovery rate will be small and the rubbery properties will be insufficient.

(E) It is 30 to 75% by weight, preferably 35 to 55% by weight in the boiling diethyl ether soluble part copolymer.

If it is less than 30% by weight, the permanent elongation will be large and it will not show rubber-like properties, and if it is more than 75% by weight, the breaking strength will be low and the surface will be sticky.

The method for producing the rubbery propylene copolymer of the present invention is not particularly limited, and it may be produced by a known method, or, for example, the method described below may be suitably adopted (Japanese Unexamined Patent Publication No. 53-243106). (see official bulletin).

That is, (a) a solid catalyst component containing magnesium, titanium, a halogen atom, and an electron donor as essential components, (b) an organoaluminum compound, and (c) a general formula (in which R1 has 1 to 20 carbon atoms) Alkyl group, R2 is a hydrocarbon group having 1 to 10 carbon atoms, hydroxyl group, or nitro group, m is an integer of 1 to 6, and n is an integer of 0 or 1 to (6-m). The rubbery propylene copolymer of the present invention can be obtained by copolymerizing propylene and an alpha-olefin in the presence of a catalyst consisting of a combination of aromatic compounds.

Examples of the magnesium compound used in the preparation of the solid catalyst component (a) include magnesium cybaride such as magnesium dichloride, magnesium oxide, magnesium hydroxide, hydrotalcite monomagnesium carboxylate, and alkoxymagnesium such as jetoxymagnesium. , alkylmagnesium, alkylmagnesium pallite such as allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, ethylbutylmagnesium, or alkylmagnesium compounds and electron donors, herrosilane, alkoxysilane, silanol and aluminum compounds, etc. Among these, preferred are magnesium parite, alkoxymagnesium, alkylmagnesium, and alkylmagnesium halide. These magnesium compounds may be used alone or in combination of two or more.

Furthermore, a reaction product of metallic magnesium, an alcohol, and a halogen may be used. in this case.

A polymer powder with improved catalytic activity, stereoregularity, titanium loading, and better morphology can be obtained. There is no particular restriction on the shape of the metal magnesium used in this case, and any shape of metal magnesium, such as granules, ribbons, or powders, can be used. Furthermore, there are no particular restrictions on the surface condition of the metal magnesium, or it is advantageous if the surface is not coated with magnesium oxide or the like.

Is there any particular restriction on the alcohol?
6 lower alcohols are preferred, and ethanol is particularly preferred since it provides a solid catalyst component that improves catalyst performance. There are no particular restrictions on the purity or water content of this alcohol, but if alcohol with a high water content is used, magnesium hydroxide will be formed on the surface of magnesium metal, so alcohol with a water content of 1% by weight or less, especially 2000ppm or less Furthermore, in order to obtain a magnesium compound having a more favorable morphology, the lower the water content, the more advantageous it is. moreover,
As the halogen, bromine and iodine are preferred. The form of the halogen is not limited to the raw form; for example, it may be dissolved in an alcoholic solvent and used as a solution.

The amount of alcohol to be used is usually selected within the range of 2 to 100 mol, preferably 5 to 50 mol, per 1 mol of metal magnesium. If the amount of alcohol is too large, it will be difficult to obtain a magnesium compound with good morphology, and if it is too small, the reaction with magnesium metal may not proceed smoothly. In addition, the halogen is usually 0.000% per mole of metallic magnesium.
1 g atom or more, preferably 0.0005 g atom or more, more preferably 0.001 g atom or more
It is used in a proportion of more than g atoms. If the amount of halogen used is less than 0,0001 g atoms, the amount of supported titanium, catalytic activity, stereoregularity and morphology of the resulting polymer will be reduced if the obtained magnesium compound is used without pulverization. Therefore, pulverization of the obtained magnesium compound is essential, which is not preferable. Further, there is no particular restriction on the upper limit of the amount of halogen used, and it may be selected as appropriate within a range that allows the desired magnesium compound to be obtained.

Furthermore, by appropriately selecting the amount of halogen used, the particle size of the resulting magnesium compound can be controlled as desired.

