U.S. patent application number 12/012380 was filed with the patent office on 2012-03-22 for polymer compositions comprising cyclic olefin polymers, polyolefin modifiers and non-functionalized plasticizers.
Invention is credited to Lisa Saunders Baugh, Enock Berluche, Bryan R. Chapman.
Application Number | 20120071605 12/012380 |
Document ID | / |
Family ID | 45818313 |
Filed Date | 2012-03-22 |
United States Patent
Application |
20120071605 |
Kind Code |
A1 |
Baugh; Lisa Saunders ; et
al. |
March 22, 2012 |
POLYMER COMPOSITIONS COMPRISING CYCLIC OLEFIN POLYMERS, POLYOLEFIN
MODIFIERS AND NON-FUNCTIONALIZED PLASTICIZERS
Abstract
This invention relates to a polymer composition comprising a
blend comprising: (a) greater than 30 wt (based upon the weight of
the composition) of a cyclic olefin polymer having a T.sub.g
greater than 60.degree. C. and having a T.sub.m heat of fusion
(.DELTA.H.sub.f) of 40 J/g or less selected from the group
consisting of: i) copolymers comprising at least one acyclic olefin
and at least 15 mole % of one or more cyclic olefins; ii) partially
or completely hydrogenated copolymers comprising at least one
acyclic olefin and at least 15 mole % of one or more cyclic
olefins; iii) metathesis copolymers comprising two or more cyclic
olefins; iv) partially or completely hydrogenated metathesis
copolymers comprising two or more cyclic olefins; v) metathesis
homopolymers comprising cyclic olefins; vi) partially or completely
hydrogenated metathesis homopolymers comprising cyclic olefins; and
vii) mixtures thereof; (b) from 1 to 50 wt % (based upon the weight
of the composition) of an acyclic olefin polymer modifier having a
glass transition temperature of less than 0.degree. C.; (c) from
0.1 to 50 wt % (based upon the weight of the composition) of a
non-functionalized plasticizer having a kinematic viscosity at
100.degree. C. of 3 to 3000 cSt, a viscosity index of 120 or more,
a pour point of 0.degree. C. or less and a flash point of
200.degree. C. or more.
Inventors: |
Baugh; Lisa Saunders;
(Ringoes, NJ) ; Chapman; Bryan R.; (Annandale,
NJ) ; Berluche; Enock; (Phillipsburg, NJ) |
Family ID: |
45818313 |
Appl. No.: |
12/012380 |
Filed: |
February 1, 2008 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11820739 |
Jun 20, 2007 |
|
|
|
12012380 |
|
|
|
|
PCT/US2007/014381 |
Jun 20, 2007 |
|
|
|
11820739 |
|
|
|
|
60835524 |
Aug 4, 2006 |
|
|
|
60836007 |
Aug 7, 2006 |
|
|
|
Current U.S.
Class: |
525/75 ;
525/211 |
Current CPC
Class: |
C08L 53/00 20130101;
C08L 23/0823 20130101; C08L 23/0823 20130101; C08L 23/16 20130101;
C08L 2314/06 20130101; C08L 23/16 20130101; C08L 2666/24 20130101;
C08L 53/00 20130101; C08L 2666/06 20130101; C08L 23/0823
20130101 |
Class at
Publication: |
525/75 ;
525/211 |
International
Class: |
C08L 45/00 20060101
C08L045/00; C08L 51/06 20060101 C08L051/06; C08L 47/00 20060101
C08L047/00 |
Claims
1. A polymer composition comprising a blend comprising: (a) about
76 wt % (based upon the weight of the composition) of an amorphous
cyclic olefin polymer having a T.sub.g greater than 60.degree. C.
and having a T.sub.m heat of fusion (.DELTA.H.sub.f) of 40 J/g or
less selected from the group consisting of: i) copolymers
comprising at least one acyclic olefin and at least 15 mole % of
one or more cyclic olefins; ii) partially or completely
hydrogenated copolymers comprising at least one acyclic olefin and
at least 15 mole % of one or more cyclic olefins; iii) metathesis
copolymers comprising two or more cyclic olefins; iv) partially or
completely hydrogenated metathesis copolymers comprising two or
more cyclic olefins; v) metathesis homopolymers comprising cyclic
olefins; vi) partially or completely hydrogenated metathesis
homopolymers comprising cyclic olefins; and vii) mixtures thereof;
(b) about 19 wt % (based upon the weight of the composition) of an
acyclic olefin polymer modifier having a glass transition
temperature of less than 0.degree. C.; (c) about 5 wt % (based upon
the weight of the composition) of a non-functionalized plasticizer
having a kinematic viscosity at 100.degree. C. of 3 to 3000 cSt, a
viscosity index of 120 or more, a pour point of 0.degree. C. or
less and a flash point of 200.degree. C. or more wherein the
non-functionalized a plasticizer is a polyalphaolefin having an
M.sub.n 300 to 21,000 g/mol, and the polyalphaolefin comprises
oligomers of one or more alpha-olefins selected from the group
consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene, and
1-decene, and blends thereof, and wherein the polymer composition
has a -18.degree. C. Izod Impact (forward notch) of from 42.7 to
64.9 J/m.
2. The composition of claim 1 wherein the amorphous cyclic olefin
polymer is selected from the group consisting of:
ethylene-norbornene copolymers; ethylene-dicyclopentadiene
copolymers; ethylene-norbornene-dicyclopentadiene terpolymers;
ethylene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene copolymers;
ethylene-tricyclodecene copolymers;
ethylene-norbornene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers;
ethylene-dicyclopentadiene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; ethylene-norbornene-tricyclodecene terpolymers;
ethylene-norbornene-tetracyclododecene terpolymers;
ethylene-norbornene-ethylidene norbornene terpolymers;
ethylene-norbornene-vinylnorbornene terpolymers;
ethylene-norbornene-1,7-octadiene terpolymers;
ethylene-cyclopentene copolymers; ethylene-indene copolymers;
ethylene-tetracyclododecene copolymers;
ethylene-norbornene-vinylcyclohexene terpolymers;
ethylene-norbornene-7-methyl-1,6-octadiene terpolymers;
propylene-norbornene copolymers; ethylene-propylene-norbornene
terpolymers; propylene-dicyclopentadiene copolymers;
ethylene-propylene-dicyclopentadiene terpolymers;
propylene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene copolymers;
ethylene-propylene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers;
propylene-norbornene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; propylene-tricyclodecene copolymers;
ethylene-propylene-tricyclodecene terpolymers;
propylene-tetracyclododecene copolymers;
ethylene-propylene-tetracyclododecene terpolymers;
ethylene-norbornene-tetracyclododecene terpolymers;
ethylene-norbornene-styrene terpolymers;
ethylene-norbornene-p-methylstyrene terpolymers; hydrogenated
ethylene-dicyclopentadiene copolymers; hydrogenated
ethylene-dicyclopentadiene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; hydrogenated propylene-dicyclopentadiene copolymers;
hydrogenated ethylene-propylene-dicyclopentadiene terpolymers;
hydrogenated ethylene-norbornene-dicyclopentadiene terpolymers;
epoxidized ethylene-dicyclopentadiene copolymers; epoxidized
ethylene-propylene-dicyclopentadiene terpolymers; epoxidized
ethylene-norbornene-dicyclopentadiene terpolymers; metathesis
homopolymers and copolymers of dicyclopentadiene,
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, tricyclodecene,
tetracyclododecene, substituted derivatives of these monomers, and
higher Diels-Alder derivatives of norbornene and these monomers;
and partially or completely hydrogenated metathesis homopolymers
and copolymers of dicyclopentadiene,
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, tricyclodecene,
tetracyclododecene, substituted derivatives of these monomers, and
higher Diels-Alder derivatives of norbornene and these
monomers.
3. The composition of claim 1 wherein the amorphous cyclic olefin
polymer is selected from the group consisting of: copolymers
comprising ethylene and norbornene, copolymers comprising ethylene
and octahydrodimethanonaphthalene, copolymers comprising ethylene
and a substituted derivative of octahydrodimethanonaphthalene,
terpolymers comprising ethylene, octahydrodimethanonaphthalene, and
a substituted derivative of octahydrodimethanonaphthalene,
copolymers comprising ethylene and
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, copolymers
comprising ethylene, norbornene, and
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene; copolymers
comprising ethylene and dicyclopentadiene or a hydrogenated
derivative of such a copolymer; copolymers comprising ethylene,
norbornene, and dicyclopentadiene or a hydrogenated derivative of
such a copolymer; or hydrogenated metathesis homopolymers or
copolymers of dicyclopentadiene or tetracyclododecene.
4. The composition of claim 1 wherein the acyclic olefin polymer
comprises an elastomeric olefin/nonconjugated diene copolymers
comprising a nonconjugated diene component and at least two
components selected from the group consisting of an ethylene
component, a propylene component and .alpha.-olefin components
having 4 to 20 carbon atoms.
5. The composition of claim 1 wherein the acyclic olefin polymer
comprises a polymer selected from the group consisting of:
elastomeric cycloolefinic random copolymers comprising an ethylene
component, a cycloolefin component selected from:
bicyclo[2,2,1]hept-2-ene;
5,10-dimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene;
hexacyclo[6,6,1,1.sup.3.6,0.sup.2.7,0.sup.9.14]-4-heptadecene;
pentacyclo[6,5,1,1.sup.3.6,0.sup.2.7,0.sup.9.13]-4-pentadecene;
pentacyclo[6,5,1,1.sup.3.6,0.sup.2.7,0.sup.9.13]-4-hexadecene;
tricyclo[4,3,0,1.sup.2.5]-3-decene; substituted derivatives of said
cycloolefins; and an .alpha.-olefin component selected from
propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,
1-octene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,
1-eicosene and mixtures thereof.
6. (canceled)
7. The composition of claim 1, wherein the acyclic olefin polymer
is graft copolymerized or functionalized with an unsaturated
carboxylic acid-based graft comonomer selected from acrylic acid,
maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid,
citraconic acid, crotonic acid, isocrotonic acid, Nadic Acid.TM.
(endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid), and
their acid halide, amide, imide, anhydride, and ester
derivatives.
8. (canceled)
9. (canceled)
10. (canceled)
11. The composition of claim 1 wherein the non-functionalized
plasticizer has a kinematic viscosity at 100.degree. C. of 10 cSt
or more.
12. (canceled)
13. The composition of claim 1 wherein the non-functionalized
plasticizer has a pour point of -20.degree. C. or less and a flash
point of 230.degree. C. or more.
14. The composition of claim 1 wherein the non-functionalized
plasticizer has a specific gravity of 0.86 or less.
15. (canceled)
16. The composition of claim 1 wherein the non-functionalized
plasticizer is a polyalphaolefin having an M.sub.n 300 to 21,000
g/mol, and the polyalphaolefin is an oligomer of decene-1.
17. (canceled)
18. (canceled)
19. (canceled)
20. The composition of claim 1 wherein the blend has a room
temperature 1% secant flexural modulus of at least 1655 MPa.
21. The composition of claim 1 wherein the cyclic olefin polymer
has a light transmittance of 89 or more.
22. An article of manufacture comprising the composition of claim
1.
23-27. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation in part of U.S. Ser. No.
11/820,739, filed Jun. 20, 2007 which claims the benefit of and
priority to U.S. Ser. No. 60/835,524, filed Aug. 4, 2006 and U.S.
Ser. No. 60/836,007, filed Aug. 7, 2006. This application is also a
continuation in part of PCT/US2007/014381, filed Jun. 20, 2007.
FIELD
[0002] The present invention relates to polymer compositions
comprising cyclic olefin polymers, polyolefin modifiers (also
referred to as acyclic olefin polymer modifiers) and
non-functionalized plasticizers.
BACKGROUND
[0003] Cyclic olefin polymers (particularly cyclic olefin
copolymers) have high glass transition temperatures (T.sub.gs) and
high stiffness, however, they suffer from very poor impact
properties and are too brittle for many applications. Numerous
attempts have been made to improve their impact properties by
blending with modifiers of many types, and their stiffness by
blending with reinforcements. None of these previous attempts has
been very successful, and for the most part, cyclic olefin polymers
and copolymers have been relegated to applications taking advantage
of only their optical clarity, moisture resistance, and good
birefringence properties.
[0004] Polyolefins, and in particular those of the polyethylene and
polypropylene groups, are low-cost, lower-density thermoplastics
which melt readily and are resistant to chemicals. These materials
therefore have many uses in areas such as general household items
and electrical and electronic parts. However, polyolefins usually
have poor mechanical properties and relatively low heat distortion
temperatures (HDT). For example, a typical polypropylene
homopolymer has a flexural modulus of 1.9 GPa, a heat distortion
temperature at 0.46 MPa of 126.degree. C., and a notched Izod
impact resistance of 48 J/m. These plastics are therefore
unsuitable for use in areas which require high heat resistance,
high mechanical strength, and/or high impact resistance.
[0005] To improve their impact resistance, polypropylene
homopolymers are often blended with ethylene-propylene rubber (EPR)
or ethylene-propylene-diene (EPDM) rubber. EPR and EPDM rubbers are
used for impact modification, because they remain ductile until
their glass transition temperatures at -45.degree. C. and
effectively toughen polypropylene even at -29.degree. C., a common
testing temperature. EPR, EPDM, and polypropylene have similar
polarities, so small rubber domains can be well dispersed in the
polypropylene. Impact resistance can also be improved by
copolymerizing the propylene with a few percent of ethylene to make
impact copolymers. However, these improved impact properties come
with decreased modulus and lowered heat distortion temperatures.
Thus, a typical polypropylene impact copolymer containing EPR has
flexural modulus of 1.0 GPa, a heat distortion temperature at 0.46
MPa of 92.degree. C., a room temperature notched Izod impact
strength so high that no test samples break (approx. 500 J/m or
more), and generally has only ductile failures in the instrumented
impact test at -29.degree. C. (approx. 43 J of energy
adsorbed).
[0006] To achieve more balanced properties, polypropylenes can be
blended with both ethylene-propylene or ethylene-propylene-diene
elastomers and inorganic fillers such as talc, mica, or glass
fibers. Talc and mica reinforcements are generally preferred to
glass fibers, because the compounded polymers have better surface
and flow properties. An example of these materials is ExxonMobil's
AS65 KW-1ATM, which has a flexural modulus of 2.4 GPa, a heat
distortion temperature at 0.46 MPa of 124.degree. C. and a notched
Izod Impact of 400 J/m. These polymer blends have a good balance of
properties and are used in automotive interior applications.
However, these blends can not be used for some automotive
structural applications, where useful materials need heat
distortion temperatures at 0.46 MPa of at least 140.degree. C. and
at 1.80 MPa of at least 120.degree. C., together with a modulus of
at least 2.5 GPa and a room temperature notched Izod impact of at
least 100 J/m.
[0007] In an attempt to achieve balanced properties that exceed
those of blended polypropylenes, blends of cyclic olefin copolymers
with polyolefins have also been proposed. Copolymers of ethylene
with norbornene and with 2,3-dihydrodicyclopentadiene are disclosed
in U.S. Pat. Nos. 2,799,668 (Jul. 16, 1957) and 2,883,372 (Apr. 21,
1959). However, these polymers use TiCl.sub.4 as the catalyst and
are polymerized by ring opening metathesis--the cyclic olefin rings
are opened during copolymerizations with ethylene, leaving a
residual double bond in the backbone of the polymer. Because the
rings open, the chains are less rigid than addition polymerization
cyclic olefin copolymers. The residual unsaturation in their
backbones also make these polymers oxidatively unstable at high
temperatures. Consequently, although these copolymers have
desirable rigidity and transparency, they are poor in heat
resistance.
[0008] U.S. Pat. No. 3,494,897 discloses a high pressure, peroxide
initiated, radical copolymerization to make ethylene/cyclic olefin
copolymers but these polymerizations can only incorporate small
amounts of the cyclic olefins. As a result, the polymers do not
have high glass transition temperatures. Several blends of
ethylene/norbornene copolymers with polyolefins were described by
researchers at VEB Leuna-Werke in the early 1980s (DE 2731445 C3,
DD 150751, DD 203061, DD 203059, DD 203062, DD 205916, DD 206783,
DD 209840, DD 214851, DD 214849, and DD 214850). However, these
blends were made before the discovery of either the Ziegler-Natta
vanadium/aluminum or metallocene addition polymerization catalysts.
The ethylene/norbornene copolymers used in these blends were made
with catalysts that open cyclic rings during polymerization and
lead to residual unsaturation in the polymer backbones. The Vicat
softening temperatures exemplified in these patents range from 114
to 133.degree. C. indicating that these polymers do not have the
heat stability required for automotive structural applications. In
this respect, it is to be appreciated that Vicat softening
temperatures are generally 10.degree. C. higher than the glass
transition temperature of a glassy polymer, whereas the glass
transition temperature of a glassy polymer is generally 10.degree.
C. higher than its heat distortion temperature at 0.46 MPa. Thus
Vicat softening temperatures from 114 to 133.degree. C. are roughly
equivalent to heat distortion temperatures of 94 to 113.degree. C.
using the 0.46 MPa load.
[0009] U.S. Pat. No. 4,614,778 discloses a random copolymer of
ethylene with a
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene and
optionally an alpha-olefin having at least three carbon atoms or a
cycloolefin, such as norbornene. The mole ratio of polymerized
units from the
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene to
polymerized units from ethylene is from 3:97 to 95:5 and the
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene is
incorporated in the ethylene polymer chain using a Ziegler-Natta
vanadium/aluminum catalyst. The cyclic olefin rings do not open
during copolymerization, and the resultant copolymers contain no
residual unsaturation in their backbone. Thus, these copolymers
have high heat distortion temperatures and glass transition
temperatures as high as 171.degree. C. However, the copolymers are
quite brittle, when pressed into films, and all are copolymers of
ethylene and cyclic olefin comonomers containing at least four
fused rings. The disadvantage of these larger comonomers is that
extra Diels-Alder addition reactions are required to build them up
from ethylene and cyclopentadiene, making them more expensive to
synthesize than norbornene or dicyclopentadiene. No blends are
exemplified in this patent.
[0010] U.S. Pat. No. 5,087,677 describes the copolymerization of
ethylene and cyclic olefins, particularly norbornene, using
zirconium and hafnium metallocene catalysts. Like the
vanadium/aluminum polymerized copolymers described in U.S. Pat. No.
4,614,778, the metallocene polymerized copolymers do not have
residual unsaturation in their backbones and the cyclic olefins do
not ring open. Consequently, these metallocene ethylene/cyclic
olefin copolymers have high heat stabilities and glass transition
temperatures, with values as high as 163.degree. C. for the glass
transition temperature being exemplified. There is brief mention,
but no exemplification, of alloying the copolymers with other
polymers, such as polyethylene, polypropylene,
(ethylene/propylene)copolymers, polybutylene,
poly-(4-methyl-1-pentene), polyisoprene, polyisobutylene, and
natural rubber. U.S. Pat. No. 4,918,133 discloses a cycloolefin
type random copolymer composition, which is alleged to exhibit
excellent heat resistance, chemical resistance, rigidity, and
impact resistance, and which comprises (A) a random copolymer
containing an ethylene component and a cycloolefin component and
having an intrinsic viscosity [.eta.] of 0.05-10 dl/g as measured
at 135.degree. C. in decalin and a softening temperature (TMA) of
not lower than 70.degree. C., and (B) one or more non-rigid
copolymers selected from the group consisting of: (i) a random
copolymer containing an ethylene component, at least one other
.alpha.-olefin component and a cycloolefin component and having an
intrinsic viscosity [.eta.] of 0.01-10 dl/g as measured at
135.degree. C. in decalin and a softening temperature (TMA) of
below 70.degree. C., (ii) a non-crystalline to low crystalline
.alpha.-olefin type elastomeric copolymer formed from at least two
.alpha.-olefins, (iii) an .alpha.-olefin-diene type elastomeric
copolymer formed from at least two .alpha.-olefins and at least one
non-conjugated diene, and (iv) an aromatic vinyl type
hydrocarbon-conjugated diene copolymer or a hydrogenated product
thereof, and optionally (c) an inorganic filler or organic filler.
The cycloolefin component of the copolymer (A) can be a large
number of 1 to 4-ring bridged cyclic olefins and, although these
include norbornene, the only material exemplified is
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene (DMON) and
a methyl-substituted version thereof.
[0011] U.S. Pat. No. 6,255,396 discloses a polymer blend useful for
fabrication into transparent articles for medical applications and
comprising 1-99% by weight of a first component obtained by
copolymerizing a norbornene monomer and an ethylene monomer, and
99% to 1% by weight of a second component comprising an ethylene
copolymer with an .alpha.-olefin having 6 carbon atoms. The first
component has a glass transition temperature of from 50.degree. C.
to 180.degree. C., but the second blend component has a softening
points above 30.degree. C. due to either its melting point
(softening temperatures are slightly below the melting point) or
its glass transition temperatures (softening point is typically
10.degree. C. above T.sub.g). No measurements of flexural modulus
or impact strength are reported in the patent and no inorganic
fillers are exemplified.
[0012] U.S. Pat. No. 6,590,033 discloses a polymer blend similar to
that described in U.S. Pat. No. 6,255,396 but with the second
component comprising a homopolymer or copolymer of a diene having
from 4 to 12 carbons. Such diene polymers typically have softening
points above 30.degree. C. or solubility parameters that are too
different from those of the cyclic olefin copolymers to be
compatible. For example, the Bicerano solubility parameter for
poly(1,4-butadiene) is 17.7 J.sup.0.5/cm.sup.1.5 compared with
16.88 J.sup.0.5/cm.sup.1.5 for the cyclic olefin copolymers.
(Values are from Table 5.2 in Prediction of Polymer Properties,
3.sup.rd edition by Jozef Bicerano published by Marcel Dekker in
2002.) In addition, poly(1,4-butadiene) is too polar to be
effective at toughening cyclic olefin copolymers.
[0013] U.S. Pat. No. 6,844,059 discloses long-fiber-reinforced
polyolefin structure of length.gtoreq.3 mm, which comprises a) from
0.1 to 90% by weight of at least one polyolefin other than b), b)
from 0.1 to 50% by weight of at least one amorphous cycloolefin
polymer, such as an ethylene/norbornenes copolymer, c) from 5.0 to
75% by weight of at least one reinforcing fiber, and d) up to 10.0%
by weight of other additives. The polyolefin a) may be obtained by
addition polymerization of ethylene or of an .alpha.-olefin, such
as propylene, using a suitable catalyst and generally is a
semi-crystalline homopolymer of an .alpha.-olefin and/or ethylene,
or a copolymer of these with one another.
[0014] In Die Angewandte Makromolekulare Chemie 256 (1998), pp.
101-104, Stricker and Mulhaupt describe blends of an
ethylene/norbornene copolymer containing only 40 wt. % norbornene
The thermal stability of this copolymer is not reported, however
the glass transition temperature can be estimated at less than
60.degree. C. The rubber used to toughen the cyclic olefin
copolymer is an
polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS)
copolymer. Polystyrene blocks in this copolymer have glass
transition temperatures in the range 83-100.degree. C., giving this
modifier a softening temperature of more than 80.degree. C.
