JPH09302038A - Butene/propylene copolymer and polybutene-1 resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in pressure resistance and heat resistance by specifying the propylene content, the crystalline melting point, the tensile modulus, the intrinsic viscosity and the content of n-decane solubles and to obtain a molding excellent in handleability, rigidity, low-temperature properties, etc. SOLUTION: A solid titanium catalyst component is mixed with an organoaluminum compound catalyst component and optionally an organosilicon compound catalyst. An olefin and the catalyst components are added to an inert hydrocarbon solvent, the olefin is prepolymerized under gentle conditions and then subjected to the main polymerization to obtain a butene/propylene copolymer having a propylene content of above 1mol% to below 10mol%, a crystalline melting point (Tm1 deg.C) satisfying formula I (wherein C is the propylene content (mol%)) as measured differential scanning calorimetry, a tensile modulus E satisfying formula II (C is as defined in formula I), an intrinsic viscosity [η]of 1-5dl/g, a content a (wt.%) of n-decane solubles satisfying formula III (wherein C is as defined informula I) and a low-temperature embrittlement temperature of -33 deg.C or below and an Mw/Mn ratio of 3-10.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a butene-propylene-based copolymer, a composition containing the copolymer, and a butene-propylene-based copolymer or a resin molded product using the composition, particularly , Butene-propylene copolymer, and its copolymerization weight, which are excellent in pressure resistance, heat resistance, and easy to handle after molding, and which can obtain a molded article having appropriate rigidity, low temperature characteristics, and dust adhesion. The present invention relates to a resin composition containing a coalesced product, and a resin molded product using the butene-propylene copolymer or the composition thereof.

[0002]

2. Description of the Related Art Conventionally, metal pipes such as zinc-plated steel pipes, copper pipes, and lead pipes have been used as pipe materials for water supply and hot water supply. In the case of steel pipes, red water or black water generated by rust, copper pipes In the case of 1, there are drawbacks such as generation of pinholes due to electrolytic corrosion or generation of blue water. In addition, it is difficult to reduce the weight, and it is not easy to increase the diameter.
New piping materials were needed. Already partly rusted,
Synthetic resin tubes made of polyvinyl chloride, polyethylene, cross-linked polyethylene, polybutene-1, etc., which are free from pinholes due to electrolytic corrosion, are being used. However, it is not easy to reduce the weight of polyvinyl chloride and there is a problem in hygiene. Polyethylene has a problem of poor pressure resistance and long-term durability. Among these synthetic resins, polybutene-1 is excellent in pressure resistance, internal pressure creep durability at high temperature (40 to 120 ° C.), high / low temperature characteristics, wear resistance, and the like, and is also excellent in flexibility. It is one of the resins that has suitable properties for water and hot water supply pipes.

However, polybutene-1 is required to have improved balance between pressure resistance, flexibility and heat resistance, and balance between rigidity and low temperature characteristics. Further, when polybutene-1 is molded from its melt, the physical properties change slowly, and it takes several days to ten and several days for the molded product to show stable physical properties. It was difficult to handle. Therefore, there has been a demand for a resin having a good balance of ease of handling a molded product and rigidity.
In addition, the polybutene-1 tends to have dust attached to the surface of a molded product, for example, a pipe during storage. Therefore, before performing the construction work using the pipe, it is necessary to blow off dust adhering to the surface by blowing air or the like, which causes a problem that workability at the time of construction is deteriorated. Therefore, there has been a demand for a polybutene resin having an improved dust adhering property that causes a reduction in workability while maintaining appropriate rigidity and flexibility.

Also in the sheet application, the sheet made of polybutene-1 has an excellent balance of heat resistance and flexibility and is suitably used as a heat resistant and waterproof sheet and a film / sheet for preventing electric shock. However, in the conventional polybutene-1, since the physical properties change immediately after being formed into a sheet, like the pipe,
There were problems such as a large change in the tightness of the obtained sheet winding roll. Therefore, also in the sheet field, there has been a demand for a resin having a good balance of handleability of a molded product and rigidity.

[0005]

Therefore, the first object of the present invention is to improve the above-mentioned problems in the conventional polybutene-1, and to have excellent pressure resistance, heat resistance, and easy handling after molding, and further to be suitable. It is intended to provide a butene-propylene-based copolymer capable of obtaining a molded article excellent in excellent rigidity, low temperature characteristics, and dust adhesion, and a resin composition containing the copolymer.

A second object of the present invention is to provide a resin molded article which is excellent in pressure resistance, heat resistance, and easy to handle, and which has appropriate rigidity, low temperature characteristics, and dust adhesion. .

[0007]

In order to achieve the object of the present invention, the present invention sets the content of propylene contained in polybutene-1 to more than 1 mol% and less than 10 mol% so that propylene and butene As a copolymer, the melting point (T _{m 1} ° C) of the crystal is 150 ≥ T _m1 ≥ -1.45 x C + 123.0 (where C is the mol% of propylene in the copolymer).
A butene-propylene-based copolymer satisfying the above conditions is provided.

Further, the present invention is the above-mentioned butene-propylene copolymer, wherein the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight is 3 or more and 10 or less.
A propylene-based copolymer is provided.

The present invention also provides a composition containing a butene-propylene copolymer.

Further, the present invention is the above-mentioned butene-propylene-based copolymer or a composition thereof, wherein the pipe at 23 ° C. is formed into a pipe having an outer diameter / thickness ratio of 5 to 20. Butene with a breaking water pressure of more than 30 kg / cm ² G
A propylene-based copolymer or a composition thereof is provided.

The present invention also provides a resin molded product containing the above-mentioned butene-propylene copolymer or a composition thereof.

The present invention also provides a pipe composition comprising the butene-propylene copolymer or the composition thereof and a butene homopolymer.

