JP2002529547A - Processed articles made from α-olefin / vinyl or vinylidene aromatic and / or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymer compositions - Google Patents

Abstract

  (57) [Summary] SUMMARY OF THE INVENTION The present invention relates to a method for producing a mixture of one or more vinyl or vinylidene aromatic monomers and / or sterically hindered fats with a trace amount of one or more thermoplastic polymers that are immiscible with a substantially random interpolymer copolymer component. COMPOSITION COMPRISING AT LEAST ONE RANDOM RANDOM COPOLYMER INTERPOLYMER CONTAINING POLYMERIZED UNITS DERIVED FROM ONE OR MORE α-OLEFIN MONOMERS WITH A SPECIFIC RATIO OF GROUP OR CYCLIP ATHYLENE Vinyl or Vinylidene Monomers To processed products manufactured from The workpiece is manufactured in a final melt processing step that includes a flow manufacturing method that can be characterized by the shear field applied in the method. After melt processing, the blended composition may exhibit low modulus, high temperature performance, chemical resistance and transparency even at low levels of the immiscible thermoplastic polymer blend component. It exhibits a unique mixing behavior and a final solid-state structure, as well as showing unexpected combined properties including limited. Workpieces according to the present invention include films, tapes, sheets, fibers, foams, injection molded articles, injection / blow molded articles, and profile extrusion.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method for producing a specific amount of one or more vinyl or vinylidene aromatic monomers and / or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers in combination with a small amount of one or more thermoplastic polymers. Together with one or more α-
A processed article made from a polymer composition comprising at least one substantially random interpolymer comprising polymer units derived from olefin monomers, wherein the thermoplastic polymer is immiscible with the substantially random interpolymer. belongs to. These workpieces are manufactured in a final melt processing step that includes a flow processing process that can be characterized by the shear field applied during processing. In accordance with the specific melt processing conditions, the blend composition may have a low concentration of the immiscible thermoplastic polymer blend components, for example, but the resulting processed product will still contain modulus, high temperature performance and clarity. Exhibit unique mixing behavior and a final solid state structure, such as exhibiting unexpected combinations of properties that are not limited to.

[0002] These processed products include films, tapes, sheets, fibers, foams, injection molded products,
Injection blow molded products, injection molded soft products, extruded deformed products, toys, injection molded toys, household goods, colorable products, furniture, auto parts, lawn and garden tools, small appliances,
It can be used for applications including, but not limited to, large instruments and the like.

[0003] These apply to substantially random interpolymers of α-olefin / hindered vinylidene monomers described in US Pat. No. 5,703,187 and to interpolymers of α-olefin / vinyl aromatic monomers. Comprehensive classes of materials, including materials, are known in the art and provide a range of material structures and properties that make them useful for various applications. These interpolymers may find use as compatibilizers for blends of polyethylene and polystyrene as described in US Pat. No. 5,460,818. Furthermore, the use of these interpolymers in film and sheet structures is described, for example, in WO 95/32095.

[0004] While they are useful in nature, there is a continuing need in the industry to increase the applicability of these interpolymers, for example, to extend the temperature range of application. Blended compositions are finding increasing use in performance applications that require a combination of properties not available in a single polymer.
WO 97/115546 pamphlet and M filed on Jul. 23, 1997
. J. No. 08 / 117,136 to Guest et al. Describes a blend of substantially random interpolymers and is described in WO 97/11736.
/ 15533 describes a blend of a substantially random interpolymer and polyethylene and is described in S.M. A. Ogoe
Co-pending U.S. Provisional Application No. 60/077663 describes a blend of a substantially random interpolymer with a polycarbonate and is disclosed in US Pat. W. Concurrent US Application No. 08/9 by Cheung et al.
No. 50983 describes a blend of a substantially random interpolymer and poly (vinyl chloride), and US Pat. No. 5,741,857 discloses a blend of a substantially random interpolymer and a styrenic block copolymer. Has been described, and K.K. No. 08 / 709,418 to Sikema et al. Describes blends of substantially random interpolymers and polystyrene, all of which are incorporated herein by reference.

[0005] Blending techniques have been recognized to be complex, especially for so-called immiscible polymer / polymer systems. Melt processing operations are often used to blend polymers and produce solid parts from mixed polymer systems. It is also known that for immiscible polymer-polymer blends, the final solid state properties are determined not only by the choice of blend components and composition ratios, but also by the solid state morphological properties (eg, Quintens et al.). al., Polym. Eng. Sci. Vol. 30, p.1474
et seq. [1990]). The basic technique is one of the developments in morphology, for which it is generally accepted that the rheological behavior, interfacial properties and processing conditions of the blend components are important (eg, Van Oene, J. et al. Coll. Interface
Sci. Vol. 40, p.448 et seq. [1972]). Fundamental explanations of the types of morphological properties include matrix-inclusions (or complex occlusions), co-continuous and fibrous or plate-like structures. It is well known in the art of polymer blending that the addition of a small volume fraction of a secondary immiscible component B to a major volume fraction of component A generally results in the form of an A / B matrix / inclusion type. I have. In such a structure, many of the properties, such as modulus and higher operating temperature, are essentially determined by those properties of the matrix layer.

[0006] We now state that articles made in melt processing operations having a critical shear rate greater than about 30 s ^-1 are those articles in which at least one substantially random interpolymer and a small amount of one It has been surprisingly found that the above-mentioned thermoplastic polymers, and if they are immiscible with one another, exhibit substantially improved properties. The improved properties include, but are not limited to, modulus, toughness, higher service temperature, transparency, and chemical resistance. The properties to be improved can be selected by selecting the minor components of the blend. For example, when polystyrene is used as the component B, the modulus and the higher operating temperature are improved, while when high density polyethylene is used as the component B, properties such as chemical resistance are further improved. Blend components A and B can have a wide range of molecular weights and molecular weight distributions, and these are selected according to the performance requirements of the final processed product.

The present invention is directed to a workpiece comprising a blend of at least two polymers made by a high critical shear rate melt processing operation and being immiscible with each other, the blend comprising 55-95. % By weight (based on the combined weight of components A and B) of (A) at least one substantially random interpolymer comprising: (1) a polymer unit obtained from: (I) at least one vinyl or vinylidene aromatic monomer, or (ii) at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer, or (iii) at least one aromatic vinyl or vinylidene monomer and at least one Together with other aliphatic or cycloaliphatic vinyl or vinylidene monomers, obtained from At least one substantially random interpolymer comprising: (B) a polymer unit obtained from ethylene and / or at least one C _3-20 α-olefin; At least one thermoplastic polymer, which is immiscible with and present in an amount of 5 to 45% by weight (based on the combined weight of components A and B), and (C) The high critical shear rate is greater than about 30 s- ¹ .

[0008] These processed products include films, tapes, sheets, fibers, foams, injection molded products,
Injection blow molded products, injection molded soft products, extruded deformed products, toys, injection molded toys, household goods, colorable products, furniture, auto parts, lawn and garden tools, small appliances,
It can be used for applications including, but not limited to, large instruments and the like.

All references herein to elements or metals belonging to a particular group are made by the CRC (CRC
Press, Inc.), published in 1989, with reference to the Periodic Table of the Elements for which the copyright is owned. Also, any reference to one or more groups shall be as indicated in the Periodic Table of the Element using the IUPAC system to number the groups.

[0010] Each of the numerical values listed here includes all values in increments of one unit from the smaller value to the larger value, provided that any smaller value and any larger value are included. It is assumed that there is a gap of at least two units between the two values. As an example,
If the amount of a component or the value of a working variable, such as, for example, temperature, pressure, time, etc., is stated, for example, between 1 and 90, preferably between 20 and 80, more preferably between 30 and 70, this specification is used. Then 15-85, 22-68, 43-51, 3
It is intended to clarify values such as 0-32 and the like. When the value is less than 1, one unit is appropriately 0.0001, 0.001, 0.01 or 0.1.
Is assumed to be These are only examples of specific intent, and in this application all possible combinations of numerical values between the smallest and the largest value listed are explicitly stated in a similar manner. Should be considered as

The term “hydrocarbyl” as used herein refers to any aliphatic, cycloaliphatic, aromatic, aryl-substituted aliphatic, aryl-substituted cycloaliphatic, aliphatic-substituted aromatic, or aliphatic-substituted Alicyclic group.

The term “hydrocarbyloxy” means a hydrocarbyl group having an oxygen bond between the hydrocarbyl group and the carbon atom to which it is attached.

The term “copolymer” as used herein refers to a polymer in which at least two different monomers have polymerized to form the copolymer.

The term “interpolymer” is used herein to refer to a polymer in which at least two different monomers are polymerized to make up the interpolymer. This includes copolymers, terpolymers, and the like.

The term “workpiece” as used herein refers to a processed composition that includes films, fibers, foams, injection molded articles, injection blow molded articles, and extruded profiles.

The term “high shear rate” as used herein refers to a critical shear rate of about 30 s ⁻¹ or higher.

As used herein, the term “high shear rate processing operation” refers to a method for producing a workpiece that exposes the polymer blend to high shear rates. Examples of high shear rate processing operations are film blowing and injection molding.

As used herein, the term “low shear rate” refers to a critical shear rate of about 30 s ⁻¹ or less.

As used herein, the term “low shear rate processing operation” refers to a method for producing a workpiece that exposes the polymer blend to a low shear rate. One example of a low shear rate processing operation is compression molding.

As used herein, the term “immiscible with each other” refers to individual blend components that are immiscible with each other. For example, in a blend of two or more polymers, individual blend components may be examined by electron microscopy as individual domains, or their characteristic thermal transitions (eg, glass transition,
A polymer is considered to be immiscible if it can still be identified by Tg).

The present invention provides a processed article produced by melt processing a blend of at least two polymers under high shear rate conditions. The blend comprises at least one substantially random interpolymer (one or more with one or more vinyl or vinylidene aromatic monomers and / or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers). (A) comprising a polymer unit derived from an α-olefin monomer of (a) and one or more other components which are immiscible with component (A) and are present in small amounts relative thereto. A component (B) which is a thermoplastic polymer component.

In a preferred embodiment, the article of the present invention has a modulus of elasticity of the article when manufactured under high shear rate conditions at a temperature greater than or equal to 20 ° C. above the Tg (DSC) of the blend.
It satisfies the criterion of being at least twice, preferably at least three times, more preferably at least ten times the elastic modulus of the article when manufactured under low shear rate conditions.

The immiscible thermoplastic polymer component (B) of the blend comprises one or more styrene homopolymers or copolymers, α-olefin homopolymers or copolymers, engineering thermoplastics, styrene block copolymers, elastomers Or a vinyl halide polymer, but is not limited thereto.

As used herein, the term “substantially random” (one or more α-olefin monomers and one or more vinyl or vinylidene aromatic monomers and / or aliphatic or cycloaliphatic vinyl or A substantially random interpolymer comprising a polymer unit derived from a vinylidene-based monomer).
The distribution of the monomer of the interpolymer is determined by JC Randall, POLYMER SEQUENCE D
ETERMINATION, Carbon-13 NMR Method, Academic Press, New York, 1977, pp.7
Bernoulli statistical model described in 1-78 or primary or secondary Ma
It means that it can be described by the rkovian statistical model. Preferably, the substantially random interpolymer does not contain more than 15% of the total amount of vinyl aromatic monomer as a block of four or more units. This means that, in the carbon- ¹³ NMR of a substantially random interpolymer, the peak area corresponding to the main chain methylene carbon and methine carbon indicates either the meso dyad configuration or the racemic dyad configuration. This means that it must not exceed 75% of the total peak area of carbon and methine carbon.

[0025] The substantially random interpolymers used to make the articles of the present invention include ethylene and / or one or more α-olefins and one or two or more α-olefins.
It was prepared by polymerizing the above vinyl or vinylidene-based aromatic monomer and / or one or more sterically hindered aliphatic or alicyclic vinyl or vinylidene-based monomer with other polymerizable monomers to be included as required. Interpolymers are included.

Examples of suitable α-olefins include α-olefins containing 3 to 20, preferably 3 to 12, more preferably 3 to 8 carbon atoms. Particularly suitable are propylene, butene-1, 4-methyl-1-pentene, heptene-1, hexene-1 or octene-1. Even more preferred are those obtained by combining ethylene with one or more α-olefins containing from 3 to 20 carbon atoms, especially ethylene with propylene, butene-1, pentene-1, 4-methyl-. It is a combination of 1-pentene, hexene-1, heptene-1 or octene-1. These α-olefins do not contain an aromatic moiety.

