Note: Descriptions are shown in the official language in which they were submitted.
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COMPATIBT~ T7h T- I,CP BLENDS
S FIELD OF THE INVEN'IION
The present invention provides alloys comprising thermotropic liquid
crystalline polymers (LCPs) and at least one thermoplastic aromatic
polyester and at least one compatibilizer.
10 BACKGROUND
High pelro,l,la-lce plastics are in widespread use in many intlllstries
and there is much interest in developing new plastics which are economical
and recyclable, as well as high pe.f~ allce. The blending and alloying of
çxistin~ polymers is a cost effective way to produce new high pel~o~ allce
15 plastics which meet these criteria.
Polymer blends cont~inin~ thPrmotropic LCPs have received
increasing ~ttention in the sci~ntific and technir~ e~alule. The range of
high perforrnance thermoplastic flexible polymers which have been blended
with TLCPs include polyimides, polyamides, poly(eth~r.elllfone) (PES~,
20 poly(etherimide) ~PEI), polyetherketone (PEEK), polycarbonate (PC~,
poly(ethylene le~},l.Llllate) (PET), poly(ethylene ~ te) (PEN~,
polyphenylene sulfide (PPS), and polyarylate.
Thermotropic LCPs are a relatively new class of high performance
polymeric m~t~ri~ls which combine the advantages of melt processability
25 and olltct~n~ling mer~h~nil~l plop~-Lies. Recall~e of their rigid backbone
structure with flexible spacer groups, co~ ;ially available thermotropic
LCPs have far higher tensile strength and flexural moduli than conventional
polymers. However, thermotropic LCPs are in many cases difficult to
process without specialized equipment and very costly as compared with
30 conventional polymers when used alone.
Blending thermotropic LCPs with other polymers has been shown to
improve processability of the other polymers, particularly LCPs based on
wholly aromatic chain segments. Fur~ermore, blending with conventional
thermoplastic polymers reduces costs, because less of the very costly LCP is
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--2 --
used. Also, because thermotropic LCPs form an ordered phase in the melt
(hence, the name thermotropic), they have shear viscosities far lower than
other polymers and thus, have potential importance as a proc~s.~ing aid in
mixtures with other polymers by red~ inE the melt viscosity of the mixture.
Thermotropic I,CP in blends with polyethylene telepl.~ te (PET),
have been reported to act as a "flow aid" at levels of 5-10% by reducing the
melt viscosity. In U.S. Patent Nos. 4,386,174, 4,433,083, and 4,438,236,
it is disclosed that blending a thermotropic LCP with other polymers such as
PET changes the melt viscosity of PET. At 10% loading (LCP) the
viscosity of PET is reduced to 25-50% of its original viscosity-. O'Brien
and Crosby (O'Brien, G.S. and Crosby, J.M., ProceeAin~ of
COMPALLOY '91 CollÇe~ ce, January 30-February 1, 1991, pp. 133-148)
described LCP/PTFE blends to improve the flow of PTFE in the melt.
The use of thermotropic LCPs in blends to provide ".eil,ruLcement,"
s~eci~lly where the LCP has a very rigid structure has been reported.
XYDAR'l9 (Poly(oxybenzoyl-co-bisphenyl terephth~l~te), Amoco, and
VECTRA~9 Poly(oxybenzoyl-co-o~y . .~ph~ yl), ~oec h~t-Cel~n~se, are
thermotropic LCPs which have been much studied as blend components.
Crevecoeur, G. and Groeninckx, G., Polymer Eng. Science, 30, 532
(1990), reported that a thermotropic LCP can be used at 5-30% levels in
polystyrene so that the LCP forms a disperse phase. In a 75:25
Poly~lylelle/VECTRA'19 A-950 LCP blend at a draw ratio of 5, the LCP
phase was reported as being slightly elongated. However at a draw ratio of
10 or more, the LCP phase was reported to show a well-developed micro-
fibrillar morphology and to display a substantial increase in elastic modulus
over a compression or injection-molded sample.
The use of LCPs in blends with thermoplastic polymers, e.g., PC
and PAT, to achieve improved m~ch~nic~l properties over those of ~e
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thermoplastic polymer alone was reported in 1989. See, Bonis, L.J.,
"Multilayer Thermoplastics Advance ~omposites By Coextrusion", 17.e
Polymer Processing Society Summer Meeting, ~mh~rst, M~s~chllcett~,
August 16-17, 1989, Paper 10F. See, also Williams, D.J., Proceerlin~ of
S COMPALLOY '91 Conference~ January 30 - Februar.,v 1, 1991, pp. 393-
408 which describes potential applications for thermotropic liquid crystal
polyester blends.
Polymer molding compositions cont~ining polycarbonates,
thermoplastic polyester, and liquid crystalline polymers, wherein the liquid
crystalline polymer is present as droplets or low aspect ratio particles, are
disclosed in U.S. Patent No. 5,262,473. In the process disclosed in U.S.
Patent No. 5,262,473, compatible blends of the polyester and polycarbonate
may be used. Other blends are disclosed in, for example, U.S. Patent Nos.
5,070,157 and 5,156,785.
A blend is a physical mixture of two or more components which
typically offers a co~ llise of prop~.Lies and economies of the individual
components. It is well known that t'ne nature and properties of the interface
of components in a blend frequently exert a limiting effect on the bulk
properties of a multi-phase blend material. In fact, the physical and
mrrh~nir~l properties of a blend are very often inferior to the m~th~m~tic~l
average of the properties of the original components. Blend components
can be miscible or immi~cihle in their behavior toward each other.
