KR20130135168A

KR20130135168A - Olefin block copolymer film having superiror thermal endurance, elasticity and adhesion strength

Info

Publication number: KR20130135168A
Application number: KR1020130062608A
Authority: KR
Inventors: 노경섭; 이난영; 김원희; 전상진; 안상은; 박승기
Original assignee: 주식회사 엘지화학
Priority date: 2012-05-31
Filing date: 2013-05-31
Publication date: 2013-12-10

Abstract

The present invention relates to an olefin block copolymer film comprising an olefin block copolymer having excellent heat resistance and elasticity and having an improved adhesive strength and a method for producing the same. The olefin block copolymer film according to the present invention exhibits stable adhesive strength to various substrates, and can be suitably used for the use of a self-adhesive film.

Description

Olefin block copolymer film excellent in heat resistance, elasticity and adhesive strength {OLEFIN BLOCK COPOLYMER FILM HAVING SUPERIROR THERMAL ENDURANCE, ELASTICITY AND ADHESION STRENGTH}

The present invention relates to an olefin block copolymer film comprising an olefin block copolymer having excellent heat resistance and elasticity and having improved adhesive strength.

In the past, an adhesive type protective film was used to protect the surface of optical film, steel, glass, and the like, and recently, a self-adhesive film having adhesive strength as a film itself has been widely used.

As such a self-adhesive film, materials, such as ethylene vinyl acetate resin (EVA resin), were used generally. The EVA resin may exhibit high adhesive strength due to a low melting temperature, but on the other hand, since the melting temperature is low, heat resistance is inferior.

Due to these problems, recently, replacement of olefin resins such as olefin elastomers has been attempted as a raw material of self-adhesive films. Conventionally, olefin elastomers such as copolymers of ethylene or propylene monomers and α-olefin monomers are known, but such olefin elastomers have relatively good elasticity, physical properties such as elasticity, low cost and versatility, and thus are replaced with such materials. Is expected to be possible.

However, in order to use the olefin elastomer for a self-adhesive film or the like, a certain level of heat resistance, elasticity and adhesive strength are required. In other words, heat resistance, elasticity and adhesive strength are required to maintain a certain level of adhesive strength even at a high temperature of a certain level or higher, to support an external load and to maintain an original shape.

However, the olefin elastomers used in the past were mainly composed of random copolymers of ethylene monomers and α-olefin monomers, and exhibited some elasticity but lacked heat resistance due to the characteristics of the random copolymers. For this reason, the development of the olefin elastomer which is excellent in heat resistance, elasticity, and adhesive strength at the same time is continuously required.

Accordingly, the present invention is to provide an olefin block copolymer film having better adhesive strength with excellent heat resistance and elasticity.

According to the present invention,

A block copolymer of an ethylene or propylene monomer and an α-olefin monomer, the block copolymer comprising a plurality of blocks or segments having different contents, crystallinity, density, melting point or glass transition temperature from the α-olefin monomer,

The block copolymer has a melting point of 100 to 130 ℃,

An olefin block copolymer film having an adhesive strength (peel speed 300 mm / min, 4 hours at room temperature after adhesion) is 10 to 20 g / inch.

Here, the block copolymer may have a melt index (Melt Index, 2.16 kg) of 0.5 to 5 g / 10 min.

In addition, the block copolymer may have a thermal mechanical analysis (Thermal Mechanical Analysis) value of 70 ℃ or more.

In addition, the block copolymer may have a density of 0.85 to 0.9 g / cm 3.

In addition, the block copolymer may have a weight average molecular weight of 50,000 to 200,000, and a molecular weight distribution of 2.0 to 4.5.

In addition, the block copolymer may have a content of 50 to 90% by weight of ethylene or propylene monomer.

In addition, the α-olefin monomers are 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, It may be at least one selected from the group consisting of 1-tetradecene, 1-hexadecene, and 1- itocene.

The block copolymer film may be used as a self-adhesive film.

According to the present invention, an olefin block copolymer film including an olefin block copolymer having excellent heat resistance and elasticity and having improved adhesive strength can be provided. Accordingly, such an olefin block copolymer film can be used as a self-adhesive film or the like by overcoming the problems of conventional EVA resin films or olefin elastomer films.

Hereinafter, an olefin block copolymer film according to a specific embodiment of the present invention will be described in more detail. It will be apparent to those skilled in the art, however, that this is not intended to limit the scope of the invention, which is set forth as an example of the invention, and that various modifications may be made to the embodiments within the scope of the invention.

First, some terms may be defined as follows unless otherwise specified throughout the present specification.

Throughout this specification, the 'olefin block copolymer' or 'block copolymer' is a polymer in which an ethylene or propylene monomer and an α-olefin monomer are copolymerized, and the physical or chemical properties, for example, repeats derived from an α-olefin monomer. One or more of the unit's content, crystallinity, density, melting point or glass transition temperature refers to a blocked copolymer, including a plurality of blocks or segments which are distinguishable by this property.