Other optionally polymerizable ethylenically unsaturated monomers include norbornenes and strained ring olefins such as C _1-10 alkyl-substituted or C _6-10 aryl-substituted norbornenes, and are examples of interpolymers. Examples include ethylene / styrene / norbornene.

Suitable vinyl or vinylidene aromatic monomers that can be used in preparing the interpolymer include those represented by the following general formula:

[0029]

Embedded image

In the above formula, R ¹ is selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen or methyl group, and R ² is each independently a hydrogen and a carbon atom Ar is selected from the group consisting of alkyl groups of formulas 1 to 4, preferably hydrogen or methyl, and Ar is selected from the group consisting of phenyl or halo, C _1-4 alkyl and C _1-4 haloalkyl It is a phenyl group substituted with 1 to 5 substituents, and the value of n is 0 to 4, preferably 0 to 2, most preferably 0. Examples of vinyl aromatic monomers include styrene, vinyltoluene, α-methylstyrene, t-butylstyrene, chlorostyrene, all isomers of these compounds, and the like. Particularly preferred among such monomers include styrene and its lower alkyl or halogen substituted derivatives. Preferred monomers include styrene,
α-methylstyrene, lower alkyl (C ₁ -C ₄ ) -substituted derivatives of styrene or phenyl ring-substituted derivatives, such as ortho-, meta- and para-methylstyrene, ring-halogenated styrene, para-vinyltoluene or mixtures thereof And the like. A more preferred aromatic vinyl monomer is styrene.

“Sterically hindered aliphatic or alicyclic vinyl or vinylidene compound” means an addition polymerizable vinyl or vinylidene monomer corresponding to the following general formula.

[0032]

Embedded image

In the above formula, A ¹ is a sterically bulky aliphatic or alicyclic substituent containing up to 20 carbon atoms, R ¹ is hydrogen and alkyl having 1 to 4 carbon atoms. R ² is independently selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen or methyl group. Yes, or as an alternative, R ¹ and A ¹ together form a ring system. Suitable aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms having ethylenic unsaturation is tertiary or quaternary substituted.

Examples of such substituents include cycloaliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or their cyclic or alkyl-substituted derivatives, t-butyl, norbornyl, and the like. The most preferred aliphatic or cycloaliphatic vinyl or vinylidene-based compounds are cyclohexene and various isomeric vinyl-ring substituted derivatives of substituted cyclohexene, and 5-ethylidene-2-norbornene. Particularly preferred are 1-, 3- and 4-vinylcyclohexene. An α-olefin containing 3 to 20 carbon atoms and having a linear aliphatic structure,
For example, propylene, butene-1, hexene-1 and octene-1 are not considered hindered aliphatic monomers.

[0035] The substantially random interpolymers are typically grafted, hydrogenated,
It can be modified by functionalization or other reactions well known to those skilled in the art. The polymer can be easily sulfonated or chlorinated according to established techniques to provide a functionalized derivative.

As one method of preparing the substantially random interpolymer, a mixture of polymerization monomers is polymerized in the presence of one or more metallocene catalysts or constrained geometry catalysts in combination with various cocatalysts. There is a way to make it happen. The substantially random interpolymer is disclosed in James C. Stevens et al., EP 0 416 815.
And Francis J. Timmers can be prepared as described in US Pat. No. 5,703,187, which is incorporated herein by reference in its entirety. Working conditions suitable for such a polymerization reaction are 0.101325 MPa
(Atmospheric pressure) to a pressure of up to 303.975 MPa (3000 atm) and a temperature of -50 ° C to 200 ° C. If the polymerization is performed at a temperature higher than the self-polymerization temperature of each monomer, and the unreacted monomer is removed, some homopolymer polymerization products may be generated by radical polymerization.

[0037] Specific examples of catalysts and methods suitable for preparing such substantially random interpolymers are described in US Patent Application No. 702,475, filed May 20, 1991 (EP-A-514828, and U.S. Patent Nos. 5,055,438 and 5,
No. 5,096,867, No. 5,064,802,
Nos. 5,132,380, 5,189,192, 5,321,10
No. 6, No. 5,347,024, No. 5,350,723, No. 5,374
No. 5,696,635, No. 5,470,993, No. 5,
Nos. 703,187 and 5,721,185, all of which are hereby incorporated by reference.

A substantially random α-olefin / vinyl aromatic interpolymer can also be prepared by the method described in JP-A-7-278230 using a compound represented by the following general formula.

[0039]

Embedded image

In the above formula, Cp ¹ and Cp ² each independently represent a cyclopentadienyl group, an indenyl group, a fluorenyl group or a substituent thereof, and R ¹ and R ² each independently represent a hydrogen atom , A halogen atom, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxyl group or an aryloxyl group, wherein M is a Group IV metal, preferably Zr or Hf
And most preferably Zr, and R ³ represents an alkylene or silanediyl group used to bridge Cp ¹ and Cp ² .

A substantially random α-olefin / vinyl aromatic interpolymer is described by Jo
hn G. Bradfute et al. (WR Grace & Co.) International Publication No. WO 95/32095;
B. Pannell (Exxon Chemical Patents Inc.) can also be prepared by the method described in WO 94/00500 and Plastics Technology, p. 25 (September 1992), and refer to these documents. Is hereby incorporated by reference in its entirety.

As substantially random interpolymers, Francis J. Timmers et al.
Also suitable are those containing at least one α-olefin / vinyl aromatic / vinyl aromatic / α-olefin-based tetrad described in U.S. patent application Ser. No. 08 / 708,809 filed Sep. 4, 2006. is there. These interpolymers include carbon
Includes an additional signal whose intensity in the ^-13 NMR spectrum is more than three times the peak-to-peak noise. These signals are in the chemical shift range 43.70-44.
. Found at 25 ppm and 38.0-38.5 ppm. Specifically, main peaks are observed at 44.1 ppm, 43.9 ppm and 38.2 ppm. Proton test NMR experiments indicate that the signal contained in the chemical shift region 43.70-44.25 ppm is methine carbon and the signal contained in the region 38.0-38.5 ppm is methylene carbon.

[0043] These novel signals are derived from configurations in which at least one α-olefin insert is included before and after two head-to-tail vinyl aromatic monomer inserts, eg, styrene monomer in ethylene / styrene / styrene / ethylene-based tetrad. It is believed that the insert is exclusively in the 1,2 (head and tail) mode. For those skilled in the art, for a tetrad containing a vinyl aromatic monomer other than styrene and an α-olefin other than ethylene, ethylene / vinyl aromatic monomer / vinyl aromatic monomer / ethylene-based tetrad has a slightly different chemical shift. Similar carbon- ¹³ NM
Understand that it produces an R peak.

These interpolymers can be prepared in the presence of a catalyst such as
It can be prepared by performing polymerization at a temperature of -30C to 250C.

[0045]

Embedded image

In the above formula, Cp each independently represents a substituted cyclopentadienyl group π-bonded to M, E represents C or Si, M represents a Group IV metal, preferably Zr or Hf , Most preferably Zr, wherein R is each independently H, hydrocarbyl,
Represents a silahydrocarbyl or hydrocarbylsilyl group containing up to 30, preferably 1 to 20, more preferably 1 to 10, carbon atoms or silicon atoms, and R 'is independently H, halo , Hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl, containing up to 30, preferably 1 to 20, more preferably 1 to 10, carbon or silicon atoms, or two R The 'groups can be combined into a C _1-10 hydrocarbyl-substituted 1,3-butadiene and, optionally, preferably in the presence of an activating cocatalyst. Particularly preferred substituted cyclopentadienyl groups include
Includes those represented by the following formula.

[0047]

Embedded image

In the above formula, R is each independently H, hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, and has up to 30, preferably 1 to 20, more preferably 1 to 10, carbon atoms or silicon atoms. Or two Rs together form a divalent derivative of such a group. R is each independently (
It is preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl (including all isomers where appropriate) and (if appropriate) two such R groups. One is connected to a fused ring system, for example,
It is preferred to form indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl or octahydrofluorenyl.

Particularly preferred catalysts include, for example, racemic (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium dichloride, racemic (dimethylsilanediyl) -bis- (2-methyl- 4-phenylindenyl)
Zirconium 1,4-diphenyl-1,3-butadiene, racemic (dimethylsilanediyl) -bis- (4-phenylindenyl) zirconium diC _1-4 alkyl, racemic (dimethylsilanediyl) -bis- (2 -Methyl-4-phenylindenyl) zirconium di-C _1-4 alkoxide, or any combination thereof.

It is also possible to use the following titanium-based forced geometry catalysts: [N- (1,
1-dimethylethyl) -1,1-dimethyl-1-[(1,2,3,4,5-η)
-1,5,6,7-tetrahydro-s-indacen-1-yl] silane aminato (2-)-N-] titanium dimethyl; (1-indenyl) (tert-butylamido) dimethylsilanetitanium dimethyl; (( 3-tert-butyl) (
1,2,3,4,5-η) -1-indenyl) (tert-butylamido) dimethylsilanetitanium dimethyl; and ((3-isopropyl) (1,2,3
4,5- [eta])-1-indenyl) (tert-butylamido) dimethylsilanetitanium dimethyl, or any combination thereof.

Other preparation methods for interpolymer (copolymer) discovery practice in the present invention are described in the literature. US Patent No. 5,652, issued to Mitsui Toatsu Chemicals
No. 315 describes copolymerization of ethylene and styrene. Longo & Grassi ( Makromol . Chem. , Vol . 191, pp. 2387-2396 [1990]) and D'Anniello et al. ( Journal of Applied Polymer Science , Vol. 58, 1701-1706 [1995]) - report the use of catalyst systems based on styrene copolymers methylalumoxane for the preparation of (MAO) and cyclopentadienyl titanium trichloride (CpTiCl _3). Xu & Lin (Polymer Preprints, Am . Chem. Soc., Div. Poly m. Chem., Vol. 35, pp. 686-687 [1994]) is, MgCl ₂ / to provide a random copolymer of styrene and propylene TiCl ₄ / NdCl ₃ / Al (iBu
₃ ) Copolymerization using _three catalysts is reported. Lu et al. ( Journal of Applied Polymer Science , Vol. 53, pp. 1453-1460 [1994]) describe TiCl ₄ / NdCl ₃ / MgC
l ₂ / Al (Et) have reported copolymerization of ethylene and styrene using ₃ catalyst. Sernets & Mulhaupt ( Macromol. Chem. Phys. , Volume 197, pp. 1071-1083, 1
997) describe the effect of _{Me 2 Si (Me 4 Cp)} (N-tert- butyl) TiCl ₂ / methylaluminoxane polymerization conditions for the copolymerization of ethylene and styrene using hexane catalyst. A copolymer of ethylene and styrene produced by a bridged metallocene catalyst is described in Arai, Toshiaki & Suzuki ( Polymer Preprints , Am. Chem. Soc., Div. Polym. Chem. , Vol . 38, pp. 349-350 [1997]). Is described. The production of alpha-olefin / vinyl aromatic monomer interpolymers such as propylene / styrene and butadiene / styrene has been described in U.S. Pat. No. 5,244,996 issued to Mitsui Petrochemical or Mitsui Petrochemical. It is described in U.S. Pat. No. 5,652,315 or in German Offenlegungsschrift 197 11 339 A1 issued to Denki Kagaku Kogyo KK. All of the above disclosed methods for preparing the interpolymer component are incorporated herein by reference. Random copolymers of ethylene and styrene, such as those disclosed by Toru Aria et al. In Polymer Preprints, Volume 1, March 1998, can also be used as a blend component in the present invention.

The immiscible thermoplastic polymer component (B) of the blend includes, but is not limited to, 1
Or a plurality of styrene homopolymers or copolymers, ethylene and / or α-olefin homopolymers or copolymers, thermoplastic polyolefins,
Industrial thermoplastics, styrene block copolymers, elastomers, or vinyl halide polymers can be mentioned.

