U.S. patent application number 15/798017 was filed with the patent office on 2018-02-15 for polyolefin-based compositions, adhesives, and multi-layered structures thereof.
This patent application is currently assigned to EQUISTAR CHEMICALS, LP. The applicant listed for this patent is Basell Poliolefine Italia S.r.l., EQUISTAR CHEMICALS, LP. Invention is credited to MAGED G. BOTROS, ENRICO CONSTANTINI, CHARLES S. HOLLAND, CHUN D. LEE, ENRICO MASARATI.
Application Number | 20180044511 15/798017 |
Document ID | / |
Family ID | 54141491 |
Filed Date | 2018-02-15 |
United States Patent
Application |
20180044511 |
Kind Code |
A1 |
BOTROS; MAGED G. ; et
al. |
February 15, 2018 |
POLYOLEFIN-BASED COMPOSITIONS, ADHESIVES, AND MULTI-LAYERED
STRUCTURES THEREOF
Abstract
The present disclosure provides a polyolefin-based composition
suitable for use as adhesives and/or tie-layer adhesive
compositions as well as a multi-layered structure made from and/or
containing the polyolefin-based composition. The polyolefin-based
composition is made from and/or contains (a) a grafted polyolefin
composition, (b) a first polymer composition, (c) a
polypropylene-containing blend composition, and (d) optionally, an
additives composition having one or more additives.
Inventors: |
BOTROS; MAGED G.; (LIBERTY
TOWNSHIP, OH) ; CONSTANTINI; ENRICO; (FERRARA,
IT) ; HOLLAND; CHARLES S.; (SPRINGBORO, OH) ;
LEE; CHUN D.; (CINCINNATI, OH) ; MASARATI;
ENRICO; (FERRARA, IT) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
EQUISTAR CHEMICALS, LP
Basell Poliolefine Italia S.r.l. |
Houston
Milano |
TX |
US
IT |
|
|
Assignee: |
EQUISTAR CHEMICALS, LP
HOUSTON
TX
BASELL POLIOLEFINE ITALIA S.R.L.
MILANO
|
Family ID: |
54141491 |
Appl. No.: |
15/798017 |
Filed: |
October 30, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14645488 |
Mar 12, 2015 |
9803074 |
|
|
15798017 |
|
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61968825 |
Mar 21, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 23/10 20130101;
C08L 51/06 20130101; C08L 51/06 20130101; C08L 23/16 20130101; C08L
51/06 20130101; C08L 23/16 20130101; C08L 23/10 20130101; C08L
23/10 20130101; C08L 23/02 20130101; C08L 2203/16 20130101; C08L
23/10 20130101; C09J 123/14 20130101; C08L 23/16 20130101; C08L
23/14 20130101; C08L 23/14 20130101; C08L 51/06 20130101; C09J
123/14 20130101 |
International
Class: |
C08L 23/10 20060101
C08L023/10 |
Claims
1. A polyolefin-based composition comprising: (a) a grafted
polyolefin composition comprising a polyolefin grafted with an
unsaturated monomer; (b) a first polymer composition comprising a
first polyolefin polymer; (c) a polypropylene-containing blend
composition comprising a polypropylene-containing blend; and (d)
optionally, an additives composition having one or more
additives.
2. The polyolefin-based composition of claim 1 wherein the
polyolefin grafted with an unsaturated monomer is a polypropylene
grafted with maleic anhydride.
3. The polyolefin-based composition of claim 1 wherein the first
polyolefin polymer being selected from the group consisting of
polyethylene polymers and polypropylene polymers.
4. The polyolefin-based composition of claim 3 wherein the first
polyolefin polymer is a polypropylene impact random copolymer.
5. The polyolefin-based composition of claim 1 wherein the
polypropylene-containing blend comprises: (a) from about 10 to
about 90 weight percent a semicrystalline polypropylene and (b)
from about 10 to about 90 weight percent an ethylene propylene
rubber having a total content of ethylene-derived units in an
amount from about 20 to about 65 weight percent, based upon the
total weight of the ethylene propylene rubber.
6. The polyolefin-based composition of claim 5 wherein the
polypropylene-containing blend is a heterophasic propylene-based
copolymer selected from the group consisting of (a) an olefin
polymer composition consisting essentially of (i) from about 10 to
about 60 weight percent, based on the total weight of the olefin
polymer composition, of (A) a propylene homopolymer with isotactic
index in the range of about 90 to about 99 percent or (B) a
crystalline propylene copolymer with ethylene, a CH.sub.2.dbd.CHR
olefin where R is a 2-8 carbon alkyl radical, or combinations
thereof, containing from about 85 to about 99 weight percent of
propylene, based on the weight of the crystalline propylene
copolymer, and having an isotactic index in the range of about 85
to about 99 percent, (ii) from about 8 to about 40 weight percent,
based on the total weight of the olefin polymer composition, of a
semicrystalline, ethylene copolymer fraction containing ethylene
and propylene, having from about 50 to about 99 weight percent of
ethylene, based upon of the total weight of the semicrystalline,
ethylene copolymer, and being insoluble in xylene at room
temperature, and (iii) from about 30 to about 60 weight percent,
based on the total weight of the olefin polymer composition, of an
amorphous ethylene-propylene copolymer fraction which (A)
optionally, contains from about 1 to about 10 weight percent of a
diene, based on the total weight of the amorphous
ethylene-propylene copolymer fraction, (B) is soluble in xylene at
room temperature, and (C) contains about 40 to about 70 weight
percent of ethylene, based on the total weight of the amorphous
ethylene-propylene copolymer fraction, and (b) an olefin polymer
composition consisting essentially of (i) from about 10 to about 50
weight percent, based on the total weight of the olefin polymer
composition, of (A) a propylene homopolymer having an isotactic
index greater from about 80 to about 99 percent, or (B) a copolymer
selected from the group consisting of (1) propylene and ethylene,
(2) propylene, ethylene, and a CH.sub.2.dbd.CHR alpha-olefin where
R is a C.sub.2-8 straight or branched alkyl, and (3) propylene and
a CH.sub.2.dbd.CHR alpha-olefin where R is a C.sub.2-8 straight or
branched alkyl, wherein the copolymer contains from about 80 to
about 99 weight percent, based on the total weight of the
copolymer, of propylene, and has an isotactic index from about 80
to about 99 percent, (ii) from 0 to about 20 weight percent, based
on the total weight of the olefin polymer composition, of a
copolymer fraction containing ethylene insoluble in xylene at room
temperature, and (iii) from about 40 to about 80 weight percent,
based on the total weight of the olefin polymer composition, of a
copolymer fraction selected from the group consisting of a
copolymer of (A) ethylene and propylene, wherein the copolymer
contains from about 20 to about 40 weight percent, based upon the
total weight of the copolymer, of ethylene, (B) ethylene,
propylene, and a CH.sub.2.dbd.CHR alpha-olefin where R is a
C.sub.2-8 straight or branched alkyl, the alpha-olefin is present
in an amount from about 1 to about 10 weight percent, based upon
the total weight of the copolymer, and the total weight of the
ethylene and alpha-olefin together is from about 20 to about 40
weight percent, based upon the total weight of the copolymer, and
(C) ethylene and a CH.sub.2.dbd.CHR alpha-olefin where R is a
C.sub.2-8 straight or branched alkyl containing from about 20 to
about 40 weight percent of the alpha-olefin, based on the total
weight of the copolymer, which (1) optionally, contains from about
0.5 to about 10 weight percent, based on the total weight of the
copolymer, of a diene, (2) is soluble in xylene at room
temperature, and (3) has an intrinsic viscosity of from about 1.5
to about 10.0 dl/g, wherein the total of the (bii) and (biii)
fractions is from about 50 to about 90 weight percent, based on the
total olefin polymer composition and the weight ratio of
(bii)/(biii) being from about 0.1 to about 0.4.
