JP6055281B2 - Functionalized α-olefin polymer, curable composition and cured product using the same - Google Patents

Description

  The present invention relates to a functionalized α-olefin polymer, a curable composition using the same, and a cured product.

In recent years, global environmental issues, workers' working environments, safety and health awareness are increasing. Under such circumstances, for example, in the field of hot-melt adhesives, conventional hot-melt adhesives have a melting point of 150 ° C. or higher and need to be heated, so a substance capable of low-temperature coating is required. .
For applications such as adhesives, materials with higher reactivity are desired, such as reactive adhesives (epoxy resin-based, polyurethane-based, polyamide-based), sealing materials, sealing materials, adhesives, plasticizers, etc. In applications, materials that are easy to handle and have high reactivity and materials that can control the reactivity are desired. In addition, there is an increasing need for olefin-based materials from the viewpoint of improving heat resistance and waterproofing.

  As such olefinic materials, Patent Documents 1 and 2 describe that hydroxyl groups can be obtained by hydroborating a terminal double bond of polyethylene or isotactic polypropylene having a double bond at one end and further oxidatively decomposing. What is introduced / added is disclosed.

JP 2004-168803 A JP 2002-161142 A

However, when a polyolefin having a hydroxyl group only at one end is mixed with a polyisocyanate compound to obtain a cured product, there is a problem that the progress of the curing reaction is slow and the obtained cured product is inferior in heat resistance. .
The problem to be solved by the present invention is to provide a polyolefin-based substrate suitable as a raw material for a cured product having good curing reactivity and excellent heat resistance.

That is, the present invention provides the following functionalized α-olefin polymer, a curable composition using the same, and a cured product.
[1] The α-olefin polymer has a hydroxyl group, and the α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, or propylene-1-butene copolymer, and the following ( A functionalized α-olefin polymer satisfying 1) to (4).
(1) The weight average molecular weight (Mw) is 1,000 to 500,000.
(2) The molecular weight distribution (Mw / Mn) is 1.1 to 2.5.
(3) The number of hydroxyl groups per molecule is 1.1 to 4.5.
(4) The melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 50 J / g or less.
[2] The functionalized α-olefin polymer according to [1], wherein a melting endotherm ΔH-D measured by a differential scanning calorimeter (DSC) is 1 J / g or less.
[3] The functionalized α-olefin polymer according to [1] or [2], wherein the number of hydroxyl groups per molecule is 1.1 to 4.0.
[4] The functional group according to any one of [1] to [3], wherein the α-olefin polymer is a propylene homopolymer or 1-butene homopolymer having a mesopentad fraction [mmmm] of 20 mol% or less. Α-olefin polymer.
[5] The functionalized α- according to any one of [1] to [3], wherein the α-olefin polymer is a propylene-1-butene copolymer having a meso-dyad fraction [m] of 70 mol% or less. Olefin polymer.
[6] The functionalized α-olefin polymer according to any one of [1] to [5], which is used for an adhesive, a sealing agent, a pressure-sensitive adhesive, or a modifier.
[7] A curable composition comprising the functionalized α-olefin polymer according to any one of (A) [1] to [6] and (B) a polyisocyanate compound.
[8] The curable composition according to [7], further comprising (C) a curing accelerating catalyst.
[9] A cured product obtained by curing the curable composition according to [7] or [8].
[10] The cured product according to [9], which is used for an adhesive, a sealing agent, a pressure-sensitive adhesive, or a modifier.
[11] Any one of [1] to [6], wherein the raw material α-olefin polymer having 1.1 to 2.0 terminal unsaturated groups per molecule is hydroxylated. A process for producing a functionalized α-olefin polymer as described in 1).

  The functionalized α-olefin polymer or curable composition of the present invention is a polyolefin-based substrate that has good curing reactivity and is suitable as a raw material for a cured product having excellent heat resistance.

[Functionalized α-olefin polymer]
The functionalized α-olefin polymer of the present invention is a functionalized propylene homopolymer obtained by functionalizing a propylene homopolymer, a functionalized 1-butene homopolymer obtained by functionalizing a 1-butene homopolymer, and propylene- There are three types of functionalized propylene-1-butene copolymers formed by functionalizing 1-butene copolymers. “Functionalization” in the present specification indicates that a hydroxyl group is added to the α-olefin polymer.
In addition, when comonomer such as ethylene is copolymerized, since the crystal component increases, fluidity at room temperature is lost, handling becomes worse, and it becomes difficult to cure at room temperature. It is difficult to use as a base material for a sealing material.
The functionalized α-olefin polymer of the present invention exhibits fluidity at room temperature. Specifically, the functionalized α-olefin polymer of the present invention exhibits fluidity at a relatively low temperature of 100 ° C. or less, more preferably fluidity at a low temperature of 60 ° C. or less.

(A) Hydroxyl group The functionalized α-olefin polymer of the present invention has 1.1 to 4.5 hydroxyl groups per molecule, and when it is intended to be used as a compatibilizer, 1 The number of hydroxyl groups per molecule is preferably 1.1 to 1.5, more preferably 1.1 to 1.2, and when used for an adhesive or a sealing material, Curing performance is important, and from the viewpoint of obtaining a crosslinked structure, the number of hydroxyl groups per molecule is preferably 1.2 or more, and more preferably 1.5 or more.
Moreover, since the maximum number of hydroxyl groups depends on the number of unsaturated groups per molecule of the α-olefin polymer described later, the number of terminal unsaturated groups in the α-olefin polymer can be controlled by controlling the number of unsaturated groups. The number of hydroxyl groups in the α-olefin polymer can be controlled.

The number of hydroxyl groups per molecule can be determined by the following measurement method.
(A) Terminal hydroxyl group concentration (mol%) determined by ¹³ C-NMR,
(B) Number average molecular weight (Mn) of functionalized α-olefin polymer determined from gel permeation chromatograph (GPC), and (C) Average molecular weight of monomer units (Mm) = Propylene unit ratio × 42.08 + 1 -Butene unit ratio x 56.11
From the following formula, the number of hydroxyl groups per molecule can be calculated.
Number of hydroxyl groups per molecule (number) = (Mn / M) x [hydroxyl concentration] / 100
Since the unsaturated concentration may be reduced by side reaction as a method for calculating the hydroxyl group concentration, as shown below, it is derived from OH—CH ₂ that appears in the vicinity of 68 to 70 ppm using ¹³ C-NMR. The peak concentration is calculated.
OH—CH ₂ CH ₂ (i): integrated value of 68-70 ppm Propylene unit CH ₂ (ii): integrated value of peak appearing at 46.4 ppm Butene unit CH ₂ (iii): appearing at 40.4 ppm Integral value of peak of hydroxyl group concentration = [(i) / ((ii) + (iii))] × 100 (mol%)

(B) melting endotherm ΔH-D
The functionalized α-olefin polymer used in the present invention has a melting endotherm ΔH-D measured by a differential scanning calorimeter (DSC) of 50 J / g or less. When the melting endotherm ΔH-D of the functionalized α-olefin polymer exceeds 50 J / g, the crystal component increases and the fluidity at normal temperature is impaired. In addition, the melting endotherm ΔH-D is 10 J / g or less, and the fluidity at room temperature depends on the molecular weight, but the fluidity can be expressed at a relatively low temperature (40 to 50 ° C.). There are advantages in terms of safety environment.
ΔH-D is obtained by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co., Ltd.), 10 mg of the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere and then heated at 10 ° C./min. Let the melting endotherm be ΔH−D.
In order to control the melting endotherm to 50 J / g or less, it is necessary to control the mesopentad fraction [mmmm], which is an index of stereoregularity, to 80 mol% or less, depending on the structure of the main catalyst and the polymerization conditions. Can be controlled. For example, when controlling by the structure of a catalyst, it is necessary to design the space where a monomer coordinates to the central metal of a catalyst to an appropriate size. Depending on the size of the coordination space, the insertion of the monomer is difficult to occur, and the activity is reduced. If the structure is a racemic structure, a highly ordered polymer is obtained, and the melting endotherm exceeds 50 J / g. A meso-type structure is likely to give a polymer with low regularity and may have a melting endotherm of 50 J / g or less, but it is difficult to synthesize a polymer having a balance between the bond ratio and the melting endotherm. . For example, by using a double-crosslinking catalyst described later, it is possible to synthesize a polymer having a balance between a bonding ratio and a melting endotherm by controlling the coordination space of the monomer.

(C) Stereoregularity When the functionalized α-olefin polymer of the present invention has a hydroxyl group in the propylene homopolymer main chain or the 1-butene homopolymer main chain, the mesopentad fraction [mmmm] is 80 mol%. It is preferably at most, more preferably at most 60 mol%, further preferably at most 40 mol%, particularly preferably at most 20 mol%.
On the other hand, when the main chain of the propylene-1-butene copolymer has a hydroxyl group, the mesodyad fraction [m] is preferably 30 to 95 mol%, more preferably 30 to 80 mol%, 30 More preferably, it is -60 mol%.
By controlling the meso pentad fraction [mmmm] and the meso dyad fraction [m] to be low and regular and completely amorphous, it becomes possible to handle at room temperature and to cure at a lower temperature. As a result, it can be used in the fields of sealing and reactive adhesion, which have been difficult to use in the past, especially in fields where adhesion to polyolefin-based substrates is required.
The control of the mesopentad fraction [mmmm] and the mesodyad fraction [m] is performed according to the structure of the main catalyst and the polymerization conditions. It is necessary to design to a suitable size. Depending on the size of the coordination space, it is difficult to insert the monomer, and the activity is reduced. If the structure is a racemic structure, a highly regular polymer is obtained. If the structure is a meso structure, a polymer having a low regularity is obtained. It becomes easy to obtain.

The functionalized α-olefin polymer of the present invention preferably has a 2,1-bond fraction of less than 0.5 mol%, more preferably less than 0.4 mol%, and even more preferably 0.2 mol%. %.
The 2,1-bond fraction is controlled by controlling the 2,1-bond fraction in the α-olefin polymer used as a raw material by a method described later.

The functionalized α-olefin polymer of the present invention preferably has a total of 1,3-bond fraction and 1,4-bond fraction of less than 0.5 mol%, more preferably less than 0.4 mol%. More preferably, it is less than 0.1 mol%.
The above “total of 1,3-bond fraction and 1,4-bond fraction” means 1,3-3-when the functionalized α-olefin polymer of the present invention has a propylene homopolymer main chain. The bond fraction means 1,4-bond fraction when having a butene homopolymer main chain, and 1,3-bond content when having a propylene-1-butene copolymer main chain. It means the sum of the rate and 1,4-bond fraction.
The control of the 1,3-bond fraction and the 1,4-bond fraction is controlled by the method described later in the α-olefin polymer used as a raw material. It is done by doing.
As the 2,1-bond fraction, 1,3-bond fraction, and 1,4-bond fraction increase, the number of terminal unsaturations in the raw material decreases, and this is used as the reaction starting point. Is not preferable because it cannot be increased.

