JP2019178254A - 1-butene copolymer, polymer composition containing 1-butene copolymer, and molded body consisting of 1-butene copolymer - Google Patents

Abstract

To provide a butene polymer short in crystal transition time, and excellent in creep resistance, rigidity and moldability.SOLUTION: The invention relates to a butene polymer having 1-butene unit amount of 80.0 to 99.9 mol%, and total content (K) of at least one kind of olefin unit selected from ethylene and α-olefin having 3 to 20 carbon atoms, other than 1-butene of 0.1 to 20.0 mol% (total of the 1-butene unit and total content (K) is 100 mol%), and satisfying requirements (i) to (iii). (i) mmmm measured byC-NMR is 94.0% to 99.9%. (ii) rr measured byC-NMR is 1.5% or less. (iii) intrinsic viscosity [η] in a decalin solvent at 135°C is 0.5 to 5.5 dl/g.SELECTED DRAWING: None

Description

  The present invention relates to a 1-butene copolymer having a specific composition and specific characteristics, a polymer composition containing the 1-butene copolymer, and the 1-butene copolymer or the 1-butene. The present invention relates to a molded article made of a polymer composition containing a copolymer.

  Pipes, pipe joints and tanks made of butene polymers have excellent creep resistance, environmental stress crack resistance, flexibility, toughness, heat resistance, high / low temperature characteristics and wear resistance.・ Used as various components for hot water supply, underfloor heating, hot spring piping, chemical spraying and drainage.

  Butene polymers mainly have two types of crystals. Immediately after the butene polymer is cooled and shaped from a molten state to a molded body, it takes a metastable type II crystal structure (tetragonal transformation). It is known that solid phase crystal transition to a more stable type I crystal structure (hexagonal transformation) takes about one week (Non-patent Document 1).

  Butene-based polymers have the disadvantages that the dimensional and rigidity changes after molding due to the above-mentioned crystal transition, and that the quality control and inventory management at the customer becomes complicated because the crystal transition time is long. That is, in the technical field of melt-molding butene-based polymers, polymers having a short crystal transition time from type II crystals to type I crystals are required.

  In response to this demand, a method of blending a radical-treated crystalline olefin polymer with a butene polymer for the purpose of shortening the crystal transition time (see Patent Document 1), and adding an additive to the butene polymer There are known methods (see Patent Document 2 and Patent Document 3).

  On the other hand, Patent Document 4 discloses a 1-butene polymer having high stereoregularity, but its crystal transition behavior and moldability are not clarified.

JP 61-037833 A Japanese Patent Laid-Open No. 57-036140 JP 57-092038 A International Publication No. 2014/050817

Journal of Polymer Science: PartA volume1 page 59-84 (1963)

  In the butene-based polymer, the effect of shortening the molding cost and crystal transition time for pipes, pipe joints, tanks and the like is still unsatisfactory, and further improvement is required. In order to shorten the crystal transition time of the butene polymer, a method of introducing a comonomer (α-olefin) can be used. However, when comonomer is introduced, there is a concern that mechanical properties, long-term physical properties, and the like are deteriorated. Even if the crystal transition time is short, it is desirable that there is no decrease in mechanical properties or long-term physical properties.

  An object of the present invention is a 1-butene copolymer having a short crystal transition time from a type II crystal to a type I crystal, and has a high elastic modulus and yield point strength, that is, excellent creep resistance, rigidity and The object is to provide a 1-butene copolymer excellent in moldability.

  The present inventors have intensively studied to solve the above problems. As a result, a 1-butene copolymer having a specific composition and specific characteristics has a short crystal transition time from a type II crystal to a type I crystal, a high elastic modulus and a high yield point strength, and The present inventors have found that the rigidity and moldability are good and have completed the present invention.

The present invention relates to the following [1] to [15].
[1] The content of structural units derived from 1-butene is 80.0 to 99.9 mol%, and at least one olefin selected from ethylene and α-olefins other than 1 to butene having 3 to 20 carbon atoms The total content (K) of the structural unit derived from 0.1 to 20.0 mol% (however, the total of the content of the structural unit derived from 1-butene and the total content (K) is 100 mol%) 1-butene copolymer satisfying the requirements (i) to (iii).
(I) The pentad isotacticity (mmmm) measured by ¹³ C-NMR is 94.0% or more and 99.9% or less.
(Ii) The syndiotactic triad fraction (rr) measured by ¹³ C-NMR is 1.5% or less.
(Iii) The intrinsic viscosity [η] in the decalin solvent at 135 ° C. is in the range of 0.5 to 5.5 dl / g.

[2] The content of the structural unit derived from 1-butene is 90.0 to 99.9 mol%, and the total content (K) is 0.1 to 10.0 mol% in the above [1] The 1-butene copolymer described.
[3] In the above [1], the content of the structural unit derived from 1-butene is 90.0 to 96.2 mol%, and the total content (K) is 3.8 to 10.0 mol% The 1-butene copolymer described.

[4] The 1-butene copolymer according to any one of [1] to [3], which further satisfies the following requirement (iv):
(Iv) The ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) measured by gel permeation chromatography (GPC) is in the range of 1.5 to 20.0.

[5] The 1-butene copolymer according to any one of [1] to [4], which further satisfies the following requirement (v).
(V) The yield point stress (YS) measured by a tensile test at a tensile speed of 30 mm / min and a measurement temperature of 23 ° C. is 16.0 MPa or more in accordance with JIS K7113.

[6] The 1-butene copolymer according to any one of [1] to [5], which further satisfies the following requirement (vi).
(Vi) The 95% crystal transition completion time measured by a differential scanning calorimeter is 45 hours or less.

  [7] The 1- of any one of [1] to [6], wherein at least one olefin selected from the ethylene and an α-olefin other than 1-butene having 3 to 20 carbon atoms is propylene. Butene copolymer.

  [8] The 1- of any one of [1] to [6], wherein the at least one olefin selected from ethylene and an α-olefin other than 1 to butene having 3 to 20 carbon atoms is ethylene. Butene copolymer.

  [9] The content of the structural unit derived from 1-butene is 90.0 to 97.0 mol%, the total content (K) is 3.0 to 10.0 mol%, and 135 ° C. The 1-butene copolymer according to [1] above, including a polymer having an intrinsic viscosity [η] in a decalin solvent in the range of 2.0 to 5.5 dl / g.

[10] The 1-butene copolymer according to [9], further including a 1-butene homopolymer having an intrinsic viscosity [η] in a decalin solvent at 135 ° C. in the range of 0.5 to 1.5 dl / g. Polymer.
[11] A polymer composition comprising the 1-butene copolymer according to any one of [1] to [10].
[12] A polymer composition comprising the 1-butene copolymer according to any one of [1] to [10] above and a nucleating agent.

[13] A composition having a shear viscosity of 65,000 Pa or less as measured by a capillograph at 190 ° C. among the polymer composition containing the 1-butene copolymer according to [11] or [12].
[14] The 1-butene copolymer described in any one of [1] to [10] or the polymer composition described in any one of [11] to [13]. Molded body.
[15] The molded article according to [14], which is a pipe or a pipe joint.

  According to the present invention, it is possible to provide a 1-butene copolymer having a short crystal transition time from a type II crystal to a type I crystal, a high elastic modulus and a high yield point strength, that is, excellent creep resistance. For this reason, it is possible to provide a molded body in which changes in dimensions and rigidity after molding are small and quality control and inventory management at the customer are easy. Further, in one preferred embodiment of the present invention, rigidity, heat resistance, high temperature A molded body having excellent creep resistance and moldability can be provided.

  Hereinafter, the molded article comprising the 1-butene copolymer of the present invention, the polymer composition containing the polymer, and the polymer composition containing the 1-butene copolymer or 1-butene copolymer, Detailed description will be given including preferred embodiments.

[1-butene copolymer]
The 1-butene copolymer of the present invention has a content of structural units derived from 1-butene of 80.0 to 99.9 mol%, and is an α-olefin other than ethylene and 1 to 3 carbon atoms of 1 to butene. The total content (K) of at least one olefin-derived structural unit selected from is 0.1 to 20.0 mol%. However, the total of the content of the structural unit derived from 1-butene and the total content (K) of the structural unit derived from the olefin is 100 mol%.

  In the present specification, “ethylene” and “α-olefin other than 1-butene having 3 to 20 carbon atoms” are also referred to as “comonomer”. The total content (K) is the total content of comonomer-derived structural units (comonomer units). When the 1-butene copolymer includes a comonomer-derived structural unit, the structural unit may be a structural unit derived from one kind of comonomer, or may be a structural unit derived from two or more kinds of comonomer. .

  In the 1-butene copolymer of the present invention, the content of the structural unit derived from 1-butene is 85.0 to 99.9 mol%, and the total content (K) is 0.1 to 15.0 mol. %, The content of structural units derived from 1-butene is 90.0 to 99.9 mol%, and the total content (K) is 0.1 to 10.0 mol%. Is more preferable.

  More preferably, the content of the structural unit derived from 1-butene is 90.0 to 96.5 mol%, and the total content (K) is 3.5 to 10.0 mol%. More preferably, the content of the structural unit derived from 90.0-96.2 mol%, the total content (K) is 3.8-10.0 mol%, derived from 1-butene It is particularly preferable that the content of the structural unit is 90.0 to 96.0 mol%, and the total content (K) is 4.0 to 10.0 mol%.

  When the content of the structural unit derived from 1-butene and the total content (K) are in the above range, the crystallinity of the butene polymer, the crystal lamella thickness, the elastic modulus, the mechanical strength such as the yield point strength, and the like. It is preferable in that the crystal transition time is shortened while maintaining high.

The comonomer composition is measured by ¹³ C-NMR.
The content of each structural unit in the 1-butene copolymer is, for example, each olefin added during the polymerization reaction (eg, 1-butene, ethylene, α-other than 1-butene having 3 to 20 carbon atoms). The amount of olefin can be adjusted.

  Examples of the α-olefin other than 1-butene having 3 to 20 carbon atoms include propylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, and 3-ethyl-1. -Pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

  Among these, propylene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene are included. preferable.

  Among these comonomers, ethylene and α-olefins having 3 to 10 carbon atoms are more preferable. Among them, ethylene and propylene are preferable, and propylene is particularly preferable. Propylene has a similar crystal helical structure to that of 1-butene, so that the crystal transition time can be shortened. On the other hand, 4-methyl-1-pentene having a different helical structure from propylene may lower the crystal transition rate.

A comonomer may be used individually by 1 type, and may use 2 or more types together.
The 1-butene copolymer of the present invention may have structural units derived from other monomers other than ethylene and an α-olefin having 3 to 20 carbon atoms as long as the requirements described later are satisfied. The upper limit value of the content of structural units derived from other monomers is, for example, 5 wt% or less with respect to the total of 100 wt% of the content of structural units derived from 1-butene and the total content (K).

The 1-butene copolymer of the present invention satisfies the following requirements (i) to (iii), and preferably further satisfies one or more of the following requirements (iv) to (vii).
The 1-butene copolymer of the present invention may be a single 1-butene copolymer, or a mixture of 1-butene copolymers having different contents of structural units derived from 1-butene, or 1-butene It may be a mixture of a copolymer and a 1-butene homopolymer (eg, a mixture of a plurality of 1-butene copolymers, a mixture of a 1-butene copolymer and a 1-butene homopolymer). When the 1-butene copolymer is a mixture, it is preferable that the mixture satisfies the following requirements (i) to (iii), and further satisfies one or more of the following requirements (iv) to (vii): .