7. An adhesive comprising a polyolefin-based composition
comprising: (a) from about 1 to about 30 weight percent of a
grafted polyolefin composition, relative to the total weight of the
polyolefin-based composition, comprising a polyolefin grafted with
an unsaturated monomer; (b) from about 10 to about 80 weight
percent of a first polymer composition, relative to the total
weight of the polyolefin-based composition, comprising a first
polyolefin polymer; (c) from about 10 to about 40 weight percent of
a polypropylene-containing blend composition, relative to the total
weight of the polyolefin-based composition, comprising a
polypropylene-containing blend; and (d) optionally, an additives
composition having one or more additives.
8. A multi-layered structure comprising a tie-layer adhesive
comprising a polyolefin-based composition comprising: (a) from
about 1 to about 30 weight percent of a grafted polyolefin
composition, relative to the total weight of the polyolefin-based
composition, comprising a polyolefin grafted with an unsaturated
monomer; (b) from about 10 to about 80 weight percent of a first
polymer composition, relative to the total weight of the
polyolefin-based composition, comprising a first polyolefin
polymer; (c) from about 10 to about 40 weight percent of a
polypropylene-containing blend composition, relative to the total
weight of the polyolefin-based composition, comprising a
polypropylene-containing blend; and (d) optionally, an additives
composition having one or more additives.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation Patent Application, which
claims benefit of priority to U.S. Non-Provisional application Ser.
No. 14/645,488, filed Mar. 12, 2015 and U.S. Provisional
Application No. 61/968,825, filed Mar. 21, 2014, the contents of
which are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
[0002] The present disclosure relates to polyolefin-based
compositions useful as adhesives and/or tie-layer adhesive
compositions for multi-layered structures. In particular, the
compositions are useful as adhesives to bind a barrier layer to a
dissimilar substrate.
DESCRIPTION OF RELATED ART
[0003] Multi-layer films and sheets are widely used for food
packaging applications. Depending on the intended application, the
number and arrangement of resin layers and the type of resins
employed will vary. Polyethylene resins are often included as one
of the layers for food contact and sealing properties.
Ethylene-vinyl alcohol (EVOH) copolymers and polyamides (nylons)
are widely used as oxygen and moisture barrier layers. Styrenic
polymers are commonly included as structural layers, especially for
thermoforming applications. However, adhering dissimilar resin
layers in multilayer films and sheets is always challenging.
[0004] Improved tie-layer adhesive compositions suitable for use in
making multi-layer structures with good adhesion and high clarity
are needed. A valuable approach would avoid expensive additives and
performance tradeoffs. Ideally, improved tie-layer adhesives could
be made using economical starting materials, commonly-used
equipment, and familiar techniques.
[0005] In addition to food packaging applications, adhesive
compositions may be used in the preparation of pipes, geomembranes,
containers, automotive parts, and wire and cable insulations and
jackets.
SUMMARY OF THE INVENTION
[0006] In general embodiments, the present disclosure provides a
polyolefin-based composition made from and/or containing a grafted
polyolefin composition, a first polymer composition, and a
polypropylene-containing blend composition. In some embodiments,
the polyolefin-based composition is further made from and/or to
contain an additives composition.
[0007] In particular embodiments, (a) the grafted polyolefin
composition is made from and/or contains a polyolefin grafted with
an unsaturated monomer, (b) the first polymer composition is made
from and/or contains a first polyolefin polymer, and (c) the
polypropylene-containing blend composition is made from and/or
contains a polypropylene-containing blend.
[0008] In particular embodiments, the polypropylene-containing
blend is made from and/or contains: [0009] (a) from about 10 to
about 90 weight percent a semicrystalline polypropylene and [0010]
(b) from about 10 to about 90 weight percent an ethylene propylene
rubber having a total content of ethylene-derived units in an
amount from about 20 to about 65 weight percent, based upon the
total weight of the ethylene propylene rubber.
[0011] In more particular embodiments, the ethylene propylene
rubber of the polypropylene-containing blend can be an interpolymer
further comprising one or more additional C.sub.4 to C.sub.10
.alpha.-olefins.
[0012] In some embodiments, the present disclosure provides an
adhesive made from and/or containing a polyolefin-based
composition. In particular embodiments, the polyolefin-based
composition is made from and/or contains [0013] (a) from about 1 to
about 30 weight percent of a grafted polyolefin composition,
relative to the total weight of the polyolefin-based composition,
comprising a polyolefin grafted with an unsaturated monomer, [0014]
(b) from about 10 to about 80 weight percent of a first polymer
composition, relative to the total weight of the polyolefin-based
composition, comprising a first polyolefin polymer, [0015] (c) from
about 10 to about 40 weight percent of a polypropylene-containing
blend composition, relative to the total weight of the
polyolefin-based composition, comprising a polypropylene-containing
blend, and [0016] (d) optionally, an additives composition having
one or more additives.
[0017] In some embodiments, the present disclosure provides a
multi-layered structure made from and/or containing a tie-layer
adhesive, wherein the tie-layer adhesive is made from and/or
contains a polyolefin-based composition.
DETAILED DESCRIPTION
[0018] The present invention now will be described more fully
hereinafter. However, this invention may be embodied in many
different forms and should not be construed as limited to the
embodiments set forth herein; rather, these embodiments are
provided so that this disclosure will satisfy applicable legal
requirements. As such, it will be apparent to those skilled in the
art that the embodiments may incorporate changes and modifications
without departing from the general scope of this invention. It is
intended to include all such modifications and alterations in so
far as they come within the scope of the appended claims or the
equivalents thereof.
[0019] As used in this specification and the claims, the singular
forms "a," "an," and "the" include plural referents unless the
context clearly dictates otherwise.
[0020] As used in this specification and the claims, the terms
"comprising," "containing," or "including" mean that at least the
named compound, element, material, particle, or method step, etc.,
is present in the composition, the article, or the method, but does
not exclude the presence of other compounds, elements, materials,
particles, or method steps, etc., even if the other such compounds,
elements, materials, particles, or method steps, etc., have the
same function as that which is named, unless expressly excluded in
the claims. It is also to be understood that the mention of one or
more method steps does not preclude the presence of additional
method steps before or after the combined recited steps or
intervening method steps between those steps expressly
identified.
