JP2017197651A - Modified olefin-based polymer and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified olefin-based polymer having excellent fluidity and capable of being usable preferably in applications such as a tackiness agent, an adhesive or a paint, and a production method thereof.SOLUTION: A modified olefin-based polymer having (1) an intrinsic viscosity (η) of 0.01-2.5 dl/g, (2) a melting point (Tm-D) that is not observed or of 0-100°C, (3)a half-crystallization time of 3 minutes or more or a crystallization peak that is not observed, (4) an amount of fusing endotherm (ΔH-D) of 0-80 J/g, (5) an acid value of 10-250 mgKOH/g, and (6) a molecular weight distribution Mw/Mn of 2.4-10.0.SELECTED DRAWING: None

Description

  The present invention relates to a modified olefin polymer and a method for producing the same, and more particularly to a modified olefin polymer that can be suitably used for applications such as pressure-sensitive adhesives and adhesives, and a method for producing the same.

Since polyolefin is an inexpensive material, it is used for various home appliances, packaging, automobile parts and the like. However, since there are various uses, it is necessary to adjust the hardness of the polymer and the affinity with other materials according to the use.
As a method for controlling the crystallinity and hardness of a polymer, it is known to control the stereoregularity of the polymer in the copolymerization of propylene, ethylene, and butene or the homopolymerization of propylene and butene-1 (for example, Patent Document 1). And 2). In addition, it is known that a polymer is modified with maleic anhydride, acrylic acid ester, chlorine, or the like in order to give polyolefin an affinity for a polar material (see, for example, Patent Document 3).

  It is also known to widen the molecular weight distribution of the polymer in order to improve the fluidity of the polymer and improve the coating property. It is generally known that the molecular weight distribution becomes wider when a Ziegler-Natta catalyst is used, and becomes narrower when a homogeneous catalyst (single site catalyst) is used.

  However, when conventional catalysts such as Ziegler-Natta catalysts are used, the molecular weight distribution of the polymer is widened, but the distribution of the stereoregularity of the polymer is also widened like a mixture of a highly stereoregular polymer and an amorphous polymer. End up. When such a polymer is added to an adhesive or paint, a component that becomes insoluble in the adhesive or paint is generated, which adversely affects adhesive strength, coating film uniformity, and the like.

JP 11-193309 A Japanese Patent No. 4242498 Japanese Patent No. 4260635

  The problem to be solved by the present invention is to provide a modified olefin polymer that has good fluidity and can be suitably used for applications such as pressure-sensitive adhesives, adhesives, and paints, and a method for producing the same.

The present invention relates to the following modified olefin polymers and methods for producing the same.
<1> A modified olefin polymer satisfying the following (1) to (6).
(1) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 dL / g or more and 2.5 dL / g or less.
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the observed peak is not observed or is 0 ° C. or higher and 100 ° C. or lower.
(3) The half crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or the crystallization peak measured with a differential scanning calorimeter (DSC) is not observed.
(4) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. The amount of heat (ΔH−D) is 0 J / g or more and 80 J / g or less.
(5) The acid value is 10 mgKOH / g or more and 250 mgKOH / g or less.
(6) The molecular weight distribution Mw / Mn is 2.4 or more and 10.0 or less.
<2> 50 mol% or more of the monomer constituting the modified olefin polymer is at least one α-olefin monomer selected from the group consisting of propylene, 1-butene and an α-olefin having 6 to 12 carbon atoms. The modified olefin polymer according to the above <1>.
<3> The modified olefin polymer according to <1> or <2>, further satisfying the following (7).
(7) Mesopentad fraction [mmmm] is 42 to 90 mol%.
<4> A method for producing the modified olefin polymer according to any one of <1> to <3> above,
A modified olefin system comprising a step of producing an olefin polymer by polymerizing an olefin monomer using a metallocene catalyst, and a step of modifying the obtained olefin polymer to obtain a modified olefin polymer. A method for producing a polymer.
<5> The metallocene catalyst is
(I) a transition metal compound represented by the following general formula (I), and (ii) (ii-1) reacting with the transition metal compound of component (i) or a derivative thereof to form an ionic complex. The method for producing a modified olefin polymer according to the above <4>, comprising a compound that can be used and (ii-2) one or more components selected from aluminoxane.

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure through A ¹ and A ² They may be the same or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]
<6> The method for producing a modified olefin polymer according to the above <5>, wherein the metallocene catalyst contains two or more transition metal compounds represented by the general formula (I).
<7> In any one of the above items <4> to <6>, in the step of producing the olefin polymer, a temperature difference between a polymerization temperature at the start of polymerization and a polymerization temperature at a later stage of polymerization is 5 ° C. or more. The manufacturing method of the modified olefin polymer as described in one.
<8> In the step of producing the olefin polymer, hydrogen is added during polymerization, and a hydrogen concentration difference (partial pressure difference) between the hydrogen concentration at the start of polymerization and the hydrogen concentration at the late stage of polymerization is 0.01 MPa or more. The method for producing a modified olefin polymer according to any one of <4> to <7> above.
<9> In the step of producing the olefin polymer, any one of the above <4> to <8>, wherein the concentration ratio of the olefin monomer concentration at the start of polymerization and the olefin monomer concentration at the late stage of polymerization is 20% or more The manufacturing method of the modified olefin polymer as described in any one.
<10> An adhesive containing the modified olefin polymer according to any one of <1> to <3>.
<11> A paint containing the modified olefin polymer according to any one of <1> to <3>.
<12> A sealing material comprising the modified olefin polymer according to any one of the above items <1> to <3>.
<13> An ink composition comprising the modified olefin polymer according to any one of the above items <1> to <3>.

  The modified olefin polymer of the present invention has good fluidity and can be suitably used for applications such as pressure-sensitive adhesives, adhesives and paints. In particular, in various adhesives or pressure-sensitive adhesives such as urethane, modified silicone, acrylic, and hot melt, ink, paint, etc., it can be suitably used as a modifier for improving the affinity for polyolefin.

  Hereinafter, the present invention will be described in detail. In this specification, the term “A to B” relating to the description of numerical values means “A or more and B or less” (when A <B) or “A or less and B or more” (when A> B). . Moreover, in this invention, the combination of a preferable aspect is a more preferable aspect.

[Modified olefin polymer]
The modified olefin polymer of the present invention satisfies the following (1) to (6), and preferably satisfies the following (1) to (7).
(1) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 dL / g or more and 2.5 dL / g or less.
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the observed peak is not observed or is 0 ° C. or higher and 100 ° C. or lower.
(3) The half crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or the crystallization peak measured with a differential scanning calorimeter (DSC) is not observed.
(4) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. The amount of heat (ΔH−D) is 0 J / g or more and 80 J / g or less.
(5) The acid value is 10 mgKOH / g or more and 250 mgKOH / g or less.
(6) The molecular weight distribution Mw / Mn is 2.4 or more and 10.0 or less.
(7) Mesopentad fraction [mmmm] is 42 to 90 mol%.

