JP2002220428A - Triblock copolymer, its production method and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel crystalline triblock copolymer which is used as a molding material of a simple substance and as a compatibilizer, surfactant, modifier and mechanical property improver of other polymers or the like. SOLUTION: The copolymer is represented by a structural formula A-B-A [A is a crystalline isotactic polypropylene block; B is an amorphous elastomer block].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a triblock copolymer comprising a crystalline isotactic polypropylene block and an amorphous elastomer block. The invention also relates to a process for preparing such a copolymer and to its use.

[0002]

2. Description of the Related Art Regardless of whether a polymer is crystalline or amorphous, it is added in the production of polymer blends and polymer alloys to improve the surface activity, modification and mechanical properties of the polymer. It is necessary to stabilize the two elastomer components to a higher order structure, for example, to disperse or emulsify in a polymer matrix. Therefore, in general, a block copolymer is used as a compatibilizer in order to improve the compatibility between the polymer component and the elastomer component, which is a second component that is immiscible in the polymer matrix.

The compatibilizers actually used are mainly block copolymers and graft copolymers containing a matrix polymer component, and in particular, block copolymers having reactive functional groups and the like (LG Lundsted,
I. R. Schmolka, "Block and G
raft Copolymerization ”, R.A.
J. Ceresa Wiley, London 197
I.I. R. Schmolka,
J. Am. Oil Chem. Soc. 54 (197
7) 110, I.P. Piirma, Macromol C
hem. , Macromol Symp. 35/36
(1990) 467).

[0004] These block copolymers have a structure in which each block portion is composed of an amorphous polymer. In polymer blends and alloys,
When both the polymer matrix and the elastomer component as the second component are amorphous polymers, the second component can be dispersed in the matrix by using a block copolymer having each as a block component as a compatibilizer. . Also, when either one is crystalline, using a block copolymer in which each block portion is composed of an amorphous polymer as a physical property improver, for example, hydrogenating a block copolymer of styrene and butadiene It has been proposed that a poly (styrene-ethylene-butylene-styrene) block copolymer (SEBS) or the like be used as a physical property improver for crystalline polypropylene (JP-A-1-149845). However, even with block copolymers that are compatible with each of these matrices and second components,
Like low molecular weight surfactants, they themselves form intramolecular aggregates or microphase separated structures that follow the composition of the block copolymer. Thus, such block copolymers can self-aggregate (microphase separation) at concentrations above their critical micelle concentration that can disperse the second component in the matrix.
The drawback is that it is easy to do. That is, components that do not contribute to compatibilization of the second component are generated. Furthermore, the stability of the phase structure of polymer blends and alloys using these block copolymers is limited by the phase transition behavior (temperature and composition dependence) of this microphase separation. That is, the substance of the second component, which has been made compatible in the manufacturing process, is changed in the composition of the system (dilution for increasing the amount of the matrix or reducing the amount of the second component, etc.) or heating (in the first to higher processing steps) Decompatibilization / deco easily by melt mixing, stagnation, and reheating during recycling.
(Position) occurs, and it is difficult to stably form a higher order structure such as a finely dispersed structure and to improve mechanical properties which are originally targeted. Therefore, in examining the ability to form micelles at low concentrations, the ability to disperse and emulsify with dilution stability, the possibility of reducing the required amount of compatibilizer, etc., the structure and length of each block portion There is a need to develop block copolymers that are optimized.

[0005] Crystallization of macromolecules is a technically most important problem. That is, as a final result of a conformational change (conformation) of a molecular chain, mechanical properties are greatly affected. receive. In particular, the problem of how a molecular chain is led to an extended chain or folded is a thermodynamic problem, so the average chain length before folding depends on the thermal history of the polymer and the external environment. However, such a difference in conformation affects mechanical properties. In improving physical properties such as impact properties of a resin having a crystalline polymer of such a property as a matrix, simply mixing a rubber-like substance or a glass-like composition as an elastomeric substance of the second component can provide a crystalline matrix molecular chain. Is affected, and the mechanical properties of the mixed composition are generally lower than the average composition of the mechanical properties of each polymer (Leszek. A. Utr).
acki, "Polymer Alloys and
Blends: Thermodynamics a
nd Rheology ", Hanser, Oxfor
d Press, New York, 1989).

On the other hand, in addition to a block copolymer composed only of an amorphous block portion, the possibility of controlling a higher-order structure including conformation by using a block copolymer containing a crystalline component has been proposed (I.W.). .Haml
ey, “Crystalization in Blo
ck Copolymers ", Advancesin
Polymer Science, 1999, 148.
Volume 113 pages). This depends on the composition and structure of each crystalline-amorphous block portion of the block copolymer.
In order to form a macroscopically stable structure including a crystal phase by controlling intramolecular aggregation (microphase separation), one kind of crystalline polymer is used in some or all of the block components. Block copolymers and graft copolymers containing the above have been proposed. In such studies, examples of the crystalline block portion generally known for block copolymers include polyethylene / polyoxyethylene / polyethylene glycol / polytetrahydrofuran / polyε-caprolactone.

However, resins containing crystalline polymers such as isotactic polypropylene typified by polyolefin having crystallinity and polyamide known as engineering plastics, which are in great demand in the crystalline polymer market. In order to improve the physical properties, these crystalline polymers differ from the monomers of the amorphous polymer in terms of polymerizability and polymerization mechanism, and furthermore, the polymerization catalyst. Block copolymers and graft copolymers containing more than one species have not been synthesized or isolated and separated with a clear primary structure (see JP-A-8-92338 and JP-A-9-9338).
241334).