[0021] Moreover, it is also to be understood that the lettering of
process steps or ingredients is a convenient means for identifying
discrete activities or ingredients and the recited lettering can be
arranged in any sequence, unless expressly indicated.
[0022] For the purpose of the present description and of the claims
which follow, except where otherwise indicated, all numbers
expressing amounts, quantities, percentages, and so forth, are to
be understood as being modified in all instances by the term
"about". Also, all ranges include any combination of the maximum
and minimum points disclosed and include any intermediate ranges
therein, which may or may not be specifically enumerated
herein.
[0023] Definitions
[0024] In the present description, the term "additives composition"
refers to a composition made from and/or containing at least one
additive.
[0025] In the present description, the terms "adhesive layer" and
"tie layer" mean a layer or material placed on one or more
substrates to promote the adhesion of that substrate to another
layer. Preferably, adhesive layers are positioned between two
layers of a multilayer structure to maintain the two layers in
position relative to each other and prevent undesirable
delamination.
[0026] In the present description, the term ".alpha.-olefin" or
"alpha-olefin" means an olefin of formula CH.sub.2.dbd.CH--R,
wherein R is a linear or branched alkyl containing from 1 to 10
carbon atoms. The .alpha.-olefin can be selected, for example,
from: propylene, 1-butene, 1-pentene, 1-hexene, 1-octene,
1-dodecene and the like.
[0027] In the present description, the term "amorphous" in
reference to a polyolefin means olefinic polymer having a
crystallinity from 0.001 to about 5 weight percent, based upon the
total weight of the olefinic polymer.
[0028] In the present description, the term "first polymer
composition" refers to a composition made from and/or containing at
least a first polyolefin polymer.
[0029] In the present description, the term "crystalline" in
reference to a polyolefin means olefinic polymer having having a
crystallinity of more than about 70 weight percent and less than
about 93 weight percent, based upon the total weight of the
olefinic polymer.
[0030] In the present description, the term "elastomer" refers to
polymer compounds having rubber-like properties and crystallinity
from 0.01 to about 10 percent, more preferably from about 0.01 to
about 5 percent, and most preferably about 0.01 percent.
[0031] In the present description, the term "grafted polyolefin"
refers to a polyolefin grafted with an unsaturated monomer. The
unsaturated monomer is typically an unsaturated polar monomer,
preferably containing one or more oxygen atoms. Preferred examples
of such unsaturated monomers will be given hereinafter.
[0032] In the present description, the term "grafted polyolefin
composition" refers to a composition made from and/or containing at
least one grafted polyolefin.
[0033] In the present description, the term "highly crystalline" in
reference to a polyolefin means olefinic polymer having a
crystallinity from about 93 to about 100 weight percent, based upon
the total weight of the olefinic polymer.
[0034] In the present description, the term "homopolymer" and
similar terms mean a polymer consisting solely or essentially all
of units derived from a single kind of monomer, e.g., ethylene
homopolymer is a polymer comprising solely or essentially all of
units derived from ethylene, propylene homopolymer is a polymer
comprising solely or essentially all of units derived from
propylene, and the like.
[0035] In the present description, the term "interpolymer" means a
polymer prepared by the polymerization of at least two types of
monomers or comonomers. It includes, but is not limited to,
copolymers (which usually refers to polymers prepared from two
different types of monomers or comonomers, although it is often
used interchangeably with "interpolymer" to refer to polymers made
from three or more different types of monomers or comonomers),
terpolymers (which usually refers to polymers prepared from three
different types of monomers or comonomers), tetrapolymers (which
usually refers to polymers prepared from four different types of
monomers or comonomers), and the like.
[0036] In the present description, the terms "monomer" and
"comonomer" are used interchangeably. The terms mean any compound
with a polymerizable moiety that is added to a reactor in order to
produce a polymer. In those instances in which a polymer is
described as comprising one or more monomers, e.g., a polymer
comprising propylene and ethylene, the polymer, of course,
comprises units derived from the monomers, e.g.,
--CH.sub.2--CH.sub.2--, and not the monomer itself, e.g.,
CH.sub.2.dbd.CH.sub.2.
[0037] In the present description, "plastic packaging" is of
particular concern and discussed throughout this description. To
facilitate that discussion, various polymer acronyms are used
herein; they are recited below. When referring to blends of
polymers, the description may use a colon (:) to indicate that the
components to the left and right of the colon are blended. When
referring to multilayer structure, the description may use a slash
"/" to indicate that components to the left and right of the slash
are in different layers and the relative position of components in
layers may be so indicated by use of the slash to indicate layer
boundaries.
[0038] Acronyms commonly employed herein include: [0039] EAA:
Copolymer of ethylene with acrylic acid [0040] EAO: Copolymers of
ethylene with at least one alpha-olefin [0041] EBA: Copolymer of
ethylene with butyl acrylate [0042] EEA: Copolymer of ethylene with
ethyl acrylate [0043] EMA: Copolymer of ethylene with methyl
acrylate [0044] EMAA: Copolymer of ethylene with methacrylic acid
[0045] EVA: Copolymer of ethylene with vinyl acetate [0046] EVOH: A
saponified or hydrolyzed copolymer of ethylene and vinyl acetate
[0047] PB: Polybutylene-1 (a butylene homopolymer and/or copolymer
of a major portion of butylene-1 with one or more alpha-olefins)
[0048] PE: Polyethylene (an ethylene homopolymer and/or copolymer
of a major portion of ethylene with one or more alpha-olefins)
[0049] PP: Polypropylene homopolymer or copolymer [0050] PET:
Polyethylene terephthalate [0051] PETG: Glycol-modified
polyethylene terephthalate [0052] PLA: Polylactic acid [0053]
PVDC:Polyvinylidene chloride (also includes copolymers of
vinylidene chloride, especially with vinyl chloride and/or methyl
acrylate (MA)).
[0054] In the present description, the term "polymer" means a
macromolecular compound prepared by polymerizing monomers of the
same or different type. The term "polymer" includes homopolymers,
copolymers, terpolymers, interpolymers, and so on.
[0055] In the present description, the term "polyolefin" is used
herein broadly to include polymers such as polyethylene,
ethylene-alpha olefin copolymers (EAO), polypropylene, polybutene,
and ethylene copolymers having a majority amount by weight of
ethylene polymerized with a lesser amount of a comonomer such as
vinyl acetate, and other polymeric resins within the "olefin"
family classification.
[0056] Polyolefins may be made by a variety of processes well known
in the art including batch and continuous processes using single,
staged or sequential reactors, slurry, solution, and fluidized bed
processes and one or more catalysts including for example,
heterogeneous and homogeneous systems and Ziegler, Phillips,
metallocene, single-site, and constrained geometry catalysts to
produce polymers having different combinations of properties. Such
polymers may be highly branched or substantially linear and the
branching, dispersity, and average molecular weight may vary
depending upon the parameters and processes chosen for their
manufacture in accordance with the teachings of the polymer
arts.