Alloys are different from blends. Although they are also composed
of two or more components, alloys exhibit strong intermolecular forces
wherein intermolecular bonding between the components of the blend is
provided by compatibilizers. This bonding in turn, creates new properties
different from those of the original components and often e~cee~ling those of
the average of the original ingredients. The types of interaction or
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"chemical bonding" between the components can include, for example, one
or more of the following me~h~ni~m~: ionic; covalent; molecular inter-
penetration; hydrogen bonding; or associative.
Successful compatibilization by one or more of these interactions
5 gives rise to interfacial a&esion to provide the formation of cohesive multi-
phase cf mp~tihilized alloys with useful ~lupellies. To achieve
compatibilization a number of strategies have emerged.
In one approach, suitable block or graft copolymers are introduced to
serve as macromolecular em~ ifiers providing covalent bonds that traverse
10 and fortify the blend interface. Block and gra~t copolymers may be
generated in-sit~ through reactive extrusion and blending to gelle,~te a
compatibilized blend.
In another approach, polymers having nucleophilic functional groups
are interacted with compatibilizers cont~ining hydrogen to form hydrogen
15 bonding. Ionomers have also served as compatibilizers. In some cases,
ionic or strong physicoch~mi-~l interactions are generated across the
interface, which in turn ~ Pe cr)mp~tibilization.
Compatibilization can also result from the addition of a similar
functional group using the "like attract like" theory, such as the use of
20 chlorinated polyethylene to compatibilizer polyvinyl chloride with
polyethylene. This has been l~ell~d to as "associative" bonding.
Finally, compatibilization has even been demonstrated by the
addition of a third immiscible phase component that exhibits relatively low
interfacial tension with each of the L~lilllaly blend components, i.e., those
25 components int~mled to be compat;bilized. The compatibilizing effects of
the mutually miscible component may result from its presumed tentlPn~y to
become enriched in the vicinity of the blend interface.
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Alloying provides a tool to lower the cost of high pelrol.llallce resins
while at the same time ret~inin~ many of the desirable L lol~elLies and/or
providing improved properties such as increased processability. The most
successful alloying procedures result in a controlled and stable morphology
with a singular thermodynamic profile. However, even when alloying is not
"complete" in the multi-component system use~ul compositions can result.
At present, there is no known direct col~l~atibility between LCPs and
thermoplastic aromatic polyesters.
Accordingly, approaches to comp~til~ilize LCPs wi~ thermoplastic
aromatic polyesters and, thereby, to provide LCP/thermoplastic aromatic
polyester alloys having properties which can be tailored to meet end-use
specifications are being sought.
SUMIUARY OF THE INVENTION
The present invention provides alloys CO~ ibillg at least one
thermotropic LCP, at least one thermoplastic aromatic polyester, and at
least one compatibilizer. In one p~r~ d embodiment, two comp~tikilizers
are present.
Preferred compatibilizers include:
(1) copolyester elastomers;
(2) ethylene ester copolymers, such as ethylene-methyl acrylate
copolymers;
(3) copolymers of ethylene and a carboxylic acid or acid derivative,
such as ethylene-maleic ~hyd.ide copolymers;
(4) ethylene ester copolymers, such as ethylene methyl acrylate
copolymers, grafted with functional monomers;
(5) ethylene copolymer-acrylic acid terpolymers, such as ethylene-
methyl acrylate-maleic anhydride terpolymers;
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(6) terpolymers of ethylene, ullsaLul~ted ester and a carboxylic acid
or acid derivative, such as e~ylene-methyl acrylate-methacrylic acid
terpolymers; and
(7) acrylic elastomers, such as acrylic rubbers.
s
Copolymers and terpolymers comprising ethylene-methyl acrylate,
copolyester elastomers and acrylic elastomers are particularly p,ere.led
compatibilizers for use in the present invention.
A particularly plel~lled:
(i) copolyester elastomer is HYTREL~ HTR-6108 from
DuPont;
(ii~ ethylene-methyl acrylate copolymer is SP 2205TN and
3306~ from Chevron /~hrmir~l G~lllpal~y;
(iii) ethylene maleic anhydride copolymer is Polybond~
3009 from BP Chemir~l~ and Fusabond'l9 E-MB-226D
from DuPont Cl~n~
(iv~ ethylene-me~yl acrylate copolymer grafted with
maleic anhydride is DS~ 1328/60 from Chevron
~hrmir~l Company and Fusabond~9 A MG-175D from
DuPont ~n~rl~;
(v) ethylene-methyl acrylate-maleic anhydride terpolymer
is Lotader~ 2400, Lotader~ 3410, and Lotader~ 5500
from Elf ~torhrm;
(vi) ethylene-methyl acrylate-methacrylic acid terpolymer
is Escor'l9 ATX-320, EscorG9 ATX-325 or Escor~ XV-
1104 from Exxon (~hemir~l; and
(vii~ acrylic rubber is Vamac~ G1 from DuPont.