[0008]

In view of such circumstances, an object of the present invention is to use a crystalline polymer as a compatibilizer, a surfactant, a modifier, a mechanical property improver, or By directly using as one component, there is substantially no change in composition or demixing during heating, a high-order structure such as dispersibility is formed stably, and the characteristics of the crystalline polymer are improved in the above improvement. By substantially eliminating the loss of conformational change, the balance of physical properties is greatly improved compared to conventional materials, the mechanical strength is high, the rigidity, heat resistance, impact resistance are excellent, and the molding temperature is low because it does not demix. A novel crystalline triblock that can provide polymer blends and alloys with a large area and reduced molding defects (such as flow marks) due to resin flow Find polymer is to provide.

[0009]

In order to solve the above-mentioned problems, the present invention has a structural formula ABA, in which A is a crystalline isotactic polypropylene block (block A). , B moiety is an amorphous elastomeric block (block B). The triblock copolymer of the present invention has a covalent bond connecting a crystal part and an amorphous part in one molecular chain.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the block A portion of the triblock copolymer of the present invention is a crystalline isotactic polypropylene block, specifically, a propylene homopolymer or other α-olefin such as propylene and ethylene or butene-1 ( (Up to about 20 carbon atoms). Α in the block portion of these copolymers
-The content of the olefin is preferably at most 10 mol% in order not to lower its crystallinity. More specifically, it is particularly preferable to include an isotactic polypropylene block having high stereoregularity. Here referred to isotactic polypropylene block portion, ¹³ C nuclear magnetic resonance spectrum by isotactic pentad ratio (I
P) is preferably at least 85.0%. More preferably, the isotactic pentad fraction (IP) is 9
5.0% or more. The larger the IP, the higher the crystallinity and the greater the effect of the present invention. IP mentioned here
Is Macromolecules
es) According to the method described in Volume 6, page 925 (1973). That is, IP refers to an isotactic fraction in pentad units in a propylene-based polymer molecular chain measured using a nuclear magnetic resonance spectrum ( ¹³ C-NMR) of isotope carbon. In the present invention, I
P is a measure of the intermediate polypropylene block portion during the preparation of the novel triblock copolymer of the present invention. Assignment of peaks is described in Macromolecules, vol. 8, p. 687 (1).
975), IP was measured based on the fractional mmmm peak intensity of all the absorption peaks in the methyl carbon region of the ¹³ C-NMR spectrum.

With respect to the molecular weight of the block A portion, it is sufficient that the polymer has a sufficient chain length to have crystallinity. Specifically, the degree of polymerization is preferably 5 or more, more preferably 10 or more, and generally a chain length that can maintain the thickness of the polypropylene crystal lamella has sufficient crystallization ability. Also, if it has a suitable fluidity at the time of melting,
There is no particular upper limit for the molecular weight. Preferably, the degree of polymerization is 200,000 or less. The narrower the molecular weight distribution of the triblock copolymer of the present invention, the better. The fact that the triblock copolymer of the present invention can control the crystal structure of the isotactic polypropylene block portion is important because it shows one of the features of the present invention. In other words, an isotactic polypropylene chain that can be crystallized, which greatly contributes to mechanical properties, has its rotamer conformation either guided to an extended chain or folded. Whereas, while being thermodynamic in nature, the novel triblock copolymers of the present invention are capable of forming equilibrium folds, and the number of equilibrium folds is less than that of the amorphous block chains B
Can be controlled by the size of In order to form a conformational chain having a uniform number of equilibrium folds in the crystalline block A portion of the triblock copolymer of the present invention, the molecular weight distribution of the crystalline block A portion is preferably narrow. Specifically, Mw / Mn is preferably 2.5 or less, and more preferably Mw / Mn is 2.0 or less. In order to obtain such a narrow molecular weight distribution, a crystalline isotactic polypropylene having a relatively wide molecular weight distribution obtained by polymerization is dissolved in a solvent, and a well-known molecular weight fractionation method is applied. Good. As a specific molecular weight fractionation, a fractionation (Deslow method, Baker Williams method, etc.) by a cross-precipitation method using a good / poor solvent or a crystallization temperature classification method by adsorption to a heating column may be performed. However, the present invention is not limited to these.

The method for producing the crystalline isotactic polypropylene portion which is the block A portion of the triblock copolymer of the present invention is not particularly limited. In particular, using a coordination polymerization catalyst that gives isotactic polypropylene,
For example, it can be produced by polymerization of propylene or copolymerization of propylene with another α-olefin using a Ziegler-Natta catalyst or a metallocene catalyst. The isotactic polypropylene portion thus prepared has a terminal having a reactive group such as a double bond of an unsaturated hydrocarbon, for use in preparing a block copolymer. Specifically, examples of a catalyst system capable of producing a crystalline isotactic polypropylene having a double bond at a terminal include a Ziegler-Natta catalyst system such as magnesium chloride-supported tetravalent titanium halide-triethylaluminum, and ethylenebis (tetrahydrogen). Metallocene catalyst systems such as, but not limited to, (indenyl) zirconium dichloride-triethylaluminum-methylaluminoxane (T. Shiono, KS).
oka, Macromolecules, 25 , 335
6 (1992); Hayashi, Y .; Inou
e, R. Chujo, Y .; Doi, Polymer, 3
0, 1714 (1989)). More preferred are metallocene catalyst systems from which crystalline isotactic polypropylene having a narrow molecular weight distribution and terminal double bonds can be easily prepared. Further, as a method for specifically detecting the terminal double bond of isotactic polypropylene, a general method is used. For example, by measuring a ¹³ C-NMR spectrum by a solution method, Macromolecules (Macromolecules) is measured. ), 21 volumes, 2675
According to the assignment of each carbon described on page 1988, it can be confirmed that a double bond exists at one end.
Generally, the other terminal structure has a structure of 1-methylbutane. The crystalline isotactic polypropylene having a terminal double bond thus prepared can be used for preparing the novel block copolymer of the present invention.