The reaction between the metal magnesium, alcohol and halogen is
This can be done using known methods. For example, a desired magnesium compound can be obtained by reacting metallic magnesium, an alcohol, and a halogen under reflux, usually for about 2 to 30 hours, until no hydrogen gas is generated. Specifically, when using iodine as a halogen, solid iodine is added to a mixture of metallic magnesium and alcohol, and then heated and refluxed, and alcohol containing iodine is used in a mixture of metallic magnesium and alcohol. It is possible to use a method in which a solution is added dropwise and then heated to reflux, or a method in which an alcoholic solution containing iodine is added dropwise while heating a mixture of metallic magnesium and alcohol. In either method, it is preferable to conduct the reaction under an inert gas atmosphere such as nitrogen gas or argon gas, using an inert organic solvent such as a saturated hydrocarbon such as n-hexane as the case may be. Regarding the introduction of metallic magnesium and alcohol, it is not necessary to add the entire amount of each to the reaction tank from the beginning, and they may be added in portions. For example, a method is to add the entire amount of alcohol from the beginning and then add metallic magnesium in several portions.

This method can prevent the temporary generation of large amounts of hydrogen gas, which is extremely desirable from a safety point of view, and allows for the reduction of the size of the reaction tank. This prevents the entrainment of alcohol and halogen droplets. The number of times to divide should be determined by considering the scale of the reaction tank, and is there any particular limit?
Considering the complexity of the operation, it is usually selected in the range of 5 to 10 times.

In addition, the reaction itself may be a hatch type or a continuous type,
Furthermore, as a modified method, a small amount of metallic magnesium is first added to the alcohol, which has been completely added from the beginning, and the products produced by the reaction are separated into another tank and removed, and then a small amount of metallic magnesium is added again. It is also possible to repeat.

The magnesium compound obtained in this way is crushed,
Alternatively, it can be used in the next step without performing a classification operation to make the particle size uniform.

Examples of the titanium compound include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, and tetra-n-propoxytitanium.
- Tetraalkoxytitanium such as butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, tetraphenoxytitanium, tetrahalogenated titanium such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide,
Methoxytitanium trichloride, ethoxytitanium trichloride, probosoxytitanium trichloride, n
- trihalogenated alkoxytitanium such as butoxytitanium trichloride, ethoxytitanium trichloride, dimethoxytitanium dichloride, jetoxytitanium dichloride, dipropoxytitanium dichloride,
Diherogenated dialkoxytitaniums such as tri-n-proboxytitanium dichloride and di-n-butoxytitanium dichloride; monohalogens such as trimethoxytitanium chloride, triethoxytitanium chloride, triproboxytitanium chloride, and tri-n-butoxytitanium chloride; Among these, high halogen-containing titanium compounds, particularly titanium tetrachloride, are preferred. These titanium compounds may be used alone or in combination of two or more.

Furthermore, the electron donor may include oxygen, nitrogen, phosphorus, sulfur,
It is an organic compound containing silicon, etc., and is basically used to improve regularity during propylene polymerization. Examples of such electron donors include esters, thioesters, amines, amides, ketones, nitriles, phosphines, ethers, thioethers, acid anhydrides, acid halides, acid amides, and aldehydes. Examples include organic acids, organic acids, etc.