(1) Intrinsic viscosity [η]
For the modified olefin polymer, the intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 2.5 dL / g, preferably 0.10 to 2.0 dL / g, more preferably. It is 0.10-1.8 dL / g, More preferably, it is 0.15-1.5 dL / g, More preferably, it is 0.3-1.0 dL / g. When the intrinsic viscosity of the modified polyolefin is in the above range, it is possible to prevent difficulty in handling due to excessive stickiness and poor fluidity.
The intrinsic viscosity [η] is calculated by measuring the reduced viscosity (η _SP / c) in tetralin at 135 ° C. with an Ubbelohde viscometer and using the following formula (Huggins formula).
η _SP / c = [η] + K [η] ² c
η _SP / c (dL / g): Reduced viscosity [η] (dL / g): Intrinsic viscosity c (g / dL): Polymer viscosity K = 0.35 (Haggins constant)

(2) Melting point (Tm-D)
The melting point (Tm-D) of the modified olefin polymer is not observed or is 0 to 100 ° C. from the viewpoint of fluidity. When the melting point is observed, from the same viewpoint, it is preferably 50 to 100 ° C, more preferably 55 to 90 ° C, and further preferably 57 to 80 ° C.
In the present invention, a differential scanning calorimeter (manufactured by Perkin Elmer, trade name: “DSC-7”) was used, and 10 mg of a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then 10 ° C./min. The peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at is defined as the melting point (Tm-D).
The melting point (Tm-D) can be controlled by appropriately adjusting the monomer concentration and reaction pressure.

(3) Semi-crystallization time The semi-crystallization time measured with a differential scanning calorimeter (DSC) of the modified olefin polymer is 3 minutes or more from the viewpoint of slow crystallization speed, or the differential scanning calorific value. The crystallization peak measured with a meter (DSC) is not observed. Preferably it is 10 minutes or more, More preferably, it is 30 minutes or more. When the crystallization rate is so slow that the half crystallization time exceeds 60 minutes, a clear crystallization peak may not be observed.
The “half crystallization time” in the present invention indicates that measured by the following measurement method.

<Measuring method of semi-crystallization time>
Using a differential scanning calorimeter (DSC) (manufactured by Perkin Elmer, trade name: “DSC-7”), the measurement is performed by the following method.
(1) 10 mg of a sample is held at 25 ° C. for 5 minutes, heated to 220 ° C. at 320 ° C./second and held for 5 minutes. By cooling to 25 ° C. at 320 ° C./second and holding for 300 minutes, the time change of the calorific value in the isothermal crystallization process is measured.
(2) When the integrated value of the calorific value from the start of isothermal crystallization to the completion of crystallization is 100%, the time from the start of isothermal crystallization until the integrated value of the calorific value becomes 50% is semi-crystallized. Define as time.

(4) Melting endotherm (ΔH−D)
The melting endotherm (ΔH-D) of the modified olefin polymer is 0 to 80 J / g, preferably 10 to 70 J / g, more preferably 20 to 60 J / g, from the viewpoint of slow crystallization rate. Preferably it is 30-50 J / g.
In the present invention, the melting endotherm (ΔH-D) is determined by using a differential scanning calorimeter (DSC), holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then increasing the temperature at 10 ° C./min. Obtain the area surrounded by the line containing the peak of the melting endotherm curve obtained by this, the line on the low temperature side without any change in calorie, and the line on the high temperature side without any change in calorie (referred to as the base line) Is calculated by

(5) Acid value The acid value of the modified olefin polymer is from 10 to 250 mgKOH / g, preferably from 10 to 200 mgKOH / g, more preferably from 10 to 100 mgKOH, from the viewpoint of the effect of modification and the viewpoint of fluidity. / G, more preferably 10 to 50 mg KOH / g.
In the present invention, the acid value is measured based on JIS K2501: 2003.

(6) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) of the modified olefin polymer is 2.4 to 10.0, preferably 2.4 to 7.0, and more preferably 3.0 to 7.0. If the molecular weight distribution is less than 2.4, the fluidity is deteriorated, and if it exceeds 10.0, a very low molecular weight body or a very large molecular weight component is increased, resulting in a decrease in adhesive force or a gel. .

  Further, the weight average molecular weight (Mw) of the modified olefin polymer is preferably 3,000 or more, more preferably 5,000 or more, and further preferably 7,000 or more, from the viewpoint of mechanical strength and processability. , Preferably 200,000 or less, more preferably 150,000 or less.

  In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those in terms of polystyrene measured with the apparatus and conditions described in the examples, and the molecular weight distribution (Mw / Mn) is the weight average of these. It is a value calculated from the molecular weight (Mw) and the number average molecular weight (Mn).

(7) Mesopentad fraction [mmmm]
The mesopentad fraction [mmmm] is an index representing the stereoregularity of the olefin polymer, and the stereoregularity increases as the mesopentad fraction [mmmm] increases.
When the olefin polymer before modification is a homopolymer, the mesopentad fraction [mmmm] of the modified olefin polymer is preferably 42 to 90 mol%, more preferably 43 to 85 mol%. When the mesopentad fraction [mmmm] is within the range, the adhesive strength and wear resistance are improved, and the solubility in the substrate is good.

  The modified olefin polymer of the present invention preferably further satisfies the following (8) to (11).

(8) [rrrr] / (1- [mmmm])
The value of [rrrr] / (1- [mmmm]) is obtained from the mesopentad fraction [mmmm] and the racemic pentad fraction [rrrr] and is an index indicating the uniformity of the regular distribution of the olefin polymer. .
When the olefin polymer before modification is a homopolymer, the value of [rrrr] / (1- [mmmm]) of the modified olefin polymer is preferably 0.1 or less, more preferably It is 0.001-0.05, More preferably, it is 0.001-0.04, Most preferably, it is 0.01-0.04. When the value is within the range, low crystal components close to amorphous are suppressed, and stickiness after crystallization is suppressed.

(9) Racemic meso racemic meso pentad fraction [rmrm]
The racemic meso racemic meso pentad fraction [rmrm] is an index representing the randomness of the stereoregularity of the olefin polymer, and the greater the value, the greater the randomness of the olefin polymer.
The racemic meso racemic meso pentad fraction [rmrm] of the modified olefin polymer is preferably more than 1.0 mol%, more preferably 1.3 mol% or more, still more preferably 1.5 mol% or more. . The upper limit is usually preferably about 10 mol%, more preferably 7 mol%, still more preferably 5 mol%, and particularly preferably 4 mol%. If the value is within this range, the randomness increases and the crystallinity of the modified olefin polymer decreases, and by adding to the adhesive, the wettability of the adhesive to the adherend is improved, and the adhesive strength Can be raised.