In addition, as a method for preparing isotactic polypropylene, a catalyst component called a half metallocene catalyst such as methoxycarbonylmethylcyclopentadienyltrichlorotitanium is used, and a conjugated diene such as propylene is used as a monomer. E-2-methyl-1,3-pentadiene, which is a dimer, is subjected to stereoregular cis-1,4-living polymerization, and a catalytic hydrogenation reaction is performed using a Lindlar catalyst while maintaining the stereoregularity. Then, a method for preparing the same is mentioned. That is,
Crystalline isotactic polypropylene can be produced by a preparation method in which stereospecific polymerization and living polymerization are carried out simultaneously, and in the case of such a preparation method, since a terminal has a reactive group having a living terminal, The terminal double bond of the unsaturated hydrocarbon, which was essential in the described process, is not required. The crystalline isotactic polypropylene can be produced by the above method, but the production method of the triblock copolymer of the present invention is not limited to these.

Next, the amorphous block B will be described. The block B portion is an amorphous elastomer block, and specifically, has the following general formula 1

Embedded image [Wherein, A represents a block A portion, X represents hydrogen,
Alternatively, two Xs bonded to adjacent carbons together form a carbon-carbon double bond, and R ^{1 to} R ⁶
Each independently represents hydrogen or an unsaturated or saturated alkyl group having 1 to 8 carbon atoms, j, k and l each independently represent an integer of 0 or 1 or more, and at least one of them represents 1 or more And an elastomer block obtained by polymerization of an olefinically unsaturated monomer. The block B portion is substantially represented by the general formula 1, but may contain a unit derived from a polymerization initiator, a coupling agent, or the like. Olefinically unsaturated monomers include those having 2 to 2 carbon atoms.
20 α-olefins (including those having an aromatic group in the side chain), for example, ethylene, propylene, butene-1,
There are styrene and the like, and a diolefin having 4 to 20 carbon atoms, preferably a conjugated diene, for example, butadiene, isoprene, 2-methyl-1,3-pentadiene and the like. Preferred examples of the amorphous elastomer block in the block B portion include ethylene-propylene copolymer rubber, ethylene-butene copolymer rubber, ethylene and olefin having 2 to 20 carbon atoms (containing an aromatic group in a side chain). Or a copolymer rubber containing two or more of these olefins, a block copolymer composed of an ethylene-propylene block copolymer obtained by multistage polymerization, and a copolymer containing one or more conjugated diene monomers. Coalescence, for example, butadiene, isoprene, 2-methyl-1,3-
Examples include, but are not limited to, copolymers of pentadiene and the like with ethylene. Block B shown here
It is important that the portion is amorphous. That is, for example, if the number of methylene chains is large or the number of methylethylene chains having high stereoregularity is large, polyethylene crystals and polypropylene crystals are respectively shown, which is not preferable.

As to the molecular weight of the block B portion in the present invention, it is sufficient that the block B has a sufficient chain length to have the properties of a polymer. The specific molecular weight is preferably 1
00 g / mol or more, more preferably 1000 g / mo
1 or more. Particularly preferably, the chain length is such that the radius of inertia or the distance between both ends can be maintained at the same level as the thickness of the polypropylene crystal lamella. There is no particular upper limit on the molecular weight as long as it has appropriate fluidity during melting. More preferably, the molecular weight is 500,000 g / mol or less. Further, the molecular weight distribution of the block B portion is the same as described above for the crystalline block A portion, and a narrower one is preferred. Preferably, Mw / Mn is 2.0 or less. Living polymerization is suitable for producing an elastomer having such a narrow molecular weight distribution. Furthermore, when living anion polymerization using an organometallic compound as an initiator is used in the preparation of the block B portion, the amorphous block structure of the block B portion can be more accurately controlled by sequentially changing the monomers. More preferable (“New Polymer Science 2, Synthesis and Reaction of Polymer (1) Synthesis of Addition Polymer” ”, edited by The Society of Polymer Science, Kyoritsu Shuppan, 133
Pp. Et seq. (1995)). Among the polymerization initiators having such properties, those suitable for preparing the triblock copolymer include a bifunctional anionic polymerization initiator. However, if it is possible to prepare the block B portion represented by the above general formula 1, a known catalyst or a reaction system is used using a known technique such as living cationic polymerization, living coordination polymerization, or group transfer polymerization. be able to. However, the method for producing the block copolymer of the present invention is not limited to these.