Such a plurality of blocks or segments include, for example, hard segments that are blocks of higher molar content of repeat units derived from ethylene or propylene monomers; And a soft segment having a lower molar content of repeating units derived from ethylene or propylene monomers and a higher molar content of repeating units derived from α-olefin monomers than the hard segment. More specifically, the hard segment has a higher content of repeating units derived from ethylene or propylene monomer among the blocks or segments constituting the block copolymer (eg, derived from ethylene or propylene monomer in the entire block copolymer). A greater content (molar ratio) than the content of one repeating unit may refer to a block or segment comprising such repeating units. In contrast, the soft segment has a smaller content of repeating units derived from ethylene or propylene monomer among the blocks or segments constituting the block copolymer (eg, derived from ethylene or propylene monomer in the entire block copolymer). A smaller content (molar ratio) than the content of the repeating unit may refer to a block or segment comprising such repeating unit).

In addition, the fact that the film according to the embodiment of the present invention includes the block copolymer means that a part or all of the film is formed by the block copolymer, and the film is the block copolymer. It may be prepared using a composition comprising a.

On the other hand, according to one embodiment of the present invention,

A block copolymer comprising an ethylene or propylene monomer and an α-olefin monomer, and a block copolymer comprising a plurality of blocks or segments having different content, crystallinity, density, melting point, or glass transition temperature from the α-olefin monomer. and,

The block copolymer has a melting point of 100 to 130 ℃,

That is, the olefin block copolymer film according to the embodiment of the present invention includes the olefin block copolymer according to the present invention. Herein, the olefin block copolymer is copolymerized with ethylene or propylene monomers and α-olefin monomers. As the α-olefin monomers are copolymerized, the olefin block copolymer may exhibit excellent elasticity at a predetermined temperature or less.

In particular, the block copolymer of the embodiment is prepared using a specific catalyst system (catalyst composition) to be described later, when molded into a film is excellent in adhesive strength and excellent heat resistance compared to the previous elastomer film, relatively high temperature It was confirmed that even in the appropriate adhesive force can be maintained.

That is, in the experiments of the present inventors, when the block copolymer is prepared using a specific catalyst system to be described later, ethylene or propylene monomers are polymerized and combined with the same monomers to form hard segments, and the α-olefin monomers are homogeneous. The α-olefin monomers may be polymerized and combined to form a soft segment. For this reason, it was confirmed that the degree of blocking of an olefin block copolymer becomes high compared with the previously known ethylene-alpha-olefin random copolymer.

As described above, the olefin block copolymer according to the embodiment exhibits a higher degree of blocking so that hard segments and soft segments are more clearly distinguished, and in particular, the heat resistance of the block copolymer is ensured due to the hard segments, and at the same time, the soft It was confirmed that the adhesive strength of the block copolymer can be further improved due to the segment. As a result, the block copolymer of the embodiment can exhibit excellent physical properties such as elasticity and heat resistance as an elastomer, compared with the previously known ethylene-α-olefin random copolymer, and excellent adhesion strength and suitable adhesion even at a relatively high temperature This makes it possible to provide a retained film.

Such a block copolymer of one embodiment, in particular, the melting point (Tm) may be 100 ℃ or more, preferably 100 to 130 ℃, more preferably 100 to 125 ℃.

In particular, the film including the block copolymer has a cohesive strength (peel speed 300 mm / min, 4 hours at room temperature after adhesion) for various substrates 10 to 20 g / inch, preferably 12 to 20 g / inch More preferably 15 to 20 g / inch. That is, the olefin block copolymer film according to one embodiment preferably has an adhesive strength of 10 g / inch or more for sufficient manifestation of self-adhesive force. However, when the adhesive strength is higher than necessary, the adhesive strength may not be easily removed from the substrate, and thus may be unsuitable for use as a self-adhesive film. Therefore, the olefin block copolymer film according to one embodiment preferably has an adhesive strength of 20 g / inch or less. In particular, the film according to the present invention includes the olefin block copolymer of the embodiment, there is an advantage that can be expressed in a stable adhesive strength in the above-described range even if the temperature rises.

As such, the block copolymer can exhibit a higher melting point and better heat resistance than previously known random copolymers, while being excellent in processability and product formability and enabling the provision of a film having a relatively high adhesive strength. As a result, the block copolymer of the embodiment enables the provision of an olefin-based elastomer having improved heat resistance along with excellent elasticity due to the copolymerization of the α-olefin monomer, and the film comprising the same exhibits excellent adhesive strength and is suitable even at high temperatures. Adhesion can be maintained.

On the other hand, the olefin block copolymer included in the film may have a melt index (Melt Index, 2.16 kg) of 0.5 to 5 g / 10 min; In particular, the melting point (Tm) is 100 ° C or more and the thermal mechanical analysis (TMA) value can exhibit excellent heat resistance of 70 ° C or more, preferably 70 to 130 ° C.

In addition, the olefin block copolymer has excellent density having a density of 0.85 to 0.9 g / cm 3, a weight average molecular weight of 50,000 to 200,000, and a molecular weight distribution of 2.0 to 4.5 as copolymerized under high temperature and high pressure conditions in the presence of the catalyst composition described above. It has physical properties. As the block copolymer has such a property, it may exhibit suitable properties as an olefin elastomer, excellent mechanical properties and processability, and the like.

In addition, the olefin block copolymer may be a block copolymer of ethylene or propylene monomer (preferably ethylene monomer) and α-olefin monomer, wherein the α-olefin monomer is 1-butene, 1-pentene, 4- Group consisting of methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-aitocene It may be at least one selected from.