(10) Mesotriad fraction [mm]
When the olefin polymer before modification is a homopolymer, the mesotriad fraction [mm] of the modified olefin polymer is preferably 55 to 90 mol%, more preferably 60 to 88 mol%, still more preferably. Is 65 to 85 mol%. The mesotriad fraction [mm] is a stereoregularity index indicating isotacticity, and if the mesotriad fraction [mm] is within the range, the crystallization rate is low without inferior handleability due to stickiness or the like. Become.

(11) [mm] × [rr] / [mr] ²
The value of [mm] × [rr] / [mr] ² is an index of randomness of the olefin polymer, and the closer to 1, the higher the randomness. The value of [mm] × [rr] / [mr] ² of the modified olefin polymer is preferably 4.0 or less, more preferably 1.0 to 4.0. When the value is within this range, the crystallinity of the modified olefin polymer is lowered, and by adding to the adhesive, the wettability of the adhesive to the adherend is improved and the adhesive strength is increased. In addition, the unit of [mm], [rr], and [mr] in the above is mol%.

Here, the mesopentad fraction [mmmm], the racemic pentad fraction [rrrr], the racemic mesoracemi mesopentad fraction [rmrm], the mesotriad fraction [mm], the racemic triad fraction [rr], and the mesoracemi triad fraction The rate [mr] is measured using ¹³ C-NMR in accordance with the method proposed by A. Zambelli et al. In “Macromolecules, 6,925 (1973)”.

  When the olefin polymer before modification is a polyolefin mainly composed of polypropylene (90% by mass or more of propylene), the mesopentad fraction [mmmm] of the modified olefin polymer can be measured by the following method. .

Device: JEOL Ltd., JNM-EX400 type ¹³ C-NMR device Method: Proton complete decoupling method Concentration: 220 mg / mL
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

The method for calculating the mesopentad fraction M is as follows.
M = (m / S) × 100
R = (γ / S) × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

When the olefin polymer before modification is a polyolefin containing polybutene as a main component (butene 90% by mass or more), the mesotriad fraction [mm], mesopentad fraction [mmmm] of the modified olefin polymer, racemic pen Tad fraction [rrrr] and racemic meso racemic meso pentad fraction [rmrm] are reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It can be measured according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
That is, the mesopentad fraction in the poly (1-butene) molecule can be determined by measuring the signals of methylene group and methine group using ¹³ C-nuclear magnetic resonance spectrum.
The measurement of ¹³ C-nuclear magnetic resonance spectrum can be performed with the above apparatus and conditions.

When the olefin polymer before modification is a polyolefin mainly composed of an α-olefin having 6 to 28 carbon atoms, the mesotriad fraction [mm], mesopentad fraction [mmmm] of the modified olefin polymer, racemic The pentad fraction [rrrr] and the racemic meso racemic meso pentad fraction [rmrm] can be measured according to the method proposed by Asakura et al. In “Macromolecules, 24, 2334 (1991)”.
The measurement of ¹³ C-nuclear magnetic resonance spectrum can be performed with the above apparatus and conditions.

  The modified olefin polymer of this invention is comprised from the organic acid and olefin monomer which are mentioned later, and an olefin monomer is 1 or more types of monomers chosen from ethylene and a C3-C28 alpha olefin. Examples of the α-olefin having 3 to 28 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene and 1- Examples include dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-icocene. The α-olefin monomer is preferably an α-olefin having 3 to 24 carbon atoms, more preferably an α-olefin having 3 to 12 carbon atoms, particularly preferably an α-olefin having 3 carbon atoms (that is, propylene), and 4 carbon atoms. An α-olefin (ie, 1-butene) and an α-olefin having 6 to 12 carbon atoms.

50 mol% or more of the α-olefin structural unit in the modified olefin polymer is at least one α-olefin monomer selected from the group consisting of propylene, 1-butene and an α-olefin having 6 to 12 carbon atoms. More preferably, it is 65 mol% or more, More preferably, it is 75 mol% or more, More preferably, it is 80 mol% or more.
The modified olefin polymer used in the present invention may contain monomers other than organic acids and α-olefins as long as the effects of the present invention are not impaired.

[Production Method of Modified Olefin Polymer]
The modified olefin polymer of the present invention can be produced by modifying the olefin polymer by a modification treatment using a radical initiator and an organic acid. In particular, as a method for producing a modified olefin polymer, a process for producing an olefin polymer by polymerizing an olefin monomer using a metallocene catalyst, and a modification treatment of the obtained olefin polymer for modification. A method including a step of obtaining an olefin polymer is preferred.

(Process for producing olefin polymer)
The olefin polymer is obtained by polymerizing one or more monomers selected from ethylene and an α-olefin having 3 to 28 carbon atoms. Specific examples of the α-olefin having 3 to 28 carbon atoms are as described above. The monomer of the olefin polymer used for the production of the modified olefin polymer is preferably an α-olefin having 3 to 24 carbon atoms, more preferably an α-olefin having 3 to 12 carbon atoms, still more preferably 3 carbon atoms. An α-olefin (ie, propylene), a C 4 α-olefin (ie, 1-butene) and a C 6-12 α-olefin.

  The olefin polymer used for the production of the modified olefin polymer can be produced, for example, using a metallocene catalyst as described in International Publication No. 2003/087172. In particular, those using a transition metal compound in which a ligand forms a cross-linked structure via a cross-linking group are preferred, and in particular, a transition metal compound that forms a cross-linked structure via two cross-linking groups and Metallocene catalysts obtained by combining promoters are preferred.

Particularly preferred metallocene catalysts are:
(I) a transition metal compound represented by the following general formula (I), and (ii) (ii-1) reacting with the transition metal compound of component (i) or a derivative thereof to form an ionic complex. And (ii-2) a component selected from one or more of aluminoxane.

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure through A ¹ and A ² They may be the same or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]

  As the transition metal compound (i), a ligand is preferably a (1,2 ′) (2,1 ′) double-bridged transition metal compound, such as (1,2′-dimethylsilylene) ( 2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) ) -Bisindenylzirconium dichloride.