The present invention also provides the above-mentioned butene-propylene copolymer; ethylene-propylene random copolymer (EPR), ethylene-butene-1-random copolymer (EBR), ethylene-propylene- Diene copolymer (EPDM), ethylene-butene-1-diene random copolymer (EBDM), styrene-based block copolymer (SEBS, SBS, SEPS, etc.), and olefin-based block copolymer (ethylene-butylene And at least one selected from the group consisting of triblock copolymers and the like).

The butene-propylene copolymer of the present invention, the composition containing the copolymer, and the resin molded product using them will be described in detail below.

The butene-propylene copolymer of the present invention has a propylene content of more than 1 mol% and 10 mo.
less than 1%, preferably 1.2 mol% or more and 9 mo
less than 1%, particularly preferably 1.2 mol% or more and 8 mol
%, More preferably 1.5 mol% or more and 8 mol
% Of butene and propylene.

In the production of the butene-propylene copolymer of the present invention, solid catalyst fine particles are used in the form of a slurry in an inert reaction medium, and gas- or liquid-phase butene and propylene are reacted in a heated state. In the gas phase in the reactor, the molar ratio of propylene and butene is 0.001-0.1, preferably 0.002-0.08.

The reaction temperature in the production of the butene-propylene copolymer of the present invention is usually about 20 to 200 ° C.
Preferably about 50 to 180 ° C., the pressure is usually atmospheric pressure to 1
It is adjusted to 00 kg / cm ² , preferably about ² to 50 kg / cm ² . In the method for producing the copolymer of the present invention, the production reaction can be carried out by any of batch method, semi-continuous method and continuous method. Further, the reaction conditions can be changed and the reaction can be performed in two or more steps.

The butene-propylene-based copolymer of the present invention may be a mixture of two or more copolymers having different propylene ratios, and a small amount of other olefin may be added within a range not impairing the properties of the copolymer. May be included. Examples of the olefins that may be included include various olefins including α-olefins such as 4-methylpentene-1, ethylene, hexene, pentene, heptene and octene, in addition to propylene and butene.

Since the butene-propylene copolymer of the present invention contains a specific amount of propylene, the melting point (Tm ₁ ° C.) of the crystal has a specific temperature range, and the elastic modulus of the specific range. Furthermore, it is a copolymer in which the amount of n-decane-soluble component is within a specific range.

That is, the butene-propylene copolymer of the present invention has a melting point T of the crystal measured by a differential scanning calorimeter.
m ₁ [° C.] is represented by the formula (1): 150 ≧ T _m1 ≧ −1.45 × C + 123.0 (1) (wherein C is the mol% of propylene in the copolymer) More preferably, the following formula ( 1-1): 150 ≧ T _m1 ≧ −1.45 × C + 123.5 (1-1) Particularly preferably, the following formula (1-2): 150 ≧ T _m1 ≧ −1.45 × C + 124.0 (1-2) It satisfies. In the present invention, the melting point of the crystal Tm ₁
[° C] is obtained by measurement by the following method. The copolymer is melt pressed at 200 ° C. and held for 5 minutes, and then cooled and pressed to room temperature at a cooling rate of about 10 ° C./min to form a sheet. The obtained sheet is allowed to stand at room temperature for 1 week and then, using a differential scanning calorimeter, 20 ° C to 10 ° C.
The temperature at the top of the melting peak of the type I crystal when the temperature was raised to 200 ° C. at / min is Tm ₁ . It should be noted that a sample whose Tm ₁ has been once measured shows different peaks even if the same measurement is performed, and therefore a new sample must be prepared when Tm _{1 is} measured. An example of the different peaks is Tm ₁
After holding for 10 minutes after measurement, from 200 ℃ to 10 ℃ / min 2
Unlike Tm ₁ that appears when the temperature is lowered to 0 ° C., held for 5 minutes, and further raised to 200 ° C. at 10 ° C./min,
A melting peak of the type II crystal at a temperature lower than m ₁ can be shown. Since the copolymer of the present invention has a melting point within the above range, it has high heat resistance.

The butene-propylene copolymer of the present invention has a tensile elastic modulus E measured at 23 ° C., expressed by the following formula (2): −80C + 4000 ≧ E ≧ −80C + 2800 (2) (wherein C is propylene Content ratio: mol%) Preferably, the following formula (2-1): -80C + 3500 ≧ E ≧ −80C + 2800 (2-1) (wherein C is a propylene content ratio: mol%) is satisfied. The butene-propylene-based copolymer having a tensile elastic modulus E within the above range has flexibility suitable for forming a pipe and performing operations such as pipe replacement and laying.
That is, it has a hardness such that it can be bent at the time of pipe replacement and installation, and that there is not too much support for preventing deformation due to its own weight after installation of the pipe.

The butene-propylene copolymer of the present invention preferably has an intrinsic viscosity in decalin of 1-5.
dl / g, preferably 1.5 to 5.0 dl / g, particularly preferably 2.0 to 5.0 dl / g. When the copolymer has an intrinsic viscosity within the above range, when the copolymer is molded into a pipe for use as described later, the strength of the pipe is sufficient and the moldability is excellent.

The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the butene-propylene copolymer of the present invention.
Is 3 or more and 10 or less, more preferably 3 or more and 9 or less,
Particularly preferably, it is 3 or more and 8 or less. The butene-propylene copolymer within the above range has appropriate flexibility and is excellent in moldability when producing a pipe.

The butene-propylene copolymer of the present invention can also be used as a composition containing the copolymer, butene forming a composition containing the butene-propylene copolymer. The polymer mixed with the propylene-based copolymer is preferably an α-olefin homopolymer or copolymer selected from C2 or more and C20 or less α-olefin, and the polymer for mixing is the above-mentioned butene-propylene. It may be a butene-propylene copolymer having a different molecular weight, composition, etc. from the copolymer, more preferably C
It is an α-olefin homopolymer or copolymer selected from α-olefins of 4 or more and C20 or less, and most preferably a butene homopolymer. The content of the butene-propylene copolymer in the composition is 40% by weight or more, preferably 65% by weight or more and 95% by weight or less, and most preferably 70% by weight or more.
The amount is not less than 90% by weight and not more than 90%.

