U.S. patent application number 11/396614 was filed with the patent office on 2006-08-31 for multilayered structures.
Invention is credited to Richard J. Jorkasky, George S. Li, Elena Simona Percec.
Application Number | 20060194012 11/396614 |
Document ID | / |
Family ID | 25535477 |
Filed Date | 2006-08-31 |
United States Patent
Application |
20060194012 |
Kind Code |
A1 |
Percec; Elena Simona ; et
al. |
August 31, 2006 |
Multilayered structures
Abstract
A novel multilayer structure in which one layer comprises a
polymer comprising a solventless, waterless, melt-processable
acrylonitrile olefinically unsaturated polymer and the other layer
comprises an organic polymer. Either polymer can be employed as the
inner layer or the outer lays component of the multilayer
structure.
Inventors: |
Percec; Elena Simona;
(Chagrin Falls, OH) ; Jorkasky; Richard J.;
(Hudson, OH) ; Li; George S.; (Solon, OH) |
Correspondence
Address: |
MCGUIREWOODS, LLP
1750 TYSONS BLVD
SUITE 1800
MCLEAN
VA
22102
US
|
Family ID: |
25535477 |
Appl. No.: |
11/396614 |
Filed: |
April 4, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09607002 |
Jun 29, 2000 |
7025918 |
|
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11396614 |
Apr 4, 2006 |
|
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08989807 |
Dec 12, 1997 |
|
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09607002 |
Jun 29, 2000 |
|
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Current U.S.
Class: |
428/35.7 |
Current CPC
Class: |
B32B 2307/554 20130101;
B32B 2439/60 20130101; B32B 27/08 20130101; Y10T 428/1352 20150115;
B32B 27/308 20130101; Y10T 428/31855 20150401; Y10T 428/31797
20150401; B32B 2250/03 20130101; Y10T 428/31583 20150401; B32B
2597/00 20130101; B32B 2307/558 20130101; B32B 2250/40 20130101;
B32B 2307/7242 20130101; B32B 2307/71 20130101; Y10T 428/3175
20150401; B32B 2307/7265 20130101; B32B 2439/40 20130101; Y10T
428/31507 20150401; B32B 2307/714 20130101 |
Class at
Publication: |
428/035.7 |
International
Class: |
B32B 27/08 20060101
B32B027/08 |
Claims
1. A non-laminated multilayer structure, said structure comprising:
a layer having an organic polymer composition; and a layer having a
solventless, waterless, melt-processable acrylonitrile olefinically
unsaturated polymer comprising about 50% to about 95% by weight
polymerizable acrylonitrile monomer and at least one of about 5% to
about 50% by weight polymerizable olefinically unsaturated monomer
and wherein the organic polymer and the acrylonitrile olefinically
unsaturated polymer are thermally stable in relationship to each
other.
2. The non-laminated multilayer structure of claim 1, wherein the
acrylonitrile olefinically unsaturated polymer is positioned
between two layers of the organic polymer and wherein the organic
polymer for each layer is the same or substantially similar polymer
composition.
3. The non-laminated multilayer structure of claim 1, wherein the
organic polymer is positioned between two layers of the
acrylonitrile olefinically unsaturated polymer wherein said
acrylonitrile olefinically unsaturated polymer for each layer is
the same or substantially similar polymer composition.
4. The non-laminated multilayer of claim 1, wherein the
distribution of the polymer in a layer is such that the adjacent
layer polymer is not exposed on its surface.
5. The non-laminated multilayer structure of claim 1, wherein the
olefinically unsaturated monomer is selected from a group
consisting of methyl acrylates, ethyl acrylates, acrylamides and
methyl acrylamides and each of their substituted alkyl and aryl
derivatives, maleic acid and its derivatives, vinylesters,
vinylethers, vinylamides, vinylketones, styrenes,
halogen-containing monomers, ionic monomers, acid-containing
monomers, base-containing monomers, olefins and combinations
thereof.