  In the present invention, from the viewpoint of obtaining an olefin polymer having a wide molecular weight distribution, the metallocene catalyst preferably contains two or more transition metal compounds of the above component (i), and a transition metal compound from which a high molecular weight polymer can be obtained. And a transition metal compound capable of producing a low molecular weight polymer are preferably used in combination. For example, a transition metal compound in which a relatively small substituent such as a hydrogen atom or a methyl group is bonded to the 3-position of the indenyl group, and a relatively large substituent such as a normal butyl group or a trimethylsilyl group is bonded to the 3-position of the indenyl group. It is preferable to use together with the transition metal compound which has couple | bonded.

  Specific examples of the compound of component (ii-1) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl tetraphenylborate (tri- n-butyl) ammonium, benzyl tetraphenylborate (tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), trikis (tetrafluorophenyl) borate triethyla Monium, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) borate Benzyl tetrakis (pentafluorophenyl) ammonium borate (tri-n-butyl), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid Methylanilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium, tetrakis (pentafluoropheny L) Trimethylanilinium borate, methyl pyridinium tetrakis (pentafluorophenyl) borate, benzyl pyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylaniline borate Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, Trakis (pentafluorophenyl) borate ferrocenium, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, tetrakis (pentafluorophenyl) silver borate, Tetrakis (pentafluorophenyl) triborate borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, hexa Examples thereof include silver fluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

  Examples of the aluminoxane as the component (ii-2) include known chain aluminoxanes and cyclic aluminoxanes.

  Trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride, etc. These organoaluminum compounds may be used in combination to produce a propylene polymer.

The use ratio of the catalyst with respect to the reaction raw material is preferably 0.01 to 20 μmol, preferably 0.1 to 15 μmol, more preferably 0.5 to 10 μmol in terms of organometallic complex per 100 g of the raw material monomer.
Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 20 MPa (G), particularly preferably normal pressure to 10 MPa (G).

  Examples of the method for adjusting the molecular weight of the polymer include selection of the type of each catalyst component, the amount used, the polymerization temperature, and polymerization in the presence of hydrogen.

  In the present invention, an olefin polymer having a wide molecular weight distribution can be obtained by controlling the reaction conditions at the start of polymerization and the reaction conditions at the latter stage of polymerization. Here, in the present invention, the “late polymerization period” means the time point when the polymer production amount exceeds 50% by mass and the subsequent time when the total mass of the finally obtained polymer is 100% by mass. The polymer production amount can be measured by sampling the reaction solution during the polymerization as needed.

  In the present invention, from the viewpoint of obtaining an olefin polymer having a wide molecular weight distribution, it is preferable to change the monomer concentration between the start of polymerization and the late stage of polymerization. The concentration ratio between the olefin monomer concentration at the start of polymerization and the olefin monomer concentration at the late stage of polymerization is preferably 20% or more, more preferably 30% or more, and further preferably 40% or more. If the concentration ratio of the olefin monomer at the start of polymerization and the late stage of polymerization is 20% or more, an olefin polymer having a wide molecular weight distribution can be obtained. The olefin monomer concentration is the concentration of the olefin monomer with respect to the total weight of the solvent, polymer, and olefin monomer added. In the case of batch polymerization, the monomer concentration decreases with time. The concentration in the latter stage of polymerization is the average concentration of each.

  The polymerization temperature is usually 0 to 200 ° C, preferably 20 to 150 ° C, more preferably 40 to 100 ° C. In the present invention, from the viewpoint of obtaining an olefin polymer having a wide molecular weight distribution, the temperature difference between the polymerization temperature at the start of polymerization and the polymerization temperature at the late stage of polymerization is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and still more preferably. Is 15 ° C. or higher. If the temperature difference between the polymerization temperature at the start of polymerization and the polymerization temperature at the later stage of polymerization is 5 ° C. or more, the difference in molecular weight between the polymer produced at the start of polymerization and the later stage of polymerization will be large, and the olefin weight having a wide molecular weight distribution will be large. Coalescence can be obtained. Although the upper limit of a polymerization temperature difference is not specifically limited, For example, it is 30 degreeC.

  When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Moreover, you may use monomers, such as an alpha olefin, as a solvent. Depending on the polymerization method, it can be carried out without solvent.

  When performing polymerization in the presence of hydrogen, in the present invention, from the viewpoint of obtaining an olefin polymer having a wide molecular weight distribution, it is preferable to change the hydrogen concentration between the start of polymerization and the late stage of polymerization. The difference in hydrogen concentration between the start of polymerization and the late stage of polymerization is preferably 0.01 MPa or more, more preferably 0.05 MPa or more, and still more preferably 0.10 MPa or more as partial pressure. When the hydrogen concentration difference is 0.01 MPa or more, an olefin polymer having a wide molecular weight distribution can be obtained. In addition, although the upper limit of a hydrogen concentration difference is not specifically limited, For example, it is 5 MPa.

(Step of obtaining a modified olefin polymer by modification treatment)
The modified olefin polymer of the present invention can be produced by modifying the olefin polymer. Examples of the modification treatment include a method of acid-modifying an olefin polymer using a radical initiator and an organic acid. As the organic acid used for the modification treatment, an unsaturated carboxylic acid or a derivative thereof can be used. In addition, polar groups can be imparted to the olefin polymer only by air oxidation without a radical initiator or organic acid.

In the case of acid modification with an organic acid, the presence of active hydrogen-free vinylamine or (meth) acrylic acid ester allows the compound to add or graft to the radical generated on the polyolefin together with the organic acid, so that only the polarity is obtained. In addition, the compatibility of the modified olefin polymer with the polyurethane or active hydrogen compound can be increased from the structural aspect.
For example, an ester polyol or polyurethane may have higher compatibility by adding an acrylic acid ester or a methacrylic acid ester. In addition, the coexistence of an active hydrogen-free vinylamine may impart a higher compatibility with a urethane compound by imparting an interaction with a urethane bond or a urea bond often present in urethane without side reactions.
As (meth) acrylic acid ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate Etc.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid and the like. In addition, as derivatives thereof, there are acid hydrates, esters, amides, imides, metal salts, etc., for example, maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, Examples thereof include butyl acrylate, 2-ethylhexyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate. Among these, maleic anhydride and acrylic acid are particularly preferable. Moreover, these may be used independently and may be used in combination of 2 or more types.

  On the other hand, the radical initiator is not particularly limited, and is appropriately selected from conventionally known radical initiators such as various organic peroxides, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Among these, organic peroxides are preferable.

  Examples of the organic peroxide include dibenzoyl peroxide, di-8,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di (2,4-dichlorobenzoyl) peroxide. Diacyl peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t- Butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 , Α, α′-bis (t-butylperoxy) diisopropylbenzene Peroxides, peroxyketals such as 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxy Alkyl peresters such as octoate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, Examples thereof include peroxycarbonates such as di-sec-butyl peroxydicarbonate and t-butylperoxyisopropyl carbonate. Of these, dialkyl peroxides are preferred. Moreover, these may be used individually by 1 type and may be used in combination of 2 or more types.