Hereinafter, each requirement will be described.
<< Requirement (i) >>
The requirement (i) is that the pentad isotacticity (mmmm) measured by ¹³ C-NMR of the 1-butene copolymer is 94.0% or more and 99.9% or less. mmmm is preferably 94.0 to 99.5%, more preferably 95.0 to 99.5%, even more preferably 95.0 to 99.0%, and particularly preferably 95.0% to 98.5%. %, Particularly preferably 95.0% to 98.0%. When mmmm is not less than the above lower limit, the crystal transition time is short and the creep resistance is excellent, and when mmmm is not more than the above upper limit, appropriate creep resistance is obtained.
mmmm can be adjusted within the above range by appropriately selecting a catalyst for olefin polymerization described later and setting polymerization conditions such as polymerization temperature.

<Requirement (ii)>
The requirement (ii) is that the syndiotactic triad fraction (rr) measured by ¹³ C-NMR of the 1-butene copolymer is 1.5% or less. rr is preferably 1.3% or less, more preferably 1.1% or less, even more preferably 1.0% or less, particularly preferably 0.8% or less, and even more preferably 0.5% or less. Especially preferably, it is 0.4% or less. When rr is less than or equal to the above upper limit, there are few stereoregular defects, the crystal transition time is short, and the creep resistance is excellent. rr is preferably as low as possible, but the lower limit may be, for example, 0.1%.
rr can be adjusted within the above range by appropriately selecting the olefin polymerization catalyst described later and appropriately setting the polymerization conditions such as the polymerization temperature.

<Requirement (iii)>
The requirement (iii) is that the intrinsic viscosity [η] (decalin solvent, 135 ° C.) of the 1-butene copolymer is in the range of 0.5 to 5.5 dl / g. [Η] is preferably 0.7 to 5.0 dl / g, more preferably 0.7 to 4.5 dl / g, still more preferably 0.7 to 4.0 dl / g, and particularly preferably 0.7 to 5.0 dl / g. 2.8 dl / g.

  When the intrinsic viscosity [η] is not less than the above lower limit, the strength of the molded product obtained from the 1-butene copolymer is excellent. When the intrinsic viscosity [η] is less than or equal to the above upper limit, the 1-butene copolymer is excellent in moldability and advantageous in terms of shortening the crystal transition time and flexibility.

The intrinsic viscosity [η] can be adjusted within the above range depending on the hydrogen concentration and pressure of the polymerization system, or may be adjusted by mixing 1-butene copolymers having different intrinsic viscosities [η].
Moreover, the weight average molecular weight (Mw) measured by GPC (standard polystyrene conversion) of 1-butene copolymer becomes like this. Preferably it is 50,000-2 million, More preferably, it is 100,000-1.7 million, More preferably, it is 200,000-150. It is ten thousand. When Mw is within the above range, the moldability of the 1-butene copolymer and the crystal transition time are shortened, and the strength of the resulting molded article is excellent.

<Requirement (iv)>
The requirement (iv) is that the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight of the 1-butene copolymer measured by gel permeation chromatography (GPC; standard polystyrene conversion) is 1.5. It is in the range of ˜20.0. Mw / Mn is preferably 1.5 to 10.0, more preferably 2.0 to 10.0, still more preferably 3.0 to 10.0, and particularly preferably 3.5 to 10.0. When Mw / Mn is within the above range, a molded article having appropriate flexibility can be obtained from the 1-butene copolymer. Mw / Mn is adjusted by appropriately selecting a catalyst for olefin polymerization, which will be described later, and mixing a multistage polymerization method, a mixed catalyst polymerization method, and 1-butene copolymers having different molecular weights as required. can do.

<mechanical nature>
<Requirement (v)>
The requirement (v) is that the yield point stress (YS) measured by a tensile test at a tensile speed of 30 mm / min and a measurement temperature of 23 ° C. is 16.0 MPa or more in accordance with JIS K7113 of 1-butene copolymer. It is. YS is preferably in the range of 16.0 to 25.0 MPa, more preferably 16.0 to 23.0 MPa.

  Moreover, it is preferable that the tensile elasticity modulus (YM) measured by the said tension test is 300 Mpa or more. YM is more preferably in the range of 300 to 800 MPa, still more preferably 300 to 700 MPa.

《Thermal properties》
The thermal properties of the 1-butene copolymer of the present invention, for example, the melting point (TmI, TmII) and the heat of fusion ΔH are determined by differential scanning calorimetry (heating rate: 10 ° C./min).
The heat of fusion ΔH of the 1-butene copolymer of the present invention is preferably 40.0 to 95.0 J / g, more preferably 50.0 to 90.0 J / g. The melting point TmI of the 1-butene copolymer of the present invention is preferably 110.0 to 150.0 ° C, more preferably 115.0 to 150.0 ° C, and further preferably 120.0 to 140.0 ° C. .

The heat of fusion ΔH, melting points TmII and TmI of the 1-butene copolymer are measured under the following conditions.
The 1-butene copolymer was heated from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), held at 200 ° C. for 5 minutes, and further 10 ° C. The temperature was lowered to 30 ° C. at a cooling rate of / min, held at 30 ° C. for 5 minutes, then heated again from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min, held at 200 ° C. for 5 minutes, and then again The temperature is lowered to 30 ° C. at a cooling rate of 10 ° C./min. Here, the melting peak developed at the second temperature rise is known as the melting point TmII derived from the type II crystal.

  The melting peak that appeared when a sample that had been allowed to stand at room temperature for 10 days after receiving the above thermal history was heated again from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min using DSC again. The melting point TmI derived from the type I crystal, and the heat of fusion based on the melting peak of the type I crystal is the heat of fusion ΔH of the 1-butene copolymer. TmI tends to be higher than TmII. When the crystal transition is not completed, the peak derived from the type II crystal appears on the low temperature side, and the peak derived from the type I crystal appears on the high temperature side.

  In the present invention, the heat of fusion ΔH, the melting points TmI and TmII of the 1-butene copolymer are within the above ranges by appropriately using the olefin polymerization catalyst described later and adjusting the content of structural units derived from 1-butene. Can be adjusted. Here, it is known that Tm and ΔH increase as mmmm (%) increases and rr (%) decreases.

<Requirements (vi)>
Requirement (vi) is that the 95% crystal transition completion time measured by a differential scanning calorimeter is 45 hours or less. The 95% crystal transition completion time is preferably 24 hours or less.

The 95% crystal transition completion time is an index of the time required for crystal transition from type II to type I as the crystalline form of 1-butene copolymer, and is specifically measured under the conditions described in the examples. .
Since the 1-butene copolymer of the present invention has high stereoregularity and contains a comonomer-derived structural unit, the crystal transition time is short. In addition to the differential scanning calorimeter, it can be observed that the crystal transition time is short in the X-ray diffraction method.

<Moldability>
<Requirements (vii)>
The requirement (vii) is that the shear stress at 190 ° C. and the extrusion speed of 50 mm / min is 65,000 Pa or less in the capillograph. Preferably it is 64,000 Pa or less, More preferably, it is 62,000 Pa or less.

  If the shear stress is 65,000 Pa or less, the resistance to resin flow during molding is small, the appearance of the resulting molded article is good, and it can be said that the moldability is excellent. Further, if the speed at which melt fracture occurs is 50 mm / min or more, the moldability is good.

  Further, the 1-butene copolymer of the present invention may be graft-modified with a polar monomer as long as the above requirements are satisfied. Details of the graft modification will be described later in the section of “graft modification”.

[Characteristics of 1-butene copolymer]
The 1-butene copolymer of the present invention has a shorter crystal transition time than 1-butene homopolymer, and further has mechanical properties such as elastic modulus and yield point strength despite having comonomer units. -It has the surprising effect of being maintained at the same level as the butene homopolymer. Moreover, these effects are recognized not only at room temperature but also in a relatively high temperature environment.

  It is known that in a copolymer having a comonomer unit, since the comonomer is usually difficult to be taken into the crystal, the crystal lamella thickness is reduced, the melting point is lowered, and the mechanical properties such as elastic modulus are lowered. However, in the 1-butene copolymer of the present invention, even if it has a comonomer unit, it is considered that the mechanical properties are maintained because the crystal lamella thickness is difficult to decrease.

  Here, it is considered that the higher the mmmm (%), the higher the degree of crystallinity, the thicker the crystal lamella, and the better the mechanical properties. Furthermore, it is considered that the lower the rr (%), the higher the crystallinity, the thicker the crystal lamella, and the better the mechanical properties.

[Mixture of 1-butene copolymer]
As described above, the 1-butene copolymer is obtained by using a multi-stage polymerization method, a mixed catalyst polymerization method, a method of mixing 1-butene copolymers having different molecular weights, and the like by using the Mw / Mn can be adjusted. Specifically, a 1-butene copolymer of the present invention can be obtained by mixing a butene polymer having a small molecular weight and a butene polymer having a large molecular weight by the above-described method or the like. In this case, when the 1-butene copolymer is a mixture with a butene polymer having a low molecular weight, it is one of preferred embodiments that the butene polymer having a low molecular weight is a 1-butene homopolymer.

  For example, a butene polymer having a large molecular weight preferably has an intrinsic viscosity [η] in a decalin solvent of 135 ° C. and a range of 2.0 to 5.5 dl / g. As one of preferred embodiments, the butene polymer having a large molecular weight has a content of structural units derived from 1-butene of 90.0 mol% or more and a total content (K) of structural units derived from the olefin of 10. The content of structural units derived from 1-butene is 90.0 to 97.0 mol%, and the total content (K) is 3.0 to 10.0 mol. % 1-butene copolymer.

Further, it is more preferable that a butene polymer having a large molecular weight alone satisfies the requirements of the 1-butene copolymer of the present invention, for example, the requirements (i), (ii) and (iv).
For example, a butene polymer having a small molecular weight preferably has an intrinsic viscosity [η] in a decalin solvent of 135 ° C. and a range of 0.5 to 1.5 dl / g. As a preferred embodiment, the butene polymer having a low molecular weight has a content of structural units derived from 1-butene of 90.0 mol% or more and the total content (K) of 10.0 mol% or less. More preferably, it is a 1-butene homopolymer.

  The crystal transition time of the resulting blend polymer (that is, the 1-butene copolymer of the present invention) is obtained by using only a butene polymer having a large molecular weight as a copolymer and a butene polymer having a low molecular weight as a homopolymer. Can be effectively shortened, and the total content (K) contained in the resulting blend polymer (that is, the butene-based polymer of the present invention) can be suppressed, so that deterioration in mechanical properties can be suppressed.

  The blend ratio (mass ratio) of the butene polymer having a large molecular weight (hereinafter (a1)) and the butene polymer having a small molecular weight (hereinafter (a2)) is the same as that of the 1-butene copolymer of the present invention. Although it does not specifically limit as long as the requirements for coalescence are satisfied, (a1) :( a2) is usually 50 to 90:10 to 50, preferably 60 to 85:15 to 40.

[Method for producing 1-butene copolymer]
The method for producing a 1-butene copolymer of the present invention is selected from 1-butene, ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) in the presence of an olefin polymerization catalyst described later. Polymerizing at least one olefin.

  When producing a blend polymer, in the method of mixing butene polymers having different molecular weights, for example, two or more butene polymers obtained by the above method are mixed, and the butene polymer obtained by the above method is mixed. Mix the butene polymer obtained by the other method with the butene polymer obtained by the above method and the butene homopolymer obtained by the other method using the catalyst. And the like.

[1-1] Olefin Polymerization Catalyst As the olefin polymerization catalyst,
(A) a bridged metallocene compound;
(B) (b-1) Organoaluminum oxy compound,
(b-2) a compound that reacts with the metallocene compound (A) to form an ion pair, and
(b-3) A catalyst containing at least one compound selected from organoaluminum compounds is preferred.

<Bridged metallocene compound (A)>
The bridged metallocene compound (A) is preferably a compound represented by the general formula [A1], and more preferably a compound represented by the general formula [A2].

