JP7014361B2 - Blends for foams, foams produced from them and articles containing them - Google Patents

Description

The present disclosure relates to blends for foams, foams produced from them, and articles containing them.

Polymer foams are often used in a variety of different applications such as insulation, sound insulation, cushioning, filters, vibration and shock damping. Applications using such polymer foams include electronic devices, food packaging materials, clothing materials, building materials, internal and external parts of automobiles and home appliances.
Includes footwear and more.

Among many commercially available foams, polyolefin foams and polyethylene vinyl / acetate foams are often used in footwear where properties such as buffering and flexibility are desired.
Polyolefin foams have lower shrinkage and compression set at high temperatures compared to poly (ethylene / vinyl acetate) foams. This difference is often due to the melting point and degree of curing of the polyolefin foam, among other factors.

Therefore, it is desirable to produce polyolefin foams that exhibit better compression set and shrinkage when compared to poly (ethylene / vinyl acetate) foams, and these foams with better compression set and shrinkage. Products that use poly (ethylene / vinyl acetate) foam will have superior properties compared to products that use poly (ethylene / vinyl acetate) foam.

As used herein, an ionomer comprising an olefin copolymer containing ethylene and an α-olefin or a propylene and an α-olefin and a copolymer of ethylene and a carboxylic acid, wherein the ionomer is neutralized with a metal ion. , A bridging agent and a foaming agent.

In the present specification, a method for producing a foam composition is an ionomer containing an olefin copolymer containing ethylene and α-olefin or propylene and α-olefin, and an ionomer containing a copolymer of ethylene and carboxylic acid. The foam composition is formed by blending ionomer, a cross-linking agent, and a foaming agent, which are neutralized with metal ions, together, and the composition is heated to activate the foaming agent. Disclosed are methods comprising cross-linking the composition.

The melting point / density relationship of the olefin block copolymer is shown. Some micrographs of some of the comparative foams and some of the foams of the present invention are shown. Some micrographs of the comparative foams are shown.

"Composition" and similar terms refer to a polymer that is blended with a mixture of two or more substances, such as other polymers, or contains additives, fillers, and the like. The composition comprises a pre-reaction, reaction and post-reaction mixture, the latter being formed from reaction products and by-products and, if present, one or more components of the pre-reaction or reaction mixture. ,
It contains unreacted components and decomposition products of the reaction mixture.

"Blend", "polymer blend" and similar terms thereof mean the composition of two or more polymers. Such blends may or may not be miscible. Such blends may or may not be phase separated. Such blends include transmitted electron spectroscopy, light scattering, small-angle X-ray scattering,
And may or may not include one or more domain arrangements, as determined from any other method known in the art. The blend is not a laminate, but one or more layers of the laminate may contain the blend.

"Polymer" means a compound prepared by polymerizing a monomer, whether it is the same or a different type of monomer. Therefore, the general term polymer includes the term homopolymer, which is usually used to refer to a polymer prepared from only one type of monomer, and the term interpolymer, as defined below. The term polymer also includes all forms of interpolymers, such as random, block and the like. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" refer to the interpolymers described below. Polymers often refer to those that are "made" of monomers, those that are "based" on a particular monomer or type of monomer, or those that "contain" a particular monomer content, which is the polymerization of a particular monomer. It should be noted that it refers to the relics that have been made and is understood to be clearly not a non-polymerized species.

"Interpolymer" means a polymer prepared by polymerization of at least two different monomers. This general term includes copolymers commonly used to refer to polymers prepared from two or more different monomers, including polymers prepared from three or more different monomers, such as terpolymers, tetrapolymers, and the like. Is done.

The terms "polyolefin", "polyolefin polymer", "polyolefin resin" and their similar terms are simple olefins (also referred to as alkenes with the general formula _{Cn H 2n )} .
Means a polymer produced as a monomer. Polyethylene is produced by polymerizing ethylene with or without one or more comonomer, polypropylene is 1
It is produced by polymerizing propylene containing or not containing more than a species of comonomer. Therefore, the polyolefins include ethylene-α-olefin copolymers,
Includes interpolymers such as propylene-α-olefin copolymers.

As used herein, the "melting point" (also referred to as the melt peak for the shape of the plotted DSC curve) is typically the melting point or peak of the polyolefin, as described in USP 5,783,638. Is measured by DSC (Differential Scanning Calorimetry) technology for measuring. It should be noted that many blends containing two or more polyolefins have two or more melting points or peaks, and many individual polyolefins contain only one melting point or peak.

The term "and / or" includes both "and" and "or". for example,
The terms A and / or B are interpreted to mean A, B or A and B.

The terms "low crystallinity", "high crystallinity" and similar terms are used in a relative sense rather than an absolute sense. However, low crystallinity layers are 1 to 25 relative to the total weight of the layers.
It has a crystallinity of 1 to 20, more preferably 1 to 15 weight percent. A layer with a high degree of crystallinity has a crystallinity of 25% by weight or more based on the total weight of the layer.

High crystalline polymers are often linear low density polyethylene (LLDPE), low density polyethylene (LDPE), LLDPE / LDPE blends, high density polyethylene (HDPE).
), Homopolypropylene (hPP), substantially linear ethylene polymer (SLEP), random propylene-based copolymers, polypropylene (PP) plastomers and elastomers, random copolymers (RCP), and various blends thereof. .. Low crystalline polymers of particular interest are preferably filed on March 17, 2005, claiming priority over US Provisional Application No. 60 / 533,906 filed on March 17, 2004. Published as WO / 2005/090427 on September 29, 2005,
Containing ethylene / α-olefin multiblock interpolymers defined and discussed in PCT Application No. 2005/0917 in co-pending, both are incorporated herein by reference. Low crystalline polymers are also propylene / ethylene, propylene / 1-butene, propylene / 1-hexene, propylene / 4-methyl-1-pentene, propylene / 1-octene, propylene / ethylene / 1-butene, propylene / ethylene. / ENB,
Includes propylene / ethylene / 1-hexene, propylene / ethylene / 1-octene, propylene / styrene, and propylene / ethylene / styrene. Representative examples of these copolymers are VERSIFY® elastic propylene copolymers and Exxon-Mobile manufactured and marketed by The Dow Chemical Company.
VISTAMAXX propylene copolymer manufactured by.

The term "polymer" generally includes, but is not limited to, homopolymers, copolymers such as blocks, grafts, random and alternating copolymers, terpolymers and the like, and blends and modifications thereof. Further, unless otherwise specified, the term "polymer" shall include all possible geometrical configurations of matter. These configurations include, but are not limited to, isotactics, syndiotactics and random symmetries.

Unless otherwise specified, all percentages described herein are weight percent. "Interpolymer" means a polymer prepared by polymerization of at least two different types of monomers. The general term "interpolymer" is the term "copolymer"
Includes (usually used to refer to polymers prepared from two different monomers) and the term "terpolymer" (usually used to refer to polymers prepared from three different types of monomers). do. It also includes polymers produced by polymerizing four or more types of monomers.

As used herein, it can be used to produce foams with bubble size and crosslink density that ensure lower compression set and shrinkage compared to other commercially available foams used in footwear applications. The foam composition is disclosed. The foam composition is a polyolefin elastomer,
Includes ionomers, foaming agents and cross-linking agents.

In an exemplary embodiment, the polyolefin elastomer can include an olefin block copolymer (OBC) and / or an olefin random copolymer. The polyolefin elastomer may be a copolymer containing ethylene and α-olefin, or may be a copolymer containing propylene and α-olefin. The polyolefin elastomer may be uniformly or non-uniformly branched.

Copolymers containing ethylene and α-olefins are also known as ethylene / α-olefin interpolymers. The term "ethylene / α-olefin interpolymer" generally refers to a polymer containing ethylene and an α-olefin having three or more carbon atoms. Preferably, ethylene comprises the majority of the mole fraction of the total polymer, i.e. ethylene constitutes at least 50 mole percent of the total polymer. More preferably, ethylene is at least 60 mol percent, at least 70 mol percent, or at least 80 mole percent.
Mol% is included with a substantial remnant of the entire polymer containing at least one other comonomer, preferably an α-olefin having three or more carbon atoms. For many ethylene / octene copolymers, the preferred composition comprises an ethylene content of greater than 80 mole percent of the total polymer and an octene content of 10-20, preferably 15-20 mole percent of the total polymer. In some embodiments, the ethylene / α-olefin interpolymers do not contain low yields, or small amounts, or those produced as by-products of chemical processes. Ethylene / α-olefin interpolymers can be blended with one or more polymers, but the raw ethylene / α-olefin interpolymers are substantially pure and are often the major reaction product of the polymerization process. Contains ingredients.

Ethylene / α-olefin interpolymers are polymerized forms of ethylene and one or more copolymerizable αs, characterized by multiple blocks or segments of two or more polymerized monomeric units with different chemical or physical properties. -Contains olefin comonomer. That is, the ethylene / α-olefin interpolymer is a block interpolymer, preferably a multi-block interpolymer or a copolymer. The terms "interpolymer" and "copolymer" are used interchangeably herein. In some embodiments, the multi-block copolymer can be represented by the following equation:
(AB) n

n is at least 1, preferably an integer greater than 1, for example 2, 3, 4, 5, 10,
15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or more, where "A" represents a hard block or segment and "B" represents a soft block or soft segment. Preferably, A and B are connected substantially linearly, as opposed to a substantially branched or substantially star-shaped form. In other embodiments, the A and B blocks are randomly distributed along the polymer chain. That is, block copolymers usually do not have the following structures.
AAA-AA-BBB-BB

In yet another embodiment, the block copolymer usually contains a third comonomer containing a different comonomer.
Does not have blocks of the type. In yet another embodiment, each of Block A and Block B has a monomer or comonomer distributed substantially randomly within the block. In other words, neither block A nor block B contains two or more partial segments (or subblocks) of different compositions, such as tip portions, which have a composition substantially different from the rest of the block.