Here, the block copolymer of the embodiment may be one containing 50 to 90% by weight of ethylene or propylene monomer. For example, the block copolymer may be a block copolymer in which this amount of ethylene or propylene monomer is copolymerized with the remaining amount, for example, 10 to 50% by weight of an α-olefin monomer. As the block copolymer includes an α-olefin monomer of such a content, the block copolymer may have excellent elasticity as an elastomer, and in addition, the content range of the ethylene or propylene monomer may be optimized to exhibit excellent heat resistance.

In addition, the block copolymer of the embodiment may have a hard segment content of 10 to 90% by weight. As described above, the hard segment refers to a block or segment including a higher content of ethylene or propylene monomer among a plurality of blocks or segments of the block copolymer, and may contribute to excellent heat resistance of the block copolymer. have. That is, as the block copolymer includes hard segments of this content, it is possible to exhibit excellent heat resistance, but also to exhibit appropriate elasticity as an elastomer.

On the other hand, the above-described olefin block copolymer can be prepared using a specific catalyst system (catalyst composition).

In particular, it is common for the previously known metallocene or post metallocene catalyst systems to have a sharp decrease in activity at high temperatures. However, the following catalyst system used in the production method of the present invention can maintain a high catalytic activity even at a temperature of 140 ℃ or more, there is an advantage that can produce a higher molecular weight polymer with high production efficiency.

According to another embodiment of the present invention, in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound in which a Group 4 transition metal is coordinated with a compound represented by Formula 1 as a ligand, and a compound represented by Formula 2 ,

There is provided a process for preparing an olefin block copolymer comprising copolymerizing an ethylene or propylene monomer with an α-olefin monomer:

[Formula 1]

In Formula 1,

m is an integer from 1 to 7,

R ¹ is hydrogen, deuterium, a halogen group, a nitrile group, an acetylene group, an amine group, an amide group, an ester group, a ketone group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms 4-10 carbon atoms substituted by one or more groups selected from the group consisting of an aryl group having 6 to 20 carbon atoms, a silyl group, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms and a heterocyclic group having 4 to 20 carbon atoms. Cycloalkyl group; Hydrogen, deuterium, halogen group, nitrile group, acetylene group, amine group, amide group, ester group, ketone group, C1-C20 alkyl group, C6-C20 cycloalkyl group, C2-C20 alkenyl group, C6 And substituted with at least one group selected from the group consisting of aryl groups of 20 to 20, silyl groups, alkylaryl groups of 7 to 20 carbon atoms, arylalkyl groups of 7 to 20 carbon atoms, and heterocyclic groups of 4 to 20 carbon atoms. Heterocyclic group having 3 to 9 carbon atoms having nitrogen (N) or sulfur (S); Hydrogen, deuterium, halogen group, nitrile group, acetylene group, amine group, amide group, ester group, ketone group, C1-C20 alkyl group, C6-C20 cycloalkyl group, C2-C20 alkenyl group, C6 An aryl group having 6 to 10 carbon atoms substituted with one or more groups selected from the group consisting of an aryl group having ~ 20, a silyl group, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a heterocyclic group having 4 to 20 carbon atoms ; Or hydrogen, deuterium, halogen group, nitrile group, acetylene group, amine group, amide group, ester group, ketone group, C1-C20 alkyl group, C6-C20 cycloalkyl group, C2-C20 alkenyl group, carbon number Substituted oxygen (O) as a hetero atom by being substituted with one or more groups selected from the group consisting of 6-20 aryl groups, silyl groups, C7-20 alkylaryl groups, C7-20 arylalkyl groups and C4-20 heterocyclic groups And a heteroaryl group having 5 to 10 carbon atoms having nitrogen (N) or sulfur (S); When R ¹ is substituted with two or more groups, the groups adjacent to each other may form a condensed ring of aliphatic or aromatic;

R ² is the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a nitrile group, an acetylene group, an amine group, an amide group, an ester group, a ketone group, an alkyl group having 1 to 20 carbon atoms, and an alke having 2 to 20 carbon atoms A silyl group, an aryl group having 6 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms; Two or more R ² may be linked to each other to form an aliphatic ring or an aromatic ring;

(2)

In Formula 2,

R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a silyl group, an alkenyl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and 7 to 20 carbon atoms. An arylalkyl group or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; R ¹ and R ² may be connected to each other by an alkylidine radical including an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;

Each R ³ is independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an amido group; Two or more R ³ may be linked to each other to form an aliphatic ring or an aromatic ring;

CY ¹ is substituted or unsubstituted aliphatic ring or aromatic ring;

M is a Group 4 transition metal;

Q ¹ and Q ² each independently represent a halogen, an alkyl group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl having 7 to 20 carbon atoms. Or an arylalkyl group having 7 to 20 carbon atoms or an alkylidene group having 1 to 20 carbon atoms.

Wherein, in the substituents of Formulas 1 and 2, the alkyl group includes a linear or branched alkyl group; The alkenyl group comprises a straight or branched alkenyl group; The silyl groups include trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris (trimethylsilyl) silyl and the like and; The aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like; The alkylaryl group means an aryl group substituted by the alkyl group.