[0015] In an article entitled "Rubber Toughened and Optically
Transparent Blends of Cyclic Olefin Copolymers" in Polymer
Engineering and Science, Vol. 40(12), p. 2590-2601, December, 2000,
Khanarian describes unfilled blends of the ethylene/norbornene
copolymer Topas.TM. 6013 with thermoplastic elastomers such as
styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene
(SEBS), and styrene-ethylene-propylene-styrene (SEPS). The
Topas.TM. 6013 has a glass transition temperature of 140.degree. C.
and it is reported that blending with less than 5 wt % of the
elastomer allows the impact strength to be increased to greater
than 50 J/m (Notched Izod) while keeping the optical haze below 5%.
Using high loadings of the styrenic block copolymers, Khanarian
achieves a notched Izod impact strengths as high as 520 J/m with 30
wt. % polystyrene-b-polybutadiene-b-polystyrene. This modifier has
a softening point above 30.degree. C. due to the glass transition
temperature of the polystyrene blocks. Khanarian also exemplifies
some blends with ethylene-propylene-diene terpolymers, but the
impact strength reported is only 188 J/m with a 20 wt. % loading.
Measured heat distortion temperatures are not presented in this
paper but, given the low glass transition temperature of the
Topas.TM. 6013, are probably less than 125.degree. C. at 0.46
MPa.
[0016] Other references of interest include U.S. Pat. No.
4,874,808; U.S. Pat. No. 4,992,511; U.S. Pat. No. 5,428,098; U.S.
Pat. No. 5,359,001; U.S. Pat. No. 5,574,100; U.S. Pat. No.
5,753,755; U.S. Pat. No. 5,854,349; U.S. Pat. No. 5,863,986; U.S.
Pat. No. 6,090,888; U.S. Pat. No. 6,225,407; US 2003/0125464 A1;
U.S. Pat. No. 6,596,810 B1; U.S. Pat. No. 6,696,524 B2; U.S. Pat.
No. 6,767,966 B2; US 2004/0236024 A1; and US 2005/0014898 A1.
[0017] Certain polyalphaolefins have been used as
non-functionalized plasticizers for simple polyolefins, to provide,
inter alia, advantages such as lowered T.sub.g, improved impact
resistance, and the like. WO 2004/014988, WO 2004/014997, US
2004/0054040, US 2005/0148720, US 2004/0260001, and US 2004/0186214
disclose blends of various polyolefins with non-functionalized
plasticizers for multiple uses. U.S. Ser. No. 11/118,925 and U.S.
Ser. No. 11/119,193 disclose blends of polypropylene and
non-functionalized plasticizers for multiple uses. WO 2006/083540
discloses blends of polyethylene and non-functionalized
plasticizers.
[0018] Plasticizers have been used to modify various properties of
neat cyclic olefin polymer resins. JP2000017087 A discloses the
modification of cyclic olefin polymer resins with the functional
plasticizers dioctyl adipate and dioctyl phthalate with improved
haziness, wetness, and flexibility. DD 202887 discloses the
modification of cyclic olefin polymer resins with low amounts (up
to 8 wt %) of naphthenic and paraffinic oils to give transparent
materials with reduced brittleness and processing properties. The
cyclic olefin polymer resins of DD 202887 are similar to the other
VEB Leuna-Werke resins prepared in the early 1980s, described in
paragraph [0007] above.
[0019] Plasticizers are also present in a variety of blends
containing elastomeric (non-high glass transition temperature
and/or highly crosslinked) cyclic olefin polymers, such as
Norsorex.TM. polynorbornene rubber and polyoctenamer
(Vestenamer.TM.) rubber, as for example in U.S. Pat. No. 4,504,604;
U.S. Pat. No. 5,250,628; EP 0 617 077 B1; JP 2002128997; and JP
61181435A. These blends typically contain additional components
such as stabilizing resins, other elastomers, and/or inorganic
fillers. The rubbery cyclic olefin polymer does not function to
provide thermoplastic structural rigidity to the blend, as is the
case for the high glass transition, high stiffness thermoplastic
cyclic olefin polymers in the blends discussed in previous
paragraphs.
[0020] U.S. Ser. No. 11/820,739, filed Jun. 20, 2007 (and its
equivalent PCT/US2007/014381), disclose that combining high glass
transition temperature cyclic olefin copolymers with compatible,
low glass transition temperature polyolefin elastomers can produce
polymer compositions having a desirable combination of high
stiffness, impact toughness, and thermal stability making the
blends suitable for use in automotive structural applications.
[0021] According to the present invention, it has been found that
combining high glass transition temperature cyclic olefin polymers
and copolymers with compatible, low glass transition temperature
polyolefin elastomers and non-functionalized plasticizers can
produce polymer compositions having even more desirable properties,
such as superior low-temperature impact toughness and modified
glass transition temperatures that provide manufacturing
advantages. The superior low-temperature impact toughness of these
compositions is an unexpected feature, as compared to the
properties of compositionally analogous two-component blends that
comprise only high glass transition temperature cyclic olefin
copolymers and non-functionalized plasticizers. The present
invention also can produce polymer compositions having a desirable
combination of high stiffness, impact toughness, and thermal
stability making the blends suitable for use at high temperature in
automotive structural applications.
SUMMARY
[0022] This invention relates to blends comprising:
[0023] (a) greater than 30 wt % (based upon the weight of the
composition) of a cyclic olefin polymer having a T.sub.g greater
than 60.degree. C. and a T.sub.m heat of fusion of 40 J/g or less
selected from the group consisting of: [0024] i) copolymers
comprising at least one acyclic olefin and at least 15 mole % of
one or more cyclic olefins; ii) partially or completely
hydrogenated copolymers comprising at least one acyclic olefin and
at least 15 mole % of one or more cyclic olefins; iii) metathesis
copolymers comprising two or more cyclic olefins; iv) partially or
completely hydrogenated metathesis copolymers comprising two or
more cyclic olefins; v) metathesis homopolymers comprising cyclic
olefins; vi) partially or completely hydrogenated metathesis
homopolymers comprising cyclic olefins; and vii) mixtures thereof;
[0025] (b) 1 to 50 wt % (based upon the weight of the composition)
of an acyclic olefin polymer modifier having a glass transition
temperature of less than 0.degree. C.;
[0026] (c) from 0.1 to 50 wt (based upon the weight of the
composition) of a non-functionalized plasticizer having a kinematic
viscosity at 100.degree. C. of 3 to 3000 cSt, a viscosity index of
120 or more, a pour point of 0.degree. C. or less and a flash point
of 200.degree. C. or more.
[0027] In another embodiment, the invention resides in a polymer
composition comprising: [0028] (a) greater than 50 wt % (based upon
the weight of the composition) of a cyclic olefin copolymer, said
cyclic olefin copolymer comprising at least one acyclic olefin and
at least 20 wt % of one or more cyclic olefins (based upon the
weight of the cyclic olefin copolymer), wherein at least a portion
of said cyclic olefin copolymer has a glass transition temperature
of greater than 150.degree. C.; [0029] (b) less than 50 wt (based
upon the weight of the composition) of an acyclic olefin polymer
modifier, at least a portion of the modifier having a glass
transition temperature of less than -30.degree. C.; and no portion
of the modifier having a softening point greater than +30.degree.
C., the Bicerano solubility parameter of the modifier being no more
than 0.6 J.sup.0.5/cm.sup.1.5 less than the Bicerano solubility
parameter of the cyclic olefin copolymer; [0030] (c) a
non-functionalized plasticizer, having a kinematic viscosity at
100.degree. C. of 10 cSt or more, a viscosity index of 120 or more,
and a pour point of 0.degree. C. or less; wherein the notched Izod
impact resistance of the composition measured at 23.degree. C. is
greater than 500 J/m and the heat distortion temperature of the
composition measured using a 0.46 MPa load is greater than
135.degree. C.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] To assist those of ordinary skill in the relevant art in
making and using the subject matter hereof, reference is made to
the appended drawings, wherein:
[0032] FIG. 1 is a graph showing the beneficial effect of
non-functionalized plasticizer on the -18.degree. C. Izod impact
strength of a cyclic olefin copolymer/polymer modifier blend
(Example 1).
[0033] FIG. 2 is a graph showing the effect of non-functionalized
plasticizer on the glass transition temperature of neat cyclic
olefin copolymers (Comparative Examples C1-C5).
[0034] FIG. 3 is a graph showing the detrimental effect of
non-functionalized plasticizer on the room temperature Izod impact
strength of a neat cyclic olefin copolymer (Comparative Examples
C1-C5).
DETAILED DESCRIPTION
[0035] When a polymer or oligomer is referred to as comprising an
olefin, the olefin present in the polymer or oligomer is the
polymerized or oligomerized form of the olefin, respectively. The
term polymer is meant to encompass homopolymers and copolymers. The
term copolymer includes any polymer having two or more different
monomers in the same chain, including terpolymers and
tetrapolymers, and encompasses random copolymers, statistical
copolymers, alternating copolymers, interpolymers, (true) block
copolymers, and copolymers possessing more than one of these
microstructures in a single chain, such as block copolymers in
which one block segment is an alternating copolymer of two monomers
and another block segment is a homopolymer segment. Thus the term
cyclic olefin polymers includes cyclic olefin copolymers and cyclic
olefin homopolymers. All numerical values within the detailed
description and the claims herein are understood as modified by
"about."
[0036] For the purposes of this invention a "liquid" is defined to
be a fluid that has no distinct melting point above 0.degree. C.
and has a kinematic viscosity at 100.degree. C. of 3000 cSt or less
and/or a KV40 of 35,000 cSt or less. Preferably the liquid has no
distinct melting point above -20.degree. C. and a KV.sub.100 of
1000 cSt or less and/or a KV.sub.40 of 10,000 cSt or less.
[0037] HDT is heat distortion temperature. KV.sub.100 is kinematic
viscosity at 100.degree. C. KV.sub.40 is kinematic viscosity at
40.degree. C. VI is viscosity index. NFP is non-functionalized
plasticizer. PAO is polyalphaolefin.
[0038] Unless noted otherwise, percents express a weight percent
(wt %), based on the total amount of the material or component at
issue; Weight average molecular weight (M.sub.w), number average
molecular weight (MO, and z average molecular weight (M.sub.z) are
each determined utilizing gel permeation chromatography (GPC) and
have units of g/mol. Molecular weight distribution (MWD) is defined
as M.sub.w/M.sub.n. For purposes of this invention an oligomer is
defined to have an M.sub.n, of less than 21,000 g/mol. Preferred
oligomers have an M.sub.n of less than 20,000 g/mol, preferably
less than 19,000 g/mol, preferably less than 18,000 g/mol,
preferably less than 16,000 g/mol, preferably less than 15,000
g/mol, preferably less than 13,000 g/mol, preferably less than
10,000 g/mol, preferably less than 5000 g/mol, preferably less than
3000 g/mol. H.sub.f is heat of fusion upon melting (T.sub.m), also
referred to as Hf, .DELTA.H.sub.f, and T.sub.m heat of fusion.
[0039] The present invention provides a polymer composition
comprising:
[0040] (a) greater than 30 wt %, preferably from 32 to 99 wt %,
more preferably from 35 to 95 wt % (based upon the weight of the
composition) of a cyclic olefin polymer having a T.sub.g greater
than 60.degree. C. and a T.sub.m heat of fusion of 40 J/g or less
selected from the group consisting of: [0041] i) copolymers
comprising at least one acyclic olefin and at least 15 mole %
(preferably at least 17.5 mole %, more preferably at least 18 mole
%) of one or more cyclic olefins; ii) partially or completely
hydrogenated copolymers comprising at least one acyclic olefin and
at least 15 mole % (preferably at least 17.5 mole %, more
preferably at least 18 mole %) of one or more cyclic olefins; iii)
metathesis copolymers comprising two or more cyclic olefins; iv)
partially or completely hydrogenated metathesis copolymers
comprising two or more cyclic olefins; v) metathesis homopolymers
comprising cyclic olefins; vi) partially or completely hydrogenated
metathesis homopolymers comprising cyclic olefins; and vii)
mixtures thereof; [0042] (b) from 1 to 50 wt %, preferably from 1
to 45 wt %, more preferably from 2 to 40 wt % (based upon the
weight of the composition) of an acyclic olefin polymer modifier
having a glass transition temperature of less than 0.degree. C.;
[0043] (c) from 0.1 to 50 wt %, preferably from 0.25 to 45 wt %,
more preferably from 0.5 to 40 wt % (based upon the weight of the
composition) of a non-functionalized plasticizer having a
KV.sub.100 of 3 to 3000 cSt (preferably 5 cSt or more, more
preferably 10 cSt or more, preferably from 3 to 1000 cSt,
preferably from 5 to 500 cSt, preferably from 4 to 200 cSt, more
preferably from 10 to 100 cSt), a VI of 120 or more (preferably 150
or more, preferably 200 or more), a pour point of 0.degree. C. or
less (preferably -10.degree. C. or less, more preferably
-20.degree. C. or less, more preferably -25.degree. C. or less) and
a flash point of 200.degree. C. or more (preferably 220.degree. C.
or more, preferably 230.degree. C. or more).
[0044] In a preferred embodiment the polymers of i) to vi) are
highly amorphous.
This invention also provides a polymer composition comprising:
[0045] (a) greater than 50 wt (based upon the weight of the
composition) of a cyclic olefin copolymer, said cyclic olefin
copolymer comprising at least one acyclic olefin and at least 20 wt
% of one or more cyclic olefins (based upon the weight of the
cyclic olefin copolymer), wherein at least a portion of said cyclic
olefin copolymer has a glass transition temperature of greater than
150.degree. C.; [0046] (b) less than 50 wt (based upon the weight
of the composition) of an acyclic olefin polymer modifier, at least
a portion of the modifier having a glass transition temperature of
less than -30.degree. C.; and no portion of the modifier having a
softening point greater than +30.degree. C., the Bicerano
solubility parameter of the modifier being no more than 0.6
J.sup.0.5/cm.sup.1.5 less than the Bicerano solubility parameter of
the cyclic olefin copolymer; [0047] (c) an NFP having a KV.sub.100
of 10 cSt or more, a viscosity index of 120 or more, and a pour
point of 0.degree. C. or less (preferably the NFP has a KV.sub.100
of 10 to 3000 cSt, a VI of 120 or more, a pour point of -20.degree.
C. or less and a flash point of 200.degree. C. or more); wherein
the notched Izod impact resistance of the composition measured at
23.degree. C. is greater than 500 J/m and the heat distortion
temperature of the composition measured using a 0.46 MPa load is
greater than 135.degree. C. Because this blend has a notched Izod
greater than 500 J/m and a heat distortion temperature measured
using a 0.46 MPa load of greater than 135.degree. C. it is highly
suitable for use in automotive structural applications.
[0048] In some embodiments, the cyclic olefin copolymer comprises
at least 30 weight %, such as at least 40 weight %, of one or more
cyclic olefins. In another embodiment, at least a portion of said
cyclic olefin copolymer has a glass transition temperature of
greater than 160.degree. C., even greater than 170.degree. C. In
one embodiment all of said cyclic olefin copolymer has a glass
transition temperature of greater than 150.degree. C.
[0049] In another embodiment, at least a portion of the polymer
modifier has a glass transition temperature of less than
-40.degree. C., such as less than -50.degree. C. In one embodiment,
all of said polymer modifier has a glass transition temperature of
less than -30.degree. C. In another embodiment, no portion of the
modifier has a softening point greater than +10.degree. C.
[0050] In some embodiments, the Bicerano solubility parameter of
the modifier is between 0.1 and 0.5 J.sup.0.5/cm.sup.1.5, such as
between 0.2 and 0.4 J.sup.0.5/cm.sup.1.5, less than the Bicerano
solubility parameter of the cyclic olefin copolymer.
[0051] In some embodiments, the polymer composition has a notched
Izod impact resistance measured at 23.degree. C. of greater than
550 J/m, for example greater than 600 J/m, even greater than 700
J/m; a notched Izod impact resistance measured at -18.degree. C.
greater than 50 J/m. such as greater than 150 J/m, for example
greater than 300 J/m, even greater than 500 J/m; an instrumented
impact energy measured at 23.degree. C. of greater than 25 J, such
as greater than 30 J; an instrumented impact energy measured at
-29.degree. C. of greater than 25 J, such as greater than 30 J; a
heat distortion temperature measured using a 0.46 MPa load of
greater than 150.degree. C., such as greater than 165.degree. C.; a
heat distortion temperature measured using a 1.80 MPa load of
greater than 115.degree. C., such as greater than 130.degree. C.,
for example greater than 145.degree. C.; and a flexural modulus (1%
secant method) of greater than 1200 MPa, such as greater than 2000
MPa, for example greater than 2500 MPa.
[0052] In another embodiment the blends of this invention have a
room temperature flexural modulus (1% secant, as determined below
in the examples section) of at least 1035 MPa and a -18.degree. C.
Izod Impact (forward notch, as determined below in the examples
section) of at least 40 J/m. Preferably the blends of this
invention have a room temperature flexural modulus of at least 1448
MPa, preferably at least 1655 MPa. Preferably the blends of this
invention have a -18.degree. C. Izod Impact (forward notch) of at
least 45 J/m, preferably at least 50 J/m.
[0053] In another embodiment, the compositions of this invention
comprise less than 5 wt % (preferably less than 3 wt %, preferably
0 wt %) of a homopolymer of ethylene or copolymer of at least 50
mole % ethylene and one or more C3 to C20 linear or branched
alpha-olefins. In another embodiment, the compositions of this
invention comprise less than 5 wt % (preferably less than 3 wt %,
preferably 0 wt %) of a homopolymer of propylene or copolymer of at
least 50 mole % propylene and one or more of ethylene and/or C3 to
C20 linear or branched alpha-olefins. In another embodiment, the
compositions of this invention comprise less than 5 wt %
(preferably less than 3 wt %, preferably 0 wt %) of a crosslinked
polyethylene. In another embodiment, the compositions of this
invention comprise less than 5 wt % (preferably less than 3 wt %,
preferably 0 wt %) of a styrenic block copolymer. Styrenic block
copolymer (SBC) means a block copolymer of styrene and or
alpha-methyl-styrene and an olefin such as an alpha-olefin
(ethylene, propylene, butene) or an alkadiene (isobutylene,
isoprene, butadiene) and hydrogenated or chemically modified
versions of the block copolymer. The block copolymers may be in
diblock, triblock, linear (including tapered) or radial (including
tapered) block form.
[0054] In a preferred embodiment, the blend is not crosslinked. In
another embodiment, the cyclic olefin polymer is not crosslinked.
Crosslinked is defined to be a polymer that has been treated with a
cure/crosslinking agent (such as heat, pressure, UV radiation, a
chemical (peroxide, etc.)) to cause bonds to form between the
polymer chains. In some embodiments, crosslinking can be evidenced
by an increase in molecular weight (M.sub.w and/or M.sub.n measured
as described below) and/or an increase in hardness (Shore A) and/or
stiffness (1% Secant flexural modulus). Typically the increase is
at least 10%, preferably at least 30%, preferably at least 50%,
preferably at least 70%, compared to the polymer prior to
crosslinking.
Cyclic Olefin Polymer/Cyclic Olefin Copolymer
[0055] In a preferred embodiment, the cyclic olefin homopolymer or
copolymer (also referred to as the first copolymer, first polymer
or first homopolymer) useful herein is a cyclic olefin homopolymer
or copolymer having a T.sub.g greater than 60.degree. C.
(preferably greater than 65.degree. C., preferably greater than
70.degree. C.) and a T.sub.m heat of fusion of 40 J/g or less
selected from the group consisting of:
[0056] i) highly amorphous copolymers comprising at least one
acyclic olefin (preferably one or more alpha-olefins, preferably
ethylene and or propylene) and at least 15 mole % (preferably at
least 17.5 mole %, preferably at least 18 mole %) of one or more
cyclic olefins (such as norbornene (bicyclo[2,2,1]hept-2-ene),
norbornadiene, dicyclopentadiene,
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, tricyclodecene (also
referred to as dihydrodicyclopentadiene,
3a,4,5,6,7,7a-hexahydro-4,7-methano-1H-indene, or
tricyclo[5.2.1.0.sup.2.6]dec-3-ene), tetracyclododecene (also
referred to as octahydrodimethanonaphthalene or
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene),
substituted derivatives thereof, and higher Diels-Alder derivates
thereof); ii) partially or completely hydrogenated highly amorphous
copolymers comprising at least one acyclic olefin (preferably one
or more alpha-olefins, preferably ethylene and or propylene) and at
least 15 mole % (preferably at least 17.5 mole %, preferably at
least 18 mole %) of one or more cyclic olefins (such as
norbornadiene, dicyclopentadiene, substituted derivatives thereof,
and higher Diels-Alder derivates thereof); iii) highly amorphous
metathesis copolymers comprising two or more cyclic olefins (such
as norbornene, norbornadiene, dicyclopentadiene,
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, tricyclodecene,
tetracyclododecene, substituted derivatives thereof, and higher
Diels-Alder derivates thereof); iv) partially or completely
hydrogenated highly amorphous metathesis copolymers comprising two
or more cyclic olefins (such as norbornene, norbornadiene,
dicyclopentadiene, 2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene,
tricyclodecene, tetracyclododecene, substituted derivatives
thereof, and higher Diels-Alder derivates thereof); v) highly
amorphous metathesis homopolymers comprising cyclic olefins (such
as norbornene, norbornadiene, dicyclopentadiene,
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, tricyclodecene,
tetracyclododecene, substituted derivatives thereof, and higher
Diels-Alder derivates thereof); vi) partially or completely
hydrogenated highly amorphous metathesis homopolymers comprising
cyclic olefins (such as norbornene, norbornadiene,
dicyclopentadiene, 2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene,
tricyclodecene, tetracyclododecene, substituted derivatives
thereof, and higher Diels-Alder derivates thereof); and vii)
mixtures thereof.
[0057] Highly amorphous cyclic olefin polymer materials are
materials in which no crystallinity, or only very small levels of
crystallinity, are present. Such polymers typically show excellent
optical properties in neat form. As referred to herein, a highly
amorphous cyclic olefin polymer (or copolymer) is defined to be a
material having a T.sub.m, heat of fusion of less than 40 J/g (DSC,
second melt). A material that has no discernible melting
temperature (T.sub.m) in its second heat differential scanning
calorimetry (DSC) spectrum is defined to have a .DELTA.H.sub.f of
zero. Preferably the cyclic olefin polymer has an .DELTA.H.sub.f of
less than 30 J/g, preferably less than 20 J/g, preferably less than
10 J/g, preferably less than 5 J/g, preferably less than 0.5 J/g,
preferably the .DELTA.H.sub.f is 0 J/g.
[0058] In another embodiment, the cyclic olefin polymer has a light
transmittance of at least 89 according to ASTM D1003, preferably at
least 90.