The styrene homopolymer or copolymer used as component (B) in the blends of the present invention is a polymer of a vinyl or vinylidene aromatic monomer, such as one or more vinyl or vinylidene aromatic monomers. Examples include homopolymers or copolymers of monomers, or copolymers of one or more vinyl or vinylidene aromatic monomers with one or more monomers other than the aliphatic α-olefin that can be copolymerized therewith. Suitable vinyl or vinylidene aromatic monomers are represented by the following formula:

[0054]

Embedded image

In the above formula, R ¹ is selected from the group consisting of hydrogen and an alkyl group having 3 or less carbon atoms, and Ar is a phenyl group or halo, C _1-4 alkyl and C _1-4
It is a phenyl group substituted by 1 to 5 substituents selected from the group consisting of haloalkyl. Representative vinyl or vinylidene aromatic monomers include styrene, p-vinyltoluene, α-methylstyrene, t-butylstyrene, chlorostyrene (including all isomers of those compounds), and the like. A particularly preferred vinyl aromatic monomer for use in the vinyl aromatic polymer in the practice of the present invention is styrene.

A preferred polymer is atactic polystyrene. During the preparation of the substantially random interpolymer component (A) of the present invention, an atactic vinyl aromatic homopolymer may be formed by homopolymerization of the vinyl aromatic monomer at elevated temperatures.
For the purposes of the present invention, such atactic vinyl aromatic homopolymers, typically atactic styrene, constitute at least a portion of the immiscible blend component (B).

Examples of suitable copolymerizable comonomers in the blend component (B) other than vinyl or vinylidene aromatic monomers include, for example, C ₄ -C ₆ conjugated dienes, especially butadiene or isoprene, n-phenylmaleimide, Acrylamide, ethylenically unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile, ethylenically unsaturated mono- and dicarboxylic acids and derivatives thereof, such as esters, and anhydrides in the case of divalent acids, such as acrylic acid , C _1-4 alkyl acrylates or methacrylates such as n-butyl acrylate and methyl methacrylate, maleic anhydride and the like. In some cases, it is also desirable to copolymerize a cross-linking monomer such as divinylbenzene in a vinyl or vinylidene aromatic polymer. The polymer of the vinyl or vinylidene aromatic monomer and another copolymerizable comonomer is preferably in its polymerized form at least 50% by weight, preferably at least 60% by weight, of one or more vinyl or vinylidene aromatics. Contains group-group monomers. Preferred styrene copolymers are styrene / acrylonitrile (SAN) copolymer, styrene / maleic anhydride copolymer (SMA), styrene / methyl methacrylate copolymer (S-MMA).
) And rubber modified copolymers such as acrylonitrile / butadiene / styrene copolymer (ABS). The number average molecular weight _Mn of the styrene homopolymer and copolymer used as the blend component of the present invention is from 1,000 to 1,000,000.
00, preferably 5,000 to 500,000, more preferably 10,000 to
350,000 and the molecular weight distribution M _w / M _n is 1.005 to 20.00
0.

[0058] Rubber-modified vinyl aromatic polymers can be prepared by polymerizing vinyl aromatic monomers in the presence of pre-dissolved rubber to prepare an impact or grafted rubber-containing product. Examples are U.S. Pat. No. 3,123,655,
Nos. 3,346,520, 3,639,522 and 4,409,
No. 369, which are incorporated herein by reference. The rubber is typically a butadiene or isoprene rubber, preferably polybutadiene. Preferably, the rubber modified vinyl aromatic polymer is high impact polystyrene (HIPS). Component (B) may be a flame resistant rubber modified styrene blend formulation. Flame resistant formulations are typically made by adding a flame retardant to a high impact polystyrene (HIPS) resin. Although the addition of a flame retardant reduces the impact strength of the HIPS, it is restored to an acceptable level by the addition of an impact modifier, typically a styrene-butadiene-styrene (SBS) block copolymer. The final formulation is called pyrophoric polystyrene (IRPS).

Further polymers suitable for use as component (B) include vinyl or vinylidene aromatic polymers having a high isotactic or syndiotactic shape. A high syndiotactic form is one in which the stereochemical structure is predominantly a syndiotactic form, i.e., phenyl or substituted phenyl groups as side chains alternate in opposite directions with respect to the main chain consisting of carbon-carbon bonds. It means the stereochemical structure in which it is located. Tacticity (stereoregularity) is measured quantitatively by 13 C-nuclear magnetic resonance as is well known in the art. Preferably, the degree of syndiotacticity as measured by 13C NMR spectroscopy is 75%
above the r-diead, more preferably greater than 90% r-diead. Examples of suitable syndiotactic polymers include polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (alkoxystyrene), poly (vinylbenzoate), mixtures thereof, and containing the polymer as a major component Copolymers. Examples of poly (alkylstyrene) include poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), and poly (tert).
-Butylstyrene) and the like. Examples of the poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of the poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

Preferred styrene copolymers having tacticity and used as component (B) are generally 10,000 to 10,000,000, preferably 100,000
It has a weight average molecular weight of 0 to 5,500,000, and 5,000 to 5,500,0
00, preferably syndiotactic polystyrene (SPS) having a number average molecular weight of 50,000 to 2,500,000. The syndiotactic polymer has a melting point of 160-310 ° C.

The ethylene and / or α-olefin homopolymer or interpolymer used as the blend component (B) in the blend of the present invention may contain ethylene and / or
Or a polymer comprising a C ₃ -C ₂₀ α-olefin. α-olefin homopolymer and interpolymer include polypropylene, propylene /
C ₄ -C ₂₀ alpha-olefin copolymers, polyethylene, and ethylene / C ₃ ~
C ₂₀ alpha-olefin copolymers. The interpolymer can be either a heterogeneous ethylene / α-olefin interpolymer or a homogeneous ethylene / α-olefin interpolymer, including a substantially linear ethylene / α-olefin interpolymer.

[0062] Aliphatic α-olefins having 3 to 20 carbon atoms and containing a polar group are also included. Suitable aliphatic α-olefin monomers for introducing a polar group into the polymer include, for example, ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile and the like; ethylenically unsaturated anhydrides such as maleic anhydride Ethylenically unsaturated amides, such as acrylamide, methacrylamide; ethylenically unsaturated carboxylic acids (monovalent or divalent), such as acrylic acid and methacrylic acid; esters of ethylenically unsaturated carboxylic acids, especially lower alkyl esters, such as lower alkyl esters, C ₁ -C ₆ alkyl esters), for example methyl methacrylate,
Ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate or methacrylate, 2-ethylhexyl acrylate, and the like; ethylenically unsaturated dicarboxylic imides, such as N-alkyl or N-arylmaleimide, such as N-phenylmaleimide. Such preferred monomers containing polar groups are acrylic acid, vinyl acetate, maleic anhydride and acrylonitrile. Typical polymers are ethylene vinyl acetate (EVA) and ethylene vinyl alcohol (EVOH). Halogen groups that can be introduced into the polymer from aliphatic α-olefin monomers include fluorine, chlorine and bromine; such polymers are preferably chlorinated polyethylene (CP
E).

[0063] In a homogeneous interpolymer, substantially all of the interpolymer molecules have the same ethylene / comonomer ratio, whereas a heterogeneous interpolymer is one in which the interpolymer molecules do not have the same ethylene / comonomer ratio. Wherein heterogeneous interpolymers are distinguished from homogeneous interpolymers. As used herein, the term "broad composition distribution" describes the comonomer distribution of a heterogeneous interpolymer, where the heterogeneous interpolymer has a "linear" portion and has multiple melting peaks by DSC. (I.e. having at least two different melting peaks) and (by weight of polymer) 10% by weight or more, preferably 15% by weight or more, especially 2% by weight.
It means having a degree of branching equal to or less than 2 methyl / 1000 carbons at 0% by mass or more. Heterogeneous interpolymers also have 2 (by weight of polymer)
Up to 5% by weight, preferably up to 15% by weight, especially up to 10% by weight, has a degree of branching equal to or greater than 25 methyl / 1000 carbons.

[0064] Ziegler catalysts suitable for the preparation of the heterogeneous components of the present invention are typically supported Ziegler-type catalysts, which are particularly useful at the high polymerization temperatures of the solution processes described above. Examples of such compositions are those derived from organomagnesium compounds, alkyl or aluminum halides or hydrogen chloride, and transition metal compounds. Examples of such catalysts are described in U.S. Pat. No. 4,314,912 (Lowery, Jr. et a.
l), 4,547,475 (Glass, et al.) and 4,612,300 (
Coleman, III). Suitable catalyst materials may be derived from inert oxide supports and transition metal compounds. Examples of such compositions suitable for use in the solution polymerization process are described in US Pat. No. 5,420,690 (Spencer et al.).

The different polymer components may be ethylene and / or α-olefin homopolymers, preferably polyethylene or polypropylene, or preferably at least one C ₃ -C ₂₀ α-olefin and / or C ₄ -C ₁₈ diolefin. It may be an ethylene interpolymer having an olefin. Heterogeneous copolymers of ethylene and 1-butene, ethylene and 1-pentene, ethylene and 1-hexene and ethylene and 1-octene are particularly preferred.

The relatively recent introduction of metallocene-based catalysts for ethylene / α-olefin polymerization has led to the production of novel ethylene interpolymers. These polymers are known as heterogeneous interpolymers and are characterized by their narrower molecular weight and composition distribution compared to heterogeneous polyolefin polymers catalyzed, for example, by traditional Ziegler catalysts. Component (B) of the present specification
Substantially linear ethylene / α-olefin polymers and interpolymers that can be utilized as are described in US Pat. No. 5,272,236 (Lai et al.) And US Pat. No. 5,278,272. Is defined herein.

The heterogeneous polymer component may be an ethylene and / or α-olefin homopolymer, preferably polyethylene or polypropylene, or preferably at least one C ₃ -C ₂₀ α-olefin and / or C ₄ -C _It may be an ethylene interpolymer with ₁₈ diolefins. Ethylene, and one or more C ₃ -C ₈ alpha-olefins heterogeneous copolymers are particularly preferred.

Commercially available products that can be utilized as component (B) include ultra low density polyethylene (UL
DPE), low density polyethylene (LDPE), linear low density polyethylene (LLD)
PE), medium density polyethylene (MDPE), high density polyethylene (HDPE),
Polyolefin plastomers such as AFFIN by Dow Chemical Company
Includes those sold under the trade name ITY ™ and polyethylene elastomers, such as those sold by Du Pont Dow Elastomers PLC under the trade name ENGAGE ™. The molecular weights of the ethylene homopolymers and interpolymers for use in the present invention are according to ASTM D-1238, condition 190.
° C. / 2.16 kg (formerly "condition (E)" is known as, and also known as were as I ₂₎ represented conveniently by using a melt flow measurement according to. Melt flow rates for ethylene homopolymers and interpolymers useful herein are typically from 0.1 g / 10 min (g / 10 min) to 1000 g / 10 min, preferably 0.5 g / min.
It is from 10 minutes to 200 g / 10 minutes, and especially from 1 g / 10 minutes to 100 g / 10 minutes.

The C ₃ α-olefin homopolymer or copolymer utilized as component (B) in the formulation of the present invention is polypropylene. The polypropylene is usually an isotactic type of homopolymer polypropylene, or other types of polypropylene may be used (eg, syndiotactic or atactic). However, polypropylene impact copolymers (e.g., utilizing a second copolymerization stage where propylene and ethylene react in a reactor) and random copolymers (
The reactor was further modified and usually copolymerized with propylene, 1.8-20 m
ol% of ethylene or C ₄ -C ₈ alpha-olefins those containing) may also be used.
A thorough discussion of various polypropylene polymers is contained in Modern Plastics Encyclopedia / 89 , mid October 1998 Issue, Volume 65, Number 11, pp. 86-92, the entire disclosure of which is incorporated herein by reference. Can be The molecular weight of propylene for use in the present invention is ASTM D-1238, conditions 230 ° C /
2.16 kg (formerly "condition (L)" is known as, and also known as were as I ₂₎ represented conveniently by using a melt flow measurement according to. Melt flow rate is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt flow rate, but the relationship is not linear. The melt flow rate of polypropylene useful herein is typically between 0.1 g / 10 min (g / 10 min) and 200 g / min.
10 minutes, preferably 0.5 g / 10 minutes to 100 g / 10 minutes, and especially 1 g / 10 minutes
Min to 50 g / 10 min.

The thermoplastic olefin (TPO) used as component (B) is usually a propylene homo- or copolymer as described above, or a blend of elastomeric materials, such as ethylene / propylene rubber (EPM) or ethylene / propylene diene. Manufactured from monomeric terpolymers (EPDM) and harder materials, such as isotactic polypropylene. Other materials or components can be added to the formulation, including oils, fillers, and crosslinkers, depending on the application. TPO in the reactor may also be used as a compounding component of the present invention.

