KR20210145022A - Composition for olefin based elastomer foam - Google Patents

Abstract

The present invention relates to a composition for olefin-based elastomer foam having improved mechanical properties. The composition for olefin-based elastomer foam includes (A) an olefin-based polymer satisfying the conditions of: (1) a melt index (MI, 190℃, 2.16 kg load) of 0.1-10.0 g/10 min; (2) a density (d) of 0.880-0.895 g/cc; (3) an elution temperature average value (Ta) of 25℃ <= Ta <= 50℃ and an elution temperature standard deviation value (σ) of 6.0<=σ<=9.0, as determined by cross fractional chromatography (CFC); and (4) a soluble fraction (SF) at -20℃ of 2 wt% or less, as determined by CFC, and (B) a foaming agent.

Description

Composition for olefin-based elastomer foams

The present invention relates to a composition for an olefin-based elastomer foam, and more specifically, to a composition for an olefin-based elastomer foam with improved mechanical properties including a low-density olefin-based polymer exhibiting high mechanical rigidity due to a reduced distribution of the introduced crystalline region. it's about

Polymer foams are widely used in building interior and exterior materials, automobile parts, packaging materials, daily necessities, and the like. For example, the polyolefin-based particle foam includes expanded polypropylene (hereinafter referred to as EPP) and expanded polyethylene (hereinafter referred to as EPE), and is used as an impact inhibitor for automobiles and packaging materials for electronic products.

When the polymer is foamed, the mechanical strength of the polymer is lowered, so by bonding the molecular chains by the crosslinking reaction of the polymer, the reduction in mechanical strength is suppressed while weight reduction by foaming is achieved. Polymer crosslinked foam is also used for flooring materials such as sports shoes (mainly mid sole), and a material that is lightweight and can suppress deformation due to long-term use, and has mechanical strength to withstand harsh conditions of use is required. am.

Conventionally, as a flooring material for shoes, a crosslinked foam of ethylene vinyl acetate copolymer was used, but the crosslinked foam of ethylene vinyl acetate copolymer has a high specific gravity, and also has a high compression set and low compression set, so it is heavy and long-term. There were problems such as loss of mechanical strength such as rebound elasticity due to compression due to use.

Accordingly, crosslinked foams including olefinic polymers have been proposed, but foams including olefinic polymers have a problem in that it is difficult to simultaneously improve mechanical properties such as burst tear strength, compression set, and rebound elasticity, which are mechanical strengths. .

Korean Patent Registration No. 10-0520278 KR 2007-0003071 A

An object of the present invention is to provide a composition for an olefin-based elastomer foam capable of exhibiting improved mechanical strength.

In order to solve the above problems, the present invention is (A) an olefin-based polymer satisfying the requirements of (1) to (4) below; and (B) a blowing agent.

(1) Melt Index (MI, 190°C, 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min, (2) Density (d) is 0.880 g/cc to 0.895 g/cc, (3) When cross-fraction chromatography (CFC) is measured, the average value (Ta) of the elution temperature is 25°C≤Ta≤50°C, the standard deviation value (σ) of the elution temperature is 6.0≤σ≤9.0, (4) the cross-fractionation chromatography The soluble fraction (SF, Soluble Fraction) at -20 ℃ when measured by graph (CFC) is 2 wt% or less.

The composition for an olefin-based elastomer foam according to the present invention contains an olefin-based polymer having a reduced distribution of the introduced crystalline region and exhibiting high mechanical rigidity. Mechanical properties such as rupture tear strength can be exhibited.

1 is a graph showing the elution amount according to the elution temperature of the polymers of Preparation Example 1 and Comparative Preparation Example 1 measured by cross-fraction chromatography (CFC).

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

As used herein, the term "polymer" means a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". Also, the term “interpolymer” refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term "copolymer" (which is commonly used to refer to polymers made from two different monomers), as well as the term "copolymer" (which is commonly used to refer to polymers prepared from three different types of monomers). used) the term "terpolymer". This includes polymers prepared by the polymerization of four or more types of monomers.

The composition for an olefin-based elastomer foam according to the present invention includes (A) an olefin-based polymer satisfying the requirements of (1) to (4) below; and (B) a blowing agent.

(1) Melt Index (MI, 190°C, 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min, (2) Density (d) is 0.880 g/cc to 0.895 g/cc, (3) When cross-fraction chromatography (CFC) is measured, the average value (Ta) of the elution temperature is 25°C≤Ta≤50°C, the standard deviation value (σ) of the elution temperature is 6.0≤σ≤9.0, (4) the cross-fractionation chromatography The soluble fraction (SF, Soluble Fraction) at -20 ℃ when measured by graph (CFC) is 2 wt% or less.

Hereinafter, each component will be described in detail.

(A) Olefin polymer

The olefin-based polymer included in the composition for an olefin-based elastomer foam according to the present invention has an ultra-low density, and the distribution of the crystalline region is reduced compared to a conventional conventional olefin-based polymer, so that the density and melt index (Melt Index, MI, 190° C., and 2.16 kg load condition), exhibiting improved tensile strength while having excellent elongation. The olefin-based polymer included in the composition for an olefin-based elastomer foam according to the present invention is prepared by a manufacturing method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for polymerization, A crystalline region having a narrow distribution is introduced according to the hydrogen gas input, thereby exhibiting excellent mechanical rigidity.

The melt index (MI) can be adjusted by controlling the amount of the catalyst used in the process of polymerizing the olefin-based polymer for comonomer, and affects the mechanical properties and impact strength, and moldability of the olefin-based polymer. In the present specification, the melt index is measured at 190 ° C., 2.16 kg load condition according to ASTM D1238 under low density conditions of 0.880 g / cc to 0.895 g / cc, 0.1 g / 10 minutes to 10 g / 10 minutes and specifically 0.2 g/10 min to 9.0 g/10 min, more specifically 0.2 g/10 min to 5.0 g/10 min.

Meanwhile, the density may be 0.880 g/cc to 0.895 g/cc, and specifically 0.880 g/cc to 0.890 g/cc.

In general, the density of the olefin-based polymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like. The olefin-based polymer included in the composition for an olefin-based elastomer foam of the present invention is polymerized using a catalyst composition including a transition metal compound having a characteristic structure, and a large amount of comonomer can be introduced. It may have a low density.

In addition, the olefin-based polymer has an average elution temperature (Ta) of 25°C≤Ta≤50°C, and an elution temperature standard deviation value (σ) of 6.0≤σ≤9.0 when measured by cross-fractionation chromatography (CFC), specifically 25°C≤Ta≤40°C, 6.5≤σ≤9.0, and more specifically, 30°C≤Ta≤40°C and 6.5≤σ≤8.8.

The elution temperature average value (Ta) and the elution temperature standard deviation value (σ) may be calculated by drawing a graph of the elution amount (dW/dT) according to the elution temperature after cross-fractionation chromatography (CFC) measurement. In addition, the elution temperature average value (Ta) may be expressed by Equation 1 below, and the elution temperature standard deviation value (σ) may be expressed by Equation 2 below.

[Equation 1]

[Equation 2]

Average in Equation (2) dissolution temperature (T) ² is given by Equation (3).

[Equation 3]

In addition, the olefin-based polymer has a soluble fraction (SF, Soluble Fraction) of 2 wt% or less at -20 °C measured by cross-fraction chromatography (CFC), specifically 0.01 wt% to 2 wt%, more specifically 0.05 It may be from 1 wt% to 1 wt%.

