JPS61103910A - 3-methyl-1-butene copolymer - Google Patents

Abstract

PURPOSE:To obtain both heat- and solvent-resistant copolymer of narrow molecular weight distribution with each specific MFR, crystallinity, melting point and solubility to n-keptane and p-xylene, by copolymerization between 3- methyl-1-butene and another alpha-olefin. CONSTITUTION:The objective copolymer can be obtained by copolymerization, using as catalyst, TiCl4 and organoaluminum compound, between (A) 3- methyl-1-butene and (B) another alpha-olefin. This copolymer has the following characteristics; 1) molar ratio (A)/(B)...85/15-99.5/0.5 2) melt flow rate (MFR) determined at 340 deg.C under a load 2.16kg in compliance with ASTM D 1238...0.001-1,000g/10min 3) ratio HMFR/MFR measured under a load 10.0kg...<=300 4) crystallinity determined by X-ray...10-70% 5) melting point (Tm) by DSC...250-305 deg.C 6) boiling n-keptane soluble (DELTAy1...a value given by the equation I (X is mol% of the component (B), a1 is 0.6; b1 is 1.0) 7) boiling p-xylene soluble (DELTAy2)...a value given by the equation II (a2 is 3.0; b2 is 10).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an olefin copolymer containing methyl-1-butene (hereinafter sometimes abbreviated as 3MB) as a main component.

[Conventional technology]

Olefin polymers such as polyethylene and polypropylene are the most commonly used polymers.

However, compared to polyester and polycarbonate, which are thermoplastic resins, the melting point (Tm) and glass transition point (Tg
), which limits its use in applications that require heat resistance. Therefore, attempts have been made to produce olefin polymers with excellent heat resistance.

Therefore, the inventors of the present invention have repeatedly investigated how to obtain an olefin polymer with excellent heat resistance, and as a result, as described below, it has been found that an olefin copolymer containing 5MB as a main component can achieve the objective, and that a conventional olefin polymer can achieve the objective. It has been found that I/), which cannot be predicted with common knowledge, represents resistance to any organic solvent.

By the way, many proposals have been made regarding 3MB polymers. For example, British Patent No. 8357
59, in the presence of a catalyst consisting of triethylaluminum and titanium trichloride or vanadium trichloride.
A technique for polymerizing B is shown. However, the polymer disclosed here is a homopolymer of 5 MB and has a boiling point R
The n-heptane extraction amount is 1.9 to 2.2%, and therefore, if the α-olefin copolymer is other than 3MB, the n-heptane extraction amount should be higher. 15 more
Since the intrinsic viscosity is measured using 5'Cj and tetralin, the polymer is soluble in at least 135"C tetralin. On the other hand, the amount of n-heptane extracted from the 3MB copolymer of the present invention is extremely small. , and does not dissolve in tetralin. (This point will be discussed later.) Similarly, British Patent No. 1117912 discloses a technique for polymerizing 3MB in the presence of a catalyst consisting of organic germanium and titanium hexachloride. This technology also concerns a 5MB homopolymer.

Moreover, this 5MB homopolymer has a Tm of around 100° C. at most and a crystallinity of up to 40%. On the other hand, the 5MB copolymer of the present invention has a Tm of 250° C. or higher and a relatively high degree of crystallinity.

U.S. Patent No. 5,299,022 discloses that trichloride
A technique has been disclosed in which 5MB is cationically polymerized alone or together with other heptamer components such as isoptylene in the presence of an aluminum catalyst. However, the polymer obtained here is amorphous and very soft.

Japanese Patent Publication No. 40-24480 and U.S. Patent No. 52
9902844 discloses a technique for polymerizing 3ME in the presence of a Friedel-Crafts catalyst.

However, this polymer is also related to 3MB homopolymer and has a crystallinity of up to 30%. Furthermore, since it is described that the intrinsic viscosity can be measured by a conventional method, it can be presumed that it is soluble in decalin.

Ikiris No. 847,686 discloses a technique for polymerizing 5MB in the presence of a catalyst consisting of triisobutylaluminum and titanium pentachloride or vanadium trichloride. However, this polymer is also a homopolymer, and moreover, it is a transparent polymer having a crystallinity of substantially 10%.

Patent Publication Fff336-16913 discloses a technique for producing a 5 MB polymer consisting of ethylaluminum sesquichloride and titanium tetrachloride in the presence of a catalyst. However, this also concerns a homopolymer, and even if it were applied to the copolymerization of 5MB and α-olefin, only a product with a wide compositional distribution and molecular weight distribution and poor solvent resistance and mechanical properties would be obtained. do not have.

Canadian Patent No. 875622 discloses that titanium composite carbon
A technique is disclosed in which 5MB and α-olefin are copolymerized in the presence of a catalyst consisting of aluminum/titanium tetrachloride], diethylaluminium chloride, and in some cases butyllithium. However, the 3MB copolymer shown here, for example, produced with a titanium composite/diethylaluminum chloride catalyst system, has a comonomer content of 1.5 mol % and an extractable amount of 9n-heptane of 0.5%. When the amount of comonomer is 5.1 mol%, 9
%, and the amount of xylene extracted is as high as 99.5%, so the composition distribution and molecular weight distribution are wide.

Alternatively, those produced with a titanium composite/diethylaluminum chloride/butyllithium catalyst system have a comonomer content of 1.5 mol%, an eff1n-heptane extraction rate of 1%, and a comonomer content of up to 2.5%. increases to 13
%, the amount of xylene extracted is also large, and like the former, the composition distribution and molecular weight distribution are wide.

Japanese Patent Publication No. 35-6238 discloses a copolymer of 5MB and unbranched α-olefin produced using a triisobutylaluminum/s titanium chloride or vanadium trichloride catalyst system. The polymer obtained in this method has a relatively low density and a wide composition distribution and molecular weight distribution, and therefore a large amount of boiling Hn-heptane extraction and boiling p-xylene extraction is obtained.