In addition, wherein, in the substituents of Formulas 1 and 2, the arylalkyl group means an alkyl group substituted by the aryl group; The halogen group means a fluorine group, a chlorine group, a bromine group or an iodine group; The alkyl amino group means an amino group substituted by the alkyl group, and includes a dimethylamino group, a diethylamino group, and the like; The aryl amino group means an amino group substituted by the aryl group, and includes a diphenylamino group and the like, and the present invention is not limited only to these examples.

Since the catalyst composition as described above can maintain high catalytic activity even under high temperature and high pressure, the method for preparing the olefin block copolymer according to the present invention is at least 140 ° C, preferably 140 to 200 ° C, more preferably 140 To 180 ° C .; And a pressure of 50 bar or more, preferably 50 to 120 bar, more preferably 70 to 100 bar. As a result, a more simplified method of preparing a copolymer having high molecular weight and high degree of polymerization can be produced.

Here, the transition metal compound in which the Group 4 transition metal is coordinated with a ligand of the compound of Formula 1 included in the catalyst composition polymerizes and bonds the ethylene or propylene monomer to form a hard segment, and thus a copolymer. The heat resistance can be given to. In addition, the compound of Chemical Formula 2 included in the catalyst composition may polymerize and bind the α-olefin monomer to form a soft segment, thereby providing elasticity to the copolymer.

Among them, the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1-1 or Chemical Formula 1-2:

[Formula 1-1]

[Formula 1-2]

In Chemical Formula 1-1 or Chemical Formula 1-2,

m and R ² are the same as defined in Formula 1,

n is an integer from 1 to 7, n 'is an integer from 1 to 5,

p is an integer from 0 to 2 + n, p 'is an integer from 0 to 5 + n',

R ³ is the same as or different from each other, and each independently deuterium, a halogen group, a nitrile group, an acetylene group, an amine group, an amide group, an ester group, a ketone group, a C1-C20 alkyl group, a C6-C20 cycloalkyl group, An alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a silyl group, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms; Two or more R ³ may be linked to each other to form an aliphatic ring or an aromatic ring.

In particular, R ³ is preferably an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and two or more R ³ are connected to each other to form an aliphatic ring. Or an aromatic ring.

In Formula 1, Formula 1-1, and Formula 1-2, m is preferably 2 or 3. In addition, in Formula 1-1 or Formula 1-2, n is preferably 2 or 3. In addition, in Formula 1-1 or Formula 1-2, n 'is preferably an integer of 1 to 3.

Specific examples of the compound represented by Formula 1 may be one or more selected from the group of compounds represented by Formula 1-3. However, the present invention is not limited thereto.

[Formula 1-3]

A general method for preparing a compound represented by Chemical Formula 1 is as follows, but is not limited thereto.

In the method for preparing a compound represented by Chemical Formula 1, R ¹ and R ² are the same as defined in Chemical Formula 1. In the preparation method, Compound 9 may be obtained by synthesizing Intermediate 8 using selective lithium substitution using Compound 7 as a starting material, and then injecting DMF (N, N-Dimethylformamide). Thereafter, when the compound 9 is reacted with R ¹ -NH ₂ by reflux or stirring, a compound represented by Chemical Formula 1 can be obtained. In particular, when R ¹ is an aryl group in the R ¹ -NH _{2 It} can be obtained by refluxing overnight after adding 4A MS, if R ¹ is an alkyl group or an alkylaryl group, the result can be obtained by stirring overnight at room temperature have.

Such a compound of Formula 1 may be a ligand compound capable of forming a bidentate chelate (NN chelate) with a metal or a tridentate chelate (NNN, NNO, or NNC) according to the kind of R ¹ . Can be.

In the method for preparing an olefin block copolymer according to the present invention, a transition metal compound in which a Group 4 transition metal is coordinated with a compound of Formula 1 as a ligand may be used as a catalyst. At this time, the transition metal may include Ti, Zr, Hf, but is not limited thereto.

The transition metal compound may be represented by one of the following structural formulas, but is not limited thereto.

In the above structural formula, M is a Group 4 transition metal, R is the same or different from each other, and each independently hydrogen, deuterium, halogen, nitrile, acetylene, amine, amide, ester, ketone, carbon number 1 Selected from the group consisting of an alkyl group of ~ 20, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, a heterocyclic group of 4 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, and an aryloxy group of 6 to 20 carbon atoms Can be.

As can be seen from the structural formula, the structure of the transition metal compound according to the present invention may be 2: 1 or molar ratio of a ligand and a metal, such as a conventional catalyst, or 1: 1 may be different. Due to the structural features as described above, the transition metal compound according to the present invention may be equal to or higher than the content of the transition metal compared to the conventional catalyst.

According to one embodiment of the present invention, the transition metal compound may be prepared by the following method. However, the present invention is not limited thereto. First, a certain amount of ligand represented by Formula 1 and 1.05 equivalent of a metal precursor are mixed, and then an appropriate amount of toluene solvent is injected at -75 ° C to -80 ° C, preferably about -78 ° C, and gradually raised to room temperature for 6 hours to 2 hours. Stir for days. After removing the solvent or knowing the amount of the injected solvent it is possible to obtain the desired transition metal compound in the solution phase.