Multiblock polymers usually contain varying amounts of "hard" and "soft" segments. The "hard" segment refers to a block of polymerization units in which ethylene is present in an amount greater than 95 weight percent, preferably more than 98 weight percent, relative to the weight of the polymer. In other words, the comonomer content (monomer content other than ethylene) in the hard segment is less than 5 weight percent, preferably less than 2 weight percent, based on the weight of the polymer. In some embodiments, the hard segment comprises all or substantially all ethylene. On the other hand, in the "soft" segment, the comonomer content (content of monomers other than ethylene) exceeds 5 weight percent, preferably more than 8 weight percent, more than 10 weight percent, or 15 weight percent based on the weight of the polymer. Refers to a block of polymerization units that exceeds. In some embodiments, the comonomer content in the soft segment exceeds 20 weight percent, exceeds 25 weight percent, exceeds 30 weight percent, exceeds 35 weight percent, exceeds 40 weight percent, and exceeds 45 weight percent. , 50 weight percent, or may exceed 60 weight percent.

Soft segments are often 1 weight percent to 99 weight percent of the total weight of the block interpolymer, preferably 5 weight percent to 95 weight percent, 10 weight percent to 90 weight percent, 15 weight percent of the total weight of the block interpolymer. Percent to 85 weight percent, 20 weight percent to 80 weight percent, 25 weight percent to 75 weight percent, 30 weight percent to 70 weight percent, 35 weight percent to 65 weight percent, 40 weight percent to 60 weight percent, or 45.
It can exist in percent to 55 percent by weight. Conversely, hard segments can exist in a similar range. The weight percent of the soft segment and the weight percent of the hard segment can be calculated based on the data obtained from DSC or NMR. Such methods and calculations are described in Colin L. et al. P. Shan, Lonnie H
Filed on March 15, 2006 in the name of azlitt et al., And at the same time Dow Global
"Ethylene / α-Orefin B" transferred to Technologies
U.S. Patent Application No. 11 / 376,8 named "lock Interpolimers"
Disclosed in No. 35, the disclosure of which is incorporated herein by reference in its entirety.

In one embodiment, the ethylene / α-olefin interpolymer used in the embodiment (
(Also also referred to as "interpolymer" or "polymer") is capable of copolymerizing one or more with ethylene, characterized by multiple blocks or segments of two or more polymerized monomeric units with different chemical or physical properties. It contains an α-olefin comonomer in a polymerized form (block interpolymer), preferably a multi-block copolymer. Ethylene / α
-The olefin interpolymer is characterized by one or more of the embodiments described below.

In one aspect, the ethylene / α-olefin interpolymer used in embodiments of the present invention has a M _w / M _n of 1.7-3.5 and at least one melting point T _m (temperature in degrees Celsius) and density d ( Has grams / cubic centimeters). The numerical values of the variables correspond to the following relationships.
T _m > -2002.9 + 4538.5 (d) -2422.2 (d) ² ,
Preferably, T _m ≧ -6288.1 + 13141 (d) -6720.3 (d) ² ,
More preferably, T _m ≧ 858.91-11825.3 (d) +112.8 (d) ² .

Such a melting point / density relationship is shown in FIG. Unlike conventional random copolymers of ethylene / α-olefins, whose melting point decreases as the density decreases, interpolymers (represented by diamonds) have a particular density between 0.87 g / cc and 0.95 g / cc. Shows a melting point that is virtually independent of density. For example, the melting point of such a polymer has a density of 0.875 g.
When it is in the range of / cc to 0.945 g / cc, it is in the range of 110 ° C to 130 ° C. In some embodiments, the melting point of such polymers has a density of 0.875 g / cc to 0.9.
When it is in the range of 45 g / cc, it is in the range of 115 ° C to 125 ° C.

In another aspect, the ethylene / α-olefin interpolymer comprises ethylene and one or more α-olefins in polymerization form, which are the highest differential scanning calorimetry (“DSC”).
Peak temperature minus highest crystallization analysis fractionation (“CRYSTAF”) Characterized by ΔT at temperatures and the heat of fusion ΔH at J / g, defined as the peak temperature, ΔT and ΔH satisfy the following relationship:
If ΔH is up to 130 J / g,
ΔT> −0.1299 (ΔH) +62.81, preferably ΔT ≧ −0.1299 (ΔH) +64.38, and more preferably ΔT ≧ −0.1299 (ΔH) +65.95.

Further, when ΔH exceeds 130 J / g, ΔT becomes 48 ° C. or higher. CRYSTA
The F-peak is determined using at least 5 percent of the cumulative polymer (ie, it is desirable to show at least 5 percent of the cumulative polymer for the peak) and less than 5 percent of the polymer is identifiable CRYST.
When having an AF peak, the temperature of CRYSTAF is 30 ° C., and ΔH is a numerical value of heat of fusion at J / g. More preferably, the highest CRYSTAF peak comprises at least 10 percent of the cumulative polymer.

In yet another embodiment, the ethylene / α-olefin interpolymer is a temperature-raised elution method (Temperature Rising Elution Fractionatio).
Separation using n (“TREF”) has a molecular fraction that elutes at 40 ° C to 130 ° C, which has a higher comonomer content in molars, preferably equivalent elution between the same temperatures. Random ethylene interpolymers that are at least 5 percent higher, more preferably at least 10 percent higher than those of the random ethylene interpolymer fraction of, and equivalent random ethylene interpolymers contain the same comonomer and have a melt index, density within 10% of the value of the block interpolymer. And has a comonomer content in molars (based on the whole polymer).
Preferably, the equivalent interpolymer Mw / Mn is also the block interpolymer Mw /
Within 10 percent of Mn and / or equivalent interpolymers have a total comonomer content within 10 percent by weight of the block interpolymer.

In yet another embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-
300 percent strain measured on compression molded film of olefin interpolymer and 1
If the elastic recovery rate Re by percentage in the cycle is characterized, has a density d in grams / cubic centimeters, and the ethylene / α-olefin interpolymer contains virtually no crosslinked phase, the values for Re and d are: Meet the relationship:
Re> 1481-1629 (d), preferably Re ≧ 1491-1629 (d), more preferably Re ≧ 1501-1629 (d), and even more preferably Re ≧ 1511-1629 (d).

In some embodiments, the ethylene / α-olefin interpolymer is 10 MPa.
Tensile strength exceeding, preferably ≧ 11 MPa, more preferably ≧ 13 MPa
At a tensile strength and / or crosshead separation rate of 11 cm / min, break point elongation of at least 600 percent, at least 700 percent, very preferably at least 800 percent, most preferably at least 900 percent.

In other embodiments, the ethylene / α-olefin interpolymer is (1) 1-50,
Storage modulus ratio G'(25 ° C.) / G'(1), preferably 1 to 20, more preferably 1 to 10.
00 ° C.) and / or (2) reduce 70 ° C. compression set to less than 80 percent, preferably less than 70 percent, especially less than 60 percent, less than 50 percent, or less than 40 percent, to 0 percent compression set. It has a 70 ° C compression permanent strain.

In yet another embodiment, the ethylene / α-olefin interpolymer is 70 percent less than 80 percent, less than 70 percent, less than 60 percent, or less than 50 percent.
It has a ℃ compression permanent strain. Preferably, the 70 ° C. compression set of the interpolymer is 40.
It is less than a percentage, less than 30 percent, less than 20 percent, and can drop to 0 percent.

In some embodiments, the ethylene / α-olefin interpolymer is 85 J / g.
Less than heat of fusion and / or 100 lbs / foot ² (4800 Pa) or less, preferably 50 lbs / ft ² (2400 Pa) or less, especially 5 lbs / ft ² (240 Pa) or less,
And has a low pellet blocking strength of 0 lbs / ft ² (0 Pa).

In other embodiments, the ethylene / α-olefin interpolymer comprises at least 50 percent ethylene in the polymerized form and is less than 80 percent, preferably less than 70 percent or less than 60 percent, most preferably 40 percent to 50 percent. Has a 70 ° C compression set of less than and as low as close to zero percent.

In some embodiments, the multi-block copolymer has a PDI that fits the Schultz-Flory distribution rather than the Poisson distribution. The copolymer is further characterized by having both a polydisperse block distribution and a block size polydisperse distribution, with the most probable distribution of block length. Preferred multi-block copolymers include four or more blocks or segments, including terminal blocks. More preferably, the copolymer comprises at least 5, 10 or 20 blocks or segments, including terminal blocks.

The comonomer content can be measured using any suitable technique and can be measured by nuclear magnetic resonance (“N”.
MR ") Spectroscopy-based technology is preferred. Further, for polymers or blends of polymers with a relatively wide range of TREF curves, it is desirable that the polymers be first fractionated using TREF into fractions, each with an elution temperature range of 10 ° C. or lower. .. That is, each eluted fraction has a recovery temperature window of 10 ° C. or lower. Using this technology,
The block interpolymer has at least one such fraction having a higher molar comonomer content than the corresponding fraction of the equivalent interpolymer.

In another embodiment, the polymers of the invention are olefin interpolymers, preferably containing ethylene and one or more copolymerizable comonomer in a polymerized form, with two or more different chemical or physical properties. It features multiple blocks (eg, at least two blocks) or segments (block-type interpolymers) of the polymerized monomeric units of the, most preferably multi-block copolymers, wherein the block interpolymers are at 40 ° C and 130 ° C. Has a peak (but not just a molecular fraction) that elutes between (but not just a molecular fraction)
However, individual fractions are not collected and / or isolated), and this peak is the full width at half maximum (
Full width at half maximum (FWHM) has a comonomer content estimated by infrared spectroscopy when developed using full width / half maximum (FWHM) area calculations.
M) Preferably at least 5 percent, more preferably at least 10 percent of the value of the comparative random ethylene interpolymer peak at the same elution temperature developed using area calculations.
It is characterized by having a percent higher average comonomer molar content, wherein the comparative random ethylene interpolymer has the same comonomer and has a melt index, density, within 10 percent of the value of the block interpolymer. And has a comonomer molar content (value relative to the entire polymer). Preferably, the Mw / Mn of the comparative interpolymer is also within 10 percent of the Mw / Mn of the blocked interpolymer, and / or the comparative interpolymer is based on the total comonomer content of the blocked interpolymer. It has a total comonomer content within 10 weight percent. The full width at half maximum (FWHM) calculation is based on the methyl to methylene response area ratio [CH ₃ / CH ₂ ] obtained from the ATREF infrared detector, where the highest (highest) peak is identified from the baseline. , The FWHM area is determined. When measuring the distribution using the ATREF peak, the FWHM area is defined as the area under the curve between T ₁ and T ₂ , where T
₁ and T ₂ are determined to the left and right of the ATREF peak by dividing the peak height by 2 and then drawing a line that intersects the left and right parts of the ATREF curve horizontally with respect to the baseline. be. The calibration curve for the comonomer content uses a random ethylene / α-olefin copolymer, and the comonomer content obtained from NMR is the FWH of the TREF peak.
Created by plotting against the M area ratio. In the case of this infrared method, a calibration curve is generated for the same comonomer type as the object of interest. The comonomer content of the TREF peak of the polymer is the FWHM methyl: methylene area ratio of the TREF peak [CH ₃ / CH.
₂ ] can be used to determine by referring to this calibration curve.