[0057] In the present description and with regard to polyethylene,
the polymer can be classified as linear low-density polyethylene
(LLDPE) having a density from about 0.910 to about 0.925 grams per
cubic centimeter, low-density polyethylene (LDPE) also having a
density from about 0.910 to about 0.925 grams per cubic centimeter,
medium-density polyethylene (HDPE) having a density from about
0.926 to about 0.940 grams per cubic centimeter, and high-density
polyethylene (HDPE) having a density from about 0.941 to about
0.970 grams per cubic centimeter.
[0058] In the present description, the term
"polypropylene-containing blend composition" refers to a
composition made from and/or containing at least one
polypropylene-containing blend.
[0059] In the present description, the term "room temperature"
refers to a temperature around 25 degrees Celsius.
[0060] In the present description, the term "semiamorphous" in
reference to a polyolefin means olefinic polymer having a
crystallinity of from about 5 to about 30 weight percent, based
upon the total weight of the olefinic polymer.
[0061] In the present description, the term "semicrystalline" in
reference to a polyolefin means olefinic polymer having a
crystallinity of more than about 30 weight percent and less than
about 70 weight percent, based upon the total weight of the
olefinic polymer.
[0062] In the present description, the term "thermoplastic polymer"
means a polymer that softens when exposed to heat and returns to
its original condition when cooled to room temperature.
[0063] Testing
[0064] ASTM D 1238 is entitled "Test Method for Melt Flow Rates of
Thermoplastics by Extrusion Plastometer." The term "ASTM D 1238" as
used herein refers to the standard test method for determining melt
flow rates of thermoplastics by extrusion plastometer. In general,
this test method covers the determination of the rate of extrusion
of molten thermoplastic resins using an extrusion plastometer.
After a specified preheating time, resin is extruded through a die
with a specified length and orifice diameter under prescribed
conditions of temperature, load, and piston position in the barrel.
This test method was approved on Feb. 1, 2012 and published March
2012, the contents of which are incorporated herein by reference in
its entirety. For the referenced ASTM standards, visit the ASTM
website, www.astm.org, or contact ASTM Customer Service at
service@astm.org.
[0065] ASTM D 1876 is entitled "Standard Test Method for Peel
Resistance of Adhesives (T-Peel Test)." The term "ASTM D 1876" as
used herein refers to a test method for determining the relative
peel resistance of adhesive bonds between flexible adherends by
means of a T-type specimen. The accuracy of the results of strength
tests of adhesive bonds will depend on the conditions under which
the bonding process is carried out. This test method was approved
on Oct. 10, 2001 and published December 2001, the contents of which
are incorporated herein by reference in its entirety. For the
referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org.
[0066] The force required to separate the layers apart in a T-peel
configuration at 25.4 cm (10 inches)/min is measured using an
INSTRON.TM. tensile tester. The average adhesion of five specimens
is recorded as the peel strength in kg/cm (1b/in).
[0067] Incorporated Unsaturated Monomer (Weight Percent): The
amount of the unsaturated monomer incorporated into the grafted
polyolefin can be measured by wet chemical methods (titration,
etc.) or more preferably, by Fourier transform infrared
spectroscopy (FTIR), according to methods that are well known in
the art.
[0068] ISO 1133 is entitled "Plastics--Determination of the Melt
Mass-Flow Rate (MFR) and the Melt Volume-Flow Rate (MVR) of
Thermoplastics." The term "ISO 1133" as used herein refers to two
procedures for the determination of the melt mass-flow rate (MFR)
and the melt volume-flow rate (MVR) of thermoplastic materials
under specified conditions of temperature and load. Procedure A is
a mass-measurement method. Procedure B is a
displacement-measurement method. These procedures were published as
the Fourth Edition in 2005, the contents of which are incorporated
herein by reference in its entirety.
[0069] ISO 1183-2 is entitled "Plastics--Methods for Determining
the Density of Non-Cellular Plastics--Part 2: Density Gradient
Column Method." The term "ISO 1183" as used herein refers to a
gradient column method for the determination of the density of
non-cellular moulded or extruded plastics in void-free form.
Density gradient columns are columns containing a mixture of two
liquids, the density in the column increasing uniformly from top to
bottom. These procedures were published in 2004, the contents of
which are incorporated herein by reference in its entirety.
[0070] In general embodiments, the present disclosure provides a
polyolefin-based composition made from and/or containing a grafted
polyolefin composition, a first polymer composition, and a
polypropylene-containing blend composition.
[0071] In particular embodiments, (a) the grafted polyolefin
composition is made from and/or contains a polyolefin grafted with
an unsaturated monomer, (b) the first polymer composition is made
from and/or contains a first polyolefin polymer, and (c) the
polypropylene-containing blend composition is made from and/or
contains a polypropylene-containing blend.
[0072] Preferably, the grafted polyolefin composition is present in
an amount from about 1 to about 30 weight percent, relative to the
total weight of the polyolefin-based composition. More preferably,
the grafted polyolefin composition is present in an amount from
about 10 to about 20 weight percent.
[0073] Suitable grafted polyolefins for use in making the grafted
polyolefin composition include grafted polyolefins prepared by
reacting polyolefins with unsaturated monomers at elevated
temperatures, with or without a free-radical initiator, under
conditions effective to graft unsaturated monomer units onto the
polyolefin backbone. Preferably, the grafting reaction occurs under
an inert gas, such as nitrogen.
[0074] Polyolefins suitable for making the grafted polyolefins
include high density polyethylenes (HDPE), medium density
polyethylenes (MDPE), low density polyethylenes (LDPE), linear low
density polyethylenes (LLDPE), polypropylenes, ethylene-propylene
copolymers, impact-modified polypropylenes, and the like, and
blends thereof.
[0075] Suitable unsaturated monomers are also well known. Preferred
unsaturated monomers are ethylenically unsaturated carboxylic acids
and acid derivatives, particularly esters, anhydrides, acid salts,
and the like. Examples include acrylic acid, methacrylic acid,
maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic
anhydride, tetrahydrophthalic anhydride,
norborn-5-ene-2,3-dicarboxylic acid anhydride, nadic anhydride,
himic anhydride, and the like, and mixtures thereof. Maleic
anhydride is particularly preferred. Other suitable unsaturated
monomers are described in U.S. Pat. No. 6,385,777 and U.S. Patent
Application Publication No. 2007/0054142, the teachings of which
are incorporated herein by reference.
[0076] The relative amounts of polyolefin and unsaturated monomer
used will vary and depend on factors such as the nature of the
polyolefin and the unsaturated monomer, the desired tie-layer
properties, the reaction conditions, the available equipment, and
other factors. Usually, the unsaturated monomer is used in an
amount within the range of about 0.1 to about 15 weight percent,
based on the total weight of the grafted polyolefin, preferably
from about 0.5 to about 6 weight percent, and most preferably from
about 1 to about 3 weight percent.