In the cross-fractionation chromatography (CFC, Cross-fractionation Chromatography) measurement, the fraction eluted at a lower temperature has lower crystallinity, and in the present specification, the cross-fractionation chromatography (CFC) at -20°C or lower The eluted soluble fraction (SF, Soluble Fraction) is defined as an ultra-low crystallinity region.

In general, the lower the density of the polymer, the lower the crystallinity, the increase in the ultra-low crystallinity region, and the impact strength is improved. However, when the ultra-low crystallinity region exceeds a certain level in a typical olefin-based polymer, mechanical properties deteriorate. The olefin-based polymer included in the composition for olefin-based elastomer foam according to the present invention exhibits excellent mechanical properties such as exhibiting improved tensile strength while having excellent elongation by reducing the ultra-low crystallinity content and increasing the relatively high crystallinity content. have.

The measurement of the CFC used herein may be measured using, for example, a CFC machine manufactured by PolymerChar, and may be measured while raising the temperature from -20°C to 120°C using o-dichlorobenzene as a solvent.

In addition, the olefin-based polymer included in the composition for an olefin-based elastomer foam according to an example of the present invention may further satisfy the requirement of (5) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol, and specifically As such, the weight average molecular weight (Mw) may be 30,000 g/mol to 300,000 g/mol, more specifically 50,000 g/mol to 200,000 g/mol. In the present invention, the weight average molecular weight (Mw) is a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).

In addition, the olefin-based polymer included in the composition for an olefin-based elastomer foam according to an example of the present invention is additionally a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) (6) molecular weight distribution (MWD) ; Molecular Weight Distribution) may satisfy the requirement of 0.1 to 6.0, and the molecular weight distribution (MWD) may be specifically 1.0 to 4.0, more specifically 2.0 to 3.0.

In addition, the olefin-based polymer included in the composition for an olefin-based elastomer foam according to an example of the present invention may additionally satisfy the requirement of (7) a melt flow rate ratio (MFRR) of 3 to 10, and the melt flow rate ratio (MFRR) is Specifically, it may be 4 to 9, more specifically 6 to 8.

The melt flow rate ratio (MFRR) _{means the ratio obtained by dividing MI 10} (melt index under a load of 10 kg and 190° C.) by MI _2.16 (melt index under a load of 2.16 kg and 190° C.) of the long side chain (LCB) of the polymer. As the number decreases, the MFRR may exhibit a low value, and mechanical properties of the polymer may be improved.

In addition, the olefin-based polymer included in the composition for an olefin-based elastomer foam according to an example of the present invention may additionally satisfy the requirement of (8) an elution temperature (Te) of 20°C to 90°C, specifically, the elution temperature (Te) ) may be 25 °C to 85 °C, more specifically 30 to 80 °C.

As used herein, the elution temperature Te (Elution temperature) means the temperature of the highest point in the CFC elution curve expressed as the elution amount (dW/dT) with respect to the elution temperature.

In calculating Te, the starting point of each peak in the elution amount (dW/dT) graph with respect to the elution temperature is defined as the point at which the polymer starts to elute based on the base line, and the end point of each peak is based on the baseline It can be defined as the point at which the elution of the polymer ends. At this time, if the end point and start point of the previous peak cannot be defined based on the baseline because the two peaks overlap, the point at which the peak eluted at a relatively low temperature begins to decrease after reaching the maximum point and then starts to increase again It is defined as the end point and the start point of the trailing peak. In addition, the peak expressed at -20 °C to -10 °C can be seen as a part of the peak appearing after -10 °C appears at this position due to the limitation of measurement, therefore, the peak appearing at this position is after -10 °C It can be treated by including it in the peaks in

When the olefin-based polymer included in the composition for an olefin-based elastomer foam according to an example of the present invention has two elution temperatures, the first elution is the relatively low elution temperature, that is, the temperature of the highest point of the peak eluted at a relatively low temperature. The temperature Te1 may be 20°C to 50°C, specifically 25°C to 45°C, and more specifically 30 to 42°C.

The olefin-based polymer is an olefin-based monomer, specifically, an alpha-olefin-based monomer, a cyclic olefin-based monomer, a diene olefin-based monomer, a triene olefin-based monomer, and a styrenic monomer, or 2 It may be a copolymer of more than one species. More specifically, the olefin-based polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 12 carbon atoms or a copolymer of ethylene and an alpha-olefin having 3 to 10 carbon atoms.

The alpha-olefin comonomer is 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-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 - It may include any one or a mixture of two or more selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

More specifically, the olefin copolymer included in the composition for an olefin-based elastomer foam according to an example of the present invention is ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1-octene, and more specifically, the olefin copolymer according to an example of the present invention may be a copolymer of ethylene and 1-butene.

When the olefinic polymer is a copolymer of ethylene and alpha-olefin, the amount of the alpha-olefin is 90 wt% or less, more specifically 70 wt% or less, and even more specifically 5 wt% to 60 wt% based on the total weight of the copolymer. It may be weight %, and more specifically, it may be 20 weight % to 50 weight %. When the alpha-olefin is included in the above range, it is easy to implement the above-described physical properties.

The olefin-based polymer included in the composition for an olefin-based elastomer foam according to an embodiment of the present invention having the above physical properties and structural characteristics is a metallocene catalyst composition containing one or more transition metal compounds in a single reactor. It can be prepared through a continuous solution polymerization reaction in which hydrogen gas is introduced in the presence of polymerizing an olefinic monomer. Accordingly, in the olefin-based polymer included in the composition for an olefin-based elastomer foam according to an embodiment of the present invention, a block is formed in which two or more repeating units derived from any one of the monomers constituting the polymer in the polymer are linearly connected. doesn't happen That is, the olefin-based polymer included in the composition for an olefin-based elastomer foam according to the present invention does not contain a block copolymer, and is a random copolymer, an alternating copolymer, and a graft copolymer. (graft copolymer) may be selected from the group consisting of, more specifically, may be a random copolymer.

Specifically, the olefin-based copolymer included in the composition for an olefin-based elastomer foam of the present invention is in the presence of a catalyst composition for olefin polymerization including a transition metal compound of Formula 1, by introducing hydrogen gas to polymerize the olefin-based monomer It can be obtained by a manufacturing method comprising the steps.

The input amount of the hydrogen gas may be 10 to 60 sccm, specifically 10 to 50 sccm, more specifically 15 to 40 sccm. When the amount of hydrogen gas input in the step of polymerizing the olefin monomer satisfies the above range, an olefin-based polymer satisfying the requirements of (1) to (4) of the present invention may be prepared.

However, in one embodiment of the present invention, the scope of the structure of the transition metal compound of Formula 1 is not limited to the specific disclosed form, and includes all changes, equivalents and substitutes included in the spirit and technical scope of the present invention. should be understood as

[Formula 1]

R ₁ to R ₁₃ are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; silyl; or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbon atoms and alkoxy having 1 to 12 carbon atoms, wherein _{two or more adjacent to each other among R 1} to R ₁₂ are connected to each other to form a ring can,

X and X' are each independently O, S or a linking group,

A is alkylene having 1 to 6 carbon atoms,

Y is C or Si,

M is a group 4 transition metal,

Q is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms.