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Thermoplastic aromatic polyesters for use in the present invention
are commonly referred to by those skilled in the art as PET polymers and
include but are not limited to PET (homopolymers and copolymers),
polybutylene terc;~ late (PBT), PETG (PET modified with
cyclohex~n~lim~thanol (CHDM)), PCTA copolymers (a polymer of CHDM
and terephth~lic acid with another acid substituted for a po~tion of the
terephthalic acid), PBT (polybutylene tere~hth~1~te), APET (amorphous
polyethylene), CPET (cyst~11i7~1e PET), PCPT (copolyester cont~ining
propylene glycol), PEN (polyethylene n~phth~1~te), and PBN (polybutylene
naphth~1~te). Preferred thermoplastic aromatic polyesters include PET
homopolymers and copolymers co~ g terephth~lir acid and
isot~re~ 1ic acid, and PCTA. F.~re~i~11y pr~rerfed thermoplastic
aromatic polyesters include F~tm~n Kodak Company's Kodar~9 or Eastar~
A150, Kodar~ or Eastar~ 9921, Kodapak~9 or F~t~r~kTM 7352, Kodara9 or
Eastar~ 9921W and F~tm~nTM 1339; Shell's Traytuff~ 8006; DuPont's
Crystar~ 1927 and Selar~ PT7067; and Shell's Traytuff~ CPET.
Preferred thermotropic LCPs include wholly or partially aromatic
polyesters or copolyesters. Particularly pl~;rt:l,ed copolyesters include
XYDARTM, VECTRA~ and ZENITE~ (E.I. duPont de Nemours).
Other ~i~re-led thermotropic liquid crystal polymers include
SUMIKASUPER~ and EKONO~TM (Sumitomo Ch~mir~l), DuPont HX~,
RODRUN'I9 (Unitika) and GRANLARTU (Grandmont).
~f~"ed LCPs for use in the present invention include any such
resins with a melt temperature in the range of 250 to 350~C. Particularly
pr~r~ d LCPs have a melt temperature in the range of 250 to 280~C.
One pl~rel,ed alloy in accordance with the present invention
comprises thermoplastic aromatic polyester, a wholly aromatic LCP
copolyester and an ethylene-methyl acrylate-acrylic acid terpolymer
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compatibilizer, for example, Escor~ ATX-320, Escora9 ATX-325, or Escor'~9
XV- 1 104.
Another prt~ ed alloy comprises thermoplastic aromatic polyester,
a wholly aromatic LCP copolyester and a ethylene maleic anhydride
S copolymer compatibilizer such as Polybond~ 3009 or Fusabond~9 E-MB-
226D.
Yet another ~refell~d alloy in accordance with ~is invention
comprises ~ermoplastic aromatic polyester, a wholly aromatic LCP
copolyester and an ethylene-methyl acrylate copolymer grafted with maleic
anhydride compatibilizer, such as DS~ 1328/60, or an ethylene acrylate
terpolymer grafted with maleic anhydride such as Fusabond~ A MG-175D,
or a copolyester elastomer such as HYTREL~ HTR 6108.
Alloys con~ g thermoplastic aromatic polyester, LCP and at least
two compatibilizers are particularly pl~;felled in ~e practice of the present
invention. The u~mr~tihilizers are preferably selected from a copolyester
elastomer, ethylene-maleic anhydride copolymer, ethylene-methyl acrylate
copolymer, ethylene-methyl acrylate copolymer grafted with maleic
anhydride, ethylene-methyl acrylate-maleic anhydride terpolymer, ethylene-
methylacrylate-methacrylic acid terpolymer, or acrylic rubber.
Preferred two compatibilizer alloys include a PCTA copolymer such
as KodarG9 or Eastar~ A150, a wholly aromatic LCP copolyester, an
ethylene-methyl acrylate-acrylic acid terpolymer and ethylene maleic
anhydride copolymer compatibilizer. Exemplary ethylene-methyl acrylate-
acrylic acid terpolymers include Escora9 ATX-320, Escor$ ATX-325, or
Escor~D XV-1104 and an exemplary ethylene maleic anhydride copolymers
are Polybond~ 3009 and Fusabond'l9 E-MB-226D.
In other ~l~relled thermoplastic aromatic polyester/LCP alloys, the
LCP comprises a wholly aromatic copolyester and the compatibilizers are a
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unsatureated ethylene ester copolymer grafted with maleic anhydride and/or
an ethylene-maleic anhydride copolymer. Lxemplary ~ t~d ethylene
ester copo1ymers grafted with maelic anhydride are the ethylene-methyl
acrylate copolymers SP 2205~ and 3306TM, and exemplary ethylene-maleic
S anhydride copolymers are Polybond'M 3009 and Fusabond'~9 E-MB-226D.
Another plere~.ed thermoplastic aromatic polyester/LCP alloy of the
present invention comprises a wholly aromatic LCP copolyester and
ethylene ester copolymer grafted with maleic anhydride and an ethylene-
maleic anhydride copolymer compatibilizer.
Yet another ~lerelled alloy comprises thermoplastic aromatic
polyester, wholly aromatic LCP copolyester, and a copolyester elastomer
such as HYTREL~ HTR 6108 and an ethylene rnaleic anhydride copolymer,
such as PolybondsY 3009 and Fusabond~ E-MB-226D.
The ethylene-methyl acrylate copolymers grafted with maleic
anhydride, DS~ 1328/60 and Fusabond~9 A MG-175D, and the ethylene
maleic anhydride copolymers, PolybondsM 3009 and Fusabond'~9 E-MB-226D,
are particularly ~lefelled when the LCP is VECTRATM A-95~. Also
e~lled when the LCP is VECTRA~ A-950 are the compatibilizers
PolybondTY 3009 or Pusabonda9 E-MB-226D and a second compatibilizer,
Escor~9 ATX-320, Escor~ ATX-325, DSTM 132~/60, Fusabond~ A MG-
175D, EscoP XV-1104, or HYTREL~ HTR-6108.
The plupellies of the LCP and thermoplastic aromatic polyester, as
well as desired ~o~ ies of the res lhin~ alloy, are all taken into
consideration in selecting suitable compatibilizers for use in the present
invention. The properties of the thermoplastic arornatic polyester/LCP
alloys of the present invention are adjusted by adjusting the amount of
compatibilizer and, in some ~l~r~ d embotlin~nt~ by the manner in which
the components are combined.