[0059] Partially hydrogenated is defined to mean that at least 1%
of the polymer's residual and/or main chain double bonds have been
saturated, as compared to the polymer prior to hydrogenation. In
preferred partially hydrogenated polymers, at least 30% of the
polymer's double bonds have been saturated, as compared to the
polymer prior to hydrogenation. (in preferred partially
hydrogenated polymers preferably at least 50%, preferably at least
75%, preferably at least 90%, preferably at least 95%, of the
polymer's double bonds have been saturated, as compared to the
polymer prior to hydrogenation.) Complete hydrogenation means at
least 99%, preferably 100% of the polymer's double bonds have been
saturated, as compared to the polymer prior to hydrogenation.
[0060] The cyclic olefin polymer component of the present polymer
composition is produced, in some embodiments, by copolymerizing at
least one cyclic olefin with at least one acyclic olefin and, in
some embodiments, possibly with one or more dienes. In this
instance, the polymerizing olefin units of both the cyclic olefin
comonomer(s) and the acyclic olefin comonomer(s) are enchained by
the formation of single bonds between the comonomer units and the
accompanying transformation of the polymerizing olefin unit into a
single bond. The total amount of all the cyclic olefins in the
first copolymer is preferably from 20 to 99 weight % of the
copolymer in some embodiments, whereas in others the total amount
of the cyclic olefins present is at least 15 mole %. The residual
double bonds in cyclic olefin copolymers may not have reacted or
may have been partially or completely hydrogenated, crosslinked, or
functionalized. Cyclic olefin copolymers may have been grafted
using free radical addition reactions or in-reactor
copolymerizations. They may be block copolymers made using chain
shuttling agents.
[0061] In other embodiments the copolymerization takes place via
the metathesis polymerization mechanism of two or more cyclic
olefins. In yet other embodiments a metathesis homopolymerization,
rather than a copolymerization, takes place with a single cyclic
olefin. In these instances, the cyclic structure containing the
polymerizing olefin unit of the cyclic olefin(s) is broken between
the olefinic carbon termini, with the concomitant formation of new
cis or trans double bonds between cyclic olefin comonomer units. In
some metathesis polymerizations, small amounts of acyclic olefins
may be added as molecular weight regulators. These species do not
function as comonomers since they are not enchained in an intact
fashion but are cleaved into two separate portions across the
olefin unit, with one portion of the acyclic monomer forming a
chain end group and the other forming a non-enchained byproduct.
The double bond units in the metathesis polymer main chain may also
remain intact, or may be partially or completely hydrogenated,
crosslinked, or functionalized.
[0062] Cyclic olefins are defined herein as olefins where at least
one double bond is contained in one or more alicyclic rings. Cyclic
olefins may also have acyclic double bonds in side chains; however,
the double bond which participates in the polymerization is the
double bond contained within the alicyclic ring structure. Suitable
cyclic olefins for use in the cyclic olefin polymer or copolymer
component include, but are not limited to, norbornene
(bicyclo[2,2,1]hept-2-ene), tricyclodecene (also referred to as
dihydrodicyclopentadiene,
3a,4,5,6,7,7a-hexahydro-4,7-methano-1H-indene, or
tricyclo[5.2.1.0.sup.2.6]dec-3-ene), dicyclopentadiene (as mixtures
of, or as individual endo or exo isomers),
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, tetracyclododecene
(also referred to as octahydrodimethanonaphthalene or
1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene),
hexacycloheptadecene, tricycloundecene, pentacyclohexadecene,
ethylidene norbornene (ENB), vinyl norbornene (VNB),
alkylnorbornenes, norbornadiene, cyclopentene, cyclopropene,
cyclobutene, cyclohexene, cycloheptene, cyclopentadiene (CP),
cyclohexadiene, cyclooctene, cyclooctadiene, cyclooctatriene,
cyclooctatetraene, cyclododecene, indene, any Diels-Alder adduct of
cyclopentadiene and an acyclic olefin, cyclic olefin, or diene; any
Diels-Alder adduct of butadiene and an acyclic olefin, cyclic
olefin, or diene; vinylcyclohexene (VCH) (enchained through its
cyclic double bond); alkyl derivatives of cyclic olefins, such as
those substituted with one or more methyl, ethyl, propyl, or butyl
substituents; and aromatic derivatives of cyclic olefins. Cyclic
olefin derivatives bearing functionalized substituents (groups
containing at least one non-carbon or non-hydrogen atom, such as an
oxygen, nitrogen, or silicon atoms), are also suitable when used in
small amounts as co- or termonomers.
[0063] Suitable acyclic olefins for use in cyclic olefin copolymer
component include, but are not limited to, alpha-olefins
(1-alkenes), isobutene, 2-butene, and vinylaromatics. Examples of
such acyclic olefins are ethylene, propylene, 1-butene, isobutene,
2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, styrene, p-methylstyrene, p-t-butylstyrene,
p-phenylstyrene, 3-methyl-1-pentene, vinylcyclohexane,
4-methyl-1-pentene, alkyl derivatives of acyclic olefins, and
aromatic derivatives of acyclic olefins.
[0064] Dienes are defined herein broadly as including any olefin
containing at least two acyclic double bonds. They may also contain
aromatic substituents. If one or more of the double bonds of diene
is contained in an alicyclic ring and participates in
polymerization using the cyclic double bond, the monomer is
classified as a cyclic olefin in this invention. Suitable dienes
for use in the cyclic olefin copolymer component are 1,4-hexadiene;
1,5-hexadiene; 1,5-heptadiene; 1,6-heptadiene; 1,6-octadiene;
1,7-octadiene; 7-methyl-1,6-octadiene; 1,9-decadiene; butadiene;
1,3-pentadiene; isoprene; 1,3-hexadiene; 1,4-pentadiene;
4-vinyl-1-cyclohexene (when enchained solely through its vinylic
double bond); p-divinylbenzene; alkyl derivatives of dienes; and
aromatic derivatives of dienes.
[0065] Suitable cyclic olefin polymers and copolymers for use as
the first polymer or copolymer component of the present composition
include, but are not limited to; ethylene-norbornene copolymers;
ethylene-dicyclopentadiene copolymers;
ethylene-norbornene-dicyclopentadiene terpolymers;
ethylene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene copolymers;
ethylene-tricyclodecene copolymers;
ethylene-norbornene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers;
ethylene-dicyclopentadiene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; ethylene-norbornene-tricyclodecene terpolymers;
ethylene-norbornene-tetracyclododecene terpolymers;
ethylene-norbornene-ethylidene norbornene terpolymers;
ethylene-norbornene-vinylnorbornene terpolymers;
ethylene-norbornene-1,7-octadiene terpolymers;
ethylene-cyclopentene copolymers; ethylene-indene copolymers;
ethylene-tetracyclododecene copolymers;
ethylene-norbornene-vinylcyclohexene terpolymers;
ethylene-norbornene-7-methyl-1,6-octadiene terpolymers;
propylene-norbornene copolymers; ethylene-propylene-norbornene
terpolymers; propylene-dicyclopentadiene copolymers;
ethylene-propylene-dicyclopentadiene terpolymers;
propylene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene copolymers;
ethylene-propylene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers;
propylene-norbornene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; propylene-tricyclodecene copolymers;
ethylene-propylene-tricyclodecene terpolymers;
propylene-tetracyclododecene copolymers;
ethylene-propylene-tetracyclododecene terpolymers;
ethylene-norbornene-tetracyclododecene terpolymers;
ethylene-norbornene-styrene terpolymers;
ethylene-norbornene-p-methylstyrene terpolymers; functionalized
ethylene-dicyclopentadiene copolymers; functionalized
ethylene-dicyclopentadiene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; functionalized propylene-dicyclopentadiene copolymers;
functionalized ethylene-norbornene-dicyclopentadiene terpolymers;
functionalized ethylene-propylene-dicyclopentadiene terpolymers;
functionalized ethylene-norbornene-diene copolymers; maleic
anhydride grafted cyclic olefin polymers and copolymers; silane
grafted polymers and cyclic olefin copolymers; hydrogenated
ethylene-dicyclopentadiene copolymers; hydrogenated
ethylene-dicyclopentadiene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; hydrogenated propylene-dicyclopentadiene copolymers;
hydrogenated ethylene-propylene-dicyclopentadiene terpolymers;
hydrogenated ethylene-norbornene-dicyclopentadiene terpolymers;
epoxidized ethylene-dicyclopentadiene copolymers; epoxidized
ethylene-propylene-dicyclopentadiene terpolymers; epoxidized
ethylene-norbornene-dicyclopentadiene terpolymers; grafted cyclic
olefin polymers and copolymers; short chain branched cyclic olefin
polymers and copolymers; long chain branched cyclic olefin polymers
and copolymers; crosslinked cyclic olefin polymers and copolymers;
non-crosslinked cyclic olefin polymers and copolymers; linear
cyclic olefin polymers and copolymers; norbornene-dicyclopentadiene
metathesis copolymers; hydrogenated norbornene-dicyclopentadiene
metathesis copolymers; metathesis copolymers of dicyclopentadiene
with alkyl-substituted cyclic olefins and hydrogenated derivatives
thereof; metathesis copolymers of norbornene with alkyl-substituted
norbornenes or other alkyl-substituted cyclic olefins and
hydrogenated derivatives thereof; metathesis copolymers of
tricyclodecene with alkyl-substituted cyclic olefins and
hydrogenated derivatives thereof; and metathesis copolymers of
tetracyclododecene with alkyl-substituted cyclic olefins and
hydrogenated derivatives thereof. Suitable cyclic olefin metathesis
homopolymers include, but are not limited to, homopolymers of
dicyclopentadiene, 2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene,
tricyclodecene, tetracyclododecene, substituted derivatives of
these monomers, higher Diels-Alder derivatives of norbornene and/or
these monomers; and partially or completely hydrogenated
derivatives of these homopolymers.
[0066] Cyclic olefin polymers or copolymers containing norbornene,
dicyclopentadiene, 2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene,
tricyclodecene, octahydrodimethanonaphthalene, tetracyclododecene,
alkyl-substituted derivatives of these monomers, higher Diels-Alder
derivatives of these monomers, or hydrogenated dicyclopentadiene
are particularly preferred. Norbornene is made from the Diels-Alder
addition of cyclopentadiene and ethylene. (Cyclopentadiene is made
commercially by a reverse Diels-Alder reaction starting with
dicyclopentadiene). Dicyclopentadiene is a byproduct of cracking
heavy feedstocks to make ethylene and propylene. Other preferred
cyclic olefins are Diels-Alder adducts of cyclopentadiene with
other olefins, leading to alkyl- or aryl-norbornenes, or with
butadiene leading to vinylnorbornene and ethylidene norbornene. The
Diels-Alder adduct of butadiene with itself leads to
vinylcyclohexene, which is another preferred monomer. A preferred
acyclic olefin for cyclic olefin copolymers is ethylene since
ethylene-cyclic olefin copolymers have slightly better impact
properties than other copolymers. Propylene, and mixtures of
ethylene and propylene, are also preferred as acyclic olefins.
Terpolymers of ethylene with norbornene and dienes containing a
double bond in alicyclic rings are also preferred, because they can
easily be crosslinked, grafted, or functionalized.
[0067] In some embodiments, such as for high temperature uses, at
least a portion of the cyclic olefin copolymer employed in the
first copolymer component of the present composition has a glass
transition temperatures greater than 150.degree. C. These high
glass transition temperature domains will start softening
10-30.degree. C. below the glass transition temperature and lead to
heat distortion temperatures using a 0.45 MPa load of 10-15.degree.
C. below their glass transition temperature and to heat distortion
temperatures using a 1.80 MPa load of 30-35.degree. C. below the
glass transition temperature. It is preferred that the glass
transition temperature of at least a portion of these cyclic olefin
copolymers is greater than 160.degree. C. and more preferably is
greater than 170.degree. C. If only a portion of the cyclic olefin
copolymers has a glass transition temperature greater than
150.degree. C., it is preferable that the remaining portion has a
softening point below 30.degree. C. Such a cyclic olefin copolymer
might be a block or graft copolymer with an elastomer. If a portion
of the cyclic olefin copolymer has a softening point above
30.degree. C. and below the softening point associated with the
glass transition temperature above 150.degree. C., it will tend to
lower the heat distortion temperature and high temperature modulus
of the composition. Cyclic olefin copolymers where all the domains
have glass transition temperatures greater than 100.degree. C. are
preferred.
[0068] For automotive applications, where the present composition
is to be injection molded, it is also preferred for the cyclic
olefin copolymers to have high melt flow rates when measured at the
processing temperatures of the injection molding machine. Melt flow
rates greater than 5 ml/10 min in the ISO 1133 test at 115.degree.
C. above the heat distortion temperature using the 1.80 MPa load
are preferred.
[0069] Preferred cyclic olefin polymers useful herein may be
selected from the group consisting of: copolymers comprising
ethylene and norbornene, copolymers comprising ethylene and
octahydrodimethanonaphthalene, copolymers comprising ethylene and a
substituted derivative of octahydrodimethanonaphthalene,
terpolymers comprising ethylene, octahydrodimethanonaphthalene, and
a substituted derivative of octahydrodimethanonaphthalene,
copolymers comprising ethylene and
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, copolymers
comprising ethylene, norbornene, and
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene; copolymers
comprising ethylene and dicyclopentadiene or a hydrogenated
derivative of such a copolymer; copolymers comprising ethylene,
norbornene, and dicyclopentadiene or a hydrogenated derivative of
such a copolymer; or hydrogenated metathesis homopolymers or
copolymers of dicyclopentadiene or tetracyclododecene.
[0070] Useful ethylene-norbornene and
ethylene-octahydrodimethanonaphthalene copolymers can be purchased
from Topas Advanced Polymers (Topas.TM.) and Mitsui Chemicals
(Apel.TM.) Ethylene/norbornene copolymers made with metallocene
catalysts are available commercially from Topas.TM. Advanced
Polymers GmbH, as Topas.TM. copolymers, for example as grades
5010L-01, 8007, 8007S-04, 8007F-04, 8007.times.10, TKX-0001, 5013,
5013S-04, 6013, 6013S-04, 6015, 6015S-04, 6017, and 6017S-04.
Topas.TM. grades 6015 and 6017 are reported to have glass
transition temperatures of 160 and 180.degree. C., respectively.
Their reported heat distortion temperatures at 0.46 MPa (150 and
170.degree. C., respectively) and at 1.80 MPa (135 and 151.degree.
C., respectively) can provide polymer compositions meeting the
preferred heat distortion temperature of at least 130.degree. C. at
0.46 MPa. Ethylene-octahydrodimethanonaphthalene copolymers are
available as, for example, Apel.TM. grades 8008T, 6509T, 6011T,
6013T, 5014DP, and 6015T.
[0071] Other useful cyclic-olefin copolymers can be made using
vanadium, Ziegler-Natta, and metallocene catalysts. Examples of
suitable catalysts are disclosed in U.S. Pat. Nos. 4,614,778 and
5,087,677.
[0072] Useful metathesis cyclic olefin polymers, such as
hydrogenated tetracyclododecene- and dicyclopentadiene-based
polymers, can be purchased from Nippon Zeon Corporation. Such
materials include Zeonex.TM., for example grades 480, 480R, E48R,
330R, and RS820, and Zeonor.TM., for example grades 750R, 1020R,
and 1060R. General methods of making such materials are disclosed
in representative form in, for example, U.S. Pat. No. 5,106,920
A.
Acyclic Olefin Second Polymer
[0073] The second polymer component of the present composition
(also referred to as the acyclic olefin polymer modifier or the
polymer modifier) comprises one or more random, blocky, or block
polymers. Many of the polymers are polymerized from at least one
olefin and, possibly, at least one diene. In one embodiment (such
as high temperature uses), the olefins in the second polymer
component can be either acyclic or cyclic olefins, as long as the
total amount of cyclic olefin in the copolymer is less than 20
weight %. In another embodiment, involving an elastomeric second
polymer component, cyclic olefins are present at 1 to 40 mole % in
a material having a cycloolefin component, an ethylene component,
and an alpha-olefin component. The residual double bonds in the
polyolefin modifiers may not have been reacted or may have been
hydrogenated, functionalized, or crosslinked. The polyolefin
modifiers may have been grafted using free radical addition
reactions or in-reactor copolymerizations. They may be block
copolymers made using chain shuttling agents.
[0074] Acyclic olefins suitable for use in the second polymer
component include alpha-olefins (1-alkenes), isobutene, 2-butene,
and vinylaromatics. Examples of such acyclic olefins are ethylene,
propylene, 1-butene, isobutene, 2-butene, 1-pentene, 1-hexene,
1-heptene, 1-octene, 1-nonene, 1-decene, styrene, p-ethylstyrene,
p-t-butylstyrene, p-phenylstryene, 3-methyl-1-pentene,
vinylcyclohexane, 4-methyl-1-pentene, alkyl derivatives of acyclic
olefins, and aromatic derivatives of acyclic olefins.
[0075] Cyclic olefins suitable for use in the second polymer
component, in particular for embodiments designed for high
temperature uses, include, but are not limited to, norbornene,
tricyclodecene, dicyclopentadiene, tetracyclododecene,
hexacycloheptadecene, tricycloundecene, pentacyclohexadecene,
ethylidene norbornene (ENB), vinyl norbornene (VNB), norbornadiene,
alkylnorbornenes, cyclopentene, cyclopropene, cyclobutene,
cyclohexene, cyclopentadiene (CP), cyclohexadiene, cyclooctatriene,
indene, any Diels-Alder adduct of cyclopentadiene and an acyclic
olefin, cyclic olefin, or diene; and Diels-Alder adduct of
butadiene and an acyclic olefin, cyclic olefin, or diene;
vinylcyclohexene (VCH); alkyl derivatives of cyclic olefins; and
aromatic derivatives of cyclic olefins.
[0076] Dienes suitable for use in the second polymer component
include 1,4-hexadiene; 1,5-hexadiene; 1,5-heptadiene;
1,6-heptadiene; 1,6-octadiene; 1,7-octadiene; 1,9-decadiene;
butadiene; 1,3-pentadiene; isoprene; 1,3-hexadiene; 1,4-pentadiene;
p-divinylbenzene; alkyl derivatives of dienes; and aromatic
derivatives of dienes. Suitable acyclic olefin copolymers for use
as the second polymer component of the present composition include
high density polyethylene (HDPE); low density polyethylene (LDPE);
linear low density polyethylene (LLDPE); isotactic polypropylene
(iPP); atactic polypropylene (aPP); syndiotactic polypropylene
(sPP); poly(1-butene); poly(isobutylene); butyl rubber;
poly(butadiene); poly(3-methyl-1-pentene);
poly(4-methyl-1-pentene); poly(1-hexene); semi-crystalline
ethylene-propylene copolymers; amorphous ethylene-propylene
copolymers; semi-crystalline propylene-ethylene copolymers;
semi-crystalline copolymers of ethylene with alpha-olefins;
semi-crystalline copolymers of ethylene with isobutylene or
2-butene; semi-crystalline copolymers of ethylene with
vinylaromatics; semi-crystalline copolymers of ethylene with dienes
such as hexadiene, vinylcyclohexene, and 7-methyl-1,6-octadiene;
semi-crystalline copolymers of propylene with alpha-olefins;
semi-crystalline copolymers of propylene with vinyl aromatics;
semi-crystalline copolymers of propylene with vinyl aromatics;
semi-crystalline copolymers of propylene with isobutene or
2-butene; semi-crystalline copolymers of propylene with dienes; in
reactor blends of isotactic polypropylene with ethylene-propylene
rubber or ethylene-propylene-diene terpolymers (ICPs); amorphous
ethylene copolymers with alpha-olefins, vinyl aromatics, cyclic
olefins, isobutene, 2-butene, or dienes; terpolymers of ethylene,
alpha-olefins including propylene, and dienes; terpolymers of
ethylene, alpha-olefins, and vinyl aromatics; terpolymers of
ethylene, alpha-olefins, and cyclic olefins; polyolefins grafted to
polystyrene; polyolefins grafted to cyclic olefin copolymers;
polyolefins grafted to other polyolefins; terpolymers of propylene,
another olefin, and dienes; amorphous copolymers of isobutene with
isoprene; amorphous copolymers of isobutene and p-methylstyrene;
polyolefins with double bonds that have been hydrogenated;
polyolefins with double bonds that have been epoxidized or
hydroxylated; polyolefins with double bonds that have been
functionalized by electrophilic additions; any functionalized
polyolefin; polyolefins with short and long chain branches,
polyolefins which have been crosslinked through their double bonds;
polyolefins which have been crosslinked through functional groups;
and polyolefins that have been grafted using free radical addition
reactions. Preferred second copolymers include ethylene propylene
rubbers (EP rubbers). The term "EP rubber" means a copolymer of
ethylene and propylene, and optionally one or more diene monomer(s)
(as described above), where the ethylene content is from 25 to 80
wt %, the total diene content is up to 15 wt %, and the balance is
propylene.
[0077] For certain embodiments (such as high temperature uses) at
least a portion of the second polymer component should have a glass
transition temperature below -30.degree. C. These low glass
transition temperature domains of the modifier remain ductile down
to their glass transition temperatures and improve the low
temperature notched Izod impact resistance and low temperature
instrumented impact energy to the present composition. Preferably,
the glass transition temperature of at least a portion of the
polyolefin modifier is less than -40.degree. C., more preferably
less than -50.degree. C. Preferably, all portions of the polyolefin
modifier have these low glass transition temperatures and are
available to toughen the brittle cyclic olefin copolymer
phases.
[0078] In addition, for certain embodiments (such as high
temperature uses) the second polymer component should contain no
portion with a softening point above 30.degree. C., and preferably,
above 10.degree. C. A softening point above 30.degree. C. is due to
a glass transition temperature above 30.degree. C. or a melting
temperature of a significant portion of the modifier above
30.degree. C. They are detectable as transitions or peaks in a
differential scanning calorimeter (DSC), a Vicat softening point, a
softening point in a thermal mechanical analyzer (TMA), or a sudden
loss of modulus of the polyolefin modifier in a differential
mechanical thermal analysis (DMTA) experiment. They are undesirable
because the softening modifier also leads to a detectable softening
and a lowered high temperature modulus for the composition.
[0079] The cyclic olefin first copolymer used in certain
embodiments of the present composition (such as high temperature
uses) has a very high glass transition temperature and preferably
should be processed at even higher temperatures. The second polymer
modifier used in the composition should be stable at these high
processing temperatures. It is therefore preferred that the
modifier contains one or more anti-oxidants effective at
stabilizing the modifier at these high processing temperatures. It
is also preferred that the modifier contains a UV stabilizer to
prevent damage during end use applications. Most preferred are
polyolefin modifiers that contain no groups that are reactive at
the processing temperatures used to blend and form the present
compositions.
[0080] For certain embodiments (such as high temperature uses), in
order for the second polymer modifier to effectively toughen the
brittle cyclic olefin first copolymer, it is desirable that the
domain size of the second copolymer is less than 1-2 .mu.m, more
preferably less than 1.0 .mu.m, in average diameter. These small
domains can be achieved, when the interfacial energy between the
second polymer and the brittle cyclic olefin copolymer is very
small, or is even zero. Minimal interfacial energy between two
phases means that breaking a large domain up into smaller domains
with more interfacial area is thermodynamically allowed.