  Specific examples of these commercially available organic peroxides include Perhexin 25B, Perbutyl D, Perbutyl C, Perhexa 25B, Park Mill D, Perbutyl P, Perbutyl H, Perhexyl H, Park Mill H manufactured by NOF Corporation. Perocta H, Parkmill P, Permenta H, Perbutyl SM, Permec N, Peromer AC, Perhexa V, Perhexa 22, Perhexa CD, Perhexa A, Perhexa C, Perhexa 3M, Perhexa HC, Perhexa TMH, Perbutyl IF, Perbutyl Z, Perbutyl A, perhexyl Z, perhexa 25Z, perbutyl E, perbutyl L, perhexa 25MT, perbutyl I, perbutyl 355, perbutyl MA, perhexyl I, perbutyl IB, perbutyl O, perhexyl O, percyclo O, -Hexa 250, Perocta O, Perbutyl PV, Perhexyl PV, Perbutyl ND, Perhexyl ND, Percyclo ND, Perocta ND, Park Mill ND, Dyper ND, Parroyl SOP, Parroyl OPP, Parroyl MBP, Parroyl EEP, Parroyl IPP, Parroyl NPP, Parroyl TCP , Parroyl IB, Parroyl SA, Parroyl S, Parroyl O, Parroyl L, Parroyl 355, Nyper BW, Nyper BMT, Nyper CS (all are trade names).

  There is no restriction | limiting in particular as the usage-amount of the said organic acid and radical initiator, Although it selects suitably according to the desired physical property of the target modified olefin polymer, with respect to 100 mass parts of olefin polymers to be used, The organic acid is usually used in the range of 0.1 to 50 parts by mass, preferably 0.1 to 30 parts by mass, while the radical initiator is usually 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass. Used in the range of parts.

  Although there is no restriction | limiting in particular as the modification method by an organic acid, For example, a propylene-type polymer, the said organic acid, and a radical initiator are 120-300 degreeC using a roll mill, a Banbury mixer, an extruder, etc., Preferably Is a method of melting and kneading and reacting at a temperature of about 140 to 250 ° C. for 0.01 to 0.5 hours. Moreover, you may make it react for 0.1 to 2 hours at the temperature of about -50-300 degreeC, Preferably about 40-180 degreeC in the organic solvent or the conditions of a non-solvent.

The organic solvent is not particularly limited, but hydrocarbon solvents such as butane, pentane, hexane, cyclohexane, and toluene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and liquefied α-olefin are used. be able to.
In the case of using an organic solvent, the amount used is preferably such that the polymer concentration is 50 to 95% by mass from the viewpoint of the reaction efficiency of the modifier.

Moreover, in this invention, in order to raise the efficiency of this organic acid modification | denaturation, it can carry out in presence of styrene compounds, such as styrene and (alpha) -methylstyrene. Moreover, the usage-amount is 0.1-10 mass parts normally with respect to 100 mass parts of olefinic polymers, Preferably it is the range of 0.1-5 mass parts.
Styrenic compounds are more reactive with radicals than organic acids, so they easily react with radicals generated on polyolefins, and can react with organic acids efficiently by reacting with organic acids. It becomes possible.

  The amount of acid modification (modified amount with an organic acid) is preferably 0.1 to 50% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 10% by mass. If the amount of acid modification is within the range, the compatibility with polyol and polyurethane can be improved.

[Uses of modified olefin polymers]
The modified olefin polymer of the present invention can be suitably used as an adhesive, a pressure-sensitive adhesive, a paint, a sealing material, an ink composition and the like. Adhesives, pressure-sensitive adhesives, paints, sealants and ink compositions containing the modified olefin polymer of the present invention have good affinity for polyolefin substrates, and therefore have excellent adhesion to polyolefin substrates. Be expected.

  Adhesives, pressure-sensitive adhesives, paints, sealing materials, ink compositions and the like to which the modified olefin polymer of the present invention can be applied are not particularly limited. For example, the modified olefin polymer of the present invention can be suitably used as a modifier for various urethane-based, modified silicone-based, acrylic-based, and hot-melt adhesives or pressure-sensitive adhesives.

The content of the modified olefin polymer of the present invention in the adhesive, pressure-sensitive adhesive or sealing material is preferably 1 to 30% by mass, more preferably 1 to 20%, based on the total mass, from the viewpoints of adhesiveness and adhesion. It is 1 mass%, More preferably, it is 1-10 mass%.
In addition, the content of the modified olefin polymer of the present invention in the paint or ink composition is preferably 0.01 to 20% by mass, more preferably 0.8%, based on the total mass, from the viewpoints of adhesion and adhesion. 1-10 mass%, More preferably, it is 0.5-5 mass%.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

<Intrinsic viscosity [η]>
Viscometer (trade name: “VMR-053U-PC · F01”, manufactured by Kogyo Co., Ltd.), Ubbelohde viscometer (time volume: 2-3 mL, capillary diameter: 0.44-0.48 mm), A solution of 0.02 to 0.16 g / dL was measured at 135 ° C. using tetralin as a solvent.

<DSC measurement>
(1) Melting point (Tm-D), glass transition temperature (Tg) and melting endotherm (ΔH-D)
By using a differential scanning calorimeter (manufactured by Perkin Elmer, trade name: “DSC-7”), 10 mg of a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. The melting endotherm (ΔH−D) was determined from the obtained melting endothermic curve. Moreover, melting | fusing point (Tm-D) was calculated | required from the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve.
Note that the melting endotherm (ΔH-D) includes the peak of the melting endotherm curve obtained with the line connecting the low-temperature point with no heat change and the high-temperature point with no heat change as the baseline. It calculated by calculating | requiring the area enclosed by a line part and the said base line.

(2) Semi-crystallization time Using a differential scanning calorimeter (manufactured by Perkin Elmer, trade name: “DSC-7”), 10 mg of a sample is held at 25 ° C. for 5 minutes, and is adjusted to 220 ° C. at 320 ° C./second. The temperature was raised and held for 5 minutes, then cooled to 25 ° C. at 320 ° C./second and held for 5 hours, whereby the time change of the calorific value in the isothermal crystallization process was measured. Assuming that the integrated value of the calorific value from the start of isothermal crystallization to the completion of crystallization is 100%, the time from the start of isothermal crystallization until the integrated value of the calorific value becomes 50% is obtained as the semi-crystallization time. It was.

<Acid value>
The acid value was measured based on JIS K2501: 2003.