The butene-propylene copolymer of the present invention or its composition is 23 ° C. when formed into a pipe having an outer diameter to thickness ratio of 5 to 20, preferably 10 to 12.
It is preferable that the pipe breaking water pressure in (1) exceeds 30 kg / cm ² G. Breaking water pressure when molded into a pipe is 30kg / c
The presence of more than m ² G indicates that the copolymer of the present invention or the composition thereof has high compressive strength.

Next, a catalyst produced by the following production method can be disclosed as an example of a preferable catalyst used in the polymerization reaction of the butene-propylene copolymer of the present invention or its composition. The catalyst to be used may be any of a Ziegler type catalyst, a metallocene type catalyst and the like as long as a polymer satisfying the physical properties defined by the present invention can be obtained, but a Ziegler type catalyst is preferable. [A] a solid titanium catalyst component containing magnesium, titanium and halogen as essential components formed by contacting a magnesium compound and a compound of Group IVB of the periodic table, [B] an organoaluminum compound catalyst component,
And [C] cyclopentyl group, cyclopentenyl group,
An example of the catalyst for olefin polymerization is an organosilicon compound catalyst component containing a cyclopentadienyl group or a derivative thereof. Here, the compound of Group IVB of the periodic table refers to a compound containing Ti, Zr, and Hf.

In the case of a Ziegler type Ti catalyst component as an example of the catalyst component [A], the titanium compound used for preparing the solid titanium catalyst component [A] is, for example, Ti (O 2
R) _g X _4-g (R is a hydrocarbon group, X is a halogen atom, 0
A tetravalent titanium compound represented by ≦ g ≦ 4) can be mentioned. These compounds may be used alone or in combination of two or more. Further, these compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

As the magnesium compound used for preparing such a Ti catalyst component, there can be mentioned a magnesium compound having a reducing property and a magnesium compound having no reducing property. Here, as the magnesium compound having a reducing property, for example, magnesium
The magnesium compound which has a carbon bond or a magnesium-hydrogen bond can be mentioned. These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Further, the non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducible magnesium compound, for example, a reducible magnesium compound is prepared from polysiloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols, etc. It may be brought into contact with the compound. In the present invention, the magnesium compound, in addition to the magnesium compound having a reducing property and the magnesium compound having no reducing property, a complex compound of the magnesium compound and another metal, a double compound or another metal compound. May be used. Further, a mixture of two or more of the above compounds may be used.

Further, when preparing such a titanium catalyst component [A], it is preferable to use an electron donor,
Such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ether acid amides, oxygen-containing electron donors such as acid anhydrides, ammonia, amines, nitriles, Examples thereof include nitrogen-containing electron donors such as isocyanate.

As the electron donor, an organosilicon compound represented by the following general formula [I] can be used. R _n Si (OR ′) _4-n [I] [wherein R and R ′ are hydrocarbon-containing groups,
0 <n <4] R is not particularly limited, but examples thereof include groups such as methyl, ethyl, isopropyl, phenyl, triethyl, aluminopropyl, cyclopentyl, cyclopentenyl, cyclopentadienyl, and R, R ′. May be the same or different.

Alternatively, it may be an ester, for example,

[Chemical 1](R here¹Is a substituted or unsubstituted hydrocarbon group,
R^Two, R^Five, R⁶Is hydrogen or substituted or unsubstituted
Hydrocarbon group, R^Three, R^FourIs hydrogen or substituted or non-
A substituted hydrocarbon group, preferably at least one
One is a substituted or unsubstituted hydrocarbon group. Also R^ThreeWhen
R^FourMay be linked together. R above ¹~ R^Fiveof
As the substituted hydrocarbon group, heteroatoms such as N, O and S are
Including, for example, C--O--C, COOR, COOH,
OH, SO_ThreeH, -C-N-C-, NH_TwoHave groups such as
Is what you do. ) Is included.

Further, as another electron donor component, R
COOR '(R and R'are hydrocarbyl groups optionally having a substituent, at least one of which is a branched chain (including alicyclic) or ring-containing chain group) mono Examples thereof include carboxylic acid esters. Further, carbonic acid ester can be selected.

When carrying these electron donors,
It is not necessary to use these as starting materials,
It is also possible to use compounds which can be changed to these during the preparation of the titanium catalyst component. Among the titanium catalyst components,
Other electron donors may coexist, but if they coexist in too large an amount, it will have an adverse effect and should be kept to a small amount.

In the present invention, the solid titanium catalyst component [A] can be produced by bringing the above-mentioned magnesium compound (or metallic magnesium), titanium compound and preferably an electron donor into contact with each other. To produce the solid titanium catalyst component [A],
A known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound and an electron donor can be adopted. The above components may be contacted in the presence of other reaction agents such as silicon, phosphorus and aluminum.

The production method of these solid titanium catalyst components [A] will be briefly described below with some examples. (1) A method of reacting a magnesium compound or a complex compound of a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be performed in the presence of a grinding aid or the like. Further, when reacting as described above, the solid compound may be pulverized. (2) A method in which a liquid magnesium compound having no reducing property is reacted with a liquid titanium compound in the presence of an electron donor to precipitate a solid titanium complex. (3) A method in which the reaction product obtained in (2) is further reacted with a titanium compound. (4) A method of further reacting the reaction product obtained in (1) or (2) with an electron donor and a titanium compound. (5) A magnesium compound or a complex compound consisting of a magnesium compound and an electron donor is pulverized in the presence of a titanium compound to treat a solid substance with halogen, a halogen compound or an aromatic hydrocarbon. how to. In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound composed of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, pre-treated with a reaction aid, and then treated with a halogen or the like. In addition, examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound. (6) A method of treating the compound obtained in (1) to (4) above with halogen, a halogen compound or an aromatic hydrocarbon. (7) A method of bringing a reaction product of a metal oxide, dihydrocarbyl magnesium and a halogen-containing alcohol into contact with an electron donor and a titanium compound. (8) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium, or aryloxy magnesium with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

Among the methods for preparing the solid titanium catalyst component [A] listed in (1) to (8) above, a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or a titanium compound is used. When using the compound, a method using a halogenated hydrocarbon is preferable.

