Polyolefin-polystyrene multi-block copolymer and preparation method thereof
阅读说明：本技术 聚烯烃-聚苯乙烯多嵌段共聚物及其制备方法 (Polyolefin-polystyrene multi-block copolymer and preparation method thereof ) 是由 林涩琪 史锡必 李贤模 朴志贤 金润坤 李琪树 申恩知 于 2020-05-15 设计创作，主要内容包括：本发明涉及具有其中聚苯乙烯链连接到聚烯烃链的两端的结构的聚烯烃-聚苯乙烯多嵌段共聚物,及其制备方法。本发明提供的聚烯烃-聚苯乙烯多嵌段共聚物具有优异的机械性质,例如拉伸强度、断裂伸长率和模量,从而用于各种工业应用。(The present invention relates to a polyolefin-polystyrene multiblock copolymer having a structure in which a polystyrene chain is connected to both ends of a polyolefin chain, and a method for preparing the same. The polyolefin-polystyrene multi-block copolymer provided by the present invention has excellent mechanical properties such as tensile strength, elongation at break and modulus, and thus is used in various industrial applications.)
1. A polyolefin-polystyrene multiblock copolymer satisfying the following conditions (a) to (c) as determined by Gel Permeation Chromatography (GPC) and having13C NMR (500MHz, tetrachloroethane-d 2, TMS standard material) spectrum satisfies the following condition (d):
(a) a weight average molecular weight of 50,000 to 150,000 g/mol;
(b) a molecular weight distribution of 1.5 to 3.0;
(c) a gaussian function modeled by a graph with logMw on the x-axis and dw/dlogMw on the y-axis with respect to the measurement result of gel permeation chromatography is represented by the following equation 1, wherein in the following equation 1, each constant value satisfies 0.006< a <0.04, 4.6< B <5.0, 0.9< C <1, and 0.5< D < 0.9; and
(d) the polyolefin block contained in the polyolefin-polystyrene multiblock copolymer comprises at least one branch point, wherein the branch point carbon atom shows a peak of 36 to 40ppm, and the terminal carbon atom of the branch derived from the branch point shows a peak of 13 to 15ppm,
[ equation 1]
In the above equation 1, Mw represents the weight average molecular weight of the polyolefin-polystyrene multi-block copolymer.
2. The polyolefin-polystyrene multiblock copolymer of claim 1, wherein each constant value in the above equation 1 is 0.007< a <0.035, 4.6< B <4.9, 0.91< C <0.99 and 0.6< D < 0.8.
3. The polyolefin-polystyrene multiblock copolymer of claim 1, wherein the weight average molecular weight thereof is 60,000 to 120,000 g/mol.
4. The polyolefin-polystyrene multiblock copolymer of claim 1, wherein the molecular weight distribution thereof is 1.6 to 2.3.
5. The polyolefin-polystyrene multiblock copolymer of claim 1, wherein the polyolefin-polystyrene multiblock copolymer is at least one selected from the group consisting of: polystyrene-poly (ethylene-co-propylene) -polystyrene block copolymers, polystyrene-poly (ethylene-co-1-butene) -polystyrene block copolymers, polystyrene-poly (ethylene-co-1-pentene) -polystyrene block copolymers, polystyrene-poly (ethylene-co-1-hexene) -polystyrene block copolymers, polystyrene-poly (ethylene-co-1-heptene) -polystyrene block copolymers, and polystyrene-poly (ethylene-co-1-octene) -polystyrene block copolymers.
Technical Field
The present invention relates to a polyolefin-polystyrene multiblock copolymer having a structure in which a polystyrene chain is connected to both ends of a polyolefin chain, and a method for preparing the same.
Background
Block copolymers are being actively researched and developed as materials widely used not only in general plastics but also in high-tech devices. In particular, a styrene-olefin copolymer resin simultaneously comprising a Polyolefin (PO) block and a Polystyrene (PS) block has excellent heat resistance, light resistance, elastic force, and the like, and thus can be used in various technical fields.
Currently, a market for polyolefin-polystyrene block copolymers, such as styrene-ethylene-butylene-styrene (SEBS) or styrene-ethylene-propylene-styrene (SEPS), has formed globally on a scale of several tens of thousands of tons. Representative examples of the styrene-olefin copolymer resin may include a polystyrene-block-poly (ethylene-co-1-butylene) -block-polystyrene (SEBS) triblock copolymer. SEBS triblock copolymers exhibit the characteristics of thermoplastic elastomers because the hard polystyrene domains in their structure are separated from the soft poly (ethylene-co-1-butene) matrix and serve as physical crosslinking sites. According to these characteristics, SEBS has been widely used in products requiring rubber, plastic, etc., and the demand for it has been greatly increased as the range of use thereof has been gradually expanded.
Meanwhile, since the molecular weight and molecular weight distribution of the copolymer are key factors for determining mechanical properties, thermal properties, etc. of the material and have a great influence on processability, it is being recognized that analyzing the molecular weight to analyze physical properties of the copolymer is the most basic and important technique. The method of determining the molecular weight includes various methods such as viscometry, end group analysis, light scattering method, and the like, but the most widely used method is a method using Gel Permeation Chromatography (GPC).
GPC is a method of separating materials according to molecular weight differences by packing a porous gel in a chromatography column and using the following phenomena: the material having a large molecular weight is not discharged through the pores in the gel, thereby reducing the retention time, while the material having a small molecular weight is discharged after passing through the pores of the gel, thereby increasing the retention time. Therefore, the number average molecular weight, the weight average molecular weight, and the like can be calculated.
Under the above-mentioned background, the present inventors studied a method for preparing a polyolefin-polystyrene multiblock copolymer exhibiting desired physical properties such as tensile strength and elongation at break, and confirmed that a polyolefin-polystyrene multiblock copolymer exhibiting desired physical properties can be prepared by controlling the weight average molecular weight and molecular weight distribution of the copolymer within specific ranges, thereby completing the present invention.
[ Prior art documents ]
[ patent document ]
(patent document 1) Korean patent No. 10-1657925
Disclosure of Invention
Technical problem
An aspect of the present invention provides a polyolefin-polystyrene multiblock copolymer having a structure in which a polystyrene chain is connected to both ends of a polyolefin chain, and more particularly, a polyolefin-polystyrene multiblock copolymer exhibiting excellent mechanical properties such as tensile strength, elongation at break, and modulus by maintaining a specific relationship of weight average molecular weight and molecular weight distribution.
Technical scheme
According to an aspect of the present invention, there is provided a Gel Permeation Chromatography (GPC) sensor satisfying the following conditions (a) to (c)13A polyolefin-polystyrene multiblock copolymer satisfying the following condition (d) in a C NMR (500MHz, tetrachloroethane-d 2, TMS as a standard material) spectrum:
(a) a weight average molecular weight of 50,000 to 150,000 g/mol;
(b) a molecular weight distribution of 1.5 to 3.0;
(c) a gaussian function modeled by a graph with logMw on the x-axis and dw/dlogMw on the y-axis with respect to the measurement result of gel permeation chromatography is represented by the following equation 1, wherein in the following equation 1, each constant value satisfies 0.006< a <0.04, 4.6< B <5.0, 0.9< C <1, and 0.5< D < 0.9; and
(d) the polyolefin block contained in the polyolefin-polystyrene multiblock copolymer includes at least one branch point, wherein the branch point carbon atom shows a peak of 36 to 40ppm, and the terminal carbon atom of the branch derived from the branch point shows a peak of 13 to 15 ppm.