On the other hand, in the method for producing an olefin block copolymer according to the present invention, the compound represented by Formula 2 may be used as a catalyst.

In this case, the compound represented by Formula 2 is preferably a compound represented by Formula 2-1 in view of the control of the electronic and three-dimensional environment around the metal in the formula (1):

[Formula 2-1]

In Formula 2-1,

R ⁴ and R ⁵ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, or a silyl group;

Each R ⁶ independently represents an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, and 1 to 20 carbon atoms. An alkoxy group, an aryloxy group having 6 to 20 carbon atoms, or an amido group; Two or more R ⁶ may be linked to each other to form an aliphatic ring or an aromatic ring;

Q ³ and Q ⁴ are each independently halogen, an alkyl group having 1 to 20 carbon atoms or an aryl amido group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

M is a Group 4 transition metal.

In the compound represented by Formula 2 or Formula 2-1, an amido group and an amino or alkoxy group are connected by a phenylene bridge, the Cp-ME angle is narrow structurally, and the Q ¹ -MQ ² angle at which the monomer approaches is wide. It is easy to access large monomers. In addition, unlike the CGC structure connected by the silicon bridge, in the compound structure represented by Formula 1, for example, oxygen, phenylene bridge, and nitrogen together with metal sites form a stable and rigid hexagonal ring structure. Therefore, when these compounds are reacted with methylaluminoxane or a cocatalyst such as B (C ₆ F ₅ ) ₃ to be activated and then applied to the olefin polymerization, the characteristics such as high activity, high molecular weight and high copolymerization even at high polymerization temperature Olefin copolymers having

On the other hand, the catalyst composition used in the preparation method of the present invention may further include one or more cocatalyst compounds selected from the group consisting of compounds represented by the following formula (3 to 5):

(3)

J (R ⁴ ) ₃

In Formula 3,

J is aluminum or boron,

Each R ⁴ is independently halogen or a C 1-20 hydrocarbyl radical unsubstituted or substituted with halogen;

[Chemical Formula 4]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Chemical Formula 4,

L is a neutral or cationic Lewis acid;

H is hydrogen;

Z is a Group 13 element;

A is independently C6-C20 aryl or C1-C20 alkyl wherein at least one hydrogen atom is substituted with halogen, C1-C20 hydrocarbyl, C1-C20 alkoxy group or phenoxy group;

[Chemical Formula 5]

^{- [Al (R 5) -O} ] a -

In Formula 5,

R ⁵ is halogen or hydrocarbyl having 1 to 20 carbon atoms unsubstituted or substituted with halogen;

a is an integer of 2 or more.

The catalyst composition used in the preparation method of the present invention may exist in an activated state by reaction with the cocatalyst, which is also referred to as an activated catalyst composition. However, since it is well known in the art that the catalyst composition is present in an activated state, the term activated catalyst composition will not be used separately herein.

Here, according to one embodiment of the present invention, the compound represented by Chemical Formula 3 is not particularly limited as long as it is an alkyl metal compound; Preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triiso Pentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, tri Isobutyl boron, tripropyl boron, tributyl boron and the like; More preferably, it may be trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, or the like.

In addition, the compound represented by the formula (4) is triethyl ammonium tetra (phenyl) boron, tributyl ammonium tetra (phenyl) boron, trimethyl ammonium tetra (phenyl) boron, tripropyl ammonium tetra (phenyl) boron, trimethyl Ammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl Boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (pentafluorophenyl) boron, di Ethyl ammonium tetra (pentafluorophenyl) boron, trimethyl phosphonium tetra (phenyl) boron, triethyl ammonium tetra (phenyl) aluminum, tributyl ammonium tetra (phenyl) aluminum, trimethyl ammonium tetra (phenyl) aluminum, Tripro Ammonium tetra (phenyl) aluminum, 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, N-diethylanilinium tetra (phenyl Aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (pentafluorophenyl) aluminum, diethylammonium tetra (pentafluorophenyl) aluminum, tri Phenylphosphonium tetra (phenyl) aluminum, trimethylphosphonium tetra (phenyl) aluminum, triethylammonium tetra (phenyl) aluminum, tributylammonium tetra (phenyl) aluminum, tripropylammonium tetra (p-tolyl) bo , Triethyl ammonium tetra (o, p-dimethylphenyl) boron, trimethyl ammonium tetra (o, p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra ( p-trifluoromethylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, triphenylphosphonium tetra (phenyl) boron, triphenylca Bonium tetra (p-trifluoromethylphenyl) boron, triphenyl carbonium tetra (pentafluorophenyl) boron, trityl tetra (pentafluorophenyl) boron, trityl tetrakis (pentafluorophenyl) borate, etc. Can be.

In addition, the compound represented by Chemical Formula 5 is not particularly limited as long as it is alkylaluminoxane; Preferably methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like; More preferably, it may be methyl aluminoxane.