SUBSTITUTE SHEET (RULE 26
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- 10 -
Because the most expensive component in the alloys of the present
invention typically is the LCP, in order to reduce costs it is preferable to
keep the LCP content o~ the composition as low as possible while achieving
the desired effect. Hence, in the present alloys the LCPs are used as the
disperse phase, whereas thermoplastic aromatic polyester is used as the
predominant or bulk phase.
When no cu~ a~ibilization exists between thermoplastic aromatic
polyester and LCP, such as when no colll~tibilizer is present, the,
m~rh~nic~l properties of the rçs~ltin~ blend are low. For example, in films
extruded from blends comprising 10% LCP / 90% PCTA (KodarG9 or
Eastar~ ~-150) a m~rhinP direction (MD) tensile strength of only about
6,000 psi and MD tensile modulus of only about 300,000 psi are obtained.
l~urthermore, the oxygen barrier properties are poor, for example, around
35 to 40 cc-mil/lOin2-24 hours-1 atm. It was unexpectedly found that when
15 thermoplastic aromatic polyester/LCP alloys were formed by adding suitable
c~ mp~ihilizers in accordance with the tearhing~ of the present invention,
improved mech~nic~l properties and/or lower gas permeation (harrier)
numbers were obtained.
The present invention also provides methods of preparing the alloys
20 described above. These methods include:
i. LCP, thermoplastic aromatic polyester and at
least one compatibilizer are mixed and melt
blended to form an alloy;
ii. LCP, thermoplastic aromatic polyester and a
2~ portion of the total compatibilizer to be used
are mixed and melt blended, the rçm~in~ler of
the compatibilizer is added at a later time and
further melt blended;
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iii. LCP, thermoplastic aromatic polyester and a first compatibilizer are mixed and melt
blended. A second compatibilizer is added to
the melt blend at a later time and ~urther melt
S blended;
iv. LCP and thermoplastic aromatic polyester are
mixed and melt blended and at least one
compatibilizer is added at a later time to the
melt blend and further melt blended;
v. Thermoplastic aromatic polyester is melted
under al~p~ ;ate conditions in an extruder and
at a later time LCP and at least one
compatibilizer are added to the thermoplastic
aromatic polyester and fur~er melt blended;
vi. Thermoplastic aromatic polyester and a first
c~ hilizer are melt blended and at a later
time LCP and a second co~ alil)ilizer are
added to the melt blend and fur~er mixed and
melt blended;
vii. Thermoplastic aromatic polyester and LCP are
mixed and melt blended and two
co~ Libilizers are added to the melt blended
and further melt blended; and
viii. Thermoplastic aromatic polyester, LCP and
2~ two compatibilizers are mixed and
~imlllt~n~ously melt blended.
SUBSTITUTE SHEET (RULE 26
_
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DETAI~ED DESCRIPI'ION OF l~; INVENTION
The LCPlthermoplastic aromatic polyester alloys of ~e present
invention are formed by use of at least one compatibilizer. In one preferred
embodiment, two compatibilizers are used to form~ the a~loys.
The alloys of the present invention comprise from about 0.5 to about
10 weight percent thermotropic liquid crystalline polymer, from about 40 to
about 90 weight percent thermoplastic aromatic polyester, and from about 1
to about 50 weight percent compatibilizer.
The liquid crystalline polymer is preferably present in amounts from
about 5 to about 10 weight percent, thermoplastic aromatic polyester is
preferably present in amounts from about 70 to about 93 weight percent and
one or more compatibilizers are present in amounts from about 2 to about
20 weight percent.
In a particularly plel~ d embodiment, the compositions of the
present invention contain from about 9 to about 12 weight percent LCP,
from about 78 to about 86 weight percent thermoplastic aromatic polyester,
and from about 5 to about 10 weight percent compatibilizer.
Thermoplastic aromatic polyesters suitable for use in the present
invention are prepared by methods well known in the art. .A variety of
methods for making suitable PET homopolymers and copolymers are well
known in the art. For example, one suitable PET for use in the present
invention is prepared by the reaction of either terephth~lic acid or d;methyl
terephth~l~te with ethylene glycol. Various copolymers of PET have been
developed and are also ~ ,d~ed by mPth~ well known to the skilled
artisan. Suitable thermoplastic aromatic polyester is also available
commercially from a number of vendors. Especially preferred
commercially available therrnoplastic aromatic polyesters include F~tm~n
Kodak Company's Kodar'l9 or Eastar~ A150, Kodar~ or Eastar~ 9921,
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Koc~ k'9Or F~t~p~k~ 7352, Kodar~ or Eastar~ 9921W and F~tm~n~
1339; Shell's TraytuffrY 8006; DuPont's Cly~ TM 1927 and Selar~ PT7û67;
and Shell's TraytufflM CPET.
Suitable PCTA copolymers e.g., Kodar~9 or Eastar~ A150, for use in
S the present invention are prepared by the reaction of terephth~tic acid
iso~hth~lic acid, and cycloh~ n~ ~lim~thznnl. Kodar'~9 or Eastarm A150 is
one plc:r~ d con~ ;ially available PCTA for use in the present
invention. Preferred comlllelcially available PETs include a PET
homopolymer produced from dimethyl terephth~lz~te and ethylene glyçol
10 such as Kodapak~ or F~t~p~k~ 7352; a PET copolymer comprising
terephth~lic acid, isotel~l h~lalic acid and ethylene glycol such as Shell's
Traytuff~ 8006; and a CPET such as Shell's T~ayLurr CPET.