The amount of each of the above-mentioned components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be unconditionally limited. For example, the amount of the electron donor is about 1 mol per mol of the magnesium compound. The titanium compound is present in an amount of 0.01 to 5 moles, preferably 0.05 to 2 moles, about 0.01 to 500 moles, preferably 0.05 to 300 moles.
It is used in molar amounts.

The solid titanium catalyst component [A] thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component [A], the halogen / titanium (atomic ratio) is about 4 to 200, preferably about 5 to 100,
The electron donor / titanium (molar ratio) is about 0.1 to 10,
Preferably, it is about 0.2 to about 6, and the magnesium / titanium (atomic ratio) is about 1 to 100, preferably about 2 to 50. The solid titanium catalyst component [A] contains a magnesium halide having a smaller crystal size than that of a commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60 to 10.
00m ² / g, more preferably from about 100~800m ² /
g. And, this solid titanium catalyst component [A] is
Since the above components together form a catalyst component, the hexane washing does not substantially change the composition.

Such solid titanium catalyst component [A] is
Although it can be used alone, it can also be used by diluting it with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound or a polyolefin. In addition, when a diluent is used, even if it is smaller than the above-mentioned specific surface area, it shows high catalytic activity.

The preparation method of such a high activity titanium catalyst component is described in, for example, JP-A-50-108385 and JP-A-50-38585.
-126590, 51-20297, 51-28189, 51-64586, 51-92885, 51
-136625, 52-87489, 52-100596
No. 52-147688, No. 52-104593, the same
53-2580, 53-40093, 53-40094, 53-43094, 55-135102, 55
-135103, 55-152710, 56-811, 56-11908, 56-18606, 58-
83006, 58-138705, 58-138706, 58-138707, 58-138708, 58-
138709, 58-138710, 58-138715, 60-23404, 61-21109, 61-
It is disclosed in Japanese Patent Nos. 37802 and 61-37803.

As the organoaluminum compound catalyst component [B], a compound having at least one aluminum-carbon bond in the molecule can be used. Examples of such compounds include (i) the general formula R ¹ _m Al (OR ² ) _n H _p X _q (wherein R ¹ and R ² are usually 1 to 15 carbon atoms,
It is preferably a hydrocarbon group containing 1 to 4 groups, which may be the same or different from each other. X represents a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q
Is a number 0 ≦ q <3, and m + n + p + q = 3
An organoaluminum compound, in (ii) general formula M ¹ AlR ¹ ₄ (formula represented by at which), M ¹ is Li, Na, a K, R ¹ is a Group 1 metal represented by the same) and the Examples thereof include complex alkylated products with aluminum. As the organoaluminum compound belonging to the above (i), the following compounds can be exemplified. General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably a number of 1.5 ≦ m ≦ 3), general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as described above, X is halogen, and m is preferably 0 <m <3), general formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above) .M is preferably 2 ≦ m <3
R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as above. X is a halogen,
0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q =
3) and the like. It is also possible to use alkylaluminum in which two or more aluminum compounds are bound.

Examples of the organosilicon compound catalyst component [C] include organosilicon compounds containing a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or derivatives thereof in the structure. Examples of such organosilicon compounds include compounds represented by the following general formula [II]. SiR ¹ R ² _m (OR ³ ) _3-m [II] In the above formula [II], R ¹ is a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a derivative thereof, and in [II] , R ^2, R ³ is a hydrocarbon group, the R ^2, R ^3, for example, an alkyl group, a cycloalkyl group, an aryl group, and a hydrocarbon group such as an aralkyl group. Further, in [II], R ¹ and R ² may be crosslinked with an alkyl group or the like. Of these, R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group,
It is preferable to use an organosilicon compound in which R ³ is an alkyl group, particularly a methyl group or an ethyl group.

In the method for polymerizing the polymer of the present invention, the olefin is polymerized in the presence of the above-mentioned catalyst, but prior to such polymerization (main polymerization), the preliminary polymerization as described below is carried out. You can also do In the prepolymerization, the solid titanium catalyst component [A] is usually used in combination with at least a part of the organoaluminum compound catalyst component [B]. At this time, part or all of the organosilicon compound catalyst component [C] can be allowed to coexist. In the prepolymerization, a catalyst having a considerably higher concentration than the catalyst concentration in the system in the main polymerization can be used.

The concentration of the solid titanium catalyst component [A] in the prepolymerization is usually about 0.01 to 200 mmol, preferably about 0.05 to 100 mmol, in terms of titanium atom, per liter of an inert hydrocarbon medium described later. It is desirable to set the range to. The amount of the organoaluminum catalyst component [B] is 0.1 to 50 per 1 g of the solid titanium catalyst component [A].
The amount may be 0 g, preferably 0.3 to 300 g of a polymer, and is usually about 0.1 to 100 mol, preferably about 0, per 1 mol of titanium atom in the solid titanium catalyst component [A]. It is desirable that the amount is 0.5 to 50 mol.
The prepolymerization is preferably carried out under mild conditions by adding an olefin and the above-mentioned catalyst component to an inert hydrocarbon medium.

As the inert hydrocarbon medium used in this case, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene: cyclopentane, cyclohexane, methyl Examples thereof include alicyclic hydrocarbons such as cyclopentane: aromatic hydrocarbons such as benzene, toluene and xylene: halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use an aliphatic hydrocarbon.

The olefin used in the prepolymerization may be the same as the olefin used in the main polymerization described below,
May be different. When such an olefin is used for prepolymerization, α- having 2 to 10 carbon atoms, preferably 3 to 10 carbon atoms is used.
Highly crystalline polymers are obtained from olefins.