6. The non-laminated multilayer structure of claim 5, wherein the
olefinically unsaturated monomer is selected from the group
consisting of methyl methacrylate, acrylamide, methacrylamide,
N-methylacrylamide, N,N-dimethyl acrylamide, N-phenyhmaleimide;
vinyl acetate, ethyl vinyl ether and butyl vinyl ether, vinyl
pyrrolidone, ethyl vinyl ketone, butyl vinyl ketone, methylstyrene
styrene, indene, vinyl chloride, vinyl bromide, vinylidene
chloride, sodium vinylsulfonate, sodium styrenesulfonate, sodium
methyl sulfonate, itaconic acid, styrene sulfonic acid, vinyl
sulfonic acid, vinyl pyridine, 2-aminoethyl-N-acrylamide,
3-aminopropyl-N-actylamide, 2-aminoethylacrylate, and
2-eminoethymethacrylate, propylene, ethylene, isobutylene and
combinations thereof.
7. The non-laminated multilayer structure of claim 1, wherein said
organic polymer is selected from the group consisting of
polyolefins, polyesters, polymides, polycarbonates, polyamides,
polyamide imides, polyester-imides, polystyrenes, polyurethanes,
polyvinyl chloride, polyvinyl alcohol, polyketones, polyphenylene
oxide, polysulphone, acrylonitrile-containing polymers, liquid
crystalline polymers, cellulosic, wood, silk, cotton and
combinations thereof.
8. The non-laminated multilayer structure of claim 7, wherein the
organic polymer is selected from the group consisting of
polypropylene, polyethylene, poly (4-methylpentene-1), polyethylene
terephthalate, polybutylene terephthalate, polyethylene
naphthalate, nylon, polybisphenol-A carbonate; polyetherimide,
copolyester of hydroxyl-benzoic acid with 2,6 naththoic acid,
solventless, waterless, melt-processable acrylonitrile containing
polymers and combinations thereof.
9. A film formed from the non-laminated multilayer structure of
claim 1.
10. A pipe formed from the non-laminated multilayer structure of
claim 1.
11. A tape formed from the non-laminated multilayer structure of
claim 1.
12. A container formed from the non-laminated multilayer structure
of claim 1.
13. A bottle formed from the non-laminated multilayer structure of
claim 1.
14. A sheet formed from the non-laminated multilayer structure of
claim 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 09/607,002, filed Jun. 29, 2000, which in turn
is a divisional of U.S. application Ser. No. 08/989/807, filed Dec.
12, 1997, now abandoned, the disclosures of which are incorporated
herein by reference in their entirety and to which priority and
benefit under 35 U.S.C. .sctn. 120 is claimed to applications.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to multilayer structures and
methods for their preparation. Mote particularly, the invention
relates to a multilayer structure having typical organic polymer
layer(s) and dissimilar organic polymer layer(s) comprising a
solventless waterless melt-processable acrylonitrile olefinically
unsaturated polymer. It is understood that the term multilayer
structure includes film, tape, sheets, containers, composites,
articles that are extruded, injection-molded, compression molded m
the like, structural body, and the like throughout this
specification.
[0003] No single polymer is capable of providing the chemical and
physical properties that are required for various applications. It
is useful to manufacture films, sheets, containers and packages
from multilayer polymer materials because different polymer
compositions provide different properties, and by combining
different polymer layers the final product will have the benefit of
the different polymer properties. Unfortunately, polymers that
provide one kind of properties do not readily combine or adhere to
polymers that provide other unique chemical and physical
properties.