In the present invention, the mesopentad fraction [mmmm] and the mesodiad fraction are 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, the signals of methylene group and methine group were measured using a ¹³ C nuclear magnetic resonance spectrum, and the mesopentad fraction [mmmm] and mesodyad fraction [m] in the polymer chain were determined.
^{The 13} C-NMR spectrum was measured using the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / ml Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

(D) Weight average molecular weight / molecular weight distribution From the viewpoint of fluidity, the functionalized α-olefin polymer of the present invention preferably has a weight average molecular weight of 3,000 to 500,000, preferably 4,000 to 450, 000 is more preferable, more preferable is 4,500 to 300,000 is particularly preferable.
When the functionalized α-olefin polymer of the present invention is used for adhesives, the weight-average molecular weight of the functionalized α-olefin polymer is 10,000 from the viewpoint that the adhesive strength after curing is strong and does not easily peel off. It is preferably ~ 500,000.

  The functionalized α-olefin polymer of the present invention preferably has a molecular weight distribution (Mw / Mn) of less than 4.5, from 1.4 to 3.0, from the viewpoint of reactivity and reaction curability. Is more preferable, and it is still more preferable that it is 1.5-2.6.

In addition, the said weight average molecular weight (Mw) and number average molecular weight (Mn) are things of polystyrene conversion measured with the following apparatus and conditions, The said molecular weight distribution (Mw / Mn) is these weight average molecular weights (Mw). ) And the number average molecular weight (Mn).
<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

(E) B viscosity From the viewpoints of reactivity, workability at room temperature, etc., the functionalized α-olefin polymer of the present invention preferably has a B viscosity (fluidity) at 30 ° C. of 5000 mPa · s or less, 2000 mPa · s. The following is more preferable.
Here, the said B viscosity shows what is measured according to ASTM-D 19860-91.

[Method for producing functionalized α-olefin polymer]
The functionalized α-olefin polymer of the present invention can be produced by hydroxylating a both-terminal unsaturated α-olefin polymer described later.
Specific examples of hydroxylation of both terminal unsaturated α-olefins include hydration of olefins in the presence of an acid catalyst such as concentrated sulfuric acid and dilute sulfuric acid, addition reaction of maleic anhydride by olefin ene reaction, lithium aluminum hydride Etc., oxidation reaction with organic peroxides such as performic acid and peracetic acid, hydroboration-oxidation reaction in which hydroboration with borane followed by treatment with peroxide and base is included.
Examples of the hydration reaction include a raw material α-olefin polymer in the presence of an acid catalyst such as sulfuric acid or phosphoric acid, zeolite, a solid acid catalyst carrying phosphoric acid or an ion exchange resin, or magnesium sulfate or magnesium chloride. In the presence of the magnesium salt, a method of treating in an aqueous system at a temperature of 100 to 300 ° C. for 10 minutes to 10 hours can be mentioned.
The ene reaction can be performed, for example, by bringing a raw material α-olefin polymer into contact with an excess amount of maleic anhydride at a temperature of 100 ° C. to 250 ° C. for 10 minutes to 10 hours. This ene reaction is preferably carried out in the presence of oxalic acid or maleic acid.
As the reduction reaction, for example, the raw material α-olefin polymer is contacted with a reducing agent such as lithium aluminum hydride in the presence of a solvent such as tetrahydrofuran (THF) at room temperature to reflux conditions for 30 minutes to 5 hours. The method of letting it be mentioned.
Examples of hydroboration include, for example, starting a α-olefin polymer in the presence of a solvent such as tetrahydrofuran (THF), dicyamilborane ((Sia) ₂ BH), texylborane ((Thx) BH ₂ ), 9-borabicyclo [3. 3.1] A method in which a boron compound such as nonane is brought into contact in the presence of a solvent such as THF at 0 ° C. to reflux conditions. The subsequent oxidation reaction is performed by treating the reaction product obtained by the hydroboration with a peroxide such as hydrogen peroxide and a base such as sodium hydroxide at room temperature for 1 to 10 hours, for example. Can do.

(Both-terminal unsaturated α-olefin polymer)
In the production method of the functionalized α-olefin polymer of the present invention, the both-terminal unsaturated α-olefin polymer used as a raw material has the following properties (a ′), and the following properties (b ′) to (f ′): ).
(A ′) The number of terminal unsaturated groups per molecule is 1.1 to 2.0.
(B ′) The melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 50 J / g or less.
(C ′) (c′-1) Mesopentad fraction [mmmm] is 80 mol% or less, or (c′-2) Mesodyad fraction [m] is 30 to 95 mol% or less.
(D1 ′) The weight average molecular weight Mw is 1,000 to 500,000.
(D2 ′) Molecular weight distribution Mw / Mn is less than 4.5.
(E ′) The 2,1-bond fraction is less than 0.5 mol%.
(F ′) The sum of 1,3-bond fraction and 1,4-bond fraction is less than 0.5 mol%.

(A ′) Number of terminal unsaturated groups per molecule The terminally unsaturated α-olefin polymer used in the present invention has 1.1 to 2.0 terminal unsaturated groups per molecule. is there. In addition, when the unsaturated α-olefin polymer at both ends is intended to be used as a compatibilizing agent, the number of terminal unsaturated groups per molecule should be 1.1 to 1.5. Preferably, it is 1.1 to 1.2, and when used for an adhesive or sealant, it is preferably 1.2 or more, and 1.5 or more. Is more preferable.

The number of terminal unsaturated groups per molecule of the both terminal unsaturated α-olefin polymer can be controlled by the structure of the main catalyst, the type of monomer, and the polymerization conditions (polymerization temperature, hydrogen concentration, etc.).
The number of terminal unsaturated groups per molecule can be controlled by selecting the molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) in the presence of a catalyst.
For example, it can be obtained by performing a polymerization reaction in a molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) in the range of 0 to 5000. In order to increase the terminal unsaturated group selectivity and the catalytic activity, it is preferable to perform the polymerization reaction in the presence of a trace amount of hydrogen.
Usually, hydrogen functions as a chain transfer agent, and it is known that polymer chain ends have a saturated structure. It also has a function of reactivating the dormant to increase the catalytic activity. Although the influence of a trace amount of hydrogen on the catalyst performance is unknown, by using hydrogen within a specific range, the terminal unsaturated group selectivity is high and high activity can be achieved.
The molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) is preferably 200 to 4500, more preferably 300 to 4000, and most preferably 400 to 3000. When this molar ratio is 5,000 or less, production of an α-olefin polymer having an extremely low number of terminal unsaturated groups is suppressed, and an α-olefin polymer having the desired number of terminal unsaturated groups can be obtained. it can.

Examples of the terminal unsaturated group include a vinyl group, a vinylidene group, and a trans (vinylene) group. The terminal unsaturated group defined in this specification means a vinyl group and a vinylidene group. Vinyl groups and vinylidene groups are radically polymerizable and have a wide range of applications for various reactions and can meet various requirements.
The terminal unsaturated group concentration and the number of terminal unsaturated groups in the both-terminal unsaturated α-olefin polymer used in the present invention mean the concentration and number of the total amount of vinyl groups and vinylidene groups. When only a vinyl group is present, it means the concentration and number of only the vinyl group, and when both vinyl group and vinylidene group are included, it means the concentration and number of both sums.

The above-mentioned terminal unsaturated group concentration and the number of terminal unsaturated groups per molecule can be determined by ¹ H-NMR measurement. Specifically, terminal vinylidene groups appearing in δ 4.8 to 4.6 (2H), terminal vinyl groups appearing in δ 5.9 to 5.7 (1H) and δ 1.05 obtained from ¹ H-NMR measurement. Based on the methyl group appearing at ˜0.60 (3H), the terminal unsaturated group concentration (C) (mol%) can be calculated.
CH _{2 of} vinylidene group (4.8 to 4.6 ppm) (i)
Vinyl group CH (5.9 to 5.7 ppm) (ii)
Side chain terminal CH ₃ (1.05 to 0.60 ppm) (iii)
Vinylidene group amount = [(i) / 2] / [(iii) / 3] × 100 mol%
Vinyl group amount = (ii) / [(iii) / 3] × 100 mol%
Terminal unsaturated group concentration = [vinylidene group amount] + [vinyl group amount]
From the terminal unsaturated group concentration (C, mol%) calculated by the above method, the number average molecular weight (Mn) and the monomer molecular weight (M) determined from the gel permeation chromatograph (GPC), per molecule The number of terminal unsaturated groups can be calculated.
Number of terminal unsaturated groups per molecule (number) = (Mn / M) × (C / 100)

(B ′) melting endotherm ΔH−D
The terminally unsaturated α-olefin polymer used in the present invention preferably has a melting endotherm ΔH-D of 50 J / g or less as measured by a differential scanning calorimeter (DSC).
In the propylene homopolymer, the melting endotherm ΔH-D is more preferably 30 J / g or less, further preferably 15 J / g or less, and particularly preferably 1 J / g or less.
In the 1-butene homopolymer, the melting endotherm ΔH-D is more preferably 40 J / g or less, further preferably 10 J / g or less, and particularly preferably 1 J / g or less.
Details of the melting endotherm ΔH-D of the α-olefin polymer are the same as those of the functionalized α-olefin polymer.

(C′-1) Mesopentad fraction [mmmm]
The mesopentad fraction [mmmm] of the both-terminal unsaturated α-olefin polymer used in the present invention is preferably less than 80 mol%.
In the propylene homopolymer, the mesopentad fraction [mmmm] is more preferably less than 60 mol%, still more preferably less than 40 mol%, and particularly preferably less than 20 mol%.
In the case of a 1-butene homopolymer, the mesopentad fraction [mmmm] is more preferably less than 70 mol%, still more preferably less than 40 mol%, and particularly preferably less than 20 mol%. .

(C′-2) Mesodyad fraction [m]
On the other hand, when the both-terminal unsaturated α-olefin polymer used in the present invention is a propylene-1-butene copolymer, the meso-dyad fraction [m] is preferably 30 to 95 mol%, and 30 to 80 It is more preferable that it is mol%, and it is still more preferable that it is 30-60 mol%.
The mesopentad fraction [mmmm] and the mesodyad fraction [m] can be controlled by the structure of the main catalyst and the polymerization conditions. For example, when controlling by the structure of a catalyst, it is necessary to design the space where a monomer coordinates to the central metal of a catalyst to an appropriate size. Depending on the size of the coordination space, it is difficult to insert the monomer, and the activity is reduced. If the structure is a racemic structure, a highly regular polymer is obtained. If the structure is a meso structure, a polymer having a low regularity is obtained. It becomes easy to obtain.

Moreover, the racemic pentad fraction [rrrr] of the both-terminal unsaturated α-olefin polymer used in the present invention is preferably less than 20 mol%.
The racemic pentad fraction [rrrr] in the propylene homopolymer is more preferably more than 1 mol% and less than 20 mol%, still more preferably more than 2 mol% and less than 15 mol%, particularly preferably 3 mol. % And less than 10 mol%.
The racemic pentad fraction [rrrr] in the 1-butene homopolymer is more preferably more than 1 mol% and less than 20 mol%, still more preferably more than 2 mol% and less than 15 mol%, particularly preferably More than 3 mol% and less than 10 mol%.
On the other hand, when the α-olefin polymer used in the present invention is a propylene-1-butene copolymer, the racemic dyad fraction [r] is preferably 1 to 50 mol%, and preferably 2 to 45 mol%. It is more preferable that it is 2-40 mol%.