[0077] Grafting of the unsaturated monomer(s) to the polyolefin is
accomplished according to known procedures, generally by heating a
mixture of the unsaturated monomer(s) and the polyolefin. Most
typically, the grafted polyolefin is prepared by melt blending the
polyolefin with the unsaturated monomer in a shear-imparting
extruder/reactor. Twin screw extruders such as those marketed by
Coperion under the designations ZSK-53, ZSK-83, ZSK-90 and ZSK-92
are especially useful for performing the grafting. A free-radical
initiator such as an organic peroxide can be employed but is not
necessary.
[0078] Grafting of the unsaturated monomer to the polyolefin is
performed at elevated temperatures, preferably within the range of
180 degrees Celsius to 400 degrees Celsius, more preferably from
200 degrees Celsius to 375 degrees Celsius, and most preferably
from 230 degrees Celsius to 350 degrees Celsius. Shear rates in the
extruder can vary over a wide range, preferably from 30 to 1000
rpm, more preferably from 100 to 600 rpm, and most preferably from
200 to 400 rpm.
[0079] For such processes, the peroxide catalyst can be introduced
into the molten propylene polymer before or after introduction of
the grafting monomer. Because substantial amounts of solvent are to
be avoided, the catalyst and grafting monomer are preferably added
in neat form to the reactor. The monomer typically constitutes from
about 1 to about 5 weight percent, relative to the total weight of
the reaction mixture.
[0080] A temperature profile wherein the temperature is gradually
increased over the length of the extruder/reactor up to a maximum
in the grafting reaction zone and then decreases toward the reactor
exit is preferred. Temperature attenuation is desirable for
pelletizing purposes. The maximum temperature within the reactor
should be such that significant vaporization losses and/or
premature decomposition of peroxide catalyst is avoided. For
example, with di-t-butyl peroxide and
2,5-dimethyl-2,5-di-(t-butylperoxy) hexane, maximum temperatures
within the reactor should be maintained at or below about 260
degrees Celsius.
[0081] In contrast, the so-called "thermal" grafting processes
which do not include catalysts, may use temperatures up to about
380 degrees Celsius. The maximum useful temperature varies with the
selection of catalyst.
[0082] Examples of useful peroxide catalysts include:
1,1-bis(tert-butylperoxy)cyclohexane;
n-butyl-4,4-bis(tert-butylperoxyvalerate);
1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane;
2,2-bis(tert-butylperoxy)butane; dicumylperoxide;
tert-butylcumylperoxide; .alpha.,
.alpha.'-bis(tert-butylperoxypreoxy-isopropyl) benzene;
di-tert-butylperoxide (DTBP); 2,5-dimethyl-2,5-di(tert-butylperoxy)
hexane; and the like.
[0083] Additional details regarding the grafting procedure and
reactor extruder are provided in U.S. Pat. No. 5,367,022 which is
incorporated herein by reference in its entirety.
[0084] The functionalized propylene polymer component, obtained in
accordance with the above-described grafting procedures, is a
propylene-ethylene impact copolymer made from and/or containing
crystalline (propylene homopolymer) and amorphous or rubber
(ethylene-propylene copolymer) phases. Ethylene contents of the
impact copolymers generally range from about 5 to about 30 weight
percent, based upon the total weight of the impact copolymers,
preferably from about 6 to about 25 weight percent. Thermoplastic
polyolefins (TPOs) and thermoplastic elastomers (TPEs) are also
encompassed within the above definition.
[0085] Preferably, the propylene-ethylene impact copolymer is a
reactor-made intimate mixture of propylene homopolymer and
ethylene-propylene copolymer produced in a gas-phase, stirred-bed,
multi-stage polymerization process. Most typically, the mixture is
produced in two reactors connected in series using high activity
supported transition metal catalysts. The propylene homopolymer is
produced in the first reactor and then introduced to the second
reactor where additional propylene, ethylene, hydrogen and
catalyst, as necessary, are metered to produce the intimate
physical mixtures which comprise the propylene-ethylene impact
copolymers utilized for the invention. Gas phase polymerizations of
this type are described J. F. Ross & W. A. Bowles, "An Improved
Gas-Phase Polypropylene Process," 24 Ind. Eng. Chem. Prod. Res.
Dev. pp. 149-54 (1985), which is incorporated herein by reference
in its entirety.
[0086] Functionalized propylene-ethylene impact copolymers having
high graft monomer contents and relatively low MFRs can be obtained
when high rubber content impact copolymers are grafted with maleic
anhydride. More specifically, these impact copolymers have rubber
contents from about 20 to about 35 weight percent, based upon the
total weight of the impact copolymer and MWDs from about 4 to about
10. More preferably, the propylene-ethylene impact copolymers have
rubber contents from about 20 to about 30 weight percent, based
upon the total weight of the impact copolymer, and MWDs from about
4 to about 8.
[0087] Most preferably, the polyolefin grafted with an unsaturated
monomer is a polypropylene grafted with maleic anhydride.
[0088] Preferably, the first polymer composition is present in an
amount from about 10 to about 80 weight percent, relative to the
total weight of the polyolefin-based composition. More preferably,
the first polymer composition is present in an amount from about 50
to about 70 weight percent.
[0089] Suitable first polymers for use in making the first polymer
composition include a first polyolefin polymer made from and/or
containing one or more C.sub.2 to C.sub.10 .alpha.-olefin monomers.
Preferably, the first polyolefin polymer is selected from the group
consisting of polyethylenes, polypropylenes, polybutenes, the like,
and mixtures thereof. More preferably, the first polyolefin polymer
is selected from the group consisting of polyethylene polymers and
polypropylene polymers.
[0090] Suitable polyethylenes include ethylene homopolymers,
copolymers of ethylene with at least one C.sub.3 to C.sub.10
.alpha.-olefin, the like, and mixtures thereof. They include HDPE,
LDPE, MDPE, LLDPE, the like, and mixtures thereof. Suitable
polyethylene has a melt index (MI.sub.2) preferably from about 0.01
to about 150 grams per 10 minutes, more preferably from about 0.01
to about 10 grams per 10 minutes, and most preferably from about
0.01 to about 5 grams per 10 minutes.
[0091] When the first polyolefin polymer is a polyethylene, the
grafted polyolefin is preferably made from a polyethylene. More
preferably, the grafted polyolefin is made from HDPE or LLDPE, and
even more preferably, HDPE.
[0092] Suitable polypropylenes for use as a first polyolefin
polymer include amorphous polypropylene, semicrystalline
polypropylene, the like, and mixtures thereof. Preferably, the
semicrystalline polypropylene is selected from the group consisting
of propylene homopolymers, copolymers of propylene with at least
one other C.sub.2 to C.sub.10 .alpha.-olefin, the like, and
mixtures thereof. Copolymers of propylene include random copolymers
and impact copolymers. Preferred .alpha.-olefins for such
copolymers include ethylene, 1-butene, 1-pentene, 1-hexene,
methyl-1-butenes, methyl-1-pentenes, 1-octene, 1-decene, the like,
and mixtures thereof. Preferably, the semicrystalline polypropylene
has a melt flow rate from about 0.001 to about 500 grams per 10
minutes. Preferably, the semicrystalline polypropylene has a
density from about 0.897 to about 0.925 grams per cubic centimeter
and a weight average molecular weight (Mw) within the range of
85,000 to 900,000.