The third edition of The Kirk-Othmer Encyclopedia of Science and Technology defines, as a thermoplastic, a pure or unreinforced or filled engineering plastic, which has dimensional stability and most 10 mechanical properties
Maintain above 0 ° C and below 0 ° C. "Engineering plastic" and "
The phrase "engineering thermoplastic" can be used interchangeably. Ingredient (B
Engineering thermoplastics which can be used as) include polyoxymethylene-based resins, for example acetal; acrylic resins (for example polymethylmethacrylate, PMMA); polyamides (for example nylon-4,6, -nylon-6).
, Nylon 6,6, and higher molecular nylons), polyimides, polyetherimides, cellulose resins, polyesters, polyarylates; aromatic polyesters (eg, polybutylene terephthalate and polyethylene terephthalate, PEN)
Liquid crystal polymers; blends or alloys of the foregoing resins; and other resins, including, for example, rigid thermoplastic polyurethanes, high temperature olefins, such as ethylene / norbornene copolymers, polycyclopentanes, copolymers thereof,
And polymethylpentane and its copolymers.

Also included are aromatic polyethers, which include, for example, polyphenylene ether (PPE) thermoplastic engineering resins, which are prepared by the oxidative coupling polymerization of alkyl-substituted phenols, known in the art. Is a commercially available material. They are usually linear, amorphous polymers having a glass transition temperature in the range from 190C to 235C. Preferred PPE materials have the formula:

[0073]

Embedded image

Wherein Q is the same or different alkyl groups having 1 to 4 carbon atoms and n is an integer of at least 100, preferably 150 to 1200). Examples of preferred polymers are poly (2,6-dialkyl-1,4-phenylene ether), such as poly (2,6-dimethyl-1,4-phenylene).
Phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether),
Poly (2,6-dipropyl-1,4-phenylene ether) and poly (2-ethyl-6-propyl-1,4-phenylene ether). A more preferred polymer is poly (2,6-dimethyl-1,4-phenylene ether). These polymers are often sold as blends with polystyrene and high impact polystyrene, and other formulation components.

Particularly preferred engineering thermoplastics are acetal, polymethyl methacrylate, nylon-6, nylon 6,6, bisphenol A-polycarbonate, poly (2,6-dimethyl-1,4-phenylene ether), and polybutylene Terephthalate and polyethylene terephthalate.

Styrene block copolymers that can be used as the compounding component (B) include, but are not limited to, styrene butadiene (SB), styrene isoprene (SI), styrene butadiene styrene (SBS), styrene isoprene styrene (SIS), α-methyl It has an unsaturated rubber monomer containing styrene-butadiene-α-methylstyrene and α-methylstyrene isoprene-α-methylstyrene.

The styrene portion of the block copolymer is preferably a polymer or copolymer of styrene and analogs and homologs thereof, including α-methylstyrene and cyclic substituted styrene, especially cyclic methylated styrene. Preferred styrenic systems are styrene and α-methylstyrene, and styrene is particularly preferred.

The block copolymer having unsaturated rubber monomer units may comprise a homopolymer of butadiene or isoprene, or they may comprise one of these two dienes having a small amount of styrenic monomer. It may comprise one or both copolymers.

Preferred styrenic block copolymers that can be utilized as component (B) include at least one styrenic unit segment and at least one ethylene butene or ethylene propylene copolymer segment. Examples of such block copolymers having saturated rubber monomer units are styrene / ethylene-butene copolymer, styrene / ethylene-propylene copolymer, styrene / ethylene-
Butene / styrene (SEBS) copolymer, styrene / ethylene-propylene /
Including styrene (SEPS) copolymer.

Elastomers that can be used as component (B) include, but are not limited to, rubbers such as polyisoprene, polybutadiene, natural rubber, ethylene / propylene rubber,
Includes ethylene / propylene diene (EPDM) rubber, silicone rubber, styrene / butadiene rubber and thermoplastic polyurethane.

The vinyl halide or vinylidene homopolymers and copolymers that can be used as the compounding component (B) have the structural unit CH ₂ ＣCXY (where X is F, C
and Y is selected from the group consisting of F, Cl, Br, I and H).

The vinyl halide or vinylidene polymer component of the formulation of the present invention includes, but is not limited to, homopolymers and copolymers of vinyl halide or vinylidene,
It has copolymerizable monomers such as ethylene and / or α-olefins, including but not limited to ethylene, propylene, vinyl esters of organic acids containing 1 to 18 carbon atoms, such as vinyl acetate, Vinyl stearate, etc .; vinyl chloride, vinylidene chloride, symmetric dichloroethylene; acrylonitrile, methacrylonitrile; alkyl acrylate esters in which the alkyl group contains 1 to 8 carbon atoms, such as methyl acrylate and butyl acrylate; corresponding alkyl methacrylate esters; Includes dialkyl esters of dibasic organic acids wherein the group contains from 1 to 8 carbon atoms, such as dibutyl fumarate, diethyl malate and the like.

Preferably, the vinyl or vinylidene halide polymer is a homopolymer or copolymer of vinyl chloride or vinylidene chloride. Polyvinyl chloride polymer (
PVC) can be further classified into two main types according to their hardness. These are "hard" PVC and "soft" PVC. Soft PVC is distinguished from hard PVC primarily by the presence and amount of plasticizer in the resin. Soft PVC typically has improved workability, low tensile strength, and high elongation as compared to hard PVC.

Among vinylidene chloride homopolymers and copolymers (PVDC), copolymers with vinyl chloride, acrylate or nitrile are typically used commercially,
And most preferred. Perhaps the most notable properties of the various PVDC are their low permeability to gases and liquids, barrier properties; and chemical resistance.

[0085] Chlorinated PVC (CPVC), typically prepared by subsequent chlorination of the base resin
Also known in the family of vinyl halide polymers for use as the blend components of the present invention are chlorinated derivatives of PVC, known as PVC. Although CPVC is based on PVC and shares some of its characteristic properties, CPVC has a much higher melting temperature range (410-450 ° C) and a glass transition temperature (239-275 ° F) than PVC.
Is a unique polymer having

Additives such as antioxidants (eg hindered phenols such as Irgan
ox® 1010, a registered trademark of Ciba Geigy), phosphites (eg, Irgafos® 168, a registered trademark of Ciba Geigy), U.S. Pat. V. Stabilizers, cling additives (e.g., polyisobutylene), slip agents (e.g., erucamide and / or stearamide), anti-blocking agents, colorants, and pigments are also blend components used to make the processed articles of the present invention. A and / or Blend Component B or can be included in the overall blend.

Processing aids, also referred to herein as plasticizers, can also be included in either blend component A and / or blend component B or the overall blend composition used to make the processed article of the present invention. These include phthalates such as dioctyl phthalate and diisobutyl phthalate, natural oils such as lanolin, and paraffins, naphthenic and aromatic oils obtained from oil refining, and liquid resins from rosin or base stocks. A typical class of oils that serve as processing aids include mineral oils (eg, Kay).
dol ^™ oil, available from Witco and is a registered trademark thereof), and Shell
flex ^™ 371 naphthenic oil (available from Shell oil Company and is a registered trademark thereof). Another suitable oil is Tuflo ^™ oil (available from Lyondell and is a registered trademark thereof).

Tackifiers can also alter the processing capabilities of the present polymers, thereby increasing the available application temperature window for the articles and the blending components A and A used to produce the processed articles of the present invention. And / or may be included in either Blend Component B or the entire blend composition. Suitable tackifiers are described in Hercules (J.
Simons, Adhesive Age , “The HMDA Concept: A New Method for Selection of
Resins ", November 1996. This reference discusses the importance of the polarity and molecular weight of the resin in determining compatibility with the polymer. In the case of a substantially random interpolymer of one α-olefin and a vinyl aromatic monomer, preferred tackifiers are, especially in the case of a substantially random interpolymer having a high content of vinyl aromatic monomer, It will have some aromatic character to promote compatibility.

Tackifying resins can be obtained by polymerization of petroleum and terpene feed streams and from derivatization of wood, rubber and tall oil rosin. Several classes of tackifiers include wood rosin, tall oil and tall oil derivatives, and cyclopentadiene, such as those described in British Patent Application GB 2,032,439A. The tackifier other classes, aliphatic C ₅ resins, polyterpene resins, hydrogenated resins, mixed aliphatic - aromatic resins, rosin esters, natural and synthetic terpenes, terpene - phenolic resins, and hydrogenated rosin ester There is.

Various organic and inorganic fillers are also potential components of the polymer composition used in the present invention,
And their identity depends on the type of application utilizing the elastic film. Fillers can be included in either the blend component A and / or the blend component B or the overall blend composition used to make the processed article of the present invention.
Representative examples of these fillers include organic and inorganic fibers such as asbestos, boron,
Graphite, ceramic, glass, metal (eg, stainless steel) or polymer (eg, aramid fiber), talc, carbon black, carbon fiber, calcium carbonate, alumina trihydrate, glass fiber, marble dust, cement dust,
Clay, feldspar, silica or glass, fumed silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanate, aluminum nitride, B ₂ Some are made from O ₃ , nickel powder or chalk.

[0091] Other typical organic or inorganic fibrous or mineral fillers include carbonates such as barium, calcium or magnesium carbonates, fluorides such as calcium or sodium, fluorides of aluminum; hydroxides such as water Aluminum oxide; metals such as aluminum, bronze, lead or zinc; oxides
For example, oxides of aluminum, antimony, magnesium or zinc, or dioxides of silicon or titanium; silicates such as asbestos, mica, clay (kaolin or calcined kaolin), calcium silicate, feldspar, glass (ground or flaked glass or hollow) Glass spheres or microspheres or beads, whiskers or filaments), nepheline, perlite, pyrophyllite, talc or wollastonite; sulphates such as barium or calcium sulphates; metal sulphides; There are cellulose; calcium terephthalate; and liquid crystals. Mixtures of more than one such filler can further be used.

[0092] These additives are used in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant used is that amount which prevents the polymer or polymer blend from oxidizing at the temperatures and environments used during storage and end use of the polymer. The amount of such antioxidants is usually between 0.01 and 10, preferably between 0.05 and 5, more preferably between 0.1 and 5, based on the weight of the polymer or polymer blend.
２2% by weight. Similarly, the amounts of any other listed additives may be such as to prevent the polymer or polymer blend from sticking, to obtain the required results, to provide the required color from the colorant or pigment, such as to provide the required color. Functionally equivalent quantities. Such additives are suitably used in a range of 0.05 to 50, preferably 0.1 to 35, more preferably 0.2 to 20% by weight based on the weight of the polymer or polymer blend. it can. The filler can be suitably used in the range of 1 to 90% by weight.

[0093] The blended polymer composition used to make the processed article of the present invention may be prepared by any conventional method, for example by dry mixing the individual components and then melt mixing or melting in a Haake torque rheometer. It can be made by synthesis, by pre-melt mixing in a separate extruder or mill (eg, Banbury mixer), by solution mixing, or by calendering.
The blend composition may be dry mixed rather than melt mixed and then directly processed in an extruder, injection mold, equipment, film blowing equipment or mill used to make the final product.

[0094] The processed article of the present invention can be made using conventional melt processing operations. Regardless of the melt processing operation used, in order to obtain a processed article of the present invention, the melt processing should have a critical shear rate greater than 30, preferably 40 to 30,000, and even more preferably 50 to 30,000.
It should be performed under high shear rate conditions, such as 5,000 sec ^-1 .

For films, such operations include, for example, simple bubble extrusion (typically with a high blow-up ratio (BUR)), biaxial stretching processes (eg, tenter or double bubble processes), simple bubble extrusion Cast / sheet extrusion, coextrusion, lamination and the like. Conventional simple bubble extrusion processes (also called hot blow film processes) are described, for example, in The Encyclopedia of Chemical Technology , Kirk-Othmer, Third Edition,
John Wiley & Sons, New York, 1981, Vol 16, pp. 416-417 and Vol. 18, pp. 1
91-192. Biaxially stretched film manufacturing process, for example USP 3,45
6,044 (Pahlke), the method described in the "double bubble" method, and US Pat.
P 4,352,849 (Mueller), USP 4,820,557 and 4,837,084 (both Warrcn), USP
4,865,902 (Golike et al.), USP 4,927,708 (Herran et al.), USP 4,952,451
(Mueller) and the methods described in US Pat. Nos. 4,963,419 and 5,059,481 (both Lustig et al.) Can also be used to make processed articles included in the present invention. The processed article of the present invention can be made permeable or "respirable" by any method known in the art, for example, by aperture, slitting, microperforating, mixing with fibers or foams and the like, and combinations thereof. "You can. Examples of such methods include USP 3,156,242 (Crowe, Jr.), USP 3,881,489 (Hartwel
l), USP 3,989,867 (Sisson) and USP 5,085,654 (Buell).