(E ′) 2,1-bond fraction The terminally unsaturated α-olefin polymer used in the present invention preferably has a 2,1-bond fraction of less than 0.5 mol%, more preferably 0. Less than 4 mol%, more preferably less than 0.2 mol%. When the 2,1-bond fraction of the both-terminal unsaturated α-olefin polymer is within the above range, the decomposition efficiency in the thermal decomposition reaction and radical decomposition reaction described later is improved.
The 2,1-bond fraction is controlled depending on the structure of the main catalyst and the polymerization conditions. Specifically, the structure of the main catalyst has a large effect, and the 2,1-bond can be controlled by narrowing the insertion field of the monomer around the central metal of the main catalyst. The number of 2,1-bonds can be increased. For example, a catalyst called half-metallocene type has a wide insertion field around the central metal, so that structures such as 2,1-bonds and long-chain branches are likely to be generated. Although it can be expected to be suppressed, in the case of the racemic type, the stereoregularity becomes high, and it is difficult to obtain an amorphous polymer as shown in the present invention. For example, even a racemic type as described later introduces a substituent at the 3-position with a double-bridged metallocene catalyst and controls the insertion site of the central metal to obtain an amorphous polymer with very few 2,1-bonds. be able to.

(F ′) 1,3-bond fraction and 1,4-bond fraction Both-terminal unsaturated α-olefin polymers used in the present invention have a 1,3-bond fraction and a 1,4-bond fraction. Is preferably less than 0.5 mol%, more preferably less than 0.4 mol%, still more preferably less than 0.1 mol%. When the sum of the 1,3-bond fraction and 1,4-bond fraction of the α-olefin polymer is within the above range, the decomposition efficiency in the thermal decomposition reaction and radical decomposition reaction described later is improved.
The above “total of 1,3-bond fraction and 1,4-bond fraction” means that when the both-terminal unsaturated α-olefin polymer used in the present invention is a propylene homopolymer, 3-bond fraction means 1,4-bond fraction when it is a butene homopolymer, 1,3-bond fraction when it is a propylene-1-butene copolymer, and It means the sum of 1,4-bond fractions.
The control of the 1,3-bond fraction and the 1,4-bond fraction is performed according to the structure of the main catalyst and the polymerization conditions in the same manner as the control of the 2,1-bond fraction.

In the present invention, mesopentad fraction [mmmm], racemic pentad fraction [rrrr], mesodyad fraction [m], racemic diad fraction [r], 1,3-bond fraction, 1,4-bond fraction Rate and 2,1-bond fraction are 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. Namely, signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum, and mesopentad fraction [mmmm], racemic pentad fraction [rrrr], mesodyad fraction in poly (1-butene) chain were measured. [M], racemic dyad fraction [r], 1,3-bond fraction, 1,4-bond fraction, and 2,1-bond fraction were determined.
^{The 13} C-NMR spectrum was measured using the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / ml Solvent: 1,2,4-trichlorobenzene / heavy benzene (volume ratio 90/10) mixed Solvent temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

<In case of propylene homopolymer>
The 1,3-bond fraction and the 2,1-bond fraction can be calculated by the following formula from the measurement result of the ¹³ C-NMR spectrum.
1,3-bond fraction = (D / 2) / (A + B + C + D) × 100 (mol%)
2,1-bond fraction = [(A + B) / 2] / (A + B + C + D) × 100 (mol%)
A: integrated value of 15 to 15.5 ppm B: integrated value of 17 to 18 ppm C: integrated value of 19.5 to 22.5 ppm D: integrated value of 27.6 to 27.8 ppm

<Butene homopolymer>
The 1,4-bond fraction and the 2,1-bond fraction can be calculated by the following formula from the measurement result of the ¹³ C-NMR spectrum.
1,4-bond fraction = E / (A + B + C + D + E) × 100 (mol%)
2,1-bond fraction = {(A + B + D) / 3} / (A + B + C + D) × 100 (mol%)
A: Integration value of 29.0 to 28.2 ppm B: Integration value of 35.4 to 34.6 ppm C: Integration value of 38.3 to 36.5 ppm D: Integration value of 43.6 to 42.8 ppm E: 31.1 ppm integrated value

(D1 ′) Weight average molecular weight (Mw)
From the viewpoint of fluidity, the terminally unsaturated α-olefin polymer used in the present invention preferably has a weight average molecular weight of 1,000 to 500,000, more preferably 6,000 to 450,000. 8000 to 300,000 is more preferable.
The details of the weight average molecular weight (Mw) of the α-olefin polymer are the same as those in the functionalized α-olefin polymer.

(D2 ′) Molecular weight distribution (Mw / Mn)
The terminally unsaturated α-olefin polymer used in the present invention preferably has a molecular weight distribution (Mw / Mn) of less than 4.5 from the viewpoint of reactivity and reaction curability, and 1.4-3. 0 is more preferable, and 1.5 to 2.6 is still more preferable.
Details of the molecular weight distribution (Mw / Mn) of the α-olefin polymer are the same as those in the functionalized α-olefin polymer.

(Production method of unsaturated α-olefin polymer at both terminals)
The α-olefin polymer used in the present invention uses, for example, a metallocene catalyst comprising a combination of the following components (Pa), (Pb) and (Pc), and hydrogen as a molecular weight regulator. The obtained one-terminal unsaturated α-olefin polymer can be further subjected to a thermal decomposition reaction or radical decomposition reaction to produce. Specifically, it can be produced by the method disclosed in WO2008 / 047860.
(P-a) substitution cyclopentadienyl group, indenyl group, substituted indenyl group transition metal compound containing zirconium having a (P-b) compound capable of reacting with the transition metal compound to form an ionic complex (P -C) Organoaluminum compound

<(P-a) component>
(P-a) component of the replacement cyclopentadienyl group, a transition metal compound containing zirconium having indenyl group or substituted indenyl group, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -Bis (3-phenylindenyl) zirconium dichloride or (1,1'-ethylene) (2,2'-tetramethyldisylylene) bisindenylzirconium dichloride is used.

<(Pb) component>
As the compound that can form an ionic complex by reacting with the (Pb) transition metal compound, a high purity terminal unsaturated olefin polymer having a relatively low molecular weight can be obtained, and a catalyst having high activity. And borate compounds are preferred. Specific examples of the borate compound include those described in WO2008 / 066168. These can be used individually by 1 type or in combination of 2 or more types. When the molar ratio of hydrogen and transition metal compound (hydrogen / transition metal compound) described later is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and tetrakis (Perfluorophenyl) methylanilinium borate and the like are preferable.
Methylaluminoxane (MAO) is also preferably used as a compound that can react with the (Pb) transition metal compound to form an ionic complex.

<(Pc) component>
The catalyst used in the method for producing a one-terminal unsaturated α-olefin polymer used in the present invention may be a combination of the (Pa) component and the (Pb) component, and the (Pa) component and In addition to the component (Pb), an organoaluminum compound may be used as the component (Pc).
Examples of the organoaluminum compound of component (Pc) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethyl. Examples thereof include aluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.
Of these, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum is preferable, and triisobutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum are more preferable. preferable.

The amount of component (Pa) used is usually 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁵ mol / L, preferably 0.15 × 10 ^{−6 to} 1.3 × 10 ⁻⁵ mol / L. L, more preferably 0.2 × 10 ^{−6 to} 1.2 × 10 ⁻⁵ mol / L, and particularly preferably 0.3 × 10 ^{−6 to} 1.0 × 10 ⁻⁵ mol / L. When the amount of the component (Pa) used is 0.1 × 10 ⁻⁶ mol / L or more, the catalytic activity is sufficiently expressed, and when it is 1.5 × 10 ⁻⁵ mol / L or less, the polymerization heat Can be easily removed.
The use ratio (Pa) / (Pb) of the component (Pa) and the component (Pb) is preferably 10/1 to 1/100, more preferably 2/1 to 1 in terms of molar ratio. 1/10. When (P−a) / (P−b) is in the range of 10/1 to 1/100, an effect as a catalyst can be obtained and the catalyst cost per unit mass polymer can be suppressed. Further, there is no fear that a large amount of boron is present in the target α-olefin polymer.
The use ratio (Pa) / (Pc) of the component (Pa) and the component (Pc) is preferably 1/1 to 1/10000, and more preferably 1/5 to 1/5 in terms of molar ratio. 1/2000, more preferably 1/10 to 1/1000. By using the component (Pc), the polymerization activity per transition metal can be improved. When (P−a) / (P−c) is in the range of 1/1 to 1/10000, the balance between the effect of adding the component (P−c) and the economy is good, and the target α -There is no fear that a large amount of aluminum is present in the olefin polymer.

  In the production method of the one-terminal unsaturated α-olefin polymer used in the present invention, the above-mentioned (P-a) component and (P-b) component, or (P-a) component, (P-b) component And a pre-contact can also be performed using (Pc) component. The preliminary contact can be performed by bringing the (P-a) component into contact with, for example, the (P-b) component, but the method is not particularly limited, and a known method can be used. Such preliminary contact is effective in reducing catalyst costs, such as improvement in catalyst activity and reduction in the proportion of the (Pb) component used as a promoter.

(Pyrolysis reaction)
The thermal decomposition reaction is performed by heat-treating the one-terminal unsaturated α-olefin polymer.
The heating temperature can be adjusted by setting a target molecular weight and taking into consideration the results of experiments performed in advance, and is preferably 300 to 400 ° C, more preferably 310 to 390 ° C. If the heating temperature is less than 300 ° C, the thermal decomposition reaction may not proceed. On the other hand, when heating temperature exceeds 400 degreeC, there exists a possibility that the both terminal unsaturated alpha-olefin polymer obtained may deteriorate.
The thermal decomposition time (heat treatment time) is preferably 30 minutes to 10 hours, more preferably 60 to 240 minutes. When the thermal decomposition time is less than 30 minutes, there is a possibility that the produced amount of the both-terminal unsaturated α-olefin polymer obtained is small. On the other hand, when the thermal decomposition time is more than 10 hours, the obtained both-terminal unsaturated α-olefin polymer may be deteriorated.

  For example, a stainless steel reaction vessel equipped with a stirrer is used as the pyrolysis reaction, and the container is filled with an inert gas such as nitrogen or argon, and one end unsaturated α-olefin heavy It can be carried out by putting the coalesced and heating and melting, bubbling the molten polymer phase with an inert gas, and heating at a predetermined temperature for a predetermined time while extracting a volatile product.