Compositions with very small or zero interfacial energies can be
effectively mixed, and the polyolefin modifiers dispersed, by
applying shear to the melted mixture. In order to achieve
toughening for a cyclic olefin copolymer, the polyolefin modifier
preferably has a zero or low interfacial energy with the first
copolymer. According to Souheng Wu in Polymer Interface and
Adhesion, Marcel Dekker, 1982, zero or low interfacial energies are
achieved when the polarity of the polyolefin modifier and cyclic
olefin copolymer are matched.
[0081] To match the polarities experimentally, surface energies or
solubility parameters need to be measured for each polyolefin
modifier and each cyclic olefin copolymer. Surprisingly, it has
been found that determining Bicerano solubility parameters can
quickly narrow the candidate polyolefin modifiers for a given
target cyclic olefin copolymer. D. W. Van Krevelen in Properties of
Polymers, Their Correlation With Chemical Structure; Their
Numerical Estimation and Prediction From Additive Group
Contributions, Elsevier, 1990 developed correlations between the
functional groups present in a polymer chain and its experimental
solubility parameter. These correlations worked fairly well but
were limited to the set of polymers containing only the functional
groups used in the original correlations. Jozef Bicerano extended
these correlations in Prediction of Polymer Properties, 3.sup.rd
Edition, Marcel Dekker, 2002, by replacing correlations with
functional groups with correlations with graph theory indices.
Graph theory indices depend only on how the polymer repeat units
are bonded together and on the elements present in the repeat
units. They can be calculated for any repeat unit and correlated
well with solubility parameters. Bicerano has tabulated Bicerano
solubility parameters for 121 common polymers in Table 5.2 of his
book. These equations have also been programmed into the Synthia
module of the Cerius.sup.2 molecular modeling software package
available from Accelerys. Using these Bicerano solubility
parameters for both the cyclic olefin copolymers and polyolefin
modifiers used in the ensuing Examples, the compositions with the
highest room temperature (23.degree. C.) notched Izod impact
resistance always occur when the Bicerano solubility parameter of
the polyolefin modifiers are between 0.0 and 0.6
J.sup.0.5/cm.sup.1.5 less than the Bicerano solubility parameters
of the cyclic olefin copolymers. See FIGS. 2 and 4 of
PCT/US07/014,381 (U.S. Ser. No. 11/820,739) for plots of room
temperature (23.degree. C.) notched Izod impact resistance versus
differences in Bicerano solubility parameters (indicated as Est.
Sol. Param.). Preferably, the Bicerano solubility parameter of the
polyolefin modifier is between 0.1-0.5 J.sup.0.5/cm.sup.1.5, more
preferably between 0.2-0.4 J.sup.0.5/cm.sup.1.5, less than the
Bicerano solubility parameter of the cyclic olefin copolymer.
[0082] Preferred polyolefins can be purchased from ExxonMobil
Chemical Company under the trade names Vistalon.TM., Exxelor.TM.,
Exact.TM., or Vistamaxx.TM., or they may be polymerized using
vanadium, Ziegler-Natta, or metallocene catalysts by methods well
known in the art.
[0083] Preferred EP rubbers useful as the second polymer in
compositions described herein include, but are not limited to,
those having one or more of the following properties: [0084] 1)
ethylene content of 25 to 80 wt % (preferably 30 to 75 wt %,
preferably 35 to 70 wt %, preferably 40 to 65 wt %); and/or [0085]
2) diene content (ASTM D 6047) of 15 wt % or less (preferably 12 wt
% or less, preferably 9 wt % or less, preferably 6 wt % or less,
preferably 3 wt % or less, preferably 0 wt %); and/or [0086] 3)
density (ASTM D 1505) of 0.87 g/cm.sup.3 or less (preferably 0.865
g/cm.sup.3 or less, preferably 0.86 g/cm.sup.3 or less, preferably
0.855 g/cm.sup.3 or less); and/or [0087] 4) heat of fusion (DSC as
described in PCT/US07/15486), if detected, of less than 20 J/g
(preferably less than 15 J/g, preferably less than 10 J/g,
preferably less than 5 J/g, preferably a heat of fusion is
indiscernible); and/or [0088] 5) ethylene or propylene
crystallinity (DSC as described in PCT/US07/15486), if measurable,
of less than 10 wt % (preferably less than 7.5 wt %, preferably
less than 5 wt %, preferably less than 2.5 wt %, preferably
crystallinity is undetected); and/or
[0089] 6) melting point (T.sub.m, peak first melt) (DSC as
described in PCT/US07/15486), if detected, of 60.degree. C. or less
(preferably 50.degree. C. or less, preferably 40.degree. C. or
less, preferably 35.degree. C. or less); and/or [0090] 7) glass
transition temperature (T.sub.g) (Dynamical Mechanical Analysis
(DMA) as described in PCT/US07/15486) of -30.degree. C. or less
(preferably -40.degree. C. or less, preferably -50.degree. C. or
less, preferably -60.degree. C. or less); and/or [0091] 8) M.sub.w
of 50,000 to 3,000,000 g/mol (Size Exclusion Chromatography (SEC)
as described in PCT/US07/15486) (preferably 100,000 to 2,000,000
g/mol, preferably 200,000 to 1,000,000 g/mol); and/or [0092] 9)
M.sub.w/M.sub.n of 1.5 to 40 (SEC as described in PCT/US07/15486)
(preferably 1.6 to 30, preferably 1.7 to 20, preferably 1.8 to 10,
preferably 1.8 to 5, preferably 1.8 to 3, preferably 1.8 to 2.5);
and/or [0093] 10) Mooney viscosity (ASTM D 1646), ML(1+4) @
125.degree. C., of 10 to 100 (preferably 15 to 10090, preferably 20
to 85).
[0094] Particularly preferred EP rubbers for use herein (including
in high temperature uses) contain no diene (i.e., an
ethylene-propylene copolymers). If diene is present (i.e., an
ethylene-propylene-diene terpolymer), preferably the diene is a
norbornene-derived diene such as ethylidene norbornene (ENB),
vinylidene norbornene (VNB), or dicyclopentadiene (DCPD). Diene
content is measured by ASTM D 6047.
[0095] The method of making the EP rubber is not critical, as it
can be made by slurry, solution, gas-phase, high-pressure, or other
suitable processes, through the use of catalyst systems appropriate
for the polymerization of polyolefins, such as Ziegler-Natta
catalysts, metallocene catalysts, other appropriate catalyst
systems or combinations thereof.
[0096] In a particularly preferred embodiment, the EP rubbers
useful herein are produced using a vanadium-based catalyst system
in a solution or slurry process. In another embodiment, the EP
rubbers useful herein are produced using a metallocene-based
catalyst system in a solution or slurry process. In yet another
embodiment, the EP rubbers useful herein are produced using any
single-sited catalyst system in a solution or slurry process.
Preferably, the EP rubbers made by a vanadium, metallocene, or
other single-sited catalyst system has a molecular weight
distribution (M.sub.w/M.sub.n) of 1.8 to 2.5.
[0097] EP rubbers that are useful in this invention include those
available from ExxonMobil Chemical (sold under the Vistalon.TM.
tradename), including:
ExxonMobil Chemical Vistalon.TM. EP Rubbers
TABLE-US-00001 [0098] Mooney Viscosity Molecular (ML1 + 4, Ethylene
Diene Weight Grade 125.degree. C.) (wt %) (wt %) Distribution 404
28 45 -- very broad 504 25 60 -- broad 606 65 54 -- broad 703 21 73
-- narrow 706 42 65 -- bimodal 707 23 72 -- very broad 722 16 72 --
narrow 785 30 49 -- narrow 805 33 78 -- narrow 878 51 60 -- narrow
MDV 91-9 18 59 -- narrow 1703P 25 77 0.9 VNB very broad 2727 44 57
2.0 ENB broad 3708 52 70 3.4 ENB broad 2504 25 58 4.7 ENB broad
2727 44 56 2.0 ENB broad 4600 90 60 4.5 ENB bimodal 4709 78 75 4.4
ENB narrow 5504 25 45 4.7 ENB medium 5601 72 68 5.0 ENB tailored
6505 53 57 9.2 ENB broad 7000 59 73 5.0 ENB narrow 7001 60 73 5.0
ENB tailored 7500 82 56 5.7 ENB bimodal 7800(P) 20 79 6.0 ENB
bimodal 8600 81 58 8.9 ENB bimodal 8609 83 68 8.0 ENB bimodal 8800
15 73 10.0 bimodal 9500 72 60 11.0 bimodal
VNB is vinyl norbornene, ENB is ethylidene norbornene.
[0099] In a particularly preferred embodiment, the second component
used herein comprises an elastomeric polymer material or materials.
Such materials are frequently amorphous polyolefins or polydienes
made up of monomeric units which can be derived from a wide variety
of sources. These elastomeric materials serve to impart favorable
impact resistance properties to the polymeric compositions in which
they are included.
[0100] Preferred elastomeric polymers used herein desirably have a
glass transition temperature, T.sub.g, of from -80.degree. C. to
0.degree. C., alternatively from -75.degree. C. to -2.5.degree. C.,
or even from -70.degree. C. to -5.0.degree. C. The elastomeric
polymer materials used herein are defined as "elastomeric" for
purposes of the present disclosure if they exhibit glass transition
temperature (T.sub.g) values of 0.degree. C. or less.
[0101] The elastomeric polymer materials used as components in the
polymer compositions herein can be fashioned form a wide variety of
olefinic monomers. They can, for example, be comprised of monomeric
units derived from .alpha.-olefins; other linear or non-linear,
acyclic, aliphatic or aromatic mono-olefins; cyclic or polycyclic
mono-olefins; conjugated or non-conjugated, linear or non-linear,
acyclic, cyclic or polycyclic dienes; or combinations of these
monomer types. These elastomeric materials can be homopolymers or
random or block copolymers and may also be grafted onto other types
of organic moieties. A number of elastomeric polymer materials of
the type which are useful herein are described in greater detail in
U.S. Pat. No. 4,918,133 which is incorporated herein by
reference.
[0102] One class of useful elastomeric polymers which can be
utilized herein is represented by flexible random copolymers
comprising an ethylene component, a cycloolefin component and an
.alpha.-olefin component having 3 to 20 carbon atoms. The
ethylene-derived units in such random copolymers can comprise from
40 mole % to 99 mole % of the copolymer. Typically, these
copolymers have a T.sub.g of from -80 to 0.degree. C., preferably
from -75 to -2.5.degree. C., preferably from -70 to -5.degree.
C.
[0103] The cycloolefins used to form such copolymers can, for
example, be selected from bicyclo[2,2,1]hept-2-ene;
5,10-dimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.0]-3-dodecene;
hexacyclo[6,6,1,1.sup.3.6,1.sup.10.13,0.sup.9.14]-4-heptadecene;
pentacyclo[6,5,1,1.sup.3.6,0.sup.2.7,0.sup.9.13]-4-pentadecene;
pentacyclo[6,5,1,1.sup.3.6,0.sup.2.7,0.sup.9.13]-4-hexadecene;
tricyclo[4,3,0,1.sup.2.5]-3-decene; and substituted derivatives of
these cycloolefins. Random repeating units derived from these
cycloolefin materials can comprise from 1 mole % to 40 mole % of
this type of elastomeric polymer component.
[0104] The C.sub.3 to C.sub.20 .alpha.-olefins used to form such
copolymers can, for example, be selected from propylene, 1-butene,
1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-dodecene,
1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and mixtures
thereof. Random repeating units derived from these C.sub.3 to
C.sub.20 .alpha.-olefin materials can comprise from 1 mole % to 45
mole % of this type of elastomeric polymer component.
[0105] Another class of useful elastomeric polymers which can be
utilized in the polymer compositions herein is represented by
amorphous or low-crystalline flexible olefinic copolymers (e.g.
those having an H.sub.f (DSC as described in PCT/US07/15486), if
detected, of less than 50 J/g, alternately less than 40 J/g,
alternately less than 30 J/g, alternately less than 20 J/g,
alternately less than 10 J/g, alternately less than 5 J/g,
alternately indiscernible (e.g. zero)) comprising at least two
components selected from the group consisting of an ethylene
component, a propylene component, and an .alpha.-olefin component
having 4 to 20 carbon atoms. Such copolymers are in general
ethylene-propylene copolymer rubbers, ethylene-.alpha.-olefin
copolymer rubbers and propylene-.alpha.-olefin copolymer rubbers.
The .alpha.-olefin in such copolymer rubbers can be selected, for
example, from 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,
1-octene and 1-decene.
[0106] In another embodiment the amorphous or low-crystalline
flexible olefinic copolymers exhibit crystallinity (DSC as
described in PCT/US07/15486), if measurable, of less than 10 wt %
(alternately less than 7.5 wt %, alternately less than 5 wt %,
alternately undetected (e.g. no discernable T.sub.m on the DSC
trace)). The percent crystallinity is calculated using the formula,
[area under the curve (Joules/gram)/B(Joules/gram)]*100, where B is
the T.sub.m heat of fusion for the homopolymer of the major monomer
component. The values for B are obtained from the Polymer Handbook,
Fourth Edition, published by John Wiley and Sons, New York 1999,
except that a value of 189 J/g is used as the heat of fusion for
100% crystalline polypropylene and a value of 290 J/g is used for
the heat of fusion for 100% crystalline polyethylene.
[0107] The molar ratio of ethylene to .alpha.-olefin in the
ethylene-.alpha.-olefin copolymer rubbers can vary depending on the
types of the .alpha.-olefins, but is generally in the range of from
30/70 to 95/5, or even from 50/50 to 95/5. When the .alpha.-olefin
is propylene, this molar ratio is generally in the range of from
50/50 to 90/10, while when the .alpha.-olefins are those of four or
more carbon atoms, this molar ratio is generally in the range of
from 80/20 to 95/5.
[0108] The molar ratio of propylene to .alpha.-olefin in the
propylene-.alpha.-olefin copolymer rubbers can also vary depending
on the types of the .alpha.-olefins, but is generally in the range
of from 50/50 to 95/5. When the .alpha.-olefin is1-butene, this
molar ratio is generally in the range of from 50/50 to 90/10, while
when the .alpha.-olefins are those of five or more carbon atoms,
this molar ratio is generally in the range of from 80/20 to
95/5.
[0109] The ethylene, propylene, and .alpha.-olefin copolymer
rubbers hereinbefore described may also be graft-modified in
conventional fashion with, for example, from 0.01 wt % to 5 wt %,
or even from 0.1 wt % to 4 wt %, of graft monomers selected from
unsaturated carboxylic acids or derivatives thereof. Examples of
the unsaturated carboxylic acids and derivatives thereof which can
used for modification of the ethylene-propylene-.alpha.-olefin
copolymer rubbers herein can include such unsaturated carboxylic
acids as acrylic acid, maleic acid, fumaric acid,
tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic
acid, isocrotonic acid, and Nadic Acid.TM.
(endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid), and
derivatives thereof such as acid halides, amides, imides,
anhydrides, and esters. Specific examples of these acid derivatives
include malenyl chloride, maleimide, maleic anhydride, citraconic
anhydride, monomethyl maleate, dimethyl maleate, and glycidyl
maleate. Among these materials, unsaturated dicarboxylic acids and
derivatives thereof such as acid anhydrides thereof are especially
useful. Maleic acid, Nadic Acid.TM. and anhydrides thererof are
specific examples of this type of acid materials.
[0110] Another class of useful elastomeric polymers which can be
utilized in the polymer compositions herein is represented by
flexible olefin/nonconjugated diene copolymers comprising a
nonconjugated diene component and at least two components selected
from the group consisting of an ethylene component, a propylene
component, and .alpha.-olefin components having 4 to 20 carbon
atoms. Such copolymers are in general ethylene-propylene-diene
monomer (EPDM) copolymer rubbers, ethylene-.alpha.-olefin-diene
copolymer rubbers and propylene-.alpha.-olefin-diene copolymer
rubbers. Examples of .alpha.-olefins which can be used in these
olefin-diene copolymers include the same materials listed
hereinbefore for the ethylene and propylene copolymer rubbers.
[0111] Examples of the diene components for the
ethylene-propylene-diene copolymer rubbers,
ethylene-.alpha.-olefin-diene copolymer rubbers, or the
propylene-.alpha.-olefin-diene copolymer rubbers include acyclic
linear or branched non-conjugated dienes, such as 1,4-hexadiene,
1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and
7-methyl-1,6-octadiene; and cyclic non-conjugated dienes such as
1,4-cyclohexadiene, dicyclopentadiene, 4-vinyl-1-cyclohexene,
methyltetrahydroindenes, 5-vinyl-2-norbornene,
5-ethylidene-2-norbornene, 5-methylene-2-norbornene,
5-isopropylidene-2-norbornene,
6-chloromethyl-5-isopropenyl-2-norbornene,
2,3-diisopropylidene-5-norbornene,
2-ethylidene-3-isopropylidiene-5-norbornene, and
2-propenyl-2,2-norbornadiene. Among these materials,
7-methyl-1,6-octadiene, 1,4-hexadiene, 1,6-octadiene, and cyclic
non-conjugated dienes such as 5-ethylidene-2-norbornene,
5-vinyl-2-norbornene, 5-methylene-2-norbornene, and
4-vinyl-1-cyclohexene are especially useful.
[0112] The molar ratio of ethylene to .alpha.-olefin in the
ethylene-.alpha.-olefin-diene copolymer rubbers can vary depending
on the types of the .alpha.-olefins, but is generally in the range
of from 50/50 to 95/5. When the .alpha.-olefin is propylene, this
molar ratio is generally in the range of from 50/50 to 90/10. When
the .alpha.-olefins are those of four or more carbon atoms, this
molar ratio is generally in the range of from 80/20 to 95/5. The
content of the diene component in the ethylene-propylene-diene or
ethylene-.alpha.-olefin-diene copolymer rubbers is generally in the
range of from 0.5 to 10 mole %, or even from 0.5 to 5 mole %.
[0113] The molar ratio of propylene to .alpha.-olefin in the
propylene-.alpha.-olefin-diene copolymer rubbers can vary depending
on the types of the .alpha.-olefins, but is generally in the range
of from 50/50 to 95/5. When the .alpha.-olefin is 1-butene, this
molar ratio is generally in the range of from 50/50 to 90/10. When
the .alpha.-olefins are those of five or more carbon atoms, this
molar ratio is generally in the range of from 80/20 to 95/5. The
content of the diene component in the
propylene-.alpha.-olefin-diene copolymer rubbers is generally in
the range of from 0.5 to 10 mole %, or even from 0.5 to 5 mole
%.
[0114] Another class of useful elastomeric polymers which can be
utilized in the polymer compositions herein is represented by
flexible diene/aromatic vinyl copolymers selected from the group
consisting of random copolymers and block copolymers, each said
copolymer comprising a conjugated diene component and an aromatic
vinyl hydrocarbon component, as well as the hydrogenation products
of these copolymers. Such copolymers are most commonly represented
by styrene-butadiene block copolymer rubbers, (d)
styrene-butadiene-styrene block copolymer rubbers, (e)
styrene-isoprene block copolymer rubbers, (f)
styrene-isoprene-styrene block copolymer rubbers, (g) hydrogenated
styrene-butadiene-styrene block copolymer rubbers, (h) hydrogenated
styrene-isoprene-styrene block copolymer rubbers, and (i) maleated
or otherwise functionalized and/or grafted derivatives of such
copolymer rubbers (SBCs).
[0115] The molar ratio of styrene to butadiene in the
styrene-butadiene block copolymer rubbers can generally be in the
range of from 1/99 to 60/40. The molar ratio of styrene to
butadiene in the styrene-butadiene-styrene block copolymer rubbers
can generally be in the range of from 1/99 to 60/40. The degree of
polymerization of styrene in each block can generally be in the
range of from 10 to 5,000, and the degree of polymerization of
butadiene in each block can generally be in the range of from 10 to
20,000.
[0116] The molar ratio of styrene to isoprene in the
styrene-isoprene block copolymer rubbers can generally be in the
range of from 1/99 to 60/40. The molar ratio of styrene to isoprene
in the styrene-isoprene-styrene block copolymer rubbers can
generally be in the range of from 1/99 to 60/40. The degree of
polymerization of styrene in each block can generally be in the
range of from 1 to 5,000, and the degree of polymerization of
isoprene in each block can generally be in the range of from 10 to
20,000.
[0117] The hydrogenated styrene-butadiene-styrene block copolymer
rubbers are copolymer rubbers wherein double bonds left in the
styrene-butadiene-styrene block copolymer rubbers are partially
hydrogenated and the weight ratio of styrene to butadiene-derived
component can generally be in the range of from 1/99 to 50/50. The
hydrogenated styrene-isoprene-styrene block copolymer rubbers are
copolymer rubbers wherein double bonds left in the
styrene-isoprene-styrene block copolymers are partially
hydrogenated and the weight ratio of styrene to isoprene-derived
component can generally be in the range of from 1/99 to 50/50.
[0118] The aromatic vinyl hydrocarbon-conjugated diene block
copolymers useful herein can have a weight-average molecular
weight, M.sub.w, as measured by GPC which ranges from 500 g/mole to
2,000,000 g/mole, or even from 10,000 g/mole to 1,000,000 g/mole.
The density of these block copolymers can range from 0.80 to 1.10
g/cm.sup.3, or even from 0.88 to 0.96 g/cm.sup.3.
[0119] Another class of useful elastomeric polymers which can be
utilized in the polymer compositions herein is represented by
amorphous or low-crystalline homopolymers, as well as the
hydrogenation products of these homopolymers. Such homopolymers and
hydrogenated homopolymers can include, for example, substantially
atactic polypropylene, polybutadiene, polyisoprene, hydrogenated
polybutadiene and hydrogenated polyisoprene. These homopolymers and
hydrogenated homopolymers useful herein can have a weight-average
molecular weight, M.sub.w, as measured by GPC which ranges from 500
g/mole to 2,000,000 g/mole, or even from 10,000 g/mole to 1,000,000
g/mole.
[0120] The aromatic vinyl/non-conjugated diene copolymers and the
elastomeric homopolymers hereinbefore described, like the ethylene,
propylene, and .alpha.-olefin copolymer rubbers, can also be
graft-modified in conventional fashion with, for example, from 0.01
wt % to 5 wt %, or even from 0.1 wt % to 4 wt %, of graft monomers
selected from unsaturated carboxylic acids or derivatives thereof.
Suitable acids and acid derivatives for such graft modification are
the same as those hereinbefore described with respect to
modification of the ethylene, propylene, and .alpha.-olefin
copolymer rubbers.
[0121] The hereinbefore-described various types of elastomeric
polymers which are useful for this particularly preferred
embodiment herein are all known materials. They can be prepared in
conventional manner by polymerizing the appropriate types and
amounts of their constituent comonomers using standard
polymerization techniques. Many of these elastomeric materials are
commerically available and can thus be readily obtained for use in
the polymer compositions herein. Elastomers particularly useful for
this particularly preferred embodiment herein, for example, are
marketed under the tradenames Vistalon.TM.
(ethylene/propylene/5-ethylidene-2-norbornene terpolymer),
Vector.TM. (styrene-butadiene triblock copolymer), Kraton.TM.
(styrene-hydrogenated butadiene diblock copolymer), and Exxelor.TM.
(maleated ethylene-propylene copolymer).