[Problem that the invention seeks to solve]

The object of the present invention is to mainly use 5-methyl-1-butene, which has a narrow composition distribution and molecular weight distribution, excellent heat resistance, solvent resistance, mechanical properties, and other properties normally found in olefin polymers. The object of the present invention is to provide a polymer as a component. In particular, the remarkable effect on solvent resistance is the most distinctive feature of the present invention.

[Means for solving problems]

That is, the present invention provides (A) 3-methyl-1-butene 15-methyl-1-
α-olefin other than butene (molar ratio) 85/15
~99.510,5 (340° according to BI ASTM D 1258
Melt flow rate (CMFR) measured under C12,16Nq conditions is 0,001 to 1000g71r100O
.

(C) Melt flow rate measured at a load of 10.0# (
HMFR) and MFR ratio HMFR/MFR is 300 or less, ■I X-ray crystallinity is 10% or more and less than 70%, (
E) Melting point (Tm) by DSO is 250-505°C
, (Fl The boiling n-heptane soluble content (Δy1) is the amount shown by the formula (11), and Δy,≦JLIX + bl(1) (here, Δy1 is the n-heptane soluble content (support)). , X is α- other than 6-methyl-1-butene in the copolymer.
Amount of olefin (mol%), a 1G10.6 and b
1+ is 1.0. ) (G) The boiling p-xylene soluble content (Δy2) is expressed by the formula (
2) is the amount shown by -.

Δy2≦a2X + 1112 (2) (where Δy2 is p-xylene soluble fraction), X is the amount of α-olefin other than 3-methyl-1-butene in the copolymer (mol%), a2 is 5.0 and b2 is 10. ) is a 3-methyl-1-butene copolymer defined by:

[For production]

The α-olefin monomer component copolymerized with 3MB of the copolymer of the present invention has 2 to 30 carbon atoms, preferably 2
~20 α- with or without branches other than 5MB
Olefins, such as ethylene, propylene,
1-butene, 3-methyl-1-pentene, 6-methyl-
1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-
Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-hebutadecene, 1
-octadecene, 1-icosene, etc. Among these, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. Particularly preferred.

The content of α-olefin other than 3MB in the copolymer of the present invention is 0.5 to 15 mol%, preferably 0.5 to 1
0 mol%, particularly 0.5 to 8 mol% is preferred.

If the α-olefin content is less than the above range, the polymer will be hard and brittle, resulting in poor impact properties. If it exceeds the above range, it becomes too soft and the solvent resistance decreases.

Incidentally, the content of α-olefin monomer components other than 3MB in the copolymer is determined by the following method. That is, the 3MB copolymer of the present invention is substantially insoluble in organic solvents and is difficult to define in a solution state (!13-NMR). Polymerize a copolymer with the components,
The α-olefin content of the copolymer other than 5MB is O-
Measure by NMR.

The resulting content value and 4-methyl-1-pentene.
A calibration curve is created based on the measured R of the α-olefin copolymer. Measure the factor F of the 5MB copolymer whose content is to be determined, and insert the measured value into the calibration curve obtained by the method described above to determine the content of α-olefins other than 3MB.

Melt 70-L/-) CMPR), which is an index indicating the molecular weight of the copolymer of the present invention, is measured at a temperature of 3,110°C and a load of 2.16 kL in accordance with ASTM D1238.
Normally 0.001-1000 g/I when measured at j
CLmin mostly 0.01-500 g710 min
, especially within the range of 0.05 to 100 g/10 m1n. In addition, the intrinsic viscosity [η
] is usually 0.05-20 dl by measuring with trans-cyclododecene solvent at 215°C.
l/g, mostly 0.1-151? /g, especially 0.
It is within the range of 5 to 10 dA/g. Here, the reason for not using decalin at 135°C as a solvent for measuring [η] is that the copolymer of the present invention cannot be dissolved and it cannot be measured substantially, but the molecular weight distribution of the copolymer of the present invention cannot be measured. As an indicator, the load condition is 10.0 kq at # constant of MP'H.
The ratio of HMFR and MFR is HM F R/M F
R is usually in the range of 500 or less, often 100 or less, and particularly 80 or less. Therefore, the molecular weight distribution is relatively narrow compared to conventional copolymers.

The crystallinity of the copolymer of the present invention is usually 10% or more and less than 70%, usually 15 to 65%, as determined by X-ray diffraction.
%, particularly in the range of 20 to 65%, and is a crystalline resin copolymer that is relatively stiff and has excellent mechanical properties.

The melting point (Ta+) is also 3MB, which is of conventional non-quality or low crystallinity.
This is an indicator that can be distinguished from other polymers. The Tm of the copolymer of the present invention is usually 250 to 305°C, often 260 to 50°C.
2"C, especially within the range of 265 to 500°C.The measurement of 'rm is performed using a differential scanning calorimeter (DSC).
It is determined by leaving the sample at 310'C for 1 minute, then leaving it at -dQ''C for 5 minutes, and then measuring from -40°C to 540°C at a heating rate of 10°C/min.

The boiling fin-peptane soluble content (Δy1>
1 and boiling point Hp-xylene soluble content (Δy, 2), for example, Δy of a conventionally known BME polymer.
1 has a relatively large value, that is, it has a large soluble content, and therefore has high surface tackiness (stickiness) and poor solvent resistance, whereas the copolymer of the present invention has a small Δy1. There is. Further, while the conventional copolymerization has a relatively large value of Δy2, which causes a decrease in strength and rigidity, the copolymerization of the present invention has a feature that Δy2 is small.

More specifically, Δy1 and Δy2 are expressed by the following formula (1)
, is within the range of formula (2).