The reaction temperature of the prepolymerization may be a temperature at which the produced prepolymer is not substantially dissolved in the inert hydrocarbon medium, and is usually about -20 to + 100 ° C, preferably about -20 to 20 ° C. + 80 ° C, more preferably 0 to +40
It is desirable to be in the range of ° C. In the preliminary polymerization, a molecular weight adjusting solvent such as hydrogen may be used. In such a molecular weight controlling solvent, the intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 135 ° C. is about 0.2 dl / g or more, preferably about 0.5.
It is desirable to use it in an amount such that it becomes 10 dl / g. The prepolymerization is carried out by the titanium catalyst component [A] as described above.
About 0.1 to 500 g per 1 g, preferably about 0.3 to 3
It is desirable to do so to produce 00 g of polymer. The prepolymerization can be performed in a batch system or a continuous system.

After carrying out the prepolymerization as described above,
Alternatively, in the presence of the catalyst for olefin polymerization formed from the solid titanium catalyst component [A], the organoaluminum catalyst component [B] and the organosilicon compound catalyst component [C] described above, without carrying out preliminary polymerization, It is preferable to carry out the main polymerization of a butene-propylene-based copolymer.

In the polymerization method of the present invention, the titanium catalyst component [A] is usually about 0.005 to 0.5 mmol, preferably about 0.01, in terms of Ti atom per liter of polymerization volume. Used in an amount of ~ 0.5 mmol. The organoaluminum compound catalyst component [B] is
The metal atom in the organoaluminum compound catalyst component [B] is usually about 1 to 2000 mol, preferably about 5 to 1 mol of the titanium atom in the titanium catalyst component [A] in the polymerization system.
It is used in an amount of 500 moles. Further, the organosilicon compound catalyst component [C] is usually 0.0 in terms of Si atom in the organosilicon compound catalyst component [C] per 1 mol of metal atom in the organoaluminum compound catalyst component [B].
01-0.5, preferably about 0.001-0.1 mol,
Particularly preferably, it is used in an amount of about 0.001 to 0.05 mol.

The copolymer of the present invention or the composition thereof obtained as described above can be a resin molded product. The resin molded product may use the copolymer of the present invention or a composition containing the copolymer alone, but may contain another polymer within a range not impairing the physical properties of the present invention. However, it may be positively contained with another polymer to have characteristics different from those of the copolymer of the present invention or the composition thereof. The butene-propylene-based copolymer of the present invention or a composition thereof, in the range not impairing the physical properties of the present invention, various compounding agents which are usually added at the time of resin molding and used, for example, a heat stabilizer and a weathering stabilizer. Agents, slip agents, nucleating agents, pigments, dyes, lubricants and the like may be added. Pipes and sheets will be described below as specific examples of the resin molded product of the present invention, but the copolymer of the present invention or the composition thereof is not limited to these molded products, and a resin plate or a box body is not limited thereto. Molded articles of various shapes such as

The following method can be exemplified as a method for forming a pipe. The butene-propylene copolymer of the present invention or a composition thereof and polybutene-1 which does not contain other propylene, if necessary, are melt blended in an appropriate ratio using a uniaxial extruder. The blend
Molded into a pipe with a pipe molding machine. Butene of the present invention
The preferable ratio of the outer diameter to the thickness of the pipe using the propylene-based copolymer or the composition thereof is in the range of 5 to 20. Since the resin molded product of the present invention, particularly the pipe, is composed of the copolymer of the present invention or a composition containing the copolymer, it has the following preferable properties. Characteristic 1) 30 kg / c when the pipe breaking water pressure at 23 ° C is such that the ratio of the outer diameter to the thickness is 5 to 20, preferably 6 to 18.
It is more than m ² G. Characteristic 2) Pipe breaking water pressure at 95 ° C is 10 kg / c when the ratio of outer diameter to thickness is 5 to 20, preferably 6 to 18.
It is more than m ² G. Characteristic 3) Embrittlement temperature is −33 ° C. or lower, preferably −35 ° C.
It is the following. The pipe of the present invention may be molded by using the butene-propylene-based copolymer of the present invention alone, but it is preferable to mold a composition containing the specific butene-propylene-based copolymer, and Polybutene-1 preferably containing no propylene, more preferably polybutene-1 polymerized using the above-mentioned preferred catalysts in 30% by weight of the total resin.
When used in a mixture of not more than wt%, the extrusion moldability is improved.
When such other resin is mixed and used, it is preferable to mix it so that the propylene content in the butene-propylene copolymer in the resin molded product is more than 1 mol% and less than 10 mol%.

The polybutene-1 preferably has a molecular weight of 1 to 5 dl / g in intrinsic viscosity [η]. Furthermore, when a butene-propylene copolymer and polybutene-1 are mixed and used, the molecular weights of the butene-propylene copolymer and polybutene-1 are the intrinsic viscosity [η] _{B of} polybutene-1 and butene-propylene. The intrinsic viscosity [η] _BP ratio [η] _B / [η] _BP of the copolymer is 0.1 to 1.0, preferably 0.2 to 0.9, and particularly preferably 0.3 to 0.
It is desirable to have a relationship that is 8.

Also, in such a composition, the content of (A) propylene in the entire composition is more than 1 mol% and 10 mo.
Less than 1% (B) Melting point of crystal (Tm measured by differential scanning calorimeter
₁ ° C.) satisfies the following formula (1) 150 ≧ T _m1 ≧ −1.45 × C + 123.0 (1) (where C is the propylene content: mol%) (C) The tensile modulus E is −80C + 4000 ≧ E ≧ −80C + 2800 satisfying the following formula (2) (2) (In the formula, C is a propylene content: mol%) (D) Intrinsic viscosity [η] is 1 to 5 dl / g (E) n− Decane-soluble amount a (% by weight) is represented by the following formula (3)
Satisfying log (a) ≦ 0.46 + 0.13 × C (3) (wherein C is a propylene content ratio: mol%), and (F) the low temperature embrittlement temperature is −33 ° C. or lower. , Preferably -35
C. or less (G) It is preferable that Mw / Mn satisfies 3 to 10.