In preparing the block B portion, when polymerizing the conjugated diene monomer, any of 1,4-polymerization, 1,2-polymerization, head-to-head and head-to-tail addition, and cis-trans-form can be used. Under the conditions of such addition polymerization and stereospecific polymerization, it can be used. For more information,
What has a carbon-carbon double bond in the main chain or the side chain of the block B portion can be used.
Further, the carbon-carbon double bond may be hydrogenated to obtain an amorphous olefin-based elastomer using a known technique. This is because hydrogenation of the carbon-carbon double bond increases the degree of rotational freedom in the molecule and dramatically increases the number of rotamers, thereby improving the performance of the elastomer by increasing entropy. preferable. As a specific hydrogenation reaction, a nickel-based catalyst or a platinum group-based catalyst (Lindlar catalyst) supporting calcium carbonate is used. As a reaction system, in various solvents such as water, a polar solvent, and a non-polar solvent, It can be carried out under various known conditions such as room temperature, normal pressure, high temperature and high pressure, fluidized bed system and fixed bed system, etc., but under mild conditions in which unsaturated hydrocarbons are almost completely hydrogenated and molecular chains are not decomposed. Is preferable (Japanese Patent Application Laid-Open No. 11-349626), but is not limited thereto.

As described above, in the triblock copolymer of the present invention, the block A portion and the block B portion may be prepared individually, simultaneously, or sequentially and sequentially. The method for preparing the block copolymer of the present invention is not limited to these. Specifically, an example of a method for preparing the triblock copolymer of the present invention will be described below. As described above, in a solvent such as a non-polar solvent, the terminal unsaturated bond of isotactic polypropylene is activated by a reaction with an organometallic compound such as naphthalene lithium, t-butyl lithium, s-butyl lithium, or the like. To obtain a terminal carbanion. Also,
As shown above, carbanions at both ends are obtained by living anionic polymerization of an olefinically unsaturated monomer with a bifunctional initiator. Furthermore, a triblock copolymer can be obtained by subjecting each of these terminal carbanions to a cross-coupling reaction. Examples of the coupling agent include, but are not limited to, a dihalogenated hydrocarbon at both ends and a halogenated silane compound. Such preparation is more preferable because the finally prepared block copolymer structure is clear by sampling at the preparation stage of each block portion. In addition, using the carbanion obtained by the reaction between the terminal unsaturated bond of the isotactic polypropylene and the organometallic compound as a polymerization starting point, the living monomer is successively anionically polymerized with the unsaturated monomer, and then the dimerization reaction is performed using a coupling agent. The method to be performed also enables the control of molecular weight and molecular weight distribution characteristic of living anionic polymerization,
This is a preferred method for producing the triblock copolymer of the present invention. Further, a conjugated diene as a monomer using a half metallocene catalyst such as methoxycarbonylmethylcyclopentadienyltrichlorotitanium,
For example, propylene dimer E-2-methyl-
Stereoregular cis-1,4-living polymerization of 1,3-pentadiene is performed, and a diene monomer such as butadiene or isoprene is added.
-After performing living polymerization to obtain a block copolymer,
A catalytic hydrogenation reaction is performed using a Lindlar catalyst or the like while maintaining stereoregularity, and propylene 2 polymerized first
Of the present invention by hydrogenating the polymer block portion of the dimer to isotactic polypropylene, and simultaneously hydrogenating the polymer block portion of the diene monomer polymerized successively to convert it to an olefinic elastomer which is a saturated hydrocarbon. The method for obtaining the novel crystalline triblock copolymer can also be exemplified, but not limited thereto.

In general, it is difficult to determine the conformation of a crystalline isotactic polypropylene chain which greatly contributes to mechanical properties, such as whether the conformation is led to an extended chain or folded. In contrast to the flow field, external fields such as stretching stress and crystallization temperature, thermodynamic problems such as temperature history, the crystalline novel triblock copolymer of the present invention obtained as described above, An equilibrium folded chain due to the microstructure can be formed, and the number of times of folding can be controlled by the size of the spatial spread of the amorphous block chain B. In addition, since not only the control of the crystal part but also the dissipation and demixing of the amorphous elastomer part can be suppressed, the novel crystalline triblock copolymer of the present invention is a novel crystalline triblock having a controlled structure. Because it is a block copolymer, it can be used not only as a molding material for the triblock copolymer of the present invention alone, but also as a product obtained by injection molding of general polymers and polymer blends, and in hollow fibers such as fibers, films, sheets and foams. The products obtained by extrusion molding, etc., have a homogeneous structure as a whole, have excellent moldability, and have a good balance of mechanical properties, and aim to stabilize the phase structure in reheating such as recyclability. For the purpose of modification, the triblock copolymer of the present invention is suitably used as a compatibilizer, a surfactant, a modifier, a mechanical property improver, and the like. It is also possible to have.

In particular, the novel crystalline triblock copolymer of the present invention is required to have various mechanical properties and its stability, and is further required to solve the problem of recyclability, and is required to solve the problem of recyclability. Also, it can be suitably used as a compatibilizing agent such as a polymer or a polymer blend, a surfactant, a modifying agent, a mechanical property improving agent and the like used for the production of packaging materials for food, cosmetic preparations and pharmaceutical preparations. . Other polymers that can be used by blending the triblock copolymer of the present invention for the above purpose include:
Examples include polyolefins such as polyethylene and polypropylene, styrene resins, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polyacrylic plastics, diene plastics, thermoplastics such as polyamides, polyesters, polycarbonates, and thermoplastic elastomers. As the polymer blend, a mixture of two or more of the other polymers or a mixture of one or more of the other polymers and additives such as a plasticizer, a stabilizer, and a coloring agent, if necessary, is used. be able to.