When the transition metal compound is used as a catalyst and applied to olefin polymerization, polyolefins having characteristics such as high molecular weight can be prepared by exhibiting high activity even at high polymerization temperatures and exhibiting high copolymerizability. In particular, it is possible to prepare a low-density olefin-based polymer having a high molecular weight density of 0.850 g/cc to 0.880 g/cc due to the structural characteristics of the catalyst.

In addition, in one example of the present invention, in the transition metal compound of Formula 1, R _{1 To} R _{12 Are} each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; silyl; or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbon atoms and alkoxy having 1 to 12 carbon atoms, wherein _{two or more of R 1} to R ₁₂ are connected to each other to form a ring can form,

wherein R ₁₃ is hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; alkylaryl having 7 to 12 carbon atoms; Or it may be an arylalkyl having 7 to 12 carbon atoms,

Wherein X and X' may each independently be O, S or a linking group,

wherein A is alkylene having 1 to 6 carbon atoms,

Y may be C or Si,

M may be Ti, Zr or Hf,

wherein Q is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.

In addition, in another example of the present invention, in the transition metal compound of Formula 1, R _{One To} R ₁₂ Each independently hydrogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; silyl; or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbon atoms and alkoxy having 1 to 12 carbon atoms, wherein _{two or more of R 1} to R ₁₂ are connected to each other to form a ring can form,

wherein R ₁₃ is hydrogen; alkyl having 1 to 12 carbon atoms; aryl having 6 to 12 carbon atoms; or an alkylaryl having 7 to 12 carbon atoms; Or it may be an arylalkyl having 7 to 12 carbon atoms,

Wherein X and X' may each independently be O, S or a linking group,

A may be an alkylene having 1 to 6 carbon atoms,

Y may be C or Si,

M may be Ti, Zr or Hf,

wherein Q is hydrogen; halogen; alkyl having 1 to 12 carbon atoms; It may be a cycloalkyl having 3 to 12 carbon atoms.

In an example of the present invention, the transition metal compound of Formula 1 may be a transition metal compound represented by Formula 1a below.

[Formula 1a]

In Formula 1a, R ₁ to R ₁₃ , X, X', M, Y, and Q are each as defined in Formula 1 above, and n is an integer of 1, 2, or 3.

In addition, in an example of the present invention, the transition metal compound of Formula 1 may be a compound specifically represented by Formula 2 below.

[Formula 2]

In Formula 2,

R ₁ to R ₄ , R ₅ , R ₈ , R ₉ and R ₁₂ may each independently be hydrogen or alkyl having 1 to 12 carbon atoms,

R ₁₃ is hydrogen, alkyl having 1 to 12 carbon atoms, aryl having 6 to 12 carbon atoms; Or it may be an alkylaryl having 7 to 12 carbon atoms,

R ₁₄ to R ₂₁ may each independently be hydrogen or alkyl having 1 to 6 carbon atoms,

X and X' may each independently be O, S or a linking group,

A may be an alkylene having 1 to 6 carbon atoms,

Y may be C or Si,

M may be Hf,

Q may be halogen or alkyl having 1 to 12 carbon atoms,

n may be 1, 2, or 3.

In addition, in the transition metal compound of Formula 2,

The R ₁ to R ₄ , R ₅ , R ₈ , R ₉ and R ₁₂ may be hydrogen,

Wherein R ₁₃ may be an aryl having 6 to 12 carbon atoms,

Wherein X and X' may each independently be O, S or a linking group,

A may be ethylene,

Y may be C,

M may be Hf,

Wherein Q may be an alkyl having 1 to 6 carbon atoms,

The n may be 1.

In one example of the present invention, the transition metal compound of Formula 2 may be a transition metal compound represented by the following Formula 2a.

[Formula 2a]

In Formula 1a, R ₁ to R ₁₃ , X, X', M, Y, and Q are each as defined in Formula 1 above, and n is an integer of 1, 2, or 3. Also, n may be 1.

The compound represented by Formula 1 may be specifically a compound represented by any one of Formulas 1-1 and 1-2.

[Formula 1-1]

[Formula 1-2]

Each of the substituents defined in the present specification will be described in detail as follows.

As used herein, the term 'halogen' means fluorine, chlorine, bromine or iodine, unless otherwise noted.

As used herein, unless otherwise stated, the term 'alkyl' refers to a straight-chain, cyclic or branched hydrocarbon residue, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , t-butyl, n-pentyl, isopentyl and hexyl.

The term 'cycloalkyl' as used herein, unless otherwise stated, refers to a non-aromatic cyclic hydrocarbon radical composed of carbon atoms. 'Cycloalkyl' includes, by way of non-limiting example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

The term 'aryl' as used herein, unless otherwise stated, refers to an optionally substituted benzene ring, or to a ring system that can be formed by fusing one or more optional substituents. Exemplary optional substituents include substituted C _1-3 alkyl, substituted C _2-3 alkenyl, substituted C _2-3 alkynyl, heteroaryl, heterocyclic, aryl, optionally having 1 to 3 fluorine substituents. Alkoxy, aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy, aroyloxy, heteroaroyloxy, sulfanyl, sulfinyl, sulfonyl, aminosulfonyl, sulfonylamino, carboxyamide, amino carbonyl, carboxy, oxo, hydroxy, mercapto, amino, nitro, cyano, halogen or ureido. Such rings or ring systems may optionally be fused to an aryl ring (eg, a benzene ring), carbocyclic ring or heterocyclic ring optionally having one or more substituents. Examples of 'aryl' groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl or phenanthryl, and substituted derivatives thereof.

As used herein, the term 'alkenyl' refers to a straight or branched chain hydrocarbon radical having one or more carbon-carbon double bonds. Examples of 'alkenyl' as used herein include, but are not limited to, ethenyl and propenyl.

As used herein, the term 'alkoxy' refers to the group _{-OR a , wherein R a} is alkyl as defined above. 'Alkoxy' includes, but is not limited to, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and t-butoxy.

In the present specification, 'silyl' means an unsubstituted silyl or a silyl group substituted with one or more substituents. 'Silyl' includes, but is not limited to, silyl, trimethylsilyl, triethylsilyl, isopropyldimethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, hexyldimethylsilyl, methoxymethylsilyl, (2-methoxyethoxy ) methylsilyl, trimethoxysilyl, and triethoxysilyl.

The transition metal compound of Formula 1 may be used as a catalyst for a polymerization reaction in the form of a catalyst composition including one or more compounds of Formulas 3 to 5 as a co-catalyst.

[Formula 3]

-[Al(R ₂₂ )-O] _a -

[Formula 4]

A(R ₂₂ ) ₃

[Formula 4]

[LH] ⁺ [W(D) ₄ ] ^- or [L] ⁺ [W(D) ₄ ] ^-

In Formulas 2 to 3,

R ₂₂ may be the same or different from each other, and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

A is aluminum or boron,

D is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, wherein the substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms and at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,

H is a hydrogen atom,

L is a neutral or cationic Lewis base,

W is a group 13 element,

a is an integer greater than or equal to 2;

Examples of the compound represented by Formula 3 include alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and two or more kinds of the alkylaluminoxane are mixed and modified alkylaluminoxane, and specifically may be methylaluminoxane and modified methylaluminoxane (MMAO).

Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and specifically may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Formula 5 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, and trimethylammoniumtetra (o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N -diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, dimethyl Anilinium tetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tri Propylammonium tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum , tributylammoniumtetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentafluorophenylaluminum, triphenyl Phosphonium tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) ) boron or triphenylcarboniumtetrapentafluorophenylboron.