Non-Functionalized Plasticizers (NFPs)
[0122] For the non-functionalized plasticizer components described
herein, kinematic viscosity (KV), also referred to merely as
viscosity, is expressed as centistokes (cSt) and is determined at
the temperature specified according to ASTM D445 (e.g., KV.sub.100
at 100.degree. C., KV.sub.40 at 40.degree. C.). Glass transition
temperature (T.sub.g) is determined according to ASTM E 1356.
Distillation range is determined according to ASTM D 86. Initial
boiling point and final boiling point are each determined according
to ASTM D 86. Pour point is determined according to ASTM D 97.
Specific gravity is determined according to ASTM D 4052,
15.6.degree. C. Flash point is determined according to ASTM D 56.
Dielectric constant is determined at 1 kHz, 20.degree. C. Density
is determined according to ASTM 4052, 15.6.degree. C. Viscosity
index is determined according to ASTM D-2270. Number average
molecular weight (M.sub.n) of the NFP is determined by GC or GPC as
described in PCT/US07/15486.
[0123] NFPs useful herein are compounds comprising carbon and
hydrogen, and do not include to an appreciable extent functional
groups selected from hydroxide, aryls and substituted aryls,
halogens, alkoxys, carboxylates, esters, carbon unsaturation,
acrylates, oxygen, nitrogen, and carboxyl. By "appreciable extent",
it is meant that these groups and compounds comprising these groups
are not deliberately added to the NFP, and if present at all, are
present at less than 5 wt % by weight of the NFP in one embodiment,
more preferably less than 4 weight %, more preferably less than 3
weight %, more preferably less than 2 weight %, more preferably
less than 1 weight %, more preferably less than 0.7 weight %, more
preferably less than 0.5 weight %, more preferably less than 0.3
weight %, more preferably less than 0.1 weight %, more preferably
less than 0.05 weight %, more preferably less than 0.01 weight %,
more preferably less than 0.001 weight %, based upon the weight of
the NFP.
[0124] In a preferred embodiment, the NFP is a hydrocarbon that
contains olefinic unsaturation to an unappreciable extent. By
"unappreciable extent of olefinic unsaturation" it is meant that
the carbons involved in olefinic bonds account for less than 10%
(preferably less than 8%, preferably less than 6%, preferably less
than 4%, preferably less than 2%, preferably less than 1%,
preferably less than 0.7%, preferably less than 0.5%, preferably
less than 0.3%, preferably less than 0.1%, preferably less than
0.05%, preferably less than 0.01%, preferably less than 0.001%) of
the total number of carbons. In some embodiments, the percent of
carbons of the NFP involved in olefinic bonds is between 0.001 and
10% of the total number of carbon atoms in the NFP (preferably
between 0.01 and 5%, preferably between 0.1 and 2%, preferably less
than 1%).
[0125] Preferred NFP's that may be used herein (typically present
in the composition at from 0.1 to 50 wt %, preferably from 0.25 to
45 wt %, preferably from 0.5 to 40 wt %, preferably 1 wt % to 35 wt
%, preferably 3 to 30 wt %, based upon the weight of the blend),
have: 1) a pour point of 0.degree. C. or less, preferably
-10.degree. C. or less, more preferably -20.degree. C. or less,
more preferably -25.degree. C. or less, 2) a KV.sub.100 of 3 cSt or
more, preferably 5 cSt or more, more preferably 10 cSt or more
(preferably from 3 to 1000 cSt, preferably from 5 to 500 cSt,
preferably from 4 to 200 cSt, more preferably from 10 to 100 cSt),
and, 3) optionally, a flash point of 200.degree. C. or more,
preferably 210.degree. C. or more, preferably 220.degree. C. or
more, and, 4) optionally, a viscosity index of 100 or more,
preferably 120 or more, preferably 140 or more, and 5) optionally a
specific gravity (15.6/15.6.degree. C.) of 0.86 or less (preferably
0.855 or less, preferably 0.85 or less, preferably 0.84 or
less.
[0126] Particularly preferred NFPs include: a) liquid
polyalpha-olefins (PAOs), b) Group III Mineral Oils, and c) high
purity hydrocarbon fluids derived from a so-called Gas-To-Liquids
process; said NFP's having a viscosity index greater than 100
(preferably greater than 120), a pour point less than -15.degree.
C. (preferably less than -20.degree. C.), a specific gravity less
than 0.86 (preferably less than 0.855), and a flash point greater
than 200.degree. C. (preferably greater than 230.degree. C.).
a) Polyalphaolefins:
[0127] In another embodiment of the present invention, the NFP
comprises a polyalphaolefin (PAO) liquid with a pour point of
-10.degree. C. or less and a kinematic viscosity at 100.degree. C.
of 3 cSt or more. In general, a PAO liquid comprises hydrocarbon
oligomers manufactured by catalytic oligomerization of
alpha-olefins, preferably linear alpha-olefins. A PAO may be
characterized by any type of tacticity, including isotactic or
syndiotactic and/or atactic, and by any degree of tacticity,
including isotactic-rich or syndiotactic-rich or fully atactic. PAO
liquids are described in, for example, U.S. Pat. No. 3,149,178;
U.S. Pat. No. 4,827,064; U.S. Pat. No. 4,827,073; U.S. Pat. No.
5,171,908; and U.S. Pat. No. 5,783,531 and in SYNTHETIC LUBRICANTS
AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS, Leslie R. Rudnick &
Ronald L. Shubkin, eds. (Marcel Dekker, 1999), p. 3-52.
[0128] PAO liquids are typically prepared by the oligomerization of
an .alpha.-olefin in the presence of a polymerization catalyst,
such as a Friedel-Crafts catalyst (including, for example,
AlCl.sub.3, BF.sub.3, and complexes of BF.sub.3 with water,
alcohols, carboxylic acids, or esters), a coordination complex
catalyst (including, for example, the ethylaluminum
sesquichloride+TiCl.sub.4 system), or a homogeneous or
heterogeneous (supported) catalyst more commonly used to make
polyethylene and/or polypropylene (including, for example,
Ziegler-Natta catalysts, metallocene or other single-site
catalysts, and chromium catalysts).
[0129] In one embodiment, the PAO comprises C.sub.15 to C.sub.1500
(preferably C.sub.20 to C.sub.1000, preferably C.sub.30 to
C.sub.800, preferably C.sub.35 to C.sub.400, most preferably
C.sub.40 to C.sub.250) oligomers of alpha-olefins. These oligomers
are dimers, trimers, tetramers, pentamers, etc. In another
embodiment, the PAO comprises C.sub.3 to C.sub.24 (preferably
C.sub.5 to C.sub.18, preferably C.sub.6 to C.sub.14, even
preferably C.sub.8 to C.sub.12, most preferably C.sub.10) branched
or linear alpha-olefins, provided that C.sub.3 and C.sub.4
alpha-olefins are present at 10 wt % or less. In another
embodiment, the PAO comprises C.sub.3 to C.sub.24 (preferably
C.sub.5 to C.sub.18, preferably C.sub.6 to C.sub.14, most
preferably C.sub.8 to C.sub.12) linear alpha-olefins (LAOs),
provided that C.sub.3 and C.sub.4 LAOs are present at 10 wt % or
less. Suitable olefins include propylene, 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,
1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
1-hexadecene, and blends thereof. Oligomers of LAOs with only even
carbon numbers between 6 and 18 (inclusive) are particularly
preferred.
[0130] In one embodiment, a single LAO is used to prepare the
oligomers. In this case, a preferred embodiment involves the
oligomerization of 1-decene, and the PAO is a mixture of oligomers
(including, for example, dimers, trimers, tetramers, pentamers, and
higher) of 1-decene. In another embodiment, the PAO comprises
oligomers of two or more C.sub.3 to C.sub.18 LAOs (preferably
C.sub.5 to C.sub.18 LAOs), to make `bipolymer` or `terpolymer` or
higher-order copolymer combinations, provided that ethylene and
C.sub.3 and C.sub.4 LAOs are present at 10 wt % or less. In this
case, a preferred embodiment involves the oligomerization of a
mixture of 1-octene, 1-decene, and 1-dodecene, and the PAO is a
mixture of oligomers (for example, dimers, trimers, tetramers,
pentamers, and higher) of 1-octene/1-decene/1-dodecene
`terpolymer`.
[0131] In another embodiment, the PAO comprises oligomers of a
single alpha-olefin species having a carbon number of 5 to 24
(preferably 6 to 18, preferably 8 to 12, most preferably 10). In
another embodiment, the NFP comprises oligomers of mixed
alpha-olefins (i.e., involving two or more alpha-olefin species),
each alpha-olefin having a carbon number of 3 to 24 (preferably 5
to 24, preferably 6 to 18, most preferably 8 to 12), provided that
alpha-olefins having a carbon number of 3 or 4 are present at 10 wt
% or less. In a particularly preferred embodiment, the PAO
comprises oligomers of mixed alpha-olefins (i.e., involving two or
more alpha-olefin species) where the weighted average carbon number
for the alpha-olefin mixture is 6 to 14 (preferably 8 to 12,
preferably 9 to 11).
[0132] In another embodiment, the PAO comprises oligomers of one or
more .alpha.-olefin with repeat unit formulas of:
--[CHR--CH.sub.2]-- where R is a C.sub.3 to C.sub.18 saturated
hydrocarbon branch. Preferably, R is constant for all oligomers. In
another embodiment, there is a range of R substituents covering
carbon numbers from 3 to 18. Preferably, R is linear, i.e., R is
(CH.sub.2).sub.zCH.sub.3, where z is 2 to 17 (preferably 3 to 11,
preferably 4 to 9). Optionally, R may contain one methyl or ethyl
branch, i.e., R is
(CH.sub.2).sub.m[CH(CH.sub.3)](CH.sub.2).sub.nCH.sub.3 or
(CH.sub.2).sub.x[CH(CH.sub.2CH.sub.3)](CH.sub.2).sub.yCH.sub.3,
where (m+n) is 1 to 15 (preferably 1 to 9, preferably 3 to 7) and
(x+y) is 1 to 14 (preferably 1 to 8, preferably 2 to 6). Preferably
m>n. Preferably m is 0 to 15 (preferably 2 to 15, preferably 3
to 12, preferably 4 to 9) and n is 0 to 10 (preferably 1 to 8,
preferably 1 to 6, preferably 1 to 4). Preferably x>y.
Preferably x is 0 to 14 (preferably 1 to 14, preferably 2 to 11,
preferably 3 to 8) and y is 0 to 10 (preferably 1 to 8, preferably
1 to 6, preferably 1 to 4.) Preferably, the repeat units are
arranged in a head-to-tail fashion with minimal heat-to-head
connections.
[0133] The PAO may be atactic, isotactic, or syndiotactic. In one
embodiment, the PAO has essentially the same population of meso [m]
and racemic [r] dyads (preferably neither [m] nor [r] greater than
60%, preferably neither greater than 55%) as measured by
.sup.13C-NMR, making it atactic. In another embodiment, the PAO has
more than 60% (preferably more than 70%, preferably more than 80%,
preferably more than 90%) meso dyads [m]. In another embodiment,
the PAO has more than 60% (preferably more than 70%, preferably
more than 80%, preferably more than 90%) racemic dyads [r]. In one
embodiment, [m]/[r] determined by .sup.13C-NMR is between 0.9 and
1.1 in one embodiment, [m]/[r] is greater than 1 in another
embodiment, and [m]/[r] is less than 1 in yet another
embodiment.
[0134] In some embodiments, preferred PAOs have a "branching ratio"
as defined in U.S. Pat. No. 4,827,064 and measured according to the
method described therein, of 0.20 or less (preferably 0.19 or less,
preferably 0.18 or less, preferably 0.17 or less, preferably 0.15
or less, preferably 0.12 or less, preferably 0.10 or less).
[0135] In one embodiment of the present invention, the PAO has a
number average molecular weight of from 100 to 20,000 g/mol
(preferably 300 to 15,000 g/mol, preferably 400 to 10,000 g/mol,
preferably 500 to 5,000 g/mol, preferably 600 to 3,000 g/mol,
preferably 600 to 1,500 g/mol). M.sub.n for the NFP's is determined
by GC or GPC as described in PCT/US07/15486.
[0136] In a preferred embodiment, the PAO has a kinematic viscosity
at 100.degree. C. of 3 cSt or more (preferably 5 cSt or more,
preferably 6 cSt or more, preferably 8 cSt or more, preferably 10
cSt or more, preferably 20 cSt or more, preferably 30 cSt or more,
preferably 40 cSt or more, preferably 100 or more, preferably 150
cSt more). In another embodiment, the PAO has a kinematic viscosity
at 100.degree. C. of 300 cSt or less (preferably 100 cSt or less).
In another embodiment, the PAO has a kinematic viscosity at
100.degree. C. of 3 to 3,000 cSt (preferably 4 to 1,000 cSt,
preferably 6 to 300 cSt, preferably 8 to 150 cSt, preferably 8 to
100 cSt, preferably 8 to 40 cSt). In another embodiment, the PAO
has a kinematic viscosity at 100.degree. C. of 10 to 1000 cSt
(preferably 10 to 300 cSt, preferably 10 to 100 cSt). In yet
another embodiment, the PAO has a kinematic viscosity at
100.degree. C. of 4 to 8 cSt.
[0137] In another preferred embodiment, the PAO has a Viscosity
Index of 120 or more (preferably 130 or more, preferably 140 or
more, preferably 150 or more, preferably 170 or more, preferably
190 or more, preferably 200 or more, preferably 250 or more,
preferably 300 or more). In another embodiment, the PAO or blend of
PAOs has a viscosity Index of 120 to 350 (preferably 130 to
250).
[0138] In yet another preferred embodiment, the PAO has a pour
point of -10.degree. C. or less (preferably -20.degree. C. or less,
preferably -25.degree. C. or less, preferably -30.degree. C. or
less, preferably -35.degree. C. or less, preferably -40.degree. C.
or less, preferably -50.degree. C. or less). In another embodiment,
the PAO or blend of PAOs has a pour point of -15 to -70.degree. C.
(preferably -25 to -60.degree. C.).
[0139] In yet another preferred embodiment, the PAO has a glass
transition temperature (T.sub.g) of -40.degree. C. or less
(preferably -50.degree. C. or less, preferably -60.degree. C. or
less, preferably -70.degree. C. or less, preferably -80.degree. C.
or less). In another embodiment, the PAO or blend of PAOs has a
T.sub.g of -50 to -120.degree. C. (preferably -60 to -100.degree.
C., preferably -70 to -90.degree. C.).
[0140] In yet another preferred embodiment, the PAO has a flash
point of 200.degree. C. or more (preferably 210.degree. C. or more,
preferably 220.degree. C. or more, preferably 230.degree. C. or
more), preferably between 240.degree. C. and 290.degree. C.
[0141] In yet another preferred embodiment, the PAO has a specific
gravity (15.6/15.6.degree. C.) of 0.86 or less (preferably 0.855 or
less, preferably 0.85 or less, preferably 0.84 or less).
[0142] Particularly preferred PAOs are those having A) a flash
point of 200.degree. C. or more (preferably 210.degree. C. or more,
preferably 220.degree. C. or more, preferably 230.degree. C. or
more); and B) a pour point less than -20.degree. C. (preferably
less than -25.degree. C., preferably less than -30.degree. C.,
preferably less than -35.degree., preferably less than -40.degree.
C.) and/or a kinematic viscosity at 100.degree. C. of 10 cSt or
more (preferably 35 cSt or more, preferably 40 cSt or more,
preferably 50 cSt or more).
[0143] Further preferred PAOs have a kinematic viscosity at
100.degree. C. of at least 3 cSt (preferably at least 6 cSt,
preferably at least 8 cSt, most preferably at least 10 cSt); a
viscosity index of at least 120 (preferably at least 130,
preferably at least 140, most preferably at least 150); a pour
point of -10.degree. C. or less (preferably -20.degree. C. or less,
preferably -30.degree. C. or less, most preferably -40.degree. C.
or less); and a specific gravity (15.6/15.6.degree. C.) of 0.86 or
less (preferably 0.855 or less, preferably 0.85 or less, most
preferably 0.84 or less).
[0144] The PAO may be comprised of one or more distinct PAO
components. In one embodiment, the NFP is a blend of one or more
PAOs with different compositions (e.g., different .alpha.-olefin(s)
were used to make the oligomers) and/or different physical
properties (e.g., kinematic viscosity, pour point, viscosity index,
and/or glass transition temperature).
[0145] Desirable PAOs are available as SpectraSyn.TM. and
SpectraSyn Ultra.TM. from ExxonMobil Chemical in Houston, Tex.
(previously sold under the SHF and SuperSyn.TM. tradenames by
ExxonMobil Chemical Company), some of which are summarized in the
table below. Other useful PAOs include Synfluid.TM. available from
ChevronPhillips Chemical Company (Pasedena, Tex.), Durasyn.TM.
available from Innovene (Chicago, Ill.), Nexbase.TM. available from
Neste Oil (Keilaniemi, Finland), and Synton.TM. available from
Chemtura Corporation (Middlebury, Conn.). The percentage of carbons
in chain-type paraffinic structures (C.sub.p) is close to 100%
(typically greater than 98% or even 99%) for PAOs.
SpectraSyn.TM. Series Polyalphaolefins
TABLE-US-00002 [0146] KV @ KV @ Pour Flash 100.degree. C.,
40.degree. C., Point, Specific Point, Grade ID cSt cSt VI .degree.
C. gravity .degree. C. 4 4 19 126 -66 0.820 220 Plus 4 4 17 122 -60
0.820 228 6 6 31 138 -57 0.827 246 Plus 6 6 30 140 -54 0.827 246 8
8 48 139 -48 0.833 260 10 10 66 137 -48 0.835 266 40 39 396 147 -36
0.850 281 100 100 1240 170 -30 0.853 283 Ultra 150 150 1,500 218
-33 0.850 >265 Ultra 300 300 3,100 241 -27 0.852 >265 Ultra
1000 1,000 10,000 307 -18 0.855 >265
b) High Purity Hydrocarbon Fluids:
[0147] In another embodiment, the NFP is a high purity hydrocarbon
fluid of lubricating viscosity comprising a mixture of C.sub.20 to
C.sub.120 paraffins, 50 wt % or more being isoparaffinic
hydrocarbons and less than 50 wt % being hydrocarbons that contain
naphthenic and/or aromatic structures. Preferably, the mixture of
paraffins comprises a wax isomerate lubricant basestock or oil,
which includes: hydroisomerized natural and refined waxes, such as
slack waxes, deoiled waxes, normal alpha-olefin waxes,
microcrystalline waxes, and waxy stocks derived from gas oils,
fuels hydrocracker bottoms, hydrocarbon raffinates, hydrocracked
hydrocarbons, lubricating oils, mineral oils, polyalphaolefins, or
other linear or branched hydrocarbon compounds with carbon number
of 20 or more; and hydroisomerized synthetic waxes, such as
Fischer-Tropsch waxes (i.e., the high boiling point residues of
Fischer-Tropsch synthesis, including waxy hydrocarbons); or
mixtures thereof. Most preferred are lubricant basestocks or oils
derived from hydrocarbons synthesized in a Fischer-Tropsch process
as part of an overall Gas-to-Liquids (GTL) process.
[0148] In a preferred embodiment, the mixture of paraffins has two
or more of the following properties:
1. a naphthenic content (ASTM D 2140) of less than 40 wt %
(preferably less than 30 wt %, preferably less than 20 wt %,
preferably less than 15 wt %, preferably less than 10 wt %,
preferably less than 5 wt %, preferably less than 2 wt %,
preferably less than 1 wt %) based on the total weight of the
hydrocarbon mixture; and/or 2. a normal paraffins (ASTM D 2140)
content of less than 5 wt % (preferably less than 4 wt %,
preferably less than 3 wt %, preferably less than 1 wt %) based on
the total weight of the hydrocarbon mixture; and/or 3. an aromatic
content (ASTM D 2140) of 1 wt % or less (preferably 0.5 wt % or
less); and/or 4. a saturates (ASTM D 2007) level of 90 wt % or
higher (preferably 95 wt % or higher, preferably 98 wt % or higher,
preferably 99 wt % or higher); and/or 5. the percentage of carbons
in chain-type paraffinic structures (C.sub.p) of 80% or more
(preferably 90% or more, preferably 95% or more, preferably 98% or
more); and/or 6. a branched paraffin:normal paraffin ratio greater
than 10:1 (preferably greater than 20:1, preferably greater than
50:1, preferably greater than 100:1, preferably greater than 500:1,
preferably greater than 1000:1); and/or 7. sidechains with 4 or
more carbons making up less than 10% of all sidechains (preferably
less than 5%, preferably less than 1%); and/or 8. sidechains with 1
or 2 carbons making up at least 50% of all sidechains (preferably
at least 60%, preferably at least 70%, preferably at least 80%,
preferably at least 90%, preferably at least 95%, preferably at
least 98%); and/or 9. a sulfur content (ASTM D2622) of 300 ppm or
less (preferably 100 ppm or less, preferably 50 ppm or less,
preferably 10 ppm or less) where ppm is on a weight basis; and/or
10. a nitrogen content (ASTM 4629) of 300 ppm or less (preferably
100 ppm or less, preferably 50 ppm or less, preferably 10 ppm or
less) where ppm is on a weight basis; and/or 11. a number-average
molecular weight of 300 to 1800 g/mol (preferably 400 to 1500
g/mol, preferably 500 to 1200 g/mol, preferably 600 to 900 g/mol);
and/or 12. a kinematic viscosity at 40.degree. C. of 10 cSt or more
(preferably 25 cSt or more, preferably between 50 and 400 cSt);
and/or 13. a kinematic viscosity at 100.degree. C. ranging from 3
to 50 cSt (preferably 3 to 30 cSt, preferably 5 to 25 cSt,
preferably 6 to 20 cSt, preferably 8 to 16 cSt); and/or 14. a
viscosity index (VI) of 100 or greater, preferably 120 or greater,
preferably 130 or greater, preferably 140 or greater, preferably
150 or greater, preferably 160 or greater, preferably 180 or
greater); and/or 15. a pour point of -5.degree. C. or lower
(preferably -10.degree. C. or lower, preferably -15.degree. C. or
lower, preferably -20.degree. C. or lower, preferably -25.degree.
C. or lower, preferably -30.degree. C. or lower); and/or 16. a
flash point of 200.degree. C. or more (preferably 220.degree. C. or
more, preferably 240.degree. C. or more, preferably 260.degree. C.
or more); and/or 17. a specific gravity (15.6.degree.
C./15.6.degree. C.) of 0.86 or less (preferably 0.85 or less,
preferably 0.84 or less); and/or 18. an aniline point (ASTM D 611)
of 120.degree. C. or more; and/or 19. a bromine number of 1 or
less, (ASTM D 1159 (or ASTM D 2710 if so directed by ASTM D
1159)).