The comonomer content can be measured using any suitable technique and can be measured by nuclear magnetic resonance (NM).
R) A technique based on spectroscopy is preferred. When using this technique, the block interpolymer has a higher comonomer molar content than the corresponding comparative interpolymer.

Preferably, in the case of an interpolymer of ethylene and 1-octene, the block interpolymer is in an amount of (−0.2013) T + 20.07 or greater, more preferably (−0.20).
13) It has a comonomer content of the TREF fraction elution between 40 and 130 ° C., which is an amount of T + 21.07 or more, and T is a numerical value of the peak elution temperature of the TREF fraction being compared.
It is a value measured at a temperature of degrees Celsius.

In addition to the above embodiments and properties described herein, polymers can be characterized by one or more additional properties. In one aspect, the polymer is an olefin interpolymer, preferably containing ethylene and one or more copolymerizable comonomer in a polymerized form, with two or more polymerized monomers having different chemical or physical properties. It features multiple blocks or segments (block-type interpolymers) of the unit, most preferably multi-block copolymers, said block interpolymer having a molecular fraction that elutes between 40 ° C and 130 ° C. When fractionated using the TREF increment, the fraction is higher, preferably at least 5% higher, more preferably at least, higher than the comonomer molar content of the comparative random ethylene interpolymer fraction that elutes at the same temperature. About 10,
It is characterized by having a comonomer molar content that is 15, 20 or 25 percent higher, wherein the comparative random ethylene interpolymer has the same comonomer as the block type interpolymer, preferably the same comonomer and block. It has a melt index, density, and comonomer molar content (value relative to the entire polymer) that is within 10 percent of the value of the type interpolymer. Preferably, the Mw / Mn of the comparative interpolymer is also within 10 percent of the Mw / Mn of the blocked interpolymer, and / or the comparative interpolymer is the total comonomer content of the blocked interpolymer. Has a total comonomer content within 10 weight percent from.

Preferably, the interpolymer of ethylene and at least one α-olefin,
Block-type interpolymers are ( ^-0.1356 ) T + 13. An amount of 89 or more, more preferably (-
0.1356) T + 14.93 or higher, most preferably (-0.2013) T + 21.
It has a comonomer content of the TREF fraction elution between 40 ° C and 130 ° C, which is an amount of 07 or more, where T is the value of the peak ATREF elution temperature of the TREF fraction being compared and is the temperature in degrees Celsius. It is a value measured in.

Preferably, the interpolymer of ethylene and at least one α-olefin,
Especially in the case of an interpolymer having a total polymer density of 0.855 to 0.935 g / cm ³ , more particularly in the case of a polymer having more than 1 mol percent of comonomer, the block type interpolymer is (-0.203) T + 20. An amount of 07 or more, more preferably (-
0.2013) TR that elutes between 40 ° C and 130 ° C, which is an amount of T + 21.07 or higher.
It has a comonomer content in the EF fraction, where T is the value of the peak elution temperature of the TREF fraction being compared and measured at temperature.

In yet another embodiment, the polymer is an olefin interpolymer, preferably containing ethylene and one or more copolymerizable comonomer in a polymerized form, with two or more different chemical or physical properties. It features multiple blocks or segments (block-type interpolymers) of polymerized monomeric units, most preferably multi-block copolymers, said block interpolymers at 40 ° C. when fractionated using TREF increments. It is characterized by having a molecular fraction eluted between and 130 ° C., and any fraction having a copolymer content of at least about 6 mol% has a melting point higher than about 100 ° C. For fractions with a comonomer content of about 3 mol percent to about 6 mol percent, each fraction has a DSC melting point of about 110 ° C. or higher. More preferably, the polymer fraction having at least 1 mol percent comonomer is of the formula:
Tm ≧ (-5,926) (molar percent of comonomer in its fraction) + 135.90
Has a DSC melting point corresponding to.

In yet another embodiment, the polymer is an olefin interpolymer, preferably containing ethylene and one or more copolymerizable comonomer in a polymerized form, with two or more having different chemical or physical properties. It is characterized by a plurality of blocks or segments (block-type interpolymers) of the above-mentioned polymerized monomer units, and is most preferably a multi-block copolymer. The block interpolymer has a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF increments and has an AT of about 76 ° C or higher.
All fractions with REF elution temperature have the formula:
Heat of fusion (J / gm) ≤ (3.1718) (ATREF elution temperature (Celsius)) -136.5
8
It is characterized by having a melting enthalpy (heat of fusion) as measured by DSC, which corresponds to.
Block interpolymers having a molecular fraction that elutes between 40 ° C and 130 ° C when fractionated using TREF increments are all fractions that have an ATREF elution temperature of 40 ° C to less than about 76 ° C. formula:
Heat of fusion (J / gm) ≤ (1.1312) (ATREF elution temperature (Celsius)) + 22.97
It is characterized by having a melting enthalpy (heat of fusion) as measured by DSC, which corresponds to.

The comonomer composition of the TREF peak is polymer Char, Valencia, et al.
Measurements can be made using an IR4 infrared detector available from Spain (http://www.polymerchar.com/).

The "composition mode" of the detector is 2800-300.
Measurement sensor (measurement) which is a fixed narrow band infrared filter in the 0 cm ^-1 region.
sensor (CH ₂ ) and composition sensor
Equipped with (CH ₃ ). The measurement sensor detects methylene (CH ₂ ) carbon on the polymer, which is directly related to the concentration of the polymer in solution, while the composition sensor detects the methyl (CH ₃ ) group of the polymer. The numerical ratio of the composition signal (CH ₃ ) divided by the measurement signal (CH ₂ ) is sensitive to the comonomer content of the polymer under test in the solution and the response is calibrated using known ethylene α-olefin copolymer standards. Will be done.

When used with ATREF equipment, this detector provides both a concentration (CH ₂ ) signal response and a composition (CH ₃ ) signal response of the polymer to be eluted during the TREF process. Polymer-specific calibration can be performed by measuring the area ratio of CH ₃ to CH ₂ for polymers with a known comonomer content (preferably measured by NMR). The comonomer content of the ATREF peak of a polymer is the calibration of the area ratio references for the individual CH ₃ and CH ₂ responses (ie, the area ratio to the comonomer content CH ₃ / CH ₂ ).
) Can be applied.

The area of the peak can be calculated using the full width at half maximum (FWHM) calculation after applying the appropriate baseline and integrating the individual signal responses from the TREF chromatogram.
This half-value full width calculation is based on the response area ratio of methyl to methylene from the ATREF infrared detector [C.
Based _{on H3 / CH 2 ]} , the FWHM area is determined here after identifying the highest (highest) peak from the baseline. For the distribution measured using the ATREF peak, the FWHM area is defined as the area under the curve between T1 and T2, where T1 and T2 are the peak height divided by 2 and then the left portion of the ATREF curve and It is a point determined on the left and right sides of the ATREF peak by drawing a line intersecting the right part horizontally with respect to the baseline.

In this ATREF-infrared method, the application of infrared spectroscopy for measuring the comonomer content of a polymer is in principle similar to the GPC / FTIR system described in the following references: Markovich, Ronald P. et al. , Hazlitt, Lonnie G
.. , Smith, Linley, "Development of gel-perme"
ation chromatography-Fourier transformform i
nfrared spectroscopy for characterizatio
no ethylene-based polyolefin
s. , Polymeric Materials Science and Engi
Neering (1991), 65, 98-100, and Deslauriers, P. et al.
J. , Rohlfing, D.I. C. , Shieh, E.I. T. , "Quantifying
short chain branching microstructures i
n ethylene-1-olefin copolymers sing siz
e-exclusion chromatography and Fourier t
transform infrared spectroscopy (SEC-FTIR)
, Polymer (2002), 43, 59-170, all of which are incorporated herein by reference in their entirety.

In other embodiments, the ethylene / α-olefin interpolymers of the invention are characterized by an average block index ABI greater than zero and up to 1.0 and a molecular weight distribution M _w / M _n greater than 1.3. The average block index ABI is the weight average of the block index (“BI”) for each of the polymer fractions obtained by preparative TREF from 20 ° C to 110 ° C in 5 ° C increments:

In the formula, BI _i is a block index for the i-th fraction of the ethylene / α-olefin interpolymer obtained by preparative TREF, and wi is the weight percentage of the _i -th fraction.

For each polymer fraction, BI is defined by one of the following two equations, both of which give the same BI value:

In the formula, TX is the preparative ATREF elution temperature (preferably a value expressed in Kelvin) for the i-th fraction, and _PX is the ethylene molar fraction for the i _- th fraction, as described above. As such, it can be measured by NMR or IR. _PAB is the ethylene molar fraction of the entire ethylene / α-olefin interpolymer (before fractionation), which can also be measured by NMR or IR. _TA and _PA are pure "hard segments" (
This refers to the crystallinity segment of the interpolymer) with the ATREF elution temperature and ethylene molar fraction. If the actual value is not available for the "hard segment"
As a first _- order approximation, the _TA and PA values are set to the values of the high density polyethylene homopolymer. In the calculation performed in this case, _TA is 372 ° K and _PA is 1.