The catalyst composition, as a first method, 1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 3 or Formula 4 to obtain a mixture; and 2) adding the compound represented by Formula 5 to the mixture.

In addition, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 5 as a second method.

In the case of the first method among the methods for preparing the catalyst composition, the molar ratio of the compound represented by Formula 4 or Formula 5 to the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 3 is 1 It may be from 2 to 1:5,000, specifically from 1:10 to 1:1,000, and more specifically from 1:20 to 1:500. When the molar ratio of the compound represented by Formula 3 or Formula 4 to the transition metal compound represented by Formula 1 is less than 1:2, the amount of the alkylating agent is very small, and there is a problem that the alkylation of the metal compound cannot proceed completely, When the ratio exceeds 1:5,000, the metal compound is alkylated, but there is a problem in that the alkylated metal compound cannot be completely activated due to a side reaction between the remaining excess alkylating agent and the activator, which is the compound of Formula 5. In addition, the molar ratio of the compound represented by Formula 5 to the transition metal compound represented by Formula 1 may be 1:1 to 1:25, specifically 1:1 to 1:10, and more specifically It may be 1:1 to 1:5. When the molar ratio of the compound represented by Formula 5 to the transition metal compound represented by Formula 1 is less than 1:1, the amount of the activator is relatively small, and the activation of the metal compound is not completely achieved, so the activity of the catalyst composition produced may fall, and if the molar ratio is more than 1:25, the metal compound is fully activated, but the unit price of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with an excess of the remaining activator.

In the case of the second method among the methods for preparing the catalyst composition, the molar ratio of the compound represented by Formula 5 to the transition metal compound of Formula 1 may be 1:1 to 1:500, specifically 1:1 to 1: 50, and more specifically 1:2 to 1:25. When the molar ratio is less than 1:1, the amount of the activator is relatively small, so that the activation of the metal compound is not completely achieved, so there is a problem in that the activity of the resulting catalyst composition is decreased, and when it is more than 1:500, the activation of the metal compound is not achieved Although complete, there is a problem in that the unit price of the catalyst composition is not economically low with the excess amount of activator remaining, or the purity of the resulting polymer is lowered.

A hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, etc. may be used as the reaction solvent in the preparation of the catalyst composition, but is not limited thereto, and all solvents available in the art are used. can be used

In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier.

The carrier may be used without particular limitation as long as it is used as a carrier in a metallocene-based catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more thereof may be used.

Among them, when the carrier is silica, since the functional group of the silica carrier and the metallocene compound of Formula 1 chemically forms a bond, there is almost no catalyst released from the surface during olefin polymerization. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall surface or polymer particles are agglomerated during the production process of the olefin-based polymer. In addition, the olefin-based polymer prepared in the presence of the catalyst including the silica carrier has excellent particle shape and apparent density of the polymer.

More specifically, the carrier may be high-temperature dried silica or silica-alumina containing a siloxane group having high reactivity on the surface through a method such as high-temperature drying.

The carrier may further include an oxide, carbonate, sulfate or nitrate component such as _{Na 2} O, K ₂ CO ₃ , BaSO ₄ or Mg(NO ₃ ) _{2 .}

The polymerization reaction for polymerizing the olefinic monomer may be performed by a conventional process applied to polymerization of the olefinic monomer, such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.

The polymerization reaction of the olefin monomer may be performed under an inert solvent, and examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, but not limited thereto.

The polymerization of the olefin-based polymer may be made at a temperature of about 25 °C to about 500 °C, specifically 80 °C to 250 °C, more preferably at a temperature of 100 °C to 200 °C. In addition, the reaction pressure during polymerization is 1 kgf/cm ² to 150 kgf/cm ² , preferably 1 kgf/cm ² to 120 kgf/cm ² , more preferably 5 kgf/cm ² to 100 kgf/cm ² can be

The composition for an olefin-based elastomer foam according to an example of the present invention may include an additional polymer in addition to the (A) olefin-based polymer, specifically (A1) ethylene vinyl acetate copolymer.

(A1) ethylene vinyl acetate copolymer

The ethylene vinyl acetate copolymer is a copolymer prepared by copolymerizing ethylene and vinyl acetate, and contains 10 to 40% by weight of vinyl acetate-derived units in the ethylene vinyl acetate copolymer, specifically 10 to 30% by weight, more specifically 15 to 30% by weight.

The composition for the olefin-based elastomer foam may include (A) the olefin-based polymer and (A1) the ethylene vinyl acetate copolymer in a weight ratio of 10:90 to 90:10, specifically 20:80 to 80:20 by weight and, more specifically, may be included in a weight ratio of 30:70 to 70:30. When the composition for an olefin-based elastomer foam contains (A) an olefin-based polymer and (A1) an ethylene vinyl acetate copolymer in the above mixing ratio, tensile strength and tear strength may be improved.

(B) blowing agent

The composition for an olefin-based elastomer foam of the present invention may contain 0.1 to 20 parts by weight, specifically 1 to 15 parts by weight, more specifically 5 to 10 parts by weight, based on 100 parts by weight of the (A) olefin-based polymer, the foaming agent. have. When the blowing agent is included in the above range, a foam having an appropriate expansion ratio can be obtained. The amount of the foaming agent used may be adjusted within the above range in consideration of the expansion ratio of the desired foam.

The blowing agent is azodicarbonamide (azodicarbonamide)-based, diazoaminoaxobenzene-based, N,N'-dinitrosopentamethylenetetramine (N,N'-dinitrosopentamethylenetetramine)-based, p-toluenesulfonylhydride Razide (p-toluene sulphonyl hydrazide), P,P'-oxybis (benzenesulfonyl hydrazide) (p,p'-oxybis (benzenesulphonyl hydrazide)) or benzene sulphonyl hydrazide ) may be at least one organic thermal decomposition foaming agent selected from the group consisting of, or an inorganic thermal decomposition foaming agent such as sodium hydrogen oxide, sodium carbonate, ammonium hydrogen carbonate, and ammonium carbonate. The organic pyrolytic foaming agent is, for example, azodicarbonamide (ADCA), N,N'-dinitorosopentamethylenetetramine, 4,4'-oxybis(benzenesulfonylhydrazide), diphenylsulfone-3 , 3'-disulfonyl hydrazide, p-toluenesulfonyl semicarbazide, or trihydrazinotriazine.

Meanwhile, the composition for an olefin-based elastomer foam may further include (C) a crosslinking agent and (D) a crosslinking aid.

(C) crosslinking agent

The crosslinking agent may bind molecular chains by a crosslinking reaction of the olefin-based polymer, and may suppress a decrease in mechanical strength of the olefin-based elastomer foam.

The composition for an olefin-based elastomer foam of the present invention contains the crosslinking agent in an amount of 0.01 parts by weight to 5 parts by weight, specifically 0.1 parts by weight to 2 parts by weight, more specifically 0.2 parts by weight to 1 parts by weight, based on 100 parts by weight of the olefin-based polymer. may include When the crosslinking agent is used together with a crosslinking aid in the above range, a crosslinked foam having an appropriate crosslinked structure can be formed.