式［Ａ１］中、Ｍは第４族遷移金属、例えばチタン原子、ジルコニウム原子またはハフニウム原子であり、Ｑはハロゲン原子、炭化水素基、炭素数１０以下の中性の共役もしくは非共役ジエン、アニオン配位子および孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれ、ｊは１〜４の整数であり、Ｒ^AおよびＲ^Bは、互いに同一かまたは異なっていてもよく、Ｍと共にサンドイッチ構造を形成することができる単核または多核炭化水素残基であり、Ｙは炭素原子またはケイ素原子であり、Ｒ^CおよびＲ^Dは、互いに同一かまたは異なっていてもよく、水素原子、炭化水素基、ケイ素含有基、ハロゲン原子およびハロゲン含有炭化水素基から選ばれ、互いに結合して環を形成していてもよい。

In the formula [A1], M is a Group 4 transition metal such as a titanium atom, a zirconium atom or a hafnium atom, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anion The ligands and neutral ligands capable of coordinating with a lone pair are selected in the same or different combinations, j is an integer of 1 to 4, and R ^A and R ^B are the same or different from each other Or a mononuclear or polynuclear hydrocarbon residue capable of forming a sandwich structure with M, Y is a carbon atom or a silicon atom, and R ^C and R ^D may be the same or different from each other , A hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group, which may be bonded to each other to form a ring.

式［Ａ２］中、Ｒ¹は炭化水素基、ケイ素含有基またはハロゲン含有炭化水素基であり、Ｒ²〜Ｒ¹⁰は水素原子、炭化水素基、ケイ素含有基、ハロゲン原子およびハロゲン含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、それぞれの置換基は互いに結合して環を形成してもよい。Ｍは第４族遷移金属であり、Ｑはハロゲン原子、炭化水素基、炭素数１０以下の中性の共役もしくは非共役ジエン、アニオン配位子および孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれ、ｊは１〜４の整数である。

In the formula [A2], R ¹ is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ^{2 to} R ¹⁰ are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group. Each may be the same or different, and each substituent may be bonded to each other to form a ring. M is a Group 4 transition metal, Q is a neutral atom capable of coordinating with a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a lone electron pair. The same or different combinations are selected from the children, and j is an integer of 1 to 4.

  Among the bridged metallocene compounds represented by the general formula [A2], the bridged metallocene compounds represented by the general formula [A3] are particularly preferable from the viewpoint of obtaining polymerization characteristics, availability, and a butene-based polymer that satisfies the above requirements. .

式［Ａ３］中、Ｒ^1bは炭化水素基、ケイ素含有基またはハロゲン含有炭化水素基であり、Ｒ^2b〜Ｒ^12bは水素原子、炭化水素基、ケイ素含有基、ハロゲン原子およびハロゲン含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、それぞれの置換基は互いに結合して環を形成してもよい。Ｍは第４族遷移金属であり、ｎは１〜３の整数であり、Ｑはハロゲン原子、炭化水素基、炭素数１０以下の中性の共役もしくは非共役ジエン、アニオン配位子および孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれ、ｊは１〜４の整数である。

In the formula [A3], R ^1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ^{2b to} R ^12b are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group. Each may be the same or different, and each substituent may be bonded to each other to form a ring. M is a Group 4 transition metal, n is an integer of 1 to 3, Q is a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, and a lone electron The neutral ligands that can be coordinated in pairs are selected from the same or different combinations, and j is an integer of 1 to 4.

<R ¹ to R ¹⁰ , R ^1b to R ^12b >
Examples of the hydrocarbon group in R ¹ to R ¹⁰ and R ^1b to R ^12b include a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a saturated hydrocarbon group. And a group formed by substituting one or two or more hydrogen atoms possessed by a cyclic unsaturated hydrocarbon group. Carbon number of a hydrocarbon group is 1-20 normally, Preferably it is 1-15, More preferably, it is 1-10.

  Examples of the linear hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. And linear alkyl groups such as n-decanyl group; linear alkenyl groups such as allyl group.

  Examples of the branched hydrocarbon group include isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 Examples thereof include branched alkyl groups such as -propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group.

  Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and methylcyclohexyl group; and polycyclic groups such as norbornyl group, adamantyl group, and methyladamantyl group. It is done.

  Examples of the cyclic unsaturated hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group; a cycloalkenyl group such as a cyclohexenyl group; and 5-bicyclo [2.2. 1] Polycyclic unsaturated alicyclic groups such as a hepta-2-enyl group.

  Examples of the group formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group, and a triphenylmethyl group. And a group formed by substituting one or two or more hydrogen atoms of the alkyl group with an aryl group.

The silicon-containing group in R ^12b from R ¹ from R ¹⁰ and R ^1b, for example, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, the formula -SiR _3, such as a triphenylsilyl group (wherein And a plurality of R's are each independently an alkyl group having 1 to 15 carbon atoms or a phenyl group.).

Examples of the halogen-containing hydrocarbon group in R ¹ to R ¹⁰ and R ^1b to R ^12b are formed by substituting one or more hydrogen atoms of the hydrocarbon group such as a trifluoromethyl group with a halogen atom. Groups.

Examples of the halogen atom in R ² to R ¹⁰ and R ^2b to R ^12b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Of the substituents R ² to R ¹⁰ and R ^2b to R ^12b , two substituents (eg, R ^2b and R ^3b , R ^3b and R ^4b , R ^5b and R ^6b , R ^6b and R ^7b , R ^8b and R ^9b , R ^9b and R ^10b , R ^10b and R ^11b , R ^11b and R ^12b ) may be bonded to each other to form a ring, and there are two or more ring formations in the molecule. May be.

  In the present specification, examples of the ring (spiro ring, additional ring) formed by bonding two substituents to each other include an alicyclic ring and an aromatic ring. Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, and a cyclopentene ring, and a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring are preferable. Such a ring structure may further have a substituent such as an alkyl group on the ring.

R ^1b is preferably a hydrocarbon group from the viewpoint of stereoregularity, more preferably a hydrocarbon group having 1 to 20 carbon atoms, still more preferably not an aryl group, and a linear hydrocarbon. Group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group is particularly preferable, and a substituent having a free valence (carbon bonded to a cyclopentadienyl ring) being a tertiary carbon is particularly preferable. preferable.

Specific examples of R ^1b include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. Is a substituent in which the carbon having a free valence is a tertiary carbon, such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group, particularly preferably a tert-butyl group, 1- An adamantyl group;

In the general formula [A3], the fluorene ring moiety is not particularly limited as long as it is a structure obtained from a known fluorene derivative, but R ^4b and R ^5b are preferably hydrogen atoms from the viewpoint of stereoregularity and molecular weight.

R ^2b , R ^3b , R ^6b and R ^7b are preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrocarbon group, and still more preferably a hydrocarbon group having 1 to 20 carbon atoms. R ^2b and R ^3b may be bonded to each other to form a ring, and R ^6b and R ^7b may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2. , 3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl-2,3, 6,7,8,10-hexahydro-1H-dicyclopenta [b, h] fluorenyl group, 1 ', 1', 3 ', 6', 8 ', 8'-hexamethyl-1'H, 8'H-dicyclopenta [B, h] fluorenyl group is exemplified, and 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- is particularly preferred. 1H-dibenzo [b, h] fluorenyl group.

R ^8b is preferably a hydrogen atom.
R ^9b is more preferably a hydrocarbon group, and R ^9b is more preferably an alkyl group having 2 or more carbon atoms such as a linear alkyl group or a branched alkyl group, a cycloalkyl group, or a cycloalkenyl group, R ^9b is particularly preferably an alkyl group having 2 or more carbon atoms. From the viewpoint of synthesis, R ^10b and R ^11b are also preferably hydrogen atoms.

Alternatively, when n = 1, R ^9b and R ^10b are more preferably bonded to each other to form a ring, and the ring is particularly preferably a 6-membered ring such as a cyclohexane ring. In this case, R ^11b is preferably a hydrogen atom.
R ^12b is preferably a hydrocarbon group, and particularly preferably an alkyl group.

<About M, Q, n, and j>
M is a Group 4 transition metal, for example, Ti, Zr or Hf, preferably Zr or Hf, particularly preferably Zr.
Q represents a halogen atom, a hydrocarbon group, a neutral conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair.
Examples of the halogen atom for Q include fluorine, chlorine, bromine and iodine.

  As a hydrocarbon group in Q, a C1-C10 alkyl group and a C3-C10 cycloalkyl group are preferable. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1 , 1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylbutyl group, 1, Examples include a 1,3-trimethylbutyl group and a neopentyl group; examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclohexylmethyl group, a cyclohexyl group, and a 1-methyl-1-cyclohexyl group. More preferably, the hydrocarbon group has 5 or less carbon atoms.

Neutral conjugated or nonconjugated dienes having 10 or less carbon atoms include s-cis- or s-trans-η ⁴ -1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4- Diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1, 3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s- cis - or s- trans eta ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

  Examples of the anionic ligand include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate.

  Neutral ligands that can be coordinated by lone electron pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; tetrahydrofuran (THF), diethyl ether, dioxane, 1,2-dimethoxy Examples are ethers such as ethane.

A preferred embodiment of Q is a halogen atom or an alkyl group having 1 to 5 carbon atoms.
n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. When n is the above value, it is preferable from the viewpoint of efficiently obtaining the produced butene polymer.
j is an integer of 1 to 4, preferably 2.

The preferred embodiments of the configuration of the bridged metallocene compound represented by the general formula [A2] or [A3], that is, R ^{1 to} R ¹⁰ , R ^{1b to} R ^12b , M, n, Q, and j have been described above. In the present invention, any combination of the preferred embodiments is also a preferred embodiment. Such a bridged metallocene compound can be suitably used to obtain the butene polymer of the present invention having the above physical properties.

  Examples of the bridged metallocene compound represented by the general formula [A3] include (8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5, 6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride or (8- (2,3,6,7-tetramethylfluorene) -12'-yl- (2- (adamantane-1 -Yl) -8-methyl-3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride is particularly preferred. Here, the above-mentioned octamethylfluorene is 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b , h] Fluorene.

In addition, examples of the bridged metallocene compound represented by the general formula [A1] include compounds in which R ^A and R ^B may be the same or different from each other, are substituted indenyl groups, and Y is a silicon atom. Can be mentioned. Examples of the substituent in the substituted indenyl group include a halogen atom, a hydrocarbon group, a silicon-containing group, and a halogen-containing hydrocarbon group. Specific examples of these include R ^{1 in the} formulas [A2] and [A3] and The groups described as R ^{2 and the} like can be mentioned, and the R ^C , R ^D and MQ _j moieties can be the same groups as the R ⁹ , R ¹⁰ and MQ _j moieties described in the columns of the formulas [A2] and [A3]. Is mentioned. Specific examples of such a bridged metallocene compound include dimethylsilylene-bis {1- (2-n-propyl-4-phenanthrylindenyl)} zirconium dichloride, dimethylsilylene-bis {1- (2- n-propyl-4-phenanthrylindenyl)} hafnium dichloride.

<Compound (B)>
<< Organic aluminum oxy compound (b-1) >>
As the organoaluminum oxy compound (b-1), a conventionally represented aluminoxane such as a compound represented by the general formula [B1] and a compound represented by the general formula [B2], a structure represented by the general formula [B3] And a modified methylaluminoxane having boron, and a boron-containing organoaluminum oxy compound represented by the general formula [B4].

式［Ｂ１］および［Ｂ２］において、Ｒは炭素数１〜１０の炭化水素基、好ましくはメチル基であり、ｎは２以上、好ましくは３以上、より好ましくは１０以上の整数である。式［Ｂ１］および［Ｂ２］において、Ｒがメチル基であるメチルアルミノキサンが好適に使用される。

In the formulas [B1] and [B2], R is a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, and n is an integer of 2 or more, preferably 3 or more, more preferably 10 or more. In the formulas [B1] and [B2], methylaluminoxane in which R is a methyl group is preferably used.