Injection molding, thermoforming, extrusion coating, profile extrusion,
And sheet extraction melt processing operations, for example, Plastics Materials and Processes, Se
ymour S. Schwartz and Sidney H. Goodman, Van Nostrand Reinhold Company,
New York, 1982, pp. 527-563, 632-647. And 596-602. The workpiece of the present invention can be manufactured by the primary extrusion process itself or by well-known post-extrusion slitting, cutting or stamping techniques. Profile extrusion, tapes, bands,
It is an example of a primary extrusion process particularly suitable for manufacturing ribbons and the like.

During the final partial processing, a substantially random interpolymer blend component (
A) and / or the immiscible thermoplastic polymer component (B) can also be modified by various crosslinking methods. These include peroxide-, silane-, sulfur, radiation-,
Or, but not limited to, azide-based curing systems. A thorough description of various cross-linking techniques can be found in U.S. patent application Ser. No. 08/921, both co-pending on cross-linking substantially random interpolymer blend component (A), filed Aug. 27, 1997. 641 and 08 / 921,642.

A dual cure system using a combination of heat, moisture cure, and radiation steps can be effectively used. A dual cure system was disclosed and claimed in KL Walton and SV Karande, US Patent Application Serial No. 536,022, filed September 29, 1995, which is incorporated herein by reference. For example, a peroxide crosslinking agent in combination with a silane crosslinking agent, a peroxide crosslinking agent in combination with radiation,
It may be required to use a sulfur-containing crosslinking agent in combination with a silane crosslinking agent.

The polymer composition used to prepare the processed article of the present invention comprises (A) 55-95, based on the combined weight of component A and immiscible polymer component B, preferably 65-92, Preferably 70-90, even more preferably 70-88% by weight of one or more substantially random interpolymers of ethylene and / or one or more vinyl or vinylidene aromatic monomers and / or one or more sterics. (B) 5 to 45, preferably 8 to 35, more preferably 8 to 35, based on the combined weight of component A and the immiscible polymer component B with the aromatically hindered aromatic or cycloaromatic vinyl or vinylidene monomer. 10-30, even more preferably 12-30% by weight of one or more thermoplastic polymers immiscible with component (A) -Components.

Component (B) comprises one or more styrenic homopolymers or copolymers, ethylene and / or α-olefin homopolymers or interpolymers, thermoplastic olefins, engineering thermoplastic polymers, styrenic block copolymers, elastomers, Or a vinyl or vinylidene halide polymer.

The properties of the resulting processed product are such that these substantially random interpolymers
1-65, preferably 2-50, more preferably 5-50 mol% of at least one vinyl or vinylidene aromatic monomer and / or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer; 35 to 99, preferably 50 to 98, more preferably 50 to 95 mol% of ethylene and / or 3
It has been discovered that it is observed when it contains at least one aliphatic α-olefin having ２０20 carbon atoms.

[0102] The melt index (I ₂ ) of the substantially random interpolymer used to make the processed article of the present invention is greater than about 0.05, preferably 0.5 to 200,
More preferably, it is 0.5 to 100 g / 10 minutes.

[0103] The molecular weight distribution (Mw / Mn) of the substantially random interpolymer used to produce the elastic film of the present invention is 1.5-20, preferably 1.8-10.
, More preferably 2 to 5.

The density of the substantially random interpolymer used to make the elastic film of the present invention is greater than about 0.900, preferably 0.930 to 1.045, more preferably 0.930 to 1.45. 040, most preferably 0.930 to 1.030 g /
cm ³ .

In one embodiment, the processed article of the present invention exhibits an increase in modulus when manufactured under a high shear rate operation compared to a sample manufactured under a low shear rate operation. This allows the modulus of elasticity of a product made under high shear rate processing at least at a temperature of 20 ° C. in excess blend Tg (DSC) to be at least as low as that of a product made under low shear rate processing. It is twice, preferably three times, more preferably ten times.

The processed articles of the present invention include films, fibers, foams, injection molded articles, injection blow molded articles, and extruded profiles, where films and injection molded articles are the most preferred embodiments. The following examples are provided to illustrate the present invention and should not be construed as limiting the scope of the invention.

EXAMPLES Test Methods (a) Melt Flow and Density Measurements The molecular weight of the polymers used in the present invention is conveniently indicated by melt index measurement according to ASTM D-1238. Here, 190 ° C / 2.16k
g of conditions (officially known as "Condition (E)", also known as I ₂₎
Was measured. Melt index is inversely proportional to the molecular weight of the polymer. Therefore, as the molecular weight becomes relatively large, the melt index becomes relatively small. However, this relationship is not linear.

[0108] Gottfert melt index (G, cm ^3/10 min) are also useful to indicate the molecular weight of the substantially random interpolymers used in this invention. This can be obtained in a similar manner to the melt index (I ₂ ) using ASTM D1238 on an automatic plastometer with the melt density set to 0.7632, the melt density of polyethylene at 190 ° C. it can.

The relation between the melt density and the styrene concentration of the ethylene-styrene interpolymer is as follows.
Measured as a function of total styrene content at 190 ° C. at 29.8% to 81.8% styrene weight percent. The atactic polystyrene content in these samples is typically 10% or less. The effect of atactic polystyrene is considered to be minimal due to the low content. Also, the melt density of atactic polystyrene is very similar to the melt density of a sample with a high total styrene content. The method used to measure melt density uses a melt density parameter of 0.
. A Gottfert melt indexer set at 7632 and collection of molten strand as a function of I ₂ weight enabled time was used. The weight and time for each molten strand were recorded and standardized to determine grams per 10 minutes. Calculated I ₂ melt index values the instrument was also recorded. The formula used to calculate the actual melt density is as follows: δ = δ _0.7632 × I ₂ / I _{2 Gottfert,} where δ _0.7632 = 0.7632, and I 2 _Gottfert = melt index indicated It is.

A linear square minimum approximation of the styrene content to the calculated melt density yields an equation with a correction factor of 0.91 for the following equation: δ = 0.00299 × S + 0.723 where S = The weight percentage of styrene in the polymer. If the styrene content is known, these equations can be used to determine the actual melt index value from the relationship between total styrene and melt density.

Thus, for a polymer with a total styrene content of 73%, where the melt flow (“Gottfert number”) is measured, the calculation is as follows: δ = 0.00299 × 73 + 0.723 = 0.9412 where 0.9412 / 0.7632 = I ₂ / G number (measured value) = 1.23

(B) Styrene Analysis The styrene content and atactic polystyrene content of the interpolymer were as follows:
It can be measured using proton nuclear magnetic resonance ( ¹ HNMR) or ¹² C nuclear magnetic resonance.

All proton NMR samples were prepared using 1,1,2,2-tetrachloroethane-d ₂ (
TCE-d ₂₎ was prepared in. The resulting solution contains 1.6-3.2 wt.
%Met. Melt index (I ₂ ) was used to determine sample concentration. Therefore, if I ₂ is greater than 2 g / 10 min, using the interpolymers of 40 mg, when I ₂ is 1.5~2g / 10 min, using the interpolymers of 30 mg, I ₂ is 1. If less than 5 g / 10 min, 20 mg of interpolymer was used. The interpolymer was metered directly into a 5 mm sample tube. An aliquot of TCE-d ₂ in 0.75ml was added via syringe and capped the tube by airtight polyethylene cap. The sample is 85 ° C
The water was heated in a water bath to soften the interpolymer. The capped sample was occasionally refluxed using a heat gun to effect mixing.

Varian VX with sample probe at 80 ° C. for proton NMR spectra
As determined by R300, with reference to the residual protons of TCE-d ₂ at 5.99Ppm. The delay time was varied between one second and three measurements were taken for each sample. For the analysis of the interpolymer samples, the following instrument conditions were used: Varian VXR-300, standard ¹ H: sweep width, 5,000 Hz data collection time, 3.002 seconds pulse width, 8 μs frequency, 300 MHx delay, 1 second decay signal, total analysis time per 16 samples was about 10 minutes.

Initially, a ¹ H-NMR spectrum of a polystyrene sample Styron ™ 680 (available from Dow Chemical Company, Midland, Mich.) Was obtained with a 1 second lag time. As shown in FIG. 2 below, the proton is
Identified. " Here, b is a branch, a is alpha, o is ortho, m
Is meta and p is para.

[0116]

Embedded image

The integration was performed on the protons shown in FIG. Here, “A” indicates aPS. The integral A _7.1 (aromatic, about 7.1 ppm) is considered to be three ortho / para protons. The integral A _6.6 (aromatic, about _6.6 ppm) is considered to be two metaprotons. 1.5 ppm of two aliphatic protons identified as α
Resonated. One proton identified in b resonated at 1.9 ppm. Aliphatic region was integrated by about 0.8～2.5Ppm, was A _al. The theoretical ratio of A _7.1 : A _6.6 : A _al is 3: 2: 3 or 1.5: 1: 1.5 and is observed for Styron ™ 680 samples with multiple 1 second delays. And correlated very well with the rate. Ratio calculation that matches the coupling used to confirm the provision of the peaks was performed by dividing the appropriate integral by the integral A _6.6. Where A _r
Was A _7.1 / A _6.6 .

The area A _6.6 was set to 1. The proportion Al was the integral A _al / A _6.6 . In all spectra collected, the ratio of (o + p): m: (α + b) is considered to be 1.5: 1: 1.5. The ratio of aromatic protons to aliphatic protons is 5 to 3. It is believed that the aliphatic proportions of 2-1 are based on protons identified as α and b, respectively, in FIG. This percentage was also observed when the two aliphatic peaks were integrated separately.

A 1 second delay was used for the ethylene / styrene interpolymer
^The integrals C _7.1 , C _6.6 and _Cal were obtained in the ¹ H-NMR spectrum. Here 7.1p
The integration in pm includes all the aromatic protons of the copolymer and the o and p protons of the aPS. Likewise, integration of the aliphatic region C _al of the spectrum of the interpolymers includes aliphatic protons from both the aPS and the interpolymer.
Here, there were no definitive criteria for the analytical signals from both polymers. 6.6pp
The integral C _6.6 at the peak at m is from another aromatic signal and is believed to be due to the aPS homopolymer only (preferably the metaproton). (6.
Peak assignment for atactic polystyrene at 6 ppm (integral A _6.6
) Was performed in comparison to an approved sample of Styron ™ 680. This was a reasonable assumption since only very weak peaks were observed when the percentage of atactic polystyrene was very low. Thus, the phenyl protons of the copolymer do not contribute to this signal. Assuming this, the integral A _6.6 is the basis for a quantitative measurement of the aPS content.

The following equation was used to determine the degree of styrene incorporated in the ethylene / styrene interpolymer sample. (C _{phenyl) = C 7.1 + A 7.1 -} (1.5 × A 6.6) (C _{Aliphatic) = C al - (15 ×} A 6.6) s c = (C -phenyl) / 5 e _c = _(C Aliphatic - (3 × s _c )) / 4 E = e _c / (e _c + s _c ) S _c = s _c / (e _c + s _c ) Also, using the following equation, the ethylene and styrene of the interpolymer The mole fraction was calculated.

[0121]

(Equation 1) as well as

(Equation 2)

Here, s _c and e _c are the fractions of styrene and ethylene protons in the interpolymer, respectively, and S _c and E are the mole fractions of the styrene monomer and ethylene monomer in the interpolymer.

The weight fraction of aPS in the interpolymer was determined by the following equation.

[0124]

(Equation 3)

Further, the total styrene content was determined by quantitative Fourier transform infrared spectroscopy (FTIR).