Δy1≦a1. x-)-blfit (where Δy1 is the n-heptane soluble portion), and
is the amount of α-olefin other than 3-methyl-1-butene in the copolymer (mol% La1 is 0.6 and bl is 1.0) ∆y2≦a2x + b2 (2) (here ∆y2 is p-xylene, soluble portion),
X is the amount (mol %) of α-olefin other than 5-methyl-1-butene in the copolymer, a2 is 3.0, and b2 is 10. ) Here, the quantitative determination of Δy1 and Δy2 is 1mmX1+r+
A strip sample of about m x 1 mm is placed in a cylindrical glass filter and extracted using a Soxhlet extractor for 7 hours with a reflux frequency of about 15 minutes at a time. (However, in this case 100~
It is better to use 500μφ glass beads. )Δ
y1 and Δy2 are determined by drying the extracted residue at a vacuum level (IQ mmHg or less) until it becomes constant clear.

The density of the copolymer of the present invention is usually 0.870 to 0.870 as measured by the density gradient tube method of ASTM D 1505.
0.90 A g/1711. More than 0.873 he 0.900 g/(711 theal. ASTM D
The measured haze is usually in the range of 20 to 9%, often 25 to 70%.

Further, the standard deviation (σJ) of the composition distribution is used as a measure of the uniformity of a copolymer. The σ of the copolymer of the present invention is usually 15 mol% or less, and often 10 mol% or less.

The composition distribution was determined using α-chlornaphthalene solvent at an extraction temperature of 50°C.
It is determined using an extraction column fractionation method in which the temperature is changed stepwise (in 10'C increments) up to ~245°C. At this time, extraction at a constant temperature is performed using 2J of α-chlornaphthalene for 10g of sample.
Extraction is carried out for 4 hours using l/. σ is defined by the following equation.

c = [f', "0<x-x)2r(x)dx]8 [Here, 7 is the average content of 3MB (mol%) in the copolymer, X is the 5MB content (mol%), f (Xl is the content X [mol%
] indicates the differential weight fraction of the component. ] Other indicators for obtaining useful molded articles include mechanical properties such as tensile strength at break, elongation at break, flexural modulus, and impact strength. The tensile strength at break of the copolymer of the present invention is usually 150 kg/C1
1i or more, often in the range of 200 to 50 kg/'', and the elongation at break is usually 5% or more, often 8 to
It is within the range of 300%. Flexural modulus is usually 8 x 1
03kg/cm2 or more, mostly 9X10~28X1
03kg/α2, and the Izotsu impact strength is normally 2.03kg/α2.
0kg・ci1/α or more, mostly 2.2 to 4 Q kq
-aIv/Clft.

Here, the tensile strength at break and the elongation at break are J Engineering SK 71.
Measured by a method according to No. 13. That is, the sample is J
Using a J-K5K7113 No. 2 test piece punched from a 1-mm-thick press sheet formed by JK SK 6758, the tensile speed was 50 mm/mi in an atmosphere at 23°C.
Measured in n. Measurement of bending elastic modulus is carried out by J.K. SK 691.
Measure according to method 1.

That is, the sample was a strip test piece made from a 2 mm thick press sheet formed by J.K. SK 6758, and measured at a speed of 50 m7 min in an atmosphere of 26°C.

Measurement of Izotsu impact strength is based on J.K. S
A test piece was prepared by cutting a figure-7 notch from the press sheet using a cutting machine.

The copolymer of the present invention may be copolymerized with a small amount of other copolymerizable monomer components within a range that does not impair the purpose of the present invention. Specific examples of the darkening monomer components include allylcyclopentane, allylcyclohexane, allylnorbornane, allylbenzene, allyltoluene, allylxylene, allylnaphthalene, 6-cyclohexyl-1-
Butene, 4-phenyl-1-butene, 4-tolyl-1-
Butene, 4-naphthyl-1-butene, 4-cyclopentyl-1-butene, 4-cyclohexyl-1-butene, 4
-dicyclo(2,2,1)hept-2-en-5-yl-1-butene, 5-cyclohexyl-1-pentene, 5
-Phenyl-1-pentene, vinylcyclopropane, vinylcyclopenkune, vinylcyclohexane, vinylcyclohexene, 4-methyl-1-vinylcyclohexane, 5-methyl-1-vinylcyclohexane, 2-vinylnorbornane, 2-vinylnorbornene, Ethylidene norbornane, ethylidene norbornene, dicyclopentadiene, styrene methyl-tetracyclo (6s2 m
l"6*0"8] Dodeca-4-ene and the like can be exemplified.

To polymerize the copolymer of the present invention, for example (a)
In the presence of a highly active titanium catalyst component containing magnesium, titanium, halogen and hyne ester as essential components, a catalyst formed from an organoaluminum compound catalyst component (bl) and an organosilicon compound catalyst component having a (cl 5i-0-0 bond). about 20 to about 200
It is obtained by copolymerizing 3MB and α-olefin at a temperature of “C”.

K Active titanium catalyst component (, il contains magnesium, titanium, halogen, and diester as essential components. Such a titanium catalyst component (, L) preferably has a magnesium/titanium (atomic ratio) of about 2 to 2. about 100, more preferably about 4 to about 70, halogen/
Titanium (atomic ratio) preferably from about 4 to about 100, more preferably from about 6 to about 40, diester/titanium c
The mole ratio) is preferably in the range of about 0.2 to about 10, more preferably about Q,1 to about 6.

Further, the specific surface area thereof is preferably about 3 m/g or more,
More preferably about 40 [n78 or more, and even more preferably about 100 m/g to about 800 m/g.

Normally, such a titanium catalyst component (al) does not substantially eliminate the titanium compound by simple means such as washing with hexane at room temperature. Regardless of the nature of the magnesium compound, it is preferably in a highly amorphous state compared to that of conventional commercial products of magnesium cybaride.

In addition to the above-mentioned essential components, the titanium catalyst component (al) may contain other elements, metals, functional groups, electron donors, etc., as long as they do not significantly deteriorate the catalyst performance.In addition, organic or inorganic diluents may be added. If it contains other elements, metals, diluents, etc., it may affect the specific surface area and amorphousness, and in that case, such other components should be removed. It is preferable that the material exhibits the specific surface area value as described above and exhibits poor quality.