The crosslinking agent may be an organic peroxide, for example, t-butyl peroxy isopropyl carbonate, t-butyl peroxy laurate, bentoyl peroxide (benzoyl peroxide) , t-butyl peroxy acetate, t-butyl peroxy benzoate, di-t-butyl diperoxy phthalate, t-butyl t-butyl peroxy maleic acid, cyclohexanone peroxide, t-butyl cumyl peroxide, t-butyl hydroperoxide, 1 -1-bis-(t-butyl peroxy)-3,3,5-trimethylcyclohexane (1,1-bis-(t-butyl peroxy)-3,3,5-trimethyl cyclohexane), dicumyl peroxide ( dicumyl peroxide), 2,2-bis-(t-butyl peroxy) butane), methyl ethyl ketone peroxide, 1,1- Di-(t-butylperoxy)cyclohexane (1,1-di-(tbutylperoxy)cyclohexane), 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane-3(2,5 -dimethyl-2,5-di-(t-butylperoxy)hexane-3), 2,5-dimethyl-2,5-di-(bentoylperoxy)hexane-3(2,5-dimethyl-2,5- di-(benzoylperoxy)hexyne-3), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane), 2,5-dimethyl -2,5-di-(benzoylperoxy)hexane-3(2,5-dimethyl-2,5-di-(benzoylperoxy)hexyne-3), 2,5-dimethyl-2,5-di(benzoylperoxy) oxy ) hexane-3 (2,5-dimethyl-2,5-di (benzoylperoxy) hexane-3), di-t-butylperoxide (di-t-butylperoxide), n-butyl-4,4-bis (t -Butylperoxy)valate (n-butyl-4,4-bis(t-butylperoxy) valelate) and 2,2'-bis(butylperoxy isopropyl)benzene (2,2'-bis(butylperoxy isopropyl) benzene) may be at least one selected from the group consisting of.

(D) crosslinking aid

The composition for an olefin-based elastomer foam of the present invention contains 0.01 parts by weight to 2 parts by weight, specifically 0.02 parts by weight to 1 part by weight, more specifically 0.05 parts by weight to 0.5 parts by weight, based on 100 parts by weight of the olefin-based polymer, the crosslinking aid. may include parts. In addition, the crosslinking aid may be used in a weight ratio of 1:30 to 5:1, specifically 1:20 to 3:1, with the crosslinking agent.

When the crosslinking aid is used together with the crosslinking agent in the above range, a crosslinked foam having an appropriate crosslinked structure can be formed.

The crosslinking aid is, for example, sulfur, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trime adjuvants for peroxycrosslinking such as tyrolpropane-N,N'-m-phenylenedimaleimide; or divinylbenzene, triallyl cyanurate (TAC), or triallyl isocyanurate (TAIC). In addition, polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, vinyl butyrite, It may be a polyfunctional vinyl monomer such as vinyl stearate.

In addition, the composition for the olefin-based elastomer foam may additionally include a foaming aid such as zinc oxide and a lubricant such as stearic acid to stabilize crosslinking and improve foaming properties, and a white agent such as titanium dioxide to impart white properties may include

The present invention also provides an olefin-based elastomer foam prepared by using the composition for an olefin-based elastomer foam.

The olefin-based elastomer foam according to an example of the present invention is manufactured by preparing a sheet-shaped molded article using a mixture including the composition for olefin-based elastomer foam and additional components using a calendar molding machine, a press molding machine, or a T-die extruder. It may be made into pellets, and then manufactured using an injection molding machine. For example, the substrate is prepared by kneading for about 10 to 20 minutes in a closed kneader at 100° C. to 120° C., and then added to the prepared substrate in a roll mill having a surface temperature of 90° C. to 110° C. A crosslinking agent, a crosslinking aid, and a foaming agent may be added and kneaded, and then the sheet may be manufactured.

In addition, in an example of the present invention, the sheet is placed in a press mold and subjected to a temperature of 130° C. to 180° C. and ^{a pressure condition of 120 kg/cm 2} to 180 kg/cm ^{2 by} thermocompression molding for 10 minutes to 60 minutes. A pre-foam can be prepared. In addition, the secondary foam (remolding-foam) by placing the primary foam in a press mold and thermocompression molding for 5 to 30 minutes at a temperature of 130 ° C. to 180 ° C., and ^{a pressure condition of 120 kg/cm 2} to 180 kg/cm ² ) can be prepared.

Example

Synthesis of ligands and transition metal compounds

Organic reagents and solvents were purchased from Aldrich, and purified by standard methods unless otherwise specified. The reproducibility of the experiment was improved by blocking the contact of air and moisture at all stages of the synthesis.

Preparation Example 1: Preparation of Ligand Compound and Transition Metal Compound

Step 1: Preparation of ((ethane-1,2-diylbis(oxy))bis(4,1-phenylene))bis(phenylmethanone)

1,2-diphenoxyethane (5.25 g, 24.5 mmol), AlCl ₃ (7.20 g) and 1,2-dichloroethane (87.5 mL) were placed in a 100 mL Schlenk flask. Benzoyl chloride (2.05 eq, 7.06 g) was slowly added dropwise at room temperature. Stir overnight at 65°C. Then, the final compound was obtained by extraction using ice water, 10% HCl, and distilled water.

¹ H NMR (CDCl ₃ ): 7.86 (d, 4H), 7.77 (d, 4H), 7.58 (m, 2H), 7.50 (m, 4H), 7.04 (d, 4H), 4.56 (s, 4H)

Step 2: Preparation of 1,2-bis(4-(cyclopenta-2,4-dien-1-ylidene(phenyl)methyl)phenoxy)ethane)

((ethane-1,2-diylbis(oxy))bis(4,1-phenylene))bis(phenylmethanone) (4.0g, 7.47mmol) prepared in step 1 in a 100 mL Schlenk flask, Pyrrolidine (2.4 mL) and THF (8.9 mL) were added. Sodium cyclopentadienide (sodium Cp) (2.0 M, 28.4 mL) was slowly added dropwise at room temperature. It was stirred at room temperature overnight. After extraction using distilled water and diethyl ether, the final compound was obtained through recrystallization of methanol.

¹ H NMR (CDCl ₃ ): 7.41 (m, 6H), 7.34 (m, 8H), 6.99 (d, 4H), 6.63 (d, 4H), 6.37 (s, 2H), 6.28 (s, 2H), 4.42 (s, 4H)

Step 3: 1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenoxy)ethane

1,2-bis(4-(cyclopenta-2,4-dien-1-ylidene(phenyl)methyl)phenoxy)ethane) prepared in step 2 in a 100 mL Schlenk flask (1.48 g, 2.85 mmol) ), MTBE (13.0 mL) was added. In another 100 mL Schlenk flask, put lithium octahydrooctamethylfluorene (2.0 g) and MTBE (26.0 mL), and 1,2-bis(4-(cyclopenta-2,4-dien-1-yl) at room temperature den (phenyl) methyl) phenoxy) ethane) was added dropwise to the contents of the flask. It was stirred at 50 °C overnight. After extraction using distilled water and diethyl ether, the final compound was obtained through recrystallization of methanol.

¹ H NMR (CDCl ₃ ): 7.65 to 6.26 (m, 34H), 5.35 (m, 4H), 4.24 (m, 4H), 1.72 (m, 16H), 1.26 (m, 48H)

Step 4: 1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenoxy)ethane-hafnium chloride

1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2, 3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenoxy)ethane (2.44 g, 1.89 mmol); Toluene (18.2 ml) and THF (1.8 ml) were added. At -20°C, n-BuLi (3.1 mL) was slowly added dropwise, and the mixture was stirred at room temperature overnight. HfCl (1.21 g) was slowly added dropwise at -20°C, and stirred at 60°C overnight. The solvent was vacuum dried and extracted with hexane and methylene chloride (MC) to obtain the final compound.