Preparation of ESI Interpolymer Used in Inventive and Comparative Examples (1) Preparation of ESI1 The interpolymer was prepared in a 400 gallon (1514 liter) stirred semi-continuous batch reactor. The reaction mixture consisted of about 250 gallons (946 liters) of solvent and styrene. Here, the solvent contains a mixture of chlorohexane (85 wt%) and isopentane (15 wt%). Prior to the addition, the solvent, styrene and ethylene were purified to remove water and oxygen. The inhibitor in styrene was also removed. Inert materials were removed by purging the vessel with ethylene. Next, the pressure in the container was controlled to a predetermined pressure with ethylene. Hydrogen was added to adjust the molecular weight. The temperature of the water in the jacket of the container was varied to adjust the temperature of the container to a predetermined temperature. Before the polymerization, the vessel is heated to the desired operating temperature and the catalyst component titanium: (N-1.1-dimethylethyl) dimethyl (1- (1,2,3,4,5-eta) -2,3 , 4,5-Tetramethyl-2,4-cyclopentadien-1-yl) silaneaminate)) (2-) N) -dimethyl (CAS No. 135072-
62-7), tris (pentafluorophenyl) boron (CAS number 00110)
9-15-5), modified methylaluminoxane type 3A (CAS No. 1469)
05-79-5) was flow-controlled at a mole fraction of 1/3/5, respectively, and added to the container in combination. After the start, ethylene required to maintain the vessel pressure was added to the vessel to allow the polymerization to proceed. Hydrogen was added to the reactor headspace to maintain the molar ratio with respect to ethylene concentration. After operation, the catalyst flow was stopped, ethylene was removed from the vessel, and 1000 ppm of Irganox® 1010 antioxidant was added to the solution to separate the polymer from the solution. The resulting polymer was separated from the solution using a devolatilizing component extruder. The processing conditions used to prepare ESI1 are summarized in Table 1 and its properties are summarized in Table 2.

[0127]

[Table 1]

[0128]

[Table 2]

1) Preparation of ESI Nos. 2 to 4 ESI 2 to ESI 4 were prepared using geometrically suppressed catalysts, ie, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium (II) 1,
A substantially random ethylene / styrene copolymer prepared using 3-pentadiene and the following cocatalyst and polymerization procedure.

Preparation of Cocatalyst B (bis (hydrogenated tallow alkyl) methylamine) Methylcyclohexane (1200 ml) was charged into a 2 liter cylindrical flask. While stirring, add bis (hydrogenated tallow alkyl) methylamine (AR
MEEN ™ M2HT, 104 g, granulated) was added and stirred until completely dissolved. To the flask was added aqueous HCl (1M, 200 ml) and the mixture was stirred for 30 minutes. Immediately, a white precipitate formed. At the end of the 30 minutes, add LiB (C ₆ F ₅ ) ₄ .Et ₂ O.3Li to the flask.
Cl (Mw = 887.3; 177.4 g) was added. The solution began to turn milky. The flask was equipped with a 6 inch Vigreux column with distillation equipment on top and the mixture was heated (outer wall temperature 140 ° C.). A mixture of ether and methylcyclohexane was distilled off from the flask. The resulting two-phase solution was slightly hazy. The mixture was allowed to cool to room temperature and the contents were placed in a 4 liter separatory funnel. The aqueous layer was removed and discarded, and the organic layer was washed twice with H ₂ O, the aqueous layer was again discarded. The methylcyclohexane solution saturated with H ₂ O was determined to contain 0.48% by weight of diethyl ether (Et ₂ O).

The solution (600 ml) was placed in a 1 liter flask, sparged thoroughly with nitrogen, and transferred into a dry box. The solution was passed through a column (1 inch in diameter, 6 inches in height) containing a 13X molecular sieve. As a result, the Et ₂ O level becomes 0.4
It decreased from 8% by mass to 0.28% by mass. The material is then passed through a new 13X sieve (20
g) and stirred for 4 hours. Next, the Et ₂ O level was determined to be 0.19% by mass. Next, the mixture is stirred overnight, further Et ₂ O level of about 40ppm
Until further reduced. The mixture was filtered using a funnel equipped with a glass frit with a pore size of 10-15 μm to give a clear solution (the molecular sieve was rinsed with another dry methylcyclohexane). The concentration was determined to be 16.7 by weight analysis.
A value of% by weight was obtained.

[0132] polymerization 6 gallons (22.7 liters) with oil jacket autoclave continuously stirred tank-type reactor (CSTR) in a ESI2~ESI4 prepared. Light
Mixing was performed with a magnetically coupled stirrer having a ning A-320 impeller. The reactor was charged with liquid at 475 psig (3,275 kPa). The process flow entered at the bottom and exited at the top. Heat transfer oil was circulated through the jacket of the reactor to remove some of the heat of reaction. At the outlet of the reactor was a fine flow meter for measuring flow rate and solution density. All lines at the reactor outlet were 50 psi (344.7 k
Pa) Traced with steam and insulated.

A toluene solvent was fed to the reactor at 30 psig (207 kPa). The feed rate to the reactor was determined with a Micro-Motion mass flow meter. The supply was regulated by a variable speed diaphragm pump. On discharge of the solvent pump, a flush line for the catalyst injection line (1 lb / h (0.45 kg / h)) and a flush line for the reactor stirrer (0.75 lb / h (0.34 kg / h)) ) Was provided. These flow rates were determined with a differential pressure flow meter and controlled by manual adjustment of a microflow needle valve.

Uninhibited styrene monomer was added to the reactor at 30 psig (207 kPa).
Supplied with The feed to the reactor was determined with a Micro-Motion mass flow meter. The supply was regulated by a variable speed diaphragm pump. The styrene stream was mixed with the remaining solvent stream. 600 psig (4,137 k
Pa). Ethylene flow was measured as Mi just before the Research valve control flow.
It was determined by a cro-Motion mass flow meter. Hydrogen was pumped into the ethylene stream at the outlet of the ethylene control valve using a Brooks flow meter / controller.
The ethylene / hydrogen mixture was combined with the solvent / styrene stream at ambient temperature. The temperature upon entering the solvent / monomer reactor was reduced to about 5 ° C. by an exchanger using -5 ° C. glycol in the jacket. This stream entered the bottom of the reactor. The ternary catalyst system and its solvent flush also entered the reactor at its bottom, but through a different inlet from the monomer stream. The preparation of the catalyst component was performed in a glove box in an inert atmosphere. Put the diluted components in a nitrogen pad cylinder,
Then, it was loaded into the catalyst feed tank in the process area. From these feed tanks,
Pressure was applied to the catalyst with a piston pump, and the flow rate was determined with a Micro-Motion mass flow meter. These streams were combined with the catalyst flush solvent just before entering the reactor through one injection line.

The polymerization was stopped by adding a catalyst deactivator (water mixed with solvent) to the reactor product line after the fine flow meter measured the density of the solution. Other polymer additives can be added with the catalyst deactivator. A static mixer in the line provided a dispersion of the catalyst deactivator and additives in the reactor effluent. This stream is then fed to a post-reactor heater (postrea) to provide additional energy for the solvent removal flash.
ctor heater). This flush occurs as the effluent exits the post-reactor heater and the pressure is 475 psig (3,3) at the reactor pressure regulator.
275 kPa) to an absolute pressure of about 250 mm. The flashed polymer entered a hot oil jacketed devolatilizer. Approximately 85% of volatile content in devolatilizer
Was removed from the polymer. The volatiles exited the top of the devolatilizer. This stream was condensed by a glycol-jacketed exchanger and entered the vacuum pump inlet and was discharged to the glycol-jacketed solvent and styrene / ethylene separation vessel. Solvent and styrene were removed from the bottom of the vessel and ethylene was removed from the top. Ethylene flow was measured with a Micro-Motion mass flow meter and analyzed for composition. The ethylene conversion was calculated from the measured values for the released ethylene and the calculated values for the gas dissolved in the solvent / styrene stream. The polymer separated in the devolatilizer was pumped to a ZSK-30 devolatilizing vacuum extruder using a gear pump. The dried polymer was extruded from the extruder as a single strand. The strand was cooled as it was drawn into the aquarium. Excess water was blown off from the strand by air, and the strand was cut into pellets using a strand chopper.

Table 3 summarizes the various catalysts, cocatalysts and process conditions used to prepare each of the various ethylene styrene copolymers (ESI Nos. 2-4), and summarizes the properties of those copolymers in Table 4. Summarized in

[0137]

[Table 3]

[0138]

[Table 4]

Preparation of ESI5 Catalyst B Preparation of (1H-cyclopenta [1] phenanthren-2-yl) dimethyl (t- butylamide ) -silanetitanium 1,4-diphenylbutadiene 1) Lithium 1H-cyclopenta [1] phenanthrene- Preparation of 2-yl In a 250 ml round bottom flask containing 1.42 g (0.00657 mol) of 1H-cyclopenta [1] phenanthrene and 120 ml of benzene, 4.2 ml of a 1.60 M n-BuLi solution in mixed hexane was added. It was added dropwise. The solution was stirred overnight. The lithium salt is isolated by filtration, washed twice with 25 ml of benzene,
Then, it was dried under reduced pressure. The yield of isolated product was 1.426 g (97.7%
)Met. ¹ H-NMR analysis showed that the main isomer was substituted at the 2-position.

2) (1H-Cyclopenta [1] phenanthren-2-yl) dimethylchlorosi
Preparation of Run 4.16 g (0.0322 mol) of dimethyldichlorosilane (Me_Two SiCl _Two ) And 250 ml of tetrahydrofuran (THF)
In Lasco, 1.45 g (0.0064 mol) of lithium 1H-cyclopenta [1
] A THF solution of phenanthren-2-yl was added dropwise. The solution is stirred for about 16 hours.
Stirring was followed by removal of the solvent under reduced pressure leaving an oily solid. This oily solid
The extract is extracted with toluene and passed through diatomaceous earth filter aid (Celite ™).
And filtered, washed twice with toluene and dried under reduced pressure. Also isolated
The yield was 1.98 g (99.5%).

[0141] 3. Preparation of (1H-cyclopenta [1] phenanthren-2-yl) dimethyl (t-butylamino) silane 1.98 g (0.0064 mol) of (1H-cyclopenta [1] phenanthren-2-yl) dimethylchlorosilane and 250 ml 500 containing hexane
In a ml round bottom flask, 2.00 ml (0.0160 mol) in t-butylamine
Of t-butylamine was added. The reaction mixture was stirred for several days, then filtered through diatomaceous earth filter aid (Celite ™) and washed twice with hexane. The product was isolated by removing the residual solvent under reduced pressure. The yield of the isolate was 1.98 g (88.9%).

[0142] 4. Preparation of dilithio (1H-cyclopenta [1] phenanthren-2-yl) dimethyl (t-butylamido) silane 1.03 g (0.0030 mol) of (1H-cyclopenta [1] phenanthren-2-yl) dimethyl (t-butylamide) Butylamino) silane) and 120 ml of benzene in a 250 ml round bottom flask, 1.6 M t-BuL in mixed hexane.
3.90 ml of i solution was added dropwise. The reaction mixture was stirred for about 16 hours. filtration,
The product was isolated by two washes with benzene and drying under reduced pressure. The yield of the isolate was 1.08 g (100%).

[0143] 5. (1H-cyclopenta [1] phenanthren-2-yl) dimethyl (t-
TiCl butyramide) silane titanium dichloride Preparation 1.17 g (0.0030 mol) ₃ · 3THF and about 120ml
Was added to a 250 ml round bottom flask containing THF at a high dropping rate with a THF solution of 1.08 g of dithio (1H-cyclopenta [1] phenanthren-2-yl) dimethyl (t-butylamido) silane. Mix the mixture at about 20 ° C for 1.5
Stir for an hour, at the end of which 0.55 g (0.002 mol) of solid PdCl ₂ was added. After stirring for a further 1.5 hours, the THF was removed under vacuum and the residue was extracted with toluene, filtered and dried under reduced pressure to give an orange solid. The yield was 1.31 g (93.5%).