To produce titanium catalyst component (a), a magnesium compound (or magnesium metal), a titanium compound and a diester or a diester-forming compound (a diester-forming compound) are mixed together with or without other reactants. It is better to adopt a method that brings the material into contact with the material. Its preparation can be carried out in the same manner as the conventionally known method for preparing highly active titanium catalyst components containing magnesium, titanium, halogen, and an electron donor as essential components. For example, JP-A-50-1
No. 08385, No. 50-126590, No. 51-20
No. 297, No. 51-28189, No. 51-64586
No. 51-92885, No. 51-156625,
52-87. ! No. 189, No. 52-100596,
No. 52-i7688, No. 52-101593, No. 5
No. 3-2580, No. 55-IIL0095, No. 55-
4509. ! No. 1, No. 55-135102, No. 55-
No. 135103, No. 56-811, No. 56-1190
It can be manufactured according to the method disclosed in No. 8, No. 56-18606, etc.

The sequence of methods for producing these titanium catalyst components (a) will be briefly described below.

(1) A magnesium compound or a complex compound of a magnesium compound and an electron donor can be ground into an electron donor and/or an organoaluminum in the presence or absence of an electron donor, a grinding aid, etc., or without grinding. A titanium compound which is in a liquid phase under the reaction conditions is reacted with a titanium compound which is in a liquid phase under the reaction conditions.
The electron donor described above is used at least once.

(2) 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.

(31(2) is further reacted with a titanium compound.

(4) The material obtained in (1) or (2) is further reacted with 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 or absence of an electron donor, a grinding aid, etc., and in the presence of a titanium compound. Alternatively, the solid obtained with or without pretreatment with a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound is treated with a halogen or a halogen compound or an aromatic hydrocarbon.

However, the above electron donor is used at least once.

Among these preparation methods, those using liquid titanium halide or those using a halogenated hydrocarbon after or during the use of a titanium compound are preferred in catalyst preparation.

The electron donor used in the above preparation must be only a diester or a diester-forming compound, such as alcohol, phenol, aldehyde, ketone, ether, carboxylic acid, carboxylic acid anhydride, carbonate ester, monoester, amine, etc. Any non-diester electron donor can be used.

The diester, which is an essential component in the highly active titanium catalyst component (a), is an ester of a dicarboxylic acid in which two carboxyl groups are bonded to one carbon atom or a diester in which two carboxyl groups are bonded to two adjacent carbon atoms. Preference is given to esters of dicarboxylic acids to which groups are attached. Examples of dicarboxylic acids in such esters of dicarboxylic acids include malonic acid, substituted malonic acid, succinic acid, substituted succinic acid, maleic acid, substituted maleic acid, fumaric acid, substituted fumaric acid, and one alicyclic acid. Alicyclic dicarboxylic acid with carboxyl groups bonded to two carbon atoms, alicyclic dicarboxylic acids with carboxyl groups bonded to two adjacent carbon atoms forming an alicyclic ring, carboxyl group in the ortho position Examples include esters of dicarboxylic acids such as aromatic dicarboxylic acids having carboxyl groups on two adjacent carbon atoms forming a heterocycle.

More specific examples of the above dicarboxylic acids include malonic acid: substituted malonic acids such as methylmalonic acid, ethylmalonic acid, isopropylmalonic acid, allyl J malonic acid, phenylmalonic acid; succinic acid; methylsuccinic acid,
Substituted succinic acids such as dimethylsuccinic acid, ethylsuccinic acid, methylethylsuccinic acid, itaconic acid; Substituted maleic acids such as maleic acid ditraconic acid and dimethylmaleic acid; cyclopentane-1,1-dicarboxylic acid, cyclopentane-1,2 -dicarboxylic acid, cyclohexane-1,2
-dicarboxylic acid, cyclohexene-1,6-dicarboxylic acid, cyclohexene-5,4-dicarboxylic acid, cyclohexene-6,5-dicarboxylic acid, nadic acid, methylnadic acid, 1-allylcyclohexane-3,4-dicarboxylic acid, etc. Alicyclic dicarboxylic acids: Aromatic dicarboxylic acids such as phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2゜5-dicarboxylic acid = 7-3.4-
Dicarboxylic m, a, 5-dihydro 7lane-2,6-dicarboxylic acid, benzobylane-6,4-dicarboxylic acid, virol-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, thio7e'';- Examples include dicarboxylic acids such as heterocyclic dicarboxylic acids such as 5,4-dicarboxylic acid and indole-2,,3-dicarboxylic acid.

At least one of the alcohol components of the dicarboxylic acid ester preferably has 2 or more carbon atoms, particularly 5 or more carbon atoms, and both alconyl components preferably have 2 or more carbon atoms, particularly preferably 3 or more carbon atoms. For example, diethyl ester, diisopropyl ester, monopropyl ester, dibutyl ester, etc. of the dicarboxylic acids mentioned above.

Examples include diisobutyl ester, di-tert-butyl ester, diisoamyl ester, di-n-hexyl ester, di-2-ethylhexyl ester, di-n-octyl ester, diisodecyl ester, and ethyl n-butyl ester.

The magnesium compound used in the preparation of the highly active titanium catalyst component (a) is a magnesium compound with or without reducing ability. In the former column, magnesium
Magnesium compounds with carbon bonds or magnesium/hydrogen bonds, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, diptyltmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride , hexyl salt [hymagnesium, amylmagnesium chloride,
Examples include butyl ethoxymagnesium, ethyl butylmagnesium, and butylmagnesium hydride. These magnesium compounds can also be used in the form of a complex compound with, for example, organoaluminium, and may be in a liquid state or a solid state. On the other hand, magnesium compounds without reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride: methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride,
Alkoxymagnesium halides such as octoxymagnesium chloride: phenoxymagnesium chloride, aryloxymagnesium halides such as methylphenoxymagnesium chloride: such as ethoxymagnesium, impropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium Examples include alyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate. Further, these magnesium compounds without reducing ability may be derived from the above-mentioned magnesium compounds having reducing ability, or may be derived during preparation of the catalyst component. Further, the magnesium compound may be a complex compound with other metals, a composite compound, or a mixture with other metal compounds. Furthermore, a mixture of two or more of these compounds may be used.