¹ H NMR (CDCl ₃ ): 8.04-7.00 (m, 34H), 4.32 (m, 4H), 1.67-0.84 (m, 64H)

Preparation Example 2: Preparation of Ligand Compound and Transition Metal Compound

Step 1: Preparation of ethane-1,2-diylbis(4,1-phenylene))bis(phenylmethanone)

1,2-diphenylethane (5.0 g, 27.4 mmol), AlCl ₃ (8.05 g), and 1,2-dichloroethane (98.0 mL) were placed in a 100 mL Schlenk flask. Benzoyl chloride (2.05 eq, 7.90 g) was slowly added dropwise at room temperature. Stir overnight at 65°C. Then, the final compound was obtained by extraction using ice water, 10% HCl, and distilled water.

¹ H NMR (CDCl ₃ ): 7.80 (m, 18H), 3.73 (s, 4H)

Step 2: Preparation of 1,2-bis(4-(cyclopenta-2,4-dien-1-ylidene(phenyl)methyl)phenyl)ethane

Ethane-1,2-diylbis(4,1-phenylene))bis(phenylmethanone) prepared in step 1 in a 100 mL Schlenk flask (6.36 g, 16.3 mmol), pyrrolidine (4.1 mL) and THF (15.4 mL). Cyclopentadienide (sodium Cp) (2.0 M, 48.8 mL) was slowly added dropwise at room temperature and stirred at room temperature overnight. After extraction using distilled water and diethyl ether, the final compound was obtained through recrystallization of methanol.

¹ H NMR (CDCl ₃ ): 7.39-7.20 (m, 18H), 6.60 (m, 4H), 6.33 (m, 4H), 3.48 (s, 4H)

Step 3: 1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenyl)ethane

1,2-bis(4-(cyclopenta-2,4-dien-1-ylidene(phenyl)methyl)phenyl)ethane (1.38 g, 2.83 mmol) prepared in step 2 above in a 100 mL Schlenk flask , MTBE (13.0 mL) was added. In another 100 mL Schlenk flask, put lithium octahydrooctamethylfluorene (2.0 g) and MTBE (26.0 mL), and 1,2-bis(4-(cyclopenta-2,4-dien-1-yl) at room temperature The contents of the flask containing den(phenyl)methyl)phenyl)ethane were added dropwise. Stir overnight at 50°C. After extraction using distilled water and diethyl ether, the final compound was obtained through recrystallization of methanol.

¹ H NMR (CDCl ₃ ): 7.69-6.30 (m, 34H), 5.41 (m, 4H), 3.78 (m, 4H), 1.64 (m, 16H), 1.28 (m, 48H)

Step 4: 1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2,3,4, Preparation of 7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenyl)ethane-hafnium chloride

1,2-bis(4-(cyclopenta-2,4-dien-1-yl(1,1,4,4,7,7,10,10-octamethyl-2, 3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluoren-12-yl)(phenyl)methyl)phenyl)ethane (2.05 g, 1.63 mmol), toluene (29.6 mL) and THF (3.0 mL) were added. At -20°C, n-BuLi (2.67 mL) was slowly added dropwise, and the mixture was stirred at room temperature overnight. HfCl (1.04 g) was slowly added dropwise at -20°C, and stirred at 60°C overnight. The solvent was vacuum dried and extracted with hexane and methylene chloride to obtain the final compound.

¹ H NMR (CDCl ₃ ): 8.05-7.17 (m, 34H), 3.76 (m, 4H), 1.72-0.85 (m, 64H)

Example Preparation Example 1: Preparation of an olefin-based copolymer

After the 1.5 L continuous process reactor was charged with hexane solvent (7 kg/h) and 1-butene (0.31 kg/h), the temperature at the top of the reactor was preheated to 139.0°C. Modified methylaluminoxane (MMAO) (0.122 mmol/min), the transition metal compound obtained in Preparation Example 1 (0.035 μmol/min), and dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (0.210 μmol/min) ) were simultaneously introduced into the reactor. Then, hydrogen gas (25 cc/min) and ethylene (0.87 kg/h) were introduced into the reactor and maintained at 139.0° C. for at least 30 minutes in a continuous process at a pressure of 89 bar to proceed with a copolymerization reaction to obtain a copolymer. . After drying in a vacuum oven for more than 12 hours, physical properties were measured.

Example Preparation 2

The copolymerization reaction was carried out in the same manner as in Preparation Example 1, and the amount of the transition metal compound, the amount of catalyst and co-catalyst, and the reaction temperature, hydrogen input amount, and the amount of comonomer were changed respectively as shown in Table 1 below to proceed with the copolymerization reaction. A copolymer was obtained.

Comparative Preparation Example 1

DF810 from Mitsui Chemicals was purchased and used.

Comparative Preparation Example 2

DF840 from Mitsui Chemicals was purchased and used.

Catalyst type Catalyst usage
(μmol
/min) cocatalyst
(μmol
/min) MMAO
(mmol
/min) ethylene
(kg/h) hexane
(Kg/h) 1-butene
(kg/h) Hydrogen
(cc/min) reaction temperature
(℃ Example Preparation Example 1 Preparation Example 1 0.035 0.210 0.122 0.87 7.0 0.31 25 139.0 Example Preparation 2 Preparation Example 1 0.029 0.171 0.115 0.87 7.0 0.29 40 138.6

Experimental Example 1: Evaluation of physical properties of olefin-based polymers

The physical properties of the copolymers of Preparation Examples 1 and 2 and Comparative Preparation Examples 1 and 2 were evaluated according to the following method, and are shown in Table 1 below.

The physical properties of the copolymers of Preparation Examples 1 and 2 and Comparative Preparation Examples 1 and 2 were evaluated according to the following method, and are shown in Table 2 below.

1) Density of the polymer

Measured by ASTM D-792.

2) Melt Index (MI) of polymer

It was measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).

3) Melt flow rate ratio (MFRR)

Measure MI10 and MI2.16 according to ASTM D-1238 [Condition E, MI10 (190℃, 10kg load), MI2.16(190℃, 2.16kg load)], then divide MI10 by MI2.16 to melt flow rate The ratio (MFRR) was calculated.

4) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (MWD)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.

- Column: PL Olexis

- Solvent: TCB (Trichlorobenzene)

- Flow rate: 1.0 ml/min

- Sample concentration: 1.0 mg/ml

- Injection volume: 200 μl

- Column temperature: 160℃

- Detector: Agilent High Temperature RI detector

- Standard: Polystyrene (corrected by cubic function)

5) Melting Temperature (Tm), Soluble Fraction, Elution Temperature (Te)

The measuring equipment was PolymerChar's CFC. First, a solution of the copolymer using o-dichlorobenzene as a solvent was completely dissolved in an oven in a CFC analyzer at 130° C. for 60 minutes, poured into a TREF column adjusted to 135° C., cooled to 95° C., and stabilized there for 45 minutes. The temperature of the TREF column was then lowered to -20°C at a rate of 0.5°C/min, and then held at -20°C for 10 minutes. Then, the amount of elution (mass %) was measured using an infrared spectrophotometer. Then, the operation of raising the temperature rise of the TREF column at a rate of 20 °C/mi to a preset temperature and maintaining the temperature at the temperature reached for a preset time (i.e., about 27 minutes) was performed when the temperature of the TREF was 130 °C. Repeat until this, and the amount (mass %) of the fraction eluted during each temperature range was measured.