Suitable thermotropic LCPs for use in the present invention include
wholly and partially aromatic polyesters and co-polyesters such as those
lS disclosed in U.S. Patent Nos. 3,991,014, 4,067,852, 4,083,829, 4,130,545,
4,161,470, 4,318,842, and 4,468,364. Plt;fe.led thermotropic ~CPs
include wholly or partially aromatic polyesters or copolyesters. Particularly
~lerell~d copolyesters include XYDAR~, VECTRA~ and ZENITE~ (E.I.
duPont de Nemours). Other pl~relled thermotropic liquid crystal polymers
20 include SUMIKASUPER~ and EKONOL~ (Sulllik~lllo Chemi~l), DuPont
HXTU, RODRUN'~9 (Unitika) and GRANLAR~ (~r~n-lm~,nt)
Vectra~ A950, sold by ('~ nese Research Corporation, Summit,
New Jersey is one ~lerelled wholly aromatic copolyester. This polymer has
been reported to consist es~enti~lly of about 25-27 percent of 6-oxy-2-
25 naphthoyl moieties and about 73-7~ percent of p-oxybenzoyl moieties, as
described in example 4 of U.S. Patent No. 4,468,364 and in G. W.
(~alllnr1~nn et al., "Anisotropic Polymers, Their Synthesis and Properties",
.lillLed from Procee~lin~ of the Robert A. Welch Co~ l-ces on
SUBSTITUTE SHEET (RULE 26)
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- 14 -
Ch~mic~l Research, XXVI Synthetic Polymers, November 15-17, ~982,
~ouston, Texas, pp. 247-291 (see especially pp. 263-265).
Another particularly ~r~r~led thermotropic LCP is ZENITE~. This
polymer has been reported to consist of hydroxy-benzoic acid/phenyl
5 hydroquinone/dimethyl-napthylene dicarboxylate units.
In form~ ting the composition of the alloys of the present invention
a number of variables jnrlll~lin~, the properties of the polymers to be
blended, ~lu~eliies of the compatibilizers, and the amount and ratio of the
components, are taken into consideration. These variables are tailored and
10 o~ d in accordance with the present tç~chin~ to provide alloys to meet
a particular end use specification. For example, if high gas barrier
properties are desired, then polymers having high individual gas barrier
properties are preferably selecte~l
The amount of c(~...~~ il>ilizer is adjusted to provide intermolecular
15 bonding among the components of the alloy to enh~nre properties and at the
same time, to avoid the formation of a quasi- or pseudo-cross linlced
network which is not readily processable.
The compatibilizers for use in the present invention are either
rniscible with each of the LCP and the thermoplastic aromatic polyester
20 through, e.g., covalent, ionic, molecular inter-pen~tr~tinn~ hydrogen
bonding or associative interactions as mentioned above, or have interactive
miscibility when the LCP and thermoplastic aromatic polyester are present
in a common phase. In other words, the functional groups of the
comp~tihilizer, LCP, and thermoplastic aromatic polyester for use in the
25 alloys are also rh~mic~lly compatible. For example, if the LCP to be
alloyed with thermoplastic aromatic polyester has an ~liph~tic type of
polyester functionality, such as acrylate or methacrylate, or an aromatic
functionality, such as a benzoate or phth~l~t~ ester linkage, then ~ref~,led
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- 15 -
compatibilizers will have a functionality, such as a polyester functional
group or a maleic anhydride functional group, that is capable of reacting
with the polyester group.
C~-mp~tihilizers for use in the present invention are also processable
in the melting and processing range of thermoplastic aromatic polyester and
the LCP and exhibit l~ elaLul~ stability at the int~ ied processing
temperature. By temperature stability is meant that a component of the
alloy es~enti~lly retains its ch~ l functionality and, hence, its interfacial
interaction with the other components of the alloy with which it interacts. If
one of the components were not th~ lly stable, it is possible that the
compatibilization achieved could fail on subsequent proces~in~.
Preferred alloys of the present invention comprise at least one
thermotropic LCP, thermoplastic aromatic polyester, and at least one
compatibilizer. Particularly plerelred embo~ ; include two or more
compatibilizers, wherein at least one colll~aLibilizer interacts with the LCP
and at least one interacts with the thermoplastic aromatic polyester. The
ratios of compatibilizers to each other and in the total composition are
adjusted to achieve alloys having the desired pL~ Lies as is shown in the
examples which follow.
The following compatibilizers are particularly ~ ed in the
practice of the present invention wherein components of the alloy comprise
thermoplastic aromatic polyesters and wholly aromatic esters and
copolyesters liquid crystal polymers, such as VECTRA~ and XYDAR~:
i. Copolyester elastomers such as HYTREL~
HTR-6108 from DuPont;
ii. Ethylene maelic arlhydride copolymers
including HDPE grafted with maleic anhydride,
such as Polybond~ 3009 from BP Chlomir~
S~J~ 111 ~JTE SHEET (RULE 26)
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- 16 -
and a linear low density polyethylene-maleic
anhydride graft such as Fusabond~ E-MB-226D
from DuPont of C~n~
iii. Ethylene-methyl acrylate copolymers, such as
S SP 2205~ and SP3306~ from Chevron
Chemi-~l Co~ lly;
iv. Ethylene-methyl acrylate copolymers grafted
with maleic anhydride, such as DS~ 1328/60
from Chevron Chemi~ :ll Colllpal-y and
Fusabond~ A MG-175D from DuPont (~n~
v. Ethylene-methyl acrylate copolymer, such as
Lotader~ 2400, Lotader~ 3410 and Lotader~
5~00 from Elf Atocll~rn;
vi. E~ylene-methyl-methacrylic acid terpolymers
(ethylene-methyl acrylate-acrylic acid
terpolymers) such as Escor'l9 ATX-320, EscoP
ATX-325, and EscoP XV-1104 from Exxon
Chemi~l; and
vii. Acrylic rubber such as VAMACTM G1 from
DuPont.