[0093] Suitable polypropylenes are available commercially,
including LyondellBasell PRO-FAX.TM. SR257M random copolymer
polypropylene, having ethylene as the comonomer, a specific gravity
of 0.90, a melt flow rate of 2.0 grams per 10 minutes, and a
polydispersity index of 3.3.
[0094] When the first polyolefin polymer is a polypropylene, the
grafted polyolefin is preferably made from a polypropylene. More
preferably, the grafted polyolefin is made from random copolymer or
an impact copolymer, and even more preferably, a impact
copolymer.
[0095] Suitable polybutene includes homopolymers of 1-butene,
copolymers of 1-butene with at least one other C.sub.2 to C.sub.10
.alpha.-olefin, the like, and mixtures thereof. Preferred
.alpha.-olefins for such copolymers include ethylene, propylene,
1-pentene, 1-hexene, methyl-1-butenes, methyl-1-pentenes, 1-octene,
1-decene, the like, and mixtures thereof. The polybutene has a melt
index preferably from about 0.01 to about 1000 grams per 10
minutes, more preferably from about 0.1 dg/min to about 750 grams
per 10 minutes. Methods for producing polybutene are known. For
instance, see U.S. Pat. No. 6,306,996, which is herein incorporated
by reference in its entirety.
[0096] Preferably, the polypropylene-containing blend composition
is present in an amount from about 10 to about 40 weight percent,
relative to the total weight of the polyolefin-based composition.
More preferably, the polypropylene-containing blend composition is
present in an amount from about 20 to about 30 weight percent.
[0097] Suitable polypropylene-containing blends are made from
and/or contain: [0098] (a) from about 10 to about 90 weight percent
a semicrystalline polypropylene and [0099] (b) from about 10 to
about 90 weight percent an ethylene propylene rubber having a total
content of ethylene-derived units in an amount from about 20 to
about 65 weight percent, based upon the total weight of the
ethylene propylene rubber.
[0100] The ethylene propylene rubber of the
polypropylene-containing blend can be an interpolymer further
comprising one or more additional C.sub.4 to C.sub.10
.alpha.-olefins.
[0101] Preferably, the polypropylene-containing blend is made from
and/or contains a heterophasic propylene-based copolymer, prepared
by sequential polymerization in at least two stages and in the
presence of Ziegler-Natta catalyst supported on a magnesium halide
in active form, selected from the group consisting of [0102] (a) an
olefin polymer composition consisting essentially of [0103] (i)
from about 10 to about 60 weight percent, based on the total weight
of the olefin polymer composition, preferably from about 20 to
about 50 weight percent, of [0104] (A) a propylene homopolymer with
isotactic index in the range of about 90 to about 99 percent or
[0105] (B) a crystalline propylene copolymer with ethylene, a
CH.sub.2.dbd.CHR olefin where R is a 2-8 carbon alkyl radical, or
combinations thereof, containing from about 85 to about 99 weight
percent of propylene, based on the weight of the crystalline
propylene copolymer, and having an isotactic index in the range of
about 85 to about 99 percent, [0106] (ii) from about 8 to about 40
weight percent, based on the total weight of the olefin polymer
composition, of a semicrystalline, ethylene copolymer fraction
containing ethylene and propylene, having from about 50 to about 99
weight percent of ethylene, based upon of the total weight of the
semicrystalline, ethylene copolymer, and being insoluble in xylene
at room temperature, and [0107] (iii) from about 30 to about 60
weight percent, based on the total weight of the olefin polymer
composition, of an amorphous ethylene-propylene copolymer fraction,
preferably from about 30 to about 50 weight percent, which [0108]
(A) optionally, contains from about 1 to about 10 weight percent of
a diene, based on the total weight of the amorphous
ethylene-propylene copolymer fraction, more preferably from about 1
to about 5 weight percent, [0109] (B) is soluble in xylene at room
temperature, and [0110] (C) contains about 40 to about 70 weight
percent of ethylene, based on the total weight of the amorphous
ethylene-propylene copolymer fraction, and [0111] (b) an olefin
polymer composition consisting essentially of [0112] (i) from about
10 to about 50 weight percent, based on the total weight of the
olefin polymer composition, preferably from about 10 to about 40
weight percent, and most preferably from about 20 to about 35
weight percent, of [0113] (A) a propylene homopolymer having an
isotactic index greater from about 80 to about 99 percent,
preferably from about 85 to about 99 percent, or [0114] (B) a
copolymer selected from the group consisting of [0115] (1)
propylene and ethylene, [0116] (2) propylene, ethylene, and a
CH.sub.2.dbd.CHR alpha-olefin where R is a C.sub.2-8 straight or
branched alkyl, and [0117] (3) propylene and a CH.sub.2.dbd.CHR
alpha-olefin where R is a C.sub.2-8 straight or branched alkyl,
wherein the copolymer contains from about 80 to about 99 weight
percent, based on the total weight of the copolymer, of propylene,
preferably from about 85 to about 99 weight percent, and most
preferably from about 90 to about 99 weight percent, and has an
isotactic index from about 80 to about 99 percent, preferably from
about 85 to about 99 percent, [0118] (ii) from 0 to about 20 weight
percent, based on the total weight of the olefin polymer
composition, of a copolymer fraction containing ethylene insoluble
in xylene at room temperature, preferably from about 5 to about 20
weight percent, more preferably from about 7 to about 15 weight
percent, and [0119] (iii) from about 40 to about 80 weight percent,
based on the total weight of the olefin polymer composition, of a
copolymer fraction, preferably from about 50 to about 70 weight
percent, selected from the group consisting of a copolymer of
[0120] (A) ethylene and propylene, wherein the copolymer contains
from about 20 to about 40 weight percent, based upon the total
weight of the copolymer, of ethylene, preferably from about 25 to
about 38 weight percent, [0121] (B) ethylene, propylene, and a
CH.sub.2.dbd.CHR alpha-olefin where R is a C.sub.2-8 straight or
branched alkyl, the alpha-olefin is present in an amount from about
1 to about 10 weight percent, based upon the total weight of the
copolymer, and the total weight of the ethylene and alpha-olefin
together is from about 20 to about 40 weight percent, based upon
the total weight of the copolymer, preferably from about 25 to
about 38 weight percent, and [0122] (C) ethylene and a
CH.sub.2.dbd.CHR alpha-olefin where R is a C.sub.2-8 straight or
branched alkyl containing from about 20 to about 40 weight percent
of the alpha-olefin, based on the total weight of the copolymer,
which [0123] (1) optionally, contains from about 0.5 to about 10
weight percent, based on the total weight of the copolymer, of a
diene, [0124] (2) is soluble in xylene at room temperature, and
[0125] (3) has an intrinsic viscosity of from about 1.5 to about
10.0 dl/g, preferably from about 1.5 to about 5.0 dl/g; more
preferably from about 1.5 to about 4.0 dl/g, most preferably from
about 1.7 to about 3.0 dl/g, [0126] wherein the total of the (bii)
and (biii) fractions is from about 50 to about 90 weight percent,
based on the total olefin polymer composition, preferably from
about 65 to about 80 weight percent, and the weight ratio of
(bii)/(biii) being from about 0.1 to about 0.4, preferably from
about 0.1 to about 0.3.