Among these, preferred magnesium compounds are those without reducing ability, and particularly preferred are halogen-containing magnesium compounds, especially magnesium chloride, alphoxymagnesium chloride, and allyloxymagnesium chloride.

There are various titanium compounds used in the preparation of the titanium catalyst component (&), such as H(oR), X4-g(
R is preferably a hydrocarbon group or a halogen, and a tetravalent titanium compound represented by 0≦g≦4). More specifically, T
It:! j? 4. Titanium tetrahalides such as TiEr4 and TiI4: T 1 (OOH,)c 1! ! 3
, Ti(002H5)C13, Ti(On-04H9)
c15,Ti(QC2H5)Br5,Ti(O1so
Trihalogenated alkoxytitanium such as C4H9)Br3: T1(OCH3]2Cβ2, T i (002H5
)2C! ! 2, T i (On 04H9) 2CI!
2, dihalogenated alkoxy titanium such as Ti(QC!2H;)2Br2; T1(OCH3)3Cβ, Ti
(002H5)3Cl11Ti(On-04H9)3O
Monohalogenated trialkoxytitanium such as N%'I'1(QO2H5)3Br: Ti(OCH3)4,T
Examples include tetraalkoxytitanium such as i (Q 02H5)4 and TL(On-04H9)4. Preferred among these are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture.

Alternatively, it may be used after being diluted with a hydrocarbon or a hydrocarbon.

In preparing the titanium catalyst component (a), a titanium compound,
The amounts of the magnesium compound and the electron donor to be supported, as well as other electron donors that may be used as necessary, such as alcohols, phenols, monocarboxylic acid esters, silicon compounds, aluminum compounds, etc. It varies depending on the method and cannot be unconditionally defined, but for example, per 1 mole of magnesium compound,
The ratio can be about 0.1 to about 10 moles of the electron donor to be supported and about 0.05 to about 1000 moles of the titanium compound.

Highly active titanium catalyst component (al
and organoaluminum compound catalyst components (bl and 5i-
0-C! Organosilicon compound catalyst component having a mixture (cl
A combination of catalysts is used.

The above (bl component) is an organoaluminum compound having at least one carbon bond in the molecule, for example, the general formula % (where R1 and R2 are carbon atoms, usually 1 to 15, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halogen, m is o<m
≦3.0≦n<3, p is O≦p<3, q is 0≦q<
3, and m + n + 1) 10q =
3), an organoaluminum compound represented by (
11) General formula %Formula % (where Ml is Ll, Na, Ni, R1 is a complex alkylated product of Group 1 metal and aluminum represented by the same (%) as above), etc. can be mentioned.

Examples of the organoaluminum compounds belonging to the above (11) include the following: general formula % formula % (where R1 is the same as above or halogen, m is preferably Q < m < 3), General formula % Formula % (Here, R1 is the same as above. Preferably 2≦m<
It is 3. ), general formula % formula %) [Here, R and R are the same as above. or halogen, 0
< m≦6.0≦n <3.0≦q<3 and m + n
+q=3].

Examples of aluminum compounds that belong to this category include the following compounds. Trialkylaluminum such as triethylaluminum, tributylaluminium, etc. Trialkenylaluminum such as nitriisoprenylaluminum: Dialkylaluminum alkoxide such as diethylaluminum ethoxide, dibutylaluminum phthoxide, etc.: Ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, etc. In addition to alkylaluminium sesquialkoxide,
R2.5A #(OR2). , 5, etc. Dialkyl aluminum halides such as diethylaluminum chloride, diptylaluminum chloride, diethylaluminum bromide: ethyl aluminum sesquichloride, butyl aluminum sesquichloride, Alkylaluminum sesquihalides such as ethylaluminum sesquipromide; ethylaluminum dichloride, propylaluminum dichloride,
Partially halogenated alkylaluminums such as alkylaluminum cybarides such as butylaluminum dibromide, etc.: Soalkylaluminum hydrides such as diethylaluminum hydride, butylaluminum hydride, etc.: ethylaluminum dihydride, probylaluminum dihydride Other partially hydrogenated alkyl aluminum dihydrides such as: ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride,
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxypromide.

As a compound belonging to the above (11), LiAn(02
Examples include H5)4, LiAl((!, H15)4, etc.).

Further, as a compound similar to (1), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. As such compounds,
For example (02H5)2AfioAfi(a2H5)
2, etc. can be exemplified.

Among these, especially trialkylaluminium
It is preferable to use a laminate or an alkyl aluminum bonded with two or more of the above-mentioned aluminums.

Organosilicon compound catalyst component having Si-0-0 bond t
c+ is, for example, alkoxysilane, aryloxysilane, or the like. An example of such a compound is the formula RnSi(OR1)4-
n [wherein, 0≦n≦3, R is a hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group, or a halogen; R1 is a hydrocarbon group, such as an alkyl group; group, cycloalkyl group, aryl group, alkenyl group, alkoxyalkyl group, etc.: However, n R, (4-n) OR
Examples include silicon compounds represented by 'The groups may be the same or different. In addition, two other examples include siloxanes having one OR group and silyl esters of carbones. Further, as another group, there can be mentioned compounds in which two or more silicon atoms are bonded to each other via oxygen or nitrogen atoms. The above organosilicon compounds can be prepared by reacting a compound not having an SL-0-0 bond with a compound having an O-a bond in advance or by reacting them at the polymerization site.
It may be used by converting it into a compound having 0 bond. Examples of such a series include, for example, a halogen-containing silane compound or silicon hydride that does not have a Si-0-C bond, and an alkoxy group-containing aluminum compound, an alkoxy group-containing magnesium compound, other metal alcoholades, alcohols, formic acid esters, ethylene oxides, etc. Examples include combination use. The organosilicon compound may also contain other metals (eg, aluminum, tin, etc.).