Particularly, according to the present invention, the addition amount of the cocatalyst compound is a transition metal compound in which a Group 4 transition metal is coordinated with a compound represented by Formula 1 as a ligand, and a compound represented by Formula 2 (hereinafter, a main catalyst compound) It may be included in a molar ratio of 1: 1 to 1:20 relative to, preferably in a molar ratio of 1: 1 to 1:18, more preferably 1: 1 to 1:15. That is, in order to express the minimum effect by the cocatalyst compound, the content of the cocatalyst compound is preferably included in a molar ratio of 1: 1 or more relative to the main catalyst compound. In addition, when the excessive amount of the cocatalyst compound is added, it may be difficult to control the physical properties of the polymer, and in particular, the activation of the alkylated transition metal compound may not be fully performed. In order to prevent this, the cocatalyst compound may be used as the main catalyst. It is preferable that it is contained in a molar ratio 1:20 or less with respect to a compound.

On the other hand, the catalyst composition used in the production method of the present invention may further include a polymerization aid.

Here, the polymerization aid is made of an aluminum compound containing a C1-C12 hydrocarbyl substituent, a zinc compound containing a C1-C12 hydrocarbyl substituent, and a gallium compound containing a C1-C12 hydrocarbyl substituent. At least one compound selected from the group; Preferably triethylaluminum or diethylzinc.

The polymerization aid improves the degree of blocking and crystallinity of the molecular structure, increases the content of the comonomer and serves to prepare a copolymer having a low melting point and a high melting point. This allows the polymerization aid to allow the alternating action of the transition metal compound and the compound represented by the formula (2) derived from formula (1), thereby alternating a plurality of segments, for example, hard segments and soft segments of the olefin block copolymer. This is because the formation can be assisted. That is, olefin block copolymers having a higher degree of blocking and higher melting point and higher heat resistance can be produced by the action of the polymerization assistant.

The addition amount of the polymerization aid is 1:10 to 1: for the transition metal compound in which Group 4 transition metal is coordinated with the compound represented by Formula 1 as a ligand and the compound represented by Formula 2 (hereinafter, referred to as main catalyst compound). It may be included in a molar ratio of 1000, preferably in a molar ratio of 1:10 to 1: 500, more preferably 1:20 to 1: 200.

That is, in order to express the minimum effect by the polymerization aid, the content of the polymerization aid is preferably included in a molar ratio of 1:10 or more with respect to the main catalyst compound. In addition, when the polymerization aid is added in an excessive amount, the activity of the main catalyst compound and the physical properties of the copolymer may be lowered. In order to prevent this, the polymerization aid is included in a molar ratio of 1: 1000 or less with respect to the main catalyst compound. desirable.

As such, the method for preparing the olefin block copolymer according to the present invention may be performed at high temperature and high pressure in the presence of the catalyst composition described above. Accordingly, the olefin block copolymer according to the above method can exhibit high molecular weight and high degree of polymerization, as well as a high degree of blocking of hard and soft segments, and thus have excellent elasticity and heat resistance.

On the other hand, the copolymerization step may be carried out in a solution process using the catalyst composition, or may be performed in a slurry process or a gas phase process using the catalyst composition with an inorganic carrier such as silica.

Hereinafter, the present invention will be described based on the continuous solution polymerization process method.

(A) polymerization process

In the method for preparing the olefin block copolymer, the polymerization process may use the catalyst composition containing a transition metal, and during the polymerization process, a scavenger may be added at 0.4 to 5 times the total moisture content in the reactor. .

The scavenger serves to remove impurities, such as water and air, which may be included in the reactants, and is introduced into the reactants before the polymerization step of the reactants. The scavenger and reactant mixture may be mixed with the scavenger and the reactant in a separate reactor other than the polymerization reactor, and the scavenger and the reactant may be mixed for a sufficient time in a supply line through which the reactant is supplied to the polymerization reactor. Can be. Preferred examples of scavengers include, but are not limited to, TiBAl (triisobutylaluminum) or TOA (trioctylaluminum).

The polymerization process according to the above-described embodiments may be carried out by introduction of the catalyst composition, monomer, polymerization aid and scavenger described above on the reactor.

In the above-described polymerization method, the catalyst composition is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, It can be injected by dissolving or diluting in hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating with a small amount of alkylaluminum, and may be carried out by further using a promoter.

The molar ratio of (ethylene or propylene monomer / α-olefin monomer) suitable for the present invention may be from 1/100 to 100, preferably from 1/10 to 10, more preferably from 1/5 to 2. When the molar ratio exceeds 100, the resulting polymer is increased in density, making it difficult to prepare a low density polymer. When the molar ratio is less than 1/100, the amount of unreacted comonomer is increased to increase the conversion rate. This decreases, and as a result, there is a problem in that the recycling in process increases.

The molar ratio of ethylene or propylene monomer to solvent suitable for the present invention should be a suitable ratio for dissolving the raw material before the reaction and the polymer produced after the reaction. Specifically, the molar ratio of (ethylene or propylene monomer / solvent) is 1 / 10,000 to 10, preferably 1/100 to 5, most preferably 1/20 to 1. When the molar ratio of (ethylene or propylene monomer / solvent) is more than 10, the amount of solvent is too small, the viscosity of the fluid is increased so that the amount of solvent is more than necessary. There is a problem such as increase.