TAB is the _ATREF temperature of a random copolymer having the same composition but having an ethylene molar fraction of _PAB . _TAB can be calculated from the following formula:

In the formula, α and β are two constants, which can be determined by calibration with several known random ethylene copolymers. It should be noted that α and β can vary from device to device. Furthermore, it is necessary to use the polymer composition of interest and to prepare each calibration curve in a molecular weight range similar to those fractions. There is a slight molecular weight effect. If the calibration curve is obtained from a similar molecular weight range, such effects could be essentially negligible. In one embodiment, the random ethylene copolymer satisfies the following relationship:

_TXO is a random copolymer A with the same composition and an ethylene molar fraction of _PX .
TREF temperature. _TXO can be calculated from LnP _X = α / T _XO + β.
Conversely, P _XO is the ethylene molar fraction of a random copolymer having the same composition and an ATREF temperature of TX, which can be calculated from _{LnP XO} = α / _TX + β.

Once the block index (BI) for each preparative TREF fraction is obtained, the weight average block index ABI for the entire polymer can be calculated. In some embodiments, the ABI is greater than zero but less than 0.3, or 0.1-0.3. In another embodiment, the ABI is greater than 0.3 and up to 1.0. Preferably,
The ABI should be in the range 0.4-0.7, 0.5-0.7, or 0.6-0.9. In certain embodiments, the ABI is 0.3-0.9, 0.3-0.8, or 0.3-.
It is in the range of 0.7, 0.3 to 0.6, 0.3 to 0.5, or 0.3 to 0.4. In another embodiment, the ABI is 0.4-1.0, 0.5-1.0, or 0.6-1.0, or 0.7-1.0, 0.8-1.0. , Or in the range of 0.9 to 1.0.

Another feature of the ethylene / α-olefin interpolymer is that the ethylene / α-olefin interpolymer contains at least one polymer fraction that can be obtained by preparative TREF, the fraction of which is greater than 0.1 and It has a block index of up to 1.0 and a molecular weight distribution of M _W / M _n greater than 1.3. In certain embodiments, the polymer fraction is greater than 0.6 and up to 1.0, greater than 0.7 and up to 1.0, greater than 0.8 and up to 1.0, or greater than 0.9. And it has a block index up to 1.0. In another embodiment, the polymer fraction is greater than 0.1 and up to 1.0, greater than 0.2 and up to 1.0, greater than 0.3 and up to 1.0, 0.
It has a block index greater than 4 and up to 1.0, or greater than 0.4 and up to 1.0. In yet another embodiment, the polymer fraction is greater than 0.1 and up to 0.5, greater than 0.2 and up to 0.5, greater than 0.3 and up to 0.5, or 0.4. It is larger and has a block index of up to 0.5. In yet another embodiment, the polymer fraction is greater than 0.2 and up to 0.9, greater than 0.3 and up to 0.8, greater than 0.4 and up to 0.7, and about 0. It has a block index greater than 5 and up to 0.6.

In the case of a copolymer of ethylene and α-olefin, the polymer of the present invention is preferably (
1) At least 1.3, more preferably at least 1.5, at least 1.7, or at least 2.0, most preferably at least 2.6, and up to a maximum value of 5.0, more preferably a maximum value of 3.5. PDI up to a maximum of 2.7; (2) heat of fusion of 80 J / g or less; (3) at least 50 weight percent ethylene content; (4) less than -25 ° C, more preferably less than -30 ° C. It has a glass transition temperature T _g and / or (5) only T _m .

Further, the polymer has a storage modulus G'alone or any other property disclosed herein such that the log (G') is 400 kPa or more, preferably 1.0 MPa or more at a temperature of 100 ° C. Can have in combination with. In addition, this polymer is 0-100
It has a relatively flat storage modulus in the ° C range as a function of temperature, which is characteristic of block copolymers and is characteristic of block copolymers, especially ethylene and one or more C _3-8 aliphatic α-olefins. Nothing is known about the copolymer with. In this context, the term "relatively flat" means that the decrease in logG'(unit: Pascal) is less than an order of magnitude between 50 ° C and 100 ° C, preferably between 0 ° C and 100 ° C. Means.

The interpolymer can be further characterized by a thermomechanical analysis needle insertion depth of 1 mm at a temperature of at least 90 ° C. and a flexural modulus of 3 kpsi (20 MPa) to 13 kpsi (90 MPa). Alternatively, the interpolymer can have a thermomechanical analysis needle insertion depth of 1 mm at a temperature of at least 104 ° C. and a flexural modulus of at least 3 kpsi (20 MPa). They can be characterized as having a wear resistance (or volume reduction) of less than 90 mm ³ . Polymers have a significantly better flexibility-heat resistance balance than other polymers.

Further, the ethylene / α-olefin interpolymer is 0.01 to 2000 g / 10.
Minutes, preferably 0.01-1000 g / 10 minutes, more preferably 0.01-500 g / 1
It can have a melt index I ₂ for 0 minutes, especially 0.01-100 g / 10 minutes. In certain embodiments, the ethylene / α-olefin interpolymer is 0.01-10.
g / 10 minutes, 0.5-50 g / 10 minutes, 1-30 g / 10 minutes, 1-6 g / 10 minutes or 0
.. It can have a melt index I ₂ of 3-10 g / 10 min. In certain embodiments, the melt index of the ethylene / α-olefin polymer is 1 g / 10 min, 3 g.
/ 10 minutes or 5 g / 10 minutes.

The polymer is 1,000 g / mol to 5,000,000 g / mol, preferably 1000.
g / mol to 1,000,000, more preferably 10,000 g / mol to 500,000 g
It can have a molecular weight Mw of / mol, particularly 10,000 g / mol 300,000 g / mol. The polymer density can be 0.80 to 0.99 g / cm ³ , preferably 0.85 g / cm ³ to 0.97 g / cm ³ for ethylene-containing polymers. In certain embodiments, the density of the ethylene / α-olefin polymer ranges from 0.860 to 0.925 g / cm ³ or 0.867 to 0.910 g / cm ³ .

Methods of making the polymer are disclosed in the following patent application: US Provisional Patent Application No. 60 / 533,906 filed March 17, 2004; US filed March 17, 2005. Provisional Patent Application No. 60 / 662,937; US Provisional Patent Application No. 60 / 662,939 filed on March 17, 2005; US Provisional Application No. 60/562938 filed on March 17, 2005. No .; PCT Application No. 2005/0 filed on March 17, 2005
08916; PCT Application No. 2005/008915 filed on March 17, 2005
No.; and PCT Application No. 2005/0917, filed March 17, 2005, both of which are incorporated herein by reference in their entirety.

Interpolymers also exhibit a unique crystallinity and bifurcation distribution relationship. That is, the interpolymer is CRYSTAF as a function of heat of fusion, especially when compared at the same overall density as a random copolymer containing the same monomer and the same monomer level or a physical blend of polymers such as a blend of high density and low density copolymers. And there is a relatively large difference between the highest peak temperatures measured using DSC. This unique feature of the interpolymer is believed to be due to the unique distribution of comonomer in the blocks within the polymer backbone. In particular, the interpolymer may alternately contain blocks with different comonomer contents (including homopolymer blocks). The interpolymer may also include a distribution in which the distribution of the number and / or block size of polymer blocks with different densities or comonomer contents is a Schultz-Flory type distribution. In addition, the interpolymer also has a unique peak melting point and crystallization temperature profile that is substantially independent of polymer density, modulus and morphology. In a preferred embodiment, the microcrystalline order of the polymer is 1.
Even PDI values of less than 7, even less than 1.5, and below 1.3 show characteristic spherulites and lamellae that can be distinguished from random or block copolymers.

In addition, interpolymers can be prepared using techniques for influencing the degree or level of blockiness. That is, the amount and length of comonomer of each polymer block or segment can be varied by controlling the ratio and type of catalyst and shutling agent, as well as the polymerization temperature and other polymerization variables. The surprising benefit of this phenomenon is the discovery that as the degree of blocking is increased, the optical properties, tear strength and high temperature recovery properties of the resulting polymer improve. In particular, as the average number of blocks in the polymer increases, fogging decreases, while transparency, tear strength and high temperature recovery properties increase. Desirable chain transfer ability (high rate of shuttling and low level of chain stop)
By selecting a combination of a shuttling agent and a catalyst having the above, other forms of polymer termination are effectively suppressed. Therefore, in the polymerization of the ethylene / α-olefin comonomer mixture according to the embodiment of the present invention, β-hydride elimination, if any, is hardly observed, and the resulting crystalline block is highly or substantially. Top completely linear, with little or no long chain branching.

Polymers with high crystalline chain ends can be selectively prepared according to embodiments of the present invention. In elastomer applications, reducing the relative amount of polymer ending in an amorphous block reduces the intramolecular dilution effect on the crystalline region. This result can be obtained by selecting a chain shuttling agent and catalyst that have an appropriate response to hydrogen or other chain terminators. Specifically, the catalyst that produces the highly crystalline polymer is (
More susceptible to chain termination reactions (eg, due to the use of hydrogen) than catalysts that cause the formation of low crystallinity polymer segments (eg, due to high comonomer incorporation, regio-error, or atactic polymer formation). If so, the highly crystalline polymer segment will preferentially occupy the terminal portion of the polymer. Not only are the resulting terminal groups crystalline, but the catalytic sites that form the highly crystalline polymer upon termination can be re-used to restart polymer formation. Therefore, the first polymer formed is another highly crystalline polymer segment. Therefore, both ends of the resulting multi-block copolymer are preferentially highly crystalline.

The ethylene α-olefin interpolymer used in some embodiments is preferably an interpolymer of ethylene and at least one C ₃ -C ₂₀ α-olefin. Copolymers of ethylene with C ₃ -C ₂₀ α-olefins are particularly preferred. The interpolymer may further contain _C4 - _C18 diolefin and / or alkenylbenzene. Suitable unsaturated comonomer useful for polymerization with ethylene includes, for example, ethylenically unsaturated monomers, conjugated or unconjugated diene, polyene, alkenylbenzene and the like. Examples of such comonomer are propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-.
Includes C ₃ -C ₂₀ α-olefins such as nonene and 1-decene. 1-Butene and 1-
Octene is particularly preferred. Other suitable monomers include styrene, halo-substituted or alkyl-substituted styrene, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadien and naphthene (eg, cyclopentene, cyclohexene and cyclooctene).