More specifically, trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, triethylmethoxysilane, tri-n-propylmethoxysilane, triisopropylmethoxysilane, tri-n-butylmethoxysilane, dimethylsomethoxysilane, dimethyl ethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, sophenyldiethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxy Silane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, ferth ethoxysilane, γ-
Aminopropylethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltriptoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy (ally
Examples include silane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxysilane, diethyltetraethoxydisiloxane, and phenyldiethoxydiethylaminosilane. Particularly preferred among these are trimethylmethoxysilane, triethylmethoxysilane, trimethyl-n-propoxysilane, triethylmethoxysilane, tri-n-propylmethoxysilane, triisopropylmethoxysilane, tri-n-butylmethoxysilane, and the like. Rn
S1(OR'). -n, especially those where n is 3 in this formula.

Copolymerization can be carried out in either a liquid phase or a gas phase, but it is particularly preferable to carry out the copolymer under conditions in which the copolymer does not dissolve in the liquid phase. When copolymerization is carried out in a liquid phase, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may also be used as the reaction medium.

The amount of the catalyst used is reaction volume *1/W, component (a) in terms of titanium atoms, about 0.01 to about 10 mmol, (
b) Component (a) per mole of titanium atoms in component (a)
b) from about 1 to about 2000 moles of metal atoms in component, preferably from about 5 to about 500 moles, and (
component (c) per mole of metal atom in component (b), (C
It is preferred that the amount of 81 atoms in the component () is about 0.001 to about 10 mol, preferably 0.01 to about 5 mol, particularly preferably about 0.05 to about 2 mol.

These catalyst components (a), (b), and (c) may be brought into contact with each other during copolymerization, or may be brought into contact with each other before copolymerization.
You can also let me know. In this contacting before copolymerization, only the desired components may be freely selected and brought into contact, or a portion of each component may be brought into contact with the components. Furthermore, each component may be brought into contact with each other before copolymerization under an inert gas atmosphere or an olefin atmosphere.

The copolymerization temperature is preferably about 20 to about 200°C,
More preferably about 50 to about 180"C, the pressure is from atmospheric pressure to about 100 kq/art2, preferably about 2
It is preferable to carry out under pressurized conditions of about 50 kq/cIII2 to about 50 kq/cIII2.

α-olefin containing mo, s ~ 15 mol% other than 3ME
The feed ratio of 5MB and other α-olefins for producing the copolymer varies depending on the polymerization pressure, but is usually 3MB/α-olefin (molar ratio) of 1 to 1000 degrees.

The molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and proportion of catalyst components used.
It is most effective to add hydrogen into the polymerization system.

The copolymer of the present invention is different from conventionally proposed copolymers in that it is excellent in solvent resistance and heat resistance, and has other outstanding properties as described above. This copolymer is molded by well-known methods. For example, storm shaft extruder, vented extruder, twin screw extruder, conical twin screw extruder, co-kneader, plateifier, mix router-1 two-wheel conical screw extruder, planetary screw extruder, gear type extruder. Extrusion molding, injection molding, blow molding, rotary molding, etc. are performed using machines, screwless extruders, etc. to form pipes, monofilaments, films, sheets, hollow containers, and various other products.

In addition, in the molding process, well-known additives such as heat stabilizers, light stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, inorganic and organic fillers, dyes, pigments, etc. are added as necessary. etc. may be added.

Examples of such additives include ferro- and sulfur-based antioxidants. Examples of phenolic antioxidants include 2,6-tert-butyl-p-cresol, stearyl (5°3-dimethyl-4
-Hydroxybenzyl cothioglyflate, stearyl-β-(4-hydroxy-6°s-tert-butylphenol)propionate, distearyl-3,5
-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzylphosphonate)
t-butyl-4-hydroxybenzylthio)-1,3,
5-triazine, distearyl (4-hydroxy-6-
methyl-5-tert-butylbenzyl) malonate,
2,2-methylenebis(4-methyl-6-tert-butylphenol), 4,4-methylenebis(2,6-tert-butylphenol), 2,2-methylenebis[6-(1-methylcyclohexyl) p-cresol ), bis[3,5-bis[4-hydroxy-3-ter
t-butylphenyl acid] glycol ester, 4.4'-butylidene bis(6-tart-butyl-m-cresol), 1.1.5-tris(2-methyl-4-hydroxy-5-tart- butylphenylumbutane, bis[2-tert-2thyl-4-methyl-
6-(2-Hydroxy-3-tert-butyl-5-methylbenzyl]phenyl]terephthalate, 1.3.5
- Tris(2,6-dimethyl-3-hydroxy-4-
tert-butyl) benzyl isocyanurate, 1,3
．． 5-tris(3,5-di-tert-butyl-4-
Hydroxybenzyl) -2*4,6-)! j Methylbenzene, tetrakis [methylene-3-(3,5-
di-tert-butyl-4-hydroxyphenyl)propionate comethane, 1,5,5-tris(5,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3.5-tris[(3,5 -Geeter
t-Butyl-4-hydroxyphenylprobionyloxyethyl]in cyanurate, 2-octylthio-4
,6-di(4-hydroxy-6,5-di-tart-butyl)phenoxy-1,3,5-triazine, 4.4'
-Thiobis(6-tert-butyl-m-cresol and other phenols and 4,4'-butylidenebis('
1-tert-butyl-5-methylphenol) carbonate oligoester (for example, polymerization degree 2, 3, 4, 5, 6°7
．． Examples include polyhydric phenol carbonate oligoesters such as 8, 9, and 10.
'As a sulfur-based antioxidant, for example, dilauryl-
polyhydric alcohols (e.g. glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (eg pentaerythritol tetralauryl thiopropionate).