The alloys of the present invention can be extruded to form various
articles of m:~mlf~ re such as films and tubes useful, e.g., in food
pack~ging, electronic circuit sllbstr~tPs and structural applications. The
25 films can be therrnoformed to provide, e.g., trays, blow molded to, e.g.,
form containers, and otherwise processed by known methods. In some
embo-limPnts, articles of m~mlf~ctnre COlll~liSillg the alloys of the present
invention are provided with a thin coating of, e.g., glass, metal or another
51u~5 ~ 1 1 UTE SHEET ~RULE 26)
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polymer both to protect the article and to provide suitable means to affix
labels and the like.
To illustrate the i~ oved properties of the alloys of the present
invention, various alloys were prepared as taught herein and extruded to
5 form films having improved tensile strength, tensile modulus and/or oxygen
barrier properties over films extruded from thermoplastic arornatic polyester
or LCP and thermoplastic aromatic polyester blends without compatibilizers.
In some films, tensile strength was increased by up to more than 2 times
and tensile mmlnlllc was increased up to more than 3 times over that of the
blend without cnmp~tihilizer. In many in~nrPc, values above 10,000 psi
and tensile strength and/or above 500,000 psi and tensile modulus were
obtained.
Films extruded from alloys CO~ ;Sil~g thermoplastic aromatic
polyesters in~ rlin~ PCTA and PET homopolymers, a wholly aromatic
15 copolyester LCP, and a co.~ Libilizer selected from a copolyester
elastomer; a copolyester elastomer and an ethylene ester copolymer grafted
with maleic anhydride; or an ethylene-methyl acrylate-mPfh~crylic acid
terpolymer.
Films extruded from alloys c~ ing therrnoplastic aromatic
20 polyester, and an anhydride-grafted ethylene-methyl acrylate copolymer,
thermotropic LCP wholly aromatic copolyester and a ethylene ester
copolymer grafted with maleic anhydride showed improved mf~rh~nir~l
properties.
Films extruded ~rom three component alloys colll~lisi~g
25 thermoplastic aromatic polyester, wholly aromatic copolyester and an
ethylene-methyl-methacrylic acid terpolymer, e.g., Escor~ ATX-320 or -
325, had superior mPch~nir~ vpel~ies. Also, three component blends
con~li~ g thermoplastic aromatic polyester, wholly aromatic copolyester
SUBSTITUTE SHEET (RULE 26~
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and a copolyester elastomer such as HYTRELTM HTR-6108 were extruded to
produce films having superior m~ch~nif~l ~rop~:llieS.
A number of films extruded from the alloys of the present invention
yielded low oxygen permeation values, ranging from about 18 to 30, well
below the 36 to 40 cc-mil/lOin~-24 hours-l atm expected for Kodar~ or
Eastar~ A150 and in another case ranging from about 8 to 22, well below
the about 28 cc-mil/lOin2-24 hours-latm expected for Kodapaka9 or
F~ct~p~kTM 7352.
Films extruded from alloys CO~ liSillg PCTA such as Kodar'~9 or
EastarlM A150, a wholly aromatic copolyester LCP and a copolyester
elastomer such as HYTRELTU HTR-6108 had excellent barrier properties.
Also, films extruded from alloys com~ g thermoplastic aromatic
polyester, a copolyester elastomer, such as HYTRELTU HTR-6108, a wholly
aromatic copolyester, and ethylene maleic anhydride copolymer, such as
Polybond~ 3009, had excellent oxygen barrier p~ ellies, e.g., from about
21 to 23 cc-mil/lOin2-24 hours-l atm. Excellent barrier l)L~pelLies were
also obtained with films extruded from alloys c~,lllprising KodapakZ9 or
F~t~r~k~ 7352, VECTRAsU A-950 and Escor~9 ATX-325 or HYTREL~
HTR-6108. One preferred alloy comprised Kodapak'~9 or F~tS~r~k~ 7352 at
about 87%, HYTRELTM HTR-6108 at about 3~'o, and VECTRA~A-950 at
about 10%. Another pl~lled alloy comprised Kl-d~r~k'l9 or F.~t~p~k~ 7352
at between about 88-89%, Escor'lDATX-325 at about 2 to 4%, and
VECTRA~ A-950 at 10%. See Table Q. The over 3 times improvement in
barrier equal to over 3 times reduction in permeability was unexpected.
2~ The o~linlulll amount of compatibilitizer to obtain the desired reduction in
permeability will vary depending upon run conditions but such opLilllulll
amounts are readily determined by the skilled artisan in view of the present
te~rhin~ .
SUBSTITUTE SHEET ~RULE 26)
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- 19 -
Optional components well known to the skilled artisan may be added
to alloys of the present invention provided that ~ey do not i~ LÇ~l~ with
formation or with the desired final properties of an alloy. Such additives
includes ~lllers and pigments, lubricants, mold release agents, plasticizers,
5 ultraviolet stabilizers and so forth.
~ n the methods of the present invention, co...~ ilizers are used
either alone or in various combinations with LCP and thermoplastic
aromatic polyester to achieve the desired results. They are also used in
single step and sequential compatibilization methods as described below.