<GPC measurement>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method to determine the molecular weight distribution (Mw / Mn). For the measurement, the following apparatus and conditions were used, and polystyrene-reduced weight average molecular weight and number average molecular weight were obtained. The molecular weight distribution (Mw / Mn) is a value calculated from these weight average molecular weight (Mw) and number average molecular weight (Mn).
(GPC measuring device)
Column: “TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation
Detector: RI detection for liquid chromatogram “WATERS 150C” manufactured by Waters Corporation
(Measurement condition)
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL
Injection volume: 160 μL
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

<NMR measurement>
The ¹³ C-NMR spectrum was measured with the following apparatus and conditions, and [mmmm], [rrrr], [rmrm], [mm], [rr] and [mr] were determined. In addition, the attribution of the peak followed the method proposed by A. Zambelli et al. In “Macromolecules, 8, 687 (1975)”.
Device: JEOL Ltd., JNM-EX400 type ¹³ C-NMR device Method: Proton complete decoupling method Concentration: 220 mg / mL
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

(a formula)
M = m / S × 100
R = γ / S × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

In addition, in the butene polymer of the present invention, ¹³ C-NMR spectrum was measured with the following apparatus and conditions, and [mmmm], [rrrr], [rmrm], and [mm] were obtained. The attribution of peaks is reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It was determined according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al. That is, signals of methylene group and methine group were measured using ¹³ C-NMR spectrum, and [mmmm], [rrrr], [rmrm] and [mm] in the butene polymer molecule were determined.
^{The 13} C-NMR spectrum was measured using the same apparatus and conditions as those for NMR in the propylene polymer except that the concentration was changed to 230 mg / mL.

The butene content when the olefin polymer was a propylene / butene copolymer was measured as follows.
Butene content was calculated by the following method using a JNM-EX400 type NMR apparatus manufactured by JEOL Ltd., measuring a ¹³ C-NMR spectrum under the following conditions.
Sample concentration: 220 mg / mL
Solvent: Mixed solvent of 1,2,4-trichlorobenzene / heavy benzene (volume ratio 90/10) Measurement temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 10 seconds Integration number: 4,000 times Under the above conditions, PP, PB and BB chains are C. Based on the method proposed in Randall, Macromolecules, 1978, 11, 592, the Sαα carbon signal of the 13C nuclear magnetic resonance spectrum was measured to determine the PP, PB, and BB dyad chain fractions in the copolymer molecular chain. It was. The butene content was determined from the following formula from each of the obtained dyad chain fractions (mol%).
Butene content (mol%) = ([BB] + [PB]) / 2
([PP] represents a propylene-propylene chain fraction, [BB] represents a butene-butene chain fraction, and [PB] represents a propylene-butene chain fraction.)

<40 ° C viscosity of 5% by weight toluene solution>
The substrate was dissolved in toluene to a concentration of 5% by mass and measured with a single cylindrical rotary viscometer (B type).

Production Example 1
[Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride]
Under a nitrogen stream, 2.5 g (7.2 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) and 100 mL of ether were added to a 200 mL Schlenk bottle. After cooling to −78 ° C. and adding 9.0 mL (14.8 mmol) of a hexane solution (1.6 mol / L) of n-butyllithium (n-BuLi), the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with 20 mL of hexane and dried under reduced pressure to quantitatively obtain a lithium salt as a white solid. In a Schlenk bottle, 6.97 mmol of a lithium salt of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (indene) was dissolved in 50 mL of tetrahydrofuran, and 2.1 mL (14 of iodomethyltrimethylsilane at room temperature) .2 mmol) was slowly added dropwise and stirred for 12 hours. The solvent was distilled off, 50 mL of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase is dried and the solvent is removed to obtain 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene). ) Was obtained (yield 84%).

Next, 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. And 50 mL of ether were added. After cooling to −78 ° C., 7.4 mL (11.8 mmol) of a hexane solution (1.6 mol / L) of n-butyllithium (n-BuLi) was added, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with 40 mL of hexane to obtain 3.06 g of a lithium salt as an ether adduct.
Under a nitrogen stream, 3.06 g of the lithium salt obtained above was suspended in 50 mL of toluene. This was cooled to −78 ° C., and 20 mL of a toluene suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride previously cooled to −78 ° C. was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 6 hours. After the solvent of this reaction solution was distilled off, the obtained residue was recrystallized with dichloromethane to obtain (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl). ) 0.9 g (1.33 mmol) of yellow fine crystals of zirconium dichloride was obtained (yield 26%).
When ¹ H-NMR of the yellow microcrystals obtained above was determined, the following results were obtained.
¹ H-NMR (90 MHz, CDCl ₃ ): δ0.0 (s, -SiMe _3- , 18H), 1.02, 1.12 (s, -Me ₂ Si-, 12H), 2.51 (dd, _{-CH 2 -, 4H), 7.1-7.6} (m, Ar-H, 8H)

Production Example 2
(Preparation of catalyst solution)
Toluene slurry (5 μmol / mL, 3.0 mL, 15.0 μmol) of dimethylanilinium tetrakis (pentafluorophenyl) borate was added to a 20 mL Schlenk bottle under a nitrogen stream. Next, with stirring, a heptane solution of triisobutylaluminum (2 mmol / mL, 0.050 mL, 0.1 mmol), followed by (1,2′-dimethylsilylene) (2,1) obtained in Production Example 1 By adding a heptane slurry (5 μmol / mL, 1.0 mL, 5.0 μmol) of '-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, capping and stirring for 30 minutes or more in a nitrogen atmosphere A catalyst solution (complex concentration = about 0.13 μmol / mL) was obtained.

Production Example 3
(Batch polymerization of 1-butene)
To a 1 L autoclave that had been dried by heating, 180 mL of toluene and 0.4 mmol of triisobutylaluminum were added, cooled to 10 ° C., and 230 mL of liquid 1-butene was added. Thereafter, hydrogen was introduced at a partial pressure of 0.03 MPa, the temperature was raised to 55 ° C., and about 0.5 μmol (0.4 mL) of the catalyst solution produced in Production Example 2 was added in terms of organometallic complex to initiate polymerization. did. The point at which the total pressure decreased to 0.16 MPa relative to the initial pressure of 0.42 MPa was set as the polymerization end point. The amount of polymer produced when the pressure drop from the initial pressure is reduced to 50% of the difference between the initial pressure and the pressure at the end point of the polymerization, and the total mass of the finally obtained polymer is 100% by mass. It was 50 mass%. Note that the pressure decreases as the polymerization proceeds.
Every 20 minutes, 0.5 μmol (0.4 mL) of the catalyst solution in terms of organometallic complex was added three times. 90 minutes after the first catalyst was charged, the total pressure was reduced to 0.16 MPa, and thus 5 mL of ethanol was added to terminate the polymerization. After depressurization, the polymerization solution was recovered and dried under reduced pressure to obtain 106 g of poly (1-butene). Table 1 shows the total pressure, the amount of 1-butene, the amount of poly (1-butene), and the 1-butene concentration at the start of polymerization, at a polymer production amount of 50% by mass, and at the end of polymerization. The 1-butene concentration is a concentration relative to the total weight of 1-butene, toluene and polymer.
The intrinsic viscosity [η] of the obtained poly (1-butene) was 0.78 dL / g, the weight average molecular weight (Mw) was 53,700, the molecular weight distribution (Mw / Mn) was 2.43, and the mesopentad fraction [mmmm. ] Was 68.9 mol%, and melting | fusing point (Tm-D) was 71.5 degreeC.