[ equation 1]
(in the above equation 1, Mw represents the weight average molecular weight of the polyolefin-polystyrene multiblock copolymer.)
Advantageous effects
The polyolefin-polystyrene multi-block copolymer provided by the present invention has excellent mechanical properties such as tensile strength, elongation at break and modulus, and thus is used in various industrial applications.
Drawings
FIG. 1 shows a ligand compound according to an embodiment of the present invention1H NMR and13c NMR spectrum;
FIG. 2 shows transition metal compounds according to an embodiment of the present invention1H NMR and13c NMR spectrum;
FIG. 3 is a graph illustrating a polyolefin-polystyrene multi-block copolymer according to an embodiment of the present invention represented by equation 1; and
FIG. 4 shows a polyolefin-polystyrene multi-block copolymer according to an embodiment of the present invention13C NMR spectrum.
Detailed Description
Hereinafter, the present invention will be described in more detail to help understanding the invention.
The terms or words used in the present specification and claims should not be construed as limited to conventional or dictionary meanings, but interpreted as meanings and concepts conforming to the technical spirit on the basis of the principle that the inventor can appropriately define the concept of the term to explain the invention in the best way.
The term "composition" as used herein includes reaction products and decomposition products formed from the materials of the composition as well as mixtures of materials included in the composition.
The term "polymer" as used herein refers to a polymer compound prepared by polymerizing monomers, whether of the same or a different type. As such, the generic term "polymer" encompasses the term "homopolymer" as commonly used to refer to polymers prepared from only one type of monomer, as well as the term "interpolymer" as defined below.
The term "interpolymer" as used herein refers to a polymer prepared by the polymerization of at least two different types of monomers. As such, the generic term "interpolymer" includes copolymers, which are conventionally employed to refer to polymers prepared from two different types of monomers, and polymers prepared from two or more different types of monomers.
The present invention will be described in detail below.
Polyolefin-polystyrene multiblock copolymer
The polyolefin-polystyrene multiblock copolymer of the present invention is characterized by satisfying the following conditions (a) to (c) as measured by Gel Permeation Chromatography (GPC) and13c NMR (500MHz, tetrachloroethane-d 2, TMS standard material) spectrum satisfies the following condition (d):
(a) a weight average molecular weight of 50,000 to 150,000 g/mol;
(b) a molecular weight distribution of 1.5 to 3.0;
(c) a gaussian function modeled by a graph with logMw on the x-axis and dw/dlogMw on the y-axis with respect to the measurement result of gel permeation chromatography is represented by the following equation 1, wherein in the following equation 1, each constant value satisfies 0.006< a <0.04, 4.6< B <5.0, 0.9< C <1, and 0.5< D < 0.9; and
(d) the polyolefin block contained in the polyolefin-polystyrene multiblock copolymer includes at least one branch point, wherein the branch point carbon atom shows a peak of 36 to 40ppm, and the terminal carbon atom of the branch derived from the branch point shows a peak of 13 to 15 ppm.
[ equation 1]
(in the above equation 1, Mw represents the weight average molecular weight of the polyolefin-polystyrene multiblock copolymer.)
The polyolefin-polystyrene multiblock copolymer of the present invention is prepared by using a specific transition metal compound having a novel structure as described below as a catalyst, and is characterized in that a weight average molecular weight, which is a key factor determining physical properties of the copolymer, satisfies equation 1 to have a specific weight average molecular weight distribution and molecular weight distribution values, thereby exhibiting excellent tensile properties (e.g., tensile strength, elongation, modulus, etc.).
With respect to the condition (a), the weight average molecular weight of the polyolefin-polystyrene multiblock copolymer may be 50,000g/mol to 150,000g/mol, particularly 60,000g/mol to 120,000g/mol, or 70,000g/mol to 100,000 g/mol.
With respect to condition (b), the polyolefin-polystyrene multi-block copolymer may have a molecular weight distribution of 1.5 to 3.0, specifically 1.6 to 2.3, or 1.6 to 2.2.
The weight average molecular weight and the number average molecular weight are both molecular weights in terms of polystyrene analyzed by Gel Permeation Chromatography (GPC), and the molecular weight distribution is calculated from the ratio of (weight average molecular weight)/(number average molecular weight).
As described below, equation 1 of the condition (c) represents a gaussian distribution in which constants B to D contained therein serve as constants representing the weight average molecular weight and the molecular weight distribution of the copolymer, respectively, and the copolymer of the present invention satisfies the numerical range of a to D described above, and satisfies the weight average molecular weight and the molecular weight distribution values of the conditions (a) and (B) at the same time.
Regarding the condition (C), when the above equation 1 is derived from a gaussian function modeled by a graph of log mw on the x-axis and dw/dlogMw on the y-axis with respect to the measurement result of gel permeation chromatography, each constant value included in equation 1 satisfies 0.006< a <0.04, 4.6< B <5.0, 0.9< C <1, and 0.5< D < 0.9. In particular, constant a can be greater than 0.006, greater than 0.007, less than 0.040, or less than 0.035, constant B can be greater than 4.6, less than 5.0, or less than 4.9, constant C can be greater than 0.90, greater than 0.91, less than 1.00, or less than 0.99, and constant D can be greater than 0.5, greater than 0.6, less than 0.9, or less than 0.8.
As described above, the above equation 1 represents a differential molecular weight distribution curve in which the horizontal axis represents the logarithm of the weight average molecular weight (Mw) (log (Mw)) ", and the vertical axis represents the value" dw/dlog (Mw)) "obtained by differentiating the concentration fraction (w) with respect to the logarithm of the weight average molecular weight (log (Mw)), which is measured by gel permeation chromatography based on polystyrene standards, which can be regarded as representing the weight fraction of the polymer having the corresponding molecular weight based on the logarithm of the weight average molecular weight.
That is, the gaussian function modeled from the graph in which the x-axis is logMw and the y-axis is dw/dlogMw is represented by equation 1 above, and it has been newly found that: each of the constants a to D calculated falls within a specific range.
In the above equation 1, the constants a to D are constants representing a curve represented by a gaussian distribution, and show the height of the distribution curve, the width of half the value of the maximum peak, the center position represented by the maximum peak, and the like. More specifically, a constant a included in the gaussian distribution represents a y-axis intercept, and a constant C represents an arithmetic mean of a graph area. In addition, constants B and D represent physical properties of the copolymer corresponding to the weight average molecular weight and the molecular weight distribution.
With respect to the condition (d), the polyolefin block contained in the polyolefin-polystyrene multiblock copolymer includes at least one branch point, wherein the branch point carbon atom shows a peak of 36 to 40ppm, and the terminal carbon atom of the branch derived from the branch point shows a peak of 13 to 15 ppm.