Ethylene / α-olefin interpolymers are preferred polymers, but other ethylene / olefin polymers can also be used. As used herein, olefin refers to a family of unsaturated hydrocarbon compounds with at least one carbon-carbon double bond. Depending on the choice of catalyst, any olefin can be used in embodiments of the present invention. Preferably, suitable olefins are C ₃ - _C20 aliphatic and aromatic compounds containing vinyl unsaturated, as well as cyclic compounds such as, for example, cyclobutene, cyclopentene, dicyclopentadiene, and, but not limited to, the 5-position and Norbornene, including norbornene substituted with a C1 _- C ₂₀ hydrocarbyl or cyclohydrocarbyl group at the 6-position. Also included are mixtures of such olefins and mixtures of such olefins with _C4 - _C40 diolefin compounds.

Examples of olefin monomers include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-dodecene, 1-tetradecene, 1-hexadecene. , 1-Octene, 1-Eikocene, 3-Methyl-1-butene, 3-Methyl-1-pentene, 4-Methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene, vinylcyclohexane , Norbornadiene, _{Echilidennorbornen} , Cyclopentene, Cyclohexene, Dicyclopentadiene, Cyclooctene, including but not limited to _C4 -C40 diene, 1
, 3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadien, 1,9-decadien, other _C4 -C ₄₀ α-olefins and the like. In certain embodiments, the α-olefins are propylene, 1-butene, 1-
Pentene, 1-hexene, 1-octene or a combination thereof. Any hydrocarbon containing a vinyl group can potentially be used in embodiments of the invention, but the availability of monomers, the cost, and the potential for convenient removal of unreacted monomers from the resulting polymer. Practical problems such as, can become more problematic if the molecular weight of the monomer is too high.

The polymerization process described herein is well suited for the production of olefin polymers containing monovinylidene aromatic monomers including styrene, o-methylstyrene, p-methylstyrene, t-butylstyrene and the like. In particular, interpolymers containing ethylene and styrene
It can be prepared according to the teachings of the present specification. In some cases, ethylene, styrene, and
Copolymers containing C3 _- C ₂₀ alpha olefins can be prepared, optionally comprising a C ₄ -C ₂₀ diene with improved properties.

Suitable non-conjugated diene monomers can be straight chain, branched or cyclic hydrocarbon dienes with 6-15 carbon atoms. Examples of suitable non-conjugated diene are, but are not limited to, straight chain acyclic diene such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadien, branched chain. Acyclic dienes such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadien; 3,7-dimethyl-1,7-octadene and dihydromylicene and dihydroosinene. Mixed isomers of (dihydroosine), monocyclic alicyclic diene such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,
5-Cyclododecadiene, as well as polycyclic alicyclic fused diene and crosslinked ring diene such as tetrahydroinden, methyltetrahydroinden, dicyclopentadiene, bicyclo-(
2,2,1) -Hepta-2,5-diene; alkenylnorbornene, alkylidene norbornene, cycloalkenylnorbornene and cycloalkylidenenorbornene, eg 5
-Methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, Examples include 5-vinyl-2-norbornene and norbornadiene. Of the diene typically used in the preparation of EPDM, the most preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-Methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD). Particularly preferred diene are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
).

One desirable polymer that can be made according to embodiments of the invention is an elastic interpolymer of ethylene, _{C3 to C 20 α} -olefins, in particular propylene, and optionally one or more diene monomers. Preferred α-olefins used in this embodiment of the present invention are represented by the formula: CH ₂ = CHR ^* , where R ^* has 1 carbon atom.
~ 12 linear or branched alkyl groups. Examples of suitable α-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. A particularly preferred α-olefin is propylene. Propylene-based polymers are commonly referred to in the art as EP polymers or EPDM polymers. Such polymers, especially Multiblock E
Suitable diene used in the preparation of PDM-type polymers include conjugated or non-conjugated, linear or branched, cyclic or polycyclic diene containing 4 to 20 carbons.
Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene-2-norbornene.

Since the present diene-containing polymer contains alternating segments or blocks containing high or low amounts of diene (including those not contained) and high or low amounts of α-olefins (including those not contained), subsequent polymers. The total amount of diene and α-olefin can be reduced without losing properties. That is, the diene and α-olefin monomers are preferentially incorporated into certain types of blocks of the polymer rather than being uniformly or randomly incorporated throughout the polymer, so that they are utilized more efficiently and subsequently. Therefore, the crosslink density of the polymer can be better controlled. Such crosslinkable elastomers and cured products have advantageous properties including higher tensile strength and better elastic recovery.

In some embodiments, interpolymers made with two catalysts incorporating different amounts of comonomer have blocks formed by them in a weight ratio of 95: 5-5: 95. The elastic polymer is preferably from 20 to 20 based on the total weight of the polymer.
90% ethylene content, 0.1-10% diene content, and 10-80%
It has a percent α-olefin content. More preferably, the multi-block elastic polymer has an ethylene content of 60-90 percent based on the total weight of the polymer, 0.1.
It has a diene content of ~ 10 percent and an α-olefin content of 10-40 percent. Preferred polymers are 10,000 to 2,500,000, preferably 20,000.
Weight average molecular weight of ~ 500,000, more preferably 20,000 ~ 350,000 (M)
w), a high molecular weight polymer having a polydispersity of less than 3.5, more preferably less than 3.0, and a Mooney viscosity of 1-250 (ML (1 + 4) 125 ° C.). More preferably, such polymers have an ethylene content of 65 to 75 percent, a diene content of 0 to 6 percent, and an α-olefin content of 20 to 35 percent.

Ethylene / α-olefin interpolymers can be functionalized by incorporating at least one functional group into the polymer structure. Exemplary functional groups include, for example, ethylene-based unsaturated monofunctional and bifunctional carboxylic acids, ethylene-based unsaturated monofunctional and bifunctional carboxylic acid anhydrides, salts thereof and esters thereof. Such functional groups can be grafted onto an ethylene / α-olefin interpolymer or copolymerized with ethylene and an optional additional comonomer to form an interpolymer of ethylene, a functional comonomer, and any other comonomer. Can be made to. Means for grafting functional groups to polyethylene are, for example, US Pat. Nos. 4,762,890, No. 4,
927,888 and 4,950,541, the disclosures of these patents are incorporated herein by reference in their entirety. One of the particularly useful functional groups is malic acid anhydrous.

The amount of functional groups present in the functional interpolymer can be varied. Functional groups can typically be present in the copolymerized functionalized interpolymer in an amount of at least 1.0 weight percent, preferably at least 5 weight percent, more preferably at least 7 weight percent. The functional groups are typically present in the copolymerized functionalized interpolymer in an amount of less than 40 weight percent, preferably less than 30 weight percent, more preferably less than 25 weight percent.

Exemplary olefin block copolymers include ethylene and octene. Commercially available olefin block copolymers that can be used in foams are Dow Chemical's INF.
It is USE (trademark).

Another exemplary ethylene as an elastomer is a uniformly branched ethylene-α-olefin copolymer. These copolymers can be made with single site catalysts such as metallocene catalysts or constrained geometric catalysts, typically below 105 ° C, specifically below 90 ° C, more specifically below 85 ° C, and even more. More specifically, it has a melting point of less than 80 ° C. and even more specifically, less than 75 ° C. The melting point is measured, for example, by the differential scanning calorimetry (DSC) described in USP 5,783,638. As α-olefin, C _3
-20 linear, branched or cyclic α-olefins are preferred. C _3-20 α-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-.
Examples thereof include octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. α-olefins also contain cyclic structures such as cyclohexane or cyclopentane and can yield α-olefins such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinylcyclohexane.

Examples of exemplary uniformly branched ethylene-α-olefin copolymers are ethylene / propylene, ethylene / butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene /
Includes styrene and the like. Exemplary terpolymers are ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene, and ethylene /
Contains butene / styrene. The copolymer may be a random copolymer or a block copolymer.

An example of a commercially available uniformly branched ethylene-α-olefin interpolymer is a uniformly branched linear ethylene-α-olefin copolymer (eg, Mitsui P).
TAFMER ™ by tetrachemicals Company Limited and EXACT ™ by Exxon Chemical Company, and uniformly branched substantially linear ethylene-α-olefin polymers (eg, Dow Ch).
AFFINITY ™ and ENGAG available from the economic Company
E (trademark) polyethylene) is included.

Copolymers containing propylene and α-olefins are also known as ethylene / α-olefin interpolymers. As mentioned above, the polyolefin elastomer can also include random or blocked propylene polymers (ie, polypropylene). Polypropylene elastomers typically contain 90 mol percent or more of propylene-derived units. The remaining units in the propylene copolymer are derived from at least one α-olefin unit.

The α-olefin component of the propylene copolymer is preferably ethylene (considered as an α-olefin for the purposes of the present invention) or C _4-20 linear, branched or cyclic α-olefins. Examples of C _4-20 α-olefins are 1-butene and 4-methyl-1-.
Examples thereof include pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. α-olefins also contain cyclic structures such as cyclohexane or cyclopentane and can result in α-olefins such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinylcyclohexane. Although not α-olefins in the classical sense, certain cyclic olefins such as norbornene and related olefins, especially 5-ethylidene-2-norbornene, are α-.
It is an olefin and can be used in place of some or all of the α-olefins described above. Similarly, styrene and related olefins (eg, α-methylstyrene, etc.)
Is an α-olefin for the purposes of the present invention. Exemplary random propylene copolymers include, but are not limited to, propylene / ethylene, propylene / 1-butene, propylene / 1-hexene, propylene / 1-octene, and the like. An exemplary terpolymer is
Includes ethylene / propylene / 1-octene, ethylene / propylene / 1-butene, and ethylene / propylene / diene monomer (EPDM).