[0004] Therefore, it would be advantageous to produce a multilayer
material using dissimilar polymer layers. The present invention
produces such a multilayer material. It would be further
advantageous to produce a multilayer structure with an
acrylonitrile olefinically unsaturated polymer. An acrylonitrile
olefinically unsaturated polymer can be characterized by high
resistance to abrasion, solvents, gas and UV light, hardness and
high puncture resistance but lower water vapor resistance rate in
comparison to other polymers such as polyolefins. An organic
polymer can be characterized by high water vapor resistance rate,
high tear strength, good heat seal and reduced shrink properties
and low density, but has poor gas and solvent barrier properties
and low UV resistance. The unique nitrile and organic polymer
multilayer structure of the present invention provides improved
gas/water barrier properties, resistance to chemicals, abrasion,
solvents, and UV light improved rigidity, weatherability, wear
performance and impact strength. These and other advantages will
become apparent as the description of the invention proceeds.
SUMMARY OF THE INVENTION
[0005] The present invention is directed to a multilayer structure
which displays improved resistance to abrasion, organic solvents,
water vapor, gas (i.e., oxygen, carbon dioxide barrier properties),
and UV light, as well as improved rigidity, impact strength, and
wear performance. The multilayer structure comprises an organic
polymer layer; and a solventless, waterless, melt processable
acrylonitrile olefinically unsaturated polymer layer which
comprises about 50% to about 95% by weight polymerizable
acrylonitrile monomer and at least one of about 5% to about 50% by
weight polymerizable olefinically unsaturated monomer.
[0006] The present invention also provides a method for preparation
of the multilayer structure which comprises the steps of providing
an organic polymer; providing a solventless, waterless,
melt-processable acrylonitrile olefinically unsaturated polymer
comprising about 50% to about 95% by weight polymerizable
acrylonitrile monomer and at least one of about 5%, to about 50% by
weight polymerizable olefinically unsaturated monomer, and melt
processing the polymeric components. The present invention may be
used in a variety of molding methods, including extrusion,
co-injection molding, multilayer extrusion molding, multilayer blow
molding, injection molding, compression molding and the like.
DETAILED DESCRIPTION OF THE INVENTION
[0007] In accordance with the present invention, the multilayer
structure comprises an organic polymer layer and a waterless,
solventless melt-processable acrylonitrile olefinically unsaturated
polymer (hereinafter "acrylonitrile olefinically unsaturated
polymer") layer. The multilayer structure comprises at least two
layers.
[0008] The layer of organic polymer includes, but is not limited
to, synthetic and natural polymers. The synthetic polymer includes,
but is not limited to, polyolefins such as polypropylene,
polyethylene and poly(4-methylpentene-1); polyesters such as
polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
and polyethylene naphthalate (PEN); polyamides (PA), including
aliphatics and aromatics, such as nylons; polycarbonates such as
polybisphenol-A carbonate (PC); polyimides (PI) such as
polyetherimide aliphatic and aromatic; poly(amide-imides);
poly(ester-imides); polystyrenes (PS); polyurethanes; polyvinyl
chloride (PVC); polyketones; polyphenylene oxide (PPO); polyvinyl
alcohol (PVA); polysulphone; liquid crystalline polymers such as
copolyesters of hydroxy-benzoic acid with 2,6 naphthoic acid
(Vectra); Kevlar.RTM. (available from DuPont); acrylonitrile
containing polymers including a waterless, solventless melt
processable acrylonitrile olefinically unsaturated polymer or an
acrylonitrile containing polymer that is soluble in a solvent; and
the like.
[0009] The monomers employed in the organic polymer can be one
monomer or a combination of monomers dependent upon the properties
desired to impart to the end use of the multilayer structure. In a
multilayer structure of three layers or more, the organic polymer
is employed as either the outer layer m the inner layer of the
structure, but not both.