The content of the ultra-low crystallinity region means the content of the fraction eluted at -20°C or less, and the elution temperature (Te) was measured as the temperature of the highest point of the peak.

The average value of the dissolution temperature (Ta) and the standard deviation value of the dissolution temperature were calculated using a graph of the dissolution amount according to the dissolution temperature.

[Equation 1]

[Equation 2]

The average of the elution temperature (T) ² in Equation 2 is expressed by Equation 3 below.

[Equation 3]

density
(g/mL) MI
(g/10min) MFRR Mw
(g/mol) MWD Tm
(℃) Te
(℃) sci-fi
(%) Ta
(℃) σ practice
Preparation Example 1 0.8839 1.01 6.56 120110 1.92 66.50 40.8
79.0 0.3 37.9 7.7 practice
Preparation 2 0.8849 3.38 6.01 90262 2.04 70.30 37.4
79.0 0.5 34.4 8.7 practice
Preparation 3 0.8871 0.82 6.70 124170 1.96 69.11 38.6 0.1 37.4 6.8 practice
Preparation 4 0.8800 0.26 7.80 153177 2.12 58.70 31.8 0.2 32.0 8.2 practice
Preparation 5 0.8806 0.47 6.57 138594 2.17 60.35 33.1 0.2 32.0 8.3 comparison
Preparation Example 1 0.8840 1.18 6.51 114216 1.90 69.30 39.5 0.8 35.8 9.2 comparison
Preparation 2 0.8869 3.55 6.20 86710 2.02 72.10 38.2 1.3 34.0 10.0

As can be seen in Table 2, the polymers of Preparation Examples 1 and 2 exhibited a smaller elution temperature standard deviation value (σ) than Comparative Preparation Examples 1 and 2, whereby melting in a narrow elution temperature range was It can be confirmed that it is made and has a narrow crystallinity distribution range.

In addition, FIG. 1 shows a graph of the amount of dissolution according to the dissolution temperature of the polymers of Preparation Example 1 and Comparative Preparation Example 1.

Referring to FIG. 1 , it can be seen that the polymer of Preparation Example 1 is melted in a narrower elution temperature range compared to the polymer of Comparative Preparation Example 1.

Example 1: Preparation of olefin-based elastomer foam

50 parts by weight of the ethylene 1-butene copolymer prepared in Example 1, and 50 parts by weight of ethylene vinyl acetate (EVA; 1328, manufactured by Hanwha Chemical), zinc oxide, stearic acid, and titanium oxide, which are conventional additives, were added to 110° C. The substrate was prepared by kneading for about 10 minutes in a closed mixer (kneader).

Then, dicumyl peroxide (DCP; BC-FF, Akzo Nobel Co., Ltd.) as a crosslinking agent on the prepared substrate in a roll mill having a surface temperature of 100° C., triallyl cyanurate (TAC; Farida, Hunan Insing Co.) and azodicarbonimide (ADCA; JTB/TL, Kumyang Co., Ltd.) as a foaming agent were added, kneaded, and then molded into a sheet shape.

The kneaded material was put in an extruder and pulled out in the form of a strand, then put into a pelletizer and prepared in the form of pellets. The prepared pellets were dried and then put into an injection machine and injected at 170° C. for 420 seconds to prepare an injection molded-foam. Table 3 shows the amount of each component used and the physical properties of the prepared foam.

Example 2, Comparative Examples 1 and 2: Preparation of olefin-based elastomer foams

In the same manner as in Example 1, except that the ethylene 1-butene copolymers of Preparation Example 1 and Comparative Examples 1 and 2 were respectively used instead of the ethylene 1-butene copolymer prepared in Example Preparation Example 1. A primary foam was prepared through the method. Table 3 shows the amount of each component used and the physical properties of the prepared foam.

Examples 3 and 4: Preparation of Olefin-Based Elastomer Foam

50 parts by weight of the ethylene 1-butene copolymer prepared in Preparation Example 1, 50 parts by weight of ethylene vinyl acetate (EVA; 1328, manufactured by Hanwha Chemical), a conventional additive in a roll mill having a surface temperature of 100° C. Zinc oxide, stearic acid, and titanium oxide were added, and dicumyl peroxide (DCP; BC-FF, Akzo Nobel) as a crosslinking agent and azodicarbonimide (ADCA; JTB/TL, manufactured by Kumyang) were added as a foaming agent to 100 The substrate was prepared by kneading for about 10 minutes in a closed mixer (kneader) at ℃.

The obtained sheet is placed in a press mold having a size of 10 mm in thickness, 100 mm in length, and 150 mm in width, and ^{heat-compression-molded at 170° C., 150 kg/cm 2} for 10 minutes and then cooled at room temperature to form a primary foam (pre- foam) was prepared.

Table 3 shows the amount of each component used and the physical properties of the prepared foam.

Examples 5 and 6: Preparation of olefinic elastomer foams

A primary foam was formed in the same manner as in Examples 3 and 4, except that the ethylene 1-butene copolymer of Preparation Example 2 was used instead of the ethylene 1-butene copolymer prepared in Preparation Example 1. was prepared. Table 4 shows the amount of each component used and the physical properties of the prepared primary foam.

Comparative Examples 3 and 4: Preparation of olefin-based elastomer foams

A primary foam was formed in the same manner as in Examples 3 and 4, except that the ethylene 1-butene copolymer of Comparative Example 1 was used instead of the ethylene 1-butene copolymer prepared in Preparation Example 1. was prepared. Table 4 shows the amount of each component used and the physical properties of the prepared primary foam.

Comparative Examples 5 and 6: Preparation of olefin-based elastomer foams

A primary foam was formed in the same manner as in Examples 3 and 4, except that the ethylene 1-butene copolymer of Comparative Example 2 was used instead of the ethylene 1-butene copolymer prepared in Preparation Example 1. was prepared. Table 4 shows the amount of each component used and the physical properties of the prepared primary foam.

Experimental Example 2: Evaluation of the physical properties of the foam

1) Hardness (Type C)

Asker C hardness was measured according to ASTM D2240.

2) specific gravity

Measured according to ASTM D792.

3) Tensile strength

Measured according to ASTM D412. Five specimens were used for the same test, and the tensile speed was set to 500 mm/min.

4) Tear strength

Measured according to ASTM D624. Five specimens were used for the same test, and the measurement speed was 100 mm/min.

5) split tear strength

It was measured at a tensile rate of 10 mm/min according to ASTM D3574.

6) compression set

The specimens prepared in the form of a cylinder having a diameter of 30±0.05 mm by making the foams prepared in Examples and Comparative Examples each have a thickness of 10 mm were measured according to ASTM D-3574. Place the test piece between two parallel metal plates, insert a spacer corresponding to 50% of the thickness of the test piece, compress it, and take out the test piece from the water compression device that was heat-treated in an air-circulating oven at 50±0.1°C for 6 hours. After cooling at room temperature for 30 minutes, the thickness was measured. In the same test example, three specimens were used, and the permanent compression set was calculated by the following formula (1).

[Formula 1]

Permanent compression set (%)=[(t ₀ -t _f )/(t ₀ -t _s )]×100

t ₀ is the initial thickness of the specimen, t _f is the thickness of the specimen when cooled after heat treatment, and t _s is the thickness of the spacer.