In particular, the branch point carbon atom may be 36.0ppm or more, 37.0ppm or more, or 37.5ppm or more, and may be 40.0ppm or less, 39.0ppm or less, or 38.5ppm or less. The terminal carbon atom of the branch derived from the branch point may be 13.0ppm or more, or 13.5ppm or more, and may be 15.0ppm or less, or 14.5ppm or less.
As described above, the polyolefin-polystyrene multiblock copolymer of the present invention has long branches in the polyolefin block, which can be identified as branches originating from branch points having terminal carbon atoms at the terminal carbon atoms13Unique peak region in C NMR. Therefore, the polyolefin-polystyrene multiblock copolymer of the present invention exhibits superior physical properties, such as high impact strength, compared to conventional copolymers.
The polyolefin-polystyrene multi-block copolymer may be at least one selected from the group consisting of: polystyrene-poly (ethylene-co-propylene) -polystyrene block copolymers, polystyrene-poly (ethylene-co-1-butene) -polystyrene block copolymers, polystyrene-poly (ethylene-co-1-pentene) -polystyrene block copolymers, polystyrene-poly (ethylene-co-1-hexene) -polystyrene block copolymers, polystyrene-poly (ethylene-co-1-heptene) -polystyrene block copolymers, and polystyrene-poly (ethylene-co-1-octene) -polystyrene block copolymers.
In addition, the polyolefin-polystyrene multiblock copolymer of the present invention may have the following tensile properties by satisfying the conditions (a) to (d).
In particular, the polyolefin-polystyrene multi-block copolymer may have a tensile strength of 10MPa to 100MPa, particularly 10MPa to 50MPa, and more particularly 20MPa to 40MPa, which shows a maximum tensile stress when the material is stretched and broken by a load uniformly applied to a cross-sectional region thereof.
The polyolefin-polystyrene multi-block copolymer may have an elongation at break, expressed as a percentage of the ratio of increased length to initial length, which is the strain in the direction of elongation caused by a stretching force, of 500% to 3,000%, 600% to 2,800%, or 800% to 2,500%.
The polyolefin-polystyrene multi-block copolymer has a 300% modulus of 2.1MPa to 10.0MPa, which is a tensile stress at 300% elongation and shows an average force per unit area, and has excellent strength and elasticity, thereby having excellent toughness.
Tensile properties such as tensile strength, elongation at break, and 300% modulus can be measured according to ASTM D412 standard measurement methods.
As such, the polyolefin-polystyrene multiblock copolymer of the present invention satisfies the tensile strength, elongation at break and 300% modulus within the above ranges, exhibits excellent physical properties as compared to conventional copolymers, and can produce a copolymer exhibiting specific physical properties according to its use by controlling the length and content of the polyolefin block using the preparation method provided in the present invention.
In addition, the polyolefin block of the copolymer of the present invention may comprise at least one repeating unit represented by the following formula a:
[ formula a ]
In the above-mentioned formula a, the compound (A),
R1is hydrogen, an alkyl group having 1 to 20 carbon atoms substituted with a silane group, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms substituted with a silane group,
n may be an integer of 1 to 10,000.
In addition, according to an embodiment of the present invention, R is1May be hydrogen or an alkyl group having 3 to 20 carbon atoms.
In addition, according to an embodiment of the present invention, R is1May be hydrogen or an alkyl group having 3 to 12 carbon atoms, and particularly, the above-mentioned R1May be hydrogen or an alkyl group having 4 to 12 carbon atoms.
In addition, the above n may be an integer of 10 to 10,000, particularly 500 to 7,000.
Meanwhile, "+" in the formulae shown in the present specification denotes a linking moiety, which is a terminal portion of the repeating unit.
When the polyolefin block includes at least two or more repeating units represented by formula a above, the polyolefin block may include the following repeating units represented by formula b below:
[ formula b ]
In the above-mentioned formula b, the,
R1' and R1"are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms substituted with a silane group, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms substituted with a silane groupWherein R is as defined above1' and R1"are different from each other in that,
0< p <1, and
n' may be an integer of 1 to 10,000.
In addition, according to an embodiment of the present invention, R is1' and R1"may be each independently hydrogen or an alkyl group having 3 to 20 carbon atoms, may be each independently hydrogen or an alkyl group having 3 to 12 carbon atoms, and may be each independently hydrogen or an alkyl group having 4 to 12 carbon atoms.
In addition, n' may be an integer of 10 to 10,000, and more particularly an integer of 500 to 7,000, in particular.
According to an embodiment of the present invention, in the above formula b, R1' and R1One of "may be hydrogen, and the other may be a substituent other than hydrogen among the above substituents.
That is, when the polyolefin block comprises at least two repeating units represented by formula a above, wherein R is1Is a structure of hydrogen and wherein R1Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a silane group, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms substituted with a silane group, other than hydrogen, may be randomly connected, and in particular, wherein R is1Is a structure of hydrogen and wherein R1Structures that are alkyl groups having 3 to 20 carbon atoms other than hydrogen may be randomly connected.
In addition, more particularly, the polyolefin block may be of the formula a above wherein R1Is a structure of hydrogen and wherein R1Is a structurally randomly linked polyolefin block having an alkyl group of 3 to 20 carbon atoms, and even more particularly the polyolefin block may be of formula a above wherein R is1Is a structure of hydrogen and wherein R1Is a structurally randomly linked polyolefin block having an alkyl group of 4 to 12 carbon atoms.
When the polyolefin block comprises at least two repeating units represented by the above formula aThe polyolefin block may be comprised in the above formula a in a weight ratio of 30:90 to 70:10, in particular in a weight ratio of 40:60 to 60:40, more in particular in a weight ratio of 45:75 to 55:25, wherein R1Is a structure of hydrogen and wherein R1Is a structure of a substituent other than hydrogen.
When the polyolefin block comprises R in the above range1Is a structure of hydrogen and wherein R1Is a structure of a substituent other than hydrogen, the prepared block copolymer includes an appropriate degree of branching within the structure, and thus may have a high 300% modulus value and elongation at break to exhibit excellent elastic properties, and may exhibit a broad molecular weight distribution as well as a high molecular weight to have excellent processability.
In addition, the first polystyrene block of the copolymer of the present invention may comprise at least one repeating unit represented by the following formula c:
[ formula c ]
In the above-mentioned formula c, the,
R2is an aryl group having 6 to 20 carbon atoms; or an aryl group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
l is independently an integer from 10 to 1,000.
R is as defined above2May be phenyl, or phenyl which is unsubstituted or substituted by halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, or aryl having 6 to 12 carbon atoms, and R2May be phenyl.
The above l may be an integer of 10 to 1,000, and particularly an integer of 50 to 700, and when l is within the above range, the polyolefin-polystyrene block copolymer prepared by the preparation method of the present invention may have an appropriate level of viscosity.
