Note: Descriptions are shown in the official language in which they were submitted.
WO 94/25526 ~ ~ PCT/US94/04512
BLENDS OF GRAFT-MODIFIED SUBSTANTIALLY LINEAR
ETHYLENE POLYMERS AND OTHER THERMOPLASTIC POLYMERS
This invention relates to elastic, substantially linear ethylene
polymers. In one aspect, this invention relates to such polymers
grafted with an unsaturated organic compound, for example, malefic
anhydride, while in another aspect, the invention relates to blends of
this grafted polymer with one or more other thermoplastic polymers,
for example, a polyester or a polyamide. In still another aspect,
this invention relates to such blends in combination with a filler.
In yet another aspect, this invention relates to such blends further
comprising one or more other olefin polymers, either grafted or
ungrafted.
The art is replete with concern for improving the toughness
1 5 (also known as ductility) of various thermoplastic resins, for
example, polyesters, polyamides. The toughness or ductility of a
thermoplastic resin is typically measured by use of the notched IZOD
impact test (ASTM D-256). However, the art typically discusses
thermoplastic toughness in the context of ambient temperature with
2 0 little, if any, recognition of the desirability of thermoplastic
toughness in many applications at low temperature (less than 0 C).
Moreover, not only do most commercially available thermoplastic resins
have less than desirable impact resistance at low temperatures, but
most also have less than desirable optical and other physical
2 5 properties.
The graft modification of polyolefins, such as polyethylene and
polypropylene, with various unsaturated monomers is also well known in
the art. Such a modification renders an essentially nonpolar material
compatible, at least to some limited extent, with a polar material.
3 0 This, in turn, impacts an certain of the properties of the polyolefin,
for example, its ability to adhere or laminate to a solid. For
example, USP 4,198,327 teaches a modified crystalline polyolefin
composition having improved adhesion to polar solid materials. USP
4,397,916 and 5,055,526 also teach adhesive resin compositions of
3 5 modified polyolefins and laminates made from such polyolefins.
As these references suggest, much of the existing art is
primarily concerned with the modification of these polyolefins to
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CA 02160794 2004-02-17
7.7252-58
develop compositions having specific adhesive properties or
improvements in adhesive properties. However, not only do
these references discuss lightly or not at all the possible
advantageous influence that these graft-modified resin can
have on these compositions, but some note that these resins
can actually have a detrimental influence on one or more
properties of the polyolefin and/or the composition. For
example, USP 4,134,927; 3,884,882 and 5,140,074 all report
undesirable changes in the rheological properties due to
l0 crosslinking of the modified material. These changes
ultimately impact the processibility of the material and
thus, its utility in commercial applications.
The subject invention is directed to,
thermoplastic compositions characterized as a substantially
homogeneous blend of at least one thermoplastic polymer and
at least one substantially linear ethylene polymer grafted
with at least 0.01 wt $, based on the weight of the grafted
ethylene polymer, of an unsaturated organic compound
containing at least one site of ethylenic unsaturation and
at least one carboxyl group, the ethylene polymer
characterized as having:
(i) a melt flow ratio, Ilo/I2 Z 5.63;
(ii) a molecular weight distribution, MW/Mn,
defined by the equation: Mw/Mn ~ (Ilo/I2) - 4.63;
(iii) a density greater than 0.850 g/cm3; and
(iv) a critical shear rate at onset of surface
melt fracture of at least 50 percent greater than the
critical shear rate at the onset of surface melt fracture of
a linear olefin polymer having the same I2 and MW/Mn.
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CA 02160794 2004-02-17
77252-58
According to one aspect of the present invention,
there is provided a substantially linear ethylene polymer
grafted with at least 0.01 wt %, based on the weight of the
grafted ethylene polymer, of an unsaturated organic compound
containing one or more site of ethylenic unsaturation and
one or more carboxyl group, the ethylene polymer
characterized as having: (i) a melt flow ration, Ilo/I2 z
5.63; (ii) a molecular weight distribution, Mw/Mn, defined by
the equation: MW/Mn S (Ilo/I2) - 4.63; (iii) a density
greater than 0.850 g/cm3; and (iv) a critical shear rate at
onset of surface melt fracture of at least 50 percent
greater than the critical shear rate at the onset of surface
melt fracture of a linear olefin polymer having about the
same I2 and Mw/Mn.
According to another aspect of the present
invention, there is provided a composition comprising one or
more grafted ethylene copolymer as described herein and one
or more thermoplastic polymer.
The inventive compositions demonstrate desirable
impact resistance at both ambient and low temperatures as
well as desirable optical properties and small particle
sizes relative to known polymers. The thermoplastic
compositions of this invention can be either filled or
unfilled. In one embodiment of the invention, these
compositions can further comprise one or more other
polyolefins, either grafted or ungrafted.
Figure 1 reports comparative notched IZOD impact
energy data at ambient temperature for PBT and various
blends of PBT with MAH-g-ITP, malefic anhydride grafted
ethylene-propylene rubber
-2a-
77252-58
CA 02160794 2004-02-17
(MAH-g-EPR), and malefic anhydride grafted ethylene-propylene-diene
monomer (MAH-g-EPDM), respectively.
TM
Figure 2 reports comparative Dynatup impact energy data at -20 F
(-28.8 C) for PBT and the same blends as identified in Figure 3.
Figure 3 reports comparative notched IZOD impact energy data at
ambient temperature for poly(butylene terephthalate) (PBT) and various
blends of PBT with a malefic anhydride grafted substantially linear
ethylene polymer (MAH-g-ITP) and a malefic anhydride grated TafmerT"
resin (MAH-g-Tafmer).
DESCRIPTION OF THE PREFERRED EMBODI1~1ENTS
The substantially linear ethylene polymers used in the. practice
of this invention are known, and they and their method of preparation
are fully described in USP 5.272,236 and UsP 5,278,272. As here used,
'substantially linear means that the polymer backbone is substituted
with from 0.0I Iong-chain branchesl1000 carbons to 3 long-chain
branches/1000 carbons, preferably from 0.01 long-chain branches/1000
carbons to 1 long-chain branch/1000 carbons, more preferably from 0.05
long-chain branches/1000 carbons to 1 long-chain branch/1000 carbons.
Long-chain branching is here defined as a chain length of at least
2 0 about 6 carbon atoms, above which the length cannot be distinguished
using 13C nuclear magnetic resonance spectroscopy'. However, the long-
chain branch can be about the same length as the length of the polymer
backbone.
These unique polymers (subsequently referred to as ~CGC
2 5 polymers') are prepared by using constrained geometry catalysts (CGC);
and are characterized by a narrow molecular weight distribution and if
an interpolymer, by a narrow comonomer distribution. As here used,
~interpolymer~ means a polymer of two or more comonomers, for example,
a copolymer, terpolymer, etc., or in other words, a polymer made by
3 0 polymerizing ethylene with at least one other comonomer. Other basic
characteristics of these CGC polymers include a low residuals content
(that is, low concentrations in the CGC polymer of the catalyst used
to prepare the polymer, unreacted comonomers, and low molecular weight
oligomers made during the course of~the polymerization), and a
3 5 controlled molecular architecture which provides good processability
even though the molecular weight distribution is narrow~relative to
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WO 94/25526 PCTIUS94/04512
conventional olefin polymers.
While the CGC polymers used in the practice of this invention
include elastic, substantially linear ethylene homopolymers,
preferably the CGC polymers used in the practice of this invention
comprise from 95 to 50 weight percent (wt o) ethylene, and from 5 to
50 wt % of at least one a-olefin comonomer, more preferably 10 to 25
wt % of at least one a-olefin comonomer. Typically, the CGC polymers
are copolymers of ethylene and an a-olefin of from 3 to 20 carbon
atoms (for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene,
1-heptene, 1-octene, styrene, etc.), preferably of from 3 to 10 carbon
atoms. More preferably these polymers are a copolymer of ethylene and
1-octene. The density of these CGC polymers is typically from 0.850
to 0.935 grams per cubic centimeter (g/cm3), preferably from 0.870 to
0.910 g/cm3. The melt flow ratio, measured as I10/I2 (ASTM D-1238),
is greater than or equal to 5.63, and is preferably from 6.5 .to 15,
more preferably from 7 to 10. The molecular weight distribution
(Mw/Mn), measured by gel permeation chromatography (GPC), is defined
by the equation:
Mw/Mn <_ (I10/I2) - 4.63,
2 0 and is preferably from 1.8 to 2.5. For substantially linear ethylene
polymers, the I10/I2 ratio indicates the degree of long-chain
branching, that is the larger the Il0/I2 ratio, the more long-chain
branching in the polymer.
According to Ramamurthy in JoLrnal_ of Rheoloav, 30(2), 337-357,
2 5 1986, above a certain critical flow rate, surface melt fracture may
occur, which may result in irregularities ranging from loss of
specular gloss to the more severe form of "sharkskin . As used
herein, the onset of surface melt fracture is characterized as the
beginning of losing extrudate gloss at which the surface roughness of
3 0 extrudate can only be detected by 40x magnification The substantially
linear ethylene polymers will further be characterized by a critical
shear rate at the onset of surface melt fracture which is at least 50
percent greater than the critical shear rate at the onset of surface
melt fracture of a linear olefin polymer having about the same I2 and
35 Mw/Mn.
The unique characteristic of the homogeneously branched,
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PCT/US94/04512
WO 94/25526
substantially linear ethylene polymers is a highly unexpected flow
property where the I10/I2 value of the polymer is essentially
independent of the polydispersity index (that is, Mw/Mn) of the
polymer. This is contrasted with conventional linear homogeneously
branched and linear heterogeneously branched polyethylene resins
having Theological properties such that to increase the I10/I2 value
the polydispersity index must also be increased.
The preferred melt index, measured as I2 (ASTM D-1238, condition
190/2.16 (formerly condition E)), is from 0.5 g/10 min to 200 g/10
min, more preferably from 1 to 20 g/10 min. Typically, the preferred
CGC polymers used in the practice of this invention are homogeneously
branched and do not have any measurable high density fraction, that
is, short chain branching distribution as measured by Temperature
Rising Elution Fractionation which is described in USP 5,089,321.
Stated in another manner, these polymers preferably do not contain any
polymer fraction that has a degree of branching less than or equal to
2 methyls/1000 carbons. These preferred CGC polymers also usually
exhibit a single differential scanning calorimetry (DSC) melting peak.
Any unsaturated organic compound containing at least one site of
2 0 ethylenic unsaturation (for example, at least one double bond), at
least one carboxyl group (-COOH), and that will graft to a CGC polymer
as described above can be used in the practice of this invention. As
here used, carboxyl group" includes carboxyl groups her ~g and
derivatives of carboxyl groups such as anhydrides, esters and salts
2 5 (both metallic and nonmetallic). Preferably, the organic compound
contains a site of ethylenic unsaturation conjugated with a carboxyl
group. Representative compounds include malefic, acrylic, methacrylic,
itaconic, crotonic, a-methyl crotonic, and cinnamic acid and their
anhydride, ester and salt derivatives, and fumaric acid and its ester
3 0 and salt derivatives. Malefic anhydride is the preferred unsaturated
organic compound containing at least one ethylenic unsaturation and at
least one carboxyl group.
The unsaturated organic compound content of the grafted CGC
polymer is preferably at least 0.01 wt o, and more preferably at least
3 5 0.05 wt o, based on the combined weight of the polymer and the organic
compound. The maximum amount of unsaturated organic compound content
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WO 94/25526 PCT/US94/04512 '
can vary to convenience, but typically it does not exceed 10 wt %,
preferably it does not exceed 5 wt o, and more preferably it does not
exceed 2 wt ~ of the grafted CGC polymer:
The unsaturated organic compound-can be grafted to the CGC
polymer by any known technique, such as those taught in USP 3,236,917
and USP 5,194,509. For example, in the '917 patent the polymer is
introduced into a two-roll mixer and mixed at a temperature of 60 C.
The unsaturated organic compound is then added along with a free
radical initiator, such as, for example, benzoyl peroxide, and the
components are mixed at 30 C until the grafting is completed. In the
'509 patent, the procedure is similar except that the reaction
temperature is higher, for example, 210 to 300 C, and a free radical
initiator is not used or is used at a reduced concentration.
An alternative and preferred method of grafting is taught in USP
4,950,541, by using a twin-screw devolatilizing extruder as the mixing
apparatus. The CGC polymer and unsaturated organic compound are mixed
and reacted within the extruder at temperatures at which the reactants
are molten and in the presence of a free radical initiator.
Preferably, the unsaturated organic compound is injected into a zone
2 0 maintained under pressure within the extruder.
In one embodiment, the graft-modified CGC polymers act as
compatibilizers for the filled compositions of this invention. Many
molded and extruded products contain fillers, for example, silica,
talc, glass, clay, carbon black, and the like, for strength and/or
2 5 some other desirable property. Often these fillers are only marginally
compatible with the resinous matrix within which they are incorporated
and as such, the amount of filler that can be incorporated into the
matrix, that is, the loading level, is limited. Compatibilizers are
used to coat or otherwise treat the filler to render it more
3 0 compatible with the matrix, and thus allow a higher loading than
otherwise possible to be achieved. The graft-modified substantially
linear ethylene polymers used in this invention are particularly
desirable compatibilizers because higher loading levels can be
achieved, that is either more filler can be incorporated into a given
.3 5 resin matrix based on the amount of compatibilizer, or less
compatibilizer is required to incorporate the same amount of filler.
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WO 94/25526 PCTIUS94104512
In addition, the compatibilizers of this invention impart desirable
properties to the composition in both fabricated and prefabricated
form. In fabricated form, the strength and impact properties (both at
ambient and low temperature) are enhanced relative to fabricated
compositions devoid of grafted substantially linear ethylene polymer.
In prefabricated form, the processability of the compositions are
enhanced relative to compositions devoid of grafted substantially
linear ethylene polymer.
The amount of graft-modified substantially linear ethylene
polymer required to effectively serve as a compatibilizer will, of
course, vary with the nature of the resinous matrix, the nature and
amount of filler, and the chemical and physical characteristics of the
substantially linear ethylene polymer and unsaturated organic compound
containing a carboxyl group (and the extent of grafting). Typically,
the weight ratio of graft-modified substantially linear ethylene
polymer to filler is from 1:50 to about 50:1, preferably from 1:40 to
20:1.
The graft-modified substantially linear ethylene polymer is dry
blended or melt blended with other thermoplastic polymers to make the
2 0 substantially homogeneous compositions of this invention, and then
these compositions are molded or extruded into a shaped article. As
here used, °substantially homogeneous" means that the components of
the composition are sufficiently mixed with one another such that the
make-up of one portion of the composition is substantially the same as
2 5 that of any other portion of the composition. Such other
thermoplastic polymers include any polymer with which the grafted
substantially linear ethylene polymer is compatible, and include both
olefin and non-olefin polymers, grafted and ungrafted. The grafted
substantially linear ethylene polymer can also be blended with another
3 0 substantially linear ethylene polymer, a conventional heterogeneously
branched or homogeneously branched linear ethylene polymer, a non-
olefin polymer, any of which can be grafted or ungrafted, or any
combination of these polymers. Examples of such polymers include high
density polyethylene (HDPE), low density polyethylene (LDPE), linear
3 5 low density polyethylene (LLDPE), ultra low density polyethylene
(ULDPE), polypropylene, ethylene-propylene copolymer, ethylene-styrene
WO 94/25526" ~ ~ ~ ~ ~ PCT/US94/04512
copolymer, polyisobutylene, ethylene-propylene-diene monomer (EPDM),
polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS),
ethylene-acrylic acid (EAA), ethylene/vinyl acetate (EVA),
ethylene/i~inyl alcohol (EVOH), polymers of ethylene and carbon
monoxide (ECO, including those described in USP 4,916,208), or
ethylene, propylene and carbon monoxide (EPCO) polymers, or of
ethylene, carbon monoxide and acrylic acid (ECOAA) polymers, and the
like. Representative of the non-olefin polymers are the polyesters,
polyvinyl chloride (PVC), epoxies, polyurethanes, polycarbonates,
polyamides, and the like. These blending polymers are characterized
by a compatibility with the grafted substantially linear ethylene
polymer such that the melt blend does not exhibit gross phase
separation, that is a separation in which the individual components of
the blend are visible to the unaided eye, after thorough blending and
during subsequent processing of the blend. If more than one of these
polymers is blended with one or more grafted substantially linear
ethylene polymers, then all usually exhibit sufficient compatibility
with each other, one-to-one or at least in combination with one or
more other polymers, such that the polymeric components do not exhibit
2 0 gross phase separation which could lead to extrusion processing
difficulties, such as extrudate surging, and film band-effects.
The amount of graft-modified substantially linear ethylene
polymer that is blended with one or more other polymers is dependent
upon many factors, including the nature of the other polymer or
2 5 polymers, the intended end use of the blend, and the presence or
absence and the nature of additives. For molded articles,
particularly engineered materials (for example, hoses, shrouds, etc.)
the grafted substantially linear ethylene polymer is blended with an
engineering plastic, for example, polyamide or polyester, such that
3 0 the blended composition typically comprises from 2 to 70 wt o,
preferably from 5 to 30 wt % of the graft modified substantially
linear ethylene polymers) on a total weight basis. In those
applications in which the grafted substantially linear ethylene
polymer is blended with other polyolefin polymers, for example, a non-
3 5 grafted substantially linear ethylene polymer or a conventional
polyolefin polymer (LLDPE, HDPE, PP, etc.), the blend typically
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WO 94/25526 PCTlUS94/04512
comprises from 2 to 70 wt o, preferably from 5 to 30 wt o, of the
graft-modified substantially linear ethylene polymer. Wire and cable
are end use applications for such polymer blends. The presence of the
graft-modified substantially linear ethylene polymer in these blends,
both for engineered materials and wire and cable, provides improved
impact and/or strength properties to the compositions.
In other embodiments, the graft-modified substantially linear
ethylene polymer comprises from a relatively minor amount (for
example, 10 wt $), up to a substantial majority, for example, 90 wt %,
of the finished article. In those applications in which the
paintability of the finished article is of importance, incorporation
from 30 to 70 wt $ of a graft-modified substantially linear ethylene
polymer will impart desirable paintability properties to an otherwise
unpaintable molded article, for example, an article prepared from a
polyolefin such as polyethylene and polypropylene.
In another application, the grafted substantially linear
ethylene polymer is made into a film comprising up to 100 wt ~ of the
graft-modified substantially linear ethylene polymer. Such films
exhibit desirable adhesive properties, and are useful as tie layers in
2 0 various packaging applications, for example, tying another polyolefin
to polypropylene, polyester, polyamide, EVOH, paperboard, foil, etc.
These laminated or coextruded structures have utility as lidding
stock, pouches for liquid foods, bag and box packaging structures, and
barrier packaging films.
2 5 As noted above, the polymer blends in which the graft-modified
substantially linear ethylene polymer is incorporated can include
other additives, such as fillers, colorants, antioxidants, antistats,
slip agents, tackifiers, and fragrances. These additives are
incorporated by known methods in known amounts.
3 0 In another embodiment of this invention, the grafted
substantially linear ethylene polymer is let-downu or diluted with
virgin substantially linear ethylene polyolefin or another grafted
substantially linear ethylene polymer prior to mixing it with a
blending polymer. For example, after the grafted substantially linear
3 5 ethylene polymer has been prepared as described in USP 4,950,541, it
is then back-blended in an extruder with virgin substantially linear
_g_
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WO 94/25526 PCT/US94/04512
ethylene polymer to a predetermined dilution. Let-down or dilution
ratios will vary with the ultimate application of the grafted
substantially linear ethylene polymer, but weight ratios from 1:10 to
10:1 are typical.
The grafted substantially linear ethylene polymers used in the
practice of this 'invention, and the compositions comprising these
polymers, are more fully described in the following examples. Unless
indicated to the contrary, the substantially linear ethylenes used in
the examples are prepared in accordance with the techniques set forth
in USP 5,272,236 via a solution polymerization process utilizing a
[((CH3)4C5)}-(CH3)2 Si-N-(t-C4H9)]Ti(CH3)z organometallic catalyst
activated with tris(perfluorophenyl)borane. Unless indicated to the
contrary, all parts and percentages are by weight, total weight basis.
Unless indicated to the contrary, the following test procedures are
utilized:
1. Notched IZOD Impact ASTM D-256 (at 23
(ft-lb/in) C, 0 C,
-18 C, -29 C and
-40 C)
2. Tensile (psi) ASTM D-638
3. Yield (psi) ASTM D-638
4. Elongation (%) ASTM D-638
5. Whiteness Index (WI) ASTM E-313
2 6. Yellowness Index (YI) ASTM E-313
5
7. Particle Size (microns) Electron
micrographs of
microtomed molded
test samples
3 8. Dynatup ASTM D-3763-86
0
(at -29C)
SPECT_FT_C E MBODIMENTS
,ample Preparation
All samples were prepared by feeding polymer as described in
3 5 Table 1 into a Werner-Pfleiderer ZSK-53/5L co-rotating twin screw
extruder operated at the conditions described in Table 2. After the
polymer was fed into the extruder, a mixture of malefic anhydride
(MAH)/methyl ethyl ketone (MEK)/LUPERSOL 130 (Initiator) at a weight
ratio of 1:1:0.032, respectively, was fed into the end of Zone 1 of
40 the extruder through an injection nozzle by a metering pump. LUPERSOL
130 is 2,5-di(t-butyl peroxy)hexyne-3 manufactured and sold by
Atochem. The extruder was maintained at a vacuum level of greater
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77252-58
CA 20160794 2004-02-17
than or equal to 26 inches of mercury (88 kPa) to facilitate
devolatization of solvent, unreacted MAH and other contaminates. The
percent of incorporation of MAH into each polymer is also reported in
Table 1. Example C1 is an ultralow density ethylene/1-octene resin
manufactured and sold by The Dow Chemical Company under the tradename
~TM
ATTANE. Example C2 is Dowlex~ 2517 resin, a LLDPE ethylene/1-octene
resin manufactured and sold by The Dow Chemical Company. Example C3
is Tafmer~ P-0180 resin, an ethylene/propylene copolymer resin
manufactured and sold by Mitsui Petrochemical. Examples C1. C2 and C3
1 0 are camparative examples. The resin used in Examples 1-4 was a
substantially linear ethylene polymer of ethylene and 1-octene.
TABLE I
Incorporation of Malefic Anhydride into
Conventional and Substantially Linear Ethylene
Pn;vmpre
Example Melt Density* Melt Flow% Incorporation
Index* (g/cm3) Ratio*
(I~) I~n/I~
C1 3.4 0.906 7.65 40.2
C2 25.0 0.917 - 25.3
C3 5.0 0.870 5.91 48.9
1 7.0 0.903 7.57 68.9
2 5.0 0.871 7.66 57.3
3 0.75 0.870 7.58 62.3
4 25.0 0.870 - 30.6
*Ungrafted polymer
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WO 94/25526 PCT/US94I04512
TABLE 2
Barrel Temp C1 C2 C3 y l~ 2 3 4
(C)
Zone 1 164 156 177 142 140 150 162
Zone 2 191 193 200 176 186 195 154
Zone 3 201 198 202 195 206 198 203
Zone 4 236 206 200 180 192 221 207
Polymer Melt177 162 162 173 162 163 N/A*
Tem (C)
Screw Speed 300 300 320 320 255 300 320
(r m
Polymer Feed
Rate
(lb per hr/ 150/ 150/ 135/ 150/ 130/ 135/ 135/
k er hr 68.2 68.2 61.4 68.2 59.1 61.4 61.4
MAH/MEK/ 6.45/ 5.92/ 5.96/ 5.57/ 5.90/ 5.84 5.46
Initiator 2.93 2.69 2.71 2.53 2.68 / /
Feed Rate 2.65 2.48
(lb per hr/
k er hr
* N/A = Not Available
The data of Table 1 show that the grafting of a substantially
linear ethylene polymer is more efficient than the grafting of a non-
substantially linear ethylene polymer having similar physical
properties of melt index, density, and melt flow ratio. The polymer
of Example 1 is a substantially linear ethylene polymer with a melt
index of 7.0 g/10 min and a density of 0.903 g/cm3, with 68.9% of the
MAH being incorporated into it. In comparison, the polymer of
Comparative Example 1 is a non-substantially linear ethylene polymer
(ULDPE) with a melt index of 3.4 g/10 min and a density of 0.906
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PCT/US94/04512
WO 94!25526
g/cm3, which incorporated only 40.20 of the MAH under similar
conditions. The substantially linear ethylene polymer incorporated
70o more MAH under similar conditions than did the comparative non-
substantially linear ethylene polymer. These results mean that the
graft-modified substantially linear ethylene polymers of this
invention can be prepared with lower loss of materials (that is lower
levels of MAH required to obtain the same level of grafting as for
non-substantially linear ethylene polymers), and lower emissions due
to the use of less volatiles.
Adhesive Proy~erties
The adhesive properties of the grafted polymer samples of
Comparative Example 1 and Example 1 were determined by heat seal
lamination. The graft-modified polymers were fabricated into blown
film having a thickness of 0.003 inches (0.008 cm). Film test
samples, one inch (2.5 cm) in width, were cut from the blown film and
heat sealed to polypropylene (PF-101, available from Pacur, Inc.),
polyamide (Nylon 6, available from Capron-Allied Co.), ethylene/vinyl
alcohol (Soranol'~' D, available from Nippon Chemical Co.),
polycarbonate (LexanT", available from General Electric Plastics) and
2 0 polyetherimide (AltemT", available from General Electric Plastics)
films at selected temperatures. The heat seal conditions were 40
lb/in2 (280 kPa) of pressure applied for 0.5 seconds by means of
heated seal bars set at the desired temperature. The strength of the
heat seals was determined on an Instron tensionmeter apparatus using a
2 5 180 degree ("T") pull at a crosshead speed of 2 in/min (5 cm/min).
The data from these tests are reported in Table 3.
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WO 94/25526 PCT/US94/04512
TABLE 3
Heat Seal Como~risons
C1 FILM EX. 1 FILM
HEAT SEAL HEAT SEAL
TEMPERA'hURESTRENGTH STRENGTH
(lb
SUBSTRATE (C) (lb. per per in/kg
in/kg per per cm)
cm)
Polypropylene 130 0 0
140 0 0
150 0.1/0.1 0.4/0.3
160 0.3/0.3 1.1/0.95
170 1.8/1.6 2.6/2.3
180 2.0/1.7 2.82/4
Polyamide 130 0.6/0.5 1.0/0.87
140 0.6/0.5 1.0/0.87
150 1.0/0.87 1.5/1.3
160 1.5/1.3 1.5/1.3
170 2.0/4.3 2.14.5
180 2.2/4.8 film failure
Ethylene/vinyl130 1.3/2.8 1.0/0.87
alcohol 140 1.3/2.8 1.0/0.87
150 1.3/2.8 1.2/2.6
160 1.6/3.5 1.5/2.6
170 2.0/4.3 2.0/4.3
180 2.5/4.8 2.3/5.0
Pol carbonate 230 0.2/0.4 1.5/2.6
Polyetherimide230 1.0/0.87 0.8/1.7
The film test samples of Example 1 gave improved adhesion to
polypropylene, polyamide and polycarbonate substrates, as well as
similar adhesion to EVOH and polyetherimide, as compared to the film
test samples of Comparative Example 1. Additional improvements in the
adhesive properties of the graft-modified substantially linear
ethylene polymers can be realized with respect to changes in resin
density and fabrication techniques, for example, extrusion lamination
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WO 94/25526 PCTIUS94/04512
or multilayer extrusion. Improvement can also be obtained in the
adhesive properties of such blends by using a grafted substantially
linear ethylene polymer that has been back-blended or let-down with an
ungrafted substantially linear ethylene polymer.
~~act Prgrerties
The use of graft-modified substantially linear ethylene polymers
to,improve the impact~properties of various polymer blends was
evaluated by incorporating the polymer into a polyamide resin (CAPRON
8207, manufactured and sold by Allied-Signal). Melt blends of the
polyamide with 0, 10 and 25 wt $ of the graft-modified substantially
linear ethylene polymer were prepared on an extruder prior to molding
on an injection molding machine. The injection molded test samples
(IZOD specimens) were evaluated for room temperature notched IZOD
impact performance. The formulations and results are reported in
Table 4.
TABLE 4
TZOD Imract Comparisons
BLEND COMPOSITION
POLYAMIDE MODIFIER (WT $) IZOD IMPACT
(WT $) (ft-lb per in/
J
er cm)
Pol amide (100$)None 1.3/0.69
Pol amide (90$) C1 (10$) 2.7/1.4
Pol amide (75$) C1 (25$) 15.4/8.22
Pol amide (90$) Ex. 1 (10$) 4.0/2.1
Polyamide (75$) Ex. 1 (25$) 16.1/8.59
2 0 As is evident from the data in this Table, polyamide blends
containing the graft-modified substantially linear ethylene polymer
have higher IZOD impact performance as compared to blends containing a
similar graft-modified ULDPE, that is, Comparative Example 1.
Additional improvements can be realized by lowering in the polymer
2 5 density.
Compatibili at,'_on Properties
These properties were evaluated by blending the graft-modified
substantially linear ethylene polymer of Example One with a base
-15-
2160"~ 1
WO 94125526 PCTlUS94/04512
composition containing an unmodified substantially linear ethylene
polymer (1 g/10 min MI, 0.902 g/cm3 density), an inorganic filler (240
parts per hundred resin (phr) viny'1'-silane treated aluminum
trihydrate), peroxide (5 phr'~Vulcup 40 KE available from Hercules
Inc.), coagent (0.8 phr TAC - triallyl cyanurate, available from Union
Carbide), and a hydrocarbon oil (80 phr sunpar 2280 available from Sun
Oil Company). Melt blends containing 0, 5 and 10 parts of the graft-
modified substantially linear ethylene polymer phr and 100, 95, and 90
parts ungrafted base resin were prepared on a small Banbury internal
mixer. The blended samples were compression molded and evaluated for
tensile strength properties before and after curing. The curing
conditions were 1 minute at 400 F (204 C). The tensile strength
properties for these blends are reported in Table 5.
TABLE 5
Tens,'_le strength Prorerti_es
Sample Ungrafted Ex 1 Tensile
Strength
Base Level
Resin (phr)
( hr)
Uncured Cured
( si/kPa) ( si/kPa)
A 100 0 709/4890 1243/8570
B 95 5 109777569 1486/10,250
C 90 10 1223/8432 1421/9797
As shown by the data in this Table, the incorporation of graft-
modified substantially linear ethylene polymer into these compositions
2 0 allows for compatibilization of an inorganic filler with a resin
matrix resulting in higher tensile strength properties. In addition,
higher tensile strength properties are obtained both before and after
curing.
Prooessi_bili_tv
2 5 The processibility of the graft-modified substantially linear
ethylene polymers as compared to graft-modified non-substantially
linear ethylene polymers was determined from the reduced melt
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WO 94!25526 ~ PCT/US94/04512
viscosity vs. shear rate data obtained from capillary rheology
evaluations at 190 C. In order to obtain these data, the apparent
melt viscosity (poise) vs. apparent shear rate (1/seconds) data was
generated according to the ASTM D-3835 method. The reduced melt
viscosity data were calculated by dividing the melt viscosity (n)
obtained at each shear rate by the melt viscosity (n*) measured at the
lowest possible shear rate. For the condition used in these
determinations, the lowest shear rate corresponds to 2.96 seconds-1.
An example of these reduced melt viscosity calculations are
illustrated below.
Capillary Rheology Data
Apparent Melt Viscosity at 2.96 seconds-1 = 74,800 poise (7480
Pas) (n*)
Apparent Melt Viscosity at 7.40 seconds-1 = 46,400 (4640 Pas)
1 5 poise (n)
Reduced Melt Viscosity at 2.96 seconds-1 = 1.000 (n*/n*)
Reduced Melt Viscosity at 7.40 seconds-1 = 0.620 (n/n*)
These reduced melt viscosity data are calculated from the lowest
(2.96 seconds-1) to the highest shear rate (2960 seconds-1) obtained
2 0 from the capillary rheology evaluations. These reduced melt viscosity
data are reported in Table 6 for Comparative Examples 1 and 3 and
Examples 1 and 2.
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21 ~ '~ ~ ~ 4
WO 94/25526 PCT/US94/04512
TABLE 6
Reduced
Melt
Viscosity
(x 103)
Apparent ~ Shear
Rate C1 C3 1 2
(second '1)
2.96 1000 1000 1000 1000
7.40 620 610 600 600
14.80 450 450 430 420
29.60 330 330 300 295
74.00 220 220 190 185
148.00 150 150 130 125
296.00 110 90 90 85
740.00 60 58 51 48
1480.00 37 N/A 31 29
2960.00 22 N/A 19 18
N/A = Not Available
The data in Table 6 illustrates the effect of shear rate on melt
viscosity (that is, reduced) for Comparative Example 1 vs. Example 1,
and Comparative Example 3 vs. Example 2. These data shows that the
compositions of this invention have significantly lower melt
viscosities as compared to the noninventive compositions at a variety
of shear rates.
The percent difference between the reduced melt viscosity values
for Example 1 and Comparative Example 1 were calculated at each
corresponding shear rate. This data is reported in Table 7.
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WO 94/25526 ~ ~ PCT/US94/04512
TABLE 7
Calculated Percent Difference in
Apparent Shear Rate Percent Difference*
(seconds-1) in
Reduced Melt Viscosit
2.96 0.0
7.40 3.3
14.80 4.7
29.60 10.0
74.00 15.8
148.00 15.4
296.00 22.0
740.00 17.6
1480.00 1
9.4
2960.00 _
_
15.8
*Percent Difference Calculation (at 7.40 seconds-1)
1620-600) x 100 = 3.3~
600
The percent difference data in Table 7 show that the graft-
modified substantially linear ethylene polymers of this invention
afford processability advantages over the graft-modified non-
substantially linear ethylene polymers (the lower the melt viscosity
at a given shear rate, generally the better the processibility of the
polymer). Moreover, the magnitude of these differences increases with
shear rate. The benefit of lower melt viscosities is improved
extrusion processability, that is, lower extrudate energy consumption,
nonsurging, and smoother extrudate.
Tact Properties of Certain Blends Contai_nina Graft-modi_fi_ed
2 0 Substantial1v T_.inear Ethylene Polymer
The following materials were used in this test:
ADMER QF 500A, a polypropylene grafted with 1.5 wt o MAH and
manufactured and sold by Mitsui Petrochemical; the grafted polymer had
a melt index of 3.0 g/10 min at 230 C and a density of 0.900 g/cm3.
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3 ~ ~ .
,; .,
WO 94/25526 PCT/US94104512
Primacor~ 3460, a copolymer of ethylene and acrylic acid
manufactured and sold by The Dow Chemical Company; this material
contained 9.7 wt ~ acrylic acid monomer and had a melt index of 20
g/10 min.
Graft-modified substantially linear ethylene polymer; ENGAGETM
EG8200 polyolefin elastomer made by The Dow Chemical Company, as
grafted with 1.3 weight percent malefic anhydride. The graft modified
material had a melt index of 0.25 g/10 min and a density of 0.870
g/cm3.
Profax~ 6524, a polypropylene manufactured and sold by
Himont; it had a melt index of 4 g/10 min at 230 C and a density of
0.9 g/cm3.
The graft-modified substantially linear ethylene polymer
(referred to below as Insite'~ Technology Polymer or ITP) was prepared
according to the procedure described in USP 4,950,541. The polymer
components were dry mixed at a certain weight ratio (as reported in
Table 8), and were then fed into a Werner-Pfleiderer ZSK-30 twin-screw
extruder operated at about 210 C. The blends were made in one
extrusion pass.
2 O TABLE 8
Sample Graft- PolypropyleneGraft- EAA
Modified (Profax~ Modified (Primacor~)
Polypropylene6524) Substantially
(Admer~ QF Linear
500A) Ethylene-
Pol mer (ITP)
C4 100 --- --- --'
C5 50 --- --- 50
5 -- --- 50 50
6 50 --- 50 ---
7 50 --- 20 30
g --- 50 20 30
Injection molded samples were prepared using a 50 ton (45 tonne)
2 5 Negri-Bossi Injection Molder operated with a barrel temperature
between 200 and 250 C, a barrel pressure of 40 bars (4 MPa), cooling
mold temperature of 85 F (29 C), and a residence time in the cooling
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WO 94/25526 ~ ~ . PCT/US94I04512 '
mold of about 12 seconds. The samples were formed into 2.5" x 6.5" x
0.075" (5 cm x 17 cm x 0.19 cm) plaques.
The flex modulus and IZOD impact properties (at room temperature
and -30 C) were measured for each of the samples in Table 8. These
properties are important in many applications, for example, automobile
parts. The properties were measured according to ASTM D-790 and D-
256, respectively, and the results are reported in Table 9. Samples 6
and 7 exhibit very good low temperature impact properties, the result
of the presence of the graft-modified substantially linear ethylene
polymer.
TABLE 9
Sample Flex Modulus IZOD at Room IZOD at -30
(kpsi/Pa) Temp (ft-lb per C
in/J er cm) (ft-lb per
in
/ J er cm)
C4 135/9.31 x 105 8.3/4.4 0.55/0.29
C5 --- 2.76/1/47 0.52/0.28
5 8/5.5 x 104 3.51/1.87 1.07/0.57
6 39/2.7 x 105 6.2/3.3 12.1/6.46
7 56/3.9 x 105 6.55/3.49 5.82/3.11
8 70/4.8 x 105 9.09/4.85 0.84/0.45
ComDari_son of Tmpact and Other ProBerties of Specimans
j~jade by_ Tn~ecrion M~l~7i_n_g of B1_ends of Pol~rester and Graft-Modi_fi_ed
Substantially Linear Ethylene Polymer
A blend containing 20o by wt substantially linear ethylene/1-
octene polymer (ITP) grafted with about 1% malefic anhydride and 80% by
2 0 wt polybutylene terephthlate (PBT) was compounded on a Welding
Engineers counter-rotating twin screw extruder operated at 200 rpm
using the temperature profile reported in Table 10.
-21-
21~~'~~
WO 94125526 PCT/US94I04512
TALE 10
Zone , Barrel Temp
(C
1 (feed) 290
2 250
3 250
4 260
260
6 260
7 260
die 250
The ITP was prepared according to the methods taught in USP
5 5,272,236 and USP 5,278,272, and it was grafted with malefic anhydride
as described in the Sample Preparation section above. Certain
physical properties of these polymers are reported in Table 11 below.
The PBT was Celenex~ 2002 manufactured and sold by Hoechst Celenese
Corporation. This polyester had a density of 1.31 g/cm3 and a melt
flow of 10 g/10 min (250 C, 2160 g). The Tafmer resin was the same as
that used in Example C3 above, and it was grafted with malefic
anhydride in the same manner as was the ITP.
TABLE 11
nPSC'7~1Dr10n of T_TP and NLAH-o-TTP Resins
Pro ert ITP MAH- -ITP
Melt Flow 1.0 0.45
(g/10 min, I~ @
190 c)
Melt Flow 7.42 5.22
(g/10 min, I~~
@ 190
C)
I /I Ratio 7.42 11.6
Densit ( /cm3) 0.87 0.87
M /M 1.86 2.32
Malefic Anhydride ---- 0.95
(wt %)
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WO 94/25526 ~ PCT/US94/04512
The resulting blend strand was cooled by means of a water bath
and pelletized using a chopper. The pellets were dryed under vacuum
and test specimens were injection molded on a Boy 30 ton (27 tonne)
' injection molder under the conditions reported in Table 12.
TABLE 12
Bo In'ection Molder O eratin Condition
Zone 1 250 C
Zone 2 260 C
Zone 3 260 C
nozzle 260 C
in'ection ressure 35-50 bar (3.5-5 MPa)
mold tem erature 70 C
c cle time 20.sec
The molder produced tensile and impact specimens which were
tested using ASTM procedures. For purposes of comparison, specimens
were also prepared from PBT, and an un-grafted ITP/PBT 20/80 blend.
The results of various physical property evaluations are reported in
Table 13.
TABLE 13
Pro ert PBT PBT/ITP PBT/MAH- -ITP
Hlei ht o ITP 0 20 20
Yield Tensile 8100/ 4800/ 5200/
( si/kPa) 55850 33090 35850
Break Tensile 5800/ 3300/ 1800/
( si/kPa) 39990 22750 12410
Elon ation (%) 123 15 25
Notched Izod 1.2/0.64 1.5/0.80 12.1/6.46
(ft-lb per in/J
er cm)
-30 C Dynatup 29.1/39.5 1.0/1.4 62.2/84.3
(ft-lb/J)
-23-
77252-58
CA 20160794 2004-02-17
As can be seen in the reported impact data, the blends
containing MAH-g-ITP demonstrate improved impact properties at ambient
temperature and at -30 C.
The notched IZOD impact energy was measured according to ASTM D-
256 for the PBT, a 20/80 wt o blend of ITP/PBT, a 20/80 wt o blend of
MAH-g-EPR/PBT, a 20/80 wt $ blend of ~9AH-g-EPDh1/PBT, a 2C/80 wt o
blend of MAH-g-ITP/PBT, a 10/10/80 wt o blend of ITP/MAH-g-ITP/PBT,
and a 20/80 wt % blend of MAH-g-Tafmer/PBT. The measurements were
made under ambient conditions, and the results are reported in Figure
i. The description of the MAH-g-EPDM, MAH-g-EPR, and MAH-g-Tafmer, as
well as their notched IZOD impact energy, are reported in Table 14.
TABLE 14
Pro ert MAH- -EPDMl MAH- -EPR2 MAH- -Tafmer3
Melt Flow 0.04 0.08 0.34
(g/10 min)
(I @ 190 C)
Melt Flow 0.71 1.64 4.71
(g/10 min)
I @ 190 C
I /I Ratio 17.7 20.5 13.8
Density 0.87 0.87 0.87
/cm3
Malefic 0.50 0.70 1.1
Anhydride
wt $
Notched IZOD 0.75 2.1 1.5
(J/cm
lEthylene-propylene diene elastomer functionalized with malefic
anhydride and sold by 'Oniroyal Chemical (Product designated - ROYALTtIF
465A).
2Ethylene-propylene elastomer .functionalized with malefic
TM
anhydride and sold by Exxon Chemical (Product designated -Exxelor VA
24 laol) .
TM
3An ethylene-propylene elastomer (Tafmer P-0180 from Mitsui)
graft modified with malefic anhydride as described above.
As can be seen from the results~reported in Tables 13 and 14,
2 5 the notched IZOD impact energy of the PBT blends of this invention
incorporating 20 weight of the MAH-grafted ITP are markedly greater
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WO 94/25526 ~ PCTIUS94/04512
than the comparative resins.
Figure 1 reports the notched IZOD impact energy under ambient
conditions of several compositions in which the amount of elastomer in
the PBT was varied. As reported, compositions containing MAH-g-ITP
display a greater impact energy over a wide array or concentrations,
and a decidedly greater impact energy when the concentration of the
elastomer is in excess of 15 wt o of the composition.
Figure 2 reports status similar to Figure 1 except the impact
energy is measured on a Dynatup at -20 F (-29 C) using ASTM D-3763-86.
At this low temperature, the composition containing MAH-g-ITP has
marketedly improved impact resistence over the entire range of
reported concentrations.
Figure 3 reports the effect of varying amounts of MAH-g-ITP and
MAH-g-Tafmer in PBT and as evidenced by this report, concentrations of
either in excess of 15 wt o increase notched IZOD impact energy of the
blend, with the blend containing MAH-g-ITP exhibiting superior impact
energy as between the two blends.
Polyamide-Po1_yo1_efi_n Compositions
Substantially homogeneous polyamide-polyolefin compositions were
2 0 prepared using the polyolefins reported in Table 15 and the polyamides
reported in Table 16. The polyamides were predried in an oven at 70 C
for 24 hours.
-25-
216~'~~4
WO 94/25526 ~ . PCT/US94/04512
TABLE 15
Description/Grade Melt Flow Density MAH
I @ 190 C ( /cm3) (wt g)
1. MAH-g-EPDM is an 0.04 0.87 0.5
ethylene/proplene/diene
elastomer
functionalized with
malefic anhydride
and
sold by Uniroyal
Chemical (ROYALTUF
465A).
2. MAH-g-EPR is an 0.08 0.87 0.7
ethylene/propylene
elastomer modified
with
malefic anhydride
and
sold by Exxon Chemical
Exxelor VA 1801).
3. MAH-g-ITP(1) is 0.45 0.87 0.95
a
substantially linear,
homogeneous ethylene/1-
octene polymer graft-
modified with malefic
anh dride.
4. MAH-g-ITP(2) is 0.46 0.91 1.3
a
substantially linear,
homogeneous ethylene/1-
octene polymer graft-
modified with malefic
anh dride.
5. ITP(A) is a 5.0 0.87 N/A
substantially linear,
homogeneous ethylene/1-
octene of er.
6. ITP(B) is a 1.0 0.87 N/A
substantially linear,
homogeneous ethylene/1-
octene of mer.
MAH - malefic anhydride
N/A - not applicable
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WO 94/25526 PCT/US94/04512
TABLE 16
Tyni_ca1_ Properties for Po1_yamide kesins
(dry as molded)
DESCRIPTION/ TENSILE YIELD ELONGATIONNOTCHED IZOD
GRADE (PSI/ (PSI/ (o) RT-(ft-lb
/kPa) kPa) per in./J
er cm)
Nylon 1000-1 12,000/ 12,000/ 40-80 1.0/0.53
is
a low MW Nylon 83,000 83,000
6,6 from
Hoechst-Celanese
used for
injection
moldin
Nylon 1200-1 12,400/ --- 75 1.3/0.69
is
a high Mw Nylon 85,000
6,6 from
Hoechst-Celanese
used for
extrusion
RT - room temperature
The blend compositions reported in Table 17 were prepared by
weighing the dried polyamide and polyolefin resins at the indicated
proportions. Each of these dry blends were then melt blended on a 30
mm Werner-Pfleiderer twin screw extruder. The extruder melt
temperatures were between 260 and 270 C. Each melt blended sample was
pelletized and subsequently dried in a vacuum oven at 70 C for 24
hours before injection molding.
The dried melt blended samples were injection molded on a 55 ton
(50 tonne) Neggi Bossi injection molder. An ASTM mold was used to
obtain the injection molded test samples (that is tensile and IZOD
bars). The injection molding temperatures were between 240 and 260 C.
The ASTM mold temperature was set at 70 C. The molded test samples
2 0 were equilibrated at 50% relative humidity, and then were tested.
-27-
WO 94/25526 ~ ~ ~ ~ ~ PCT/US94I04512
TABLE 17
B1ended:Com~ositi_ons
Blend # % 6,6 & Grade o
Nylon Polyolefin
&
Grade
(b wt.) (b wt.)
Comparative 80~ of 1000-1(low 200 ofMAH-g-EPR
1 Mu,)
Com arative 80~ of 1000-1(low 200 ofMAH- -EPDM
2 M )
Comparative 80g of 1200-1(high 20% ofMAH-g-EPR
3 MW)
Com arative 80~ of 1200-1(hi 20% ofMAH- -EPDM
4 h M )
Example 1 80% of 1000-1(low 20% ofMAH-g-ITP(1)
M,,,)
Exam le 2 800 of 1000-1(low 200 ofMAH- -ITP(2)
M )
Example 3 80~ of 1200-1(high 200 ofMAH-g-ITP(1)
MW)
Exam le 4 800 of 1200-1(hi 200 ofMAN- -ITP(2)
h M )
Example 5 80% of 1000-1(low 10% ofMAH-G-ITP(1)
M~,,)
plus
Example 6 800 of 1000-1(low loo ITP(A)
MW)
l00 ofMAH-g-ITP(1)
plus
lOg ITP(B)
Example 7 65$ of 1000-1(low 350 ofMAH-g-ITP(1)
MW)
Exam le 8 65$ of 1000-1(low 35% ofMAH- -ITP(2)
M )
The test data obtained on the injection molded blend samples
prepared from low molecular weight polyamide (that is Nylon 1000-1)
and high molecular weight polyamide (that is Nylon 1200-1) resins are
shown in Tables 18 and 19, respectively.
-28-
WO 94125526 ~ PCT/US94/04512
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-29-
21~t~'~~4
WO 94/25526 PCT/US94I04512
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-30-
WO 94/25526 ~ PCT/US94/04512 '
These IZOD impact data may be plotted as a function of
temperature. From these plots, the ductile-brittle transition
temperature (DBTT) value for each composition, for example, the
temperature which marks the transition from ductile to brittle
failure, can be calculated. A comparison of these DBTT values are
reported in Tables 20 and 21.
TABLE 20
Ductile-Brittle Transition Temperature Values
1 0 for Low M~ Nvlon Blends
Blend DBTT Dispersed
# C) Particle
Size
(microns)
Min.
-
Max.
-
Av
.
Com 8 0.10 2.5 0.5
arative
1
Com 5 0.17 10.0 1.0
arative
2
Exam 1 -12 0.05 1.3 0.3
le
Exam 2 3 -- -- --
le
Exam S - 9 -- -- --
le
Exam 6 - 9 -- -- --
le
Exam 7 -27 -- -- --
le
Exam 8 -13 -- -- --
le
TABLE 21
Ductile-Brittle Transition Temperature Values
1S for High M~ Nylon Blends
Blend # DBTT Dispersed Particle Size
(C) (microns)
Min. - Max. - Av .
Com arative - 11 -- -- --
3
Com arative - 10 -- -- --
4
Exam le 3 - 26 0.05 1.0 0.1
Exam le 4 - 10 -- -- --
The ductile-brittle transition temperatures clearly show that
the compositions which contain the malefic anhydride graft-modified
2 0 substantially linear, ethylene/octene polymers have superior low
temperature toughness as compared to the other compositions evaluated.
These unexpected results are especially evident for the compositions
which contain the malefic anhydride graft-modified substantially linear
ethylene/octene polymer having a low specific gravity (that is 0.870
2 5 g/cm3). Compositions which exhibit low temperature toughness have
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~1~(~'~ 9~
WO 94/25526 PCT/US94/04512
commercial advantages over other compositions, especially those used
in outdoor applications.
In addition, the comparative polyolefins must have a specific
value of modulus and are not effective when used in small amounts for
example, less than about 25 wt o. The IZOD impact data clearly show
that malefic and hydride graft-modified substantially linear,
ethylene/octene polymer can effectively impact modify polyamide-
polyolefin resin compositions at reduced or low concentrations. At
these reduced concentrations, these novel polyamide-polyolefin resin
compositions exhibit the superior low temperature toughness that was
previously not available. These improved properties are indicative of
compositions having superior heat aging and weatherability
performance.
Although this invention has been described in considerable
detail through the preceding examples, such detail is for the. purpose
of illustration only and is not to be construed as a limitation upon
the invention. Many variations can be made upon the preceding
examples without departing from the spirit and scope of the invention
as described in the following claims.
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