The following methods have been found to provide alloys having
improved properties which can be used, e.g., to provide films having
improved ~n~pe~lies over films of LCP and thermoplastic aromatic polyester
blends. These methods include:
i. LCP, thermoplastic aromatic polyester
1~ and at least one compatibilizer are mixed
and melt blended to form an alloy;
ii. LCP, thermoplastic aromatic polyester
and a portion of the total compatibilizer
to be used are mixed and melt blended,
the rem~in~ler of the comp~tihilizer is
added at a later time and further melt
blended;
iii. LCP, thermoplastic aromatic polyester
and a first compatibilizer are mixed and
melt blended. A second compatibilizer is
added to the melt blend at a later time
and further melt blended;
SU~ I ~ I UTE SHEET (RULE 2
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-20 -
iv. LCP and thermoplastic aromatic polyester
are mixed and melt blended and at least
one compatibilizer is added at a later time
to the melt blend and furt'ner melt
blended;
v. Thermoplastic aromatic polyester is
melted under applol liate conditions in an
extruder and at a later time LCP and at
least one con~ ibilizer are added to the
thermoplastic aromatic polyester and
further melt blended;
vi. Thermoplastic aromatic polyester and a
first compatibilizer are melt blended and
at a later time LCP and a second
comp~tihilizer are added to the melt blend
and further mixed and melt blended;
vii. Thermoplastic aromatic polyester and
LCP are mixed and melt blended and two
compatibilizers are added to the melt
blended and further melt blended; and
viii. Thermoplastic aromatic polyester, LCP
and t~,vo compatibilizers are mixed and
simlllt,.n~ously melt blended.
25 By controlling the order in which ~e components of the alloys are mixed
and melt blended the properties of the alloy are controlled to enable the
production of articles of m~mlf~-~t~lre, e.g., films, which have improved
properties over the plup~l~ies of a similar article of m~m~f~ct~lre composed
SUBSTITUTE SHEET (RULE 26)
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solely of thermoplastic aromatic polyester or of LCP and thermoplastic
aromatic polyester.
In the production of films from the alloys described above, the meld
blend is extruded, e.g., through a slot die, a circular, counter-rotating die,
or a circular rotating trimodal die.
In alloys cont~ining two compatibilizers, sequential compatibilization
according to methods (iii) and (vi) above are pler~l,ed pl~a.dLion methods.
It was unexpectedly discovered that these unique methods of combining two
or more compatibilizers, provided alloys having irnproved properties.
While not wishing to be bound by theory, it is believed that in this novel
process, two compatibilizers interact sequentially to provide the desired
compatibilization and in some cases also interact with each other. In the
case of thermoplastic aromatic polyester-LCP blends of the present
invention, the interaction is between the thermoplastic aromatic polyester
and a first comp~tihilizer, and the LCP int~r~ts with a second
comr~tihilizer. The products of these two interactions, then seq~nti~lly
react with one another to form an alloy.
The methods of the present invention provide a great deal of
flexibility to achieve the desired compatibilization through the wide array of
possibilities for the compatibilizers to interact with the major colllponellL~ of
the alloy, which is the object of the co,-,p~lihilization. The methods of
the present invention provide an innovative yet efficient way to achieve the
desired end results.
In one ~ rell~d embodiment of the present invention, Chevron DSTU
1328/60, an a-ll~ydlide-grafted ethylene-methyl acrylate copolymer, was
melt blended with thermoplastic aromat;c polyester and then Polybond~
3009, and VECTRA~ A-950 were added to the mixture and further melt
blended to produce alloys which were extruded to produce films having
SUBSTITUTE SHEFT (RULE 26~
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greatly improved mP-~h~nic~l properties. For example, a tensile strength of
14,800 psi was obtained in one i~llm extruded from an alloy made by
feeding 5% of the Chevron DS~ 1328/60 in the hopper with the
thermoplastic aromatic polyester, and then by feeding 2% Polybond~ 3009
S with the LCP VECTRA~ A-950 into the vent feed port.
In another preferred embo~limf~nt~ Escor~9 ATX-325, an ethylene-
methyl-mPth~crylic acid terpolymer, was melt blended with thermoplastic
aromatic polyester and then Polybondn' 3009 and VectraTM A950 were added
to the mixture and further melt blended. A tensile m~ lhlC value of 1.09
10 million psi was obtained in a film extruded from an alloy made by feeding
~% of Exxon ATXTY 320 in the hopper with the PAT, and then feeding 2%
Polybond~ 3009 with the LCP VECTRA~ A-950 into the vent feed port.
Accol.lhlgly, it can be seen that films produced from the alloys of
the present invention have surprisingly improved plu~llies over films of
15 LCP and PAT blends or of PAT alone.
Conventional extrusion e~lui~ ellt was used to produce the alloys of
the present invention and to extrude films from these alloys. Mixing and
melt blending of components to form the alloys of the present invention is
carried out using conventional single or double screw extruders. It is
20 pl~fellc:d that the extruder system has not less than 25/l L/D ratio.
Extrusion conditions such as processing tempeldLul~ s, rotation speed of the
screw, feed rate and through put were optimized for the particular alloy by
taking into consideration the pl~")elLies of the polymers being melt blended
to form the alloy, including res~llting viscosity of the melt blend. Typically,
25 higher shear screw configurations were found to give better dispersions of
the LCP and better compatibilization remlting in alloys that could be used
to produce films having improved properties. Typical L~ Lules
SuBsTlTuTE SHEET (RULE 26~
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employed for the processing were 525 to 620~F. The rotation rate of the
screw was, typically between 50 to 300 rpm.