In particular, the copolymer of the present invention may form a composite block represented by the following formula d, which is formed by combining a polyolefin block including a repeating unit represented by the above formula a and a first polystyrene block including a repeating unit represented by the above formula c:
[ formula d ]
In the formula (d), the first and second groups,
R1is hydrogen, an alkyl group having 1 to 20 carbon atoms substituted with a silane group, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms substituted with a silane group,
R2is an aryl group having 6 to 20 carbon atoms; or an aryl group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
l is an integer of 10 to 1,000, and
n is an integer of 1 to 10,000.
In addition, in the above formula d, R1、R2Each of l and n is the same as defined in formula a and formula c above.
In addition, when the polyolefin block includes a repeating unit represented by the above formula a, a composite block formed by combining the first polystyrene block including a repeating unit represented by the above formula c may be represented by the following formula e:
[ formula e ]
In the above formula e, the above R1'、R1", p, l and n' are each the same as defined in formula a or c above.
In addition, when preparing the copolymer of the present invention, the styrene monomer may form a polyolefin block, and at the same time, the styrene monomer may be bonded and polymerized to the organozinc compound to form a separate styrene polymer block. The individual styrene polymer blocks described herein are referred to as second polystyrene blocks. The second polystyrene block may comprise repeating units represented by the following formula f:
[ formula f ]
In the above-mentioned formula f, the,
R3is an aryl group having 6 to 20 carbon atoms; or an aryl group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms; and
m is independently an integer of 10 to 1,000.
Further, according to an embodiment of the present invention, R is3May be phenyl, or phenyl which is unsubstituted or substituted by halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, or aryl having 6 to 12 carbon atoms, and R3May be phenyl.
The above m may be an integer of 10 to 1,000, particularly an integer of 50 to 700.
That is, the copolymer of the present invention may include: a first polystyrene block comprising repeating units represented by formula c above and a second polystyrene block comprising repeating units represented by formula f above.
Thus, the block copolymer composition may comprise a triblock copolymer comprising: a polyolefin block comprising at least one repeating unit represented by the following formula a; a first polystyrene block comprising a repeating unit represented by the following formula c; and a second polystyrene block comprising repeating units represented by the following formula f:
[ formula a ]
[ formula c ]
[ formula f ]
In the above-mentioned formula, the compound of formula,
R1is hydrogen, an alkyl group having 1 to 20 carbon atoms substituted with a silane group, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms substituted with a silane group,
R2and R3Is an aryl group having 6 to 20 carbon atoms; or an aryl group having 6 to 20 carbon atoms substituted with halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
n is an integer of 10 to 10,000, and
l and m are each independently an integer of 10 to 1,000.
In the above formula, R represents1、R2、R3N, l and m are the same as defined in formulae a, c and f.
Preparation method of polyolefin-polystyrene multi-block copolymer
The preparation method of the polyolefin-polystyrene multi-block copolymer is characterized by comprising the following steps: (S1) polymerizing an olefin monomer using an organozinc compound as a chain transfer agent in the presence of a catalyst composition comprising a transition metal compound represented by the following formula 1 to form a polyolefin block; and (S2) anionically polymerizing the polyolefin block with a styrene monomer in the presence of a silicon atom-containing alkyllithium compound and a triamine compound to form a polystyrene block.
As described below, the preparation method of the present invention forms a polyolefin-polystyrene multiblock copolymer having a height and a half-peak width of a specific tan δ peak by forming a polyolefin chain using a transition metal compound represented by formula 1, which is effectively used for olefin monomer polymerization, as a catalyst, and then continuously performing styrene anion polymerization to form a polyolefin-polystyrene block.
Step (S1)
The step (S1) is a step of polymerizing an olefin monomer using an organozinc compound as a chain transfer agent in the presence of a catalyst composition comprising a transition metal compound represented by the following formula 1 to form a polyolefin block:
[ formula 1]
In the above-mentioned formula 1, the,
R1to R11Each independently is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, arylalkoxy having 7 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, alkylsilyl having 1 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms,
R1to R11May be combined to form an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, and
X1and X2Each independently of the others hydrogen, halogen, hydroxy, amino, mercapto, silyl, cyano, nitro, alkyl having 1 to 20 carbon atoms,An alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an arylsilyl group having 6 to 20 carbon atoms.
When an excess of chain transfer agent (e.g., (Et) is present in comparison to the catalyst2Zn), olefin polymer chains can be uniformly grown from dialkylzinc by initiating living polymerization, known as Coordination Chain Transfer Polymerization (CCTP), by causing rapid transalkylation between zinc (Zn) and hafnium (Hf). Since metallocene catalysts conventionally used cannot perform living polymerization through a β -elimination process, several catalysts suitable for CCTP are known to be only capable of mono-polymerizing ethylene, and it is difficult to perform copolymerization of ethylene and α -olefin through CCTP, and it is very difficult to perform living polymerization through CCTP using a general transition metal compound as a catalyst and to prepare a block copolymer.
On the other hand, the hafnium compound represented by the above formula 1 is [ N ] containing a 1,2,3, 4-tetrahydro-1, 10-phenanthroline skeleton and a Hf-C (aryl) bondAmino radical，N，CAryl radicals]HfMe2The type complex, which shows excellent α -olefin introducing ability in polymerization of ethylene and α -olefin, and particularly, the molecular weight of olefin polymer or the content of α -olefin varies depending on the content of chain transfer agent, indicating that the compound has been successfully used in CCTP and that β elimination reaction hardly occurs, seemingly negligible. That is, copolymerization of ethylene and α -olefin monomers can be performed by living polymerization using CCTP of the hafnium compound represented by the above formula 1, and block copolymers having various block compositions can be successfully prepared.
In addition, CCTP using a hafnium compound may be converted into anionic styrene polymerization to synthesize polyolefin-polystyrene block copolymers. Thus, the hafnium compound can be usefully used as a catalyst for preparing olefin polymers, which is a unique feature that can be achieved by the novel structure of the hafnium compound represented by the above formula 1.
In particular, in the above formula 1, R is as described above1To R11May each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably, R1To R10Can be hydrogen, while R11May be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20, and more preferably, R1To R10Is hydrogen, with R11May be hydrogen or an alkyl group having 1 to 20 carbon atoms.
Or, in the above formula 1, the above R1To R11May each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, wherein R3And R4May be combined to form an aromatic ring having 5 to 20 carbon atoms (e.g., benzene ring), and preferably, R3And R4Can combine to form a benzene ring, and at the same time R11May be an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
Or, in the above formula 1, the above R1、R2And R5To R10May be hydrogen, R mentioned above3、R4And R11May each independently be hydrogen or an alkyl group having 1 to 20 carbon atoms, and R as described above3And R4May be combined to form an aromatic ring having 5 to 20 carbon atoms (e.g., benzene ring).
At the same time, X is as defined above1And X2May each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and is preferably each independently an alkyl group having 1 to 20 carbon atoms, and the above X1And X2May be identical to each other.
The term "alkyl" as used herein refers to a straight or branched chain hydrocarbon group.
The term "alkenyl" as used herein refers to straight or branched chain alkenyl groups.