(Radical decomposition reaction)
The radical decomposition reaction can be carried out at a temperature of 160 to 300 ° C. by adding 0.05 to 2.0 mass% of an organic peroxide with respect to the one-terminal unsaturated α-olefin polymer.
The decomposition temperature is preferably 170 to 290 ° C, more preferably 180 to 280 ° C. When the decomposition temperature is less than 160 ° C., the decomposition reaction may not proceed. On the other hand, when the decomposition temperature is higher than 300 ° C., the decomposition proceeds vigorously, and the decomposition may be completed before the organic peroxide is sufficiently diffused uniformly into the molten polymer by stirring, which may reduce the yield.

  The organic peroxide to be added is preferably an organic peroxide having a 1 minute half-life temperature of 140 to 270 ° C., and specific examples of the organic peroxide include the following compounds: diisobutyryl peroxide, Cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecano Eight, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-hexyl Peroxypivalate, t-butyl peroxypivalate, di (3,5 5-trimethylhexanoyl) peroxide, dilauryl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethyl) Hexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) ) Peroxide, dibenzoyl peroxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylpropylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane Sasan, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy- 3,5,5-trimethylhexanate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 3,5-di -Methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl4 , 4-Di- (t-butylperoxy) valate, di (2-t-butylperoxyisopropyl) Benzoate, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-Menthans hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydro Peroxide, cumene hydroperoxide, t-butyl hydroperoxide.

  The addition amount of the organic peroxide is preferably 0.1 to 1.8% by mass, more preferably 0.2 to 1.7% by mass with respect to the one-terminal unsaturated α-olefin polymer. When the addition amount is less than 0.05% by mass, the decomposition reaction rate may be slowed and the production efficiency may be deteriorated. On the other hand, when the addition amount exceeds 2.0 mass%, the odor resulting from the decomposition of the organic peroxide may cause a problem.

  The decomposition time of the decomposition reaction is, for example, 30 seconds to 10 hours, and preferably 1 minute to 1 hour. When the decomposition time is less than 30 seconds, not only does the decomposition reaction not proceed sufficiently, but a large amount of undecomposed organic peroxide may remain. On the other hand, when the decomposition time is longer than 10 hours, there is a concern that the cross-linking reaction, which is a side reaction, may be progressed, and that the obtained both-terminal unsaturated α-olefin polymer may turn yellow.

  The radical decomposition reaction can be performed by using, for example, any one of decomposition by a batch method and decomposition by a continuous melt method.

When the radical decomposition reaction is carried out by a batch method, an inert gas such as nitrogen or argon is filled in a reaction vessel made of stainless steel or the like equipped with a stirrer, and the one-terminal unsaturated α-olefin polymer is placed and heated and melted. The radical thermal decomposition reaction can be carried out by dropping the organicated oxide into the molten one-terminal unsaturated α-olefin polymer and heating it at a predetermined temperature for a predetermined time.
The organic peroxide may be dropped within the range of the decomposition time, and the dropping may be either continuous dropping or divided dropping. The reaction time from the dropping end time is preferably within the above reaction time range.

The organic peroxide may be dissolved in a solvent and dropped as a solution.
The solvent is preferably a hydrocarbon solvent, and specific examples include aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, hexadecane, and nanodecane; methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, And alicyclic hydrocarbons such as cyclododecane; and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. Among these solvents, a solvent having a boiling point of 100 ° C. or higher is preferable.

  Moreover, you may dissolve a one terminal unsaturated alpha-olefin polymer in a solvent in the case of decomposition | disassembly. The decomposition temperature when the one-terminal unsaturated α-olefin polymer is dissolved in a solvent for decomposition is usually in the range of 100 to 250 ° C, preferably in the range of 120 to 200 ° C.

When the radical decomposition reaction is carried out by the melt continuous method, the reaction time as viewed from the average residence time is, for example, 20 seconds to 10 minutes. The melt continuous method can improve the mixing state and shorten the reaction time compared to the batch method.
The apparatus can use a single-screw or twin-screw melt extruder, preferably an extruder having an inlet in the middle of the barrel and capable of degassing under reduced pressure, and L / D = 10 or more. Machine.

  The radical decomposition reaction by the melt continuous method is performed by impregnating a single-end unsaturated α-olefin polymer with a single-end unsaturated α-olefin polymer using the above-mentioned apparatus, or A method of individually supplying and mixing can be applied.

Specifically, impregnation of the organic peroxide into the one-end unsaturated α-olefin polymer is carried out by adding a predetermined amount of the organic peroxide to the one-end unsaturated α-olefin polymer in the presence of an inert gas such as nitrogen. By adding and stirring in the range of room temperature to 40 ° C., raw material pellets can be uniformly absorbed and impregnated. The obtained one-end unsaturated α-olefin polymer impregnated with the organic peroxide (hereinafter referred to as “impregnated pellet”) is decomposed by melt extrusion, or the impregnated pellet is used as a master batch for one-end unsaturated α- A terminally unsaturated α-olefin polymer can be obtained by adding to the olefin polymer and decomposing it.
In the case where the organic peroxide is solid or the organic peroxide has low solubility in the one-terminal unsaturated α-olefin polymer, a solution in which the organic peroxide is previously dissolved in a hydrocarbon solvent. It is better to absorb and impregnate the one-terminal unsaturated α-olefin polymer.

  Mixing by separately supplying the single-terminal unsaturated α-olefin polymer and the organic peroxide is performed by supplying the raw material α-olefin polymer and the organic peroxide at a constant flow rate to the extruder hopper, or by mixing the organic peroxide. It can be carried out by supplying oxide at a constant flow rate in the middle of the barrel.

[Curable composition]
The curable composition of the present invention comprises (A) the above functionalized α-olefin polymer and (B) a polyisocyanate compound, and (C) a diluent and (D) a tackifier. (E) 1 or more types selected from a hardening acceleration catalyst may be mix | blended.

(B) Polyisocyanate Compound The (B) polyisocyanate compound used in the present invention is an organic compound having two or more isocyanate groups in one molecule, and is based on the hydroxyl group of the functionalized α-olefin polymer. It has a reactive isocyanate group. Examples of the (B) polyisocyanate compound include ordinary aromatic, aliphatic, and alicyclic compounds.
Specifically, for example, 4,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, a mixture of 4,4′- and 2,2′-diphenylmethane diisocyanate (all MDI), tolylene diisocyanate (TDI) Carbodiimide modified diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, naphthalene-1,5-diisocyanate, o-toluidine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, isopropylbenzene-2,4-diisocyanate Aromatic polyisocyanates such as
Aliphatic-aromatic polyisocyanates such as xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) (isocyanate groups do not have isocyanate groups directly bonded to aromatic rings via aliphatic hydrocarbons, ie Polyisocyanate having no isocyanate group directly bonded to an aromatic ring in the molecule);
Further, hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, Aliphatic polyisocyanates such as trimethylhexamethylene diisocyanate;
Furthermore, transcyclohexane-1,4-diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate Alicyclic polyisocyanates such as
In addition, the cyclized trimer (isocyanurate-modified product), burette-modified product, ethylene glycol, 1,4-butanediol, propylene glycol, dipropylene glycol, trimethylolpropane, polyether polyol, polymer Polyols such as polyol, polytetramethylene ether glycol, polyester polyol, acrylic polyol, hydrogenated dimer acid diisocyanate, polyalkadiene polyol, hydride of polyalkadiene polyol, partially saponified ethylene-vinyl acetate copolymer, castor oil-based polyol Examples include addition reaction products of a compound and the polyisocyanate compound.
These polyisocyanate compounds may be used in combination of two or more, and the isocyanate groups of these polyisocyanate compounds are further converted to phenols, oximes, imides, mercaptans, alcohols, ε-caprolactam, ethyleneimine, α- A so-called blocked isocyanate compound blocked with a blocking agent such as pyrrolidone, diethyl malonate, sodium bisulfite, boric acid or the like can also be used.

Although there is no restriction | limiting in particular about the mixture ratio of the said (A) functionalized alpha-olefin polymer and (B) polyisocyanate compound in the curable composition of this invention, (A) The hydroxyl group of a functionalized alpha-olefin polymer (OH) (B) The final ratio (NCO / OH) of the isocyanate groups (NCO) of the polyisocyanate compound is preferably 0.3 to 5 and more preferably 0.5 to 4 in terms of molar ratio.
Here, the term “final ratio” is used because various methods as described below are used in the production of an actual cured body.
One-shot method: First, at least the components other than the polyisocyanate compound are blended and mixed among all the blended components to obtain a mixture. To this mixture, a polyisocyanate compound and components not used in the previous mixing are added and mixed to obtain a liquid polymer composition. A preferable NCO / OH ratio at this time is 0.5 to 2.5 in terms of molar ratio.
Prepolymer method (1): The functionalized α-olefin polymer and the polyisocyanate compound are mixed with a predetermined equivalent ratio NCO / OH in the range of 1.7 to 25 in the presence of part or all of other additives. Alternatively, it is reacted in the absence to obtain a prepolymer. The remaining components are mixed with this prepolymer to obtain a liquid polymer composition. A preferable NCO / OH ratio at this time is 0.5 to 2.5 in terms of molar ratio. In this case, since the molar ratio NCO / OH ratio of the functional groups involved in the reaction when the prepolymer was obtained is substantially 1.0, the final NCO / OH ratio is 0.5 to 2.5. Is in range.
Prepolymer method (2): All the components are blended in a predetermined equivalent ratio NCO / OH in the range of 1.7 to 5, and reacted to obtain a prepolymer. This prepolymer is reacted with moisture (water) in the air.

(C) Diluent Examples of the diluent include oils such as naphthenic oil, paraffinic oil, and aroma oil, and oils obtained by mixing them, and liquid rubbers such as liquid polybutene and liquid isopolybutylene. You may use these individually by 1 type or in mixture of 2 or more types.
The content of the diluent (C) in the curable composition of the present invention is usually 1 to 50% by mass, preferably 2 to 40% by mass with respect to 100% by mass of the curable composition of the present invention. .

(D) Tackifiers Tackifiers (tackifier resins) include rosin and its derivatives, terpene resins and hydrogenated resins, styrene resins, coumarone-indene resins, dicyclopentadiene (DCPD) Resin and its hydrogenated resin, aliphatic (C5) petroleum resin and its hydrogenated resin, aromatic (C9) petroleum resin and its hydrogenated resin, and copolymer of C5 and C9 From many commonly used tackifiers such as petroleum resins and hydrogenated resins thereof, those having good compatibility with the functionalized α-olefin polymer are selected. One of these tackifiers may be used alone, or two or more thereof may be used as a mixture.
Preferred tackifiers include terpene resins and their hydrogenated resins, styrene resins, and dicyclopentadiene (DCPD) resins from the viewpoint of the balance between removability and adhesion to curved and uneven surfaces. And its hydrogenated resin, aliphatic (C5) petroleum resin and its hydrogenated resin, aromatic (C9) petroleum resin and its hydrogenated resin, and C5 -C9 copolymer petroleum resin It is preferable to use one kind of resin or a mixture of two or more kinds selected from the group of hydrogenated resins.
Content of (D) tackifier in the curable composition of this invention is 1-50 mass% normally with respect to 100 mass% of curable compositions of this invention, Preferably it is 2-45 mass%. It is.