[0020]

The present invention will be further described below with reference to examples. The physical properties of the polymers in Examples and Comparative Examples were measured by the following methods. The present invention is not limited by these examples. Molecular weight (Mw) and molecular weight distribution (Mw / Mn) Measured using GPC under the following conditions. Preparation of calibration curve 1,2,4-trichlorobenzene 1 containing 0.1% by weight of 2,6-di-t-butyl-p-cresol (BHT)
In 0 ml, 2 mg of each of three kinds of standard polystyrene samples (manufactured by Showa Denko KK) having different molecular weights were added, dissolved at room temperature for 1 hour in a dark place, and then the elution time of the peak top was measured by GPC measurement. . This measurement was repeated, and based on the molecular weight at a total of 12 points (molecular weight of 580 g / mol to 8.5 million g / mol) and the elution time of the peak top, 1
A calibration curve was prepared by approximation of the following equation. The value measured in this way is a value in terms of polystyrene. Measurement of Sample 2 mg of a sample was placed in 5 ml of 1,2,4-trichlorobenzene containing 0.1% by weight of BHT, and dissolved while stirring at 160 ° C. for 2 hours, followed by GPC measurement. Other measurement conditions Apparatus: 150C manufactured by Waters Co., Ltd. Moving bed: 1,2,4-trichlorobenzene (BHT0.
Column: Showdex HT-G (1% by weight)
), Showdex HT-806M (2 pcs) Measurement temperature: 140 ° C Sample preparation: About 2 mg was added to 3.5 ml of 1,2,4-trichlorobenzene (containing 0.1% by weight of BHT).
Dissolved at 0 ° C. for 2 hours. Sample injection volume: 0.5 ml Flow rate: 1.0 ml / min

Isotactic pentad fraction (IP)
Measurement and Confirmation of Terminal Double Bond The IP measurement of crystalline isotactic polypropylene and confirmation of the terminal double bond were performed using GSX4 manufactured by JEOL Ltd.
The measurement was performed under the following measurement conditions using 00 ( ^13C nuclear resonance frequency: 100 MHz). IP is calculated according to the method described in Macromolecules, vol. 6, p. 925 (1973), and the confirmation of the terminal double bond is determined by Macromolecules (Macromocules).
recules, vol. 21, p. 2675 (1988). Measurement mode: Proton decoupling method Pulse width: 8.0 μs Pulse repetition time: 3.0 μs Number of integration: 20,000 times Solvent: 1,2,4-trichlorobenzene / deuterated benzene mixed solvent (75/25 weight) Ratio) Internal standard compound: hexamethyldisiloxane Sample concentration: 300 mg / 3.0 ml (solvent) Measurement temperature: 120 ° C. Confirmation of phase stability The crystallization temperature of a suggestive scanning calorimeter (DSC) was used as an index. As the DSC, Perkin Elmer's DSC7
The temperature was raised at a rate of 20 ° C./min and the temperature was lowered at 10 ° C./min, and the enthalpy ΔH of the crystallization temperature at the second temperature decrease was measured.

Example 1 (1) Preparation of olefin polymerization catalyst (metallocene catalyst)
Stirrer, reflux condenser, temperature sensor with internal temperature adjusted
And a double jacketed reactor with gas inlet
Indene (0.4 mol, 46.2
g) in THF (700 ml) while stirring.
176m of 2.5M n-butyllithium-hexane solution
1 was added dropwise over 40 minutes. Then, hexamethylphos
Horastriamide (HMPA: 0.44 mol, 76 m
1), cooled to -78 ° C,
Tan solution (0.22mol, 19ml) in THF 100
ml was added slowly. Slowly turn the resulting purple solution
Return to room temperature, cool to 0 ° C again, and in this state
Hydrolysis by adding a saturated aqueous solution of monium (200 ml)
did. Diethyl ether is added to the mixed solution separated into two phases.
100 ml was added, and the solution was transferred to a separating funnel.
After thoroughly washing the tellurium layer with water, washing with an aqueous copper sulfate solution
Remove MPA. Dry using anhydrous magnesium sulfate
And filtration gives a mixture of solid and oil, which is
The precipitate was reprecipitated with acetone-ethanol. This gives 1,
37 g of 2-bis (3-indenyl) ethane were obtained. this
1,2-bis (3-indenyl) ethane (38.8 mm
ol, 10 g) in a THF solution (150 ml) at 0 ° C.
1.6M n-butyllithium-hexane solution
48.5 ml of the liquid was added dropwise over 40 minutes. This solution is
Zirconium tetrachloride / THF complex prepared in another reactor
At once to a THF solution (14.7 g / 150 ml).
And stirred for 8 hours. Evaporate this mixed solution
Dry to dryness, add 100 ml of methylene chloride, filter and
A solid was obtained. After washing this yellow solid with toluene, ether
Wash the filtrate with water to make it clear and colorless,
(Et [Ind]_Two ZrCl_Two ) Got. Water of this complex
The digestion is shown below. In 1 liter stainless steel autoclave
This complex (Et [Ind]_Two ZrCl _Two ) Is 163m
g was added and suspended in 50 ml of methylene chloride. Black
Calcium carbonate supported Lindlar catalyst (Pd / Ca
CO_Three ), Hydrogen pressure 6.8 MPa, temperature 7
The reaction was performed at 0 ° C. for 100 minutes. After the reaction, return to normal pressure and chloride
After addition of 50 ml of methylene, the catalyst mixture was filtered and obtained.
The dried liquid is evaporated to dryness using an evaporator,
Et [H]_Four Ind] _Two Z
rCl_Two 110 mg was obtained. Recrystallized Et [H_Four In
d)_Two ZrCl_Two 0.4 g (0.96 mmol) of
Dehydrate well and place in a dry 500 ml flask,
Dissolve in 200 ml of anhydrous toluene and cool to 0 ° C in an ice water bath
While a 1.4 M methyllithium-ether solution
Add 1.34 ml and stir for 2 hours to methylate. Anti
The reaction mixture was filtered under dehydrated nitrogen and the filtrate was concentrated to -20.
While cooling to ° C, methylated Et [H_Four Ind]_Two 
ZrMe_Two Was recrystallized and recovered.
Wash three times with liters, dry and dry about 0.12 g
A fin polymerization catalyst component was obtained.