[0149] In a preferred embodiment, the mixture of paraffins
comprises a GTL basestock or oil. GTL basestocks and oils are
fluids of lubricating viscosity that are generally derived from
waxy synthesized hydrocarbons, that are themselves derived via one
or more synthesis, combination, transformation, and/or
rearrangement processes from gaseous carbon-containing compounds
and hydrogen-containing compounds as feedstocks, such as: hydrogen,
carbon dioxide, carbon monoxide, water, methane, ethane, ethylene,
acetylene, propane, propylene, propyne, butane, butylenes, and
butynes. Preferably, the feedstock is "syngas" (synthesis gas,
essentially CO and H.sub.2) derived from a suitable source, such as
natural gas and/or coal. GTL basestocks and oils include wax
isomerates, comprising, for example, hydroisomerized synthesized
waxes, hydroisomerized Fischer-Tropsch (F-T) waxes (including waxy
hydrocarbons and possible analogous oxygenates), or mixtures
thereof. GTL basestocks and oils may further comprise other
hydroisomerized basestocks and base oils. Particularly preferred
GTL basestocks or oils are those comprising mostly hydroisomerized
F-T waxes and/or other liquid hydrocarbons obtained by a F-T
synthesis process.
[0150] The synthesis of hydrocarbons, including waxy hydrocarbons,
by F-T may involve any suitable process known in the art, including
those involving a slurry, a fixed-bed, or a fluidized-bed of
catalyst particles in a hydrocarbon liquid. The catalyst may be an
amorphous catalyst, for example based on a Group VIII metal such as
Fe, Ni, Co, Ru, and Re on a suitable inorganic support material, or
a crystalline catalyst, for example a zeolitic catalyst. The
process of making a lubricant basestock or oil from a waxy stock is
characterized as a hydrodewaxing process. A hydrotreating step,
while typically not required for F-T waxes, can be performed prior
to hydrodewaxing if desired. Some F-T waxes may benefit from
removal of oxygenates while others may benefit from oxygenates
treatment prior to hydrodewaxing. The hydrodewaxing process is
typically conducted over a catalyst or combination of catalysts at
high temperatures and pressures in the presence of hydrogen. The
catalyst may be an amorphous catalyst, for example based on Co, Mo,
W, etc. on a suitable oxide support material, or a crystalline
catalyst, for example a zeolitic catalyst such as ZSM-23 and ZSM-48
and others disclosed in U.S. Pat. No. 4,906,350, often used in
conjunction with a Group VIII metal such as Pd or Pt. This process
may be followed by a solvent and/or catalytic dewaxing step to
lower the pour point of the hydroisomerate. Solvent dewaxing
involves the physical fractionation of waxy components from the
hydroisomerate. Catalytic dewaxing converts a portion of the
hydroisomerate to lower boiling hydrocarbons; it often involves a
shape-selective molecular sieve, such as a zeolite or
silicoaluminophosphate material, in combination with a catalytic
metal component, such as Pt, in a fixed-bed, fluidized-bed, or
slurry type process at high temperatures and pressures in the
presence of hydrogen.
[0151] Useful catalysts, processes, and compositions for GTL
basestocks and oils, Fischer-Tropsch hydrocarbon derived basestocks
and oils, and wax isomerate hydroisomerized basestocks and oils are
described in, for example, U.S. Pat. Nos. 2,817,693; 4,542,122;
5,5456,74; 4,568,663; 4,621,072; 4,663,305; 4,897,178; 4,900,407;
4,921,594; 4,923,588; 4,937,399; 4,975,177; 5,059,299; 5,158,671;
5,182,248; 5,200,382; 5,290,426; 5,516,740; 5,580,442; 5,885,438;
5,935,416; 5,935,417; 5,965,475; 5,976,351; 5,977,425; 6,025,305;
6,080,301; 6,090,989; 6,096,940; 6,103,099; 6,165,949; 6,190,532;
6,332,974; 6,375,830; 6,383,366; 6,475,960; 6,620,312; and
6,676,827; European Patents 324528, 532116, 532118, 537815, 583836,
666894, 668342, 776959; WO patent applications 97/31693, 99/20720,
99/45085, 02/64710, 02/64711, 02/70627, 02/70629, 03/33320; and
British Patents 1350257; 1390359; 1429494; and 1440230.
Particularly favorable processes are described in European Patent
Applications 464546 and 464547. Processes using Fischer-Tropsch wax
feeds are described in U.S. Pat. Nos. 4,594,172; 4,943,672;
6,046,940; 6,103,099; 6,332,974; 6,375,830; and 6,475,960.
[0152] As used herein, the following terms have the indicated
meanings: "hydroisomerized" describes a catalytic process in which
normal paraffins and/or slightly branched isoparaffins are
converted by rearrangement into more branched isoparaffins (also
known as "isodewaxing"); "wax" is a hydrocarbonaceous material
existing as a solid at or near room temperature, with a melting
point of 0.degree. C. or above, and consisting predominantly of
paraffinic molecules, most of which are normal paraffins; "slack
wax" is the wax recovered from petroleum oils such as by solvent
dewaxing, and may be further hydrotreated to remove
heteroatoms.
c) Group III Mineral Oils:
[0153] In another embodiment, the NFP comprises a Group III Mineral
Oil. Preferably the NFP has a saturates levels of 90% or more
(preferably 92% or more, preferably 94% or more, preferably 95% or
more, preferably 98% or more); a sulfur content of less than 0.03%
(preferably between 0.001 and 0.01%); and a VI of 120 or more
(preferably 130 or more, preferably 140 or more). Preferably the
Group III Mineral Oil has a kinematic viscosity at 100.degree. C.
of 3 to 50, preferably 4 to 40 cSt, preferably 6 to 30 cSt,
preferably 8 to 20; and/or a number average molecular weight of 300
to 5,000 g/mol, preferably 400 to 2,000 g/mol, preferably 500 to
1,000 g/mol. Preferably the Group III Mineral Oil has a pour point
of -10.degree. C. or less, a flash point of 200.degree. C. or more,
and a specific gravity (15.6.degree. C./15.6.degree. C.) of 0.86 or
less.
[0154] Preferably, the Group III Mineral Oil is a Group III
basestock. Desirable Group III basestocks are commercially
available from a number of sources and include those described in
the table below. The percentage of carbons in chain-type paraffinic
structures (C.sub.P) in such liquids is greater than 80%.
Commercially available Group III Basestocks
TABLE-US-00003 Pour Flash KV @ 100.degree. Point, Specific Point,
C., cSt VI .degree. C. gravity .degree. C. UCBO 4R .sup.1 4.1 127
-18 0.826 216 UCBO 7R .sup.1 7.0 135 -18 0.839 250 Nexbase 3043
.sup.2 4.3 124 -18 0.831 224 Nexbase 3050 .sup.2 5.1 126 -15 0.835
240 Nexbase 3060 .sup.2 6.0 128 -15 0.838 240 Nexbase 3080 .sup.2
8.0 128 -15 0.843 260 Yubase YU-4 .sup.3 4.2 122 -15 0.843 230
Yubase YU-6 .sup.3 6.5 131 -15 0.842 240 Yubase YU-8 .sup.3 7.6 128
-12 0.850 260 Ultra-S 4 .sup.4 4.3 123 -20 0.836 220 Ultra-S 6
.sup.4 5.6 128 -20 0.839 234 Ultra-S 8 .sup.4 7.2 127 -15 0.847 256
VHVI 4 .sup.5 4.6 128 -21 0.826 VHVI 8 .sup.5 8.0 127 -12 0.850 248
Visom 4 .sup.6 4.0 210 Visom 6 .sup.6 6.6 148 -18 0.836 250 .sup.1
Available from ChevronTexaco (USA). .sup.2 Available from Neste Oil
(Finland). .sup.3 Available from SK Corp (South Korea). .sup.4
Available from ConocoPhillips (USA)/S-Oil (South Korea). .sup.5
Available from PetroCanada (Canada). .sup.6 Available from
ExxonMobil (USA).
[0155] In another embodiment, plasticizers such as those described
as non-functionalized plasticizers (NFP's) in WO 04/014998 at pages
9 to 28, particularly pages 16 line, 14 to page 20, line 17) are
added to the compositions of this invention. Page 16, line 14 to
Page 20, line 15 describes the following NFP's:
[0156] The NFP comprises polyalphaolefins comprising oligomers of
linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12
carbon atoms, more preferably 10 carbon atoms having a Kinematic
viscosity of 10 or more (as measured by ASTM D 445); and preferably
having a viscosity index ("VI"), as determined by ASTM D-2270 of
100 or more, preferably 110 or more, more preferably 120 or more,
more preferably 130 or more, more preferably 140 or more; and/or
having a pour point of -5.degree. C. or less (as determined by ASTM
D 97), more preferably -10.degree. C. or less, more preferably
-20.degree. C. or less.
[0157] In another embodiment polyalphaolefin oligomers useful in
the present invention comprise C.sub.20 to C.sub.1500 paraffins,
preferably C.sub.40 to C.sub.1000 paraffins, preferably C.sub.50 to
C.sub.750 paraffins, preferably C.sub.50 to C.sub.500 paraffins.
The PAO oligomers are dimers, trimers, tetramers, pentamers, etc.
of C.sub.5 to C.sub.14 .alpha.-olefins in one embodiment, and
C.sub.6 to C.sub.12 .alpha.-olefins in another embodiment, and
C.sub.8 to C.sub.12 .alpha.-olefins in another embodiment. Suitable
olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene and 1-dodecene. In one embodiment, the olefin
is 1-decene, and the NFP is a mixture of dimers, trimers, tetramers
and pentamers (and higher) of 1-decene. Preferred PAO's are
described more particularly in, for example, U.S. Pat. No.
5,171,908, and U.S. Pat. No. 5,783,531 and in SYNTHETIC LUBRICANTS
AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 1-52 (Leslie R. Rudnick
& Ronald L. Shubkin, ed. Marcel Dekker, Inc. 1999).
[0158] PAO's useful in the present invention typically possess a
number average molecular weight of from 100 to 21,000 in one
embodiment, and from 200 to 10,000 in another embodiment, and from
200 to 7,000 in yet another embodiment, and from 200 to 2,000 in
yet another embodiment, and from 200 to 500 in yet another
embodiment. Preferred PAO's have viscosities in the range of 0.1 to
150 cSt at 100.degree. C., and from 0.1 to 3000 cSt at 100.degree.
C. in another embodiment (ASTM 445). PAO's useful in the present
invention typically have pour points of less than 0.degree. C. in
one embodiment, less than -10.degree. C. in another embodiment, and
less than -20.degree. C. in yet another embodiment, and less than
-40.degree. C. in yet another embodiment. Desirable PAO's are
commercially available as SHF and SuperSyn PAO's (ExxonMobil
Chemical Company, Houston Tex.), some of which are summarized in
the Table 2 below.
TABLE-US-00004 TABLE 2 SHF and SuperSyn** Series Polyalphaolefins
Specific Gravity Viscosity @ Pour Point, PAO (15.6/15.6.degree. C.)
100.degree. C., cSt VI .degree. C. SHF-20 0.798 1.68 -- -63 SHF-21
0.800 1.70 -- -57 SHF-23 0.802 1.80 -- -54 SHF-41 0.818 4.00 123
-57 SHF-61/63 0.826 5.80 133 -57 SHF-82/83 0.833 7.90 135 -54
SHF-101 0.835 10.0 136 -54 SHF-403 0.850 40.0 152 -39 SHF-1003
0.855 107 179 -33 SuperSyn 2150 0.850 150 214 -42 SuperSyn 2300
0.852 300 235 -30 SuperSyn 21000 0.856 1,000 305 -18 SuperSyn 23000
0.857 3,000 388 -9 **SHF grades now sold under SpectraSyn tradename
and SuperSyn grades now sold under the name SpectraSyn Ultra
[0159] Other useful PAO's include those sold under the tradenames
Synfluid.TM. available from ChevronPhillips Chemical Co. in
Pasedena Tex., Durasyn.TM. available from BP Amoco Chemicals in
London England, Nexbase.TM. available from Fortum Oil and Gas in
Finland, Synton.TM. available from Crompton Corporation in
Middlebury Conn., USA, EMERY.TM. available from Cognis Corporation
in Ohio, USA.
[0160] In other embodiments the PAO's have a Kinematic viscosity of
10 cSt or more at 100.degree. C., preferably 30 cSt or more,
preferably 50 cSt or more, preferably 80 cSt or more, preferably
110 or more, preferably 150 cSt or more, preferably 200 cSt or
more, preferably 500 cSt or more, preferably 750 or more,
preferably 1000 cSt or more, preferably 1500 cSt or more,
preferably 2000 cSt or more, preferably 2500 or more. In another
embodiment the PAO's have a kinematic viscosity at 100.degree. C.
of between 10 cSt and 3000 cSt, preferably between 10 cSt and 1000
cSt, preferably between 10 cSt and 40 cSt.
[0161] In other embodiments the PAO's have a viscosity index of 120
or more, preferably 130 or more, preferably 140 or more, preferably
150 or more, preferably 170 or more, preferably 190 or more,
preferably 200 or more, preferably 250 or more, preferably 300 or
more.
[0162] In another embodiment, the non-functionalized plasticizer
comprises a high purity hydrocarbon fluid composition comprising a
mixture of paraffins having 6 to 1500 carbon atoms, preferably 8 to
1000 carbon atoms, preferably 10 to 500 carbon atoms, preferably 12
to 200 carbon atoms, preferably 14 to 150 carbon atoms, preferably
16 to 100 carbon atoms in the molecule. The hydrocarbon fluid
composition has an isoparaffin:n-paraffin ratio ranging from 0.5:1
to 9:1, preferably from 1:1 to 4:1. The isoparaffins of the mixture
contain greater than fifty percent, 50%, mono-methyl species, e.g.,
2-methyl, 3-methyl, 4-methyl, .gtoreq.5-methyl or the like, with
minimum formation of branches with substituent groups of carbon
number greater than 1, i.e., ethyl, propyl, butyl or the like,
based on the total weight of isoparaffins in the mixture.
Preferably, the isoparaffins of the mixture contain greater than 70
percent of the mono-methyl species, based on the total weight of
the isoparaffins in the mixture. These hydrocarbon fluids
preferably have viscosities KV at 25.degree. C. ranging from 1 to
100,000 cSt, preferably 10 cSt to 2000 cSt and, optionally low pour
points typically below -20.degree. C., more preferably below
-30.degree. C., more preferably ranging from -20.degree. C. to
-70.degree. C. These hydrocarbon fluids preferably have viscosities
KV at 40.degree. C. ranging from 1 to 30,000 cSt, preferably 10 cSt
to 2000 cSt and, optionally low pour points typically below
-20.degree. C., more preferably below -30.degree. C., more
preferably ranging from -20.degree. C. to -70.degree. C.
[0163] Further, page 23, line 8-14 states: In some embodiments any
NFP described herein may have a specific gravity (ASTM D 4052,
15.6/15.6.degree. C.) of less than 0.920 in one embodiment, and
less than 0.910 in another embodiment, and from 0.650 to 0.900 in
another embodiment, and from 0.700 to 0.860, and from 0.750 to
0.855 in another embodiment, and from 0.790 to 0.850 in another
embodiment, and from 0.800 to 0.840 in yet another embodiment,
wherein a desirable range may comprise any upper specific gravity
limit with any lower specific gravity limit described herein.
[0164] In one embodiment of compositions of the present invention,
conventional plasticizers such as are commonly used for poly(vinyl
chloride) are substantially absent. In particular, plasticizers
such as phthalates, adipates, trimellitate esters, polyesters, and
other functionalized plasticizers as disclosed in, for example,
U.S. Pat. No. 3,318,835; U.S. Pat. No. 4,409,345; WO 02/31044 A1;
and PLASTICS ADDITIVES 499-504 (Geoffrey Pritchard, ed., Chapman
& Hall 1998) are substantially absent. By "substantially
absent", it is meant that these compounds are not added
deliberately to the compositions and if present at all, are present
at less than 0.5 wt %.
[0165] In some embodiments, "naphthenic" mineral oils and
"aromatic" mineral oils are substantially absent; i.e., present at
less than 0.5 wt % of the inventive composition. In another
embodiment, if such oils are present in the composition, the
aggregate of such oils is at most 5 wt % of the total liquid
modifier in the composition. Also, aromatic moieties and
carbon-carbon unsaturation are substantially absent from the
modifiers used in the present invention in yet another embodiment.
Aromatic moieties include a compound whose molecules have the ring
structure characteristic of benzene, naphthalene, phenanthrene,
anthracene, etc. By "substantially absent", it is meant that these
aromatic compounds or moieties are not added deliberately to the
compositions, and if present, are present to less than 0.5 wt % of
the composition.
Additives
[0166] Many additives may be incorporated in the present polymer
composition in addition to the cyclic olefin first polymer or
copolymer component, the acyclic second copolymer component, and
the non-functionalized plasticizer component. Some additives aid in
the processing of molded parts; others are added to improve the
stability or aesthetics of molded parts. Useful additives include
lactones, hydroxylamines, phosphates, clarifying agents, hindered
amine anti-oxidants, aromatic amine anti-oxidants, hindered phenol
anti-oxidants, divalent sulfur anti-oxidants, trivalent phosphorus
anti-oxidants, metal deactivator anti-oxidants, heat stabilizers,
low profile additives, UV stabilizers, lubricants, mold release
agents, odorants, antistatic agents, antimicrobial agents, slip
agents, anti-blocking agents, anti-foaming agents, blowing agents,
anti-fogging agents, titanates, flame retardants, dyes, and
colorants. Anti-oxidants and titanates are used in some of the
compositions of this invention. Preferred anti-oxidant additives
are Irganox.TM. 1010, Capow.TM. L-12/H, and Irgafos.TM. 168
combined with FS-042.TM.. Irganox.TM. 1010, Irgafos.TM. 168, and
FS-042.TM. are available from Ciba. Capow.TM. L-12/H is a titanate
available from Kenrich.
[0167] Processing oils can be added in compounding to improve the
moldability of the present composition. Useful processing oils for
the compositions of this invention include aliphatic petroleum
distillates, aromatic petroleum distillates, alicyclic petroleum
distillates, wood byproducts, natural oils, and synthetic oils.
[0168] Crosslinking agents can also be added to the present
compositions to vulcanize the second copolymer component, to create
grafts between the cyclic olefin first polymers or copolymers and
the second copolymer, to functionalize either the cyclic olefin
polymer or copolymer or the second copolymer, and to cure the
composition into a thermoset. Useful crosslinking agents include
hydrogen peroxide, alkylhydroperoxides, diacylperoxides,
dialkylperoxides, peracids, peresters, sulfur with and without
accelerators, zinc with benzothiazole acceleration, phenolic resin
curatives, silanes with Pt catalysts or free radical initiators,
benzoquinone derivatives, bismaleimides, and metal oxides.
Method of Making the Polymer Composition
[0169] The present composition can be prepared by any one of the
following methods:
1. Melt blending of a preformed cyclic olefin polymer or copolymer
(also referred to as the first polymer or copolymer), a preformed
polyolefin modifier (also referred to as the second copolymer or
acyclic olefin polymer modifier), the NFP, and any other components
in a mixer such as a Braebender Plasticorder, Haake mixer, or
Banbury mixer, or in an extruder. A preferred method is a twin
screw extruder with a high mixing intensity. (The NFP may be
provided as a liquid or may be 1) compounded (preferably with a
polyolefin (such as polypropylene (such as e.g. iPP)) or 2) or
pre-physically-mixed with one or both of the polymer components,
for systems where solid components are preferred over liquid
components.)
[0170] 2. Mixing solutions or suspensions of the modifier and the
cyclic olefin polymer or copolymer (with or without the NFP),
possibly followed by extrusion or melt mixing to add other
components (such as the NFP, if not previously added).
3. Polymerization in a staged reactor, where the polyolefin
modifier is made in the first reactor and the cyclic olefin polymer
or copolymer is made in a second reactor, possibly followed by
extrusion or melt mixing to add other components. The NFP can be
added in either or both of the reactors, or may be added later in
the melt mixing stage. 4. Polymerization in a staged reactor, where
the cyclic olefin polymer or copolymer is made in a first reactor
and a polyolefin modifier is made in a second reactor, possibly
followed by extrusion or melt mixing to add other components. The
NFP can be added in either or both of the reactors, or may be added
later in the melt mixing stage. 5. Polymerization of the polyolefin
modifier in a solvent containing dissolved cyclic olefin polymer or
copolymer (and optional NFP), possibly followed by extrusion or
melt mixing to add other components (such as the NFP). 6.
Polymerization of the cyclic olefin polymer or copolymer in a
solvent containing dissolved polyolefin modifier (and optional
NFP), possibly followed by extrusion or melt mixing to add other
components (such as the NFP). 7. Polymerization of both the
polyolefin modifier and the cyclic olefin polymer or copolymer in
the same reactor using two or more catalysts, possibly followed by
extrusion or melt mixing to add other components. A chain shuttle
agent may or may not be used to make block copolymers in this type
of polymerization. The NFP can be added to the reactor, or may be
added later in the melt mixing stage. 8. Polymerization where the
second double bond of a diene in the polyolefin modifier or the
cyclic olefin polymer or copolymer is partially incorporated into
other chains of the same type by the polymerization catalyst,
leading to long chain branched or gelled polyolefin modifiers or
cyclic olefin polymers or copolymers. The NFP can be added to the
reactor, or may be added later in the melt mixing stage. 9.
Polymerization where the second double bonds of a diene in the
polyolefin modifier or cyclic olefin polymer or copolymer is
incorporated into chains of other types of polymers by the
polymerization catalyst leading to graft copolymers between
different polyolefin modifiers, different cyclic olefin polymers or
copolymers, or between a polyolefin modifier and cyclic olefin
polymer or copolymer. The NFP can be added to the reactor, or may
be added later in the melt mixing stage. 10. Crosslinking where an
agent is added during mixing to crosslink a second double bond or
main chain double bond of either the polyolefin modifiers or the
cyclic olefin polymers or copolymers with other double bonds in the
composition, typically leading to long chain branched or gelled
polyolefin modifiers or cyclic olefin polymers or copolymers and/or
grafts between polyolefin modifiers, between cyclic olefin polymers
or copolymers, or between polyolefin modifiers and cyclic olefin
polymers or copolymers. The NFP can be added before during or after
crosslinking, and is typically added later in the melt mixing
stage. 11. Functionalization where the main chain double bonds or
second double bonds of dienes in either cyclic olefin polymers or
copolymers or polymer modifiers or both are functionalized after
the cyclic olefin polymers or copolymers and polymer modifiers are
already mixed together by one of the preparation methods 1 through
9. The NFP can be added before or after functionalization, and is
typically added later in the melt mixing stage. 12. Compositions
containing functionalized polyolefin modifiers or cyclic olefin
polymers or copolymers made by preparation methods 1, 2, or 11,
which are crosslinked as described in preparation methods 8-10,
except that reaction occurs between the functional groups instead
of a second double bond. 13. Any combination of the techniques
described in preparation methods 1-12. 14. Any of the techniques
described in preparation methods 1-13 in conjunction with a
hydrogenation step in which the main chain or residual (second)
double bonds in either the cyclic olefin polymers or copolymers or
the polymer modifiers, or both, are partially or completely
hydrogenated. The hydrogenation step may occur in a separate
reactor, or in the same reactor, as polymerization, mixing,
extrusion, dissolution, precipitation, suspension, crosslinking,
functionalization, and/or any other preparation steps; and it may
utilize the same or different catalysts, including homogeneous
and/or heterogeneous catalysts, as other preparation steps.
Polymer Composition
[0171] The present three-component polymer compositions comprising
cyclic olefin polymers, polyolefin modifiers and non-functionalized
plasticizers are advantageous when compared to similar
two-component compositions of only cyclic olefin polymers and
polyolefin modifiers, or of cyclic olefin polymers and
non-functionalized plasticizers. When non-functionalized
plasticizers are added to neat cyclic olefin polymers, the Izod
impact strength of the resultant cyclic olefin polymer-based blends
is decreased. This offers the advantage of independently tuning the
T.sub.g of a cyclic olefin polymer to obtain processing or
fabrication advantages (e.g., enabling use of a lower injection
molding temperature) without simultaneously having to alter the
composition or other desirable molecular properties of the cyclic
olefin polymer. However, this useful feature is mitigated by
increased brittleness, which limits performance and end usage.
[0172] In contrast, addition of a non-functionalized plasticizer to
a two-component blend of cyclic olefin polymer and polymer modifier
results in an enhancement of Izod impact strength for the blend.
Thus, the superior low-temperature impact toughness of these
three-component blends is an unexpected feature as compared to the
properties of compositionally analogous two-component blends that
comprise only cyclic olefin polymer and non-functionalized
plasticizer. The capability to independently tune and lower the
blend component T.sub.gs (bestowing processing and low-temperature
performance advantages) is retained, while simultaneously providing
the added advantage of further reducing brittleness and enhancing
low-temperature properties.
[0173] Some preferred embodiments herein (e.g. those comprising
cyclic olefin copolymers having at least 20 mole % cyclic monomer
and a T.sub.g of greater than 150.degree. C., and for high
temperature uses) have many outstanding properties, including a
room temperature (23.degree. C.) notched Izod impact resistance at
23.degree. C. greater than 500 J/m, such as greater than 550 J/m,
for example greater than 600 J/m, even greater than 700 J/m. In
these tests no breaks are observed. The composition also has no
breaks in notched Izod impact tests at -18.degree. C. and exhibits
an impact resistance at this temperature of greater than 50 J/m,
such as greater than 150 J/m, for example greater than 300 J/m,
even greater than 500 J/m.
[0174] Some preferred embodiments herein (e.g. those comprising
cyclic olefin copolymers having at least 20 mole % cyclic monomer
and a T.sub.g of greater than 150.degree. C., and for high
temperature uses) showed only ductile failures at room temperature
(23.degree. C.) and at -29.degree. C. in instrumented impact tests
and in particular exhibit instrumented impact energy measured at
23.degree. C. of greater than 25 J, even greater than 30 J and
instrumented impact energy measured at -29.degree. C. of greater
than 25 J, even greater than 30 J. These impact properties are
comparable to polycarbonates, ABS, poly(methylmethacrylate), and
the best high impact polypropylene blends.
[0175] However, the heat distortion temperature of certain
preferred embodiments of the compositions (those comprising cyclic
olefin copolymers having at least 20 mole % cyclic monomer and a
T.sub.g of greater than 150.degree. C., and for high temperature
uses), using both 0.45 and 1.80 MPa loads, is much higher than can
be achieved with toughened polypropylene blends. In particular, the
present polymer composition exhibits a heat distortion temperature
measured using a 0.46 MPa load of greater than 150.degree. C.,
typically greater than 165.degree. C., and a heat distortion
temperature measured using a 1.80 MPa load of greater than
115.degree. C., typically greater than 130.degree. C., even greater
than 145.degree. C.
[0176] Moreover, the flexural modulus (1% secant method) of certain
preferred embodiments of the compositions (those comprising cyclic
olefin copolymers having at least 20 mole % cyclic monomer and a
T.sub.g of greater than 150.degree. C.), is greater than 1200 MPa,
such as greater than 1600 MPa, for example greater than 2000 MPa,
even greater than 2500 MPa, which is significantly higher than that
of current high impact polypropylene thermoplastic polyolefins
(TPOs). These properties are much better than any others reported
in the literature for blends of polyolefin modifiers and cyclic
olefin copolymers.
[0177] In another embodiment, the blends of this invention have a
room temperature flexural modulus (1% secant, as determined below
in the examples section) of at least 1035 MPa and a -18.degree. C.
Izod Impact (forward notch, as determined below in the examples
section) of at least 40 J/m. Preferably the blends of this
invention have a room temperature flexural modulus of at least 1448
MPa, preferably 1655 MPa. Preferably the blends of this invention
have a -18.degree. C. Izod Impact (forward notch) of at least 45
J/m, preferably at least 50 J/m.
Production of Articles
[0178] Articles can be formed using the present composition by
injection molding, compression molding, transfer molding, reaction
injection molding, thermoforming, pressing, rotational molding,
blow molding, extrusion, extrusion covering, co-extrusion with
other polymers, pultrusion alone or with other polymeric materials,
lamination with other polymers, coating, fiber spinning, film
blowing, film casting, calendaring, or casting. Articles can also
be made by any of these methods, where double bonds remaining in
the polyolefin modifier or cyclic olefin polymer or copolymer or
their functional groups are crosslinked after the articles are
formed either thermally or with one of the crosslinking agents.
[0179] The polymer compositions described herein are specifically
useful for the fabrication of parts of an automobile including:
1. Chassis, mechanics and under the hood applications including gas
tanks; bumpers beams; bumper energy absorbers; bumper fascias;
grille opening reinforcements; grille opening panels; front end
fascia and grilles; front end modules; front end carriers;
bolsters; valve covers; rocker arm covers; cylinder head covers;
engine covers; engine splash shields; engine timing belt covers;
engine air cleaners; engine oil pans; battery cases and trays;
fluid reservoirs; cooling system components including cooling fans
and shrouds and supports and radiator supports and end tanks; air
intake system components; air ducting; wheel covers; hub caps;
wheel rims; suspension and transmission components; and switches
and sockets. 2. Interior applications including parts of instrument
panels (IP) including IP carriers and retainers, IP basic
structures, IP uppers, IP lowers, and IP instrument clusters; air
bag housings; interior pedals; interior consoles including center
and overhead consoles and console trim; steering column housings;
seat structures including seat backs and pans; interior trim
including pillar trim, IP trim, and door trim panels; liftgate and
hatch inner panels; door and window handles; HVAC housing; load
floors; trunk liners; storage systems; package trays; door cores
and door core modules. 3. Body applications including underbody
panels and streamlining; rocker panels; running boards; pickup
boxes; vertical body panels including fenders, quarter panels,
liftgate and hatch outer panels, and door outer panels; horizontal
body panels including hoods, trunks, deck lids, and roofs and roof
modules; spoilers; cowl vent leaf catchers, grilles, and screens;
spare wheel wells; fender liners; exterior trim; exterior door
handles; signal lamp housings; head and rear lamp housings; and
mirror housings.
[0180] The polymer compositions described herein can also be used
to fabricate parts similar to those listed for automobiles but for
heavy trucks and mass transit vehicles, such as buses, trains, and
airplanes, as well as for recreational vehicles such as
snowmobiles, all-terrain vehicles, sailboats, powerboats, and jet
skis. Other uses for the polymer compositions described herein
include the fabrication of (a) recreational goods such as toys,
helmets, bicycle wheels, pool equipment housings, and rackets; (b)
parts for large consumer appliances, such as washing machine tubs,
refrigerator interior liners, and appliance exterior housings; (c)
housings for business machines, hand tools, laboratory instruments,
electronic equipment, small machinery and appliances; (d) parts for
furniture; (e) structural elements in residential and commercial
building and construction such as exterior panels and curtain
walls, window and door frames, fascia and soffits, shutters, and
HVAC components; (f) medical devices, cookware and storage ware,
sterilizable devices and sterilization containers, decorative and
household articles; and (g) fabricated large waste management
containers.
[0181] This invention further relates to:
1. A polymer composition comprising a blend comprising:
[0182] (a) greater than 30 wt % (based upon the weight of the
composition) of a cyclic olefin polymer having a T.sub.g greater
than 60.degree. C. and having a Tm heat of fusion of 40 J/g or less
selected from the group consisting of: [0183] i) copolymers
comprising at least one acyclic olefin and at least 15 mole % of
one or more cyclic olefins; [0184] ii) partially or completely
hydrogenated copolymers comprising at least one acyclic olefin and
at least 15 mole % of one or more cyclic olefins; [0185] iii)
metathesis copolymers comprising two or more cyclic olefins; [0186]
iv) partially or completely hydrogenated metathesis copolymers
comprising two or more cyclic olefins; [0187] v) metathesis
homopolymers comprising cyclic olefins; [0188] vi) partially or
completely hydrogenated metathesis homopolymers comprising cyclic
olefins; and [0189] vii) mixtures thereof; [0190] (b) from 1 to 50
wt (based upon the weight of the composition) of an acyclic olefin
polymer modifier having a glass transition temperature of less than
0.degree. C.;
[0191] (c) from 0.1 to 50 wt (based upon the weight of the
composition) of a non-functionalized plasticizer having a kinematic
viscosity at 100.degree. C. of 3 to 3000 cSt, a viscosity index of
120 or more, a pour point of 0.degree. C. or less and a flash point
of 200.degree. C. or more.
2. The composition of paragraph 1 wherein the cyclic olefin polymer
is selected from the group consisting of: [0192]
ethylene-norbornene copolymers; ethylene-dicyclopentadiene
copolymers; ethylene-norbornene-dicyclopentadiene terpolymers;
ethylene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene copolymers;
ethylene-tricyclodecene copolymers;
ethylene-norbornene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers;
ethylene-dicyclopentadiene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; ethylene-norbornene-tricyclodecene terpolymers;
ethylene-norbornene-tetracyclododecene terpolymers;
ethylene-norbornene-ethylidene norbornene terpolymers;
ethylene-norbornene-vinylnorbornene terpolymers;
ethylene-norbornene-1,7-octadiene terpolymers;
ethylene-cyclopentene copolymers; ethylene-indene copolymers;
ethylene-tetracyclododecene copolymers;
ethylene-norbornene-vinylcyclohexene terpolymers;
ethylene-norbornene-7-methyl-1,6-octadiene terpolymers;
propylene-norbornene copolymers; ethylene-propylene-norbornene
terpolymers; propylene-dicyclopentadiene copolymers;
ethylene-propylene-dicyclopentadiene terpolymers;
propylene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene copolymers;
ethylene-propylene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers;
propylene-norbornene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; propylene-tricyclodecene copolymers;
ethylene-propylene-tricyclodecene terpolymers;
propylene-tetracyclododecene copolymers;
ethylene-propylene-tetracyclododecene terpolymers;
ethylene-norbornene-tetracyclododecene terpolymers;
ethylene-norbornene-styrene terpolymers;
ethylene-norbornene-p-methylstyrene terpolymers; hydrogenated
ethylene-dicyclopentadiene copolymers; hydrogenated
ethylene-dicyclopentadiene-2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene
terpolymers; hydrogenated propylene-dicyclopentadiene copolymers;
hydrogenated ethylene-propylene-dicyclopentadiene terpolymers;
hydrogenated ethylene-norbornene-dicyclopentadiene terpolymers;
epoxidized ethylene-dicyclopentadiene copolymers; epoxidized
ethylene-propylene-dicyclopentadiene terpolymers; epoxidized
ethylene-norbornene-dicyclopentadiene terpolymers; metathesis
homopolymers and copolymers of dicyclopentadiene,
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, tricyclodecene,
tetracyclododecene, substituted derivatives of these monomers, and
higher Diels-Alder derivatives of norbornene and these monomers;
and partially or completely hydrogenated metathesis homopolymers
and copolymers of dicyclopentadiene,
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, tricyclodecene,
tetracyclododecene, substituted derivatives of these monomers, and
higher Diels-Alder derivatives of norbornene and these monomers. 3.
The composition of paragraph 1 wherein the cyclic olefin polymer is
selected from the group consisting of: copolymers comprising
ethylene and norbornene, copolymers comprising ethylene and
octahydrodimethanonaphthalene, copolymers comprising ethylene and a
substituted derivative of octahydrodimethanonaphthalene,
terpolymers comprising ethylene, octahydrodimethanonaphthalene, and
a substituted derivative of octahydrodimethanonaphthalene,
copolymers comprising ethylene
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene, copolymers
comprising ethylene, norbornene, and
2,3,3a,4,7,7a-hexahydro-4,7-methano-1H-indene; copolymers
comprising ethylene and dicyclopentadiene or a hydrogenated
derivative of such a copolymer; copolymers comprising ethylene,
norbornene, and dicyclopentadiene or a hydrogenated derivative of
such a copolymer; or hydrogenated metathesis homopolymers or
copolymers of dicyclopentadiene or tetracyclododecene. 4. The
composition of paragraph 1, 2 or 3 wherein the acyclic olefin
polymer comprises a polymer selected from the group consisting of:
[0193] (A) elastomeric flexible cycloolefinic random copolymers
comprising an ethylene component, a cycloolefin component and an
.alpha.-olefin component having 3 to 20 carbon atoms; [0194] (B)
amorphous or low-crystalline flexible olefinic copolymers
comprising at least two components selected from the group
consisting of an ethylene component, a propylene component, and
.alpha.-olefin components having from 4 to 20 carbon atoms, [0195]
(C) elastomeric olefin/nonconjugated diene copolymers comprising a
nonconjugated diene component and at least two components selected
from the group consisting of an ethylene component, a propylene
component and .alpha.-olefin components having 4 to 20 carbon
atoms, [0196] (D) elastomeric diene/aromatic vinyl copolymers
selected from the group consisting of random copolymers and block
copolymers, each of said copolymers comprising a conjugated diene
component and an aromatic vinyl hydrocarbon component, and the
hydrogenation products of said diene/aromatic vinyl copolymers; and
[0197] (E) elastomeric homopolymers selected from the group
consisting of substantially atactic polypropylene, polybutadiene
and polyisoprene, and the hydrogenated products of polybutadiene
and polyisoprene. 5. The composition of paragraph 1, 2 or 3 wherein
the acyclic olefin polymer comprises a polymer selected from the
group consisting of: propylene homopolymer rubbers;
ethylene-propylene copolymer rubbers; ethylene-.alpha.-olefin
copolymer rubbers or propylene-.alpha.-olefin copolymer rubbers,
wherein the .alpha.-olefin in said copolymer rubbers is selected
from 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene
and 1-decene; elastomeric cycloolefinic random copolymers
comprising an ethylene component, a cycloolefin component selected
from:
[0198] bicyclo[2,2,1]hept-2-ene;
[0199]
5,10-dimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene;
[0200]
hexacyclo[6,6,1,1.sup.3.6,1.sup.10.13,0.sup.2.7,0.sup.9.14]-4-hepta-
decene;
[0201]
pentacyclo[6,5,1,1.sup.3.6,0.sup.2.7,0.sup.9.13]-4-pentadecene;
[0202]
pentacyclo[6,5,1,1.sup.3.6,0.sup.2.7,0.sup.9.13]-4-hexadecene;
[0203] tricyclo[4,3,0,1.sup.2.5]-3-decene;
[0204] substituted derivatives of said cycloolefins; and
[0205] an .alpha.-olefin component selected from propylene,
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene
and mixtures thereof; styrene-butadiene block copolymer rubbers;
styrene-butadiene-styrene block copolymer rubbers; styrene-isoprene
block copolymer rubbers; styrene-isoprene-styrene block copolymer
rubbers; hydrogenated styrene-butadiene-styrene block copolymer
rubbers; hydrogenated styrene-isoprene-styrene block copolymer
rubbers; graft-modified derivatives of styrene-butadiene block
copolymer rubbers, styrene-butadiene-styrene block copolymer
rubbers, styrene-isoprene block copolymer rubbers,
styrene-isoprene-styrene block copolymer rubbers, hydrogenated
styrene-butadiene-styrene block copolymer rubbers, hydrogenated
styrene-isoprene-styrene block copolymer rubbers; polybutadiene;
polyisoprene; hydrogenated polybutadiene; hydrogenated
polyisoprene.
6. The composition of paragraph 1, 2 or 3 wherein the acyclic
olefin polymer comprises a polymer selected from the group
consisting of: ethylene-propylene-diene copolymer rubbers, an
ethylene-.alpha.-olefin-diene copolymer rubber or a
propylene-.alpha.-olefin-diene copolymer rubbers wherein the
.alpha.-olefin in said copolymer rubbers is selected from 1-butene,
1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, and
wherein the diene in said copolymer rubbers is selected from
1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene,
6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene,
1,4-cyclohexadiene, dicyclopentadiene, 4-vinyl-1-cyclohexene,
methyltetrahydroindenes, 5-vinyl-2-norbornene,
5-ethylidene-2-norbornene, 5-methylene-2-norbornene,
5-isopropylidene-2-norbornene,
6-chloromethyl-5-isopropenyl-2-norbornene,
2,3-diisopropylidene-5-norbornene,
2-ethylidene-3-isopropylidene-5-norbornene, and
2-propenyl-2,2-norbornadiene. 7. The composition of any of
paragraphs 1 to 6, wherein the acyclic olefin polymer is graft
copolymerized or functionalized with an unsaturated carboxylic
acid-based graft comonomer selected from acrylic acid, maleic acid,
fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic
acid, crotonic acid, isocrotonic acid, Nadic Acid.TM.
(endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid), and
their acid halide, amide, imide, anhydride, and ester derivatives.
8. The composition of any of paragraphs 1 to 8 wherein the
non-functionalized plasticizer has a kinematic viscosity at
100.degree. C. of 10 cSt or more and/or a viscosity index of 150 or
more, and/or a pour point of -20.degree. C. or less and/or a flash
point of 230.degree. C. or more, and/or a specific gravity of 0.86
or less. 9. The composition of any of paragraphs 1 to 8 wherein the
non-functionalized plasticizer is a polyalphaolefin having an
M.sub.n of 300 to 21,000 g/mol, wherein the polyalphaolefin
comprises oligomers of one or more alpha-olefins selected from the
group consisting of 1-pentene, 1-hexene, 1-heptene, 1-octene,
1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,
1-tetradecene, 1-pentadecene, 1-hexadecene, and blends thereof,
preferably the polyalphaolefin is an oligomer of decene-1. 10. The
composition of any of paragraphs 1-8 wherein the non-functionalized
plasticizer is a high purity hydrocarbon fluid of lubricating
viscosity comprising a mixture of C.sub.20 to C.sub.120 paraffins,
50 wt % or more being isoparaffinic hydrocarbons and less than 50
wt % being hydrocarbons that contain naphthenic and/or aromatic
structures. 11. The composition of any of paragraphs 1 to 10
wherein the blend has a room temperature 1% secant flexural modulus
of at least 1655 MPa and/or a -18.degree. C. Izod Impact (forward
notch) of at least 50 J/m. 12. The composition of any of paragraphs
1 to 11 wherein the cyclic olefin polymer has a light transmittance
of 89 or more. 13. An article of manufacture comprising the
composition of any of paragraphs 1 to 12. 14. A polymer composition
comprising:
[0206] a) greater than 50 wt (based upon the weight of the
composition) of a cyclic olefin copolymer, said cyclic olefin
copolymer comprising at least one acyclic olefin and at least 20
weight % of one or more cyclic olefins (based upon the weight of
the cyclic olefin copolymer), wherein at least a portion of said
cyclic olefin copolymer has a glass transition temperature of
greater than 150.degree. C.;
[0207] b) less than 50 wt % (based upon the weight of the
composition) of an acyclic olefin polymer modifier, at least a
portion of the modifier having a glass transition temperature of
less than -30.degree. C.; and no portion of the modifier having a
softening point greater than +30.degree. C., the Bicerano
solubility parameter of the modifier being no more than 0.6
J.sup.0.5/cm.sup.1.5 less than the Bicerano solubility parameter of
the cyclic olefin copolymer;
[0208] c) a non-functionalized plasticizer, having a kinematic
viscosity at 100.degree. C. of 10 cSt or more, a viscosity index of
120 or more, and a pour point of 0.degree. C. or less;
[0209] d) wherein the notched Izod impact resistance of the
composition measured at 23.degree. C. is greater than 500 .mu.m and
the heat distortion temperature of the composition measured using a
0.46 MPa load is greater than 135.degree. C.
15. The polymer composition of paragraph 14 wherein said cyclic
olefin copolymer comprises at least 30 weight % of one or more
cyclic olefins, and the polymer modifier comprises a copolymer of
ethylene, a higher alpha-olefin, and at least 5 wt % but less than
20 wt % of a cyclic olefin, and the modifier has a glass transition
temperature of less than -30.degree. C.
[0210] In the foregoing description and the claims, the following
test methods are employed to measure the various parameters
identified. Additional details for the test methods used in the
Examples to measure the properties listed in Tables 1-3 are
specified in the relevant Examples themselves, specifically
Comparative Examples C1 and C4, and the Table footnotes.
[0211] Mole percent of cyclic and acyclic monomers in the polymeric
components of the blends were measured by standard characterization
techniques, such as solution .sup.1H and/or .sup.13C nuclear
magnetic resonance (NMR) spectroscopy at concentrations and
temperatures of sufficient polymer solubility, utilizing
integration of characteristic resonances for the various types of
enchained comonomer units. .sup.1H NMR is typically used to
characterize hydrogenated polymers via the integration of (or
complete absence of) olefinic resonances for the polymer's main
chain or residual double bonds compared to the integral
representing saturated units and other comonomer units. For
purposes of this invention, a one to one numerical average of mole
% comonomer values obtained by .sup.13C NMR and .sup.1H NMR shall
be used to calculate mole percents. In cases of disagreement
between these techniques (greater than 5.0 mole % variability for
any comonomer units quantified), the technique with the best
resolution of the characteristic, chemically distinct resonances
integrated to quantify mole % shall be used.
[0212] Glass transition temperature (T.sub.g), melting temperature
(T.sub.m), and T.sub.m heat of fusion (.DELTA.H.sub.f) for cyclic
olefin polymer and polymer modifier components of the invention
were measured by differential scanning calorimetry (DSC) using a
scan rate of 10.degree. C. per minute. After conducting a first
heat and first cool cycle that span the temperature range of the
expected transitions, the T.sub.g and T.sub.m (if any) midpoints
(and onset, if desired) and the heat of fusion (if any) are
calculated from the second heat cycle. Areas under the DSC curve
are used to determine the heat of fusion upon melting (T.sub.m)
(also referred to as H.sub.f, .DELTA.H.sub.f, and T.sub.m heat of
fusion).
[0213] Kinematic viscosity, viscosity index, pour point, specific
gravity, flash point, and molecular weight (M.sub.n) for
non-functionalized plasticizers are measured as described above.
Number average molecular weight (M.sub.n) of the NFP is determined
by GC or GPC as described in PCT/US07/15486. Unless otherwise noted
below physical properties of the NFP's and polyolefin components
are determined by the methods listed or described in PCT/US07/15486
which is incorporated by reference herein.
[0214] Heat distortion temperatures (HDT) were measured using ASTM
methods D648-06 and D1525-00. Before testing, the samples were
conditioned for at least 40 hours @ 23.degree. C..+-.2.degree. C.
and 50%.+-.5% humidity. ASTM test bars were 0.125'' thick.times.5''
wide x 5'' length.
[0215] Flexural modulus data at 1% secant are collected according
to ASTM method D-790 (or D790-03). At least five specimens per
sample are tested. Before testing, the samples are optionally
conditioned for 40 hours at 23.degree. C..+-.2.degree. C. and
50%.+-.5% relative humidity in bags. Tests noted only as "room
temperature" (as opposed to 23.degree. C.) were performed under
ambient conditions with no preconditioning and are noted as such;
room temperature was typically found to be .about.20.degree. C. (In
event of any conflict between D-790 and D790-03, D790 shall be
used).
[0216] Room temperature (ambient, i.e. .about.20.degree. C., or
when specified, 23.degree. C.) and low temperature (-18.degree. C.)
notched Izod were measured according to ASTM method D256(E) (or
D256-06). Test specimens tested via D256-06 at 23.degree. C. were
2.5 inches long, 0.5 inches wide, and 0.125 inches thick. At least
five specimens were cut using a clipper belt cutter from the
uniform center of Type 1 tensile bars. Samples were notched using a
TMI Notching cutter. Samples were conditioned at 23.+-.2.degree. C.
and 50.+-.5% relative humidity for a minimum of 40 hours after
cutting and notching. For sub-ambient testing, notched test
specimens were conditioned at the specified test temperature for a
minimum of one hour before testing. The types of break observed in
the notched Izod impact tests are coded and classified as follows:
[0217] C means complete break, [0218] NB means no break, [0219] P
is a partial break where the top stays above the line of the break,
and [0220] H is a hinged partial break where the top portion hangs
below the line of the break. Test specimens tested by D256 Method E
at ambient room temperature (.about.20.degree. C.) or -18.degree.
C. were molded directly into test bars of the proper dimension (63
mm.times.12 mm.times.3 mm) and were not preconditioned for tests
only noted as "room temperature". At least five specimens per
sample were tested. (In event of any conflict between D256 (E) or
D256-06, D256 (E) shall be used).
[0221] Instrumented impact at room temperature (23.degree. C.) and
low temperature (-18.degree. C. or -9.degree. C.) was measured
according to ASTM method D3763-02. Standard test specimens are 4.0
in. diameter disks. A minimum of five specimens were tested for
each sample at each temperature. Before testing, samples were
conditioned at 23.+-.2.degree. C. and 50.+-.5% relative humidity
for a minimum of 40 hours. If low temperature testing was
performed, the specimens to be tested were conditioned for 4 hours
prior to testing. The types of breaks observed in the instrumented
impact tests are coded and classified as follows: [0222] B means a
brittle failure, [0223] BD means a brittle failure showing some
ductile flow, [0224] DB is a ductile failure where the polymer has
deformed out of the way of the projectile but has cracked, [0225] D
is a failure where the polymer deformed out of the way of the
projectile without any cracking.
[0226] Melt flow rates at 230.degree. C. (2.16 kg), were measured
according to ASTM method D1238-04c (or D1238 Procedure B). (In
event of any conflict between D1238-04c and D1238 procedure B,
D1238 procedure B shall be used).
[0227] Bicerano solubility parameters were determined by the Van
Krevelen method described in chapter 5 of Jozef Bicerano's
Prediction of Polymer Properties, 3.sup.rd Edition, Marcel Dekker,
Inc., 2002. A programmed version of this estimation method was used
in the example tables. It is available in the Polymer Module of the
molecular modeling software package, Cerius.sup.2, version 4.0,
available from Accelrys, Inc.
[0228] Softening points (Vicat) of acyclic olefin polymer modifiers
are determined by ASTM D 1525 (10N, 50.degree. C./hr).
EXAMPLES
[0229] The invention will now be more particularly described with
reference to the following non-limiting Examples.
[0230] Table 1 presents the properties of the materials used in the
Examples and Comparative Examples.
TABLE-US-00005 TABLE 1 Properties of Cyclic Olefin Copolymers,
Polymer Modifier, and Non-Functionalized Plasticizer Used in
Example 1 and Comparative Examples C1-C6. T.sub.g Midpt T.sub.m
Kinematic Polymer or Composition (.degree. C.) (.degree. C.);
.DELTA.H.sub.f T.sub.m.sup.b M.sub.w; M.sub.n.sup.c viscosity PAO
(mol %).sup.a (onset).sup.b (J/g).sup.b (.degree. C.) (g/mol)
(100.degree. C., cSt).sup.d Topas .TM. 36.7 NB 76.2 None none
47,350; -- 8007S-04 63.3 E (73.6) (0) 28,810 Topas .TM. 54.0 NB
134.9 None none 38,420; -- 6013S-04 46.0 E (131.4) (0) 22,120
Vistalon .TM. 1.1 ENB -41.8 40.9 40.9 169,800; -- 7001 15.4 P
(-47.6) (v. br.) (v. br.) 83,870.sup.e 83.5 E (26.1) SpectraSyn
.TM. -- -85.0 -57.3 -57.3 -- 10.0 10.sup.f (-85.8) (.sup.f) .sup.aE
= ethylene; NB = norbornene; P = propylene; ENB =
5-ethylidene-2-norbornene; average of .sup.1H and .sup.13C Nuclear
Magnetic Resonance (NMR) measurements. .sup.bDSC, 2.sup.nd heat,
midpoint (T.sub.g) or maximum (T.sub.m) using the test method
described in Comparative Example 1; v. br. = very broad. Gel
Permeation Chromatography in 1,2,4-trichlorobenzene; Waters
Associates 2000 GPC with three Polymer Laboratories mixed bed
high-porosity Type LS B columns (10 .mu.m particle size, 7.8 mm
inner diameter, 300 mm length) and an internal waters Differential
Refractive Index detector at 135.degree. C.; typical sample
concentration 2 mg/mL; polyethylene standards. .sup.dReported by
manufacturer. .sup.eBy light scattering analysis using conditions
and instrumentation similar to that described in (c) with
polyethylene parameters and a Wyatt MiniDawn EOS 3-angle light
scattering detector. .sup.fSpectraSyn .TM. 10 has a specific
gravity of 0.835, a viscosity index of 137, a pour point of
-48.degree. C., and a flash point of 266.degree. C.; .DELTA.H.sub.f
was not calculable due to interference from T.sub.g hysteresis in
DSC spectrum.
Comparative Example C1
Preparation of Cyclic Olefin Copolymer /Non-Functionalized
Plasticizer Blend Containing 5 wt % Plasticizer
[0231] This Comparative Example and Comparative Examples C2-C4
illustrate the effects of adding non-functionalized plasticizer to
neat cyclic olefin copolymer. The base T.sub.g of the cyclic olefin
copolymer (76.6.degree. C.) is increasingly depressed towards that
of the non-functionalized plasticizer (-85.0.degree. C.) as
predicted by the Fox equation for two-component blends. The T.sub.g
of the cyclic olefin copolymer is also increasingly broadened, as
evidenced by a greater temperature difference between onset and
midpoint. Both flexural modulus and room temperature Izod impact
are also decreased upon addition of plasticizer, until the T.sub.g
is lowered so significantly (Comparative Example C3) that room
temperature test data are affected. The increased brittleness of
the "plasticized" cyclic olefin copolymers is also evidenced by
complete break of the bars during flexural modulus testing;
associated stress-strain curves showing lessened yield; and the
appearance of internal defects in the test bars after flexural
deformation. Data for Comparative Examples C1-C5 is summarized and
shown in Table 2 and FIGS. 2 and 3. FIG. 2 is a graph showing the
effect of non-functionalized plasticizer on the glass transition
temperature of neat cyclic olefin copolymers. FIG. 3 is a graph
showing the detrimental effect of non-functionalized plasticizer on
the room temperature Izod impact strength of a neat cyclic olefin
copolymer.
[0232] A 500 g portion of Topas.TM. 8007S-04 resin (Topas.TM.
Advanced Polymers GmbH, see Table 1) was ground to a 2 mm mesh size
using a Thomas-Wiley Model 4 Laboratory Mill and mixed on a rolling
mixer overnight with 0.5 g Irganox B215-FF stabilizer.
Subsequently, a 42.75 g portion of the stabilized resin was
dry-mixed with 2.25 g of SpectraSyn 10 PAO (ExxonMobil Chemical
Co., See Table 1). This mixture was added over a period of 3:10 min
(3 minutes 10 seconds) to a Thermo Electron Corp. Haake PolyLab
System mixer equipped with a Haake Reomix 600 mixing head,
operating at 30 rpm, and a 50 g capacity bowl which had been
preheated to 160.degree. C. The rotor speed was increased to 60 rpm
for a 1 minute period. The rotor speed was then lowered back to 30
rpm and the material was mixed for an additional 5 minutes. After
halting the stirrer, the blend was removed from the mixer bowl and
cut into small pieces with a scissors while warm. The blend was
then re-ground to a 2 mm mesh size and subjected to Differential
Scanning calorimetry (DSC) analysis using a TA Instruments model
2920 calorimeter with a scan rate of 10.degree. C./minute from
.ltoreq.-100 to .gtoreq.160.degree. C. The ground blend was
injection-molded into rectangular test bars of dimension
63.times.12.times.3 mm using a DSM Research B.V. Model 2002-16-16
Injection Molding machine equipped with a DSM 5 cc Micro Extruder.
The parameters used were: 100 rpm mixing, 2 minute mixing time,
mixer barrel temperature 200.degree. C.; transfer tool temperature
190.degree. C.; mold temperature 25.degree. C. The resultant bars
were transparent with a slight brown tint. Five bars were subjected
to room temperature 1% Secant Flexural Modulus testing following
ASTM D 790 using an Instron tester (Series IX software, 5500 Series
Interface, System 8.02.00, 224.8 lb load cell, 10.000 pts/sec
sample rate, 0.0500 in/min crosshead speed). Room temperature was
approximately 20.degree. C. An additional five bars were subjected
to a reverse notch room temperature (ca. 20.degree. C.) Izod Impact
testing protocol based on ASTM D 256 (Method E) using a Tinius
Olsen Model 66 Plastic Impact Tester with a manual readout scale.
An 0-25 inch-lb capacity scale was used without additional weight
on the hammer. All bars exhibited complete break (C) upon impact.
Impact data was converted from in-lb to ft-lb and then into units
of ft-lb/in by dividing by the thickness of the bars (all 0.12 in
(0.3 cm) as measured during modulus testing), and then into units
of J/m (1 ft-lb/in =53.4 J/m). Results are given in Table 2.
TABLE-US-00006 TABLE 2 Properties of the Cyclic Olefin
Copolymer/Non-Functionalized Plasticizer Blends of Comparative
Examples C1-C5. Wt % T.sub.g Midpt RT Flex. RT Izod RT Izod
SpectraSyn .TM. (.degree. C.) mod..sup.b Flex. mod. impact impact
MFR.sup.f Ex. Resin 10 (onset).sup.a (Kpsi) notes.sup.c
(RN).sup.b,d (J/m) (FN).sup.d,e (J/m) (g/10 min) (C4) Topas
.TM.8007S-04 0 76.2 413.1 .+-. 2.5 No break, yield, 164.1 .+-. 43.6
18.5 8.712 (as received) (73.6) No cracks C4 Topas .TM. 8007S-04 0
76.6 410.8 .+-. 3.4 No break, yield, 168.7 .+-. 26.0 13.9 ("mixed")
(73.2) No cracks C1 Topas .TM. 8007S-04 5 55.5 397.4 .+-. 3.2
Break, no yield, 136.3 .+-. 12.1 18.5 --.sup.h (50.6) Some cracks
C2 Topas .TM. 8007S-04 10 45.2 342.1 .+-. 2.9 Break, no
yield,.sup.g 136.3 .+-. 7.4 18.5 --.sup.h (40.0) Cracks C3 Topas
.TM. 8007S-04 15 31.1 108.3 .+-. 9.7 No break, yield, .sup. 261.4
.+-. 66.8.sup.i 27.8 --.sup.h (21.1) No cracks (C5) Topas
.TM.6013S-04 0 134.9 --.sup.h --.sup.h --.sup.h --.sup.h --.sup.h
(as received) (131.4) C5 Topas .TM. 6013S-04 15 73.6 409.3 .+-. 2.4
Break, --.sup.h 116.8 .+-. 13.0 18.5 21.46 (65.3) Some cracks
.sup.aNo T.sub.ms were seen for these materials. .sup.bRT = room
temperature; ".+-." indicates greatest difference between average
and highest/lowest value. .sup.c1% Secant; "yield" = sample yield
observed on modulus test stress-strain curve; "cracks" = internal
cracks/voids observed in used (broken) test bars. .sup.dRT = room
temperature; RN = reverse notch; FN = forward notch. .sup.eOnly one
bar used for forward notch tests. .sup.fMelt Flow Rate, analyzed as
described in Comparative Example C4. .sup.gTo a lesser extent than
C1 bars. .sup.hNot measured. .sup.iGreater variability in these
samples may partially be due to variations in mold temperature;
some samples exhibited thin spots (best value = 324.5 J/m).
Comparative Example C2
Preparation of Cyclic Olefin Copolymer/Non-Functionalized
Plasticizer Blend Containing 10 wt % Plasticizer
[0233] A Haake mixing procedure similar to Comparative Example C1
was carried out using 40.5 g of stabilized, powdered Topas.TM.
8007S-04 resin and 4.5 g SpectraSyn.TM. 10 PAO. The resin/PAO mix
was added to the mixer over a 3:30 min period. The resultant blend
was injection molded and analyzed similarly to the material in
Comparative Example C1 to give similarly appearing test bars.
Results are given in Table 2.
[0234] A similar Haake procedure, in which the resin and PAO were
not pre-mixed, but in which the PAO was added to the mixer at 30-40
rpm and mixed for 5 minutes after the resin had been previously
added and agitated at 60 rpm for 1 minute, gave an oily material
showing signs of inadequate blending (T.sub.g 73.7.degree. C.).
Comparative Example C3
Preparation of Cyclic Olefin Copolymer/Non-Functionalized
Plasticizer Blend Containing 15 wt % Plasticizer
[0235] A Haake mixing procedure similar to Comparative Example C1
was carried out using 38.25 g of stabilized, powdered Topas.TM.
8007S-04 resin and 6.75 g SpectraSyn.TM. 10 PAO. The resin/PAO mix
was added to the mixer over a 4:00 min period. The resultant blend
was injection molded and analyzed similarly to the material in
Comparative Example C1 to give similarly appearing test bars. The
mold temperature used during injection molding varied between 25
and 55.degree. C. Results are given in Table 2.
[0236] The T.sub.g onset for this blend (21.1.degree. C.) was
approximately the same temperature as the test temperature (room
temperature) for the flexural modulus and Izod impact data shown in
Table 2. As a result, the Izod impact exhibited an apparent
increase (enhancement) rather than a decrease. This is an artifact
arising from self-plasticization of the cyclic olefin copolymer,
which has partially transitioned through its T.sub.g, as further
evidenced by an extreme and uncharacteristic decrease in flexural
modulus, a test stress-strain curve exhibiting yield, and the lack
of observed test bar break or defects following modulus
testing.
Comparative Example C4
Preparation of Control Cyclic Olefin Copolymer Resin Sample
[0237] A Haake mixing procedure similar to Comparative Example C1
was carried out using only 45 g of stabilized, powdered Topas.TM.
8007S-04 resin. No SpectraSyn.TM. 10 PAO was added. The resin/PAO
mix was added to the mixer over a 2:37 min period. The resultant
blend was injection molded and analyzed similarly to the material
in Comparative Example C1 to give similarly appearing test bars.
Injection molding was also carried out on pellets of commercial
Topas.TM. 8007S-04 resin to give transparent bars with no brown
tint. Results for both materials are given Table 2. Used Izod and
modulus test bars of commercial Topas.TM. 8007S-04 resin were
subsequently ground into a 2 mm mesh size powder and used for Melt
Flow Rate (MFR) testing at 230.degree. C. following ASTM D 1238
(Procedure B) using a Kayeness Polymer Test System Series 4000
(Model 4003) Melt Indexer with a 2.16 kg weight, assuming a melt
density of 0.738 g/mL.
Comparative Example C5
Preparation of Cyclic Olefin Copolymer/PAO Blend Containing 15 wt %
PAO Using Higher-T.sub.g Cyclic Olefin Copolymer
[0238] This Comparative Example duplicates the procedure of
Comparative Example C3 (addition of 15 wt % non-functionalized
plasticizer) using a cyclic olefin copolymer resin of higher
T.sub.g. This was performed to confirm that the apparent
"enhancement" in Izod impact seen for the 15 wt % blend of
Comparative Example C3 was an artifact of its T.sub.g onset nearing
the test temperature. As expected, the blend exhibited similar
properties to the blends of Comparative Examples C1 and C2, such as
a flexural modulus and Izod impact of the expected magnitude and
visual evidence of increased brittleness (complete test bar break
and internal cracks following modulus testing).
[0239] A Haake mixing procedure similar to Comparative Example C1
was carried out at 205.degree. C. using 38.25 g of stabilized,
powdered Topas.TM. 6013S-04 resin and 6.75 g SpectraSyn.TM. 10 PAO.
The resin/PAO mix was added to the mixer over a 4:00 min period.
The resultant blend was injection molded (mold temperature
25-29.degree. C.) and analyzed similarly to the materials in
Comparative Examples C1 and C4 to give similarly appearing test
bars. Results are given in Table 2.
Comparative Example C6
Preparation of 80:20 Weight Ratio Cyclic Olefin Copolymer/Polymer
Modifier Blend
[0240] A Haake mixing procedure similar to Comparative Example C1
was carried out using 36.0 g of stabilized, powdered Topas 8007S-04
resin and 9.0 g of Vistalon.TM. 7001 rubber (pre-cut into 0.5 mm
pieces). The Topas resin was added to the mixer at 30 rpm over a 3
minute period, and the rotor speed was then increased to 60 rpm for
1 minute. After reducing the rotor speed back to 30 rpm, the
Vistalon.TM. 7001 was added over a 2 minute period and the rotor
speed was again increased to 60 rpm for 1 minute. The mixture was
then agitated at 30 rpm for another 3 minutes. The resultant blend
was injection molded and analyzed similarly to the material in
Comparative Example C1 to give opaque, off-white test bars (Izod
impact testing was carried out at -18.degree. C. rather than at
room temperature). Results are given in Table 3.
[0241] Addition of the polymer modifier to the cyclic olefin
copolymer resin did not significantly effect its T.sub.g
(suggesting phase separation). The used test bars containing the
modifier exhibited stress whitening and internal defects, unlike
the used bars of the neat cyclic olefin copolymer resin.
TABLE-US-00007 TABLE 3 Effect of Non-Functionalized Plasticizer on
a Cyclic Olefin Copolymer/Polymer Modifier Blend Wt % Wt % Wt %
T.sub.g Midpt RT Flex. -18.degree. C. Izod Topas .TM. Vistalon .TM.
SpectraSyn .TM. (.degree. C.) mod..sup.b Flex. mod. Impact
(FN).sup.b Ex. 8007S-04 7001 10 (onset).sup.a (Kpsi) notes.sup.c
(J/m) C4 100 0 0 76.6 410.8 .+-. 3.4 No break, yield, --.sup.d
(73.2) No cracks C6 80 20 0 .sup. 75.6.sup.e 268.2 .+-. 3.6 No
break, minor 38.9 .+-. 7.4 (72.3) stress crack/wht. 1 76 19 5 60.9
(58.1), 244.3 .+-. 3.6 No break, no 53.8 .+-. 11.1 -56.8 (-63.4)
cracks, Stress (weak) whitening .sup.aNo T.sub.ms were observed for
these materials. .sup.b1% Secant; RT = room temperature; ".+-."
indicates greatest difference between average and highest/lowest
value. .sup.c"Cracks" (crk) = internal cracks/voids observed in
used (broken) test bars; "wht" (stress whitening) = stress
whitening near yield point. .sup.dFN = forward notch. .sup.dNot
measured. .sup.eT.sub.g of elastomeric modifier phase (predicted
~-42.degree. C.) was too weak for observation.
Example 1
Preparation of Cyclic Olefin Copolymer/Polymer
Modifier/Non-Functionalized Plasticizer Blend with an 80:20 Weight
Ratio of Cyclic Olefin Copolymer:Polymer Modifier and Overall 5 wt
% Plasticizer (76:19:5 Cyclic Olefin
Copolymer:Modifier:Plasticizer)
[0242] A Haake mixing procedure similar to Comparative Example C6
was carried out using 34.2 g of stabilized, powdered Topas.TM.
8007S-04 resin, 8.55 g of Vistalon.TM. 7001 rubber, and 2.25 g of
SpectraSyn.TM. 10 PAO. The pre-mixed Topas.TM. resin and
SpectraSyn.TM. 10 (36.45 g) were added to the mixer at 30 rpm over
a 3 minute period, and the rotor speed was then increased to 60 rpm
for 1 minute. After reducing the rotor speed back to 30 rpm, the
Vistalon.TM. 7001 was added over a 1 minute period and the rotor
speed was again increased to 60 rpm for 1 minute. The mixture was
then agitated at 30 rpm for another 4 minutes (10 minute total run
time). The resultant blend was injection molded and analyzed
similarly to the material in Comparative Example C6 to give test
bars of similar appearance. Results are given in Table 3.
[0243] This three-component blend containing non-functionalized
plasticizer showed a significant enhancement in low-temperature
properties (higher -18.degree. C. Izod impact) as compared to the
two-component blend C6 lacking plasticizer. Visual evidence of
reduced brittleness at room temperature (no internal defects in
test bars after modulus testing) was also seen. The three-component
blend exhibited two T.sub.gs corresponding to apparent separate
cyclic olefin copolymer and polymer modifier phases. Both were
depressed from the T.sub.gs of the neat components (and the T.sub.g
seen for the two-component blend C6) towards the T.sub.g of the
plasticizer (-85.0.degree. C.). This suggests that the plasticizer
enters both the cyclic olefin copolymer phase and the elastomeric
polymer modifier phase. A broadening of T.sub.g of the cyclic
olefin copolymer phase (as evidenced by a greater temperature
difference between onset and midpoint) was not apparent as was
observed in the cyclic olefin copolymer material C1 containing 5 wt
% plasticizer.
[0244] Applicants have attempted to disclose all embodiments and
applications of the disclosed subject matter that could be
reasonably foreseen. However, there may be unforeseeable,
insubstantial modifications that remain as equivalents. While the
present invention has been described in conjunction with specific,
exemplary embodiments thereof, it is evident that many alterations,
modifications, and variations will be apparent to those skilled in
the art in light of the foregoing description without departing
from the spirit or scope of the present disclosure. Accordingly,
the present disclosure is intended to embrace all such alterations,
modifications, and variations of the above detailed
description.
[0245] All patents, test procedures, and other documents cited
herein, including priority documents, are fully incorporated by
reference to the extent such disclosure is not inconsistent with
this invention and for all jurisdictions in which such
incorporation is permitted.
[0246] When numerical lower limits and numerical upper limits are
listed herein, ranges from any lower limit to any upper limit are
contemplated.
* * * * *