[0144] 6. Preparation of (1H-cyclopenta [1] phenanthren-2-yl) dimethyl (t-butylamido) silanetitanium 1,4-diphenylbutadiene (1H-cyclopenta [1] phenanthrene-2-yl) in about 80 ml of toluene
Yl) dimethyl (t-butylamido) silanetitanium dichloride (3.48 g, 0
. 0075 mol) and 1.551 g (0.0075 mol) of 1,4-diphenylbutadiene at 70 ° C. in 9.9 ml of 1.6 M n-BuLi (
0.0150 mol). The solution darkened immediately. The mixture was refluxed with increasing temperature and the mixture was maintained at that temperature for 2 hours. The mixture was cooled to -20 ° C and the volatiles were removed under reduced pressure. 60m of the residue
Slurry in 1 liter of mixed hexane at about 20 ° C. for about 16 hours. The mixture was allowed to cool to -25 C for 1 hour. The solid was collected on a glass frit by vacuum filtration and dried in vacuo. The dried solid was placed in a glass fiber thimble and the solid was continuously extracted with hexane using a Soxhlet extractor. After 6 hours, crystalline solids were observed in the boiling pot. About -2
Cool to 0 ° C., isolate from the cold mixture by filtration and dry under reduced pressure to give 1
. 62 g of a dark crystalline solid were obtained. The filtrate was discarded. The solids in the extractor were stirred and extraction continued with the addition of an appropriate amount of mixed hexane to give an additional 0.46 g of the desired product as a dark crystalline solid.

Polymerization of ESI5 ESI5 was prepared by continuously operating a loop reactor (36.8 gal, 139 L). An Ingersoll-Dresser twin-screw pump provided mixing. This reactor is full of liquid and at 475 psig (3,275 kPa), about 25
The operation was performed with a residence time of 2,000 minutes. Feed and catalyst / cocatalyst streams were fed into the inlet of the twin-screw pump via injectors and a Kenics steady mixer. This twin-screw pump discharges into a 2 ″ diameter line, which is a continuous two Ch
An emineer-Kenics Model 10-68 BEM multi-tube heat exchanger is provided. The tubes of these exchangers included twisted tape to enhance heat transfer. Upon exiting the last exchanger, the loop flow returns to the pump inlet via the injector and steady state mixer. The heat transfer oil is circulated through the jacket of the exchanger and controls the loop temperature probe located just before the first exchanger. The exit stream of the loop reactor exits between the two exchangers. The flow rate and solution density of this exit flow were measured by Micro Motion.

[0146] The feed solvent to this reactor was supplied from two different sources. Micr
o While measuring the flow rate with a Motion flow meter, 8480-SE
A fresh toluene stream from the Pulsesafeder diaphragm pump was used to provide a flush stream (20 lb / hr (9.1 kg / hr)) for the reactor seal. Five sets of 8480-5-E Pu with recycled solvents arranged in parallel
It was mixed with unblocked styrene monomer on the suction side of the lsafeder diaphragm pump. The five Pulsesafeder pumps supply solvent and styrene at 650 psig (4.583 kPa) to the reactor. Fresh styrene flow was measured by a Micro Motion flow meter, and total recycled solvent / styrene flow was measured by another Micro Motion flow meter. Ethylene was fed to the reactor at 687 psig (4,838 kPa). The ethylene flow was measured with a Micro-Motion mass flow meter. Hydrogen was introduced into the ethylene stream using a Brooks flow meter / controller at the outlet of the ethylene control valve.

This ethylene / hydrogen mixture was combined with a solvent / styrene stream at ambient temperature. The temperature of the entire feed stream as it entered the reactor loop was reduced to 2 ° C by an exchanger containing -10 ° C glycol on the jacket. The preparation of the three catalyst components was performed in three independent tanks: fresh solvent and concentrated catalyst / promoter premix were added and mixed in their corresponding operating tanks, and variable speed 680-S -A
The feed was fed to the reactor via an EN7 Pulsesafeder diaphragm pump. As described above, this three-component catalyst system enters the intake side of the twin-screw pump via the injector and the steady-state mixer and enters the reactor loop. The feed stream was also fed to the reactor loop via an injector and a stationary mixer downstream of the catalyst injection point, but upstream of the twin-screw pump inlet.

The polymerization was stopped by adding a catalyst terminator (Kill) (water mixed with solvent) to the reactor product line behind the Micro Motion flow meter for measuring solution density. A stationary mixer in this line is responsible for dispersing the catalyst terminator and additives in the reactor effluent. This stream then enters the reactor heater after providing additional energy for the solvent removal flash.
The flush discharges the post-reactor heater and the pressure at the reactor pressure control valve rises from 475 psig (3,275 kPa) to 450 mmH.
Occurs when dropping to an absolute pressure of g (60 kPa).

The flashed polymer enters the first of two hot oil jacketed devolatilizers. The volatiles flushed from this first devolatilizer are condensed in a glycol jacketed exchanger, passed through the inlet of a vacuum pump, and discharged to the solvent and styrene / ethylene separation tank. Solvent and styrene are removed from the bottom of this vessel as recycle solvent and at the same time ethylene is evacuated from the top. Ethylene flow is measured with a Micro Motion mass flow meter.
The sum of the measured ethylene exhaust and the calculated dissolved gas in the solvent / styrene stream was used to calculate ethylene conversion. The polymer and residual solvent separated in this devolatilizer were pumped by a gear pump to a second devolatilizer. By setting the pressure inside the second volatile matter remover to an absolute pressure of 5 mmHg (0.7 kPa),
The residual solvent was flushed. This solvent is condensed in a glycol heat exchanger,
Pumped with another vacuum pump and transported to waste tank for disposal. The dry polymer (<1000 ppm total volatiles) is pumped with a gear pump into a 6 hole die underwater pelletizer, pelletized, spin-dried and 1000 l
b.

The various catalysts, cocatalysts and process conditions used to prepare ESI5 are summarized in Table 5 and their properties are summarized in Table 6.

[0151]

[Table 5] ^* N / A = invalid^a Catalyst A is: (1H-cyclopenta [1] phenanthren-2-yl) dimethyl
(T-butylamide) -silane titanium 1,4-diphenylbutadiene). ^b Promoter B is tris (pentafluorophenyl) borane (CAS # 00110)
9-15-5).^c Akzo Nobel to MMAO-3A (CAS # 146905-79-
5) Modified methylaluminoxane available as

[0152]

[Table 6]

Test sections and characterization data for the interpolymers and their blends were made according to the following procedure.

Differential Scanning Calorimetry (DSC) The thermal transition temperature and the transition heat of the interpolymer were measured using Dupont DSC-2920. The sample was first heated to 200 ° C. to eliminate any prior thermal history. The heating and cooling curves were recorded at 10 ° C./min. Melting (from the second heating) and crystallization temperature were recorded from the respective endothermic and exothermic peak temperatures.

The compression molded sample was melted at 190 ° C. for 3 minutes and 20,000 at 190 ° C.
It was compression molded under a pressure of lb (9.072 kg) for an additional 2 minutes. Next, the molten material was quenched in a press equilibrated to room temperature.

Example 1 A sample of ESI # 1 (10.3% by weight atactic polystyrene) was
It was extruded at 190 ° C. from a ettfert Rheograph 2003 capillary rheometer through a 1 mm diameter, 20 L / D (length versus diameter) capillary. Using a 1000 bar pressure transducer, accurately measure the pressure drop,
Shear stress was determined. 0.46, 4.5, 46, 100, 214, 464, 10
Shear rates of 00 and 2150 s ^-1 were utilized. As the extrudates were extruded at each shear rate, the extrudates were collected and saved for subsequent testing. The corresponding viscosities and the corresponding shear stresses for each of the aforementioned shear rates are shown in Table 7:

[0157]

[Table 7]

A portion of each of these strands was then replaced with Rheometrics Solids
Used for Analyzer II. A single fragment gripper was used for all tests. The sample diameter was accurately measured with a micrometer, as was the sample length. The approximate diameter is 1.3 mm and the approximate length is 26 m
m. 10 rad / temperature sweep
At a frequency of s, the test was performed from -90 ° C. to 200 ° C. or a temperature at which the sample began to melt and thus the elastic modulus was so low that no force could be measured. This dynamic temperature test was performed at each test temperature at a stage of 5 degrees with an immersion time of 30 seconds. 0.005%
Was used. Using self-tension, the static force follows a dynamic force option of tension. The initial static force was 120 g and the self-tension sensitivity was 2 g. The static force was determined to be 9% stronger than the dynamic force, with a minimum static force of 2 g. Using self-distortion, 2
% Maximum applied strain, 2 g minimum allowable force, 200 g maximum allowable force and 20% strain adjustment.

The storage modulus plot for each extrudate showed an increase in storage modulus with increasing extrusion shear rate. This increase was evident from 4.6 s ^-1 to 46 s ^-1 . Samples between 100 and 464 s ^-1 exhibited similar behavior and high modulus. This suggested a significant change in the microstructure of these resins upon extrusion, as shown in FIG.

Examples 2-4 Samples of ESI # 2-4 were processed into blown films and compression molded plaques as follows. The results of the modulus as a function of Tg and temperature are summarized in Table 9.

Film Preparation Films were prepared by standard methods using a 1.25 inch Killion extruder with a 12/6/6 24: 1 L / D screw at a melt temperature of about 415 ° F. and a diameter of 3 mm. And a die gap of 40 mils. In all cases, the shear rates used to process the films ranged from 50 to 100 sec ^-1 . The extrusion conditions for the various samples are shown in Table 8. Summarized.

[0162]

[Table 8]

[0163]

[Table 9]

Example 5 A blend of 70% by weight of a substantially random interpolymer (ESI # 5) and 30% by weight of a styrene acrylonitrile copolymer was processed into cast films and compression molded plaques. Tumble blend the pellets of each compounded component and use a 2 inch diameter Killion with an L: D ratio of 30: 1.
It was injected into the hopper of the extruder. The processed sheet was formed by extruding through a coat hanger type flat die of about 360 mm (14 inches) width with a die gap of about 0.38 mm (15 mil (0.015 inches)). The film was collected at a rate of approximately 4.5 kg / hr (approximately 10 lb / hr) on polishing rolls and a take-off unit. The shear rate was estimated to be 100-200 / sec. The results of the modulus tests as a function of Tg and temperature are summarized in Table 10.

[0165]

[Table 10]

Examples 2-5 demonstrate that the individual formulation components were not compatible with each other as indicated by the presence of a recognizable Tg of the ethylene styrene interpolymer component under high and low shear rate melt processing conditions. This indicates that it was immiscible. These examples also show that the modulus for a work piece prepared under high shear rate conditions (ie, a film in this case) is similar to the sample prepared under low shear rate conditions (ie, plaque in this case). It also shows that it is relatively high. All examples show that at least 20 ° C. above the Tg (DSC) of the formulation, the modulus of the workpieces manufactured under high shear rate conditions is less than the elasticity of the workpieces manufactured under low shear rate conditions. It meets the criterion of being at least twice, preferably three times, more preferably ten times the rate.

[Brief description of the drawings]

FIG. 1 is a graph showing storage modulus as a function of shear rate for extruded extrudates at a temperature of Tg + 20 ° C.

[Procedure amendment]

[Submission date] May 23, 2001 (2001.5.23)

[Procedure amendment 2]

[Document name to be amended] Drawing

[Correction target item name] Fig. 1

[Correction method] Change

[Correction contents]

FIG.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // (C08L 23/00 (C08L 23/00 101: 00) C08L 101: 00) (C08L 25/00 ( C08L 25/00 C08L 101: 00) C08L 101: 00) (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE) , LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Invention Guest, Martin Jay. United States, Texas 77566, Lake Jackson, Greenbrier 106 (72) Inventor Van Volkenberg, William Earl. United States, Texas 77566, Lake Jackson, Sequoia 126 (72) Inventor Caljara, Telesapi. United States, Texas 77566, Lake Jackson, Mandevilla Court 56 F term (reference) 4F071 AA02 AA10 AA11 AA12 AA12X AA14 AA14X AA15 AA15X AA16 AA17 AA18 AA19 AA20X AA21X AA AA AA AA AA AA AA AA AA AA AA AA AA AA75 AA80 AA82 AA88 AF02 AF14 AF30 AH07 AH19 BB04 BB05 BB06 BC01 4J002 AB012 AC012 AC032 AC062 AC082 BB032 BB052 BB062 BB072 BB082 BB101 BB132 BB141 BB151 BB152 BB171 BC03 BC02BC032 BC032 BC032 BC032 BC032 CH072 CK022 CL012 CL032 CM042 FD010 FD020 FD170 GC00 GK01 GN00 4J100 AA02P AA03P AA04P AA16P AA17P AA19P AB02Q AB03Q AB04Q AB08Q AB09Q AB10Q AS15Q AU21Q CA04 DA04 DA42 FA10 JA28 JA57 JA57

Claims (40)