Alternatively, phosphorus-containing compounds may be added, such as trioctyl phosphite, trilauryl phosphite,
Tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-tert-butylphenyl) phosphite, triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl penta Erythritol diphosphite, tetra(tridecyl) −=1.1
．． 3-) Lis(2-methyl-5-tert-butyl-
4-hydroxyphenyl)butane diphosphite, tetra(c12-015 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, tetra(tridecyl-4,4'-butylidenebis(3-methyl-6-t)
ert-butylphenol nodiphosphite, tris(
3゜5-tert-butyl-4-hydroxyphenyl) phosphite, tris(mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis(octylphenyl) )・bis(4,4'-butylidene bis(3-
Methyl-6-tert-butylphenol]]・1.6
-Hexanediol diphosphite, phenyl 4.4
'-isopropylidene diphenol pentaerythritol diphosphite, bis(2,4-di-tart-butylphenyl) pentaerythritol diphosphite,
Bis(2,6-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(
4,4'-isopropylidene bis(2-tert-butylphe/-luno)phosphite, phenyl diisodecylphosphite, cy(nonylphenyl]pentaerythritol diphosphite), tris(1,5-';-stearoyloxy Isopropyl] phosphite, 4.4-
Isobropylidene bis(2-tert-butylphenol) + di(nonylphenyl)phosphite, 9. IQ
-';-hydro9-oxa9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis(
2,4-di-tert-butylphenyl) -4,4-
Examples include biphenylene diphosphonite.

Also, 6-hydroxychroman derivatives such as α, μ, r
, various tocopherols of δ and mixtures thereof, 2-(4
-Methyl-pent-3-enyl)-6-hydroxychroman with 2,5-dimethyl substitution, 2,5゜8-trimethyhfl substitution, 2,5,7.8-tetramethyl substitution, 2
．． 2.7-drimethyl-5 tlrt-butyl-6-
Hydroxychroman, 2.2.5-1-limethyl-7-
tcrt-butyl-6-hydroxychroman, 2,2.
5-trimethyl-3-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5tert-butyl-
6-Hydroxychroman, etc. Alternatively, the general formula % formula % (where M is Mg, (a or Zn, A is an anion other than a hydroxyl group, X, y and 2 are positive numbers, and a is a positive number spanning 0) Compounds represented by [hail], such as M!, 6A 112 (OH) 16 CO3・4
H20, M g s A N 2 (OH) 2 (1
003・5H20, Mg5AA72(OH)14Co3
-4H20, Mg1oA12(oIi)22(CO3)
2・4H20, Mg6fi/12COH)16HPO4
・4H20, Oa AJ? (OHJ16Co3”A
H20, zn6AII2COH)16co, ・4H2
Q, zn6AI! 2(o)i)1,5so4・4H20
,” g 6 Al 2 (0”) 16S Oa・
4H20, Mg6kl12COH) 1200.・6H2
0, etc. may be blended.

Examples of light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2'-di-hydro
Hydroxybenzophenones such as xy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, 2-(2'-hydroxy-3'-tert-butyl-5-methylfecol)-5-chlorobenzotriazole, 2- (2'-hydroxy-5', 5-ter
t-butylphenyl)-5-chlorobenzotria 7'
-/I/, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3
, 5-'; benzotriazoles such as -tert-aminophenyl)benzotriazole, phenyl salicylate, p-tert-butylphenyl salicylate.

2.4-di-tert-butylphenyl-3,5-di-tert-butylphenyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc.) [,2,2 '-thiobis(4-tert-off-thousandylphenol) Ni salt,
2,2-thiobis(4-tert-octylphenolate)]-]n dithylamine N1,3,5-di-t
Nickel compounds such as tert-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester mt#X, substituted acrylonitriles such as α-cyano-β-methyl-β-(p-methoxyphenylene methyl acrylate), and N'-2-ethylphenyl-N-2-ethoxy-5
-tert-butylphenyl oxalic acid diamide, N-
Oxalic acid dianilides such as 2-ethylphenyl-N-2-ethoxyphenyl oxalic acid diamide, bis(2,2
, 6; 6-tetramethyl-4-piperidine] Sepaciade, poly(((6-(1,1,3,3-tetramethylbutylcoimino 1-1.3.5-) riazine-2゜4-
Diyl(4-(2,2,6,6-titramethylbipericyl)imino)hexamethylene 1,2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl)ethanol and dimethyl succinate Examples include hindered amine compounds such as condensates with

Examples of lubricants include aliphatic hydrocarbons such as paraffin wax, polyethylene wax, and polypropylene wax, and higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, araxic acid, and behenic acid. or their metal salts, such as lithium salts, calcium salts, sodium salts, magnesium salts, potassium salts, aliphatic alcohols such as palmityl alcohol, cetyl alcohol, and stearyl alcohol, caproic acid amide, caprylic acid amide, and capric acid. Aliphatic amides such as amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, esters with fatty acid alcohols, fluoroalkyl carbon face or its metal salt,
Examples include fluorine compounds such as fluoroalthylsulfosic acid metal salts.

Fillers include inorganic or organic fibrous fillers such as glass fiber, silver-coated glass fiber, stainless steel fiber, aluminum fiber, potassium titanate fiber, carbon fiber, Kevlar [F] woven fiber, ultra-high modulus polyethylene fiber, and talc. , calcium carbonate, magnesium hydroxide, calcium oxide, magnesium sulfate, graphite, nickel powder,
Examples include powdered, granular, or flaky inorganic or organic fillers such as silver powder, copper powder, carbon black, silver coated glass pieces, aluminum coated glass pieces, aluminum flakes, stainless steel flakes, and nickel coated graphite.