[0127] Preferably, component (b)(ii) is selected from the group
consisting of [0128] (a) ethylene and propylene containing over
about 55 weight percent, based on the total weight of the
copolymer, of ethylene, preferably from about 55 weight percent to
about 99 weight percent, [0129] (b) ethylene, propylene, and a
CH.sub.2.dbd.CHR alpha-olefin where R is a C.sub.2-8 straight or
branched alkyl, containing from about 1 weight percent to about 10
weight percent, based on the total weight of the copolymer, of the
alpha-olefin and from over about 55 weight percent to about 98
weight percent, based on the total weight of the copolymer, of the
sum of the ethylene and alpha-olefin components, preferably from
about 80 weight percent to about 95 weight percent, and [0130] (c)
ethylene and a CH.sub.2.dbd.CHR alpha-olefin where R is a C.sub.2-8
straight or branched alkyl, containing from over about 55 weight
percent to about 98 weight percent, based on the total weight of
the copolymer, of the alpha-olefin, preferably from about 80 weight
percent to about 95 weight percent.
[0131] The polymerization process, which can be continuous or
batch, is carried out following known techniques and operating in
liquid phase, in the presence or not of inert diluent, or in gas
phase, or by mixed liquid-gas techniques.
[0132] The stereospecific polymerization catalysts comprise the
product of the reaction between: 1) a solid component, containing a
titanium compound and an electron-donor compound (internal donor)
supported on magnesium dihalide (preferably chloride); 2) an
aluminum alkyl compound (cocatalyst); and, optionally, 3) an
electron-donor compound (external donor).
[0133] Suitable polypropylene-containing blends are available
commercially, including LyondellBasell's polymers under the
tradenames CATALLOY.TM., ADFLEX.TM., HIFAX.TM., and
SOFTELL.TM..
[0134] In some embodiments, the polyolefin-based composition is
further made from and/or to contain an additives composition.
Suitable examples include adhesion promoters, elastomeric polymers,
UV inhibitors, antioxidants, thermal stabilizers, and the like. For
some examples of these, see U.S. Pat. No. 6,835,777, which is
incorporated herein by reference in its entirety.
[0135] In some embodiments, the present disclosure provides an
adhesive made from and/or containing a polyolefin-based
composition. In particular embodiments, the polyolefin-based
composition is made from and/or contains [0136] (a) from about 1 to
about 30 weight percent of a grafted polyolefin composition,
relative to the total weight of the polyolefin-based composition,
comprising a polyolefin grafted with an unsaturated monomer, [0137]
(b) from about 10 to about 80 weight percent of a first polymer
composition, relative to the total weight of the polyolefin-based
composition, comprising a first polyolefin polymer, [0138] (c) from
about 10 to about 40 weight percent of a polypropylene-containing
blend composition, relative to the total weight of the
polyolefin-based composition, comprising a polypropylene-containing
blend, and [0139] (d) optionally, an additives composition having
one or more additives.
[0140] The adhesives are particularly useful as a tie-layer for
making multi-layer structures.
[0141] Tie-layer adhesives can be used in numerous multi-layer
constructions, including structures having five, seven, nine, or
more layers.
[0142] In some embodiments, the present disclosure provides a
multi-layered structure made from and/or containing a tie-layer
adhesive, wherein the tie-layer adhesive is made from and/or
contains a polyolefin-based composition. A multi-layer structure
can can be made by many methods or processes, including by
coextrusion, coating, and other laminating processes.
[0143] Multi-layer structures, typically made by coextrusion,
frequently include a polyolefin layer such as PP, LDPE, LLDPE,
HDPE, EVA, ethylene-acrylic acid copolymers, ethylene-methacrylic
acid copolymers, ethylene-acrylic acid ester copolymers,
ethylene-methacrylic acid ester copolymers, ionomers, and the like.
Barrier resins used are typically polar polymers such as
ethylene-vinyl alcohol (EVOH) or polyamide resins such as
nylon.
[0144] Illustrative multi-layer constructions include the
following: [0145] PP/adhesive/EVOH/adhesive/PP [0146]
PP/adhesive/polyamide/adhesive/PP [0147]
PP/adhesive/polyamide/EVOH/polyamide/adhesive/PP [0148]
HDPE/adhesive/EVOH/adhesive/HDPE [0149]
HDPE/adhesive/polyamide/adhesive/HDPE [0150]
EVOH/adhesive/HDPE/adhesive/EVOH [0151]
LDPE/adhesive/polyamide/adhesive/LDPE [0152]
LDPE/adhesive/EVOH/adhesive/LDPE [0153]
LLDPE/adhesive/EVOH/adhesive/LLDPE [0154]
LLDPE/adhesive/polyamide/adhesive/LLDPE [0155]
HDPE/adhesive/polyamide/EVOH/polyamide/adhesive/HDPE
[0156] Some commonly used sealable multilayer constructions
include: [0157] LLDPE/adhesive/EVOH/adhesive/sealant [0158]
HDPE/adhesive/polyamide/adhesive/sealant [0159]
HDPE/adhesive/EVOH/adhesive/sealant a where the sealant layer is,
for example, EVA, LLDPE or ionomer.
EXAMPLES
[0160] The following examples are included to demonstrate preferred
embodiments of the invention. It should be appreciated by those of
skill in the art that the techniques disclosed in the examples
which follow represent techniques discovered by the inventor to
function well in the practice of the invention, and thus can be
considered to constitute preferred modes for its practice. However,
those of skill in the art should, in light of the present
disclosure, appreciate that many changes can be made in the
specific embodiments which are disclosed and still obtain a like or
similar result without departing from the spirit and scope of the
invention.
[0161] For the comparative example and the examples of an
embodiment of the present invention, a grafted polyolefin was
prepared by feeding a polypropylene impact copolymer (specific
gravity: 0.90; Melt Flow Rate: 1.8 grams per 10 minutes;
Polydispersity Index: 9.7) and maleic anhydride (2 weight percent,
based on total charged reactants) to a COPERION.TM. ZSK-92
twin-screw extruder having zones heated at temperatures ranging
from 160 degrees Celsius to 192 degrees Celsius and operated at
shear rates within the range of 300-400 rpm and under nitrogen. The
extruder had eleven heating zones, which were heated as followed:
zone 1 (160 degrees Celsius); zones 2-5 (143 degrees Celsius);
zones 6-9 (195 degrees Celsius); and zones 9-11 (193 degrees
Celsius).