[0010] The other polymer layer is an acrylonitrile olefinically
unsaturated polymer comprising an acrylonitrile monomer polymerized
with at least one olefinically unsaturated monomer. The
acrylonitrile olefinically unsaturated polymer comprises about 50%
to about 95% by weight, preferably about 75% to about 93% by
weight, and most preferably about 85% to show 92% by weight of
polymerized acrylonitrile monomer, and at least one of about 5% to
about 50% by weight, preferably about 7% to about 25% by weight,
and most preferably about 8% to about 15% by weight of polymerized
olefinically unsaturated monomer. The acrylonitrile olefinically
unsaturated polymer is employed as the outer layer or the inter
layer or both.
[0011] The olefinically unsaturated monomer employed is one of more
of olefinically unsaturated monomer with a C.dbd.C double bond
polymerizable with an acrylonitrile monomer. The olefinically
unsaturated monomer can be a single polymerizable monomer resulting
in a co-polymer, or a combination of polymerizable monomers
resulting in a multi-polymer. The choice of olefinically
unsaturated monomer or a combination of monomers depends upon the
properties desired to impart to the resulting multilayer structure
and its end use.
[0012] The olefinically unsaturated monomer generally includes, but
is not limited to, acrylates such as methyl acrylates and ethyl
acrylates; methacrylates, such as methyl methacrylate; acrylamides
and methacrylamides and each of their N-substituted alkyl and aryl
derivatives, such as acrylamide, methactylamide,
N-methylacrylamide, N, N-dimethyl acrylamide; maleic acid and its
derivatives, such as N-phenylmaleimide; vinylesters, such as vinyl
acetate; vinylethers, such as ethyl vinyl ether and butyl vinyl
ether, vinylamides, such as vinyl pyrrolidone, vinylketones, such
ethyl vinyl ketone and butyl vinyl ketone; styrenes, such as
methylstyrene, styrene and indene; halogen containing monomers,
such as vinyl chloride, vinyl bromide, and vinylidene chloride;
ionic monomers, such sodium vinylsulfonate, sodium
styrenesulfonate, and sodium methyl sulfonate; acid containing
monomers such as itaconic acid, styrene sulfonic acid and vinyl
sulfonic acid; base-containing monomers, such as vinyl pyridine,
2-aminoethyl-N-acrylamide, 3-aminopropyl-N-acrylamide,
2-aminoethylacrylate, 2-aminoethymathacrylate; and olefins, such as
propylene, ethylene, isobutylene.
[0013] The multilayer structure is a minimum of two layers, or an
unlimited number of layers, depending on the end use application.
For example, a three-layer structure employs an inner layer of
either the organic polymer or the acrylonitrile olefinically
unsaturated polymer with the inner layer sandwiched therebetween
the outer layers which is the organic polymer or the acrylonitrile
olefinically unsaturated polymer, depending on the desired end use
of the product.
[0014] The polymer employed as the inner layer has a dissimilar
composition or a dissimilar molecular weight or dissimilar
theological properties in comparison to the polymer employed as the
outer layer. The organic polymer and the acrylonitrile olefinically
unsaturated polymer are thermally stable in relationship to each
other. The organic polymer or the acrylonitrile olefinically
unsaturated polymer is either the inner layer or the outer layer of
the multilayer structure depending on the end use application and
on the chemical and physical properties of the polymers such as
melt flow and thermal characteristics, molecular weight,
composition and the like. In the invention, the polymer employed as
the inner layer of the multilayer structure is in the range of
about 1% weight to about 99% weight, preferably about 5% weight to
about 95% weight and more preferable about 10% weight to about 90%
weight of the multilayer structure. The polymer employed as the
otter layer in the multilayer structure is in the range of about
99% weight to about 1% weight, preferably about 95% weight to about
5% weight and more preferable about 90% weight to about 10% weight
of the multilayer. The minimum amount of polymer for a layer is
such that the polymer of the adjacent layer is not excessively
exposed on the surface.
[0015] The composition of the polymer used for the outer layer and
the composition of the polymer used for the inner layer are
prepared separately. The acrylonitrile olefinically unsaturated
polymer is prepared by known polymerization processes. An exemplary
method to make the melt-processable high-nitrile multi-polymer is
described in U.S. Pat. No. 560,222 entitled "A Process for Making a
Polymer of Acrylonitrile/Methacrylonitrile/Olefinically Unsaturated
Monomers" and U.S. Pat. No. 5,618,901 entitled "A Process for
Making a High Nitrile Multipolymer Prepared from Acrylonitrile and
Olefinically Unsaturated Monomers," both incorporated herein by
reference. The organic polymer is prepared by known polymerization
processes.
[0016] The multilayer structure is produced by a melt process. The
thickness of the layers depend on the desired end use and is in the
range of about 1 micron m any thickness depending on the end use
application. The melt processing temperature is dependent on the
melt temperature and the thermal degradation temperature of the
composition of the outer layer polymer and the inner layer
polymer.
[0017] The acrylonitrile olefinically unsaturated polymer is melt
processed in a waterless, solventless system; however trace amounts
of water as an impurity may exist up to 3%, preferably 1% or less.
A process for producing the multilayer structure of this invention
comprises preparing separately the organic polymer and the
acrylonitrile olefinically unsaturated polymer; combining the
components; and extruding the polymer components through
conventional means.
[0018] In a one-step injection molding process, the various melt
polymer components are combined in a mold and the mold allowed to
cool.
[0019] In a one-step extrusion process, the various melt polymer
components are coextended in a conventional manner.
[0020] Additional treatment may be employed to further modify the
characteristics of the multilayer structure by the addition of
reinforcement materials such as carbon fibers, glass fibers and the
like; additives; Mustering agents; coloring agents and the like. It
is understood that any additive possessing the ability to function
in such a manner can be used so long as it does not have a
deleterious effect on the properties of the nitrite multilayer
structure. The invention is not limited to any specific lamination,
extrusion, injection or molding techniques.
[0021] These multilayer structures are used for packaging
applications, subsequent fabricated articles prepared from sheet
precursors. In particular, the multilayer structures are used as
films, packaging films, tapes, sheets, pipes, packages, trays,
bottles, containers, composites, fabricated articles, structural
bodies and the like. Further, the multilayer structure is employed
in packaging applications, including automotive fuel tanks, as well
as containers including those that can go from hot filling to
freezer to microwave, building materials, pipes and the like.
SPECIFIC EMBODIMENT
[0022] The following examples demonstrate the advantages of the
present invention. The polymers used were: 1) acrylonitrile
olefinically unsaturated polymer crumb employing 85% acrylonitrile
monomer polymerized with 15% methyl acrylate polymer; and 2) an
organic polymer of polypropylene pellets (melt index=18) with an 18
melt flow index or polyethylene polymer pellets with high density
and a 1 melt flow index.
[0023] The acrylonitrile methyl acrylate polymer and polyolefin of
either polypropylene or polyethylene were mixed together in a one
gallon pail. The mixture was extruded using a three zone, 0.75 inch
extruder fitted with a film (tape) die. The mixture of polymer
resin was added to a hopper and extruded at about 35 rpm. The
material coming out of the die was taken up on a film (tape)
machine comprising two rollers. The rollers could optionally be
heated. The rollers were compressed to regulate the thickness of
the film (tape) and the speed of the rollers was adjusted to
regulate the thickness and width of the film (tape). The resulting
multilayer structure was three layers in a sandwich configuration.
The following Table I describes the ratios of each polymer and
condition employed. PP stands for polypropylene; PE stands for
polyethylene; and AMLON.TM. stands for acrylonitrile olefinically
unsaturated polymer employing 85% acrylonitrile copolymerized with
15% methyl acrylate. TABLE-US-00001 Ratio Extruder Temps Film Roll
Speed 100PP (comparison) 215/215/215/215.degree. C. 7.0 100 AMLON
.TM. (comparison) 215/215/215/215.degree. C. 7.0 80 PP/20 AMLON
.TM. 215/215/215/215.degree. C. 7.0 70 PP/30 AMLON .TM.