式［Ｂ３］において、Ｍｅはメチル基であり、Ｒは炭素数２〜１０の炭化水素基であり、ｍおよびｎはそれぞれ独立に２以上の整数である。複数あるＲは相互に同一でも異なっていてもよい。修飾メチルアルミノキサン［Ｂ３］は、トリメチルアルミニウムとトリメチルアルミニウム以外のアルキルアルミニウムとを用いて調製することができる。このような修飾メチルアルミノキサン［Ｂ３］は、一般にＭＭＡＯ（ｍｏｄｉｆｉｅｄ ｍｅｔｈｙｌ ａｌｕｍｉｎｏｘａｎｅ）と呼ばれている。ＭＭＡＯは、具体的には米国特許第４９６０８７８号および米国特許第５０４１５８４号で挙げられる方法で調製することが出来る。

In the formula [B3], Me is a methyl group, R is a hydrocarbon group having 2 to 10 carbon atoms, and m and n are each independently an integer of 2 or more. A plurality of R may be the same or different from each other. The modified methylaluminoxane [B3] can be prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [B3] is generally called MMAO (modified methyl aluminoxane). MMAO can be specifically prepared by the methods mentioned in US Pat. No. 4,960,878 and US Pat. No. 5,041,584.

  In addition, modified methylaluminoxanes prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. (that is, R is an isobutyl group in the general formula [B3]) are trade names such as MMAO and TMAO. Is produced commercially.

  MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, unlike a compound that is insoluble or hardly soluble in benzene such as a compound represented by the general formula [B1] or [B2], MMAO is an aliphatic hydrocarbon, alicyclic hydrocarbon, and aromatic. It is soluble in group hydrocarbons.

式［Ｂ４］において、Ｒ^cは炭素数１〜１０の炭化水素基である。複数あるＲ^dはそれぞれ独立に水素原子、ハロゲン原子または炭素数１〜１０の炭化水素基である。上記オレフィン重合用触媒を用いた製法では、後述するような高温においてもブテン系重合体を製造することができる。したがって、特開平２−７８６８７号公報に例示されているようなベンゼン不溶性または難溶性の有機アルミニウムオキシ化合物をも使用できることができる。また、特開平２−１６７３０５号公報に記載されている有機アルミニウムオキシ化合物、特開平２−２４７０１号公報、特開平３−１０３４０７号公報に記載されている２種以上のアルキル基を有するアルミノキサンなども好適に使用できる。

In the formula [B4], R ^c is a hydrocarbon group having 1 to 10 carbon atoms. A plurality of R ^d are each independently a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms. In the production method using the olefin polymerization catalyst, a butene polymer can be produced even at a high temperature as described later. Therefore, benzene-insoluble or hardly soluble organoaluminum oxy compounds as exemplified in JP-A-2-78687 can also be used. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxane having two or more alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be used suitably.

The above-mentioned “benzene insoluble or hardly soluble” organoaluminum oxy compound means that the dissolved amount of the compound dissolved in benzene at 60 ° C. is usually 10% by mass or less, preferably 5% by mass or less in terms of Al atom. An organoaluminum oxy compound that is insoluble or hardly soluble in benzene, particularly preferably 2% by mass or less.
The organic aluminum oxy compound (b-1) exemplified above may be used alone or in combination of two or more.

<< Ionic Compound (b-2) >>
As compound (b-2) (hereinafter also referred to as “ionic compound (b-2)”) which reacts with the bridged metallocene compound (A) to form an ion pair, JP-A-1-501950, Kaihei 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, JP-A-2004-51676, US Patent No. Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in No. 5321106. Furthermore, heteropoly compounds and isopoly compounds are also exemplified. In these, as an ionic compound (b-2), the compound represented by general formula [B5] is preferable.

式［Ｂ５］において、Ｒ^e+としては、Ｈ⁺、オキソニウムカチオン、カルベニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンが例示される。Ｒ^f、Ｒ^g、Ｒ^hおよびＲⁱはそれぞれ独立に有機基を示し、好ましくはアリール基またはハロゲン置換アリール基を示す。

In the formula [B5], R ^{e +} is exemplified by H ⁺ , oxonium cation, carbenium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^f , R ^g , R ^h and R ⁱ each independently represents an organic group, preferably an aryl group or a halogen-substituted aryl group.

  Examples of the carbenium cation include trisubstituted carbenium cations such as a triphenyl carbenium cation, a tris (methylphenyl) carbenium cation, and a tris (dimethylphenyl) carbenium cation.

  Examples of ammonium cations include trialkylammonium cations, triethylammonium cations, tri (n-propyl) ammonium cations, triisopropylammonium cations, tri (n-butyl) ammonium cations, triisobutylammonium cations, and the like; N, N -N, N-dialkylanilinium cations such as dimethylanilinium cation, N, N-diethylanilinium cation, N, N, 2,4,6-pentamethylanilinium cation; diisopropylammonium cation, dicyclohexylammonium cation, etc. Examples include dialkylammonium cations.

  Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

In the above examples, R ^{e +} is preferably a carbenium cation or an ammonium cation, and particularly preferably a triphenylcarbenium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

1. When R ^{e +} is a carbenium cation (carbenium salt)
Examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methylphenyl) carbe. Examples thereof include nium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

2. When R ^{e +} is an ammonium cation (ammonium salt)
Examples of ammonium salts include trialkylammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.

  Specific examples of the trialkylammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis ( o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4 -Dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) bore Tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o -Tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, di Octadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate , Dioctadecyl methyl ammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and N, N-dimethylaniliniumtetrakis. (3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5 -Ditrifluoromethylphenyl) borate, N, N, 2,4,6-pentamethylanilinium tetraphenylborate, N, N, 2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate The

Specific examples of the dialkylammonium salt include diisopropylammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.
An ionic compound (b-2) may be used independently and may be used in combination of 2 or more type.

<< Organic aluminum compound (b-3) >>
Examples of the organoaluminum compound (b-3) include an organoaluminum compound represented by the general formula [B6] and a complex alkylated product of a group 1 metal of the periodic table represented by the general formula [B7] and aluminum. The
R ^a _m Al (OR ^b ) _n H _p X _q ... [B6]
In the formula [B6], R ^a and R ^b are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is 0 <m ≦ 3, and n is 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.
M ² AlR ^a ₄ [B7]
In the formula [B7], M ² is Li, Na or K, and a plurality of R ^a are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

Examples of the organoaluminum compound [B6] include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, Tri-branched alkylaluminum such as tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triphenyl Triarylaluminum such as aluminum and tolylylaluminum; diisopropylaluminum Hydride, diisobutyl aluminum dialkyl hydride such as hydride; formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y and z are positive numbers, z ≦ 2x Alkenyl aluminum alkoxides such as isoprenylaluminum and the like; alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide ; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide; in the general formula ^{_{R a 2.5 Al (oR b)}} 0.5 ( wherein R ^a and R ^b wherein [ . 6 is the same meaning as R ^a and R ^b in the alkylaluminum partially alkoxylated with an average composition represented by); diethylaluminum phenoxide, diethylaluminum (2,6-di-tert- butyl-4 Alkyl aluminum aryloxides such as -methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquichloride Alkyl aluminum sesquihalides such as bromide; partially halo such as alkyl aluminum dihalides such as ethylaluminum dichloride Alkylated alkylaluminum; Dialkylaluminum hydride such as diethylaluminum hydride and dibutylaluminum hydride; Partially hydrogenated alkylaluminum such as alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride; Ethylaluminum ethoxy Illustrative examples include partially alkoxylated and halogenated alkylaluminums such as chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, and the like.

Examples of the complex alkylated product [B7] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . A compound similar to the complex alkylated product [B7] can also be used, and an organic aluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom is exemplified. An example of such a compound is (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

  As the organoaluminum compound (b-3), trimethylaluminum and triisobutylaluminum are preferable because they are easily available. Moreover, an organoaluminum compound (b-3) may be used by 1 type, and may use 2 or more types together.

<Carrier (C)>
The carrier (C) may be used as a component of the olefin polymerization catalyst. The carrier (C) is an inorganic compound or an organic compound, and is a granular or particulate solid.

<Inorganic compounds>
Inorganic compounds include porous oxides, inorganic halides, clay minerals, clay (usually composed of the clay mineral as a main component), ion-exchange layered compounds (most clay minerals are ion-exchange layered) A compound)). Examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ ; a composite or a mixture containing these oxides. . The composite or mixture includes natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —. An example is TiO ₂ —MgO. Among these, porous oxides containing as a main component one or both of SiO ₂ and Al ₂ O ₃ are preferable.

The properties of the porous oxide vary depending on the type and production method, but the particle size is preferably 10 to 300 μm, more preferably 20 to 200 μm; the specific surface area is preferably 50 to 1000 m ² / g, more preferably. Is in the range of 100 to 700 m ² / g; the pore volume is preferably in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary. Examples of inorganic halides include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Moreover, after dissolving the said inorganic halide in solvents, such as alcohol, the component made to deposit into a fine particle form with a depositing agent can also be used.

  The clay, clay mineral, and ion-exchange layered compound are not limited to natural products, and artificial synthetic products can also be used. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the contained ions can be exchanged.

Specifically, as clay and clay minerals, kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, synthetic mica, etc., ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, Examples include kaolinite, nacrite, dickite, hectorite, teniolite, halloysite; examples of ion-exchangeable layered compounds include ions having a layered crystal structure such as hexagonal close-packed type, antimony type, CdCl ₂ type, and CdI ₂ type Examples include crystalline compounds. Specifically, as the ion exchange layered compound, α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α- Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ And crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

  It is also preferable to subject the clay and clay mineral to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

  In addition, the ion-exchangeable layered compound may be a layered compound in which the interlayer is expanded by exchanging the exchangeable ions between the layers with another large bulky ion using the ion-exchangeability. Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. For example, an oxide column (pillar) can be formed between layers by intercalating the following metal hydroxide ions between layers of the layered compound and then heat-dehydrating. The introduction of another substance between the layers of the layered compound is called intercalation.

Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ ; metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ and B (OR) ₃ ( R is a hydrocarbon group); metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Is exemplified. These guest compounds may be used alone or in combination of two or more.

In addition, when intercalating a guest compound, it is obtained by hydrolysis and polycondensation of a metal alkoxide (R is a hydrocarbon group, etc.) such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) _4. In addition, a polymer, a colloidal inorganic compound such as SiO ₂ can be coexisted.
Among inorganic compounds, clay minerals and clays are preferable, and montmorillonite group, vermiculite, hectorite, teniolite and synthetic mica are particularly preferable.

《Organic compound》
Examples of the organic compound include a granular or particulate solid having a particle size in the range of 10 to 300 μm. Specifically, (co) polymer synthesized with ethylene and α-olefin having 3 to 20 carbon atoms as main components; (co) polymer synthesized with vinylcyclohexane and styrene as main components; these (co) Examples are polymer modifications.

<Organic compound component (D)>
An organic compound component (D) may be used as a component of the olefin polymerization catalyst. The organic compound component (D) is used for the purpose of improving the polymerization performance in the polymerization reaction of α-olefin and the physical properties of the olefin polymer, if necessary. Examples of the organic compound component (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

<Configuration of olefin polymerization catalyst>
When copolymerizing 1-butene with ethylene and an α-olefin other than 1-butene having 3 to 20 carbon atoms using the olefin polymerization catalyst, the amount of each component that can constitute the olefin polymerization catalyst is as follows: It is as follows. In the olefin polymerization catalyst, the content of each component can be set as follows.

(1) When 1-butene is copolymerized using an olefin polymerization catalyst, the crosslinked metallocene compound (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻ , per liter of reaction volume. ^The amount used is ⁸ to 10 ⁻² mol.

  (2) When the organoaluminum oxy compound (b-1) is used as a component of the olefin polymerization catalyst, the compound (b-1) is composed of an aluminum atom (Al) and a crosslinked metallocene compound in the compound (b-1). It is used in such an amount that the molar ratio [Al / M] to all transition metal atoms (M) in (A) is usually 0.01 to 5000, preferably 0.05 to 2000.