Specifically, diphenyldimethoxysilane, diphenyljethoxysilane, dibenzyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxy Organosilicon compounds such as silane, benzyltrimethoxysilane, dimethyl phthalate, diethyl phthalate, dipropylphthalate, diisobutyl phthalate, methylethyl phthalate, methylpropyl phthalate, methylisobutyl phthalate, ethylpropyl phthalate, ethylpropyl phthalate, propylisobutyl phthalate, dimethyl Terephthalate 1 Diethyl terephthalate, dipropyl terephthalate, diisophthyl terephthalate, methyl ethyl terephthalate, methyl propyl terephthalate, methyl propyl terephthalate, ethyl pro and luterephthalate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dipropylisophthalate Aromatic dicarboxylic acid diesters such as phthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methyl propyl isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl isobutyl terephthalate 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 dichlorohexanecarboxylate , ethyl benzoate, propyl benzoate 1 phtyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, pencil benzoate, ethyl toluate,
Monoesters such as amyl toluate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl 0-chlorobenzoate and ethyl naphthoate, γ
- Esters with 2 to 18 carbon atoms such as valerolactone, coumarin, and phthalide ethylene carbonate, organic acids such as benzoic acid and p-oxybenzoic acid, and acids such as succinic anhydride, benzoic anhydride, and P-)ruyl anhydride. anhydrides, acetone,
Ketones with 3 to 15 carbon atoms such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone, aldehydes with 2 to 15 carbon atoms such as acetaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthylaldehyde, acetyl chloride, pencil clois acid parites having 2 to 15 carbon atoms such as toluic acid cucoride, anisic acid chloride, methyl ether, ethyl ether, inpropyl ether, n-butyl ether, t-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene Symmetrical or asymmetrical ethers having 2 to 20 carbon atoms such as glycol phthyl ether, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, tributylamine, N,N"-dimethylpiperazine, 1\topencylamine, Aniline, pyridine 1
Amines such as picoline, tetramethylethylenediamine, nitriles such as acetonitrile, hendinitrile, tolnitrile, 2.2'-azobis(2-methylpropane), 2.2'-azobis(2-ethylpropane), 2.2 ″-azobis(2-methylpentane), α,
α°-azobisophthyronitrile, 1,1゛-azobis(1-cyclohexanecarbon #), (1-phenylmethyl)-azodiphenylmethane, 2-phenylazo-
Examples include azo compounds in which a sterically hindered substituent is bonded to an azo bond such as 2,4-dimethyl-4-tryloxybentanenitrile; one type of these may be used, or two types may be used.
You may use combinations of more than one species.

Among these, esters, ethers, diketones, and acid anhydrides are preferred, and in particular, n-phthyl phthalate,
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 toluic acid. Aromatic dicarboxylic acid diesters are particularly preferred since they improve the catalyst activity and activity persistence, as well as the stereoregularity of the resulting polymer.

The solid catalyst component (a) can be prepared by a known method (Japanese Unexamined Patent Application Publication No. 1983-1999).
Publication No. 43094, Japanese Patent Application Publication No. 135102/1983,
JP-A-55-135103, JP-A-55-186
For example, (1) a magnesium compound or a derivative compound of a magnesium compound and an electron donor is ground in the presence of an electron donor and a grinding aid used as desired, and then reacted with a titanium compound. (2) A method in which a liquid magnesium compound having no reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium complex; (3) a method in which a solid titanium complex is precipitated by 1) or (2) a method of reacting the obtained product with a titanium compound; (4) a method of reacting the product obtained in the above (1) or (2) with an electron donor and a titanium compound; 5) A magnesium compound or a derivative 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. Method (6) It can be prepared by, for example, treating the compounds obtained in the above (1) to (4) with a halogen or a halogen compound.

Furthermore, methods other than these (Japanese Unexamined Patent Publication No. 56-156205
No. 109, JP 57-63: 109, JP 57
~1,! Publication No. 10004, JP-A-57-300407
(Japanese Patent Application Laid-Open No. 58-47003),
The solid catalyst component (a) can be prepared.

In addition, oxides of elements belonging to groups U to ■ of the periodic table, such as silicon oxide, magnesium oxide, and pentaaluminum oxide, or composite oxides containing at least one oxide of elements belonging to groups ■ to ■ of the periodic table. For example, a solid material in which the magnesium compound is supported on silica alumina, an electron donor, and a titanium compound are mixed in a solvent at 0 to 20°C.
c, preferably at a temperature in the range of 10 to 150°C.
A solid catalyst component can be prepared by contacting for minutes to 24 hours.

In preparing the solid catalyst component, a 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,
It is possible to use halogenated hydrocarbons such as mono- and polyhalogen compounds of alicyclic and aromatic hydrocarbons.

The composition of the solid catalyst component (a) prepared in this way is usually about a magnesium/titanium atomic ratio of 2 to 10.
0. 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.

In the above catalyst, the organoaluminum compound used as component (b) 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, p is a number from 1 to 3) A compound represented by the following can be used. Examples of such aluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, and trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum. Dialkyl aluminum chitubalite such as monochloride, alkyl aluminum sesquihalide such as ethyl aluminum sesquichloride, etc. can be suitably used. These aluminum compounds may be used alone or in combination of two or more.