The term "aryl" used herein is preferably an aryl group having 6 to 20 carbon atoms, and may particularly include, but is not limited to, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilino, anisyl (anisyl) and the like.
The term "alkylaryl" as used herein refers to an aryl group substituted with an alkyl group.
The term "arylalkyl" as used herein refers to an alkyl group substituted with an aryl group.
The term "alkylsilyl group" as used herein may be a silyl group substituted with an alkyl group having 1 to 20 carbon atoms, and for example, may be a trimethylsilyl group or a triethylsilyl group.
The term "alkylamino" as used herein refers to an amino group substituted with an alkyl group and may include, but is not limited to, dimethylamino or diethylamino.
The term "hydrocarbyl" as used herein, unless otherwise specified, refers to a monovalent hydrocarbon radical having 1 to 20 carbon atoms, consisting solely of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl, or arylalkyl.
More specifically, the hafnium compound represented by the above formula 1 may be a hafnium compound represented by the following formula 1a or 1 b:
[ formula 1a ]
[ formula 1b ]
In the above formulas 1a and 1b,
R11is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkoxy group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and
X1and X2Each independently hydrogen, halogen, hydroxy, amino, mercapto, silyl, cyano, nitro, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkynyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or an arylsilyl group having 6 to 20 carbon atoms.
The hafnium compound may be represented by any one of the following formulas 1-1 to 1-5, but is not limited thereto, and the present invention includes all hafnium compounds corresponding to formula 1.
[ formula 1-1]
[ formulae 1-2]
[ formulae 1 to 3]
[ formulae 1 to 4]
[ formulae 1 to 5]
The hafnium compound of the present invention may be prepared by a process including the step of reacting a compound represented by the following formula 2 with a compound represented by the following formula 3:
[ formula 2]
[ formula 3]
Hf(X1X2)2
In the above-mentioned formula, the compound of formula,
R1to R11And X1And X2As defined above.
Meanwhile, as described below, when the hafnium compound represented by the above formula 1 is prepared, the step of preparing the ligand compound may be variously performed according to the final structure of the prepared hafnium compound.
For example, when R is present in the ligand compound3And R4Does not form a ring, and R11Is a hydrogen atom, a ligand compound can be prepared by hydrogenation under a ruthenium catalyst as shown below, and then reacted with a compound represented by formula 3, which is a hafnium precursor, to prepare a hafnium compound.
[ reaction formula 1]
In addition, when in the ligand compound structure, R3And R4Does not form a ring and R11When the substituent is a substituent other than a hydrogen atom, R is first introduced using an organolithium compound as shown in the following reaction scheme 211And then hydrogenated under a ruthenium catalyst to prepare a ligand compound:
[ reaction formula 2]
In addition, when in the ligand compound structure, R3And R4Are bonded to each other to form an aromatic ring having 5 to 20 carbon atoms and R11When R is a substituent other than a hydrogen atom, R may be introduced first using an organolithium compound as shown below11The ligand compound may then be prepared by hydrogenation over a Pd/C catalyst to prevent hydrogenation of the aromatic ring (e.g. naphthyl):
[ reaction formula 3]
That is, the hafnium compound may be prepared by preparing a ligand compound by performing alkylation and hydrogenation under suitable reagents and reaction conditions for a compound as a precursor of the ligand compound and introducing hafnium thereto, and a person skilled in the art may appropriately change the specific type of the alkylating reagent, the reaction temperature and the pressure in consideration of the structure and experimental conditions of the final compound.
In the present invention, the organozinc compound is a substance used as a chain transfer agent in polymerization for preparing a copolymer to allow chain transfer during preparation, and in particular, may be a compound represented by the following formula 4:
[ formula 4]
In the above-mentioned formula 4, the,
a is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms substituted with a halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and
b is an arylene group having 6 to 12 carbon atoms substituted with an alkenyl group having 2 to 12 carbon atoms.
Further, the above A may be an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an arylene group having 6 to 12 carbon atoms substituted with a halogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and
the above B may be an arylene group having 6 to 12 carbon atoms substituted with an alkenyl group having 2 to 8 carbon atoms.
The above formula 4 may have a structure having a double bond at both ends thereof, for example, when the above B is an arylene group substituted with an alkenyl group, the arylene group may be connected to the above a, and the double bond of the alkenyl group substituted on the arylene group may be located at the outermost portion in the above formula 4.
When the organozinc compound is reacted with at least one olefin monomer in the presence of the catalyst composition, polymerization may be initiated while the olefin monomer is interposed between zinc (Zn) and the organic group (a) of the organozinc compound.
The organozinc compound may be mixed in an amount of 1 to 200 equivalents based on 1 equivalent of the transition metal compound of the above formula 1, and particularly, the organozinc compound may be mixed in an amount of 10 to 100 equivalents based on 1 equivalent of the transition metal compound of the above formula 1.
The organozinc compound does not contain impurities such as THF and a large amount of magnesium salt, and thus can be provided in high purity, and thus can be used as a chain transfer agent, and is advantageously used for olefin polymerization.
The catalyst composition may further comprise a cocatalyst compound. In this case, the cocatalyst compound may function to activate the transition metal compound represented by formula 1, and any one known in the art may be used as the cocatalyst, for example, at least one selected from the following formulae 5 to 7 may be used as the cocatalyst.
[ formula 5]
-[Al(Ra)-O]m-
[ formula 6]
D(Ra)3
[ formula 7]
[L-H]+[Z(A)4]-Or [ L]+[Z(A)4]-
In the above-mentioned formula, the compound of formula,
Raeach independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with a halogen,
m is an integer of 2 or more,
d is aluminum or boron, and the metal is aluminum or boron,
l is a neutral or cationic Lewis acid,
z is an element of the group 13,
a is each independently an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms, in which at least one hydrogen atom may be substituted with a substituent, and
the substituent of the above A is halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.
The compound represented by the above formula 5 is not particularly limited as long as it is alkylaluminoxane. Preferred examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like, and a particularly preferred compound is methylaluminoxane.
The compound represented by the above formula 6 is not particularly limited, but preferable examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylmethoxyaluminum, dimethylethoxyaluminum, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and particularly preferable compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
For example, when Z is boron, examples of the compound represented by the above formula 7 may include, but are not limited to, bis (octadecyl) methylammonium tetrakis (pentafluorophenyl) borate [ (C)18H37)2N(H)Me]+[B(C6F5)4]-Bis (octadecyl) methylammonium tetraphenylborate, bis (octadecyl) methylammonium tetrakis [3, 5-bis (trifluoromethyl) phenyl]Borate tetraphenylborate, triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl) borate, tributylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetraphenylborate, N-diethylanilinium tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylphosphonium tetraphenylborate, trimethylammoniumtetraphenylborate, and mixtures thereof, Tripropylammonium tetrakis (p-tolyl) borate, triethylammonium tetrakis (o, p-dimethylphenyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl) borate, tributylammonium tetrakis (p-trifluoromethylphenyl) borate, trimethylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetraphenylborate, N-diethylanilinium tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetraphenylborate, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) borate, triphenylcarbonium tetrakis (p-dimethylphenyl) borate, and triphenylcarbonium tetrakis (p-trifluoromethylphenyl) borate(pentafluorophenyl) borate, or a combination thereof, and for example, when Z is aluminum, examples of such compounds can include, but are not limited to, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetra (pentafluorophenyl) aluminum, N-diethylphenylammonium tetraphenylaluminum, N-diethylphenylammonium tetra (pentafluorophenyl) aluminum, diethylammonium tetra (pentatetraphenyl) aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, Triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, or combinations thereof.