[0162] The following materials were also used to prepare the
exemplified polyolefin-based compositions and the corresponding
test specimen: (1) LyondellBasell PRO-FAX.TM. SR257M random
copolymer polypropylene, having ethylene as the comonomer, a
specific gravity of 0.90, a melt flow rate of 2.0 grams per 10
minutes, and a polydispersity index of 3.3; (2) ExxonMobil
Company's VISTALON.TM. 722 ethylene propylene rubber, having 72
weight percent ethylene recurring units, based upon the total
weight of the EPR (Melt Index of 1.0 grams per 10 minutes); (3)
LyondellBasell HIFAX.TM. CA10A polypropylene copolymer, having a
density of 0.88 grams per cubic centimeter, a melt flow rate of 0.6
grams per 10 minutes, a rubber content of about 70 weight percent,
and an ethylene content of 22 weight percent; (4) LyondellBasell
HIFAX.TM. CA138A polypropylene copolymer, having a density of 0.88
grams per cubic centimeter, a melt flow rate of 2.8 grams per 10
minutes, a rubber content of about 55 weight percent, and an
ethylene content of 30 weight percent; (5) LyondellBasell HIFAX.TM.
CA207A polypropylene copolymer, having a density of 0.90 grams per
cubic centimeter, a melt flow rate of 7.5 grams per 10 minutes, a
rubber content of about 70 weight percent, an ethylene content of
about 55 percent, and a butene content of about 10 weight percent;
(6) LyondellBasell ADFLEX.TM. KS021P polypropylene copolymer,
having a density of 0.88 grams per cubic centimeter, a melt flow
rate of 0.9 grams per 10 minutes, a rubber content of about 60
weight percent, and an ethylene content of 40 weight percent; (7)
LyondellBasell SOFTELL.TM. Q020F polypropylene copolymer, having a
density of 0.87 grams per cubic centimeter, a melt flow rate of
0.60 grams per 10 minutes, a rubber content of about 85 weight
percent, and an ethylene content of about 25 weight percent; (8)
LyondellBasell ADFLEX.TM. Q200F polypropylene copolymer, having a
density of 0.88 grams per cubic centimeter, a melt flow rate of 0.8
grams per 10 minutes, a rubber content of about 70 weight percent,
and an ethylene content of 20 weight percent; (9) Ciba IRGANOX.TM.
1010 phenolic primary antioxidant; and (10) Ciba IRGAFOS.TM. 168
trisarylphosphite processing stabilizer.
[0163] The materials were admixed in the weight percents, based
upon the total weight of the composition, shown in the table. Each
composition contained 10 weight percent of the grafted polyolefin,
0.1 weight percent of Ciba IRGAFOS.TM. 168 trisarylphosphite
processing stabilizer, and 0.1 weight percent of Ciba IRGANOX.TM.
1010 phenolic primary antioxidant, based upon the total weight of
the composition.
[0164] For the comparative example and the examples of an
embodiment, (a) the grafted polyolefin, (b) the first polyolefin
polymer, (c) the polypropylene-containing blend composition, and
(d) the additives were dry blended and then melt extruded at 230
degrees Celsius and 220 rpm to form tie-layer adhesives.
[0165] More specifically, five-layer structures (20 mils) were
produced using the tie-layer adhesives of the comparative example
(C. Ex. 1) and the inventive examples (Exs. 2-13). Each multi-layer
structure was made on a Killion extruder (comprised of 3 extruders
in this case) with a barrel length to barrel diameter (L/D) ratio
of 24:1, a barrel diameter of about 2.54 cm (1 inch) to about 3.18
cm (1.25 inches), and 3 barrel heating zones. Killion extruders may
be obtained from Killion Extruders, Inc. of Cedar Grove, N.J.
TABLE-US-00001 Extruder XL:D Heating Extruder Barrel Diameter Ratio
Zones Extruder 1 3.18 cm (1.25 inches) 24:1 3 Extruders 2 & 3
2.54 cm (1 inch) 24:1 3
[0166] Each multi-layer structure has the following layers: PP/tie
layer/EVOH/tie layer/PP.
[0167] The PP is PETROTHENE.TM. PP31KK01, a product of EQUISTAR.TM.
Chemicals, LP, which has an Melt Flow Rate of 5 grams per 10
minutes at 230 degrees Celsius and density of 0.9 grams per cubic
centimeter. The ethylene-vinyl alcohol copolymer (EVOH) is
SOARNOL.TM. DC3203 FB grade, product of Nippon Gohsei.TM. Kagaku K.
K., Japan.
[0168] The layer distribution was 43 thickness percent, 4 thickness
percent, 6 thickness percent, 4 thickness percent, and 43 thickness
percent, respectively based on total structure thickness.
TABLE-US-00002 TABLE I Component C. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5
Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Grafted 10 10
10 10 10 10 10 10 10 10 10 10 10 Polyolefin SR257M 69.8 69.8 64.8
69.8 64.8 69.8 64.8 69.8 64.8 69.8 64.8 69.8 64.8 VISTALON 20 -- --
-- -- -- -- -- -- -- -- -- -- 722 CA10A -- 20 25 -- -- -- -- -- --
-- -- -- -- CA138A -- -- -- 20 25 -- -- -- -- -- -- -- -- CA207A --
-- -- -- -- 20 25 -- -- -- -- -- -- KS021P -- -- -- -- -- -- -- 20
25 -- -- -- -- Q020F -- -- -- -- -- -- -- -- -- 20 25 -- -- Q200F
-- -- -- -- -- -- -- -- -- -- -- 20 25 IRGAFOS 0.1 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 168 IRGANOX 0.1 0.1 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 0.1 1010 Adhesion 0.838 1.331 1.900 1.568
1.131 1.766 2.045 1.765 1.806 1.806 1.927 1.684 1.809 (1 Day) kg/cm
(lb/in) (4.69) (7.45) (10.64) (8.78) (6.33) (9.89) (11.45) (9.88)
(10.11) (10.11) (10.79) (9.43) (10.13)
[0169] Although the present invention and its advantages have been
described in detail, it should be understood that various changes,
substitutions and alterations can be made herein without departing
from the spirit and scope of the invention as defined by the
appended claims. Moreover, the scope of the present application is
not intended to be limited to the particular embodiments of the
process, machine, manufacture, composition of matter, means,
methods and steps described in the specification. As one of the
ordinary skill in the art will readily appreciate from the
disclosure of the present invention, processes, machines,
manufacture, compositions of matter, means, methods, or steps,
presently existing or later to be developed that perform
substantially the same function or achieve substantially the same
result as the corresponding embodiments described herein may be
utilized according to the present invention. Accordingly, the
appended claims are intended to include within their scope such
processes, machines, manufacture, compositions of matter, means,
methods, or steps.
* * * * *
References