In one embodiment, the random polypropylene copolymer has a _Tm and / / above 120 ° C.
Alternatively, it has a heat of fusion greater than 70 J / g (both measured by DSC) and is preferably, but not necessarily, produced by a Ziegler-Natta catalyst.

In another embodiment, the polyolefin elastomer is a propylene / α-olefin interpolymer and is characterized by having a substantially isotactic propylene sequence. Propylene / α-olefin interpolymers include propylene-based elastomers (PBEs). The "substantially isotactic propylene sequence" has a sequence of ¹³ C.
Isotactic triads (mm) greater than 0.85, greater than 0.90 for alternatives, greater than 0.92 for alternatives, greater than 0.93 for alternatives, measured by NMR. Have. Isotactic triads are well known in the art and are described, for example, in USP 5,504,172 and WO 00/01745, which is a triad in a copolymer molecular chain determined by a ¹³ C NMR spectrum. Refers to an isotactic sequence for a unit.

Propylene / α-olefin copolymers include units derived from propylene and polymer units derived from one or more α-olefin comonomer. Propene-α-
Exemplary comonomeres used to make olefin copolymers are C ₂ and C ₄
~ C ₁₀ α-olefins, such as C ₂ , C ₄ , C ₆ and C ₈ α-olefins.

The propylene / α-olefin interpolymer contains 1 to 40 weight percent of one or more α-olefin comonomer. All individual values and subranges of 1-40 weight percent are included herein and disclosed herein. Propylene / α-olefin interpolymers were measured according to ASTM D-1238 (230 ° C / 2.16 kg).
It can have a melt flow rate in the range of 0.1-500 grams (g / 10 min) per 10 minutes. Propylene / α-olefin interpolymers crystallize in the range of at least 1 weight percent (at least 2 joules / gram (J / g) heat of fusion (H _f )) to 30 weight percent (less than 50 J / g H _f ). Have a degree. Propylene / α-olefin interpolymers typically have a density of less than 0.895 g / cm ³ . Propylene / α-olefin interpolymers have a melting temperature ( _Tm ) of less than 120 ° C. and 70, as measured by differential scanning calorimetry (DSC), described in USP7,199,203.
It has a heat of fusion (H _f ) of less than joules / gram (J / g). Propylene / α-olefin interpolymers are defined as having a weight average molecular weight of 3.5 or less, 3.0 or less, or 1.8 to 3.0 divided by a number average molecular weight (Mw / Mn). Molecular weight distribution (M
WD).

Such propylene / α-olefin interpolymers are USP6,960,63.
5 and 6,525,157 are further described, the entire contents of which are incorporated herein by reference. Such a propylene / α-olefin interpolymer is described in The D.
From ow Chemical Company under the trade name of VERSIFY ™, or from Exxon Mobile Chemical Company to VISTAMAXX (
It is commercially available under the trade name of).

The elastomer (ie, ethylene / α-olefin interpolymer or propylene / α-olefin interpolymer) is in the foam composition in an amount of 10 to 99% by weight, preferably 50% based on the total weight of the foam composition. ~ 97% by weight, more preferably 70 ~
It can be used in an amount of 94% by weight.

This composition also contains ionomers. Ionomers play a useful role in controlling bubble size and include neutralized or unneutralized carboxylated olefin copolymers. In an exemplary embodiment, the carboxylated olefin copolymer is neutralized with metal ions. Alkali metal ions are preferred metal ions. The ionomer is not covalently or ionic to the elastomer (olefin block or random copolymer) prior to the cross-linking reaction.

The carboxylated olefin copolymer comprises an ethylene or propylene polymer grafted with an unsaturated carboxylic acid or an anhydride thereof, an ester, an amide, an imide or a metal salt, which is hereinafter referred to as a "grafting compound". The graphing compound is preferably an aliphatic unsaturated dicarboxylic acid adduct or anhydride, an ester, amide, imide or metal salt derived from such an acid. The carboxylic acid preferably contains up to 6 carbon atoms, more preferably up to 5 carbon atoms. Examples of unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, crotonic acid, and citraconic acid. Examples of unsaturated carboxylic acid derivatives are maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, methacryl. Glycidyl acid, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconate, diethyl itaconate, acrylamide, methacrylamide, monomaleamide, N, N-diethylmaleamide, N-monobutylmaleamide , N, N-dibutylmaleamide, monofmalamide, difmalamide, N-monoethyl fumalamid, N, N-diethylfumalamid, N, N-monobutyl fumalamid, N, N-dibutyl fumalamid, maleimide, N-butyl Maleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate and potassium methacrylate.

Examples of carboxylic acid copolymers are ethylene / (meth) acrylic acid copolymers, ethylene /
(Meta) acrylic acid / n-butyl (meth) acrylate copolymer, ethylene / (meth)
Acrylic acid / isobutyl (meth) acrylate copolymer, ethylene / (meth) acrylic acid / tert-butyl (meth) acrylate copolymer, ethylene / (meth) acrylic acid / methyl (meth) acrylate copolymer, ethylene / (meth) acrylic acid / Ethyl (meth) acrylate copolymer, ethylene / maleic acid and ethylene / maleic acid monoester copolymer, ethylene / maleic acid monoester / n-butyl (meth) acrylate copolymer, ethylene / maleic acid monoester / methyl (meth) acrylate copolymer, Includes ethylene / maleic acid monoester / ethyl (meth) acrylate copolymers, or a combination of two or more thereof.

One or more, preferably one graphing compound, is grafted onto an ethylene or propylene polymer. Maleic anhydride is the preferred graphing compound. Exemplary unsaturated carboxylic acids are acrylic acid or methacrylic acid.

The grafting process can be initiated, in particular, by degrading initiators that form free radicals, including azo-containing compounds, carboxylic acid peracids and peroxy esters, alkyl hydroperoxides, and dialkyl and diacyl peroxides. Many of these compounds and their properties have been described (Reference: J. Branderup,
E. Immunogut, E.I. Grulke, eds. "Polymer Handboo
k, "4th ed. , Wiley, New York, 1999, Section II
, Pp. 1-76. ). Alternatively, the graphing compound can be copolymerized with ethylene by typical tubular and autoclave processes.

The grafted ethylene polymer, as well as the ethylene polymer used for grafting, are ultra-low density polyethylene (ULDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene. ((
HDPE), high melt strength high density polyethylene (HMS-HDPE), ultra high density polyethylene (UHDPE), or a combination thereof.

In one embodiment, the grafted ethylene or propylene polymer, as well as the ethylene or propylene polymer used in the graft, is preferably 0.902 g / cm ³
More preferably 0.850 to 0.902 g / cm ³ , most preferably 0.860.
It has a density of ~ 0.890 g / cm ³ , especially at 0.865 to 0.880 g / cm ³ . However, it should be understood that the polymer density changes slightly upon grafting. For ethylene polymers, the polymer density is important to provide a primer with sufficient mechanical strength and flexibility, and to achieve sufficient solubility of the grafted ethylene polymer in organic solvents. Do you get it.

Ionomers can be prepared from acid copolymers by treatment with a basic compound capable of neutralizing the acid portion of the copolymer. The acid group is 0.1 to 90%, preferably 15 to 8 by an alkaline earth metal ion, an alkali metal ion, or a transition metal ion.
It can be nominally neutralized to any level of 0%, more preferably 40-75%. Ionomers can also be prepared at nominal neutralization levels above 70% as disclosed above when blended with organic acids.

The content of the grafted compound in the olefin copolymer is 0.05, more particularly 0.5, and most specifically 2.
It ranges from 0 to 30, specifically 15, and most specifically 8 weight percent. Preferred copolymers are ethylene acrylic acid copolymers (UNCREL® or Primac).
Or®), sodium or zinc salt-neutralized ethylene-acrylic acid copolymers (commercially available as SURLYN® or AMPLIFI IO®) and / or maleic anhydride grafting It is polyethylene. In an exemplary embodiment, a carboxylic acid-ethylene copolymer neutralized with sodium, zinc or aluminum is used in the foam composition. The carboxylic acid is acrylic acid or methacrylic acid, preferably methacrylic acid. In one embodiment, both copolymers can be optionally used with the neutralized copolymer.

The ionomer is used in an amount of 0.5 to 10% by weight, preferably 0.8 to 5% by weight, and more preferably 1 to 3% by weight based on the total weight of the foam composition.

The foam composition also contains a cross-linking agent. Crosslinking agents include one or more organic peroxides, including dialkyl peroxides, peroxyesters, peroxydicarbonates, peroxyketals, diacyl peroxides, or combinations thereof. Examples of peroxides are
Dicumyl peroxide, di (3,3,5-trimethylhexanoyl) peroxide, t-
Butyl Peroxy Pivalate, t-Butyl Peroxy Neodecanoate, Di (sec-Butyl) Peroxy Dicarbonate, t-Amil Peroxy Neodecanoate, 1,1-di-t-Butyl Peroxy-3,3,5- With trimethylcyclohexane, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (tersary butylperoxy) hexane, 1,3-bis (tersary butylperoxyl-isopropyl) benzene, or a combination thereof be. An exemplary crosslinker is from Arkema under the trade name LUPEROX.
Dicumyl peroxide commercially available under (registered trademark) or under the trade name TRIGONOX® from Akzo Nobel.

The cross-linking agent is 1 to 10% by weight, preferably 1.5 to 10% by weight, based on the total weight of the foam composition.
It is used in an amount of 4% by weight, more preferably 2 to 3% by weight.

The foam composition may also contain a foaming agent suitable for producing porosity for forming foams by heating. Decomposes at about the same temperature as the crosslinker decomposes (releases gas)
It is desirable to use a foaming agent. This allows the formation of foam with subsequent cross-linking, which facilitates the retention of the foam's porosity.

It is generally desirable to use an effective amount of foaming agent to produce a fairly uniform bubble size in the foam. The foaming agent generally works with the curing agent to promote a uniform crosslink density as well as a uniform pore size of the foam. The foaming agent may be a physical foaming agent or a chemical foaming agent. Physical foaming agents are released from the composition as a result of vinyl decomposition and expand during the foaming process to form foams, whereas chemical foaming agents decompose during the foaming process and gas ( For example, an azo compound) is liberated to form a foam.