(E) Curing accelerating catalyst (E) Specific examples of the curing accelerating catalyst include triethylenediamine, tetramethylguanidine, N, N, N′N′-tetramethylhexane-1,6-diamine, N, N, N ′. N ″ N ″ -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, 1,2-dimethylimidazole, N-methyl-N ′-(2-dimethylamino) ethylpiperazine, diazabicycloundecene, etc. Tertiary amines: stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marker peptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin marker peptide, dioctyltin thiocarboxylate, phenylmercury propionate , Organometallic compounds such as lead octenoate; Carboxylic acid salts of grade amines.
(E) When the addition amount of the curing accelerating catalyst is 10 parts by mass or less with respect to 100 parts by mass of the functionalized α-olefin polymer, the curing accelerating effect is less likely to reach a peak, and a local abnormal reaction (gelation) is caused. Risk is reduced.

(Other ingredients)
The curable composition of the present invention may contain additives such as fillers, pigments or antioxidants as long as the effects of the present invention are not impaired.
The filler includes an inorganic filler and an organic filler.
Inorganic fillers include silica, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, Calcium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, sepiolite, imogolite, cerissato, glass fiber, glass beads, silica balun , Aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, zinc borate, and various magnetic powders.
An inorganic filler may be used in place of the inorganic filler, and surface treatment may be performed with various coupling agents such as silane and titanate. As this treatment method, a method of directly treating an inorganic filler with various coupling agents such as a dry method, a slurry method or a spray method, an integral blend method such as a direct method or a masterbatch method, or a dry concentrate method, etc. The method is mentioned.
Organic fillers include starch (for example, powdered starch), fibrous leather, natural organic fibers (for example, those made of cellulose such as cotton and hemp), and synthetic fibers made of synthetic polymers such as nylon, polyester, and polyolefin. Can be mentioned.
Examples of the pigment include inorganic pigments and organic pigments (for example, azo pigments and polycyclic pigments).
Inorganic pigments include oxides (titanium dioxide, zinc white (zinc oxide), iron oxide, chromium oxide, iron black, cobalt blue, etc., hydroxides: alumina white, iron oxide yellow, viridian, etc.), sulfides ( Zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, etc.), chromate (yellow lead, molybdate orange, zinc chromate, strontium chromate, etc.), silicate (white carbon, clay, talc, ultramarine blue, etc.), sulfate (Precipitated barium sulfate, barite powder, etc., as carbonates: calcium carbonate, lead white, etc.), ferrocyanide (bitumen), phosphate (manganese violet), carbon (carbon black), etc. are also used be able to.
Examples of azo pigments that are organic pigments include soluble azo (Kermin 6B, Lakelet C, etc.), insoluble azo (Disazo Yellow, Lakelet 4R, etc.), condensed azo (chromophthalo Yellow 3G, chromophthalscarlet RN, etc.), azo complex salts (nickel) Azo yellow, etc.) and pendidalone azo (permanent orange HL, etc.). Polycyclic pigments that are organic pigments include isoindolinone, isoindoline, quinophthalone, pyrazolone, flavatron, anthraquinone, diketo-pyrrolo-pyrrole, pyrrole, pyrazolone, pyranthrone, perinone, perylene, quinacridone, indigoid, oxazine, imidazolone Xanthene, carbonium, violanthrone, phthalocyanine, nitroso and the like.

The curable composition of this invention can be manufactured by mixing the said component by arbitrary methods.
(E) The curing accelerating catalyst is preferably mixed and used. (E) The curing acceleration catalyst is added by preparing a catalyst master batch in which the (E) curing acceleration catalyst is in a high concentration, blending the catalyst master batch and other components, and kneading or melting. Is preferred.
Moreover, the curable composition of this invention can also be manufactured using a solvent.

The curable composition of the present invention can be dissolved in a solvent and used as a solvent-type adhesive, and can be applied and sprayed to form a film on the surface of an adhesive substrate to adhere to an adherend.
Furthermore, the polymerizable composition of the present invention can also be used as an adhesive by dispersing it in a polar solvent such as water or forming an emulsion. In addition, the curable composition of the present invention can be formed into a sheet shape or a film shape, sandwiched between adhesive substrates, heated to a temperature higher than the temperature at which the curable composition flows, and bonded by cooling and solidification. .

[Cured product]
The present invention also provides a cured product obtained by curing the curable composition.
The curable composition of the present invention can carry out a curing reaction at a low temperature. Specifically, a cured product can be obtained by subjecting the curable composition of the present invention to a curing reaction at 100 ° C. or lower. In the curing reaction, the curable composition of the present invention is prepared and the functionalized α-olefin polymer and the polyisocyanate compound are reacted as they are, or the prepolymer obtained by the above-mentioned prepolymer method (2) is treated with moisture or Examples include a method of curing by contacting with moisture and curing under heat treatment or room temperature. In order to bring moisture or moisture into contact, for example, the curable adhesive composition of the present invention may be left in the air, or may be immersed in a water tank or steam. Moreover, although room temperature (25 degreeC) may be sufficient as temperature, it can bridge | crosslink in a short time if it makes high temperature.

The curable composition of the present invention comprises a resin compatibilizer, a polyolefin emulsion, a reactive adhesive, a reactive hot melt adhesive, other adhesives, an adhesive, a sealing material, a sealing material, a potting material, and a reactivity. It can be used for applications such as plasticizers and modifiers.
The cured product of the present invention is used for applications such as reactive adhesives, reactive hot melt adhesives, other adhesives, pressure-sensitive adhesives, sealing materials, sealing materials, potting materials, reactive plasticizers, modifiers, etc. Can do. Moreover, since the hardened | cured material obtained by the said hardening method has heat resistance, it can be used also in the environment of high temperature.

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

[ ¹³ C-NMR measurement]
The ¹³ C-NMR spectrum was measured under the following apparatus and conditions, and the 2,1-bond fraction, 1,3-bond fraction, 1,4-bond fraction, mesopentad fraction [mmmm], and racemic The pentad fraction [rrrr] was determined.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / ml Solvent: 1,2,4-trichlorobenzene / heavy benzene (volume ratio 90/10) mixed Solvent temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

[DSC measurement]
Using a differential scanning calorimeter (Perkin Elmer, DSC-7), a sample 10 mg was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. The amount of heat was determined as ΔH-D and glass transition temperature Tg.

[GPC measurement]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). For the measurement, the following apparatus and conditions were used, and a weight average molecular weight in terms of polystyrene was obtained.
<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
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)

[Terminal unsaturated group concentration]
Terminal vinylidene groups appearing in δ 4.8 to 4.6 (2H), terminal vinyl groups appearing in δ 5.9 to 5.7 (1H) and δ 1.05 to 0.60 (1H-NMR measurement obtained from ¹ H-NMR measurement) Based on the methyl group appearing in 3H), the terminal unsaturated group concentration (C) (mol%) was calculated.
CH _{2 of} vinylidene group (4.8 to 4.6 ppm) (i)
Vinyl group CH (5.9 to 5.7 ppm) (ii)
Side chain terminal CH ₃ (1.05 to 0.60 ppm) (iii)
Vinylidene group amount = [(i) / 2] / [(iii) / 3] × 100 mol%
Vinyl group amount = (ii) / [(iii) / 3] × 100 mol%
Terminal unsaturated group concentration (C) = [vinylidene group amount] + [vinyl group amount]

[Number of terminal unsaturated groups per molecule]
From the terminal unsaturated group concentration (C, mol%) calculated by the above method, the number average molecular weight (Mn) and the monomer molecular weight (M) determined from the gel permeation chromatograph (GPC), per molecule The number of terminal unsaturated groups was calculated.
Number of terminal unsaturated groups per molecule (number) = (Mn / M) × (C / 100)

[Number of terminal hydroxyl groups per molecule]
(A) Terminal hydroxyl group concentration determined by ¹³ C-NMR (mol%)
(B) Number average molecular weight (Mn) of functionalized α-olefin polymer determined from gel permeation chromatograph (GPC)
(C) Average molecular weight of monomer units (Mm) = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11
From the following formula, the number of terminal hydroxyl groups per molecule can be calculated.
Number of terminal hydroxyl groups per molecule (number) = (Mn / M) × [terminal hydroxyl group concentration] / 100
As the calculation method of the terminal hydroxyl group concentration, there is a possibility that the terminal unsaturated concentration may be reduced by side reaction. Therefore, as shown below, OH—CH appearing in the vicinity of 68 to 70 ppm using ¹³ C-NMR. The concentration of the peak derived from ₂ is calculated.
OH—CH ₂ CH ₂ (i): integrated value of 68-70 ppm Propylene unit CH ₂ (ii): integrated value of peak appearing at 46.4 ppm Butene unit CH ₂ (iii): appearing at 40.4 ppm Value of terminal hydroxyl group concentration = [(i) / ((ii) + (iii))] × 100 (mol%)

[B viscosity]
Measured according to ASTM-D 19860-91.

[Handling at normal temperature]
The fluidity at a relatively low temperature was confirmed visually and evaluated according to the following criteria.
A: Fluidity at 60 ° C.
○: Fluidity at 100 ° C.
Δ: The viscosity was fairly high at 100 ° C., but somehow fluid.
X: No fluidity at 100 ° C.

[Curing reactivity at relatively low temperature]
In the examples and comparative examples, the curing conditions of the cured products obtained by curing the curable compositions were evaluated according to the following criteria.
A: Completely cured at 60 ° C.
○: Completely cured at 100 ° C.
Δ: Partially cured at 100 ° C.
X: It did not harden even at 100 ° C.

[Heat resistance of cured product]
The cured product was heated in a glass oven at 120 ° C. for 10 minutes, the form of the cured product was visually observed, and the rubber elasticity of the cured product was evaluated by touch using the following evaluation criteria.
○: The shape is maintained and rubber elasticity is exhibited.
X: The shape cannot be maintained and rubber elasticity is not shown.

Production Example 1
[Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-phenylindenyl) zirconium dichloride (complex A)]
Under a nitrogen stream, 76.5 ml (229.5 mmol) of a phenyl ether bromide diethyl ether solution was placed in a 1000 ml flask and cooled in an ice bath. To this, 30 g (227.2 mmol) of 1-indanone was dissolved in 300 ml of diethyl ether and slowly added dropwise. After stirring at room temperature for 1 hour, the mixture was cooled in an ice bath and 6 mol / l hydrochloric acid was added dropwise. After stirring at room temperature, the organic layer was extracted with diethyl ether and washed with a saturated aqueous sodium hydrogen carbonate solution. After separating the aqueous phase, the organic phase was dried and the solvent was removed to obtain 37.2 g (193.4 mmol) of 1-phenylindene (yield 85%).

  Next, 16.7 g (87.1 mmol) of the obtained 1-phenylindene was placed in a 300 ml flask and dissolved in 70 ml of dimethyl sulfoxide. 4 ml of water was added and cooled in an ice bath. To this, 15.6 g (87.1 mmol) of N-bromosuccinimide was slowly added, followed by stirring at room temperature for 10 hours. This was cooled in an ice bath, 60 ml of water was added, and the organic layer was extracted with diethyl ether. After separating the aqueous phase, the organic phase was dried and the solvent was removed to obtain 24.0 g (83.3 mmol) of a crude product of 2-bromo-1-indan-1-ol (crude yield 96). %).