Furthermore, a stabilizer such as benzopranon disclosed in Japanese Patent Publication No. 55-501/181 may be added.

The copolymer of the present invention can also be used in combination with other thermoplastic resins. Examples of these are high density, medium density or low density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene/1-butene copolymers.

Examples include propylene/1-butene copolymer, ethylene/vinyl acetate copolymer, ionomer, ethylene/vinyl alcohol copolymer, polystyrene, and maleic anhydride grafted products thereof.

〔Example〕

Preferred embodiments of the present invention are shown below, but the present invention is not limited to these embodiments unless otherwise specified.

Example 1 Titanium catalyst component (preparation of &1) Anhydrous magnesium chloride 4.76 g (50 mmal),
De'1 can 25mJ? and 2-ethylhexyl alcohol 23-4 mjl? (150mmo1)
was heated at 130"C for 2 hours to form a homogeneous solution, and 1.11 g of phthalic anhydride (7.5 mm
ol) is added and stirred and mixed for an additional hour at 130°C to dissolve phthalic anhydride into the homogeneous solution. After cooling the homogeneous solution obtained in this way to room temperature, -20-
Titanium tetrachloride 200+nj held in C? (1,8
mol) over a period of 1 hour. After charging, the temperature of this mixture was increased to 110-(!
When the temperature reached 110° C., 2.68 mA (12.5 mmol) of diisobutyl phthalate was added and the mixture was maintained at the same temperature for 2 hours with stirring. After the completion of the 2-hour reaction, the solid portion was collected by heating E-filtration, and this solid portion was
00mjl? After resuspending at T t 'I14, the reaction is heated again at 110°C for 2 hours. After the reaction is completed, the solid portion is again collected by hot filtration and thoroughly washed with 110"C decane and hexane until no free titanium compound is detected in the washing solution. The titanium catalyst component (a) is stored as a hexane slurry, and a portion of it is dried for the purpose of examining catalyst m5!2.

The composition of the titanium catalyst component (1L) obtained in this way was 3.1% titanium, 56.0% by weight chlorine, 17.0% by weight magnesium, and diisobutyl phthalate.
It was 0.9%.

Polymerization> While keeping the glass autoclave No. 21 at 60°C, 1/hour of 3-methyl-1-butene, 10 mm
○1 triethylaluminum, 10 mmol trimethylmethoxysilane, 1 m1n01 titanium catalyst component (
al, 3 g of 1-decene were added successively. Hydrogen was continuously added so that the H2 partial pressure in the gas phase of the autoclave was 0.1 atm.

The slurry level inside the autoclave is 1! Continuously extract the slurry so that
After adding J7 inpropyl alcohol and reacting at 60° C. for 1 hour, the mixture was filtered and further washed with 60”C n-hexane/isopropyl alcohol (9/1% volume ratio).

256 g of polymerized powder with a bulk density of 0.4 s g/m# was obtained per hour, and the physical properties of this polymer are listed in Table 1. Among these, chemical resistance and solvent resistance were determined by immersing a test piece for 20 hours and observing the appearance, and observing color change, deformation, dissolution, cracking, etc.

Q: Good Δ: Changes such as partial dissolution were observed Examples 2 to 9 Polymerization was carried out in the same manner as in Example 1, using the comonomers listed in Table 1 and changing the comonomer and hydrogen addition needles as appropriate. The physical properties are listed in Table 1.

Comparative Example 1 Polymerization was carried out in exactly the same manner as in Example 1 except that the addition of 1-decene was stopped and the hydrogen partial pressure was changed to 0.3 atm, and the physical properties are shown in Table 1. Comparative Example 2 1-decene was added every hour. Polymerization was carried out in exactly the same manner as in Example 1, except that 100 g was added and the hydrogen partial pressure was changed to 0.3 atm. The physical properties are shown in Table 1.

Comparative Example 3 Titanium trichloride (Toho Titanium Co., Ltd., 'rAc) was used as a catalyst.
-131) (!Use Nidiethylaluminium chloride, the former at 100 mmol per hour, the latter at 2Q Q
Add mmol and 15 g of 1-decene per hour.

Polymerization was carried out in exactly the same manner as in Example 1, except that the hydrogen partial pressure was changed to 0.2 atm, and the physical properties are listed in Table 1.

Comparative Example 4 The copolymer of the present invention was polymerized in exactly the same manner as Comparative fR3 except that 40 g of 1-dodecene was added per hour as a comonomer. .

In addition to having excellent mechanical properties, it has excellent solvent resistance in that it does not dissolve at all in organic solvents at room temperature and does not dissolve in most organic solvents even when heated.

Claims (1)

[Scope of Claims] (A) 3-methyl-1-butene/α-olefin other than 3-methyl-1-butene (molar ratio) is 85/15 to 99
．． 5/0.5, (B) 340°C, 2 according to ASTM D 1238
．． Melt flow rate (M
FR) is 0.001 to 1000g/10min, (C)
Melt flow rate (HM
FR) and MFR ratio HMFR/MFR is 300 or less, (D) crystallinity by X-ray is 10% or more and less than 70%, (E) melting point (Tm) by DSC is 250 to 305°C,
(F) Boiling n-heptane soluble content (Δy_1) is expressed by formula (1)
Δy_1≦a_1x+b_1 (1) (where Δy_1 is the n-heptane soluble content (%), and x is the amount of α- other than 3-methyl-1-butene in the copolymer.
The amount of olefin (mol%), a_1, is 0.6 and b_1 is 1.0. ) (G) Boiling p-xylene soluble content (Δy_2) is expressed by formula (2)
Δy_2≦a_2x+b_2 (2) (where Δy_2 is the p-xylene soluble content (%), and x is the amount of α- other than 3-methyl-1-butene in the copolymer.
The amount of olefin (mol%), a_2, is 3.0 and b_2 is 10. ) A 3-methyl-1-butene copolymer defined by: