U.S. patent application number 11/805126 was filed with the patent office on 2008-11-27 for half panel.
This patent application is currently assigned to NOVA CHEMICALS (INTERNATIONAL) S.A. Invention is credited to Christopher John Brooke Dobbin, Alexei Kazakov.
Application Number | 20080289274 11/805126 |
Document ID | / |
Family ID | 40030433 |
Filed Date | 2008-11-27 |
United States Patent
Application |
20080289274 |
Kind Code |
A1 |
Dobbin; Christopher John Brooke ;
et al. |
November 27, 2008 |
Half panel
Abstract
The present invention provides a half panel having on its back
ribs defining symmetrically complimentary closed wall open faced
cells and ribs having spaces there between. The half panel may be
placed in back to back relationship and rotated through a required
degree of rotation so that the open faced closed wall cells and
ribs having spaces there between interlock so the open faced closed
wall cells have at least one diagonal cross member. This provides a
rigid panel suitable for a number of applications including forms
for pouring concrete.
Inventors: |
Dobbin; Christopher John
Brooke; (Calgary, CA) ; Kazakov; Alexei;
(Calgary, CA) |
Correspondence
Address: |
Kenneth H. Johnson
P.O. Box 630708
Houston
TX
77263
US
|
Assignee: |
NOVA CHEMICALS (INTERNATIONAL)
S.A
|
Family ID: |
40030433 |
Appl. No.: |
11/805126 |
Filed: |
May 22, 2007 |
Current U.S.
Class: |
52/275 |
Current CPC
Class: |
E01C 5/22 20130101; E01C
9/08 20130101; E04C 2/388 20130101; E04G 2009/028 20130101; E01C
13/00 20130101; E04C 2/22 20130101; B29L 2007/002 20130101; E04G
9/10 20130101; B29C 33/42 20130101; B29C 45/37 20130101 |
Class at
Publication: |
52/275 |
International
Class: |
E04B 1/00 20060101
E04B001/00 |
Claims
1. A modular half panel comprising a web having a planar upper
surface having integrally on its back arrays of substantially
vertical ribs of uniform depth defining open faced closed wall
cells and cooperating arrays of ribs having spaces there between so
when two half panels are placed back to back and rotated to align
the cells and cooperating arrays of ribs having spaces there
between the closed wall cells interlock and intersect with the
cooperating arrays of ribs having spaces there between so that the
closed wall cells have at least one reinforcing rib traversing said
cell, said half panel further comprising two or more vertical side
wall portions descending in the same direction and to the same
depth as said ribs said side wall portions positioned on the
periphery of said web so that when two half panels are
interconnected the wall portions form a complete outer wall for the
resulting panel.
2. The half panel according to claim 1, wherein the ribs taper
inwardly to an upper radiused edge.
3. The half panel according to claim 2, wherein the open faced
closed wall cells are in the shape of a parallelogram or
hexagon.
4. The half panel according to claim 3, wherein the side length of
the open faced closed wall cells are from 2 inches to 12
inches.
5. The half panel according to claim 4, wherein the half panel is a
square or a rectangle.
6. The half panel according to claim 5, wherein in the cooperating
arrays of ribs having spaces there between further comprise contact
members descending from the web at locations which will contact
corners of the closed wall cells.
7. The half panel according to claim 6, wherein the side wall
portions depend from two opposed corners of the half panel and
extend along the perimeter of the panel for one half of length of
the panel edge.
8. The half panel according to claim 7, wherein the open faced
closed wall cells are in an array symmetrically arranged about the
center point of the half cell and the cooperating arrays of ribs
having spaces there between are arranged about the center point of
the half panel in a complimentary symmetrical array.
9. The half panel according to claim 8, wherein the open faced
closed wall cells define a square, rectangle or hexagon and the
cooperating arrays of ribs having spaces there between define a
diagonal cross or six pointed star.
10. The half panel according to claim 9, wherein the web is a metal
or alloy comprising one or more metals selected from the group
consisting of titanium, molybdenum, chromium, aluminum, magnesium,
iron, nickel, and tungsten.
11. The half panel according to claim 9, wherein the web is a
thermoset resin selected from the group consisting of unsaturated
polyesters, phenolic resins, epoxide resins, polyimides and novolak
resins, and urethane resins.
12. The half panel according to claim 11, wherein the web further
optionally comprises from 0 to 40 weight % of one or more
components selected from the group consisting of talc, calcium
carbonate, silica, mica, wollastonite, hollow glass spheres and
fibers selected from the group consisting of glass, polyester,
polyamide, aramid and carbon fibers.
13. The half panel according to claim 12, wherein the fibers have a
length of not less than 0.5 cm.
14. The half panel according to claim 11, wherein the web further
optionally comprises from 0 to 30 weight % of one or more flame
retardants, heat and light stabilizers, and release agents.
15. The half panel according to claim 9, wherein the web comprises
a compression or injection moldable thermoplastic resin.
16. The half panel according to claim 15, wherein the web further
optionally comprises from 0 to 40 weight % of one or more
components selected from the group consisting of talc, calcium
carbonate, silica, mica, wollastonite, and hollow glass
spheres.
17. The half panel according to claim 15, wherein the web further
optionally comprises from 0 to 30 weight % of one or more flame
retardants, heat and light stabilizers, and release agents.
18. The half panel according to claim 15, wherein the web further
comprises from 0.5 to 40 weight % of one or more reinforcing fibers
selected from the group consisting of glass, polyester, polyamide,
aramid and carbon fibers.
19. The half panel according to claim 18, wherein the web
thermoplastic further optionally comprises from 0 to 10 weight % of
a compatibilizer.
20. The half panel according to claim 19, wherein the thermoplastic
resin is selected from the group consisting of polyamides,
polyesters, polymers of one or more C.sub.2-8 olefins optionally
further comprising from 0 to 50 weight % of one or more C.sub.3-6
ethylenically unsaturated carboxlic acids, anhydrides, amides, or
nitrites, polymers of one or more C.sub.8-12 vinyl aromatic
monomers optionally further comprising from 0 to 50 weight % of one
or more C.sub.3-6 ethylenically unsaturated carboxlic acids,
anhydrides, amides, or nitriles; polyacrylonitrile; polycarbonates;
acetals; polyetherkeones; and polysulfones.
21. The half panel according to claim 20, wherein the thermoplastic
further includes from 5 to 30 weight % of a rubbery impact
modifier.
22. The half panel according to claim 20, where the compatibilizer
is selected from the group consisting of homopolymers of one or
more C.sub.3-6 ethylenically unsaturated carboxylic acids,
anhydrides or amides; copolymers comprising from 5 to 95 weight %
of one or more C.sub.3-6 ethylenically unsaturated carboxylic
acids, anhydrides or amides and from 95 to 5 weight % of one or
amides, esters, or C.sub.2-8 olefins and C.sub.2-8 polyolefins,
which have been grafted with from 5 to 30 weight % of one or more
C.sub.3-6 ethylenically unsaturated carboxylic acids, anhydrides or
amides, polyesters which have been grafted with from 5 to 30 weight
% of C.sub.3-6 ethylenically unsaturated carboxylic acids,
anhydrides or amides and polyamides which have been grafted with
from 5 to 30 weight % of C.sub.3-6 ethylenically unsaturated
carboxylic acids or anhydrides.
23. The half panel according to claim 22, wherein the thermoplastic
is selected from the group consisting of polyesters, polyamides,
polyolefins, copolymers of styrene and maleic acid, copolymers of
styrene and maleic anhydride, copolymers of styrene and maleimide,
copolymers of styrene and acrylonitrile copolymers, styrene and
acrylic acid or methacrylic acid, and polyacrylonitirle.
24. The half panel according to claim 23, wherein the thermoplastic
has a density greater than 0.930 g/cc.
25. The half panel according to claim 24, wherein the thermoplastic
is a polyolefin.
26. The half panel according to claim 25, wherein the polyolefin
comprises from 99 to 90 weight % of ethylene and from 1 to 10
weight % of one or more C.sub.3-8 alpha olefins.
27. The half panel according to claim 26, wherein the thermoplastic
is reinforced with from 10 to 40 weight % of glass fiber.
28. The half panel according to claim 27, wherein the total
thermoplastic composition further comprises from 1 to 8 weight % of
a compatibilizer.
29. The half panel according to claim 28, wherein the compatiblizer
is selected from the group consisting of glycidyl methacrylate,
ionomers of 80 to 95 weight % of ethylene and 20 to 5 weight % of
one or more C.sub.3-6 carboxylic acids; copolymers of 80 to 95
weight % of ethylene and 20 to 5 weight % of one or more C.sub.3-6
carboxylic acids, copolymers of 80 to 95 weight % of ethylene and
20 to 5 weight % of one or more anhydrides of C.sub.3-6 carboxylic
acids and copolymers of 80 to 95 weight % of ethylene and 20 to 5
weight % of one or more imides of C.sub.3-6 carboxylic acids and
ethylene vinyl acetate.
30. A process for forming a panel comprising fixing two half panels
according to claim 9, in back to back relationship so that the
cells on each half panel intersect and interlock with the cells on
the facing half panel.
31. A process for forming a panel comprising fixing two half panels
according to claim 11, in back to back relationship so that the
cells on each half panel intersect and interlock with the cells on
the facing half panel.
32. A process for forming a panel comprising fixing two half panels
according to claim 15, in back to back relationship so that the
cells on each half panel intersect with the cells on the facing
half panel.
33. A mold having spaces defining a planar upper surface having
integrally on its back arrays of substantially vertical ribs of
uniform depth defining open faced closed wall cells and cooperating
arrays of ribs having spaces there between, and two or more
vertical side wall portions descending in the same direction and to
the same depth as said ribs.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to stiff light weight panels,
typically polymer composites. The panels are structurally rigid
(stiff) and suitable for use in a number of applications such as a
protective overlay (i.e. turf cover) for playing areas for arenas
or stadiums and also for concrete forms. The panels have a
sufficient stiffness (don't bend) for such applications. Depending
on the composition of the matrix (e.g. metal, thermoset or
thermoforming plastic) the panels may not have a suitable flexural
and/or compressive strength to be load bearing. The panels are
modular being made from two half panels which have a planar surface
(e.g. flat or textured for grip) and on the back a number of ribs
which define open faced closed wall cells and ribs which are not
connected in a complimentary symmetrical arrangement so that when
the half panels are placed back to back and rotated, typically
through 180.degree., the panels may be fitted together so that the
closed cells and ribs which are not interconnected fit together so
that the cells have at least one diagonal member. Preferably, the
half panels comprise a portion of the perimeter having an edge so
that on joining the half panels together the outer perimeter is
sealed. One advantage of this panel is that only one mold is needed
to form the half panel.
BACKGROUND OF THE INVENTION
[0002] A number of forms of double laminate structures are known.
This includes the honeycomb structure typically in which two planar
surfaces are adhered to opposite sides of a cellular honeycomb
matrix. The double laminate structure also includes corrugated
structures in which two planar surfaces are adhered to opposite
sides of a central corrugated member (e.g. a cardboard type
structure). Depending on the material of construction the laminate
has reasonable compressive strength but doesn't have sufficient
stiffness.
[0003] There are a number of patents in which there are layer
structures having layers parallel to the top and bottom surface and
parallel walls dividing the matrix into a number of parallel
channels. Representative of this type of art are U.S. Pat. No.
5,348,790 issued Sep. 20, 1994 to Ben-Zev et al. assigned to
Dan-Pal and U.S. Pat. No. 5,580,620 issued Dec. 3, 1996 assigned to
21.sup.st Century Limited. This art does not suggest the subject
matter of the present invention. It teaches away from it as there
are no transverse reinforcing members (cross braces) that could
have easily been incorporated.
[0004] U.S. Pat. No. 5,970,899 issued Oct. 26, 1999 to Michaelson
et al. assigned to the United States of America as represented by
the Secretary of the Navy, discloses a crisscrossed latticed
pattern for hatches in decks for container ships. The deck provides
increased resistance to tension stress. The patent is of interest
but fails to teach the interlocking half panels of the present
invention.
[0005] U.S. Pat. No. 5,028,474 issued Jul. 2, 1991 to Czaplicki
discloses a core of a laminate in which the core comprises
continuous parallelograms defining alternating ridges and valleys
in a cross pattern. The concept of the patent is similar to the
honeycomb. The interior web is continuous and upper and lower
surfaces are adhered to the web. This teaches away from the half
panel of the present invention.
[0006] U.S. Pat. No. 5,958,551 issued Sep. 28, 1999 to Jorge-Isaac
Garcia-Ochoa is in some senses similar to U.S. Pat. No. 5,028,474
except that the reinforcing matrix is not continuous. The matrix is
in the form of truncated open pyramids with supports at the corners
and a truncated or flattened top for attachment to a web or a
further layer of reinforcing matrix. The patent teaches away from
the present invention disclosure. The reinforcing parts do not
interlock and further strengthen/stiffen each other. Also it fails
to teach the half panel concept.
[0007] U.S. Pat. No. 4,348,442 issued Sep. 7, 1982 to Figge teaches
a half panel comprising a web and integral truncated polyhedral
(tetrahedral) elements. The polyhedral elements have a flattened
surface for attachment to a second planar web. The patent does
teach that the panels can be flipped over so that the polyhedrons
on one face interlock (abut rather than interpenetrate) with those
on the other face. The patent fails to teach different shapes or
rotated interlocking/interpenetrating cells.
[0008] Applicant's co-pending U.S. patent application Ser. No.
11/435,329 filed May 16, 2006 discloses some of the polyolefin
compositions which are useful in the present invention. However,
the case does not disclose the specific cell structure of the
present invention.
[0009] United States Patent Application 2006/0275600 published Dec.
7, 2006 discloses a double laminated sheet of plywood. The patent
teaches that a relatively thin sheet of a polymer composite may be
adhered to solid substrate such as metal or plywood to provide a
sheet material suitable for use in pouring concrete. This is
similar to the teachings of U.S. Pat. Nos. 5,537,797 and 5,836,126
issued Jul. 23, 1996 and Nov. 17, 1998 in the names of Harkenrider
et al. assigned to The Salk Institute of Biological Studies which
teach plywood having a polymer layer adhered to only one face of
the plywood. These references teach away from the subject matter of
the present patent application as they teach a solid substrate.
[0010] The half panels of the present invention have ribs defining
(arrays of) open faced closed wall cells and cooperating (arrays)
of ribs having spaces there between so that when the half panels
are placed back to back and interlocked there is not only a
perimeter defining the outside of the open faced closed wall cell
but there is also at least one internal diagonal member within the
cell.
[0011] The present invention seeks to provide a low cost (per use)
structurally rigid panel typically for non-structural applications
as plywood or composite board replacements such as turf covers and
concrete forms.
SUMMARY OF THE INVENTION
[0012] In one aspect the present invention provides a modular half
panel comprising a web having a planar upper surface having
integrally on its back arrays of substantially vertical ribs of
uniform depth defining open faced closed wall cells and cooperating
arrays of ribs having spaces there between so when two half panels
are placed back to back and rotated to align the cells and
cooperating arrays of ribs having spaces there between the closed
wall cells interlock and intersect with the cooperating arrays of
ribs having spaces there between so that the closed wall cells have
at least one reinforcing rib traversing said cell, said half panel
further comprising two or more vertical side wall portions
descending in the same direction and to the same depth as said ribs
said side wall portions positioned on the periphery of said web so
that when two half panels are interconnected the wall portions form
a complete outer wall for the resulting panel.
[0013] The present invention further provides a process for forming
a panel comprising fixing two half panels as described above, in
back to back relationship so that the open faced closed wall cells
on each half panel intersect and interlock with the ribs having
spaces there between on the adjacent half panel .
[0014] In another aspect the present invention further provides a
panel formed from two half panels as described above.
[0015] In a further aspect the present invention provides a light
weight structurally rigid panel for use typically in non structural
applications such as construction applications such as concrete
forms and coverings for the floor of an arena or the field of a
stadium (turf cover).
[0016] The present invention further provides a mold (die) having
spaces defining a planar upper surface having integrally on its
back arrays of substantially vertical ribs of uniform depth
defining open faced closed wall cells and cooperating arrays of
ribs having spaces there between, and two or more vertical side
wall portions descending in the same direction and to the same
depth as said ribs.
[0017] The present invention also distinguishes itself by only
requiring a single mold or tooling design to form the key (half)
panel component. Since tooling design and construction represents a
substantial capital outlay, particularly for large panels, the use
of a single mold or tooling design provides for significant cost
reductions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a diagram of the back of a half panel according to
the present invention in which the open faced closed wall cells are
parallelograms and the ribs having spaces there between are in
complimentary symmetry (e.g. symmetrical quadrants).
[0019] FIG. 2 is a blow up of the section bounded by A-A and B-B of
the half panel of FIG. 1.
DETAILED DESCRIPTION
[0020] In the present specification unless otherwise specified
weight % means weight % of the total composition of or used to form
the half panel.
[0021] Complimentary symmetry means that for any (each) open faced
closed wall cell on the back of a half panel there is at a
symmetrical location through a plane (e.g. center line ) or through
a point (center point) a complimentary series of ribs having spaces
there between which will form one or more diagonal ribs of the
closed wall open faced cell of a half panel rotated through an
appropriate degree of rotation ( e.g. 180.degree. for a rectangle
and 90.degree. for a square). This is illustrated by FIG. 2 in that
the figure can be folded along either center line and the ribs
having spaces there between will fit into the ribs defining open
faced closed wall cells.
[0022] The present invention relates to a half panel having a
planar upper surface, either flat or textured and depending from
the bottom a number of ribs which define open faced closed cells
and ribs with spaces there between which provide diagonal
reinforcement across the closed cells when two half panels are
joined together in back to back relationship. The ribs, typically
but not necessarily, are in continuous arrays arranged in
complimentary symmetry. The arrays may for example cover diagonally
opposed quarter sections of the half panel. The ribs could also be
arranged so there are alternating ribs defining open faced closed
wall cells with ribs having spaces there between provided in any
row or column the number of closed wall cells and ribs having space
there between are even. As a result when two panels are rotated
through the appropriate degree of symmetry and placed back to back
the cells will interlock and intersect with the ribs having spaces
there between in such a manner that each open faced closed wall
cell will have at least one transverse rib or member, typically a
diagonal rib. The advantage of such a half panel is that only one
mold is required to form two half panels which may be
interconnected to form the complete panel. The half panel may be
formed in any conventional manner including compression molding or
injection molding.
[0023] Preferably the ribs are solid (continuous) but they could
contain perforations (regions of voids or cut -outs to reduce
weight). However, from the point of view of ease of mold
manufacture and ease of ejecting parts from the mold preferably the
ribs do not have "perforations". The ribs have a substantially
vertical axis having straight or tapered sides coming to a blunt or
flat end (e.g. square ended) or possibly a "bull nose", having
equal beveled sides leading to the flat front, but preferably the
end is rounded or is radiused. In a particularly preferred
embodiment the ribs are tapered, narrowing towards the radiused
upper edge. This embodiment makes it easier to remove the half
panel from the mold.
[0024] The interlocking nature of the design allows the assembled
panel to provide sufficient stiffness at a reduced overall
thickness compared to a single sided panel. This in turn reduces
the depth of the rib structures necessary to achieve specific
modulus targets. Since the required rib depth is reduced, tooling
costs associated with cutting deep rib structures into the mold are
therefore lowered significantly
[0025] The open faced closed wall cells defined by the ribs may be
of any shape provided the weight of the combined panel is not
excessive for the application. Also the more intricate the shape of
the cell the more costly the mold. For example the cell could be
hexagonal and the ribs which have a space there between could
define up to three cross members (e.g. a star of six points to fit
into the corners of the hexagon cell). Preferably, the open faced
closed wall cells are parallelograms, preferably rectangles or
squares, of uniform size and the corresponding ribs having spaces
there between may be in the form of a single cross member or a
diagonal cross (e.g. triangles, scissors, or cells which are
rotated relative to the closed wall open faced cells) or a six
pointed star (or snowflake) for hexagons.
[0026] Typically the open faced closed wall cells may have a side
length from about 2 inches (5 cm) to 12 inches (30.5 cm),
preferably from about 6 inches (15.24 cm) to about 8 inches (20.32
cm). The ribs may have any height but typically are from a quarter
of an inch (0.635 cm) to about two inches (5 cm), preferably from a
half an inch (1.27 cm) to an inch (2.54 cm) most preferably from a
half an inch (1.27 cm) to three quarters of an inch (1.905 cm) and
a thickness from an eighth of an inch (0.32 cm) to a quarter of an
inch (0.64 cm). The planar surface may have a thickness from an
eighth of an inch (0.32 cm) to a quarter of an inch (0.64 cm).
[0027] In some cases the ribs having spaces there between may be in
symmetrically opposed segments about the center point of said web,
(typically quadrants) may be viewed as open walled open faced cells
that are rotated at an angle from 30 to 90 degrees, preferably 30
to 45 degrees to the open faced closed wall cells in the adjacent
quadrant.
[0028] Generally the half panel is also a parallelogram such as a
square or a rectangle.
[0029] The half panel also has on its perimeter walls or edges
descending an equal distance as the ribs at locations which are
rotationally symmetrical relative to the half panel (preferably
enclosing the array of open faced closed wall cells if they re in
quadrants (see below)). In one embodiment the walls or edges
descend at two adjacent sides of the half panel and extend along
the perimeter of the panel for the full length of the panel edge.
In an another embodiment the walls are at two opposed corners of
the panel and extend along the perimeter of the panel for one half
of length of the panel edge. For a square the sides or walls could
be on opposite faces. This is a matter of ease of design and
operation of the mold and assembly of the panels.
[0030] In one embodiment in the ribs having spaces there between
further comprise contact members (tabs) descending from the web at
locations which will contact corners of the closed wall cells.
Generally these tabs are short members, typically from an inch
(2.54 cm) to a half an inch (1.27 cm) typically about three
quarters of an inch (1.905 cm) long, generally extending for the
full height of the rib but possibly half or three quarter height of
the rib could be used. If the half panels are glued or fused
together the tabs provide points to glue or fuse the transverse
ribs into the closed cell.
[0031] The half panels could be of any size but generally may have
a length from 6 feet (1.83 meters) to 10 feet 3.02 meters,
preferably 8 feet (2.44 meters) and a width from 2 feet (0.60
meters) to 6 feet (1.83 meters), preferably 4 feet (1.22 meters) by
8 feet (2.44 m)( e.g. plywood size). For some uses in the
construction industry (e.g. concrete forms) the panel will
preferably have a weight from about 70 to 85 pounds (31.75 kg to
38.6 kg) preferably from 70 to 80 pounds (31.75 kg to 36.28 kg) and
a displacement under a 600 psf (pounds per square foot) force over
a 16 inch span backed by 2.times.4 inch (5 cm .times.10 cm) wood
reinforcements at 16 inch centers of not more than 0.044 inches
(0.111 cm), typically in the range from 0.021 inches (0.053 cm) to
0.014 inches (0.0356 cm).
[0032] The present invention will now be described with reference
to FIGS. 1 and 2 in which like parts have like numbers.
[0033] The half panel 1 comprises a back, web 2 from which a number
of ribs 3 depend. The ribs 3 may be joined or continuous to define
an open faced closed wall cell 4 or the ribs may be discontinuous
having spaces 5 there between. In the figures the open faced closed
wall cells 4 and the ribs having spaces there between define arrays
symmetrically arranged (preferably rotationally symmetrically
arranged) in quadrants about the center point of the half cell. The
ribs 3 having spaces there between are positioned to engage the
walls of the open faced closed wall cells 4 when two half panels
are placed back to back and one of them is rotated through the
rotational symmetry (in this case 180.degree.). At the points of
engagement of the ribs having spaces there between and the corners
of the open faced closed wall cells there are tabs 6 on the ribs
having spaces there between. Additionally the half panel has an
edge 7 depending from the web or back 2 enclosing two symmetrically
opposed quadrants of the half panel. In this case the quadrants of
the half panel having open faced closed wall cells so that when two
half panels are interlocked or in cooperating arrangement the
resulting panel has an edge extending the full length around the
panel. Preferably, but not necessarily the peripheral walls are in
the portions (quadrants) of the half panel having the open faced
closed wall cells. By doing this, one saves a little bit of weight,
since an exterior edge on the open interlocking side would likely
require that one of the closed cells from the opposite side would
have be inserted along it. This would form a double thickness of
material at each box wall-outer edge intersection. By placing the
edge along the closed cell section, the outer wall is an integral
part of the outer cell walls, thereby reducing the amount of
material (and therefore the critical weight of assembled
panel).
[0034] The panel of the present invention may be made from any
suitable material such as metal or alloy. The metal or alloy
comprises a light weight high tensile material. Typically the a
metal or alloy comprises one or more metals selected from the group
consisting of titanium, molybdenum, chromium, aluminum, magnesium,
iron, nickel, and tungsten.
[0035] The half panel may be an organic material such as
thermosetting resins or plastic (thermoset) or a thermoplastic
resin.
[0036] Thermoset resins or plastics may be selected from the group
consisting of unsaturated polyesters, phenolic resins, epoxide
resins, polyimides and novolak resins, and urethane resins. The raw
(uncompounded) thermoset resins or plastics will generally have a
density from about 1.2 g/cc to about 1.6 g/cc. The web or matrix of
the thermoset half panel may further optionally comprise from 0 to
40 weight % of one or more components selected from the group
consisting of talc, calcium carbonate, silica, mica, wollastonite,
hollow glass spheres and fibers selected from the group consisting
of glass, polyester, polyamide, aramid and carbon fibers. Generally
the fibers will have a nominal length of at least 0.5 cm,
preferably 1.25 cm (1/2 inch) typically from about 2 to 25 cm. The
fibers may have a diameter from about 10 to 20 .mu.m, preferably
from 10 to 15 .mu.m, most preferably from 10 to 13 .mu.m. The
thermoset may optionally further comprise from 0 to 30 weight % of
one or more flame retardants, heat and light stabilizers, and
release agents. If the web or matrix of the thermoset half panel
comprises fiber the thermoset may optionally further comprise from
0 to 10 weight % of a compatibilizer (as disclosed below).
[0037] The web or matrix of the half panel may be compression or
injection moldable thermoplastic resin. The web of thermoplastic
may optionally further comprise from 0 to 40, typically from 0.5 to
40 weight % of one or more components selected from the group
consisting of talc, calcium carbonate, silica, mica, wollastonite,
and hollow glass spheres. Generally the fibers will have a nominal
length of at least 0.5 cm, preferably 1.25 cm (1/2 inch) typically
from about 2 cm to 25 cm. The fibers may have a diameter from about
10 to 20 .mu.m, preferably from 10 to 15 .mu.m, most preferably
from 10 to 13 .mu.m. The thermoplastic may comprise from 0 to 30
weight % of one or more flame retardants, heat and light
stabilizers, and release agents. If the web or matrix of the
thermoplastic half panel comprises fiber the thermoplastic may
optionally further comprise from 0 to 10 weight % of a
compatibilizer.
[0038] The thermoplastic may be selected from the group consisting
of polyamides, polyesters, polymers of one or more C.sub.2-8
olefins optionally further comprising from 0 to 50 weight % of one
or more C.sub.3-6 ethylenically unsaturated carboxlic acids,
anhydrides, amides, or nitriles, polymers of one or more C.sub.8-12
vinyl aromatic monomers optionally further comprising from 0 to 50
weight % of one or more C.sub.3-6 ethylenically unsaturated
carboxlic acids, anhydrides, amides, or nitriles;
polyacrylonitrile; polycarbonates; acetals; polyetherkeones; and
polysulfones. In cases where there is concern about the toughness
of the thermoplastic, the thermoplastic may further comprise from 5
to 30 weight % of a rubbery impact modifier. There are a number of
patents assigned to E.I. Du Pont naming Bennett N. Epstein as
inventor teaching toughening polyamides (e.g. nylon) or polyesters
using toughening agents. Two patents which are particularly
relevant are U.S. Pat. Nos. 4,172,859 and 4,174,358 issued Oct. 30,
1979 and Nov. 13, 1979 respectfully, the texts of which are herein
incorporated by reference.
[0039] For polymers or copolymers of styrene, acrylonitrile and
C.sub.1-4 alkyl esters of C.sub.3-6 ethylenically unsaturated
carboxylic acids (e.g. acrylic acid and methacrylic acid) rubbery
polymers which may be used may be selected from the group of
polymers consisting of:
[0040] (i) homopolymers of C.sub.4-6 conjugated diolefins which are
unsubstituted or substituted by a chlorine atom;
[0041] (ii) homogeneous homo- and copolymers of C.sub.4-8 alkyl
esters of acrylic and methacrylic acid which homo- and copolymers
have a Tg less than 20.degree. C.;
[0042] (iii) heterogeneous polymers comprising 40 to 60 weight
percent of a first domain comprising 100 to 70 weight percent of
one or more C.sub.4-8 acrylate or methacrylate esters which form
homopolymers having a Tg less than 020 C., and from 0 to 30 weight
percent of one or more monomers selected from the group consisting
of methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl
methacrylate; and from 60 to 40 weight percent of a subsequent
domain comprising a homopolymer or a copolymer of one or more
monomers selected from the group consisting of methyl acrylate,
ethyl acrylate, methyl methacrylate, and ethyl methacrylate;
[0043] (iv) linear and radial block copolymers having a molecular
weight of at least 75,000 and a styrene content from 20 to 50
weight percent selected from the group consisting of
styrene-butadiene diblock copolymers, styrene-butadiene-styrene
triblock copolymers, styrene-isoprene diblock copolymers,
styrene-isoprene-styrene triblock copolymers, partially
hydrogenated styrene-butadiene-styrene triblock copolymers, and
partially hydrogenated styrene-isoprene-styrene triblock
copolymers; and
[0044] (v) copolymers comprising 100-60 weight percent of a
C.sub.4-6 conjugated diolefin and 0-40 weight percent of one or
more monomers selected from the group consisting of C.sub.2-6
alkenyl nitrile monomers, C.sub.8-12 vinyl aromatic monomers;
C.sub.1-4 alkyl esters of acrylic acid; C.sub.1-4 esters of
methacrylic acid.
[0045] The thermoplastic resins may be compounded in the same
manner as the thermoset resins.
[0046] If fibers are present in the web or matrix of the half panel
they may be present in amounts from 10 to 40, preferably from 20 to
40, most preferably from 25 to 40 weight % based on the weight of
the thermoplastic (or thermoset) resin.
[0047] In compression molding one wouldn't expect any appreciable
orientation of the fibers except for incidental orientation
resulting from the direction of material flow. This situation
produces panels with essentially anisotropic properties.
[0048] Alternately, in injection molding, one would expect a higher
degree of fiber orientation, in part due to the higher shear rates
typically experienced and dependent on the number of injection
ports or gates in the mold. Injection molding may be used to
produce panels with isotropic properties, i.e. to enhance physical
properties in a particular direction. Preferably, the fibers will
have a low degree, less than 25%, preferably less than 15%, most
preferably less than 10% of orientation in the same direction. As a
result the physical properties of the half panel when measured in
different directions (e.g. the x, y, and z planes) are not the
same.
[0049] In cases where the thermoplastic or thermoset resin has a
low degree of adhesion to the fiber the thermoplastic or thermoset
resin may, as noted above, further comprise a compatibiliser or
adhesion promoter in amounts from 1 to 10 weight %, preferably from
2 to 8 weight %. Typically the compatibilizer or adhesion promoter
comprises a polar polymer.
[0050] Some polar polymers which may be suitable as compatibilizers
include polymers selected from the group consisting of homopolymers
of one or more C.sub.3-6 ethylenically unsaturated carboxylic
acids, anhydrides or amides; copolymers comprising from 5 to 95
weight % of one or more C.sub.3-6 ethylenically unsaturated
carboxylic acids, anhydrides or amides and from 95 to 5 weight % of
one or amides, esters, or C.sub.2-8 olefins and C.sub.2-8
polyolefins, which have been grafted with from 5 to 30 weight % of
one or more C.sub.3-6 ethylenically unsaturated carboxylic acids,
anhydrides or amides, polyesters which have been grafted with from
5 to 30 weight % of C.sub.3-6 ethylenically unsaturated carboxylic
acids, anhydrides or amides and polyamides which have been grafted
with from 5 to 30 weight % of C.sub.3-6 ethylenically unsaturated
carboxylic acids or anhydrides.
[0051] The polar polymer may also be selected from (but not limited
to) the following groups of polymers.
[0052] (i) Olefinic homopolymers and copolymers (e.g. polymers
comprising from 90 to 100 weight % of ethylene and from 0 to 10
weight % of one or more C.sub.3-10, preferably C.sub.4-8 olefins,
preferably alpha olefins) that have been modified through grafting
with up to 10 weight %, preferably from 2 to 8 weight %, typically
from 4 to 8 weight % of one or more C.sub.3-6 ethylenically
unsaturated carboxylic acids, anhydrides and imides. Examples
include, but are not limited to, so-called compatibilizers such as
BYNEL.RTM. products (from DuPont Company) maleic anhydride modified
polyolefins available under the POLYBOND.RTM. (Chemtura) product
range.
[0053] (ii) Copolymers comprising from about 99 to 50 weight %,
preferably from 99 to 80, typically from 95 to 80 of one or more
C.sub.2-8 olefin monomers (e.g. ethylene) and which incorporate
from 1 to 50 weight %, preferably from 1 to 20 weight %, typically
from 5 to 20 weight % of one or more C.sub.3-8 ethylenically
unsaturated polar monomers including but not limited to carboxylic
acids, anhydrides, imides, glycidyl methacrylate and carboxylic
acid derivatives, including vinyl acetate esters (ethylene vinyl
acetate) and ionomers (alkali or alkali earth metal salts of acidic
polymers ( e.g. ethylene acrylate salts).
[0054] In one embodiment the polar polymer is selected from the
group consisting of glycidyl methacrylate, ionomers of 80 to 95
weight % of ethylene and 20 to 5 weight % of one or more C.sub.3-6
carboxylic acids; copolymers of 80 to 95 weight % of ethylene and
20 to 5 weight % of one or more C.sub.3-6 carboxylic acids,
copolymers of 80 to 95 weight % of ethylene and 20 to 5 weight % of
one or more anhydrides of C.sub.3-6 carboxylic acids and copolymers
of 80 to 95 weight % of ethylene and 20 to 5 weight % of one or
more imides of C.sub.3-6 carboxylic acids and ethylene vinyl
acetate.
[0055] In one embodiment the thermoplastic resin may be selected
from the group consisting of polyesters, polyamides, polyolefins,
copolymers of styrene and maleic acid, copolymers of styrene and
maleic anhydride (such as those sold by NOVA Chemicals Incorporated
under the trademark DYLARK.RTM.), copolymers of styrene and
maleimide, copolymers of styrene and acrylonitrile copolymers,
styrene and acrylic acid or methacrylic acid, and
polyacrylonitirle.
[0056] If the thermoplastic is a polyolefin preferably it has a
density greater than 0.930 g/cc, preferably from 0.939 to 0.959
g/cc, most preferably from 0.945 to 0.959 g/cc. Typically the
polymer comprises from 90, preferably 95, to 99.9 weight % of one
or more C.sub.2-4 alpha olefin monomers and from 0.01 to 10,
preferably 5 weight % of one or more C.sub.6-8 alpha olefin
monomers. The polymer may comprise from 99 to 90 weight % of
ethylene and from 1 to 10 weight % of one or more C.sub.3-8,
preferably C .sub.6-8 alpha olefins. Typically the polymer has a
melt index (ASTM D1238, 2.16 kg, 190.degree. C.) from 0.5 to 10
g/10 min, preferably from 2 to 8 g/10 min
[0057] The polyolefin may be made using gas phase, solution or
slurry processes.
[0058] Solution and slurry polymerization processes are fairly well
known in the art. These processes are conducted in the presence of
an inert hydrocarbon solvent typically a C.sub.4-12 hydrocarbon
which may be unsubstituted or substituted by a C.sub.1-4 alkyl
group such as butane, pentane, hexane, heptane, octane,
cyclohexane, methylcyclohexane or hydrogenated naphtha. An
additional solvent is Isopar E (C.sub.8-12 aliphatic solvent, Exxon
Chemical Co.).
[0059] The polymerization may be conducted at temperatures from
about 20.degree. C. to about 250.degree. C. Depending on the
product being made, this temperature may be relatively low such as
from 20.degree. C. to about 180.degree. C., typically from about
80.degree. C. to 150.degree. C. and the polymer is insoluble in the
liquid hydrocarbon phase (diluent) (e.g. a slurry polymerization).
The reaction temperature may be relatively higher from about
180.degree. C. to 250.degree. C., preferably from about 180.degree.
C. to 230.degree. C. and the polymer is soluble in the liquid
hydrocarbon phase (solvent). The pressure of the reaction may be as
high as about 15,000 psig for the older high pressure processes or
may range from about 15 to 4,500 psig.
[0060] In the gas phase polymerization a gaseous mixture comprising
from 0 to 15 mole % of hydrogen, monomers as noted above, and from
0 to 75 mole % of an inert gas at a temperature from 50.degree. C.
to 120.degree. C., preferably from 75.degree. C. to about
110.degree. C., and at pressures typically not exceeding 3447 kPa
(about 500 psi), preferably not greater than 2414 kPa (about 350
psi) is contacted with a supported catalyst as noted above and
polymerized.
[0061] The catalyst may be a Ziegler Natta catalyst typically based
on Ti and activated with a trialkyl aluminum (e.g. triethyl
aluminum) or an alkyl aluminum alkoxide ( diethyl aluminum
ethoxide) compound, a Phillips type catalyst based on Cr or it may
be a single site catalyst.
[0062] If the process is a gas phase or slurry polymerization
typically the catalyst is supported.
[0063] The catalyst system of the present invention may be
supported on an inorganic or refractory support, including for
example alumina, silica and clays or modified clays or an organic
support (including polymeric support such as polystyrene or
cross-linked polystyrene). The catalyst support may be a
combination of the above components. However, preferably the
catalyst is supported on an inorganic support or an organic support
(e.g. polymeric) or mixed support. Some refractories include
silica, which may be treated to reduce surface hydroxyl groups and
alumina. The support or carrier may be a spray-dried silica.
Generally the support will have an average particle size from about
0.1 to about 1,000, preferably from about 10 to 150 microns. The
support typically will have a surface area of at least about 10
m.sup.2/g, preferably from about 150 to 1,500 m.sup.2/g. The pore
volume of the support should be at least 0.2, preferably from about
0.3 to 5.0 ml/g.
[0064] Generally the refractory or inorganic support may be heated
at a temperature of at least 200.degree. C. for up to 24 hours,
typically at a temperature from 500.degree. C. to 800.degree. C.
for about 2 to 20, preferably 4 to 10 hours. The resulting support
will be essentially free of adsorbed water (e.g. less than about 1
weight %) and may have a surface hydroxyl content from about 0.1 to
5 mmol/g of support, preferably from 0.5 to 3 mmol/g.
[0065] A silica suitable for use in the present invention has a
high surface area and is amorphous. For example, commercially
available silicas are marketed under the trademark of Sylopol.RTM.
958 and 955 by Davison Catalysts, a Division of W. R. Grace, and
Company and ES-70W sold by Ineos Silica.
[0066] The amount of the hydroxyl groups in silica may be
determined according to the method disclosed by J. B. Peri and A.
L. Hensley, Jr., in J. Phys. Chem., 72 (8), 2926, 1968, the entire
contents of which are incorporated herein by reference.
[0067] While heating is the most preferred means of removing OH
groups inherently present in many carriers, such as silica, the OH
groups may also be removed by other removal means, such as chemical
means. For example, a desired proportion of OH groups may be
reacted with a suitable chemical agent, such as a hydroxyl reactive
aluminum compound (e.g. triethyl aluminum) or a silane compound.
This method of treatment has been disclosed in the literature and
two relevant examples are: U.S. Pat. No. 4,719,193 to Levine in
1988 and by Noshay A. and Karol F. J. in Transition Metal Catalyzed
Polymerizations, Ed. R. Quirk, 396, 1989. For example the support
may be treated with an aluminum compound of the formula
Al((O).sub.aR.sup.1).sub.bX.sub.3-b wherein a is either 0 or 1, b
is an integer from 0 to 3, R.sup.1 is a C.sub.1-8 alkyl radical,
and X is a chlorine atom. The amount of aluminum compound is such
that the amount of aluminum on the support prior to adding the
remaining catalyst components will be from about 0 to 2.5 weight %,
preferably from 0 to 2.0 weight % based on the weight of the
support.
[0068] The clay type supports are also preferably treated to reduce
adsorbed water and surface hydroxyl groups. However, the clays may
be further subject to an ion exchange process, which may tend to
increase the separation or distance between the adjacent layers of
the clay structure.
[0069] The polymeric support may be cross linked polystyrene
containing up to about 50 weight %, preferably not more than 25
weight %, most preferably less than 10 weight % of a cross linking
agent such as divinyl benzene.
[0070] In one embodiment of the invention the catalyst is a single
site catalyst of the formula (selected from the group consisting
of):
(L).sub.n-M-(Y).sub.p
wherein M is selected from the group consisting of Ti, Zr, and Hf;
L is a monoanionic ligand independently selected from the group
consisting of cyclopentadienyl-type ligands, and a bulky heteroatom
ligand containing not less than five atoms in total of which at
least 20%, numerically are carbon atoms and further containing at
least one heteroatom selected from the group consisting of boron,
nitrogen, oxygen, phosphorus, sulfur and silicon said bulky
heteroatom ligand being sigma or pi-bonded to M; Y is independently
selected for the group consisting of activatable ligands; n may be
from 1 to 3; and p may be from 1 to 3, provided that the sum of n+p
equals the valence state of. M, and further provided that two L
ligands may be bridged, and an activator.
[0071] The polymer is prepared in the presence of a single site
catalyst.
[0072] In one embodiment, the single site catalyst may be a
metallocene type catalyst wherein L is a cyclopentadienyl type
ligand and n, may be from 1 to 3, preferably 2.
[0073] The cyclopentadienyl-type ligand is a C.sub.5-13 ligand
containing a 5-membered carbon ring having delocalized bonding
within the ring and bound to the metal atom (i.e. the active
catalyst metal or site) through .eta..sup.5 bonds and said ligand
being unsubstituted or up to fully substituted with one or more
substituents selected from the group consisting of C.sub.1-10
hydrocarbyl radicals in which hydrocarbyl substituents are
unsubstituted or further substituted by one or more substituents
selected from the group consisting of a halogen atom and a
C.sub.1-8 alkyl radical; a halogen atom; a C.sub.1-8 alkoxy
radical; a C.sub.6-10 aryl or aryloxy radical; an amido radical
which is unsubstituted or substituted by up to two C.sub.1-8 alkyl
radicals; a phosphido radical which is unsubstituted or substituted
by up to two C.sub.1-8 alkyl radicals; silyl radicals of the
formula --Si--(R).sub.3 wherein each R is independently selected
from the group consisting of hydrogen, a C.sub.1-8 alkyl or alkoxy
radical, and C.sub.6-10 aryl or aryloxy radicals; and germanyl
radicals of the formula Ge--(R).sub.3 wherein R is as defined
above. Preferably the cyclopentadienyl ligand (Cp) is independently
selected from the group consisting of a cyclopentadienyl radical,
an indenyl radical and a fluorenyl radical.
[0074] In the single site type catalyst two cyclopentadienyl ligand
may be bridged or joined. If two cyclopentadienyl ligands are
bridged or joined together the catalyst may be a constrained
geometry catalyst. Non-limiting examples of bridging group include
bridging groups containing at least one Group 13 to 16 atom, often
referred to a divalent moiety such as but not limited to at least
one of a carbon, oxygen, nitrogen, silicon, boron, germanium and
tin atom or a combination thereof. Preferably, the bridging group
contains a carbon, silicon or germanium atom, most preferably at
least one silicon atom or at least one carbon atom. The bridging
group may also contain substituent radicals as defined above
including halogens.
[0075] Some bridging groups include but are not limited to, a di
C.sub.1-6 alkyl radical (e.g. alkylene radical for example an
ethylene bridge), di C.sub.6-10 aryl radical (e.g. a benzyl radical
having two bonding positions available), silicon or germanium
radicals substituted by one or more radicals selected from the
group consisting of C.sub.1-6 alkyl, C.sub.6-10 aryl, phosphine or
amine radical which are unsubstituted or up to fully substituted by
one or more C.sub.1-6 alkyl or C.sub.6-10 aryl radicals, or a
hydrocarbyl radical such as a C.sub.1-6 alkyl radical or a
C.sub.6-10 arylene (e.g. divalent aryl radicals); divalent
C.sub.1-6 alkoxide radicals (e.g. --CH.sub.2CHOH CH.sub.2--) and
the like.
[0076] Exemplary of the silyl species of bridging groups are
dimethylsilyl, methylphenylsilyl, diethylsilyl, ethylphenylsilyl,
diphenylsilyl bridged compounds. Most preferred of the bridged
species are dimethylsilyl, diethylsilyl and methylphenylsilyl
bridged compounds.
[0077] Exemplary hydrocarbyl radicals for bridging groups include
methylene, ethylene, propylene, butylene, phenylene and the like,
with methylene being preferred.
[0078] Exemplary bridging amides include dimethylamide,
diethylamide, methylethylamide, di-t-butylamide, diisopropylamide
and the like.
[0079] The activatable ligands (Y) may be independently selected
from the group consisting of a hydrogen atom; a halogen atom, a
C.sub.1-10 hydrocarbyl radical; a C.sub.1-10 alkoxy radical; a
C.sub.5-10 aryl oxide radical; each of which said hydrocarbyl,
alkoxy, and aryl oxide radicals may be unsubstituted by or further
substituted by one or more substituents selected from the group
consisting of a halogen atom; a C.sub.1-8 alkyl radical; a
C.sub.1-8 alkoxy radical; a C.sub.6-10 aryl or aryloxy radical; an
amido radical which is unsubstituted or substituted by up to two
C.sub.1-8 alkyl radicals; and a phosphido radical which is
unsubstituted or substituted by up to two C.sub.1-8 alkyl radicals.
Preferably Y is independently selected from the group consisting of
a hydrogen atom, a chlorine atom and a C.sub.1-4 alkyl radical.
[0080] In one embodiment of the invention the catalyst may contain
a bulky heteroatom ligand. The bulky heteroatom ligand is selected
from the group consisting of phosphinimine ligands, ketimide
ligands, silicon-containing heteroatom ligands, amido ligands,
alkoxy ligands, boron heterocyclic ligands and phosphole
ligands.
[0081] If the catalyst contains one or more bulky heteroatom
ligands the catalyst would have the formula:
##STR00001##
wherein M is a transition metal selected from the group consisting
of Ti, Hf and Zr; D is independently a bulky heteroatom ligand (as
described below); L is a monoanionic ligand selected from the group
consisting of cyclopentadienyl-type ligands; Y is independently
selected from the group consisting of activatable ligands; m is 1
or 2; n is 0 or 1; and p is an integer and the sum of m+n+p equals
the valence state of M, provided that when m is 2, D may be the
same or different bulky heteroatom ligands.
[0082] Bulky heteroatom ligands (D) include but are not limited to
phosphinimine ligands and ketimide (ketimine) ligands.
[0083] In a further embodiment, the catalyst may contain one or two
phosphinimine ligands (PI) which are bonded to the metal and the
second catalyst has the formula
##STR00002##
wherein M is a group 4 metal; PI is a phosphinimine ligand; L is a
monoanionic ligand selected from the group consisting of a
cyclopentadienyl-type ligand; Y is independently selected from the
group consisting of activatable ligands; m is 1 or 2; n is 0 or 1;
p is an integer and the sum of m+n+p equals the valence state of
M.
[0084] The phosphinimine ligand is defined by the formula:
##STR00003##
wherein each R.sup.21 is independently selected from the group
consisting of a hydrogen atom; a halogen atom; C.sub.1-20,
preferably C.sub.1-10 hydrocarbyl radicals which are unsubstituted
by or further substituted by a halogen atom; a C.sub.1-8 alkoxy
radical; a C.sub.6-10 aryl or aryloxy radical; an amido radical; a
silyl radical of the formula:
--Si--(R.sup.22).sub.3
wherein each R.sup.22 is independently selected from the group
consisting of hydrogen, a C.sub.1-8 alkyl or alkoxy radical, and
C.sub.6-10 aryl or aryloxy radicals; and a germanyl radical of the
formula:
--Ge--(R.sup.22).sub.3
wherein R.sup.22 is as defined above.
[0085] The preferred phosphinimines are those in which each
R.sup.21 is a hydrocarbyl radical, preferably a C.sub.1-6
hydrocarbyl radical.
[0086] Suitable phosphinimine catalysts are Group 4 organometallic
complexes which contain one phosphinimine ligand (as described
above) and one ligand L which is either a cyclopentadienyl-type
ligand or a heteroatom ligand.
[0087] As used herein, the term "ketimide ligand" refers to a
ligand which:
[0088] (a) is bonded to the transition metal via a metal-nitrogen
atom bond;
[0089] (b) has a single substituent on the nitrogen atom (where
this single substituent is a carbon atom which is doubly bonded to
the N atom); and
[0090] (c) has two substituents Sub 1 and Sub 2 (described below)
which are bonded to the carbon atom.
[0091] Conditions a, b and c are illustrated below:
##STR00004##
[0092] The substituents "Sub 1" and "Sub 2" may be the same or
different. Exemplary substituents include hydrocarbyl radicals
having from 1 to 20, preferably from 3 to 6, carbon atoms, silyl
groups (as described below), amido groups (as described below) and
phosphido groups (as described below). For reasons of cost and
convenience it is preferred that these substituents both be
hydrocarbyls, especially simple alkyls and most preferably tertiary
butyl. "Sub 1" and "Sub 2" may be the same or different and can be
bonded to each other to form a ring.
[0093] Suitable ketimide catalysts are Group 4 organometallic
complexes which contain one ketimide ligand (as described above)
and one ligand L which is either a cyclopentadienyl-type ligand or
a heteroatom ligand.
[0094] The term bulky heteroatom ligand (D) is not limited to
phosphinimine or ketimide ligands and includes ligands which
contain at least one heteroatom selected from the group consisting
of boron, nitrogen, oxygen, phosphorus, sulfur and silicon. The
heteroatom ligand may be sigma or pi-bonded to the metal. Exemplary
heteroatom ligands include silicon-containing heteroatom ligands,
amido ligands, alkoxy ligands, boron heterocyclic ligands and
phosphole ligands, as all described below.
[0095] Silicon containing heteroatom ligands are defined by the
formula:
--(Y)SiR.sub.xR.sub.yR.sub.z
wherein the--denotes a bond to the transition metal and Y is sulfur
or oxygen.
[0096] The substituents on the Si atom, namely R.sub.x, R.sub.y and
R.sub.z are required in order to satisfy the bonding orbital of the
Si atom. The use of any particular substituent R.sub.x, R.sub.y or
R.sub.z is not especially important to the success of this
invention. It is preferred that each of R.sub.x, R.sub.y and
R.sub.z is a C.sub.1-2 hydrocarbyl group (i.e. methyl or ethyl)
simply because such materials are readily synthesized from
commercially available materials.
[0097] The term "amido" is meant to convey its broad, conventional
meaning. Thus, these ligands are characterized by (a) a
metal-nitrogen bond; and (b) the presence of two substituents
(which are typically simple alkyl or silyl groups) on the nitrogen
atom.
[0098] The terms "alkoxy"and "aryloxy" is also intended to convey
its conventional meaning. Thus, these ligands are characterized by
(a) a metal oxygen bond; and (b) the presence of a hydrocarbyl
group bonded to the oxygen atom. The hydrocarbyl group may be a
C.sub.1-10 straight chained, branched or cyclic alkyl radical or a
C.sub.6-13 aromatic radical where the radicals are unsubstituted or
further substituted by one or more C.sub.1-4 alkyl radicals (e.g.
2,6 di-tertiary butyl phenoxy).
[0099] Boron heterocyclic ligands are characterized by the presence
of a boron atom in a closed ring ligand. This definition includes
heterocyclic ligands which also contain a nitrogen atom in the
ring. These ligands are well known to those skilled in the art of
olefin polymerization and are fully described in the literature
(see, for example, U.S. Pat. Nos. 5,637,659; 5,554,775; and the
references cited therein).
[0100] The term "phosphole" is also meant to convey its
conventional meaning. "Phospholes" are cyclic dienyl structures
having four carbon atoms and one phosphorus atom in the closed
ring. The simplest phosphole is C.sub.4PH.sub.4 (which is analogous
to cyclopentadiene with one carbon in the ring being replaced by
phosphorus). The phosphole ligands may be substituted with, for
example, C.sub.1-20 hydrocarbyl radicals (which may, optionally,
contain halogen substituents); phosphido radicals; amido radicals;
or silyl or alkoxy radicals. Phosphole ligands are also well known
to those skilled in the art of olefin polymerization and are
described as such in U.S. Pat. No. 5,434,116 (Sone, to Tosoh).
[0101] In one embodiment the catalyst may contain no phosphinimine
ligands as the bulky heteroatom ligand. The bulky heteroatom
containing ligand may be selected from the group consisting of
ketimide ligands, silicon-containing heteroatom ligands, amido
ligands, alkoxy ligands, boron heterocyclic ligands and phosphole
ligands. In such catalysts the Cp ligand may be present or
absent.
[0102] The preferred metals (M) are from Group 4 (especially
titanium, hafnium or zirconium), with titanium being most
preferred.
[0103] The catalysts in accordance with the present invention may
be activated with an activator selected from the group consisting
of:
[0104] (i) a complex aluminum compound of the formula
R.sup.12.sub.2AlO(R.sup.12AlO).sub.mAlR.sup.12.sub.2 wherein each
R.sup.12 is independently selected from the group consisting of
C.sub.1-20 hydrocarbyl radicals and m is from 3 to 50, and
optionally a hindered phenol to provide a molar ratio of
Al:hindered phenol from 2:1 to 5:1 if the hindered phenol is
present;
[0105] (ii) ionic activators selected from the group consisting of:
[0106] (A) compounds of the formula
[R.sup.13].sup.+[B(R.sup.14).sub.4].sup.- wherein B is a boron
atom, R.sup.13 is a cyclic C.sub.5-7 aromatic cation or a triphenyl
methyl cation and each R.sup.14 is independently selected from the
group consisting of phenyl radicals which are unsubstituted or
substituted with a hydroxyl group or with 3 to 5 substituents
selected from the group consisting of a fluorine atom, a C.sub.1-4
alkyl or alkoxy radical which is unsubstituted or substituted by a
fluorine atom; and a silyl radical of the formula
--Si--(R.sup.15).sub.3; wherein each R.sup.15 is independently
selected from the group consisting of a hydrogen atom and a
C.sub.1-4 alkyl radical; and [0107] (B) compounds of the formula
[(R.sup.18).sub.tZH].sup.+[B(R.sup.14).sub.4].sup.- wherein B is a
boron atom, H is a hydrogen atom, Z is a nitrogen atom or
phosphorus atom, t is 2 or 3 and R.sup.18 is independently selected
from the group consisting of C.sub.1-18 alkyl radicals, a phenyl
radical which is unsubstituted or substituted by up to three
C.sub.1-4 alkyl radicals, or one R.sup.18 taken together with the
nitrogen atom may form an anilinium radical and R.sup.14 is as
defined above; and [0108] (C) compounds of the formula
B(R.sup.14).sub.3 wherein R.sup.14 is as defined above; and
[0109] (iii) mixtures of (i) and (ii).
[0110] Preferably the activator is a complex aluminum compound of
the formula R.sup.12.sub.2AlO(R.sup.12AlO(R.sup.12AlO).sub.mAlR
.sup.12.sub.2 wherein each R.sup.12 is independently selected from
the group consisting of C.sub.1-20 hydrocarbyl radicals and m is
from 3 to 50, and optionally a hindered phenol to provide a molar
ratio of Al:hindered phenol from 2:1 to 5:1 if the hindered phenol
is present. In the aluminum compound preferably, R.sup.12 is methyl
radical and m is from 10 to 40. The preferred molar ratio of
Al:hindered phenol, if it is pr 3.25:1 to 4.50:1. Preferably the
phenol is substituted in the 2, 4 and 6 position by a C.sub.2-6
alkyl radical. Desirably the hindered phenol is
2,6-di-tert-butyl-4-ethyl-phenol.
[0111] The aluminum compounds (alumoxanes and optionally hindered
phenol) are typically used as activators in substantial molar
excess compared to the amount of metal in the catalyst.
Aluminum:transition metal molar ratios of from 10:1 to 10,000:1 are
preferred, most preferably 10:1 to 500:1 especially from 40:1 to
120:1.
[0112] Ionic activators are well known to those skilled in the art.
The "ionic activator" may abstract one activatable ligand so as to
ionize the catalyst center into a cation, but not to covalently
bond with the catalyst and to provide sufficient distance between
the catalyst and the ionizing activator to permit a polymerizable
olefin to enter the resulting active site.
[0113] Examples of ionic activators include: [0114]
triethylammonium tetra(phenyl)boron, [0115] tripropylammonium
tetra(phenyl)boron, [0116] tri(n-butyl)ammonium tetra(phenyl)boron,
[0117] trimethylammonium tetra(p-tolyl)boron, [0118]
trimethylammonium tetra(o-tolyl)boron, [0119] tributylammonium
tetra(pentafluorophenyl)boron, [0120] tripropylammonium
tetra(o,p-dimethylphenyl)boron, [0121] tributylammonium
tetra(m,m-dimethylphenyl)boron, [0122] tributylammonium
tetra(p-trifluoromethylphenyl)boron, [0123] tributylammonium
tetra(pentafluorophenyl)boron, [0124] tri(n-butyl)ammonium
tetra(o-tolyl)boron, [0125] N,N-dimethylanilinium
tetra(phenyl)boron, [0126] N,N-diethylanilinium tetra(phenyl)boron,
[0127] N,N-diethylanilinium tetra(phenyl)n-butylboron, [0128]
di-(isopropyl)ammonium tetra(pentafluorophenyl)boron, [0129]
dicyclohexylammonium tetra(phenyl)boron, [0130]
triphenylphosphonium tetra(phenyl)boron, [0131]
tri(methylphenyl)phosphonium tetra(phenyl)boron, [0132]
tri(dimethylphenyl)phosphonium tetra(phenyl)boron, [0133]
tropillium tetrakispentafluorophenyl borate, [0134]
triphenylmethylium tetrakispentafluorophenyl borate, [0135]
tropillium phenyltrispentafluorophenyl borate, [0136]
triphenylmethylium phenyltrispentafluorophenyl borate, [0137]
benzene(diazonium)phenyltrispentafluorophenyl borate, [0138]
tropillium tetrakis(2,3,5,6-tetrafluorophenyl)borate, [0139]
triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)borate,
[0140] tropillium tetrakis(3,4,5-trifluorophenyl)borate, [0141]
benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, [0142]
tropillium tetrakis(1,2,2-trifluoroethenyl)borate, [0143]
triphenylmethylium tetrakis(1,2,2-trifluoroethenyl)borate, [0144]
tropillium tetrakis(2,3,4,5-tetrafluorophenyl)borate, and [0145]
triphenylmethylium tetrakis(2,3,4,5-tetrafluorophenyl)borate.
[0146] Readily commercially available ionic activators include:
[0147] N, N-dimethylaniliniumtetrakispentafluorophenyl borate;
[0148] triphenylmethylium tetrakispentafluorophenyl
borate(tritylborate); and [0149] trispentafluorophenyl borane.
[0150] Ionic activators may also have an anion containing at least
one group comprising an active hydrogen or at least one of any
substituent able to react with the support. As a result of these
reactive substituents, the ionic portion of these ionic activators
may become bonded to the support under suitable conditions. One
non-limiting example includes ionic activators with
tris(pentafluorophenyl)(4-hydroxyphenyl)borate as the anion. These
tethered ionic activators are more fully described in U.S. Pat.
Nos. 5,834,393; 5,783,512; and 6,087,293.
[0151] It has been well recognized that a semi-crystalline
polyethylene resin consists of at least three phases, i.e.,
crystalline, amorphous and interfacial phases. The amount of
interfacial phase actually contains the contribution of tie chains
which has long been known as one of the key fundamental resin
parameters in determining many polyethylene product properties such
as toughness, environmental stress cracking resistance, etc. The
amount of interfacial phase can be used as an indication of the
amount of tie chains. Hence, within the same resin category (e.g.,
HDPE or MDPE), a resin with the higher amount of interfacial phase
would typically be expected to provide a higher toughness than
another with a lower amount of interfacial phase, either alone or
in a system such as composites. The single sited catalyzed
polyethylenes of the present invention have a higher amount of
polymer in the interfacial phase between the crystalline phase and
the amorphous phase and as such have a higher degree of tie chains
between these phases in the polymer. The increase in the amount of
interfacial phase in the single site catalysed (SSC) polyethylenes
over those of comparable, conventional Ziegler-Natta catalyzed
polyethylenes (e.g. comparable polyethylenes having a composition
within 5 weight %, preferably within 2 weight % of the single site
catalysed polyethylene, density within 0.005 g/cm.sup.3 of the
single site catalysed polyethylene, and a melt index within 0.5
g/10 min, preferably 0.2 g/10 min. of the single site catalysed
polyethylene) may range from about 1.5 to 7 weight %, preferably
from about 2 to 6 weight % as inferred using Raman spectroscopy
(using a 514.5 nm laser Raman Spectroscopy).
[0152] The polymers used to make the half panel may be compounded
in any conventional manner known to those skilled in the art such
as dry blending (e.g. tumble blending ) or melt blending (e.g.
extrusion blending). The resulting blend may then be injection or
compression molded to form the half panel. The conditions of these
processes are well known to those skilled in the art.
[0153] There are several types of compression molding processes. In
one process a pre-impregnated composite of long or chopped glass
fiber randomly oriented is prepared in a sheet form and put into a
suitable mold and the polyolefin composite (e.g. polyethylene
composition) is then injected into the mold. When the mold cools a
solid sheet is formed. Another compression process uses a low shear
screw in an injection machine to deliver the polymer fiber,
preferably glass, composition into half of a compression mold and
the other half of the mold is applied in a separate step.
Preferably the injection machine is fitted with a low shear screw
or screw having a distance between adjacent flights on the screw
greater than the desired length of the fiber used to reinforce the
composite. This tends to reduce fiber length attrition. Preferably
the forming process (extrusion, etc.) is such that fiber length
attrition (loss of initial fiber length in the feed to the molding
machine measured by comparing the fiber length in the molded part
versus the fiber length fed to the extruder) is less than 30%,
preferably less than 20%, most preferably less than 15%.
[0154] As noted above the resulting half panels may then be rotated
through the axis of symmetry (e.g. such as 180.degree. for
rectangles) and placed back to pack and fixed together. The half
panels may be glued together or heat welded together. Some
commercially available glues which may be useful include
GLUCO.RTM., BONDUIT.RTM., GORILLA GLUE.RTM., ScotchWeld.RTM.
DP8005, 3M.RTM. 4932, 3M.RTM. 4085, 3M.RTM. 9495LE etc.
[0155] In one application the full panels may be used to replace
plywood in a number of applications such as forms to pour concrete.
The supports or bracing for such forms typically comprise 2.times.4
inch (5 cm .times.10 cm) boards in a frame structure typically
having 18 inch (45.7 cm) vertical centers.
EXAMPLES
[0156] The present invention will now be illustrated by the
following non-limiting example.
Example 1
[0157] Applicants collected data for the deflection of 3/4 inch
plywood under a force of 600 psf when the plywood is in a frame
having 2''.times.4'' reinforcements on 16 inch centers. Using this
data the modulus for plywood was determined to be
1.1.times.10.sup.6 psi. Using this modulus a maximum deflection in
the center between 16 inch center 2''.times.4'' framework of a
piece of plywood under a force of 600 pounds per square foot was
calculated to be 0.0085 inches.
[0158] Using this data and assuming a modulus of 1.1.times.10.sup.6
psi and a deflection of 1/360 inches over a 16 inch reinforced span
various models of a panel according to the present invention with a
cell structure as shown in FIG. 1 using 6 and 8 inch cells for a
panel (e.g. two half panels assembled together) having a thickness
of 1.53 inches with ribs 0.125 inches thick and a skin thickness of
0.156 inches the following were calculated.
TABLE-US-00001 Maximum Deflection Panel (inches) under Description
Weight (lbs) 600 psf load Comments Base line 70-80 0.0085 Maximum
(plywood) allowed 0.044 inches 8 inch cell 80.68 0.021 6 inch cell
87.64 0.014
[0159] The data shows that the panels are competitive with plywood.
In field trials it was noted the panels of the invention do not
adsorb water to anywhere near the extent of plywood so a good
comparison for weight is towards the 80 lbs per sheet. The panels
release well from the mold and appear on average to be capable of
more uses per sheet than plywood reducing the cost per pour of
concrete.
* * * * *