The solvent is introduced into the reactor at a temperature of -40 ~ 150 ℃ using a heater or a freezer, the polymerization reaction is started with the monomer and the catalyst composition. When the temperature of the solvent is less than -40 ℃, there will be some differences depending on the reaction amount, but the temperature of the solvent is too low, the reaction temperature is also accompanied by a problem that is difficult to control the temperature, the temperature of the solvent is 150 ℃ If it exceeds, the solvent temperature is too high, there is a problem that the heat removal of the reaction heat due to the reaction is difficult.

A high capacity pump raises the pressure above 50 bar to feed the feeds (solvent, monomer, catalyst composition, etc.), thereby passing the mixture of feeds without further pumping between the reactor arrangement, pressure drop device and separator. You can.

The polymer produced in the reactor is maintained at a concentration of less than 20 mass% in the solvent and is passed to the primary solvent separation process for solvent removal after a short residence time. The residence time of the suitable polymers according to the invention in the reactor is from 1 minute to 10 hours, preferably from 3 minutes to 1 hour, most preferably from 5 minutes to 30 minutes. If the residence time is less than 1 minute, there is a problem such as a decrease in productivity and a loss of the catalyst due to a short residence time, such as an increase in the manufacturing cost. It becomes large, and accordingly, there is a problem of an increase in equipment costs.

(B) solvent separation process

The solvent separation process is performed by varying the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor. The polymer solution transferred from the reactor is kept molten through the heater, the unreacted raw material solvent is vaporized in the separator, and the resulting polymer is granulated using an experimental extruder.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

Example One

Synthesis of Olefin Block Copolymer

144 ml of 1-octene diluted / prepared to 0.7 M with hexane (1.0 L) solvent and hexane was added to a 2 L autoclave reactor, and the reactor temperature was preheated to 100 ° C.

To a 25 ml catalyst storage tank were added titanium compounds (5.0 μmol) treated with triisobutylaluminum compound (125 μmol) followed by trityl tetrakis (pentafluorophenyl) borate (25 μmol) promoter. At this time, ethylene was added to the catalyst tank at a pressure of 30 bar and catalyst 1 compound ((E) -N-((1,2,3,4-tetrahydroquinolin-8-yl) methylene was prepared using a high-pressure argon gas. 2μmol) -2-methylcyclohexanamine zirconiumbenzyl) and 2μmol of catalyst 2 compound (1,2,3,4-tetrahydro-8- (2,3,4-trimethyl-5-methylenecyclopenta-1,3-dienyl) quinoline dimethyltitanium) Injected into.

Thereafter, the copolymerization reaction was carried out at 120 ° C. for 10 minutes, and the remaining ethylene gas was removed, and the obtained polymer solution was added to excess ethanol to induce precipitation. The obtained polymer was washed two to three times with ethanol and acetone, and then an olefin block copolymer was obtained by drying in a vacuum oven at 80 ° C. for at least 12 hours.

(Preparation of film containing block copolymer)

Using the olefin block copolymer as a raw material, a force of 3 minutes was applied at a pressure of 100 bar at 190 ° C. using a hot press to obtain a film having a thickness of about 1.1 mm.

Example 2

The olefin block copolymers were synthesized under the same conditions and methods as in Example 1 except that the trityl tetrakis (pentafluorophenyl) borate cocatalyst input amount was 30 μmol; In the same manner as in Example 1, a film containing the olefin block copolymer was obtained.

Example 3

The olefin block copolymer was synthesized under the same conditions and methods as in Example 1 except that the amount of the catalyst 1 compound was 3 mol, the amount of the catalyst 2 compound was 1 mol, and 0.4 mol of diethyl zinc was further added; In the same manner as in Example 1, a film containing the olefin block copolymer was obtained.

Example 4

The olefin block copolymers were synthesized under the same conditions and methods as in Example 1 except that the amount of the catalyst 1 compound was 2 μmol and the amount of trityl tetrakis (pentafluorophenyl) borate cocatalyst was 25 μmol; In the same manner as in Example 1, a film containing the olefin block copolymer was obtained.

Example 5

(E) -1,2,3,4-tetrahydro-N-((1,2,3,4-tetrahydroquinolin-8-yl) methylene) naphthalen-1-amine zirconiumbenzyl 3 μmol is used instead of the catalyst 1 compound, The olefin block copolymers were synthesized under the same conditions and methods as in Example 1 except that the amount of the catalyst 2 compound was 2 μmol; In the same manner as in Example 1, a film containing the olefin block copolymer was obtained.

Comparative Example One

An olefin copolymer was synthesized under the same conditions and methods as in Example 1, except that Catalyst 1 and Catalyst 2 having the following structure were used instead of Catalyst 1 and Catalyst 2 of Example 1; In the same manner as in Example 1, a film containing the olefin copolymer was obtained.

[Catalyst 1]

[Catalyst 2]

Control Example 1 and Control Example 2

As the olefin block copolymer, E180F (control example 1, manufacturer: Samsung Total) and LC180 (control example, LG Chemical, Inc.), which are commercial products, were prepared, respectively, and the olefin block air was prepared in the same manner as in Example 1. A film containing coalescing was obtained.

Test Example

The physical properties of the copolymers prepared in Examples and Comparative Examples and the copolymers prepared as controls were measured by the following methods, and the results are shown in Table 1 or Table 2 below.