In particular, the cocatalyst used herein may be a compound represented by the above formula 7, and particularly bis (octadecyl) methylammonium tetrakis (pentafluorophenyl) borate.
In addition, the co-catalyst used herein may be prepared in an anhydrous hydrocarbon solvent. For example, the hydrocarbon solvent may be at least one selected from the group consisting of butane, pentane, neopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene, and ethylbenzene, but is not limited thereto, and any hydrocarbon solvent available in the art may be used in an anhydrous form.
In the present invention, when the cocatalyst is prepared in the presence of an anhydrous hydrocarbon solvent1At least one peak in the H NMR spectrum appears in the range of 1.75ppm to 1.90ppm and in the range of 1.90ppm to 2.00 ppm. This is because protons linked to α -carbons adjacent to nitrogen, sulfur, or phosphorus contained in L show different peaks. For example, when the compound represented by formula 1 is [ (C)18H37)2N(H)Me]+[B(C6F5)4]-When it is in1The presence of NCH in the H NMR spectrum2May each show a different signal.
In addition, the hafnium compound represented by the above formula 1 and the co-catalyst may be used in a form supported on a carrier. Silica or alumina may be used as the support, but is not limited thereto.
Examples of the olefin monomer charged as a reactant in the step (S1) may include monomers formed of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, or a mixture thereof. The olefin monomer may be used alone or in combination of two or more thereof.
The step (S1) may be performed, for example, in a homogeneous solution state. In this case, a hydrocarbon solvent may be used as the solvent, or an olefin monomer itself may be used as the medium. Examples of the hydrocarbon solvent may include aliphatic hydrocarbon solvents having 4 to 20 carbon atoms, particularly isobutane, hexane, cyclohexane, methylcyclohexane, and the like. The solvent may be used alone or in combination of two or more thereof.
The polymerization temperature of step (S1) may vary depending on the reaction materials, reaction conditions, etc., but in particular, the polymerization may be carried out at 70 ℃ to 170 ℃, particularly 80 ℃ to 150 ℃, or 90 ℃ to 120 ℃. Within this range, the catalyst may be thermally stable while increasing the solubility of the polymer.
The polymerization of step (S1) may be carried out in a batch, semi-continuous or continuous manner, or may also be carried out in two or more steps having different reaction conditions.
The compound prepared in the above step (S1) may be used as a precursor for preparing the polyolefin-polystyrene multiblock copolymer of the present invention by the anionic polymerization of the following step (S2).
Step (S2)
The step (S2) is a step of preparing a polyolefin-polystyrene multi-block copolymer by forming a polystyrene block through anionic polymerization of the polyolefin block with a styrene monomer in the presence of the silicon atom-containing alkyllithium compound and the triamine compound after the step (S1).
In the step (S2), styrene monomer may be addedThe body is continuously inserted into (polyolefin) contained in the compound formed in the above step (S1)2The styrene group between the zinc-carbon bonds of Zn, and at the same time, the terminal of the compound formed in step (S1), may participate as a copolymerization site with a styrene monomer and be linked to a polystyrene chain. In addition, the end group of the multiblock copolymer prepared by the method can be easily quenched by reacting with water, oxygen or an organic acid, thereby converting the multiblock copolymer into a polyolefin-polystyrene multiblock copolymer which is industrially useful.
The styrene monomer may be a styrene monomer having 6 to 20 carbon atoms. More particularly, the styrene monomer (e.g., styrene) may include ethylene substituted with an aryl group having 6 to 20 carbon atoms, ethylene substituted with a phenyl group, and the like.
The silicon atom-containing alkyllithium compound may be a compound represented by the following formula 8:
[ formula 8]
(CH3)3Si(CH2)Li
Such silicon atom-containing alkyllithium compounds are readily available as materials widely used as initiators for anionic polymerization and thus can be easily used in the present invention.
The triamine compound may be a compound represented by the following formula 9:
[ formula 9]
Since the triamine compound is easily coordinated with lithium, a compound of the triamine compound used as a base or a nucleophile for the purpose of improving the reactivity of the alkyllithium compound is easily available and inexpensive.
The present invention can maximally produce the objective polyolefin-polystyrene multiblock copolymer of the present invention, while newly using the above-mentioned compounds of formulas 8 and 9 (e.g., Me)3SiCH2Li (PMDETA)) as an initiator in the step (S2) to suppress polystyrene homopolymer, polyolefin-polystyrene diblock copolymerThe yield of (2).
The silicon atom-containing alkyl lithium compound represented by the above formula 8 and the triamine compound represented by the above formula 9 may be mixed in an aliphatic hydrocarbon solvent and then added, or the silicon atom-containing alkyl lithium compound represented by the above formula 8 and the triamine compound represented by the above formula 9 may be sequentially added to the reactor.
The anionic polymerization temperature of the step (S2) may vary depending on the reaction material, reaction conditions, etc., and particularly, the polymerization may be performed at 40 to 170 ℃, 60 to 150 ℃, or 90 to 100 ℃.
The anionic polymerization of step (S2) may be carried out in a batch, semi-continuous or continuous manner, or may also be carried out in two or more steps having different reaction conditions.
The anionic polymerization time of the step (S2) may vary depending on the reaction material, reaction conditions, etc., and particularly may be 0.5 to 10 hours, 1 to 8 hours, 2 to 7 hours, or 4 to 6 hours. Within this range, it is advantageous to convert the total amount of styrene monomer to be incorporated into the multiblock copolymer.
Thus, in the preparation method of the present invention, the polyolefin-polystyrene multiblock copolymer is prepared by: the polyolefin chain is grown by olefin polymerization using the organozinc compound represented by formula 4, and then styrene anion polymerization is continuously performed, thereby efficiently preparing a polyolefin-polystyrene multiblock copolymer having improved physical properties compared to existing copolymers and being easily used in industrial applications.
Examples
Hereinafter, the present invention will be described in more detail according to examples. However, the following examples are only intended to describe the present invention, and the scope of the present invention is not limited thereto.
< preparation of transition Metal Compound >
Preparation example 1
(i) Preparation of ligand compounds
Isopropyllithium (0.45mL, 0.36mmol, 0.79M in pentane) was slowly added to toluene (8mL) at-10 deg.C2-naphthyl-1, 10-phenanthroline (0.789g, 2.58 mmol). After stirring at room temperature for 3 hours, degassed H was added thereto2O (3 mL). In N2The aqueous layer was removed with a syringe. The solvent was removed using a vacuum line, and the residue was dissolved in degassed ethanol (15mL) and THF (5 mL). In N2Next, the solution was transferred to a bomb reactor (bombreactor) containing Pd/C (0.242mmol, 10 mol%). H is to be2The gas was charged to 5 bar and then stirred at room temperature for 12 hours. Liberation of H2The gas was purged and the catalyst residue was removed by filtration through celite. The solvent was removed and the residue was purified by silica gel column chromatography using ethyl acetate/hexane (1/3, v/v). Pale yellow viscous solid (0.085g, 73%) was obtained. The 1H NMR and 13C NMR spectra are shown in FIG. 1.