(2) Preparation of Block A Part The olefin polymerization catalyst Et [H ₄ Ind] ₂ Zr prepared above was placed in a 100 ml flask under a nitrogen atmosphere.
Me ₂ (5 mg) and 50 ml of a 10.7 wt% toluene solution of methylalumoxane (manufactured by Tosoh Akzo) were reacted at room temperature for 20 minutes. 4 ml of a 0.5 mol / l toluene solution of tri-i-butylaluminum (hereinafter abbreviated as TIBA) and 20 mol of propylene were introduced into an autoclave having an inner volume of 6.0 liter, and the temperature was raised to 50 ° C. Thereafter, the above-mentioned metallocene catalyst was injected into an autoclave and polymerization was carried out for 60 minutes. The resulting polymer was purified by a conventional method to obtain isotactic polypropylene having a melting point of 149.1 ° C. ^When confirmed by ¹³ C-NMR, IP was 9
5%, and a carbon-carbon double bond was present at one end. As a result of GPC measurement, the molecular weight Mw was 230,000, and the molecular weight distribution Mw / Mn was 1.8. Δ in DSC measurement
H was 80 J / g. (3) Preparation of Bifunctional Anion Polymerization Initiator A 200-ml flask equipped with a side tube and a stirrer was attached to a side tube under a vacuum line from which impurities were sufficiently removed so that living anion polymerization could be performed. Sodium (1.0 g) was liquefied by heating and charged into a flask, and the flask was further heated to form a sodium mirror in the flask with sodium vapor. When 150 ml of a THF solution of sufficiently purified α-methylstyrene (3.4 g) was added to the flask from a separately installed side tube, a clear red color was formed, and the reaction was further stirred for 3 hours. This was filtered through a glass filter to remove excess sodium, and a THF solution (0.192 mmol / l) of α-methylstyrene oligomer disodium salt (tetramer) used as a bifunctional anion polymerization initiator was obtained. . (4) Preparation of Block B Part Living Anion Polymerization in Vacuum Line A 300 ml flask was attached to a vacuum line from which impurities were sufficiently removed to enable living anion polymerization, and sufficiently purified [(1) Reflux and stirring with CaH _2. After the overnight operation, (2) the mixture was brought into contact with the granular sodium at room temperature and stirred for 24 hours or more. At this time, a small amount of oligomer is generated.
(3) Contacted with n-butyllithium at room temperature, (4) Distilled into a Schlenk tube and subdivided. 3.4 g of isoprene and 4.11 of 2-methyl-1,3-pentadiene
g of distilled water was introduced into the flask from each Schlenk tube under vacuum, and sufficiently purified n-hexane was introduced into the flask by distillation under vacuum. Return to room temperature, stir uniformly, and cool to 0 ° C. in an ice-water bath. When 10 ml of a THF solution of an anionic polymerization initiator α-methylstyrene oligomer disodium salt (tetramer) was added from a previously installed inlet tube with a breakable seal, the clear red initiator was once decolorized. A new transparent yellow color,
It was confirmed that a carbanion of the charged monomer was formed, and living anion polymerization was performed. After reacting for 12 hours or longer, the reaction solution was cooled in a liquid nitrogen bath to solidify the reaction solution. 0.0040 mmol of 1,2-dibromoethane previously prepared in the introduction tube was added at a stretch, and the mixture was heated to -70 ° C. with dry ice methanol to liquefy and react. A part of the reaction mixture was sampled, poured into 100 ml of methanol, and the filter rinse was dried under vacuum to obtain a polymer. Analysis shows that the molecular weight Mn is 2.6 × 10 ⁴ g / mol and the molecular weight distribution M
It was confirmed that the polymer was a poly ((1-methyl-1-butenylene) -CO- (1,3-dimethyl-1-butenylene)) having a w / Mn of 1.32. (5) Preparation of block copolymer A three-necked flask equipped with a refluxer from which impurities were sufficiently removed, an inlet tube and a stirrer was connected to a vacuum line, and the isotactic polypropylene obtained in (2) was recrystallized from hot xylene. Then, 0.3 g of a sufficiently purified product was added, and 80 ml of the purified toluene was added thereto while distilling under vacuum, and the inside of the system was replaced with argon gas. When the temperature was lowered to 90 ° C and a 0.01 M sec-butyllithium n-hexane solution was gradually added from the inlet tube, the solution suddenly turned orange fluorescent at 0.165 ml, and the terminal of isotactic polypropylene. It was confirmed that a double bond lithium carbanion was formed. While keeping the carbanion at 90 ° C. or higher, the cream-colored mixture prepared in (3) was added and reacted sufficiently with stirring. The discolored reaction mixture was returned to room temperature with stirring overnight, the filtered filtrate was poured into 2 liters of methanol, and the solid was separated by filtration and dried. The block copolymer was further purified by filtering off with hot xylene, returning to room temperature from the hot xylene solvent and recrystallizing. Next, the block copolymer was hydrogenated in the same manner as in the case of the catalyst preparation. That is, 0.2 g of this block copolymer was added to a 1-liter stainless steel autoclave, and suspended in 100 ml of toluene. Black calcium carbonate supported L
16 mg of an indlar catalyst (Pd / CaCo ₃ ) was added, and the mixture was reacted at a hydrogen pressure of 6.2 MPa and a temperature of 90 ° C. for 80 minutes. After the reaction, the pressure was returned to normal pressure, 100 ml of toluene was added, the catalyst mixture was filtered, the obtained liquid was evaporated to dryness by an evaporator, and this was recrystallized from hot xylene to obtain a nearly 100% hydrogenated block. A copolymer was obtained. Analysis of this purified block copolymer shows that G
According to PC measurement, Mw was 248.6 million, and Mw / Mn
Was 2.0. The isotactic polypropylene prepared in (2) and the amorphous elastomer poly ((1-methyl-1-butenylene) -CO- prepared in (4)
(1,3-dimethyl-1-butenylene)) was mixed at a composition of 5.6 wt% corresponding to the weight composition of this block copolymer, and the ΔH measured by DSC was 38 J / g. And the degree of crystallinity decreased with simple mixing. However, the ΔH of this block copolymer measured by DSC was 78 J
/ G, stabilization of the crystal phase was achieved.