7) Rebound elasticity

Measured according to ASTM D2632.

8) shrinkage

After heat treatment at a constant temperature of 70° C. for 60 minutes, the difference in length before and after heat treatment was measured.

composition formulation
(parts by weight) Example comparative example One 2 One 2 olefinic
copolymer 50 50 50 50 Ethylene/Vinyl Copolymer 50 50 50 50 crosslinking agent 1.0 1.0 1.0 1.0 Crosslinking aid (phr) 0.2 0..2 0.2 0.2 blowing agent (phr) 5.0 5.0 5.0 5.0 Foaming aid (phr) 5.0 5.0 5.0 5.0 lubricant (phr) 1.0 1.0 1.0 1.0 whitening agent (phr) 4.0 4.0 4.0 4.0 Foam properties Foaming ratio (%) 160.1 160.0 160.3 160.0 Hardness (Type C) 49.2 47.2 47.4 45.0 Specific gravity (g/cc) 0.199 0.194 0.196 0.190 Tensile strength (kgf/cm ² ) 37.0 29.6 37.5 24.8 Tear strength (kgf/cm) 16.5 13.8 16.4 11.8 Bursting tear strength (kgf/cm) 2.57 2.49 2.56 2.38 Permanent compression set (%) 57.9 69.7 63.0 80.4 Rebound elasticity (%) 55.2 54.2 55.2 53.9 Shrinkage (70℃60min %) 0.25 0.30 0.25 0.15

composition formulation
(parts by weight) Example comparative example 4 5 6 7 4 5 6 7 olefinic
copolymer 50 50 50 50 50 50 50 50 Ethylene/Vinyl Copolymer 50 50 50 50 50 50 50 50 Crosslinking agent (phr) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Crosslinking aid (phr) 0.2 0..2 0.2 0.2 0.2 0.2 0.2 0.2 blowing agent (phr) 5.0 7.0 5.0 7.0 5.0 7.0 5.0 7.0 Foaming aid (phr) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 lubricant (phr) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 whitening agent (phr) 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Foam properties Foaming ratio (%) 143 162 157 174 153 162 164 183 Hardness (Type C) 63.0 54.0 54.2 43.4 58.0 51.0 47.0 37.0 Specific gravity (g/cc) 0.2923 0.1982 0.2221 0.1603 0.2442 0.1999 0.1972 0.1354 Tensile strength (kgf/cm ² ) 2.6 2.2 2.2 2.0 2.5 2.5 2.1 1.8 Tear strength (kgf/cm) 15.13 10.68 11.36 8.36 13.64 11.75 9.71 7.61 Bursting tear strength (kgf/cm) 5.27 2.75 3.91 2.26 4.12 2.60 3.10 2.05 Permanent compression set (%) 72.60 69.50 67.01 61.43 70.90 67.79 61.55 60.98 Rebound elasticity (%) 51 54 50 51 53 55 51 53 Shrinkage (70℃, 60min %) 3.52 3.81 5.69 8.13 3.64 4.75 6.78 6.71

As shown in Table 3, the foams prepared using the composition for olefin-based elastomer foams of Examples during injection and foaming have an equivalent level of specific gravity compared to the foams prepared using the composition for olefin-based elastomer foams of Comparative Examples. It can be confirmed that mechanical properties such as improved tear strength and rupture tear strength are exhibited.

In addition, as shown in Table 4, the foams prepared using the composition for olefin-based elastomer foams of Examples even during die cut press were compared to the foams prepared using the composition for olefin-based elastomer foams of Comparative Examples. In comparison, it can be confirmed that mechanical properties such as improved tear strength and rupture tear strength are exhibited.

Claims (16)

(A) an olefin-based polymer satisfying the requirements of (1) to (4) below; and
(B) a composition for an olefin-based elastomer foam comprising a blowing agent:
(1) Melt Index (MI, 190 ℃ 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min,
(2) the density (d) is from 0.880 g/cc to 0.895 g/cc,
(3) When cross-fractionation chromatography (CFC) is measured, the average value (Ta) of the elution temperature is 25℃≤Ta≤50℃, the standard deviation value (σ) of the elution temperature is 6.0≤σ≤9.0,
(4) The soluble fraction (SF, Soluble Fraction) at -20 ℃ measured by cross-fraction chromatography (CFC) is 2% by weight or less.
The method of claim 1,
The (A) olefin-based polymer further satisfies the requirement of (5) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol.
The method of claim 1,
The (A) olefin-based polymer further satisfies the requirement of (6) having a molecular weight distribution (MWD) of 0.1 to 6.0. A composition for an olefin-based elastomer foam.
The method of claim 1,
The (A) olefin-based polymer further satisfies the requirement of (7) a melt flow rate ratio (MFRR) of 3 to 10. A composition for an olefin-based elastomer foam.
The method of claim 1,
The (A) olefin-based polymer further satisfies the requirement of (8) an elution temperature (Te) of 20°C to 90°C.
The method of claim 1,
In the (A) olefin-based polymer, the elution temperature average value (Ta) is represented by the following Equation 1, and the elution temperature standard deviation value (σ) is the olefin-based elastomer foam composition represented by the following Equation 2:
[Equation 1]

[Equation 2]

The average of the elution temperature (T) ² in Equation 2 is expressed by Equation 3 below.
[Equation 3]

The method of claim 1,
The (A) olefin-based polymer is a composition for an olefin-based elastomer foam, which is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms.
8. The method of claim 7,
The alpha-olefin comonomer is 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-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 - A composition for an olefin-based elastomer foam comprising any one or a mixture of two or more selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
The method of claim 1,
The (A) olefin-based polymer is a composition for an olefin-based elastomer foam, which is a copolymer of ethylene and 1-butene.
The method of claim 1,
The (A) olefin-based polymer is an olefin obtained by a manufacturing method comprising the step of polymerizing an olefinic monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below Compositions for elastomeric foams based on:
[Formula 1]

In Formula 1,
R ₁ to R ₁₃ are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; silyl; or silyl having 1 to 3 substituents selected from the group consisting of alkyl having 1 to 12 carbon atoms and alkoxy having 1 to 12 carbon atoms, wherein _{two or more adjacent to each other among R 1} to R ₁₂ are connected to each other to form a ring can,
X and X' are each independently O, S or a linking group,
A is alkylene having 1 to 6 carbon atoms,
Y is C or Si,
M is a group 4 transition metal,
Q is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms.
11. The method of claim 10,
The input amount of the hydrogen gas is 10 to 60 sccm of the composition for an olefin-based elastomer foam.
11. The method of claim 10,
The (A) olefin-based polymer is a composition for an olefin-based elastomer foam prepared by a continuous solution polymerization reaction using a continuous stirred tank reactor (Continuous Stirred Tank Reactor) by introducing hydrogen gas in the presence of the catalyst composition for olefin polymerization.
The method of claim 1,
The composition for an olefin-based elastomer foam further comprises (A1) an ethylene-vinyl acetate copolymer.
The method of claim 1,
The composition for an olefin-based elastomer foam is a composition for an olefin-based elastomer foam comprising (A) an olefin-based polymer and (A1) an ethylene vinyl acetate copolymer in a weight ratio of 10:90 to 90:10.
The method of claim 1,
The composition for an olefin-based elastomer foam further comprises (C) a crosslinking agent and (D) a crosslinking aid.
An olefin-based elastomer foam prepared by using the composition for an olefin-based elastomer foam according to claim 1.

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