Physical foaming agents containing hydrogen atom-containing components can be used alone or as a mixture with each other, or with other types of foaming agents such as azo compounds (eg, chemical foaming agents). The physical foaming agent can be selected from a wide range of substances including hydrocarbons, ethers, esters and partially halogenated hydrocarbons (eg, perfluorinated hydrocarbons), ethers and esters and the like. Typical physical foaming agents are -50 ° C to 100 ° C, preferably -50 ° C.
It has a boiling point of ° C to 50 ° C. Among the hydrogen-containing foaming agents that can be used are 1,1-dichloro-1.
-HCFCs (halochlorofluorocarbons) such as fluoroethane, 1,1-dichloro-2,2,2-trifluoroethane, monochlorologicfluoromethane and 1-chloro-1,1-difluoroethane; 1,1,1,3 , 3,3-hexafluoropropane, 2,2,4
, 4-Tetrafluorobutane, 1,1,1,3,3,3-hexafluoro-2-methylpropane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2,2 -Pentafluoropropane, 1,1,1,2,3-pentafluoropropane, 1,1,2,3,3-
Pentafluoropropane, 1,1,2,2,3-pentafluoropropane, 1,1,1,
3,3,4-hexafluorobutane, 1,1,1,3,3-pentafluorobutane, 1,
1,1,4,4,4-hexafluorobutane, 1,1,1,4,4-pentafluorobutane, 1,1,2,2,3,3-hexafluoropropane, 1,1,1, HFCs (halofluorocarbons) such as 2,3,3-hexafluoropropane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane and pentafluoroethane; methyl-1,1
, 1-Trifluoroethyl ether and HFE (halofluoroether) n-pentane such as difluoromethyl-1,1,1-trifluoroethyl ether, and hydrocarbons such as isopentane and cyclopentane.

Gaseous non-CFC or non-HCFC physical foaming agents are, for example, carbon dioxide, nitrogen, dinitrosopentamethylene-tetramine, SF ₆ , nitrousopentamethylene, argon, helium, noble gases such as xenone, air (nitrogen and oxygen mixture) and It is a blend of these gases. These gases can be used as foaming agents in gas, liquid or supercritical states.

Chemical foaming agents include azobisisobutyronitrile (AIBN), azodicarbonamide,
Dinitrosopentamethylene-tetramine, p-toluenesulfonyl hydrazide, p, p
Includes'-oxy-bis (benzenesulfonyl hydrazide) or a combination of these that can be used to produce foam. An exemplary azo compound is azobisisobutyronitrile. To regulate the expansion-decomposition temperature and foaming process, the foaming agent may be a mixture of foaming agents or a mixture of foaming agent and activator.

The foaming agent is 1 to 10% by weight, preferably 1.5 to 10% by weight, based on the total weight of the foam composition.
It is used in an amount of 5% by weight, more preferably 2-4% by weight.

The foam composition is also 0.1-1 to reduce the decomposition temperature / profile of the foaming agent.
It can contain 0% by weight, preferably 1-5% by weight of activator. The activator can be one or more metal oxides, metal salts, or organometallic complexes, or a combination thereof. Examples include zinc oxide, zinc stearate, magnesium oxide, or a combination of two or more thereof.

Other additives that may be present in the composition at 0.1-20 or 2-12% by weight relative to the total weight of the composition are pigments (TiO ₂ and other compatible coloring pigments), adhesion promotion. Agents (to improve the adhesion of foams to other materials), fillers (eg calcium carbonate, barium sulphate, and / or silicon oxide), nucleating agents (pure or concentrated forms, eg CaCO)
₃ , ZnO, SiO ₂ , or a combination of two or more thereof), rubber (eg, to improve rubber-like elasticity such as natural rubber, SBR, polybutadiene and / or ethylene propylene terpolymer), stabilizers (eg, for improving rubber-like elasticity). Antioxidants, UV absorbers and / or flame retardants)
, And processing aids (eg, Octene Co., Octene R-, manufactured by Taiwan).
130) can be included. Antioxidants (modifying sensory properties such as odor or taste reduction) are available from Ciba Geigy Inc. IRGA from (Tarrytown, NY)
Phenolic antioxidants such as NOX can be included.

Foams can be produced by many processes such as compression molding, injection molding, or a combination of extrusion and molding. Foam compositions can be prepared by blending elastomers, ionomers, cross-linking agents, foaming agents, and any other desired additive together. The blending may be done in an extruder or the ingredients may be preblended in a drive render prior to being extruded in an extruder.

In one embodiment, the production of the foam can include mixing the elastomer, ionomer, foaming agent and cross-linking agent with heating to form a melt. This can be done in Banbury, an intensive mixer, a two-roll mill, or an extruder. Time, temperature and shear rates can be adjusted to ensure optimal dispersion without premature cross-linking or foaming. Mixing at high temperatures can result in premature cross-linking and foaming due to decomposition of peroxides and foaming agents. Appropriate temperatures may be desirable to ensure good mixing and dispersion of other components. The upper temperature limit for safe operation may depend on the starting decomposition temperature of the peroxides and foaming agents used. Ingredients are 60 ° C to 25
A uniform mixture can be formed by blending at a temperature of 0 ° C., preferably 70 ° C. to 170 ° C., more preferably 80 ° C. to 160 ° C., even more preferably 90 ° C. to 150 ° C.
The polymer can be melt blended prior to blending with other ingredients.

After mixing, molding can be performed. Seating rolls or calendar rolls are often used to make sheets of appropriate dimensions for foaming. An extruder can be used to mold the composition into pellets.

Foaming can be carried out by compression or injection molding at a temperature and time to complete the decomposition of the peroxide and foaming agent. The pressure, molding temperature, and heating time can be controlled.
Foaming can be performed in an injection molding machine by using a pellet-shaped foam composition. The resulting foam can be further molded to the dimensions of the final product by any means known in the art, such as thermoforming and compression molding.

The foam produced from this composition may be substantially closed cells and may be applied to footwear (eg, midsole or insole), automobile seats and interiors, furniture armrests, etc.
It may be useful for a variety of articles, including railroad pads and other industrial foam material applications.

The foam composition and the method for producing the same are disclosed by the following non-limiting examples.

This example was performed to show the preparation and properties of the disclosed foam composition. The materials used in the examples and comparative examples are detailed in Table 1 below.

These ingredients were mixed together in an internal mixer. The compounded formulation was then produced on a two-roll mill and subsequently bun-foamed. The prepared foam plaque was sliced to the appropriate dimensions for further testing. The compounding and van foaming production operations are described in detail below.

The composition of the foam composition is as follows. Polymer pellets (having the compositions shown in Tables 2 and 3 below) were added to a 1.5 liter Banbury mixer. After the polymer has melted (about 5 minutes), a filler containing zinc oxide (ZnO), zinc stearate (ZnSt) and calcium carbonate (CaCO ₃ ) is added to the Banbury. After the filler is uniformly dispersed, the foaming agent and peroxide are finally added, and the contents are further mixed for 3 to 5 minutes, for a total mixing time of 15.
It was a minute. The batch temperature was checked using a thermoprobe detector immediately after the compound was released. The actual temperature of the composition is generally the indicated temperature on the device (the composition temperature is about 100 ° C.).
It was 10 to 15 ° C higher than (was). Therefore, it is better to maintain a lower display device temperature to ensure that the temperature of the formulation does not exceed the decomposition temperature of the curing agent and the decomposition temperature of the foaming agent during the compounding process. Next, the compounded formulation is rolled into a two-roll mill (maintained at a temperature of about 100 ° C.).
The compound was molded into a sheet (or roll mill ground blanket) about 5 mm thick.

The production of bun foam is described in detail below. Roll mill ground blankets were cut into squares (3 or 4 "6" x 6 "squares) and placed in preheated van foam molds measuring approximately 49 square inches. A mold release agent was sprayed on the surface of the chase to prevent the foam from sticking to the chase during demolding. Two compression forming processes were involved: first a preheating process to remove air pockets inside the sample and between the laminated blanket layers before curing, and then a second heating step to accelerate the curing / foaming process. Preheating is performed at 110 ° C. (low melting point polymer such as ENGAGE) or 120 ° C. (high melting point polymer such as INFUSE) for 8 minutes to form a solid mass in the mold before foaming for 4 minutes.
Pressed with 10 tons. Transfer the preheated mass to a foam press, 100 kg / cm ² and 18
It was held at 0 ° C. for 8 minutes. When the pressure is released, quickly remove the van foam from the tray and
It was placed in a ventilated hood on some non-adhesive sheets and the length of the top surface was measured as soon as possible.
The foam surface had to be insulated from the bench top using a cardboard box. By insulating the surface of the newly created pan-like foam, it prevents uneven cooling on the top and bottom surfaces. The foam was cooled in the hood for 40 minutes, then transferred to a storage vessel and cooled for 24 hours.

The following tests were performed on the foam composition.

Foam Density: Van foam is weighed closest to 0.1 g and length, width and thickness are 0
.. The volume is determined by measuring to the value closest to 01 cm. Density can be calculated in terms of weight and volume.

Falling Ball Rebound: Elasticity test (resilie)
ncy test) was performed according to ASTM D2632. A steel ball having a diameter of 5/8 inch was dropped from a height of 500 mm onto the van foam skin layer and the foam layer (before and after aging), and the repulsion% was measured. The repulsion% is calculated as the repulsion height (mm) × 100/500.

Compression Permanent Strain: Compression Permanent Strain (C-Set) was measured according to ASTM D395 Method B for 6 hours under conditions of 50% compression at 50 ° C. Two buttons were tested per foam and average values were reported. The compression set was calculated using the following equation.
Compressive permanent strain = (T ₁ -T ₂ ) / (T ₁ -T ₀ ) x 100%
Here, T ₀ is the distance between the devices, T ₁ is the sample thickness before the test, and T ₂ is the sample thickness after the test.