-1H NMR(C6D6):δ8.58(d,J＝7.8Hz,H),7.75(d,J＝9.0Hz,H),7.70(d,J＝9.6Hz,H),7.66(d,J＝7.2Hz,H),7.63(d,J＝6.6Hz,H),7.32(m,4H),7.18(d,J＝8.4Hz,H),6.99(d,J＝7.8Hz,H),6.39(s,H,NH),2.93(m,H),2.79(m,H),2.70(dt,J＝4.8Hz,H),1.70(m,H),1.63(m,H),1.47(m,H),0.81(d,J＝7.2Hz,3H,CH(CH3)2),0.76(d,J＝7.2Hz,3H,CH(CH3)2)ppm.
-13C{1H}NMR(C6D6):δ18.34,18.77,24.43,26.78,32.52,56.73,112.78,116.67,122.62,125.59,126.10,126.51,126.61,126.86,128.14,128.69,129.03,129.28,132.20,134.71,136.41,137.64,139.79,141.75,155.92ppm.
Calculated value of M/z ([ M ]+]C25H24N2)352.4800. Measured value: 352.1942.
(ii) preparation of transition metal compounds
[ formulae 1 to 3]
To stirred HfCl at-78 deg.C4(0.300g, 0.938mmol) in toluene (8mL) MeMgBr (1.24mL, 3.11M)Ether solution). After stirring at a temperature in the range of-40 ℃ to-35 ℃ for 1 hour, the solution was cooled again to-78 ℃. A solution (0.24g, 0.94mmol) of the ligand compound (0.366g, 1.00mmol) in toluene (4mL) was added dropwise thereto. The resulting solution was stirred at a controlled temperature ranging from-40 ℃ to-35 ℃ for 2 hours and then at room temperature overnight. The solvent was removed using a vacuum line, and the residue was extracted with toluene (50 mL). Dark brown powder (0.226g, 47%) was obtained by trituration in hexane. Shown in FIG. 21H NMR and13c NMR spectrum.
-1H NMR(C6D6):δ8.66(d,J＝7.8Hz,H),8.50(d,J＝7.8Hz,H),7.92(d,J＝9.0Hz,H),7.83(d,J＝7.2Hz,H),7.76(d,J＝8.4Hz,H),7.62(d,J＝7.8Hz,H),7.40(td,J＝7.2Hz,H),7.32(m,H),7.14(d,J＝7.8Hz,H),6.77(d,J＝7.2Hz,H),4.02(m,H),2.80(m,H),2.62(dt,J＝6.0Hz,H),2.55(m,H),1.88(m,H),1.72(m,H),1.09and 1.04(d,J＝6.6Hz,6H,CH(CH3)2),0.82(s,3H,HfCH3),0.81(s,3H,HfCH3)ppm.
-13C{1H}NMR(C6D6):δ18.55,21.28,23.07,25.44,32.58,60.98,63.06,66.88,112.37,119.64,120.21,124.55,125.48,126.81,126.97,129.31,129.97,130.26,131.25,133.82,135.51,140.97,141.44,143.94,150.14,164.58,209.13ppm.
Analytical calculation (C)27H28HfN2)：C，58.01；H，5.05；N，5.01％。
-measured values: c, 57.91; h, 5.01; and N,5.11 percent.
< preparation of Co-catalyst >
Excess K was allowed to stand at room temperature in a glove box+[B(C6F5)4]-(0.633g, 0.881mmol, assuming pure) with [ (C)18H37)2N(H)Me]+[Cl]-A solution of (0.404g, 0.705mmol) in toluene (anhydrous, 10mL) was reacted for 1 hour. After filtration through celite, the solvent was removed using a vacuum line. The residue was dissolved in methylcyclohexane (4mL) and filtered again through Celite. Removal of the solvent gave a yellow oily compound whichUsed without further purification (0.797g, 93%).
-1H NMR(C6D6):δ3.15(br,H,NH),1.97(m,2H,NCH2),1.80(m,H,NCH2),1.51(d,J＝6.0Hz,3H,NCH3) 1.45-1.29(m,48H),1.26 (quintuple, J ═ 7.2Hz,4H),1.13 (quintuple, J ═ 7.2Hz,4H),0.94(t, J ═ 7.8Hz,6H),0.88 (quintuple, J ═ 7.8Hz,4H),0.81(m,4H) ppm.
-19F NMR(C6D6):δ-132.09,-161.75,-165.98。
< preparation of organozinc Compound >
Borane dimethyl sulfide (1.6mL, 3.2mmol) was added slowly to triethylborane (0.6g) with stirring and reacted for 90 minutes. The mixture was slowly added to divinylbenzene (3.8g) dissolved in anhydrous ether (10mL) cooled to-20 ℃. The solvent was removed by a vacuum pump, and diethyl zinc (0.8g) was added thereto. While the reaction was carried out, the resulting triethylborane was removed by distillation at 0 ℃ under reduced pressure for 5 hours. Excess divinylbenzene and diethylzinc were removed by distillation at 40 ℃ under reduced pressure. After the product was dissolved again by adding methylcyclohexane (150mL), a solid compound produced as a by-product was filtered and removed by using celite to obtain an organozinc compound represented by the above formula.
< preparation of polyolefin-polystyrene multiblock copolymer >
Example 1
A Parr reactor (600mL) was dried under vacuum at 120 ℃ for 2 hours. Addition of Oc to the reactor3A solution of Al (349.0mg, 238. mu. mol-Al) in methylcyclohexane (200 g). The mixture was stirred at 120 ℃ for 1 hour using a heating mantle, and then the solution was removed using a cannula.
The reactor was filled with a solution containing Oc as scavenger3Methylcyclohexane (200g) of Al (349.0mg, 238. mu. mol-Al/25 wt% hexane solution), and 1-hexene (1-hexene) (b) as an olefin monomer50.475g) and then the temperature was set to 90 ℃. A solution of an organozinc compound (479.5. mu. mol) in methylcyclohexane (1.58g) as a chain transfer agent was filled, and then a solution containing [ (C) for use in methylcyclohexane was injected18H37)2N(H)Me]+[B(C6F5)4]-(5.0. mu. mol) of the activated solution of the transition metal compound (5.0. mu. mol-Hf) of preparation example 1 in methylcyclohexane (0.7 g). The polymerization was carried out for 40 minutes while opening the valve of the ethylene tank to maintain the pressure in the reactor at 20 bar. The temperature was controlled in the range of 90-120 c and the remaining ethylene gas was vented.