  (3) When the ionic compound (b-2) is used as a component of the olefin polymerization catalyst, the compound (b-2) is a transition metal in the compound (b-2) and the bridged metallocene compound (A). The molar ratio [(b-2) / M] with the atom (M) is usually 1 to 10, preferably 1 to 5.

  (4) When the organoaluminum compound (b-3) is used as a component of the olefin polymerization catalyst, the compound (b-3) is a transition metal in the compound (b-3) and the bridged metallocene compound (A). The molar ratio [(b-3) / M] with the atom (M) is usually 10 to 5000, preferably 20 to 2000.

  (5) When the organic compound component (D) is used as a component of the olefin polymerization catalyst, when the compound (B) is the organoaluminum oxy compound (b-1), the organic compound component (D) and the compound ( the molar ratio [(D) / (b-1)] to b-1) is usually 0.01 to 10, preferably 0.1 to 5; compound (B) is ionic. When it is the compound (b-2), the molar ratio [(D) / (b-2)] of the organic compound component (D) and the compound (b-2) is usually 0.01 to 10, preferably Is an amount such that 0.1 to 5; when the compound (B) is an organoaluminum compound (b-3), the molar ratio of the organic compound component (D) to the compound (b-3) [( D) / (b-3)] is usually used in such an amount that it is 0.01 to 2, preferably 0.005 to 1.

[1-2] Polymerization Method In the production of the 1-butene copolymer of the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. An inert hydrocarbon medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. In addition, a so-called bulk polymerization method in which liquefied olefin itself that can be supplied to the polymerization is used as a solvent can also be used.

  In the production method, the polymerization temperature of 1-butene copolymer is usually −50 to + 200 ° C., preferably 0 to 180 ° C .; the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa. Gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the resulting butene polymer can be adjusted by allowing hydrogen or the like to exist in the polymerization system, changing the polymerization temperature, or using the component (B).

  The production method can produce a 1-butene copolymer having high stereoregularity, high melting point, and high molecular weight while maintaining high catalytic activity even under high temperature conditions advantageous in industrial production methods. Is possible. Under such high temperature conditions, the polymerization temperature is usually 40 ° C. or higher, preferably 40 to 200 ° C., more preferably 45 to 150 ° C., particularly preferably 50 to 150 ° C. (in other words, particularly preferably industrializable. Temperature.).

  In particular, hydrogen can be said to be a preferable additive because it can improve the polymerization activity of the catalyst and increase or decrease the molecular weight of the polymer. When hydrogen is added to the system, the amount is suitably about 0.00001 to 100 NL per 1 mol of 1-butene. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system is not limited to the method of generating or consuming hydrogen in the system, the method of separating hydrogen using a membrane, It can also be adjusted by releasing the gas out of the system.

  For the 1-butene copolymer obtained by the production method, after synthesizing by the above method, a post-treatment step such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step is performed as necessary. You can go.

(Polymer composition)
The polymer composition of the present invention is a composition containing the 1-butene copolymer of the present invention described above.
The 1-butene copolymer of the present invention is optionally added with at least one selected from other polymers and additives for resins within a range that does not impair the effects of the present invention, depending on the application. -It can be set as the polymer composition containing a butene copolymer. Hereinafter, the 1-butene copolymer of the present invention is also referred to as “1-butene copolymer (A)”, and another polymer different from 1-butene copolymer (A) is referred to as “other polymer (B ) ”, And the additive for resin is also referred to as“ additive (C) ”.

  In addition, the polymer composition of the present invention may be partly or wholly graft-modified with a polar monomer. Details of the graft modification will be described later in the section of “graft modification”.

<< 1-butene copolymer (A) >>
The content of the 1-butene copolymer (A) is preferably 0.1 to 99.9% by mass with respect to the total mass of the polymer composition of the present invention, and the lower limit is preferably 20% by mass. In one embodiment, the lower limit value of the content of 1-butene copolymer (A) is, for example, 40% by mass, more preferably 60% by mass, particularly preferably 80% by mass, and most preferably 85% by mass. %.

  A part or all of the 1-butene copolymer (A) may be graft-modified with a polar monomer as long as the above requirements are satisfied. Details of the graft modification will be described later in the section of “graft modification”.

<< Other polymer (B) >>
The other polymer (B) is a polymer different from the 1-butene copolymer (A) of the present invention, and various known upper rigid bodies can be widely used. The content of the other polymer (B) is preferably 0.001 to 99.9% by mass with respect to the total mass of the polymer composition of the present invention, and the upper limit is preferably 80% by mass. In one embodiment, the upper limit of the content of the other polymer (B) is more preferably 60% by mass, further preferably 40% by mass, particularly preferably 20% by mass, and most preferably 15% by mass. is there.

  The other polymer (B) is not particularly limited as long as it is different from the 1-butene copolymer (A), but various known thermoplastic resins, amorphous or low crystalline copolymers or elastomers shown below. Can be used.

Polyolefin-based resin: For example, polyethylene such as low density, medium density, high density polyethylene, high pressure method low density polyethylene, polypropylene such as isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1- Pentene, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer, 4 -Methyl-1-pentene / α-olefin copolymer, cyclic olefin copolymer, chlorinated polyolefin, and modified polyolefin resin obtained by modifying these olefin resins,
Among the thermoplastic polyolefin-based resins described above, for example, polyethylene and polypropylene can be used as a crystal nucleating agent, and the preferable content in that case is 0.001 to 5% by mass with respect to the total mass of the resin composition. .

Thermoplastic polyamide resin: For example, aliphatic polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612),
Thermoplastic polyester resin: For example, polyethylene terephthalate, polybutylene terephthalate, polyester elastomer,
Thermoplastic vinyl aromatic resin: For example, polystyrene, ABS resin, AS resin, styrene elastomer (styrene / butadiene / styrene block polymer, styrene / isoprene / styrene block polymer, styrene / isobutylene / styrene block polymer, hydrogenation thereof) object),
Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; vinyl acetate copolymer such as ethylene / vinyl acetate copolymer; ethylene / methacrylic acid acrylate copolymer; ionomer; ethylene / vinyl alcohol copolymer; Alcohol; Fluorine resin; Polycarbonate; Polyacetal; Polyphenylene oxide; Polyphenylene sulfide polyimide; Polyarylate; Polysulfone; Polyethersulfone; Rosin resin; Terpene resin and petroleum resin;
Elastomer (rubber): for example, ethylene / α-olefin / diene copolymer, propylene / α-olefin / diene copolymer, 1-butene / α-olefin / diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene Rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, silicone rubber;
Etc. are exemplified.

  Among thermoplastic resins, low density, medium density, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly-4-methyl-1-pentene, poly-3-methyl-1 -Pentene, poly-3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer, 4-methyl-1-pentene / α -Olefin copolymer, styrene elastomer, vinyl acetate copolymer, ethylene / methacrylic acid acrylate copolymer, ionomer, fluororesin, rosin resin, terpene resin and petroleum resin, more preferably heat resistant Polyethylene, isotactic poly in terms of improvement, low temperature resistance, flexibility Lopylene, syndiotactic polypropylene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer, 4-methyl-1-pentene / α-olefin copolymer Vinyl acetate copolymers, styrene elastomers, rosin resins, terpene resins and petroleum resins.

Part or all of the other polymer (B) may be graft-modified with a polar monomer. Details of the graft modification will be described later in the section of “graft modification”.
Another polymer (B) may be used individually by 1 type, and may use 2 or more types together.

<< Additive (C) >>
Examples of additives (C) include nucleating agents, anti-blocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, and surfactants. , Antistatic agent, weathering stabilizer, heat resistance stabilizer, anti-slip agent, foaming agent, crystallization aid, antifogging agent, anti-aging agent, hydrochloric acid absorbent, impact modifier, crosslinking agent, co-crosslinking agent, crosslinking aid Agents, pressure-sensitive adhesives, softeners, and processing aids.

An additive (C) may be used individually by 1 type, and may use 2 or more types together.
Although content of an additive (C) is not specifically limited according to a use within the range which does not impair the objective of this invention, It is with respect to the total mass of 1-butene copolymer or the polymer composition of this invention. It is preferable that it is 0.001-30 mass% about each additive mix | blended.

  As the nucleating agent, a known nucleating agent can be used to further improve the moldability of the 1-butene copolymer or polymer composition, that is, to increase the crystallization temperature and increase the crystallization speed. Specifically, dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di-t -Butylphenyl) sodium phosphate, pimelic acid and its salt, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, ethylene bis stearic acid amide and the like.

  Although the compounding quantity of a nucleating agent is not specifically limited, Preferably it is 0.001-5 mass parts with respect to 100 mass parts of 1-butene copolymers or polymer compositions. The nucleating agent can be appropriately added during polymerization, after polymerization, or during molding.

  As the anti-blocking agent, known anti-blocking agents can be used. Specifically, fine powder silica, fine powder aluminum oxide, fine powder clay, powdered or liquid silicon resin, tetrafluoroethylene resin, fine powder cross-linked resin, such as cross-linked acrylic, methacrylic resin powder, amide lubricant, etc. Is mentioned. Of these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferred.

  Examples of the pigment include inorganic contents (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of the dye include azo series, anthraquinone series, and triphenylmethane series. The addition amount of these pigments and dyes is not particularly limited, but is generally 5% by mass or less, preferably 0.1 to 5% by mass with respect to the total mass of the 1-butene copolymer or the polymer composition of the present invention. 3% by mass.

  Examples of the filler include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal Examples thereof include oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate) and various metal (magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, and glass flakes.

  Examples of the lubricant include wax (such as carnauba wax), higher fatty acid (such as stearic acid), higher alcohol (such as stearyl alcohol), and higher fatty acid amide (such as stearic acid amide).

  Examples of the plasticizer include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetylricinoleate), aliphatic dialcolic acid esters (such as adipic acid-propylene glycol polyester), and aliphatics. Examples include tricarboxylic acid esters (such as triethyl citrate), phosphoric acid triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

  Examples of mold release agents include lower fatty acid (C1-4) alcohol esters (such as butyl stearate) of higher fatty acids, polyhydric alcohol esters (such as hardened castor oil) of fatty acids (C4-30), glycol esters of fatty acids, fluid Paraffin is mentioned.

  A known antioxidant can be used as the antioxidant. Specifically, phenolic (2,6-di-t-butyl-4-methylphenol and the like), polycyclic phenolic (2,2′-methylenebis (4-methyl-6-t-butylphenol and the like), phosphorus System (tri (2,4-di-t-butylphenyl) phosphate, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate, etc.), sulfur system (thiodipropion) Acid dilauryl etc.), amine type (N, N-diisopropyl-p-phenylenediamine etc.), lactone type antioxidant and the like.

  Examples of flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.), inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.) ).

Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylic acid, and acrylate ultraviolet absorbers.
Examples of the antibacterial agent include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodine.

  Surfactants can include nonionic, anionic, cationic or amphoteric surfactants. Examples of the nonionic surfactant include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, polyethylene oxide, and glycerin. Polyhydric alcohol type nonionic surfactants such as fatty acid ester, fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, and the like. Examples of the anionic surfactant include sulfate salts such as alkali metal salts of higher fatty acids, sulfonate salts such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates, higher alcohol phosphate salts, and the like. Examples thereof include phosphate ester salts. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric surfactant include amino acid-type double-sided surfactants such as higher alkylaminopropionate, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyl hydroxyethylbetaine.

  Examples of the antistatic agent include the above-described surfactants, fatty acid esters, and polymer type antistatic agents. Examples of the fatty acid ester include stearic acid and oleic acid esters, and examples of the polymer antistatic agent include polyether ester amide.