The following method can be exemplified as the method for forming the sheet. The butene-propylene copolymer of the present invention or a composition thereof is molded into a sheet by a sheet molding machine equipped with a T-die. The thickness of the sheet is usually 0.1 mm to 3 mm. The sheet of the present invention has an excellent balance of heat resistance and flexibility, and is suitably used as a heat resistant and waterproof sheet and a film sheet for preventing electric shock. The sheet of the present invention may be the butene-propylene copolymer of the present invention or a composition thereof alone, but may be mixed with another resin such as ethylene-propylene-diene copolymer (EPDM). In addition to EPDM, specific examples of the butene-propylene copolymer or the flexible resin that can be mixed with the composition thereof include ethylene-propylene random copolymer (EPR) and ethylene-butene-1-random copolymer. (EBR), ethylene-butene-1-diene random copolymer (EBDM), styrene-based block copolymer (S
EBS, SBS, SEPS, etc.) and olefin block copolymers (ethylene-butylene triblock copolymers, etc.) are exemplified, and the blend range is usually 10 to 50 w.
t%, preferably 15 to 45 wt% is preferable. Especially,
When using EPDM, the blend range is 30 wt.
% Or less is preferable, and the sheet formed by mixing EPDM in this range has high flexibility.

[0056]

EXAMPLES Hereinafter, according to Examples and Comparative Examples of the present invention,
Further, the present invention will be described in detail, but the present invention is not limited to these examples. In the following examples and comparative examples, a butene-propylene-based copolymer of the present invention, or a polybutene-1 resin composition containing a butene-propylene-based copolymer and a polybutene-1 homopolymer in a ratio of 4: 1. Was prepared (however, in Comparative Example 7, a pipe composed of a butene-ethylene copolymer and a butene homopolymer) was produced, and its physical properties were measured. The butene-propylene-based copolymer used for producing the pipe was produced under 13 different conditions by changing the organic compound and the catalyst used in the polymerization reaction, and each was designated as Reference Examples 1 to 13.
However, Reference Example 6 is a polymer of polybutene-1 alone, and Reference Example 13 is a copolymer of ethylene and butene instead of propylene. Preparation method of the catalyst used in each reference example,
And the polymerization method of the butene-propylene-type copolymer performed in Reference Example 1 is shown below. The propylene content, melting point Tm ₁ , tensile modulus, 90% physical property arrival time of the butene-propylene copolymer of the present invention produced in each Reference Example, ratio of weight average molecular weight to number average molecular weight (Mw / M
n), pipe breaking water pressure, embrittlement temperature, intrinsic viscosity and n-
The method for measuring the amount of decane-soluble matter is also shown below.

[Preparation of Solid Titanium Catalyst Component [A]] Anhydrous magnesium chloride 4.28 kg (45 mol), decane 2
2.5 liters and 2-ethylhexyl alcohol 2
1.1 liter (135 mol) was heated and reacted at 140 ° C. for 5 hours to obtain a uniform solution. Then, 1.00 kg (6.78 mol) of phthalic anhydride was added to this solution, and 1
The mixture was further stirred at 30 ° C. for 1 hour and mixed to dissolve phthalic anhydride in a uniform solution.

After cooling the homogeneous solution thus obtained to room temperature, titanium tetrachloride 12 kept at -20.degree.
The total amount was dropped into 0 liter (1080 mol) over 2 hours. After the dropping, the temperature of the obtained solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., diisobutyl phthalate 3.02 liters (11.3 mol)
Was added. Stirred for an additional 2 hours at 110 ° C. After the completion of the reaction for 2 hours, a solid part was collected from the reaction mixture by hot filtration, and the solid part was resuspended in 165 liters of TiCl ₄ and then heated at 110 ° C. for 2 hours again. . After the reaction was completed, the solid portion was collected from the reaction mixture by hot filtration again, and washed with decane and hexane at 110 ° C. This washing is carried out until no titanium compound is detected in the washing liquid to obtain the solid titanium catalyst component [A].
I got

The solid titanium catalyst component [A] synthesized as described above was obtained as a hexane slurry. A part of the catalyst was collected and dried. When the dried product was analyzed, the composition of the obtained solid titanium catalyst component [A] was 2.5% by weight of titanium, 58% by weight of chlorine, 18% by weight of magnesium and 13.8% by weight of diisobutylphthalate.

[Polymerization method] A continuous polymerization reactor having an internal volume of 200 L was charged with 73 L of hexane / hour and 16 of butene-1 at 16 / hour.
kg, propylene 0.07 kg / h, hydrogen 10 / h
NL, while supplying 0.38 mmol / hour of the solid titanium catalyst component [A] prepared above as titanium atom, 38 mmol / hour of triethylaluminum and 1.3 mmol / hour of dicyclopentyldimethoxysilane,
Butene-1 and propylene were copolymerized. At this time, the polymerization temperature was 57 ° C, the average residence time was 1 hour, and the total pressure was 4.5 kg.
/ cm ² G As a result, 4.8 kg of polymer was obtained per hour. A heat stabilizer was added to this polymer and granulated. The above-mentioned polymerization method and the produced polymer were referred to as Reference Example 1, and the polymerization method performed under different conditions and the produced polymer were referred to as Reference Examples 2 to 13. Note that only Reference Example 6 is a polymer of polybutene-1 alone containing no propylene. In each reference example, the physical properties of the produced polymer were
It is shown in the table. In addition, D in the table represents dicyclopentyldimethoxysilane and cyclohexylmethyldimethoxysilane.

[0061]

[Table 1]

[0062]

[Table 2]

The methods for measuring the physical properties of the butene-propylene copolymer are shown below. 1) Propylene content of butene-propylene copolymer was measured by superconducting NMR (JSH, GSH-27).
0) was used. 30 to 50 mg of butene-propylene copolymer or polymer of each reference example was used as a sample and dissolved in 0.5 cc of hexachlorobutadiene, and the measurement temperature was set to 11
5 to 120 ° C, measuring range 180 ppm, integration count 50
Measurement is performed under the conditions of 0 to 10000, pulse interval of 4.5 to 5 sec, and pulse width of 45 °.