[Claims] 1. A workpiece produced by a high critical shear rate melt processing operation and comprising a blend of at least two polymers that are immiscible with each other, wherein the blend comprises: (A) at least one At least one vinyl or vinylidene aromatic monomer; or (ii) at least one aliphatic or cycloaliphatic. A polymer unit derived from vinyl or vinylidene monomer, or (iii) a combination of at least one aromatic vinyl or vinylidene monomer and at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer; and (2) ethylene And / or derived from at least one C _3-20 -α-olefin 55-95% by weight, based on the total weight of components A and B, of an interpolymer comprising: (B) immiscible with component A and the total weight of components A and B 5 to 45 for
A workpiece comprising at least one thermoplastic polymer present in an amount of weight percent and (C) said high critical shear rate is greater than about 30 sec- ¹ . 2. The processed article according to claim 1, wherein (I) said substantially random interpolymer, component A, comprises 65 to 92% by weight, based on the total weight of components A and B. And having an I _{2 of} greater than about 0.05 g / 10 min and a Mw / Mn of 1.5-20, and (1) from about 1 to about 65 mol% of polymer units, i) The following formula: (Wherein R ¹ is selected from the group of radicals consisting of hydrogen and alkyl radicals containing 3 or less carbon atoms, each R ² is hydrogen and 1 to 4 carbon atoms Is independently selected from the group of radicals consisting of alkyl radicals containing: and Ar is a phenyl group or halo, C _1-4 -alkyl,
And a phenyl group substituted with 1 to 5 substituents selected from the group consisting of C _1-4 -haloalkyl) and the vinyl or vinylidene aromatic monomer represented by the following general formula: Embedded image (Where A ¹ is sterically bulky and is an aliphatic or alicyclic substituent of up to 20 carbons, containing R ¹ , hydrogen and 1 to 4 carbon atoms Selected from the group consisting of alkyl radicals, wherein each R ² is hydrogen and 1
It is independently selected from the group of radicals consisting of alkyl radicals containing from 4 to 4 carbon atoms, or R ¹ and A ¹ together form a ring system. A) a polymer unit derived from the aliphatic or cycloaliphatic vinyl or vinylidene monomer represented by the formula: and (2) ethylene and / or propylene, 4-methyl-1-pentene, butene-1, hexene-1. Or 35-99 mol% of polymer units derived from said α-olefin containing at least one of octene-1; and (II) component B is based on the total weight of components A and B A) a styrenic homopolymer or copolymer, b) an ethylene and / or α-olefin homopolymer or copolymer, c) a thermoplastic olefin, d) an engineering thermoplastic, e. ) Styrenic block copolymer, f) elastomer, if Is g) vinyl halide or vinylidene halide polymer, comprise becomes one or more selected from, and (III) the high critical shear rate is 40～30,000 sec ^-1, processed products. 3. The processed article of claim 1, wherein (I) the substantially random interpolymer, Component A, comprises Component A and Component A.
And B in an amount of 70 to 92% by mass based on the total weight of the mixture, and 0.5 to 200 g / 1
0 minutes I_Two And Mw / Mn of 1.8 to 10, and (1) 2 to 50 mol% of polymer units, i) styrene, α-methylstyrene, ortho-, meta-, and para-
Butyl styrene, and those styrenes whose rings are halogenated.
Vinyl or vinylidene aromatic monomers, or ii) 5-ethylidene-2-norbornene or 1-vinylcyclohexene
Including cene, 3-vinylcyclohexene, and 4-vinylcyclohexene,
A polymer unit derived from an aliphatic or cycloaliphatic vinyl or vinylidene monomer, and (2) ethylene, or ethylene and propylene, 4-methyl-1-pentene
At least one of butene-1, butene-1, hexene-1 or octene-1
And (II) component B in an amount of from 8 to 30% by weight, based on the total weight of components A and B,
A) polystyrene, high impact polystyrene, styrene / acrylonitrile (
SAN) copolymer, styrene / maleic anhydride copolymer (SMA), polystyrene
/ Methyl methacrylate copolymer (S-MMA), acrylonitrile / butadi
Ene / styrene copolymer (ABS), syndiotactic polystyrene, eye
Sotactic polystyrene, b) ultra low density polyethylene (ULDPE), low density polyethylene (LDPE)
), Linear low density polyethylene (LLDPE), medium density polyethylene (MDPE)
, High density polyethylene (HDPE), polyolefin elastomer, polyethylene
An elastomer, a substantially linear ethylene / α-olefin interpolymer,
Uneven ethylene / C_Three ~ C₈ α-olefin interpolymer, propylene / C _Four ~ C₈ α-olefin interpolymer, isotactic polypropylene,
Ethylene vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), c) thermoplastic olefin, d) polymethyl methacrylate, nylon-6, nylon-66, polyaceta
, Rigid thermoplastic polyurethane, bisphenol A-polycarbonate, poly
Ethylene terephthalate, polybutylene terephthalate, e) styrene / ethylene-butene copolymer, styrene / ethylene-propylene
Styrene copolymer, styrene / ethylene-butene / styrene (SEBS) copolymer
-, Styrene / ethylene-propylene / styrene (SEPS) copolymer, f) polyisoprene, polybutadiene, natural rubber, ethylene / propylene rubber
Rubber, ethylene / propylene diene (EPDM) rubber, styrene / butadiene rubber
G) a homopolymer or copolymer of vinyl chloride or vinylidene chloride
And (III) wherein said high critical shear rate is between 50 and 5,000 seconds.^-1Is a processed product. 4. The method of claim 1, wherein (I) said substantially random interpolymer, component (A)
) Is present in an amount of 70 to 92 weight percent (based on the combined weight of component A and component B) and has an I _{2 of} 0.5 to 100 g / 10 min and a Mw / Mn of 2 to 5 And (1) the following: i) said vinyl or vinylidene aromatic monomer, including styrene, α-methyl styrene, ortho-, meta-, and para-methylstyrene; or ii) 5-ethylidene-2. From 5 to 50 mole percent of polymerized units obtained from said aliphatic or cycloaliphatic vinyl or vinylidene, including -norbornene or 1-vinylcyclo-hexene, 3-vinylcyclo-hexene, and 4-vinylcyclohexene; Or ethylene and polyethylene, 4-methyl-1-
At least one of pentene, butene-1, hexene-1 or octene-1 comprising from 50 to 95 mole percent of polymerized units obtained from said α-olefin;
Or (II) component (B) is present in an amount of 8 to 30 weight percent (based on the combined weight of component A and component B), and: a) polystyrene, high impact polystyrene , Syndiotactic polystyrene, isotactic polystyrene, and styrene / acrylonitrile (
B) ultra low density polyethylene (ULDPE), low density polyethylene (LDPE)
), Linear low density polyethylene (LLDPE), medium density polyethylene (MDPE)
), High density polyethylene (HDPE), substantially linear ethylene / α-olefin copolymer or heterogeneous ethylene / C ₃ -C ₈ α-olefin copolymer; c) ethylene / propylene rubber ( EPM), ethylene / propylene diene monomer terpolymer (EPDM), isotactic polypropylene; d) poly (methylene methacrylate), poly (amide), poly (carbonate); e) styrene / ethylene-butene copolymer Styrene / ethylene-propylene copolymer, styrene / ethylene-butene / styrene (SEBS) copolymer, styrene / ethylene-propylene / styrene (SEPS) copolymer; f) ethylene / propylene rubber, ethylene / propylene diene (EPD)
The processed article of claim 1, comprising one or more polymers comprising: M) rubber, styrene / butadiene rubber, thermoplastic polyurethane; g) a homopolymer or copolymer of vinyl chloride or vinylidene chloride. 5. The composition of claim 4, wherein component (A) 1 is styrene, component (A) 2 is ethylene, and component (B) is either polystyrene or high impact polystyrene. Processed goods. 6. Component (A) 1 is styrene, component (A) 2 is ethylene, and component (B) has a melt index of 0.1 to 100 g / 10 min.
I _2), it has a density of 0.855~0.975g / cm ^3, and low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE 5. The processed article of claim 4, comprising one or more of the following. 7. Component (A) 1 is styrene; and component (A) 2 is ethylene and propylene, 4-methyl-1-pentene, butene-1, hexene-.
5. The processed product of claim 4, wherein at least one of octene-1 or 1; and component (B) is polystyrene. 8. Component (A) 1 is styrene; and component (A) 2 is ethylene and propylene, 4-methyl-1-pentene, butene-1, hexene-.
1 or at least one of octene-1; and component (B) is 0.1 to
100g / 10 minutes melt index (I _2); 0.855~0.975g /
5. A material having a density of cm ³ and comprising one or more of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE). Processed product described in. 9. A film, sheet or as a component of a multilayer structure resulting from calendering blowing or (co) extrusion melt processing operations.
The processed product according to claim 1. 10. The processed article according to claim 2, in the form of a film, sheet or as a component of a multilayer structure resulting from calendering, blowing or (co) extrusion melt processing operations. 11. The processed article according to claim 3, in the form of a film, sheet or as a component of a multilayer structure resulting from calendering, blowing or (co) extrusion melt processing operations. 12. The processed article according to claim 4, in the form of a film, sheet or as a component of a multilayer structure resulting from calendering, blowing or (co) extrusion melt processing operations. 13. A processed article according to claim 5, in the form of a film, sheet or as a component of a multilayer structure resulting from calendering, blowing or (co) extrusion melt processing operations. 14. A processed article according to claim 6, in the form of a film, sheet or as a component of a multilayer structure resulting from calendering, blowing or (co) extrusion melt processing operations. 15. The processed article according to claim 7, which is in the form of a film, sheet or as a component of a multilayer structure resulting from calendering, blowing or (co) extrusion melt processing operations. 16. The processed article according to claim 8, in the form of a film, sheet or as a component of a multilayer structure resulting from calendering, blowing or (co) extrusion melt processing operations. 17. The processed article of claim 1 in the form of a foam or fiber. 18. The article of claim 2, wherein the article is in the form of a foam or a fiber. 19. The processed article according to claim 3, which is in the form of a foam or a fiber. 20. The article of claim 4, in the form of a foam or fiber. 21. The processed article according to claim 5, which is in the form of a foam or a fiber. 22. The processed article according to claim 6, which is in the form of a foam or a fiber. 23. The article of claim 7, in the form of a foam or fiber. 24. The article of claim 8, in the form of a foam or a fiber. 25. The workpiece of claim 1, in the form of a molded part resulting from an injection molding, profile extrusion, or blow molding melt processing operation. 26. The workpiece of claim 2 in the form of a molded part resulting from an injection molding, profile extrusion or blow molding melt processing operation. 27. The workpiece of claim 3, in the form of a molded part resulting from an injection molding, profile extrusion or blow molding melt processing operation. 28. The workpiece of claim 4, in the form of a molded part resulting from an injection molding, profile extrusion or blow molding melt processing operation. 29. The workpiece of claim 5, in the form of a molded part resulting from an injection molding, profile extrusion or blow molding melt processing operation. 30. The workpiece of claim 6, in the form of a molded part resulting from an injection molding, profile extrusion or blow molding melt processing operation. 31. The workpiece of claim 7, in the form of a molded part resulting from an injection molding, profile extrusion or blow molding melt processing operation. 32. The workpiece of claim 8, in the form of a molded part resulting from an injection molding, profile extrusion or blow molding melt processing operation. 33. The composition of claim 5, wherein said component B is atactic polystyrene formed by homopolymerization as an integral part of the production of said substantially random ethylene-styrene copolymer. Processed goods. 34. The processed article of claim 7, wherein component B is atactic polystyrene formed by homopolymerization as an integral part of the production of the substantially random ethylene / styrene copolymer. 35. The processed article according to claim 1, wherein component A and / or component B is crosslinked during or after the melt processing operation. 36. At least 20 ° C. above the Tg (DSC) of the blend, the modulus of the article produced under the high shear rate melt processing operation was produced under low shear rate conditions. The processed article of claim 1, wherein the processed article is at least about twice the modulus of the article. 37. At least 20 ° C. above the Tg (DSC) of the blend, the modulus of the article produced under the high shear rate melt processing operation was produced under low shear rate conditions. The processed article of claim 1, wherein the processed article is at least about three times the modulus of the article. 38. At least 20 ° C. above the Tg (DSC) of the blend, the modulus of the article produced under the high shear rate melt processing operation was produced under low shear rate conditions. The processed article of claim 1, wherein the processed article is at least about 10 times the modulus of the article. 39. In the form of an injection molded toy that can be painted.
A processed product according to claim 6. 40. In the form of an injection molded toy that can be painted.
A processed product according to claim 8.