Shore A / Asker C hardness: The Shore A hardness test was performed according to ASTM D2240. Hardness is measured over the surface of the sample 5 readings (waiting time of 5 seconds)
Was measured again after aging at both 70 and 100 ° C. for 40 minutes.

Mechanical Properties: The van foam skin layer and the foam layer were subjected to ASTM D638 (tension, type 4) and ASTM D624 (tear, type C) mechanical property tests at 20 inches / min. The thickness of the sample was about 3 mm. Split tear strength
strength) measures 6 inches (length) x 1 inch (width) x 0.4 inches (thickness)
And using a test piece having a notch depth of 1 to 1.5 inches, measurements were taken at a test speed of 2 inches / min.

Tables 2 and 3 show the compositions of Examples (IE) and Comparative Examples (CE) of the present invention. All numbers in each composition are percentages. Comparative examples (CE-1 to CE-4) do not contain ionomers. All the examples (IE-1 to IE-8) of the present invention are 1% by weight (IE-1 to IE-4).
) Or 2% by weight (IE-5 to IE-8) of ionomer.

From Tables 2 and 3, it can be seen that CE1 to CE4 are comparative examples based on ionomer-free olefin block copolymers and random copolymer blends. IE1 to IE4 are similar to CE1 to CE4, but with a 1 phr ionomer (SURLYN86).
60) is an embodiment of the present invention. IE5 to IE8 are examples of the present invention that are similar to CE1 to CE4 but have a 2 phr ionomer. CE-5 is a comparative example similar to IE-7, having 2 phr POE-g-MAH (unneutralized ethylene-carboxylic acid copolymer) rather than an ionomer. CE-6 is a comparative example similar to IE-7, having 2 phr of ethylene acrylic acid (an unneutralized ethylene-carboxylic acid copolymer) rather than an ionomer. CE-7 is not an ionomer,
It is a comparative example similar to IE-7 having 2 phr poly (ethylene vinyl acetate) (EVA) (having 21% by weight vinyl acetate). CE-8 is a comparative example similar to IE-7, having 2 phr EVA (having 40 wt% vinyl acetate) rather than an ionomer. CE-9 is a comparative example similar to IE-7 having an ionomer (SURLYN8660) 10 phr.

The bubble morphology was studied using a scanning electron microscope. 2 and 3 show changes in bubble morphology of the compositions listed in Tables 2 and 3. Table 4 shows the changes in properties for some selected compositions.

Table 4 lists the performance of the selected foams of the present invention and comparative examples. CE-2 and CE-
3 has the same formulation but different foaming agent levels (2.5 phr for CE-2, CE
-3 is a comparative example having 3 phr). IE-1 and IE-7 are examples of the present invention corresponding to CE-3, but for IE-3, 1 phr ionomer and IE.
For -7, it has a 2 phr ionomer. CE-5 to CE-8 are comparative examples corresponding to IE-7, but have additives of different polymers rather than ionomers. IE-
It is clear that 3 and IE-7 have much higher tensile strength and tear strength than Comparative Examples (CE-2 and CE-3) at equivalent or lower foam densities. CE-5 used POE-g-MAH to replace the ionomer and did not improve mechanical strength. CE-6 uses ethylene acrylic acid to replace ionomers and has a smaller expansion ratio than other compositions of the present invention. CE-7 used 21 wt% vinyl acetate EVA to replace the ionomers in compositions IE-3 and IE-7, but did not improve mechanical strength. Similarly, CE-8 is 40% by weight vinyl acetate EVA (Elvax40L-).
03) is used but shows inferior mechanical properties.

FIG. 2 is a series of scanning electron micrographs showing foam bubble morphology of Comparative Examples CE1 to CE-4 and Examples IE-1 to IE-8 of the present invention. CE-1 to CE-4 are comparative examples having different foaming agent filling amounts without the use of ionomers. From the micrographs of CE-1 to CE-4, the expansion ratio increases with the increase in the foaming agent filling amount, and the foam bubble size also increases. The bubbles in the foam are large and exceed 100 micrometers in size. IE-1 to IE-4 are
Comparative Example CE, except that all contain 1 phr ionomer (SURLYN).
It is an embodiment of the present invention corresponding to -1 to CE-4. IE-1 to IE-4 are Comparative Example CE-
It is clear that it has much smaller foam bubbles (about 50 micrometers) than 1-CE-4. Examples IE-5 to IE-8 of the present invention are similar to IE-1 to IE-4 but contain 2 phr ionomers. These examples of the present invention are also Comparative Example C.
It shows a much smaller bubble size compared to E-1 to CE-4.

FIG. 3 shows the foam bubble morphology of Comparative Examples CE-5, CE-7, CE-8 and CE-9.
Non-neutralized ethylene-carboxylic acid copolymer POE-g-MAH (CE-5), ionomer at equivalent doses of 21% by weight vinyl acetate EVA (CE-7) or 40% by weight vinyl acetate EVA (CE-8) After substituting (SURLYN), the foam cells show no significant reduction compared to the bubble size obtained for samples with 2 phr ionomer (IE-7) at the same foaming agent level (3 phr). CE-9 also has a very small bubble size,
Not desirable due to the very low expansion ratio (1.17). CE-6 uses ethylene acrylic acid to replace the ionomer, but this formulation exhibits a smaller expansion ratio (see Table 3) that may be due to the delayed degradation of azodicarbonamide by acrylic acid in the EAA. Was found, and therefore the comparison under the same conditions did not work.

From Table 4 and FIGS. 2 and 3, the foam composition containing the elastomer and ionomer is 3
5 to 90 micrometers, preferably 40 to 70 micrometers, more preferably 4
It can be seen that it has an average bubble size of 5 to 65 micrometers.

The foamed composition also exhibits a Type C tear strength of 14.5 to 17 Newton / mm (N / mm), preferably 15 to 16.5 N / mm. The average stress at break is 2.75
Over Newton / mm2.

In summary, the techniques of the invention are OBC-rich based lightweight foamed articles (0) with very fine bubble size (less than 100 micrometer) while meeting the corresponding applicable performance requirements, especially improved tensile and tear properties. .2 grams / cubic centimeter (g / cc)
) Can be provided with a density less than). The small and uniform bubble size can contribute to even better tactile and adhesion of the foam.

Examples of the invention of the present application include the following.
[1] A foam composition, which is a foam composition.
Olefin copo containing ethylene and α-olefin or propylene and α-olefin
With Rimmer
An ionomer containing a copolymer of ethylene and a carboxylic acid, said ionomer.
Is neutralized with metal ions, with ionomers,
With a cross-linking agent,
A foam composition comprising, and a foaming agent.
[2] The olefin copolymer is an olefin block copolymer, and the foam assembly
It is present in the foam composition in an amount of 10-99% by weight based on the total weight of the adult [1].
The foam composition according to.
[3] The foam composition according to [1], wherein the α-olefin is an octene.
[4] The ionomer is 0.5 to 10% by weight based on the total weight of the foam composition.
The foam composition according to [1], which is present in the foam composition in an amount of.
[5] The carboxylic acid is (meth) acrylic acid, and the metal ions are zinc and sodium.
, Aluminum, or a combination thereof, the foam composition according to [1].
[6] In [1], the cross-linking agent is a peroxide and the foaming agent is an azodicarbonamide.
The foam composition described.
[7] The foam produced from the composition has an average bubble size of 45 to 90 micrometers.
The foam has a Type C tear strength of 14.5-17 Newton / mm.
However, the average stress at break exceeds 2.75 Newton / mm2, according to [1].
Foam composition.
[8] An article produced from the foam composition according to any one of [1] to [7].
[9] The article according to [8], wherein the article is footwear.
[10] A method for producing a foam composition.
Olefin copo containing ethylene and α-olefin or propylene and α-olefin
An ionomer containing a limer and a copolymer of ethylene and a carboxylic acid, the above-mentioned ionomer.
Nommers are neutralized with metal ions, ionomers, cross-linking agents, and foaming agents, together.
By blending to form the foam composition,
By heating the composition to activate the foaming agent,
A method comprising cross-linking the composition.
[11] The method according to [10], further comprising molding the foam composition.

Claims (8)

It is a foam composition and
An olefin copolymer containing ethylene and an α-olefin or a propylene and an α-olefin, including a block copolymer and a random copolymer, and an olefin copolymer.
With 0.5-5% by weight ionomer, which contains a copolymer of ethylene and carboxylic acid and is neutralized with metal ions.
With a cross-linking agent,
With foaming agent,
And all of the weight percent is for the total weight of the foaming agent composition.
The foam produced from the composition has an average cell size of 45-90 micrometers, the foam has a Type C tear strength of 14.5-17 Newton / mm, and an average stress at break. A foam composition in which is a foam in excess of 2.75 Newtons / mm2. The foam composition according to claim 1, wherein the α-olefin is octene. The foam composition according to claim 1, wherein the carboxylic acid is (meth) acrylic acid and the metal ion is zinc, sodium, aluminum or a combination thereof. The foam composition according to claim 1, wherein the cross-linking agent is a peroxide and the foaming agent is an azodicarbonamide. An article produced from the foam composition according to any one of claims 1 to 4 . The article according to claim 5 , wherein the article is footwear. A method for producing a foam composition, which is a method for producing a foam composition.
An ionomer comprising an olefin copolymer containing ethylene and α-olefin or propylene and α-olefin and a copolymer of ethylene and carboxylic acid, wherein the ionomer is neutralized with metal ions, an ionomer, a cross-linking agent, and the like. In the step of forming the foam composition by blending the foaming agent together with the foaming agent, the ionomer is present in an amount of 0.5 to 5% by weight based on the total weight of the composition. The process, wherein the olefin copolymer comprises a block copolymer and a random copolymer.
A step of heating the composition to activate the foaming agent,
The step of cross-linking the composition and
The foam produced from the composition has an average cell size of 45-90 micrometers and the foam has a Type C tear strength of 14.5-17 Newton / mm. A method of foam having an average stress at break of more than 2.75 Newtons / mm2. The method of claim 7 , further comprising molding the foam composition.

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