Furthermore, the general formula (r) used as the component (c)
The alkoxy group-containing aromatic compound represented by
For example, m-methoxytoluene, 0-methoxyphenol, m-methoxyphenol, 2-methoxy-4-methylphenol, vinylanisole, p-(1-propenyl)anisole, p-allylaninol, 1,3-bis(
p-methoxyphenyl) 2-1-pentene, 5-allyl-2-methoxyphenol, 4-allyl-2-methoxyphenol, 4-hydroxy-3-methoxybenzyl alcohol, methoxypencyl alcohol, nitroanisole, nitrophenethol, etc. monoalkoxy compounds, 0-dimethoxybenzene, m-dimethoxybenzene,
p-dimethoxybenzene, 3,4-dimethoxytoluene, 2゜6-simethoxyphenol, l-allyl-3,4
- dialkoxy compounds such as dimethoxybenzene and 1
, 3.5-trimethoxybenzene, 5-awalu 1,2
．． 3-trimethoxybenzene, 5-allyl-1,2,4
-trimethoxybenzene, 1.2.3-trimethoxy-
3-(l-propenyl)benzene, 1,2.4-)-dimethoxy-3-(l-propenyl)benzene,! , 2.
Examples include trialkoxy compounds such as 3-upper 2° toxybenzene and 1,2.4-)dimethoxybenzene, and among these, dialkoxy compounds and trialkoxy compounds are preferred. These alkoxy group-containing compounds may be used alone or in combination of two or more.

Regarding the usage amount of each catalyst component, 1 normal (a) component is T
In terms of i atoms, 0.0005 to 1 m per 11 reaction volumes
Component (b) is used in such a way that the molar ratio of component (b) to Ti is 1 to 3,000, preferably 40 to 800, and component (eight) is used in a molar ratio of component (c) to Ti.
They are used in a molar ratio of 0.01 to 500, preferably 1 to 300.

To produce the propylene copolymer of the present invention, the catalyst component is added to the reaction system, and then propylene and α-
Just introduce olefin.

Above (a), (b) and (c)! After mixing the prescribed amounts of # and #, and bringing them into contact, immediately add propylene and α.
-Olefin may be introduced to initiate polymerization, or propylene and α-olefin may be introduced and polymerization may be carried out after aging for about 0.2 to 3 hours after contact.

Note that the α-olefin is supplied at the same time as the propylene so that the α-olefin content in the copolymer is 0.1 to 15 mol %.

There are no particular limitations on the polymerization method, and any method such as solution polymerization, suspension polymerization, and gas phase polymerization may be used. Further, both continuous polymerization method and discontinuous polymerization method are possible. In particular, from the viewpoint of efficiency and quality, continuous solution polymerization and continuous suspension polymerization are preferred.

Furthermore, regarding the reaction conditions in the polymerization reaction, the polymerization pressure is usually 1 to 40 Kg/c@2.G, preferably 6 to 40 Kg/c@2.G.
30g/cm2・G, polymerization temperature is usually 40~90°
C1 is preferably selected as appropriate within the range of 55 to 75°C.

The molecular weight of the polymer can be adjusted by known means, for example by adjusting the hydrogen concentration in the polymerization vessel.6 Polymerization time is usually about 2 minutes to 5 hours, preferably 10 minutes to 2 hours. .

[Examples and Comparative Examples] Next, the present invention will be specifically illustrated by Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1 (1) Preparation of solid component catalyst (a) In a glass Mitsuro flask with an internal volume of 500 mJ1 that was sufficiently purged with nitrogen, 20 m, l of purified hebutane, Mg (OE
t): Add 4 g and 1.2 g of sea-n-butyl phthalate, maintain the system at 90°C, and stir without stirring.
After dropping 4 ml of a, further T I Cf
Additional L 4111 mfL was added, the temperature was raised to 110°C, the reaction was carried out for 2 hours, and the mixture was then washed with purified butane at 80°C. Next, T1Cu, 115
After adding mM, the reaction was further carried out at 110°C for 2 hours. After the reaction was completed, the product was washed several times with 100 mM of purified butane to obtain a solid catalyst component (a).