Production Example 4
(Semi-batch polymerization of 1-butene)
To a heat-dried 2 L autoclave, 600 mL of heptane, 0.6 mmol of triisobutylaluminum, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) obtained in Production Example 1 ) Zirconium dichloride (6.0 μmol) and dimethylanilinium tetrakis (pentafluorophenyl) borate (18.0 μmol) were added, and hydrogen was further introduced at a partial pressure of 0.02 MPa, and then the supply was stopped. While raising the polymerization temperature to 53 ° C., 1-butene was introduced, the total pressure was increased to 0.24 MPa, and polymerization was performed for 60 minutes while maintaining 0.24 MPa as it was. Polymerization was stopped by charging 5 mL of ethanol through the catalyst charging tube. After completion of the polymerization reaction, the pressure was released, and the reaction product was dried under reduced pressure to obtain 240 g of poly (1-butene).
The resulting poly (1-butene) has an intrinsic viscosity [η] of 0.69 dL / g, a weight average molecular weight (Mw) of 114,100, a molecular weight distribution (Mw / Mn) of 1.8, and a mesopentad fraction [mmmm. ] Was 68.8 mol%, and melting | fusing point (Tm-D) was 70.2 degreeC.

Example 1
(Production of maleic anhydride-modified poly (1-butene))
Into a 0.5 L Separa flask equipped with a nitrogen introduction tube, a Dimroth tube, and a stirrer, 30 g of the poly (1-butene) obtained in Production Example 3 and 20 mL of toluene bubbled with nitrogen were added, and the temperature was 140 ° C. under a nitrogen atmosphere. A viscous uniform solution was obtained by heating in an oil bath. Thereafter, 0.9 g of maleic anhydride was added and dissolved, and then 0.6 g of “Perhexa 25B” (manufactured by NOF Corporation) was added. The oil bath was heated to 150 ° C. and stirred for 5 hours. The obtained reaction product was dried under heating and reduced pressure to obtain the desired product.
The obtained maleic anhydride-modified poly (1-butene) has an intrinsic viscosity [η] of 0.60 dL / g, a weight average molecular weight (Mw) of 127,100, a molecular weight distribution (Mw / Mn) of 3.27, and mesopentad. The fraction [mmmm] is 68.9 mol%, the mesotriad fraction [mm] is 82.5 mol%, the melting point (Tm-D) is 70.5 ° C., and the melting endotherm (ΔH-D) is 32 J / g, The glass transition temperature (Tg) was −35 ° C., the acid value was 25 mg KOH / g, the half crystallization time was 65 minutes, and the 40 ° C. viscosity of the 5 mass% toluene solution was 14.0 mPa · s.

Comparative Example 1
(Production of maleic anhydride-modified poly (1-butene))
In Example 1, in place of the poly (1-butene) obtained in Production Example 3, the same procedure as in Example 1 was carried out except that the poly (1-butene) obtained in Production Example 4 was used. Thus, the target product was obtained.
The resulting maleic anhydride-modified poly (1-butene) has an intrinsic viscosity [η] of 0.63 dL / g, a weight average molecular weight (Mw) of 113,300, a molecular weight distribution (Mw / Mn) of 2.24, and mesopentad. The fraction [mmmm] is 68.8 mol%, the mesotriad fraction [mm] is 82.3 mol%, the melting point (Tm-D) is 69.5 ° C., the melting endotherm (ΔHD) is 32 J / g, The glass transition temperature (Tg) was −35 ° C., the acid value was 22 mgKOH / g, the half crystallization time was 72 minutes, and the 40 ° C. viscosity of a 5 mass% toluene solution was 62.6 mPa · s.

Production Example 5
(Production of propylene homopolymer)
(1) First-stage polymerization A 1 L stainless steel pressure-resistant autoclave with a stirrer was heated to 80 ° C. and sufficiently dried under reduced pressure, and then returned to atmospheric pressure with dry nitrogen and cooled to room temperature. Under a dry nitrogen stream, dry deoxygenated heptane 400 mL, triisobutylaluminum heptane solution (2.0 M) in 0.5 mL (1.0 mmol) and dimethylanilinium tetrakis (pentafluorophenyl) borate heptane slurry (2 μmol / mL, 0.8 mL, 1.6 μmol) was added and stirred at 350 rpm for a while. Then, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylindenyl) zirconium dichloride heptane slurry (5 μmol / mL, 0.08 mL, 0.4 μmol) was added, Hydrogen was charged up to 0.01 MPa.
Then, stirring was started at 400 rpm, propylene was introduced, the pressure was increased to about 0.8 MPa over about 5 minutes, and simultaneously the temperature was raised to 70 ° C. over about 5 minutes, followed by polymerization for 20 minutes. Carried out.
(2) Second-stage polymerization Thereafter, the temperature was lowered to 40 ° C. over 5 minutes, and polymerization was further carried out for 35 minutes. After completion of the reaction, unreacted propylene was removed by depressurization. The reaction mixture was heated and dried under reduced pressure to obtain polypropylene.
From the ratio of the integrated value of propylene flow rate from the total pressure of 0.8 MPa in the first stage polymerization to the yield of 125 g, after 20 minutes and after that, the temperature is lowered to 40 ° C. and the polymerization is completed. The polymerization ratio between the polymerization and the second stage polymerization was 75:25.
The obtained polypropylene had an intrinsic viscosity [η] of 1.0 dL / g, a weight average molecular weight (Mw) of 165,700, a molecular weight distribution (Mw / Mn) of 6.1, and a mesopentad fraction [mmmm] of 46.9. The mol% and melting point (Tm-D) were 71.5 ° C.