Example 2 (1) and (2) of Example 1 were carried out in the same manner as described above. Without performing (3) and (4) of Example 1, the operation of (5) of Example 1 was changed as follows, and using a carbanion of isotactic polypropylene as an initiator,
After preparing the amorphous elastomer portion, a dimerization coupling reaction was performed. (5) Preparation of block copolymer A three-necked flask equipped with a refluxer from which impurities were sufficiently removed, an inlet tube and a stirrer was connected to a vacuum line, and (2) of Example 1 was used.
After recrystallizing the isotactic polypropylene obtained in the above from hot xylene, adding 0.3 g of a sufficiently purified product, adding 80 ml of dehydrated and purified toluene while distilling under vacuum, and replacing the system with argon gas. The mixture was heated to reflux at 110 ° C. to completely dissolve the polypropylene. The temperature was lowered to 90 ° C., and 0.01 M sec-butyllithium n-hexane solution was gradually added from the inlet tube to obtain 0.1%.
At 65 ml, the solution suddenly turned orange fluorescent, confirming the formation of lithium carbanion at the terminal double bond of isotactic polypropylene. While maintaining the carbanion at 90 ° C. or higher, a toluene solution of isoprene (10 mmol) previously charged in an introduction tube was added, and the mixture was sufficiently reacted with stirring. The reaction mixture in which the isoprene had a carbanion color (clear yellow) was stirred for 6 hours while gradually returning to room temperature. The reaction mixture was solidified in a liquid nitrogen bath, and the 1,2-
0.0040 mmol of dibromoethane in toluene 1
0 ml at a time and dry ice methanol to -70
The mixture was liquefied by heating to ℃ C, and a coupling reaction was performed. The mixture was returned to room temperature, filtered, the filtrate was poured into 2 liters of methanol, and the solid was separated by filtration and dried. The block copolymer was further purified by filtration with hot xylene and recrystallization from the hot xylene solvent to room temperature. Here, polyisoprene polymerized from excess s-butyllithium is soluble in xylene, and when analyzed, has a Mw of 2200 and a Mw / M
It is a poly (isoprene) wherein n is 1.20, and it was found that it corresponds to the molecular weight and the molecular weight distribution of the amorphous part B of the generated block copolymer from the living anionic polymerizability. A mixture of the isotactic polypropylene prepared in (2) of Example 1 and the poly (isoprene) recovered from xylene in (5) of Example 2 at a composition of 8: 1 was prepared.
The ΔH in the SC measurement was 53.7 J / g, which was much lower than the value of the isotactic polypropylene alone, and the crystallinity was reduced by simple mixing. However, ΔH of this block copolymer measured by DSC was 77 J / g, and stabilization of the crystal phase was achieved. Further, ΔH by DSC measurement of a mixture of the block copolymer and the polyisoprene prepared in (5) of Example 2 at a composition of 9: 1 was 8%.
It was 0 J / g, and it was found that the elastomer phase was stably contained.