(2) Copolymerization of propylene and 1-butene.
M! ; L, A n E t 31 , 0 mm
on, 1-allyl-3,4-dimethoxybenzene (A
0.1 mmoi of DMB) and the solid catalyst component (a) obtained in (1) were added. Next, 10 g of 1-butene and propylene were added at an internal pressure of 8 g/cya, and heated to 70°C for 15 g/cya.
The copolymerization reaction was carried out for minutes. In addition, the internal pressure is 8 Kg/c
Propylene was continuously fed to maintain m2.

Examples 2 to 4 The amount of 1-butene charged was 7 g (Example 2) and 19 g, respectively.
(Example 3) and 13 g (Example 4) were carried out in the same manner as in Example 1 except that the amount was changed to 13 g (Example 4).

Comparative Example 1 The same procedure as Example 1 was carried out except that 1-butane was not added.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the amount of 1-butene charged was changed to 60 g.

Example 5 O-dimethoxybenzene (o-DM
The same procedure as in Example 1 was carried out except that B) was used.

Comparative example 3 The same procedure as in Example 1 was carried out except that ADMB was not added.

Comparative Example 4 Dimethoxydiphenylsilane (DM
The same procedure as in Example 1 was conducted except that DPS) was used.

Example 6 The same procedure as in Example 1 was carried out except that A n B u :l was used instead of AuEt.

In Example 1, the following steps were carried out except that instead of Mg(OEt)z, a solid product obtained by drying the product of the reaction of metallic magnesium, ethanol, and iodine was used. The same procedure as in Example 1 was carried out.

[Reaction of metallic magnesium, ethanol, and iodine] After thoroughly replacing the atmosphere with nitrogen gas in a glass reactor equipped with a stirrer (inner volume: approximately 6 tons), 160 g of metallic magnesium, approximately 2430 g of ethanol, and 16 g of iodine were added, and the mixture was stirred. The reaction was carried out under heating under reflux conditions until no hydrogen gas was generated from the system, to obtain a reaction product.

1 Example 7 The same procedure as in Example 7 was carried out, except that the product obtained by the reaction of magnesium metal, ethanol, and iodine was washed with heptane without being dried.

Next, the physical properties of the polymers obtained in the above Examples and Comparative Examples were measured using the following methods. The results are shown in Table 1.

Measuring method: As an α-olefin content measuring device, JNM-FX-20 manufactured by JEOL Ltd.
0 ('CoC nuclear resonance frequency 50, IMH'') was used.

The measurement conditions are as follows.

Measurement mode: Proton complete decoubling method Pulse width:
6.9 End 5 (45°) Pulse repetition time: 5S Integration number + 1.0000 times Solvent: 1,2.4-trichlorobenzene 7-fold benzene (90/10% by volume) Sample concentration: 250mg/2.5m solvent Measurement temperature 1
30°C Intrinsic viscosity [η] Measured in decalin at 135°C.

Melting peak temperature (T m ) Differential calorimeter (DS manufactured by Perkin-E1mer)
C-7) in accordance with J I SK7121.

Residual elongation after 100% elongation (PSI..) JIS K
Measured according to 2SO3.

Boiling diethyl ether soluble fraction (DEE soluble fraction) Measured by Soxhlet extraction method with distilled diethyl ether for 6 hours.

Stress at break Measured in accordance with JIS K2SO3.

Elongation at break Measured in accordance with JIS K2SO3.

Hardness Shore A Measured in accordance with JIS K2SO3.

Heat compression set Measured in accordance with JIS K2SO3.

Passing through the streets It was investigated using the following evaluation criteria.

0Surface stickiness or not at all 0Surface stickiness or little to no It exhibits a good elastic recovery rate when heated, and has low surface tackiness. Therefore, the rubbery propylene copolymer of the present invention can be effectively used as a special rubber for resin modification.

Claims (1)

[Claims] (1) A copolymer of propylene and an α-olefin having 4 to 20 carbon atoms, wherein (A) the content of α-olefin having 4 to 20 carbon atoms is 0.1
~15 mol%, (B) Intrinsic viscosity [η] is 1.5 to 10 dl/g, (C)
Melting peak temperature T_m determined by differential scanning calorimetry
is 100-155℃, (D) Residual elongation PS_1_0_0 after 100% elongation is 4
0% or less; (E) A rubbery propylene copolymer defined as having a boiling diethyl ether soluble portion of 30 to 75% by weight.