  The crude product of 2-bromo-1-indan-1-ol obtained above (24.0 g, 83.3 mmol) was placed in a 300 ml flask, dissolved in 200 ml of toluene, and p-toluenesulfonic acid 0.48 g (2 0.5 mmol) was added. A Dean-Stark tube was attached to the flask and refluxed for 2 hours. The solvent was distilled off, and the organic layer was extracted with diethyl ether and washed with a saturated aqueous sodium hydrogen carbonate solution. After the aqueous phase was separated, the organic phase was dried and the solvent was removed to obtain a crude product of 2-bromo-1-phenylindene. This was purified by a column to obtain 17.9 g (66.4 mmol) of 2-bromo-1-phenylindene (yield 80%).

Next, under a nitrogen stream, 2.7 g (10.0 mmol) of 2-bromo-1-phenylindene obtained was put into a 200 ml Schlenk bottle, dissolved in 50 ml of diethyl ether, cooled to 0 ° C., and n-butyl. 3.8 ml (10.0 mmol) of a hexane solution (concentration 2.6 mol / l) of lithium (n-BuLi) was added and stirred at room temperature for 3 hours. This was cooled again to 0 ° C., 30 ml of diethyl ether and 12.5 ml (20.0 mmol) of a pentane solution (concentration 1.6 mol / l) of t-butyllithium (t-BuLi) were added and stirred at room temperature for 3 hours. did.
After stirring, this was cooled to −78 ° C., 0.6 ml (5.0 mmol) of dichlorodimethylsilane was added dropwise, and the mixture was stirred overnight at room temperature. This was again cooled to −78 ° C., 0.6 ml (5.0 mmol) of dichlorodimethylsilane was added dropwise, and the mixture was stirred overnight at room temperature. Thereafter, when water was added to stop the reaction, 1.1 g (2.2 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-phenylindene) was precipitated. Was collected by filtration (44% yield).

Next, in a Schlenk bottle, 1.6 g (3.2 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-phenylindene) obtained above was added to diethyl ether 12 The solution was dissolved in .6 ml, cooled to 0 ° C., added with 2.6 ml (6.6 mmol) of n-butyllithium (n-BuLi) in hexane (concentration 2.6 mol / l), and returned to room temperature for 1 hour. Stir.
The solvent was distilled off from the resulting solution, and the remaining solid was washed with 20 ml of hexane and then dried under reduced pressure to give (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3- An ether adduct of a lithium salt of phenylindene) was quantitatively obtained as a white solid.

Under a nitrogen stream, the ether adduct of the lithium salt obtained above was suspended in 18 ml of methylene chloride, cooled to −78 ° C., and 0.74 g (3.2 mmol) of zirconium tetrachloride previously cooled to −78 ° C. ) In methylene chloride (8 ml) was added dropwise, and the mixture was returned to room temperature and stirred for 4 hours.
The resulting solution was filtered and the filtrate was concentrated to precipitate a yellow solid. When this was washed with 10 ml of hexane, 1.3 g of yellow microcrystals of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride (complex A) (2. 0 mmol) was obtained. (Yield 62%)
When the ¹ H-NMR spectrum of the yellow fine crystals was obtained, the following results were obtained.
¹ H-NMR (500 MHz, CDCl 3): δ 0.31 (s, —Me ₂ Si—, 6H), 1.21 (s, —Me ₂ Si—, 6H), 7.18-7.69 (m, Ar-H, 18H)

Production Example 2
[Production of (1,1′-ethylene) (2,2′-tetramethyldisilylene) bisindenylzirconium dichloride (complex B)]
Magnesium (12 grams, 500 mmol) and tetrahydrofuran (30 ml) were charged into a 500 ml two-necked flask, and magnesium was activated by dropwise addition of 1,2-dibromoethane (0.2 ml). To this was added dropwise 2-bromoindene (20 grams, 103 mmol) dissolved in tetrahydrofuran (150 milliliters), and the mixture was stirred at room temperature for 1 hour. Thereafter, 1,2-dichlorotetramethyldisilane (9.4 ml, 5.1 mmol) was added dropwise at 0 ° C. After stirring the reaction mixture at room temperature for 1 hour, the solvent was distilled off, the residue was extracted with hexane (150 ml × 2), and 1,2-di (1H-inden-2-yl) -1,1,2 was extracted. , 2-tetramethyldisilane was obtained as a white solid (15.4 grams, 44.4 mmol, 86% yield).
This was dissolved in diethyl ether (100 ml), n-butyllithium (2.6 mol / l, 38 ml, 98 mmol) was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 1 hour to precipitate a white powder. The supernatant was removed and the solid was washed with hexane (80 ml) to give the lithium salt as a white powdery solid (14.6 grams, 33.8 mmol, 76%).
This was dissolved in tetrahydrofuran (120 ml), and 1,2-dibromoethane (2.88 ml, 33.8 mmol) was added dropwise at -30 ° C. The reaction mixture was stirred at room temperature for 1 hour and then evaporated to dryness, and the residue was extracted with hexane (150 milliliters) to give the bibridged ligand as a colorless oily liquid (14.2 grams, 37.9 millimoles). ).
This was dissolved in diethyl ether (120 ml), n-butyllithium (2.6 mol / liter, 32 ml, 84 mmol) was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 1 hour to precipitate a white powder. The supernatant was removed, and the solid was washed with hexane (70 ml) to give a lithium salt of the bi-bridged ligand as a white powder (14.0 grams, 31 mmol, 81% yield).
To a suspension of the obtained lithium salt of the bi-bridged ligand (3.00 g, 6.54 mmol) in toluene (30 mL) at −78 ° C., zirconium tetrachloride (1.52 g, 6.54 mmol). ) In toluene (30 ml) was added dropwise with a cannula. After the reaction mixture was stirred at room temperature for 2 hours, the supernatant was separated, and the residue was further extracted with toluene.
Under reduced pressure, the solvent of the supernatant and the extract was distilled off to dryness to give (1,1′-ethylene) (2,2′-tetramethyldisilene) bis represented by the following formula (1) as a yellow solid. Indenyl zirconium dichloride (complex B) was obtained (2.5 grams, 4.7 mmol, 72% yield).

The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (CDCl ₃ ): δ 0.617 (s, 6H, —SiMe ₂ —), 0.623 (s, 6H, —SiMe ₂ —), 3.65-3.74, 4.05-4 _{.15 (m, 4H, CH 2} CH 2), 6.79 (s, 2H, CpH), 7.0-7.5 (m, 8H, Aromatic-H)

Production Example 3
[Production of Raw Material α-Olefin Polymer (A)]
To a heat-dried 1 liter autoclave, 400 ml of heptane, 0.5 mmol of triisobutylaluminum, 0.2 μmol of complex A, 0.8 μmol of tetrakispentafluorophenylborate were added, and 0.05 MPa of hydrogen was further introduced. While stirring, propylene was charged, the total pressure was increased to 0.7 MPa, and polymerization was performed at a temperature of 60 ° C. for 30 minutes. After completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization solution was heated and dried under reduced pressure to obtain 100 g of a raw material α-olefin polymer (A).
About the obtained raw material α-olefin polymer (A), melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of terminal unsaturated groups per molecule, mesopentad fraction [Mmmm], 2,1-bond fraction, 1,3-bond fraction, and glass transition temperature Tg were measured. The results are shown in Table 1.

Production Example 4
[Production of Raw Material α-Olefin Polymer (B)]
70 g of the raw material α-olefin polymer (A) produced in Production Example 3 was charged into a stainless steel reactor (with an internal volume of 500 ml) equipped with a stirrer. The mixture was stirred for 30 minutes under a nitrogen stream.
Stirring was started and the resin temperature was raised to 160 ° C. using a mantle heater. The mantle heater was controlled so that the resin temperature was constant at 280 ° C. To this, 0.4 ml of Park Mill P (trade name, manufactured by NOF Corporation) was dropped over 4 minutes. After completion of the dropwise addition, the reaction was performed for 15 minutes, and then cooled to 110 ° C.
After completion of the reaction, drying under reduced pressure at 100 ° C. was carried out for 10 hours to radically decompose to obtain a raw material α-olefin polymer (B).
About the obtained raw material α-olefin polymer (B), melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of terminal unsaturated groups per molecule, mesopentad fraction [Mmmm], 2,1-bond fraction, 1,3-bond fraction, and glass transition temperature Tg were measured. The results are shown in Table 1.
Moreover, the yield of the obtained raw material α-olefin polymer (B) was 99.3% by mass with respect to the charged raw material α-olefin polymer (A), and the amount of by-products was very small.

Production Example 5
[Production of Raw Material α-Olefin Polymer (C)]
In a heat-dried 1 liter autoclave, heptane (200 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), 1-butene (200 mL), complex B (10 μmol / mL, 0.20 mL, 2.0 μmol) Then, MAO (2000 μmol) manufactured by Tosoh Finechem Co. was added, and 0.1 MPa of hydrogen was further introduced. The temperature was raised to 70 ° C. while stirring, and then polymerization was performed for 30 minutes. After completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 82 g of 1-butene homopolymer. The obtained raw material α-olefin polymer (C) was melted. Endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of terminal unsaturated groups per molecule, mesopentad fraction [mmmm], 2,1-bond fraction, 1,3 -Bond fraction and glass transition temperature Tg were measured. The results are shown in Table 1.

Production Example 6
[Production of Raw Material α-Olefin Polymer (D)]
70 g of the raw material α-olefin polymer (C) produced in Production Example 5 was charged into a stainless steel reactor (with an internal volume of 500 ml) equipped with a stirrer. The mixture was stirred for 30 minutes under a nitrogen stream.
Stirring was started, and the resin temperature was raised to 200 ° C. using a mantle heater. The mantle heater was controlled so that the resin temperature was constant at 280 ° C. To this, 0.4 ml of Park Mill P (trade name, manufactured by NOF Corporation) was dropped over 4 minutes. After completion of the dropwise addition, the reaction was performed for 15 minutes, and then cooled to 110 ° C.
After completion of the reaction, drying under reduced pressure at 100 ° C. was carried out for 10 hours to radically decompose to obtain a raw material α-olefin polymer (D).
About the obtained raw material α-olefin polymer (D), melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of terminal unsaturated groups per molecule, mesopentad fraction [Mmmm], 2,1-bond fraction, 1,3-bond fraction, and glass transition temperature Tg were measured. The results are shown in Table 1.
Moreover, the yield of the obtained raw material α-olefin polymer (D) was 99.3% by mass with respect to the charged raw material α-olefin polymer (C), and the amount of by-products was very small.