(1) Melt Index (g / 10min): The melt index (Melt index, MI) of the polymer was measured by ASTM D-1238 (Condition E, 190 ° C, 2.16 kg load).

(2) Density (g / cm 3): The sample was made into a sheet having a thickness of 3 mm and a radius of 2 cm with a 180 ° C. press mold, and measured on a Mettler balance at 10 ° C./min.

(3) Melting point (° C.): After increasing the temperature to 200 ° C., holding at that temperature for 5 minutes, then down to 30 ° C., and increasing the temperature again, the DSC (Differential Scanning Calorimeter, manufactured by TA) curve The top was taken as the melting point. At this time, the rate of temperature rise and fall is 10 ℃ / min, the melting point was used in the result measured in the section where the second temperature rises.

(4) Thermal Mechanical Analysis: Using TMA Q400 manufactured by TA, a sample penetration test was conducted with 1 Ndml force, and the temperature increase rate was increased from 25 ° C. to 5 ° C./min. The probe penetration distance was measured as a function of temperature and was taken as an experimental value when the probe penetrated 1 mm of the sample.

(5) adhesive strength (g / inch)

: Surfaces of substrates (1.1t, area 65 × 140 mm ² ) of PMMA or ABS / PC, respectively, were wiped 2-3 times with a tissue moistened with ethyl acetate and left for 30 minutes under constant temperature and humidity conditions. On the substrate pretreated by the above method, each copolymer sample was laminated with an area of 25 × 100 mm ² . The backing PET film (thickness 100 μm) was attached to the end of the sample attached to each substrate and then stored at room temperature. After about 4 hours, each sample was subjected to a 180 degree peel test (peel test-measure force in tension, peel speed 300 mm / min).

The melt index (g / 10 min) Density (g / cm3) Melting point (캜) Example 1 1.5 0.875 123 Example 2 1.7 0.874 123 Example 3 1.0 0.877 123 Example 4 1.8 0.872 122 Example 5 1.5 0.875 123 Comparative Example 1 5.0 0.866 120 Control Example 1 2.0 0.940 90 Control Example 2 1.1 0.880 60

Adhesive Strength (g / inch) materials PMMA ABS / PC Example 1 19.5 17.6 Example 2 18.8 17.0 Example 3 16.6 16.5 Example 4 20.0 18.8 Example 5 19.3 17.2 Comparative Example 1 24.2 21.4 Control Example 1 28.6 8.3 Control Example 2 7.6 3.7

As can be seen from Test Example 1 and Test Example 2, the block copolymers according to Examples 1 to 5 were excellent in heat resistance. In addition, the film including the block copolymer according to Examples 1 to 5 was excellent in elasticity, in particular, it was confirmed that it can exhibit a stable adhesive strength of 15 to 20 g / inch with respect to various substrates such as PMMA, ABS / PC .

In comparison, the film of Control Example 2 was found to be too low in adhesive strength to be suitable for use as a self-adhesive film. In addition, the film of Comparative Example 1 exhibited an adhesive strength opposite to that of the PMMA substrate and the ABS / PC substrate, and there was a problem in that reliability of the adhesive strength could not be secured. In addition, the films of Comparative Examples 1 and 2 had a low melting point and were easily melted in a high temperature environment, making it impossible to use them as adhesive films.

And it was confirmed that the film of the comparative example 1 has too high adhesive strength, and shows the intensity | strength corresponding to an adhesion | attachment area | region beyond the adhesion area. That is, the film of the embodiments can maintain the proper adhesive strength even if the ambient temperature rises, whereas the film of Comparative Example 1 does not fall off from the substrate well when the ambient temperature rises, it does not satisfy the stable physical properties as an adhesive film Confirmed.

Claims

A block copolymer of an ethylene or propylene monomer and an α-olefin monomer, the block copolymer comprising a plurality of blocks or segments having different contents, crystallinity, density, melting point or glass transition temperature from the α-olefin monomer,
The block copolymer has a melting point of 100 to 130 ℃,
An olefin block copolymer film having an adhesive strength (peel speed 300 mm / min, 4 hours at room temperature after adhesion) of 10 to 20 g / inch.

The method of claim 1,
An olefin block copolymer film having an adhesive strength of 12 to 20 g / inch measured under the above conditions.

The method of claim 1,
The block copolymer is an olefin block copolymer film having a melt index (Melt Index, 2.16 kg) of 0.5 to 5 g / 10 min.

The method of claim 1,
The block copolymer has an olefin block copolymer film having a thermal mechanical analysis value of 70 ° C. or higher.

The method of claim 1,
The block copolymer is an olefin block copolymer film having a density of 0.85 to 0.9 g / cm 3.

The method of claim 1,
The block copolymer has a weight average molecular weight of 50,000 to 200,000, molecular weight distribution of 2.0 to 4.5 olefin block copolymer film.

The method of claim 1,
The block copolymer is an olefin block copolymer film having an ethylene or propylene monomer content of 50 to 90% by weight.

The method of claim 1,
The α-olefin monomer is 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1- At least one olefin block copolymer film selected from the group consisting of tetradecene, 1-hexadecene, and 1-atocene.

The method of claim 1,
Olefin block copolymer film used as self adhesive film.