215/215/215/215.degree. C. 5.5 50PP/50 AMLON .TM.
225/225/225/225.degree. C. 6.0 20PP180 AMLON .TM.
235/235/235/235.degree. C. 3.0 50PP/50 AMLON .TM.
200/200/200200.degree. C. 80 PE/20 AMLON .TM.
215/215/215/215.degree. C. 4.0
[0024] The composite tapes were examined by optical microscopy
using a Leitz cross polarizing optical microscope (Laborlux 12 pol)
equipped with a Mettler hot stage. It was determined by optical
microscopy that the tape had a multilayer configuration.
[0025] FIG. 1(a) shows the morphology of an acrylonitrile methyl
acrylate extruded tape which is used for a comparison.
[0026] FIG. 1(b) shows the morphology of an acrylonitrile methyl
acrylate/polypropylene 8020 extruded tape.
[0027] FIG. 1(c) shows the morphology of an acrylonitrile methyl
acrylate/polypropylene 50/50 extruded tape.
[0028] FIG. 1(d) shows the morphology of an acrylonitrile methyl
acrylate/polypropylene 20180 extruded tape.
[0029] FIG. 1 demonstrates that the acrylonitrile methyl
acrylate/polypropylene laminar morphologies are obtained from a
large range of different ratios of polymer.
[0030] FIG. 2(a) shows the morphology of an acrylonitrile methyl
acrylate extruded tape which is used for comparison.
[0031] FIG. 2(b) shows the morphology of a polypropylene extruded
tape which is used for comparison.
[0032] FIG. 2(c) shows the morphology of an acrylonitrile methyl
acrylate/polypropylene 30/70 extruded tape.
[0033] FIG. 2(d) shows the morphology of an acrylonitrile methyl
acrylate/polypropylene 20/80 extruded tape.
[0034] FIG. 2 demonstrates that the extruded tapes were in a
sandwich configuration with the polypropylene as the inside layer
and the acrylonitrile methyl acrylate as the outside layers. This
is demonstrated by the pictures which show in FIG. 2(a) that the
acrylonitrile methyl acrylate has crystallites too small in size m
be distinguished by optical microscopy in comparison to FIG. 2(b)
polypropylene which exhibits a distinct crystalline pattern. This
crystalline structure, is not observed for FIG. 2(c) and (d) which
indicates that the acrylonitrile methyl acrylate is present as both
outside layers, while the polypropylene forms the inside layer.
[0035] FIGS. 3(a) and (b) show the morphology of an acrylonitrile
methyl acrylate/polypropylene 50/50 extruded tape.
[0036] FIGS. 3(c) and (d) show the same tape after extraction with
DMF (dimethylformamide) for about 40 hours at room temperature.
FIG. 3 demonstrates that before extraction the morphology of the
50/50 acrylonitrile methyl acrylate (polypropylene extruded tape is
laminar, with acrylonitrile methyl acrylate present as the outside
layers. After extraction with the DMF, the acrylonitrile methyl
acrylate layer is removed, and the polypropylene crystalline
pattern is readily observed.
[0037] FIG. 4(a) and (b) show the morphology of an acrylonitrile
methyl acrylate/polyethylene 20/80 extruded tape and FIGS. 4(c) and
(d) show the same tape after extraction with DMF for about 40 hours
at room temperature. FIG. 4 indicates that the laminar morphology
is also characteristic for acrylonitrile methyl
acrylate/polyethylene combinations. It also demonstrates that in
this case the polyethylene is present as the outside layers,
because after the DMF extraction, the morphology of the extruded
tape remains unchanged.
[0038] From the above description and examples of the invention,
those skilled in the art will perceive improvements, changes, and
modifications in the invention. Such improvements, changes and
modifications within those skilled in the art are intended to be
covered by the appended claims.
* * * * *