Example 3 In the same manner, (1), (2) and (3) of Example 1 were performed, and the operation of (4) of Example 1 was changed as follows. Further, the operation of (5) of Example 1 was carried out in the same manner except that the amorphous elastomer portion changed in (4) of Example 3 was used. (4) Preparation of Block B Part Living Anion Polymerization in Vacuum Line A 300 ml flask was attached to a vacuum line from which impurities were sufficiently removed to enable living anion polymerization.
40 ml of fully purified isoprene and 40 butadiene
mmol, 2-methyl-1,3-pentadiene 20
mmol [diene monomer was purified as follows. (1) After reflux stirring with CaH ₂ overnight,
(2) Contacted with granular sodium at room temperature and stirred for 24 hours or more. At this time, a small amount of oligomer is generated.
(3) It was brought into contact with n-butyllithium at room temperature, and (4) distilled into a Schlenk tube. Was distilled into the flask through a Schlenk tube under vacuum, and 30 ml of sufficiently purified toluene was similarly introduced into the flask by distillation under vacuum. The mixture was returned to room temperature, stirred uniformly, and cooled to 0 ° C. in an ice water bath. The bifunctional anionic polymerization initiator α obtained above was obtained from a pre-installed introduction tube with a breakable seal.
-Methylstyrene oligomer disodium salt (tetramer)
When a THF solution (10 ml) was added, the clear red initiator was once erased, and a new transparent yellow color was formed, whereby it was confirmed that the charged carbanion was formed, and living anion polymerization was carried out. After reacting for 10 hours or more, the reaction solution was solidified by cooling in a liquid nitrogen bath.
10 ml of a toluene solution of 0.0040 mmol of 1,2-dibromoethane previously prepared in an introduction tube was added at a dash, and the mixture was heated to -70 ° C. with dry ice methanol to liquefy and react. A part of this yellowish cream reaction mixture was sampled to give 1
Poured into 00 ml methanol, the filter residue was thoroughly rinsed and dried in vacuo to give the polymer. Analysis shows that the molecular weight Mn is 2600 g / mol and the molecular weight distribution Mw
/(Mn=1.2) poly ((1-methyl-1-butenylene) -CO- (1-butenylene) -CO- (1,3-
Dimethyl-1-butenylene)). (5) Preparation of block copolymer The same operation as in (5) of Example 1 was performed, except that the reaction mixture as the amorphous elastomer part in (4) of Example 3 was used. Δ in DSC measurement of a mixture of the isotactic polypropylene prepared in Example 1 (2) and the elastomer prepared in Example 3 (3) at a composition of 8: 1.
H was 62.4 J / g, which was much lower than the value of the isotactic polypropylene alone, and the crystallinity was reduced by simple mixing. However, the DSC of this block copolymer
ΔH in the measurement was 80 J / g, and stabilization of the crystal phase was achieved.

[0026]

The novel crystalline triblock copolymer of the present invention is a novel crystalline block copolymer having a controlled structure, so that it can be used not only as a molding material for the block copolymer alone but also as a general polymer. Products obtained by injection molding of polymers and polymer blends and products obtained by hollowing out fibers, films, sheets, foams, and extrusion molding, etc., have a uniform structure as a whole, and have excellent moldability and good mechanical properties. This triblock copolymer is a compatibilizer, a surfactant, a modifier, and a mechanical property improver for the purpose of resin modification. It can also be suitably used as such.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4J002 AC02X BB03X BB12X BC03X BD04X BE02X BG01X BG10X BP02W BP03W CF00X CG00X CL00X 4J026 HA04 HB02 HB39 HB45 HC05 HE02

Claims (10)

[Claims] 1. An olefinic elastomer block (block A) wherein the portion A is a crystalline isotactic polypropylene block (block A) and the portion B is an amorphous olefinic elastomer block (block A) B) a triblock copolymer. 2. The triblock copolymer according to claim 1, wherein the block A part has an average degree of polymerization m of 5 to 200,000 and the molecular weight distribution Mw / Mn is 2.5 or less. 3. The block B portion is represented by the following general formula 1. [Wherein, A represents a block A portion, X represents hydrogen,
Alternatively, two Xs bonded to adjacent carbons together form a carbon-carbon double bond, and R ^{1 to} R ⁶
Each independently represents hydrogen or an unsaturated or saturated alkyl group having 1 to 8 carbon atoms, j, k and l each independently represent an integer of 0 or 1 or more, and at least one of them represents 1 or more And an olefinic elastomer block obtained by polymerization of an olefinically unsaturated monomer.
Or the triblock copolymer according to 2. 4. The block B portion is 100 to 500,00
The triblock copolymer according to any one of claims 1 to 3, which has a molecular weight of 0 g / mol and a molecular weight distribution Mw / Mn of 2.0 or less. 5. The method according to claim 5, wherein the block A portion has an isotactic pentad fraction (I) determined by ¹³ C nuclear magnetic resonance spectrum analysis.
The triblock copolymer according to any one of claims 1 to 4, wherein P) is 85.0% or more, and the average degree of polymerization m of the block chain is 10 to 100,000. 6. A carbanion obtained by reacting a terminal unsaturated bond of isotactic polypropylene with an organometallic compound and a carbanion obtained by living anionic polymerization of an olefinically unsaturated monomer with a bifunctional initiator, Either a coupling reaction with a ring agent or a living anionic polymerization of an olefinically unsaturated monomer is carried out successively with a carbanion obtained by the reaction of a terminal unsaturated bond of isotactic polypropylene with an organometallic compound, followed by dihalogenation. The method for producing a triblock copolymer according to claim 1, comprising dimerization with a hydrocarbon or a coupling agent. 7. The method according to claim 6, wherein the block A portion is an isotactic polypropylene block having a terminal unsaturated bond obtained by a metallocene-based catalyst. 8. Use of the triblock copolymers according to claim 1 as molding materials or as compatibilizers, surfactants, modifiers or property enhancers for other polymers or polymer blends. 9. For the manufacture of automobiles or home appliances,
Use according to claim 8. 10. Use according to claim 8, for the production of packaging materials for foodstuffs, cosmetic preparations or pharmaceutical preparations.