  Examples of the heat resistance stabilizer include conventionally known stabilizers such as an amine stabilizer, a phenol stabilizer, and a sulfur stabilizer. Specifically, aromatic secondary amine stabilizers such as phenylbutylamine and N, N′-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene and tetrakis [methylene (3,5-di-t- Butyl-4-hydroxy) hydrocinnamate] methane, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and other phenolic stabilizers; bis [2-methyl-4- (3- thioether stabilizers such as n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide; dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate; zinc salts of 2-mercaptobenzoylimidazole and 2-mercaptobenzimidazole; Dilauryl thiodipropionate and di And sulfur stabilizers such as stearyl thiodipropionate. These stabilizers may be used alone or in combination of two or more.

As the crosslinking agent, for example, an organic peroxide is used.
Examples of the organic peroxide include dicumyl organic peroxide, di-tert-butyl organic peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-dioxide. -(Tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl- 4,4-bis (tert-butylperoxy) valerate, benzoyl organic peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl organic peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropylcarbo Ne Salts, diacetyl organic peroxide, lauroyl organic peroxide, tert-butyl cumyl organic peroxide.

The organic peroxide is preferably used at a ratio of 0.05 to 10 parts by mass with respect to 100 parts by mass of the 1-butene copolymer or polymer composition.
In the crosslinking treatment with organic peroxide, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, tri Peroxy crosslinking aids such as methylolpropane-N, N′-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Polyfunctional methacrylate monomers such as allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

  By using the above compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is preferably used in the present invention. Divinylbenzene is easy to handle, has good compatibility with the 1-butene copolymer, has an action of solubilizing the organic peroxide, and acts as a dispersant for the organic peroxide. For this reason, a homogeneous cross-linking effect is obtained, and a dynamic heat-treated product having a balance between fluidity and physical properties is obtained.

The crosslinking aid is preferably used at a ratio of 0.05 to 10 parts by mass with respect to 100 parts by mass of the 1-butene copolymer or polymer composition.
Examples of the softener include mineral oil softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly, coal tar softeners such as coal tar and coal tar pitch, castor oil, rapeseed oil, Fatty oil-based softeners such as soybean oil and coconut oil, waxes such as tall oil, beeswax, carnauba wax and lanolin, fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate or metal salts thereof, Naphthenic acid or its metal soap, pine oil, rosin or its derivatives, terpene resin, petroleum resin, coumarone indene resin, synthetic polymer materials such as atactic polypropylene, ester plastic such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate Agent, diisododecyl carbonate, etc. Carbonic ester plasticizers, other microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid Thiokol, and a hydrocarbon-based synthetic lubricating oils. Of these, petroleum softeners and hydrocarbon synthetic lubricants are preferred.

  The amount of the softening agent is not particularly limited, but is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the 1-butene copolymer or the polymer composition. The softening agent facilitates processing and aids dispersion of carbon black and the like when preparing a 1-butene copolymer or polymer composition.

<Graft modification>
Examples of polar monomers used for graft modification include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives. , Vinyl ester compounds, vinyl chloride, and carbodiimide compounds. In particular, an unsaturated carboxylic acid or a derivative thereof is preferable. Examples of the unsaturated carboxylic acid or derivative thereof include unsaturated compounds having one or more carboxylic acid groups, esters of a compound having a carboxylic acid group and an alkyl alcohol, and unsaturated compounds having one or more carboxylic anhydride groups. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group.

  Specific examples of the polar monomer include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endocis-bicyclo [2.2.1]). ] As unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid) and derivatives of unsaturated carboxylic acids, for example, acid halides, amides, imides, anhydrides and esters may be mentioned. Specific examples of such derivatives include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

  These unsaturated carboxylic acids and / or derivatives thereof may be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferably used.

  The modification is obtained by graft polymerization of a polar monomer to a modified body (1-butene copolymer or polymer composition). When the polar monomer is graft-polymerized on the object to be modified, the polar monomer is usually used in an amount of 1 to 100 parts by mass, preferably 5 to 80 parts by mass with respect to 100 parts by mass of the object to be modified. This graft polymerization is usually performed in the presence of a radical initiator.

  As the radical initiator, organic peroxides and azo compounds can be used. The radical initiator can be used as it is mixed with the modified substance and the polar monomer, but can also be used after being dissolved in a small amount of an organic solvent. As the organic solvent, any organic solvent that can dissolve the radical initiator can be used without particular limitation.

When the polar monomer is graft-polymerized on the object to be modified, a reducing substance may be used. When a reducing substance is used, the graft amount of the polar monomer can be improved.
Graft modification of a modified body with a polar monomer can be performed by a conventionally known method. For example, the modified body is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution. The reaction can be carried out by reacting at a temperature of preferably 80 to 190 ° C. for usually 0.5 to 15 hours, preferably 1 to 10 hours.

  A resin composition containing a modified body can also be produced by reacting the body to be modified with a polar monomer using an extruder or the like. This reaction is usually carried out above the melting point of the object to be modified. Specifically, when the other polymer (B) is modified, it is usually carried out at a temperature of usually 120 to 300 ° C., preferably 120 to 250 ° C., usually for 0.5 to 10 minutes. When modifying the 1-butene copolymer of the present invention, for example, it is usually performed at a temperature of 160 to 300 ° C., preferably 180 to 250 ° C., usually for 0.5 to 10 minutes.

  The modified amount of the modified product thus obtained (the graft amount of the polar monomer) is usually 0.1 to 50% by mass, preferably 0.2 to 30% by mass, when the modified product is 100% by mass, More preferably, it is 0.2-10 mass%.

  In the present invention, the modified product is kneaded with one or more of the unmodified product selected from the unmodified product of the 1-butene copolymer (A) and the unmodified product of the other polymer (B). Thus, a polymer composition can be obtained.

  Further, the polymer composition of the present invention can be modified by incorporating a polar monomer. Although content of a polar monomer is not specifically limited, 0.001-50 mass% is preferable with respect to 100 mass% of polymer compositions, More preferably, it is 0.001-10 mass%, More preferably, it is 0.001. It is -5 mass%, Most preferably, it is 0.01-3 mass%. The content of the polar monomer can be easily designed according to the purpose, for example, by appropriately selecting the grafting conditions.

  It can also be graft-modified using a silane coupling agent. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropylmethyldiethoxy Lan, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldi Ethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1- Propanamine, N, N'-bis (3- (trimethoxysilyl) propyl) ethylenediamine, polyoxyethylenepropyltrialkoxysilane, polyethoxydimethylsiloxane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysila And the like.

  When crosslinking is performed using a silane coupling agent, a dry processing method or a wet (slurry method) processing method may be used. Water cross-linking of polymers using a silane coupling agent is used for applications where a uniform cross-linked state is obtained and strength and durability such as industrial electric wires and pipes are required.

  When the modified body is used, the adhesiveness and compatibility with other resins are excellent, and the wettability of the surface of the obtained molded body may be improved. In some cases, compatibility or adhesion with other materials can be added by using a modified product.

  Further, since the graft amount of the polar monomer (eg, unsaturated carboxylic acid and / or derivative thereof) is in the above range, the butene polymer graft body of the present invention and / or the thermoplastic resin graft body described above can be obtained. The containing composition shows high adhesive strength with respect to a polar group-containing resin (for example, polyester, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyamide, PMMA, polycarbonate, etc.).

[Production method of polymer composition]
The method for producing the polymer composition of the present invention is not particularly limited. For example, the 1-butene copolymer of the present invention, the other polymer (B), and other optional components as necessary are added as described above. After mixing at a ratio, it is obtained by melt-kneading.

  The method of melt-kneading is not particularly limited, and can be performed using a melt-kneading apparatus such as a commercially available extruder. For example, the temperature of the part that is kneaded by the melt kneader is usually 120 to 250 ° C, preferably 120 to 230 ° C. The kneading time is usually 0.5 to 30 minutes, particularly preferably 0.5 to 5 minutes.

[Molded body]
Various molded articles formed from the 1-butene copolymer or the polymer composition containing the 1-butene copolymer of the present invention can be widely used for conventionally known polyolefin applications. The molded body is obtained by a known thermoforming method such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc. It is done.

  There is no restriction | limiting in particular in the thickness of a molded object, Although it can decide suitably by a use, Usually, it is 0.1-20 mm, Preferably it exists in the range of 0.15-10 mm (however, except a stretched film). Within this range, the balance between rigidity and uniform workability is good.

  There are no particular limitations on the shape and product type of the extruded product. Examples thereof include a sheet, a stretched or unstretched film, a pipe, a hose, an electric wire coating, and a tube, and particularly a sheet (skin material), a film, a tube, a catheter, a monofilament, a multifilament, and a nonwoven fabric.

  For the extrusion molding, a conventionally known extrusion apparatus and molding conditions can be employed. For example, a melted 1-butene copolymer using a single screw extruder, a kneading extruder, a ram extruder, a gear extruder, or the like can be used. The polymer or polymer composition can be formed into a desired shape by extruding from a specific die or the like.

  A stretched film is obtained by stretching an extruded sheet or an unstretched film as described above by a known stretching method such as a tenter method (longitudinal and transverse stretching or transverse and longitudinal stretching), a simultaneous biaxial stretching method, a uniaxial stretching method, or the like. Can do. The stretching ratio when stretching the sheet or unstretched film is usually about 20 to 70 times in the case of biaxial stretching, and usually about 2 to 10 times in the case of uniaxial stretching. By stretching, a stretched film having a thickness of 1 to 500 μm, preferably about 5 to 200 μm can be obtained.

  The filament molded body can be produced, for example, by extruding a molten 1-butene copolymer or polymer composition through a spinneret. The filament thus obtained may be further stretched. This stretching may be performed so that at least one uniaxial direction of the filament is molecularly oriented, and it is usually desirable to perform the stretching at a magnification of about 5 to 10 times. The filament is excellent in transparency, rigidity, heat resistance, impact resistance and stretchability. Specifically, the nonwoven fabric can be produced using a spunbond method or a meltblown method.

  The injection-molded product can be produced by injection molding the 1-butene copolymer or polymer composition into various shapes using a known injection molding apparatus under known conditions. Injection molded products are difficult to be charged, and have excellent transparency, rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, and abrasion resistance. Pipe joints, automotive interior trim materials, automotive exteriors It can be widely used for materials, household appliance housings, containers and the like.

  An inflation film can also be manufactured as a film. Inflation film includes, for example, daily miscellaneous goods packaging materials, food packaging materials, food containers, retort containers, protective films, decorative films and sheets, shrink films, infusion bags, heat-sealing films, stretched films, stretched raw material films, medical It can be suitably used as a material for containers and the like.

  Here, the shrink film is obtained by stretching a film made of the 1-butene copolymer or polymer composition of the present invention uniaxially or biaxially in a temperature range of usually 60 to 100 ° C., preferably 60 to 80 ° C. be able to. Examples of the stretching method include conventional polyolefin resin film stretching methods (e.g., uniaxial stretching and biaxial stretching), such as a uniaxial stretching method using a heating roll, and the biaxial stretching method. And a simultaneous biaxial stretching method using a tubular method, a sequential biaxial stretching method using a heated roll / tenter, or a simultaneous biaxial stretching method using a tenter. The draw ratio of the film is usually 3 times or more, preferably 3 to 10 times, more preferably 4 to 8 times.

  Sheets and films are hard to be charged and have excellent rigidity such as tensile modulus, heat resistance, stretchability, impact resistance, aging resistance, transparency, transparency, gloss and heat sealability. It can be widely used as a film, a protective film and the like. In this case, the sheet and the film may be a laminate (laminated sheet, film).

  Here, the laminated film is a method of extruding and laminating the 1-butene copolymer or polymer composition of the present invention on at least one side of the base film, the base film and the 1-butene copolymer or heavy polymer of the present invention. A method in which a film made of a coalescence composition is made into a dry laminator using an anchor coating agent, or a thermoplastic polymer as a raw material for a base film and a 1-butene copolymer or polymer composition of the present invention are multilayered It can be manufactured by various known manufacturing methods such as a method of obtaining a coextruded film using a die. In the laminated film of the present invention, the thickness of the film made of 1-butene copolymer or polymer composition is usually 5 to 500 μm, preferably 10 to 300 μm, more preferably 20 to 200 μm.