Production Example 7
[Production of Raw Material α-Olefin Polymer (E)]
To a heat-dried 1 liter autoclave, heptane (400 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), complex B (10 μmol / mL, 0.20 mL, 2.0 μmol), MAO manufactured by Tosoh Finechem Corporation ( 2000 μmol) was added, and 0.1 MPa of hydrogen was further introduced. While stirring, propylene was charged, the total pressure was increased to 0.7 MPa, and polymerization was performed at a temperature of 50 ° C. for 60 minutes. After completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization solution was heated and dried under reduced pressure to obtain 105 g of a raw material α-olefin polymer (E).

Production Example 8
[Production of Raw Material α-Olefin Polymer (F)]
Next, 70 g of the obtained raw material α-olefin polymer (E) was charged into a stainless steel reactor (with an internal volume of 500 ml) with a stirrer. The mixture was stirred for 30 minutes under a nitrogen stream.
Stirring was started, and the resin temperature was raised to 200 ° C. using a mantle heater. The mantle heater was controlled so that the resin temperature was constant at 280 ° C. To this, 0.4 ml of Park Mill P (trade name, manufactured by NOF Corporation) was dropped over 4 minutes. After completion of the dropwise addition, the reaction was performed for 15 minutes, and then cooled to 110 ° C.
After completion of the reaction, drying under reduced pressure at 100 ° C. was carried out for 10 hours to radically decompose to obtain a raw material α-olefin polymer (F).
About the obtained raw material α-olefin polymer (F), melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of terminal unsaturated groups per molecule, mesopentad fraction [Mmmm], 2,1-bond fraction, 1,3-bond fraction, and glass transition temperature Tg were measured. The results are shown in Table 1.
Moreover, the yield of the obtained raw material α-olefin polymer (F) was 99.5% by mass with respect to the charged raw material α-olefin polymer (E), and the amount of by-products was very small.

Production Example 9
[Production of Raw Material α-Olefin Polymer (G)]
A complex C [dimethylsilylene (η ¹ -tert-butylamide) (η ⁵ -tetramethylcyclopentadiene) titanium dichloride] was synthesized with reference to the description of Organometallics 2000, 19, 1870-1878.
To a heat-dried 1 liter autoclave, 400 ml of heptane, 0.5 mmol of triisobutylaluminum, 0.2 μmol of complex C, 0.8 μmol of tetrakispentafluorophenylborate were added, and 0.05 MPa of hydrogen was further introduced. While stirring, propylene was put in, the pressure was increased to 0.5 MPa, and polymerization was performed at a temperature of 90 ° C. for 60 minutes. After completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization solution was heated and dried under reduced pressure to obtain 50 g of a raw material α-olefin polymer (G).
About the obtained raw material α-olefin polymer (G), melting endotherm ΔHD, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of terminal unsaturated groups per molecule, mesopentad fraction [Mmmm], 2,1-bond fraction, 1,3-bond fraction, and glass transition temperature Tg were measured. The results are shown in Table 1.

Production Example 10
[Production of Dimethylsilylene (2-indenyl) (1- (2-Methyl-4,5-benzoindenyl)) zirconium Dichloride (Complex D)]
(Synthesis of 2-methyl-4,5-benzo-1-indanone)
Methylene chloride (100 mL), naphthalene (5 g, 0.039 mol) and 2-bromoisobutyryl bromide (9 g, 0.039 mol) were charged into a 300 mL three-necked flask equipped with a nitrogen inlet tube. Under a nitrogen stream, aluminum chloride (6 g, 0.047 mol) was slowly added. After 1 hour, the reaction solution was poured into cold water (200 mL), and the organic phase was separated using a separatory funnel. The organic phase was dried over magnesium sulfate, filtered, and the solvent was distilled off to obtain the target compound (6.4 g) (yield 84%).

(Synthesis of 2-methyl-4,5-benzoindene)
2-Methyl-4,5-benzo-1-indanone (6.4 g) was dissolved in methanol (100 mL). Sodium boron hydride (1 g, 0.026 mol) was slowly added into the solution. After 30 minutes, water (100 mL) and ether (100 mL) were added to perform extraction. The organic phase was separated using a separatory funnel. The organic phase was dried over magnesium sulfate, filtered, and the solvent was distilled off to obtain 2-methyl-4,5-benzoindanol (5.7 g). The obtained 2-methyl-4,5-benzoindanol (5.7 g) was dissolved in toluene (100 mL), pyridinium p-toluenesulfonic acid (0.5 g) was added, and the mixture was added using a Dean-Stark apparatus. The mixture was refluxed for a dehydration reaction. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to column purification (solvent: hexane) to obtain the target compound (3 g) (yield 48%).

(Synthesis of 2-indenyl-dimethylchlorosilane)
Magnesium powder (1.3 g), iodine (0.01 g), and dehydrated THF (20 mL) were charged into a 200 mL three-necked flask equipped with a Dimroth tube and a dropping funnel. 2-Bromoindene (synthesized according to J. Org. Chem. 47, (4), 705 (1982)) (5.4 g, 27.2 mmol) and dehydrated THF (40 mL) were charged into a dropping funnel, and under a nitrogen atmosphere. It was dripped slowly enough to gently reflux. After completion of dropping, the mixture was stirred for 30 minutes at room temperature. Thereafter, trimethylsilyl chloride (3.1 g, 28.5 mmol) and dehydrated THF (20 mL) were added to the dropping funnel, and the solution was added dropwise at -78 ° C. After completion of dropping, the mixture was stirred for 8 hours at room temperature. The solvent was distilled off under reduced pressure and extracted with dehydrated hexane (100 mL). The solvent was distilled off under reduced pressure to obtain 5.3 g of the target compound (yield 91%).

(Synthesis of (2-Indenyl) (1- (2-Methyl-4,5-benzoindenyl)) dimethylsilane)
2-methyl-4,5-benzoindene (1.26 g, 7 mmol) and dehydrated hexane (50 mL) were added to a 200 mL Schlenk purged with nitrogen. A n-butyllithium hexane solution (1.50 M, 4.7 mL, 7 mmol) was added dropwise to the solution at −78 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours, and 2-methyl-4,5-benzoindenyl lithium was precipitated. The suspension was allowed to stand, and the supernatant was removed by decantation. Dehydrated THF (25 mL) was added thereto, cooled to −78 ° C., and a dehydrated THF solution (25 mL) of 2-indenyl-dimethylchlorosilane (1.46 g, 7 mmol) synthesized earlier was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 4 hours. After completion of the reaction, water (50 mL) was added and extracted with ether (200 mL). The extracted solution was collected with a separatory funnel, and the obtained organic phase was dried over magnesium sulfate, filtered, and the solvent was distilled off to obtain the target compound (2.2 g) (yield 89%).

(Synthesis of dimethylsilylene (2-indenyl) (1- (2-methyl-4,5-benzoindenyl)) zirconium dichloride)
Nitrogen-substituted 200 mL Schlenk was synthesized with (2-indenyl) (1- (2-methyl-4,5-benzoindenyl)) dimethylsilane (1.0 g, 2.8 mmol) and dehydrated hexane (40 mL). Was introduced. A n-butyllithium hexane solution (1.50 M, 3.7 mL, 5.6 mmol) was added dropwise to the solution at −78 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours. As a result, (2-indenyl) (1- (2-methyl-4,5-benzoindenyl)) dimethylsilanedilithium was precipitated. The suspension was allowed to stand, and the supernatant was removed by decantation. Thereto was added dehydrated toluene (25 mL), and the mixture was cooled to -78 ° C., and a dehydrated toluene (25 mL) suspension of zirconium tetrachloride (0.9 g, 2.8 mmol) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the mixture was filtered through a cannula, the filtrate was concentrated, and dehydrated hexane was added. The resulting precipitate was filtered and dried to obtain 0.2 g of the target compound (yield 12%). The results of ¹ H-NMR measurement are shown below.
¹ H-NMR (δ ppm / CDCl ₃ ): 8.0-7.0 (m, 8H), 6.50 (s, 1H), 6.08 (d, 1H), 5.93 (d, 1H) , 2.45 (s, 3H), 1.12 (s, 3H), 0.99 (s, 3H)

Production Example 11
[Production of Raw Material α-Olefin Polymer (H)]
(Slurry polymerization of propylene)
A 1 liter stainless steel pressure-resistant autoclave with a stirrer was heated to 80 ° C. and sufficiently dried under reduced pressure, then returned to atmospheric pressure with dry nitrogen and cooled to room temperature. Under a dry nitrogen stream, 400 ml of dry deoxygenated toluene and 0.5 ml (1.0 mmol) of a heptane solution of triisobutylaluminum (2.0 M) were added and stirred at 350 rpm for a while. Thereafter, the toluene solution of MAO (2.03 M, 0.5 ml, 1.0 mmol) and the complex D heptane slurry (10 μmol / liter, 2.0 ml, 20.0 μmol) obtained in the above (Production Example 10) were placed in an autoclave. I put it in quickly. Thereafter, stirring was started at 400 rpm. Next, hydrogen was increased to 0.01 MPa, and then propylene was increased to a total pressure of 0.75 MPa over 3 minutes. At the same time, the temperature was increased to 50 ° C. and polymerization was carried out for 1 hour. After completion of the reaction, 20 ml of methanol was charged into the autoclave, and unreacted propylene was removed by depressurization. And the reaction mixture was thrown into 2 liters of methanol, polypropylene was precipitated, and it filtered and dried, and 54g of raw material alpha-olefin polymers (H) were obtained.

Production Example 12
[Production of Raw Material α-Olefin Polymer (I)]
20 g of the obtained raw material α-olefin polymer (H) was charged into a stainless steel reactor (with an internal volume of 500 ml) with a stirrer. The mixture was stirred for 30 minutes under a nitrogen stream.
Stirring was started, and the resin temperature was raised to 200 ° C. using a mantle heater. The mantle heater was controlled so that the resin temperature was constant at 280 ° C. To this, 0.11 ml of Park Mill P (trade name, manufactured by NOF Corporation) was dropped over 4 minutes. After completion of the dropwise addition, the reaction was performed for 15 minutes, and then cooled to 110 ° C.
After completion of the reaction, drying under reduced pressure at 100 ° C. was carried out for 10 hours to radically decompose to obtain raw material α-olefin polymer (I).
About the obtained raw material α-olefin polymer (I), melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), number of terminal unsaturated groups per molecule, mesopentad fraction [Mmmm], 2,1-bond fraction, 1,3-bond fraction, and glass transition temperature Tg were measured. The results are shown in Table 1.
Moreover, the yield of the obtained raw material α-olefin polymer (I) was 99.5% by mass relative to the charged raw material α-olefin polymer (H), and the amount of by-products was very small.

Example 1
[Production of Functionalized α-Olefin Polymer]
(Hydroboration reaction)
In a 500 ml flask, 10 g of the raw material α-olefin polymer (B) synthesized in Production Example 4 was dissolved in 50 ml of tetrahydrofuran, and then 50 ml of a 1.2 N borane tetrahydrofuran solution was added dropwise under a nitrogen atmosphere, and overnight at room temperature. Reacted.