2) Melting point Tm ₁ The butene-propylene copolymer or polymer of each reference example was sandwiched between a 50 μm polyester sheet, a 100 μm aluminum plate and a 1 mm iron plate using a 0.1 mm thick metal frame. after 5 minute hold at 190 ° C., and air vent at 50 kg / cm ^2, and further kept at 50 kg / cm ² for 5 minutes. Next, 50k with a cooling press that is water-cooled to 20 ° C.
A plate-like sheet obtained by cooling at g / cm ² for 5 minutes was obtained. Then, 4 to 5 mg of what was left at room temperature for 7 days was measured by a differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-2).
Type) sample pan and raise the temperature from 20 ° C to 200 ° C at a speed of 10 ° C / min. The temperature at the apex of the melting peak at the time of temperature rise is defined as Tm ₁ .

3) Tensile elastic modulus is measured by a universal testing machine ASTM IV manufactured by Instron
No. and JIS K 71132 were used. The butene-propylene-based copolymer or polymer of each reference example was prepared in the melting point measurement except that a metal frame having a thickness of 2 mm was used.
A plate-shaped sheet of m was prepared, and after 7 days, it was used as a measurement sample. The tensile speed was set to 50 mm / min, the tensile stress within the tensile proportional limit and the elongation corresponding to the tensile stress were measured, and the ratio thereof was determined. The distance between chucks of each device is 64 mm for ASTM IV, JIS K
No. 71132 has a length of 80 mm. The tensile elastic modulus at 95 ° C indicates the hardness under use conditions and is a measure of heat resistance.

4) Measurement of 90% physical property arrival time With respect to the measurement sample prepared at the time of measuring the tensile elastic modulus, 2 hours, 4 hours, 6 hours, 8 hours, 16 hours, and 24 hours after molding, and then continued. Then, the tensile modulus at 23 ° C. was measured every 24 hours. The abscissa indicates the elapsed time, and the ordinate indicates the measured value of the tensile elastic modulus of the measurement sample after 7 days, which is 100.
%, The ratio (%) of the measured values of the tensile elastic modulus after each time elapsed is plotted, and the plot at the elapsed time when the measured value exceeds 90% and the plot at the immediately preceding elapsed time Was connected by a straight line on the figure, and the elapsed time when the tensile elastic modulus was 90% on this straight line was read from the figure and taken as the physical property 90% arrival time.

5) Mw / Mni) A standard polystyrene (monodisperse polystyrene, manufactured by Toyo Soda Co., Ltd.) having a known molecular weight was used to count GPC (gel permeation chromatography) corresponding to the molecular weight M of polystyrene. taking measurement. Then, a calibration curve of the molecular weight M and EV (Elution Volume) is prepared. ii) The gel permeation chromatogram of the measurement sample is measured by GPC, and the number average molecular weight (M
n = ΣMi ² Ni / ΣNi) and weight average molecular weight (Mw = Σ
Mi ² Ni / ΣMiNi) is calculated to determine Mw / Mn.

6) Brittleness temperature A brittleness temperature tester manufactured by Toyo Seiki was used for the measurement. Vertical x horizontal x thickness = (38 ± 2) x (6 ± 2) x (2 or 3) mm multiple test pieces are fixed to the tester and 1.97
The temperature at which 50% of the test pieces break at a speed of ± 0.15 m / sec is determined.

7) Intrinsic Viscosity The intrinsic viscosity [η] was measured at 135 ° C. in a decalin solvent.

The methods for measuring the physical properties of a resin molded product containing a butene-propylene copolymer or its composition, especially a pipe, are shown below. 7) A water pressure breakage tester manufactured by Kuki Pump was used for measuring the water pressure at breakage of the pipe.
A pipe with an inner diameter of 13 mm, a wall thickness of 2 mm, and a length of 1 m (after molding, and allowed to stand at room temperature for 7 days) was attached to a water pressure breaking jig, and a water temperature of 23
Condition in water bath at ℃ for 1.5 hours or more. After that, the pump is operated, air is removed from the pipe while water is flowing, and after confirming that there is no water leakage, water pressure is applied to the pipe at a test flow rate of 550 cc / min to obtain the pressure at breakage.

8) Amount of n-decane-soluble component 100 mg of BHT was dissolved in 100 ml of n-decane,
The temperature is raised to 110 ° C. Next, add about 1 g of polymer sample,
Stir for about 30 minutes. After confirming that the polymer sample is completely dissolved, it is cooled in an ice-water bath for about 10 minutes while stirring. After standing at about 3 ° C for 12 hours, the precipitate is filtered off,
The entire filtrate is dried in a dryer at 150 ° C., 60 mmHg, and nitrogen atmosphere to remove the entire amount of solvent. The residual content is determined as the n-decane soluble content, and the weight is measured, and the weight% of the total weight of the polymer sample that is initially dissolved is determined to be the n-soluble content.