  The blow molded article can be produced by blow molding a 1-butene copolymer or polymer composition using a known blow molding apparatus under known conditions. In this case, the blow molded article may be a multilayer molded article.

  For example, in extrusion blow molding, a 1-butene copolymer or polymer composition is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison is placed in a mold having a desired shape. After being held, air can be blown in and a hollow molded body can be produced by mounting on a mold at a resin temperature of 130 ° C to 300 ° C. The stretching (blowing) magnification is preferably about 1.5 to 5 times in the lateral direction.

  For example, in injection blow molding, a 1-butene copolymer or polymer composition is injected into a parison mold at a resin temperature of 100 ° C. to 300 ° C. to mold a parison, and then the parison is held in a mold having a desired shape. A hollow molded body can be produced by blowing after-air and mounting the mold on a mold at a resin temperature of 120 ° C to 300 ° C. The stretching (blowing) magnification is preferably 1.1 to 1.8 times in the longitudinal direction and 1.3 to 2.5 times in the transverse direction.

  The blow molded product is excellent in transparency, rigidity or flexibility, heat resistance and impact resistance, and also in moisture resistance. Blow molded products are, for example, foods, seasonings, cosmetics, hair styling agents, drinking water, soft drinks, carbonated beverages, alcohols, bleaching agents, detergents, shampoos, rinses, conditioners, softeners, softeners, drugs, It can be used for adhesives, agricultural chemicals, medical use, baby bottles, laboratory equipment, kerosene cans, containers such as generators, lawn mowers, motorcycles, automobiles and other gasoline tanks, bottles and cups.

  In press molding, for example, a melt-kneaded product of 1-butene copolymer or polymer composition is pressurized at 5 to 20 MPa for 1 to 15 minutes using a press machine set at 120 to 250 ° C. If necessary, pressurization and cooling is performed at 5 to 20 MPa for 1 to 15 minutes using a press set at 10 to 20 ° C. In this way, a press sheet can be obtained. The thickness of the press sheet is, for example, 0.1 to 6.0 mm.

  Examples of the press-molded body include a mold stamping molded body. For example, 1-butene copolymer is used as a base material when a base material and a skin material are press-molded at the same time and both are integrally formed (mold stamping molding). A polymer or polymer composition can be used. Specific examples of such a mold stamping molded body include automotive interior materials such as door trims, rear package trims, seat back garnishes, and instrument panels. The press-molded body is hardly charged and is excellent in rigidity or flexibility, heat resistance, transparency, impact resistance, aging resistance, surface gloss, chemical resistance, wear resistance, and the like.

  When manufacturing using a molded object using vacuum forming, for example, a 1-butene copolymer or polymer composition is obtained in advance by obtaining a sheet or film by a known extrusion process and then vacuum forming. Although there is no restriction | limiting in particular in the thickness of a sheet | seat or a film, For example, it is preferable that it is 0.1-3 mm.

  There is no particular limitation on the vacuum forming method. Usually, a sheet or film-like molded body is heated and softened to be in close contact with the mold, air is exhausted from an exhaust port provided in the mold, the molded body is brought into close contact with the mold, and then the molded body is cooled. Subprocessed compacts can be manufactured.

  Although the surface temperature of the molded object at the time of vacuum forming is a temperature range of 120-250 degreeC normally, Preferably it is a temperature range of 120-220 degreeC, More preferably, it is a temperature range of 120-200 degreeC. When the surface temperature is in the above range, the drawdown property and the shapeability are good, and the thickness is uniform.

  Vacuum molded bodies include, for example, automobile interior materials, automobile exterior materials, packaging cases, protective cases, protective sheets, food and beverage containers, bottles, cups, information terminal cases, information terminal protective covers, It can be suitably used for display material frames and covers, furniture, and furniture frames.

  In the present invention, vacuum molded articles such as interior skin materials such as automobile instrument panels and door trims can also be manufactured. The molded body is hardly charged and is excellent in flexibility, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, wear resistance, and the like.

  In the present invention, powder slush moldings such as automobile parts, home appliance parts, toys, and miscellaneous goods can also be manufactured. The molded body is hardly charged and is excellent in flexibility, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, wear resistance, and the like.

  Examples of the molded article of the present invention also include a multilayer molded article having at least one layer composed of the 1-butene copolymer or polymer composition of the present invention. The multilayer molded body is a molded body in which at least one layer thereof is a layer formed from the butene polymer of the present invention or a resin composition thereof. Specifically, a multilayer film, a multilayer sheet, a multilayer container, a multilayer tube, a multilayer pipe, a multilayer coating film laminate included as a constituent component of a water-based paint, and the like can be given.

  The 1-butene copolymer or polymer composition of the present invention is suitable as a material for forming a container or a nonwoven fabric, for example. Examples of containers include food containers such as frozen storage containers and retort pouches, and bottle containers. Moreover, a medical container, an infusion bag, etc. can be illustrated.

  Since the 1-butene copolymer or polymer composition of the present invention has the above-described properties, it is a tank such as a pipe, a pipe joint, or a blow tank, a sheet, an unstretched or stretched film, a filament, and other various shapes. It can be used as a molded body. Examples of the blow tank include a water supply / hot water supply tank. Among these, pipes and pipe joints are preferable, and used for gas transportation, and more preferably, for water supply / hot water supply, for underfloor heating, for hot water heating, for hot spring piping, for chemical spraying, for drainage, for watering, Used for liquid transport pipes and their fittings for washing machines, dishwashers, toilets, bathrooms, solar systems, mist generators, agriculture, etc. Particularly preferred are pipes and fittings for water and hot water supply. .

EXAMPLES Although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.
[Synthesis of transition metal complexes]
[Production Example 1]
According to polymerization example 4 of WO 2014/050817, (8-octamethylfluoren-12′-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6, 7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride was synthesized. This compound is also referred to as “catalyst (a)”.

[Production Example 2]
With reference to the production example of the catalyst (a), (8- (2,3,6,7-tetramethylfluorene) -12'-yl- (2- (adamantan-1-yl) -8-methyl- 3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene)) zirconium dichloride was synthesized. This compound is also referred to as “catalyst (b)”.

[Production Example 3]
According to Journal of Organometallic Chem. 288 (1985), pp. 63-37, European Patent Application Publication No. 0320762 and Examples, Dimethylsilylene-bis {1- (2-n-propyl-4-phenane) Tolylindenyl)} zirconium dichloride was synthesized. This compound is also referred to as “catalyst (c)”.

[Production Example 4]
According to Production Example 3, dimethylsilylene-bis {1- (2-n-propyl-4-phenanthrylindenyl)} hafnium dichloride was synthesized. This compound is also referred to as “catalyst (d)”.

[Polymerization Example 1] 1-butene / propylene copolymer A magnetic stirrer was placed in a Schlenk tube that had been thoroughly dried and purged with nitrogen, and 2.0 μmol of catalyst (a) was added as a metallocene compound, and a suspension of modified methylaluminoxane was prepared. 300 equivalents to the catalyst (a) (n-hexane solvent, 0.60 mmol in terms of aluminum atom) are added at room temperature with stirring, and then heptane is added in such an amount that the catalyst (a) is 1 μmol / mL, A catalyst solution was prepared.

  A SUS autoclave with an internal volume of 1,500 ml sufficiently dried and purged with nitrogen was charged with 500 mL of heptane as a polymerization solvent and 1.5 mL of a hexane solution of triisobutylaluminum (Al = 0.5 M, 0.75 mmol), Next, 180 g of 1-butene was added while stirring at 850 rpm, and then the temperature was raised to a polymerization temperature of 60 ° C. After adding 8.9 NmL of hydrogen at that temperature, nitrogen was added until the internal pressure of the autoclave reached 0.59 MPaG, and further pressurized with propylene until the total pressure reached 0.6 MPaG.

  The autoclave was charged with the catalyst solution prepared above to start polymerization, and propylene was supplied so as to maintain a total pressure of 0.6 MPaG until the polymerization was stopped, and methanol was added 28 minutes after the start of the polymerization to stop the polymerization. .

  The polymer solution taken out from the cooled / depressurized autoclave was put into methanol, and the polymer was precipitated and collected by filtration. Thereafter, the recovered polymer was dried under reduced pressure at 80 ° C. for 12 hours to obtain a 1-butene / propylene copolymer.

[Polymerization Example 2] 1-Butene Homopolymer A magnetic stirrer is placed in a Schlenk tube that has been sufficiently dried and purged with nitrogen, and 2.0 μmol of catalyst (a) is added as a metallocene compound, and a suspension of modified methylaluminoxane is prepared as a catalyst ( 300 equivalents to a) (n-hexane solvent, 0.60 mmol in terms of aluminum atom), added at room temperature with stirring, and then heptane was added in an amount such that the catalyst (a) was 1 μmol / mL. Was prepared.

  A SUS autoclave with an internal volume of 1,500 ml sufficiently dried and purged with nitrogen was charged with 500 mL of heptane as a polymerization solvent and 1.5 mL of a hexane solution of triisobutylaluminum (Al = 0.5 M, 0.75 mmol), Next, 180 g of 1-butene was added while stirring at 850 rpm, and then the temperature was raised to a polymerization temperature of 60 ° C. After adding 284 NmL of hydrogen at that temperature, nitrogen was added until the internal pressure of the autoclave reached 0.5 MPaG.

The autoclave was charged with the catalyst solution prepared above to start polymerization, and methanol was added 20 minutes after the start of polymerization to stop the polymerization.
The polymer solution taken out from the cooled / depressurized autoclave was put into methanol, and the polymer was precipitated and collected by filtration. Thereafter, the collected polymer was dried under reduced pressure at 80 ° C. for 10 hours to obtain a polymer for evaluation.

[Polymerization Example 3] 1-butene / propylene copolymer 90 g of 1-butene was added, hydrogen was adjusted to 177.5 NmL, and pressurization with nitrogen was performed to an autoclave internal pressure of 0.58 MPaG. 1-butene / propylene copolymer was obtained in the same manner as in Polymerization Example 1 except that the polymerization time was 10 minutes.

[Polymerization Example 4] 1-butene homopolymer The same procedure as in Polymerization Example 2 was conducted except that hydrogen was 17.8 NmL, the pressure in nitrogen was up to 0.5 MPaG and the polymerization time was 30 minutes. A 1-butene homopolymer was obtained.

[Example 1]
Mixture of 1-butene copolymer 70 mass% of 1-butene / propylene copolymer polymerized in polymerization example 1 and 30 mass% of 1-butene homopolymer obtained in polymerization example 2 were mixed, A mixture of butene copolymers was obtained.

[Example 2]
Polymer composition containing a mixture of 1-butene copolymer Example 1 mixture: 0.2 parts by mass of an ethylene polymer as a nucleating agent is added to 100 parts by mass of a 1-butene copolymer. A polymer composition containing a mixture of coalesced was obtained.

[Example 3]
Mixture of 1-butene copolymer 70 mass% of 1-butene / propylene copolymer polymerized in Polymerization Example 1 and 30 mass% of 1-butene / propylene copolymer polymerized in Polymerization Example 3 were mixed, A mixture of 1-butene copolymers was obtained.

[Example 4]
Polymer composition containing a mixture of 1-butene copolymers A mixture of 1-butene copolymers of Example 3: 0.2 parts by mass of an ethylene polymer as a nucleating agent was added to 100 parts by mass. Thus, a polymer composition containing a mixture of 1-butene copolymers was obtained.

[Comparative Example 1]
Mixture of 1-butene copolymer 70 mass% of the 1-butene polymer polymerized in Polymerization Example 4 and 30 mass% of the 1-butene polymer polymerized in Polymerization Example 2 were mixed to obtain a 1-butene copolymer. A coalescence mixture was obtained.