(Oxidation (hydroxylation) reaction)
To the above reaction product, 7.5 ml of distilled water was slowly added dropwise, 20 ml of 3N-NaOH aqueous solution was added, and then 20 ml of 30% hydrogen peroxide solution was slowly added dropwise. The reaction solution was stirred at room temperature overnight. Distilled water (200 ml) was added to the reaction solution, extracted with toluene (200 ml), and washed with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 8 g of a viscous liquid functionalized α-olefin polymer (A).
About the obtained functionalized α-olefin polymer (A), the number of terminal hydroxyl groups per molecule, melting endotherm ΔHD, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm ], B viscosity and glass transition temperature Tg were measured, and fluidity was evaluated. The results are shown in Table 2.

[Production of curable composition and cured product]
While stirring 4.0 g of the functionalized α-olefin polymer (A) produced as described above using a separable flask under normal temperature nitrogen flow, 0.4 g of isophorone diisocyanate and normal butyltin dilaurate (cured) Catalyst) 0.04 g was added to obtain a curable composition. The obtained curable composition was poured into a 2.5 × 2.5 cm container and allowed to stand at room temperature for 1 hour to prepare a cured product.
The obtained cured product was heated on a hot plate controlled at 120 ° C. for 10 minutes, and its shape change was observed. As a result, it was confirmed that it was a cured product that retained its shape in a heated state and exhibited rubber elasticity.

Example 2
[Production of Functionalized α-Olefin Polymer]
Functionalized α-olefin polymer (B) in the same manner as in Example 1 except that the raw material α-olefin polymer (D) synthesized in Production Example 6 was used instead of the raw material α-olefin polymer (B). Manufactured.
About the obtained functionalized α-olefin polymer (B), the number of terminal hydroxyl groups per molecule, melting endotherm ΔHD, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm ], B viscosity and glass transition temperature Tg were measured, and fluidity was evaluated. The results are shown in Table 2.

[Production of curable composition and cured product]
A curable composition and a cured product were obtained in the same manner as in Example 1 except that the functionalized α-olefin polymer (B) produced as described above was used instead of the functionalized α-olefin polymer (A). Was made.
The obtained cured product was heated on a hot plate controlled at 120 ° C. for 10 minutes, and its shape change was observed. As a result, it was confirmed that it was a cured product that retained its shape in a heated state and exhibited rubber elasticity.

Example 3
[Production of Functionalized α-Olefin Polymer]
Functionalized α-olefin polymer (C) in the same manner as in Example 1 except that the raw material α-olefin polymer (F) synthesized in Production Example 8 was used instead of the raw material α-olefin polymer (B). Manufactured.
About the obtained functionalized α-olefin polymer (C), the number of terminal hydroxyl groups per molecule, melting endotherm ΔHD, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm ], B viscosity and glass transition temperature Tg were measured, and fluidity was evaluated. The results are shown in Table 2.

[Production of curable composition and cured product]
A curable composition and a cured product were obtained in the same manner as in Example 1 except that the functionalized α-olefin polymer (C) produced as described above was used instead of the functionalized α-olefin polymer (A). Was made.
The obtained cured product was heated on a hot plate controlled at 120 ° C. for 10 minutes, and its shape change was observed. As a result, it was confirmed that it was a cured product that retained its shape in a heated state and exhibited rubber elasticity.

Example 4
[Production of Functionalized α-Olefin Polymer]
Into a 100 mL separable flask equipped with a stirring blade, 40 g of the α-olefin polymer (F) produced in Production Example 8, 4.0 g of maleic anhydride, and 0.024 g of oxalic acid were added, and then 200 nm with a mantle heater in a nitrogen atmosphere. Heated to ° C. and stirred for 5 hours. After the temperature was lowered to room temperature, the reaction product was washed four times with acetone (80 mL) and dried by heating to obtain a polymer having maleic acid added to the terminal.
About the obtained polymer with maleic acid added to the terminal, the number of terminal hydroxyl groups per molecule, melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm] , B viscosity and glass transition temperature Tg were measured, and fluidity was evaluated. The results are shown in Table 2.

  To a 500 mL three-necked flask equipped with a Dimroth tube and a dropping funnel, 0.4 g of lithium aluminum hydride and 100 mL of dehydrated tetrahydrofuran (THF) were charged. A solution obtained by dissolving 40 g of a polymer having maleic acid added to the terminal in 100 mL of dehydrated THF was charged into a dropping funnel, and the above THF slurry of lithium aluminum hydride was added dropwise over 30 minutes while stirring. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After completion of the reaction, 50 mL of water was slowly added, 100 mL of hexane was further added, and the organic layer was separated with a separatory funnel. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a functionalized α-olefin polymer having a hydroxyl group end.

[Production of curable composition and cured product]
Instead of the functionalized α-olefin polymer (A), a curable composition and a cured product were obtained in the same manner as in Example 1 except that the functionalized α-olefin polymer having a hydroxyl group terminal obtained above was used. Manufactured.
The obtained cured product was heated on a hot plate controlled at 120 ° C. for 10 minutes, and its shape change was observed. As a result, it was confirmed that it was a cured product that retained its shape in a heated state and exhibited rubber elasticity.

Comparative Example 1
A functionalized α-olefin polymer will be produced in the same manner as in Example 1 except that the raw material α-olefin polymer (G) synthesized in Production Example 9 was used instead of the raw material α-olefin polymer (B). However, since there was no terminal unsaturated group, a hydroxyl group could not be added.
For this polymer, the number of terminal hydroxyl groups per molecule, melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm], B viscosity, glass transition temperature Tg Measured and evaluated for fluidity. The results are shown in Table 2.
Although a hydroxyl group could not be provided, while stirring 4.0 g of the obtained polymer using a separable flask under a normal temperature nitrogen flow, 0.4 g of isophorone diisocyanate and normal butyltin dilaurate (curing catalyst) 04 g was added to obtain a composition. The obtained composition was poured into a 2.5 × 2.5 cm container and allowed to stand at room temperature for 1 hour, but the curing reaction did not proceed and a cured product could not be obtained. For this reason, the composition after standing could not retain its shape on a hot plate controlled at 120 ° C. and did not exhibit rubber elasticity.
For this polymer, the number of terminal hydroxyl groups per molecule, melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm], B viscosity, glass transition temperature Tg Measured and evaluated for fluidity. The results are shown in Table 2.

Comparative Example 2
A functionalized α-olefin polymer will be produced in the same manner as in Example 1 except that the raw material α-olefin polymer (H) synthesized in Production Example 11 was used instead of the raw material α-olefin polymer (B). However, the solubility in the THF solvent was poor, and a hydroxyl group could not be imparted.
For this polymer, the number of terminal hydroxyl groups per molecule, melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm], B viscosity, glass transition temperature Tg Measured and evaluated for fluidity. The results are shown in Table 2.
Although a hydroxyl group could not be provided, while stirring 4.0 g of the obtained polymer using a separable flask under a normal temperature nitrogen flow, 0.4 g of isophorone diisocyanate and normal butyltin dilaurate (curing catalyst) 04 g was added to obtain a composition. The resulting composition was poured into a 2.5 × 2.5 cm container and allowed to stand at room temperature for 1 hour, but the curing reaction did not proceed, and the shape could not be maintained on a hot plate controlled at 120 ° C., There was no rubber elasticity.

Comparative Example 3
A functionalized α-olefin polymer will be produced in the same manner as in Example 1 except that the raw material α-olefin polymer (I) synthesized in Production Example 12 was used instead of the raw material α-olefin polymer (B). However, the solubility in the THF solvent was poor, and a hydroxyl group could not be imparted.
For this polymer, the number of terminal hydroxyl groups per molecule, melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm], B viscosity, glass transition temperature Tg Measured and evaluated for fluidity. The results are shown in Table 2.
Although a hydroxyl group could not be provided, while stirring 4.0 g of the obtained polymer using a separable flask under a normal temperature nitrogen flow, 0.4 g of isophorone diisocyanate and normal butyltin dilaurate (curing catalyst) 04 g was added to obtain a composition. The resulting composition was poured into a 2.5 × 2.5 cm container and allowed to stand at room temperature for 1 hour, but the curing reaction did not proceed, and the shape could not be maintained on a hot plate controlled at 120 ° C., There was no rubber elasticity.

Comparative Example 4
A functionalized α-olefin polymer was produced in the same manner as in Example 1 except that the raw material α-olefin polymer (A) synthesized in Production Example 3 was used instead of the raw material α-olefin polymer (B). . For this polymer, the number of terminal hydroxyl groups per molecule, melting endotherm ΔH-D, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), mesopentad fraction [mmmm], B viscosity, glass transition temperature Tg Measured and evaluated for fluidity. The results are shown in Table 2.
While stirring 4.0 g of the obtained polymer using a separable flask under a nitrogen flow at room temperature, 0.4 g of isophorone diisocyanate and 0.04 g of normal butyltin dilaurate (curing catalyst) were added to obtain a composition. Obtained. The obtained composition was poured into a 2.5 × 2.5 cm container and allowed to stand at room temperature for 1 hour, but the curing reaction was very slow, and the obtained cured product was not sufficiently crosslinked. On the hot plate controlled at 120 ° C., the shape could not be maintained and rubber elasticity was not exhibited.

  The functionalized α-olefin polymer of the present invention and the curable composition containing the same are used as a resin compatibilizing agent, polyolefin emulsion, reactive adhesive, reactive hot melt adhesive, other adhesives, pressure-sensitive adhesives, sealing agents. It can be widely used as a material and a raw material for stopping materials, sealing materials, potting materials, reactive plasticizers and the like.

Claims (9)

The α-olefin polymer has a hydroxyl group, and the α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, or propylene-1-butene copolymer, and the following (1) to (1) to A functionalized α-olefin polymer satisfying (4).
(1) The weight average molecular weight (Mw) is 1,000 to 500,000.
(2) The molecular weight distribution (Mw / Mn) is 1.1 to 2.5.
(3) The number of the hydroxyl groups per molecule is 1.1 to 4.0 .
(4) The melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 1 J / g or less. The functionalized α-olefin polymer according to claim 1 , wherein the α-olefin polymer is a propylene homopolymer or a 1-butene homopolymer having a mesopentad fraction [mmmm] of 20 mol% or less. The functionalized α-olefin polymer according to claim 1 , wherein the α-olefin polymer is a propylene-1-butene copolymer having a meso-dyad fraction [m] of 70 mol% or less. The functionalized α-olefin polymer according to claim 1 , wherein the functionalized α-olefin polymer is used for an adhesive, a sealing agent, a pressure-sensitive adhesive, or a modifier. (A) A curable composition comprising the functionalized α-olefin polymer according to any one of claims 1 to 4 and (B) a polyisocyanate compound. Furthermore, the curable composition of Claim 5 containing the (C) hardening acceleration | stimulation catalyst. Hardened | cured material formed by hardening | curing the curable composition of Claim 5 or 6 . The cured product according to claim 7 , wherein the cured product is used for an adhesive, a sealing agent, a pressure-sensitive adhesive, or a modifier. The number of terminal unsaturated groups per molecule and wherein the hydroxylating material α- olefin polymer is 1.1 to 2.0 units, functionalization of any one of claims 1 to 4 A method for producing an α-olefin polymer.