In the following examples and comparative examples, pipes were molded using the polymers shown in the above-mentioned reference examples and the physical properties were evaluated. The molding methods in Examples and Comparative Examples are as follows. Example 1 The polymer of Reference Example 1 and the polybutene-1 of Reference Example 6 were melt-blended in a ratio of 4: 1 using a 40 mmφ-screw extruder with a heat-resistant stabilizer. The blended product is set at a temperature of 180 ° C, a cooling water temperature of 11 ° C, and a molding speed of 1
A pipe having an inner diameter of 13 mm and a wall thickness of 2 mm was produced by a 90 mmφ pipe molding machine under the condition of 5 m / min. (Example 2) Polymerization was carried out in the same manner as in Example 1 except that the polymer of Reference Example 2 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Example 3) Polymerization was performed in the same manner as in Example 1 except that the polymer of Reference Example 3 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Example 4) Polymerization was performed in the same manner as in Example 1 except that the polymer of Reference Example 4 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Example 5) Polymerization was performed in the same manner as in Example 1 except that the polymer of Reference Example 5 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Comparative Example 1) Polymerization was carried out in the same manner as in Example 1 except that the polymer of Reference Example 7 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Comparative Example 2) Polymerization was carried out in the same manner as in Example 1 except that the polymer of Reference Example 8 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Comparative Example 3) Polymerization was carried out in the same manner as in Example 1 except that the polymer of Reference Example 9 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Comparative Example 4) Polymerization was carried out in the same manner as in Example 1 except that the polymer of Reference Example 10 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Comparative Example 5) Polymerization was performed in the same manner as in Example 1 except that the polymer of Reference Example 11 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Comparative Example 6) Polymerization was performed in the same manner as in Example 1 except that the polymer of Reference Example 12 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. (Comparative Example 7) Polymerization was carried out in the same manner as in Example 1 except that the polymer of Reference Example 13 and the polybutene-1 of Reference Example 6 were melted at a ratio of 4: 1. Table 2 shows the physical properties of the pipes of the above Examples and Comparative Examples.

[0073]

[Table 3]

[0074]

In the following Examples and Comparative Examples, sheets were molded using the polymer or the composition thereof shown in the above Reference Example, and the physical properties were evaluated. The molding methods in Examples and Comparative Examples are as follows. (Example 6) The polymer of Reference Example 1 or the composition thereof was loaded on a 60 mmφ sheet molding machine equipped with a T-shaped die having a die width of 450 mm and a lip opening of 1.8 mm, and a take-up speed of 1 m / m.
It was formed into a sheet having a wall thickness of 2 mm as min. Example 14 The procedure of Example 1 was repeated except that the polymer of Reference Example 2 or the composition thereof was used. (Examples 15 to 17) Examples 15 to 17 were the same as Example 1 except that the polymers of Reference Examples 3 to 5 or the compositions thereof were used. (Comparative Examples 8 to 13) Comparative Examples 8 to 13 are reference examples 7 respectively.
The same procedure as in Example 1 was carried out except that the polymer of No. 12 to 12 or its composition was used. (Comparative Example 14) EPDM (Mitsui EPT 3072EP,
Mooney viscosity 74, ethylene content 78 at 100 ° C
mol%, diene content 6.2 wt%) 40 parts and Reference Example 4
60 parts of the polymer or the composition thereof was blended, a sheet was molded in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 3. The sheet tensile modulus is a value measured 7 days after the sheet was formed.

[0076]

[Table 4]

[0077]

[0078]

The butene-propylene copolymer of the present invention or the composition containing the copolymer has a pressure resistance, heat resistance,
Further, it is possible to obtain a molded product which is excellent in handleability after molding, and has appropriate rigidity, low temperature characteristics, and dust adhesion.

The resin molding of the present invention is excellent in pressure resistance, heat resistance, moderate rigidity, low temperature characteristics, and dust adhesion.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08L 23/20 LCN C08L 23/20 LCN

Claims (12)

[Claims] 1. A melting point of crystal (Tm) measured by a differential scanning calorimeter (A) with a propylene content of more than 1 mol% and less than 10 mol%
₁ ° C.) satisfies the following formula (1) 150 ≧ T _m1 ≧ −1.45 × C + 123.0 (1) (where C is the propylene content: mol%) (C) The tensile modulus E is −80C + 4000 ≧ E ≧ −80C + 2800 satisfying the following formula (2) (2) (In the formula, C is a propylene content: mol%) (D) Intrinsic viscosity [η] is 1 to 5 dl / g (E) n− Decane-soluble amount a (% by weight) is represented by the following formula (3)
Satisfying the following condition: log (a) ≦ 0.46 + 0.13 × C (3) (wherein C is a propylene content rate: mol%), butene-propylene copolymer. 2. The tensile elastic modulus E satisfies the following formula (4): −80C + 3500 ≧ E ≧ −80C + 2800 (4) (wherein C is a propylene content ratio: mol%). Butene-propylene copolymer. 3. The butene-propylene copolymer according to claim 1, which has a low temperature embrittlement temperature of −33 ° C. or lower. 4. The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn is 3 or more and 10 or less.
The butene-propylene copolymer according to any one of 3 above. 5. The butene according to any one of claims 1 to 4.
A polybutene-1 resin composition containing a propylene-based copolymer. 6. The polybutene-1 resin composition according to claim 5, further comprising a homopolymer of butene. 7. The melting point (Tm) of the crystal measured by a differential scanning calorimeter (Tm) (A) the content of propylene is more than 1 mol% and less than 10 mol%
₁ ° C.) satisfies the following formula (1) 150 ≧ T _m1 ≧ −1.45 × C + 123.0 (1) (where C is the propylene content: mol%) (C) The tensile modulus E is −80C + 4000 ≧ E ≧ −80C + 2800 satisfying the following formula (2) (2) (In the formula, C is a propylene content: mol%) (D) Intrinsic viscosity [η] is 1 to 5 dl / g (E) n− Decane-soluble amount a (% by weight) is represented by the following formula (3)
Satisfying the following condition: log (a) ≦ 0.46 + 0.13 × C (3) (wherein C is the content ratio of propylene: mol%), The polybutene-1 resin composition according to claim 6. 8. The butene according to any one of claims 1 to 4.
A resin molded product made of a propylene copolymer. 9. A resin molded product comprising the polybutene-1 resin composition according to claim 5. 10. A pipe made of the butene-propylene copolymer according to any one of claims 1 to 4. 11. A pipe made of the polybutene-1 resin composition according to claim 5. 12. A butene-propylene copolymer according to claim 1, an ethylene-propylene random copolymer (EPR), an ethylene-butene-1-random copolymer (EBR), At least one selected from the group consisting of ethylene-propylene-diene copolymer (EPDM), ethylene-butene-1-diene random copolymer (EBDM), styrene block copolymer, and olefin block copolymer. And a polymer for a sheet containing the polymer.