[Comparative Example 2]
Mixture of 1-butene-based copolymer Mixture of 1-butene-based copolymer of Comparative Example 1: 0.2 parts by mass of an ethylene-based polymer as a nucleating agent was added to 100 parts by mass. A polymer composition containing a mixture of butene copolymers was obtained.

[Comparative Example 3]
1-butene homopolymer In Comparative Example 3, propylene is not used, and a known pressure using a Ti-based catalyst described in [Production Example 1] of JP-A-2002-241553 is used except that the total pressure is 0.5 MPaG. The 1-butene homopolymer as a polymer for evaluation was obtained by the polymerization method of the butene polymer.

[Comparative Example 4]
1-butene polymer 1-butene homopolymer obtained in Comparative Example 3: 0.07 parts by mass of EBSA (ethylenebisstearic acid amide, manufactured by Kyoeisha Chemical Co., Ltd.) as a nucleating agent is added to 100 parts by mass, and the composition Got.

[Comparative Example 5]
1-Butene-propylene polymer In Comparative Example 5, a conventionally known butene-based heavy polymer using a Ti-based catalyst described in [Production Example 1] of JP-A-2002-241553 except that the total pressure was 0.5 MPaG. A 1-butene / propylene copolymer was obtained by a polymerization method of the polymer.

[Comparative Example 6]
1-butene / propylene copolymer 1-butene / propylene copolymer obtained in Comparative Example 5: 0.5 parts by mass of an ethylene-based polymer as a nucleating agent was added to 100 parts by mass to obtain a composition. .

[Methods for producing various measurement press sheets]
The mixture of 1-butene copolymers obtained in the examples and comparative examples, using a hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set at 200 ° C., has a residual heat of about 3 to 5 minutes, After pressurizing for 2 minutes, it was compressed (cooled) at 10 MPa for about 5 minutes using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set at 20 ° C., and a 0.5 mm thick, 2 mm thick press sheet (measurement) Sample) was prepared. A 5 mm thick brass plate was used as the hot plate. A mixture of 1-butene copolymer produced by the above method was used for various measurement samples such as DSC and tensile test.

[Measurement conditions for various physical properties]
In the examples and comparative examples, various physical properties of the samples were measured by the following methods.
The results are shown in Table 1.

[Comonomer composition]
A structural unit (comonomer) derived from at least one olefin selected from ethylene in a 1-butene copolymer or a mixture of 1-butene copolymers and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) The content of (unit) was calculated from a ¹³ C-NMR spectrum with the following apparatus and conditions.

Using an AVANCE III cryo-500 type nuclear magnetic resonance apparatus manufactured by Bruker Biospin, the solvent is o-dichlorobenzene / benzene-d ₆ (4/1 v / v) mixed solvent, the sample concentration is 60 mg / 0.6 mL, and the measurement temperature Is 120 ° C, the observation nucleus is ¹³ C (125 MHz), the sequence is single pulse proton broadband decoupling, the pulse width is 5.0 μsec (45 ° pulse), the repetition time is 5.5 seconds, the number of integration is 128 times, butene A side chain methylene signal of 27.5 ppm was measured as a reference value for chemical shift. Using the integral value of the main chain methylene signal, the content of comonomer units was calculated by the following formula.

Comonomer unit content (mol%) = [P / (P + M)] × 100
Here, P represents the total peak area of the comonomer main chain methylene signal, and M represents the total peak area of the 1-butene main chain methylene signal.

[Mmmm fraction]
The mmmm fraction (%) is represented by the following formula.
mmmm fraction (%) = Smmmm / S × 100
Here, in the ¹³ C-NMR spectrum, Smmmm represents the peak area of the butene side chain methylene signal derived from mmmm having a peak top of 27.50 ppm, and S represents the butene side which appears in the range of 29.0 ppm to 25.0 ppm. The total peak area of the chain methylene signal is shown.

[Rr fraction]
The rr fraction (%) is represented by the following formula.
rr fraction (%) = Srr / S × 100
Here, in the ¹³ C-NMR spectrum, Srr indicates the peak area of the butene side chain methylene signal derived from rr that appears in the range of 26.6 ppm to 25.0 ppm, and S appears in the range of 29.0 ppm to 25.0 ppm. , Shows the total peak area of the butene side chain methylene signal.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] (dl / g) of a 1-butene copolymer or a mixture of 1-butene copolymers was measured at 135 ° C. using a decalin solvent. Specifically, about 20 mg of the butene polymer obtained by the above polymerization was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[Η] = lim (ηsp / C) (C → 0)

[Molecular weight (Mn, Mw), molecular weight distribution (Mw / Mn)]
The molecular weight and molecular weight distribution of 1-butene copolymer or a mixture of 1-butene copolymers, etc., are TSKgelGMH ⁶ -HT × 2 and TSKgelGMH ⁶ -HTL × 2 manufactured by Tosoh Corp. The diameter was also measured using a liquid chromatograph (Waters Alliance / GPC2000 type) connected in series with a diameter of 7.5 mm and a length of 300 mm. The mobile phase medium uses o-dichlorobenzene and 0.025% by mass of BHT (Takeda Pharmaceutical) as an antioxidant, the sample concentration is 0.15% (V / W), the flow rate is 1.0 ml / min, and 140 ° C. Measurements were made. As the standard polystyrene, those manufactured by Tosoh Corporation were used for molecular weights of 500 to 20,600,000. Mn, Mw, and Mw / Mn were calculated by analyzing the obtained chromatogram using a calibration curve using a standard polystyrene sample by a known method using data processing software Empower2 manufactured by Waters.

[95% crystal transition completion time]
An exothermic / endothermic curve was obtained using a DSC measuring apparatus (DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the maximum melting peak position at the time of temperature rise was defined as the melting point Tm. Further, the heat of fusion ΔH was calculated from the integrated value of the crystal melting peak.

  The measurement was performed as follows. About 5 mg of a sample was cut out from a 0.5 mm thick press sheet, put in an aluminum pan for measurement, heated from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min, held at 200 ° C. for 5 minutes, and then 10 ° C. The temperature was lowered to 30 ° C. at a cooling rate of / min, held at 30 ° C. for 5 minutes, then heated again from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min, held at 200 ° C. for 5 minutes, and then again The temperature was lowered to 30 ° C. at a cooling rate of 10 ° C./min. The melting peak that appeared during the second temperature increase was defined as the melting point TmII derived from type II crystals.

  The sample that had been allowed to stand at room temperature for 10 days after receiving the above thermal history was re-examined using DSC, and the melting peak that appeared when the sample was heated from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min. The melting point TmI derived from the I-type crystal was taken as ΔH and the heat of fusion based on this melting peak was taken as ΔH. In the above measurement, when a plurality of peaks were observed, the low temperature side peak was assigned as a peak derived from a type II crystal, and the high temperature side peak was assigned as a peak derived from an I type crystal.

  The 95% crystal transition completion time was determined as follows. After receiving the heat history, samples left at room temperature for 8 hours, about 1 day, 3 days, 5 days, 7 days, and 10 days were each heated at a heating rate of 10 ° C./min using DSC. A melting peak that was developed when the temperature was raised from 200C to 200C was observed. The areas of the peaks derived from the I-type crystal and the II-type crystal are divided by the ratio of the peak heights of the respective peaks derived from the I-type crystal and the II-type crystal. The heat of fusion was calculated. The amount of heat of fusion derived from type I crystals is plotted against the elapsed time (a graph connecting the data plots with a straight line), and ΔH is 95% of the value of heat of fusion ΔH 10 days after the crystal transition is considered to be completed. The time to reach the value of was taken as the crystal transition completion time.

[Yield point stress (YS), tensile modulus (YM)]
After placing a 2 mm-thick press sheet for 10 days or longer, a No. 2 1/2 size dumbbell-shaped test piece was prepared in accordance with JIS K7113, and the tensile speed was 30 mm / in with an Intesco tensile tester equipped with a thermostatic bath. A tensile test was performed under the conditions of min, measurement temperatures of 23 ° C. and 95 ° C., and yield point stress (YS) and tensile elastic modulus (YM) were measured.

[Capillograph]
Viscosity measurement and moldability evaluation were performed with a Toyo Seiki Capillograph.
The barrel diameter is 10 mm, the capillary length is 22 mm, and the capillary diameter is 1 mm. Using a 4 mmφ tube die, the shear stress was measured when the extrusion speed was changed to 1, 2, 5, 10, 20, 50, 100, 200, 500 mm / min at 190 ° C.

  Further, as the moldability evaluation, the rate at which melt fracture occurs when the extrusion speed was changed to 5, 10, 15, 20, 30, 50, 75, 100, 200 mm / min was observed.

Claims (15)

The content of the structural unit derived from 1-butene is 80.0 to 99.9 mol%, the structural unit derived from at least one olefin selected from ethylene and an α-olefin other than 1-butene having 3 to 20 carbon atoms. The total content (K) is 0.1 to 20.0 mol% (however, the total of the content of the structural unit derived from 1-butene and the total content (K) of the structural unit derived from olefin is 100 mol) %) And the following requirements (i) to (iii):
(I) The pentad isotacticity (mmmm) measured by ¹³ C-NMR is 94.0% or more and 99.9% or less.
(Ii) The syndiotactic triad fraction (rr) measured by ¹³ C-NMR is 1.5% or less.
(Iii) The intrinsic viscosity [η] in the decalin solvent at 135 ° C. is in the range of 0.5 to 5.5 dl / g.   The content of the structural unit derived from 1-butene is 90.0 to 99.9 mol%, and the total content (K) is 0.1 to 10.0 mol%. Butene copolymer.   The content of structural units derived from 1-butene is 90.0 to 96.2 mol%, and the total content (K) of structural units derived from olefins is 3.8 to 10.0 mol%. The 1-butene copolymer according to 1. The 1-butene copolymer according to any one of claims 1 to 3, further satisfying the following requirement (iv):
(Iv) The ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) measured by gel permeation chromatography (GPC) is in the range of 1.5 to 20.0. Furthermore, the 1-butene copolymer of any one of Claims 1-4 which satisfy | fills the following requirements (v).
(V) The yield point stress (YS) measured by a tensile test at a tensile speed of 30 mm / min and a measurement temperature of 23 ° C. is 16.0 MPa or more in accordance with JIS K7113. Furthermore, the 1-butene copolymer of any one of Claims 1-5 which satisfy | fills the following requirements (vi).
(Vi) The 95% crystal transition completion time measured by a differential scanning calorimeter is 45 hours or less. The 1-butene copolymer according to any one of claims 1 to 6, wherein at least one olefin selected from α-olefins other than ethylene and 1 to butene having 3 to 20 carbon atoms is propylene.   The 1-butene copolymer according to any one of claims 1 to 6, wherein at least one olefin selected from ethylene and an α-olefin other than 1 to butene having 3 to 20 carbon atoms is ethylene.   The content of the structural unit derived from 1-butene is 90.0 to 97.0 mol%, the total content (K) is 3.0 to 10.0 mol%, and 135 ° C, a decalin solvent The 1-butene copolymer according to claim 1, comprising a polymer having an intrinsic viscosity [η] in the range of 2.0 to 5.5 dl / g.   The 1-butene copolymer according to claim 9, further comprising a 1-butene homopolymer having an intrinsic viscosity [η] in a decalin solvent at 135 ° C in a range of 0.5 to 1.5 dl / g.   The polymer composition containing the 1-butene copolymer of any one of Claims 1-10.   The polymer composition which contains a nucleating agent in the 1-butene copolymer of any one of Claims 1-10.   The composition whose shear viscosity is 65,000 Pa or less in the polymer composition containing the 1-butene copolymer of Claim 11 or 12 in the 190 degreeC measurement by a caprograph.   The molded object formed from the 1-butene copolymer of any one of Claims 1-10, or the polymer composition of any one of Claims 11-13.   The molded body according to claim 14, which is a pipe or a pipe joint.