When the temperature reached 90 ℃, Me was added by mixing3SiCH2Me prepared by mixing Li (64.6mg, 0.686mmol) and PMDETA (130.7mg, 0.755mmol) with methylcyclohexane (3.85g)3SiCH2Li (PMDETA) solution. While stirring, the temperature was kept at 90 ℃ for 30 minutes, and then styrene (15.0g) was injected. The temperature was controlled in the range of 90-100 c using a heating mantle.
The viscosity gradually increased over 5 hours to almost an invisible state. Aliquot of the sample1H NMR analysis confirmed complete conversion of styrene. After complete conversion of the styrene, 2-ethylhexanoic acid and ethanol were continuously injected. The resulting polymer mass (29g) was dried in a vacuum oven at 80 ℃ overnight.
Examples 2 to 7
Examples 2 to 7 were prepared in the same manner as in example 1 above, except that the reaction conditions were changed as shown in table 1 below.
Comparative examples 1 to 4
G1650, G1651, G1652 and G1654 from Kraton as commercially available SEBS were used, respectively.
Comparative example 5
By using the compound represented by the above formula as the transition metal compound, comparative example 5 was prepared as follows:
[ comparative formula 1]
A solution of trimethylaluminum (14.4mg, 200. mu. mol-Al) dissolved in methylcyclohexane (17g) was injected into the high-pressure reactor. The catalyst poison in the high-pressure reactor was purified at 100 ℃ for 1 hour, and the solution was removed using a cannula.
An organozinc compound (49.1mg, 150. mu. mol) was dissolved in methylcyclohexane (40g) and placed in a high pressure reactor, and the temperature was raised to 80 ℃. The transition metal compound (C) is added18H37)N(Me)H+[B(C6F5)4]-(4.0. mu. mol) A solution stirred in benzene for 2 hours was diluted with a solution (1.0g) of trioctylaluminum (50. mu. mol, 18.3mg) dissolved in methylcyclohexane (15 g). Immediately after the injection of the catalyst solution into the high-pressure reactor, an ethylene-propylene mixed gas was injected at a pressure of 20 bar. The temperature was controlled in the range of 95 to 115 ℃. As the monomer was consumed, the pressure slowly decreased and after 55 minutes of the polymerization process at 45 ℃, the remaining gas was released.
Mixing Me with water3SiCH2Li (150. mu. mol, 14.1mg) and PMDETA (150. mu. mol, 26mg) were mixed with methylcyclohexane (1.0g), poured into the reactor, and stirred for 30 minutes. The stirring temperature was maintained at 90 to 100 ℃. Styrene (7.8g) was injected into the high pressure reactor and reacted for 5 hours while maintaining the temperature between 90 ℃ and 100 ℃ to convert all styrene monomer. After complete conversion of the styrene monomer, acetic acid and ethanol were continuously injected. The polymer was obtained and then dried in a vacuum oven at 180 ℃ overnight.
Comparative examples 6 and 7
A copolymer was prepared in the same manner as in comparative example 5, except that the reaction conditions were changed as shown in the following table.
[ Table 1]
Experimental example 1
For the polyolefin-polystyrene multiblock copolymers of examples and comparative examples, the physical properties of each copolymer were determined according to the following conditions and methods, and the results are shown in table 2.
(1) Determination of ethylene, alpha-olefin and styrene content
The content was determined by NMR. Determined using a Bruker 600MHz AVANCE III HD NMR apparatus under conditions of ns-16, d 1-3 s, solvent-TCE-d 2 and 373K1After H NMR, the peak of TCE-d2 solvent was adjusted to 6.0ppm, and CH of 1-propene was confirmed at 1ppm3And CH due to butyl branching of 1-hexene was confirmed at approximately 0.96ppm3Correlation peaks (triplets) and then the content was calculated. In addition, the styrene content was calculated from the aromatic peak near 6.5ppm to 7.5 ppm.
(2) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (polydispersity index, PDI)
The weight average molecular weight (Mw, g/mol) and the number average molecular weight (Mn, g/mol) were measured using Gel Permeation Chromatography (GPC), respectively, and the molecular weight distribution (polydispersity index, PDI) was calculated by dividing the weight average molecular weight by the number average molecular weight.
-a chromatographic column: PL Olexis
-a solvent: TCB (trichlorobenzene)
-flow rate: 1.0ml/min
-sample concentration: 1.0mg/ml
-injection amount: 200 μ L
Column temperature: 160 deg.C
-a detector: agilent high temperature RI detector
-standard: polystyrene
Using Mark-Howink equation (K ═ 40.8 × 10)-5α ═ 0.7057) molecular weight was calculated by general calibration
(3) Calculation of constants A to D in equation 1
To calculate the constants a to D, GPC measurement data was fitted to a gaussian function using nonlinear curve fitting in Origin.
[ Table 2]
Experimental example 2
With respect to the polyolefin-polystyrene multiblock copolymers of examples and comparative examples, shown in FIG. 413The C NMR spectrum, and in particular, the peak values of the branch point carbon atom and the terminal carbon atom of the branch from the branch point are summarized in table 3 below.
Specifically, using a Bruker AVANCEIII 500MHz NMR instrument, about 50mg of the sample was added to 1.2mL of TCE-d2 (tetrachloroethane-d 2) solvent and heated in a heater at 100 ℃ for 1 hour, vortexed 2-3 times during heating. After confirming that the sample was uniformly dissolved, the solution was transferred to an NMR tube and measured at 100 ℃13C NMR spectrum.
[ Table 3]
Branched carbon atoms
Terminal carbon atom of branched chain
Example 1
38
14
Example 2
38
14
Example 3
38
14
Example 4
38
14
Example 5
38
14
Example 6
38
14
Example 7
38
14
Comparative example 1
34
11
Comparative example 2
34
11
Comparative example 3
34
11
Comparative example 4
34
11
Comparative example 5
30
23
Comparative example 6
30
23
Comparative example 7
30
23
Experimental example 3
(1) Tensile Properties
Each test sample was prepared and tested for tensile strength, elongation at break, 300% modulus according to the tensile test method of ASTM D412.
[ Table 4]
Tensile Strength (MPa)
Elongation at Break (%)
300% modulus (MPa)
Example 1
21.5
1,799
2.7
Example 2
26.5
1,710
3.8
Example 3
26.7
2,363
2.9
Example 4
32.69
1,801
5.2
Example 5
25.3
1,476
5.7
Example 6
34.3
1,405
6.9
Example 7
22.3
2,047
2.4
Comparative example 1
29.9
1,305
2.9
Comparative example 2
27.6
1,849
1.8
Comparative example 3
30.7
1,325
3.3
Comparative example 4
30.6
1,584
2.2
Comparative example 5
2.9
480
3.5
Comparative example 6
6.1
469
4.2
Comparative example 7
4.25
486
2.3
As shown in table 4 above, it was confirmed that the block copolymers of examples 1 to 7 satisfying all conditions (a) to (d) proposed by the present invention exhibited tensile properties of tensile strength, elongation at break, and 300% modulus, which are uniformly superior at a certain level, as compared to the copolymer of the comparative example not satisfying all conditions.