Production Example 6
(Production of propylene homopolymer)
To a heat-dried 1 L autoclave, 400 mL of heptane, 0.5 mmol of triisobutylaluminum, 0.8 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, (1,2′-dimethylsilylene) (2,1′- Polymerization is performed at 70 ° C. for 30 minutes by adding 0.2 μmol of dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, introducing 0.02 MPa of hydrogen, and introducing propylene to a total pressure of 0.8 MPa. did. After completion of the polymerization reaction, 120 g of polypropylene was obtained by drying the reaction product under reduced pressure.
The obtained polypropylene had an intrinsic viscosity [η] of 1.0 dL / g, a weight average molecular weight (Mw) of 123,000, a molecular weight distribution (Mw / Mn) of 1.9, and a mesopentad fraction [mmmm] of 47.6. The mol% and melting point (Tm-D) were 83 ° C.

Example 2
In Example 1, instead of the poly (1-butene) obtained in Production Example 3, the same procedure as in Example 1 was carried out except that the polypropylene obtained in Production Example 5 was used. Obtained.
The obtained maleic anhydride-modified polypropylene has an intrinsic viscosity [η] of 0.95 dL / g, a weight average molecular weight (Mw) of 104,500, a molecular weight distribution (Mw / Mn) of 6.9, and a mesopentad fraction [mmmm]. Is 46.9 mol%, the mesotriad fraction [mm] is 68.3 mol%, the melting point (Tm-D) is 71.0 ° C., the melting endotherm (ΔHD) is 33 J / g, the glass transition temperature (Tg ) Was -1 ° C, the acid value was 25 mgKOH / g, the half-crystallization time was 35 minutes, and the 40 ° C viscosity of the 5 mass% toluene solution was 18.5 mPa · s.

Comparative Example 2
(Production of maleic anhydride-modified polypropylene)
In Example 1, in place of the poly (1-butene) obtained in Production Example 3, the same procedure as in Example 1 was performed except that the polypropylene obtained in Production Example 6 was used. Obtained.
The obtained maleic anhydride-modified polypropylene has an intrinsic viscosity [η] of 0.98 dL / g, a weight average molecular weight (Mw) of 103,000, a molecular weight distribution (Mw / Mn) of 2.3, and a mesopentad fraction [mmmm]. Is 47.6 mol%, the mesotriad fraction [mm] is 69.5 mol%, the melting point (Tm-D) is 70.0 ° C., the melting endotherm (ΔH-D) is 32 J / g, and the glass transition temperature (Tg ), −1 ° C., acid value was 28 mg KOH / g, half-crystallization time was 38 minutes, and the 40 ° C. viscosity of a 5 mass% toluene solution was 82.4 mPa · s.

The maleic anhydride-modified poly (1-butene) of Example 1 and Comparative Example 1 both have a glass transition temperature of −35 ° C. and a weight average molecular weight of about the same. Therefore, when compared with the modified polyolefin having the same molecular weight from Example 1 and Comparative Example 1, the modified polyolefin of Comparative Example 1 having a narrow molecular weight distribution of less than 2.4 has high viscosity, whereas the molecular weight distribution is high. It can be seen that the modified polyolefin of Example 1 has a low viscosity and excellent fluidity.
Similarly, the maleic anhydride-modified polypropylenes of Example 2 and Comparative Example 2 both have a glass transition temperature of −1 ° C., and the weight average molecular weight is substantially the same. Therefore, when compared with the modified polyolefin having the same molecular weight from Example 2 and Comparative Example 2, the modified polyolefin of Comparative Example 2 having a narrow molecular weight distribution of less than 2.4 has high viscosity, whereas the molecular weight distribution is high. It can be seen that the modified polyolefin of Example 2 has a low viscosity and excellent fluidity.

  The modified olefin polymer of the present invention has good fluidity and can be suitably used for applications such as pressure-sensitive adhesives, adhesives and paints. In particular, in various adhesives or pressure-sensitive adhesives such as urethane, modified silicone, acrylic, and hot melt, ink, paint, etc., it can be suitably used as a modifier for improving the affinity for polyolefin.

Claims (13)

A modified olefin polymer satisfying the following (1) to (6).
(1) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 dL / g or more and 2.5 dL / g or less.
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the observed peak is not observed or is 0 ° C. or higher and 100 ° C. or lower.
(3) The half crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or the crystallization peak measured with a differential scanning calorimeter (DSC) is not observed.
(4) Using a differential scanning calorimeter (DSC), the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. The amount of heat (ΔH−D) is 0 J / g or more and 80 J / g or less.
(5) The acid value is 10 mgKOH / g or more and 250 mgKOH / g or less.
(6) The molecular weight distribution Mw / Mn is 2.4 or more and 10.0 or less.   50 mol% or more of the monomer constituting the modified olefin polymer is at least one α-olefin monomer selected from the group consisting of propylene, 1-butene and α-olefin having 6 to 12 carbon atoms. Item 2. The modified olefin polymer according to Item 1. The modified olefin polymer according to claim 1 or 2, further satisfying the following (7).
(7) Mesopentad fraction [mmmm] is 42 to 90 mol%. A method for producing the modified olefin polymer according to any one of claims 1 to 3,
A modified olefin system comprising a step of producing an olefin polymer by polymerizing an olefin monomer using a metallocene catalyst, and a step of modifying the obtained olefin polymer to obtain a modified olefin polymer. A method for producing a polymer. The metallocene catalyst is
(I) a transition metal compound represented by the following general formula (I), and (ii) (ii-1) reacting with the transition metal compound of component (i) or a derivative thereof to form an ionic complex. The manufacturing method of the modified olefin polymer of Claim 4 containing the compound chosen 1 or more types from the compound which can be obtained, and (ii-2) aluminoxane.

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure through A ¹ and A ² They may be the same or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]   The method for producing a modified olefin polymer according to claim 5, wherein the metallocene catalyst contains two or more transition metal compounds represented by the general formula (I).   The modified olefin according to any one of claims 4 to 6, wherein in the step of producing the olefin polymer, a temperature difference between a polymerization temperature at the start of polymerization and a polymerization temperature at a later stage of polymerization is 5 ° C or more. A method for producing a polymer.   In the step of producing the olefin polymer, hydrogen is added at the time of polymerization, and the partial pressure difference between the hydrogen concentration at the start of polymerization and the hydrogen concentration at the late stage of polymerization is 0.01 MPa or more. The manufacturing method of the modified olefin polymer as described in any one.   The process for producing the olefin polymer according to any one of claims 4 to 8, wherein a concentration ratio of an olefin monomer concentration at the start of polymerization and an olefin monomer concentration at a later stage of polymerization is 20% or more. A method for producing a modified olefin polymer.   The adhesive which contains the modified olefin polymer as described in any one of Claims 1-3.   The coating material containing the modified olefin polymer as described in any one of Claims 1-3.   The sealing material containing the modified olefin polymer as described in any one of Claims 1-3.   An ink composition comprising the modified olefin polymer according to any one of claims 1 to 3.