The alloy components are ~Iu~iately conditioned, e.g., dried and
then fed to the extNder using convPntio~l methods. For example, the
S components can be melt blended and extruded to form pellets. The pellets
can then be extruded or injection molded to form the desired article of
m~mlf~ lre. ~ ;vely, the dry components can be blended, fed into
the extruder, and extruded, e.g., to a film directly.
The rnasterblending or masterb~tching technique in which typically, a
10 blend of two components is processed into pellets to form the "masterblend"
can also be used. The masterblend can be run through an extruder a second
time with additional components added in accordance with the tP~rhin~c of
the present invention. This is a convenient method of m~mlf~rtllre, because
an inventory of masterblend material can be made and then combined with
15 dirrel~llL components as desired. One advantage to the masterblending
process is that small and very controlled amounts of additional components
can be added to the l,la~L~ lend. For example, if the llla~L~.l,atch has 10%
LCP, the ma~LelbaLcll can be passed through the extruder again with, for
example, 10% of the masterbatch and 90% of the other polymers, providing
20 a masterbatch that is 1 ~o in LCP.
Through ma~L~lb~ hinp, controlled low concentration of a
component in the alloy can be obtained; and ~ itiQn~l mixing and ~h~ring
through multi-passes in the extruder can be achieved, if desired.
Masterbaching also provides advantages when working with a
25 component having a low melt temperature, such as the compatibilizer
Fusabond~9 A MG-175D which has a melt temperature of about 45~C. It
can be added over time at the vent feed with the LCP. However, in one
pl~Lred method of the present invention the LCP and low melt
SUBSTITUTE SHEET ~RULE 26~
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-24 -
temperature compatibilizer are masterb~trhPc~, thus allowing greater control
over the processing of this low melt temperature component which is also
present at a low conr~ntr~tion.
The present invention will be fur~er illustrated with reference to the
S following example which is inten-le(l to aid in the underst~n(iin~ of the
present invention, but which is not to be construed as a limitation thereof.
E~LE
The alloy components should be appioL~liately treated, e.g., dried,
before processing as would be readily apparent to the skilled artisan.
The work described in the following exarnple was carried out using a
conventional 25 mm or 40 mm co-rotating, non-hl~ p~ twin screw
extruder m~nnf~rtllred by Berstorff Corporation. Mixing and knP~(1ing
elemPnt~ for the screw configuration were varied according to conventional
wisdom to achieve the desired degree of mixing.
E~ilms were extruded from a slot die, approximately 8 inches wide
with die gap of approximately 0.010 to 0.020 inches. Also, a counter-
rotating die or circular trimordal die ~see, U.S. Patents 4,975,312 and
5,288,529) can be used to extrude films coll~lisillg one or more alloys of
the present invention. Since the degree of llni~xi~l orient~ti~ n produced in
the extruded film has an impact on the properties, films having similar
extrusion conditions were cOlll~al~d in the work cli~r~c~e~ below.
A universal testing m~rhin~ was used for testing the tensile
properties based on ASTM standard tests, e.g., ASTM #0882.
The LCP used was Vectra~ A-950 from Hoechst-Cel~n~se
Corporation. A PCTA copolymer purchased from F~ctm~n Chemiral~
under the tr~(len~m~ Kodar'9 or Eastar~ A150 was used in the following
work. Also used was a PET homopolymer purchased from F~tm~n
SlJ~ JTE SHEET (RULE 26)
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l~hPmir~l under the tr~den~m~ Kodapak~ or F~t~r~k~ 7352 and a CPET
purchased from Shell under the tr~ n~m~ Traytuf~ CPET. The
compatibilizers used included: HYTRELTM HTR-6108; PolybondTY 3009; and
Fusabond~ E-MB-226D; SP 2205TU and 3306TM; DSsM 1328/60 and
S Fusabond39 A Mal75D; Lotader~ 240~); Escor'l9 ATX-320, Escor~9 ATX-
325, and; Escor39 XV-1104; and Vamac~ G1.
The run conditions and results are shown in Tables I-VII. In the
Tables, the thermoplastic aromatic polyesters used are inr1ie~terl as follows:
Kodar'l9 or Eastar~ A150 as "A150," or Kodar'l9 or Eastar~ 9921 as "9921,"
or Kodapak~9 or F~t~r~krM 7352 as "7352" and Shell's TraytuffrM CPFT as
"CPET." The VECTRA~ LCP is in~ tt-d as "A950." "Ten Yld St."
intli(~t~s Tensile Yield Streng~; and "Ten. Mod. " in-lir~t~s Tensile
Modulus Values. In ~e Tables, compatibilizers listed are itl~.ntifi~cl as
~ollows: HYTl~ELTU HTR-6108 as Hytrel 6108; Polybond~ 3009 as
"BP3009"; SP 2205TU as "SP2205"; DS~ 1328/60 as "Chev DS"; Lotader~
2400 as "Lotader 2400"; Escor~9 ATX-320, ATX-325 and XVl104s
"ATX320", "ATX325" and "XVllO4" respectively, and Fusabond~9 E-MB-
226D as "Fusabond226".
SUBSTITUTE SHEET (RULE 26)
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TABLE A
LCP, themoplastic aromatic polyester and at least one
compatibilizer are mixed and melt blended to forrn an alloy.
s
RUN # HOPPER ~ ;D TEN YLD TEN MOD OX-
ST MD(Kpsi)MD(Kpsi) BARRlER
6299-7 85.7%A150+9.5%A950 10.6 800 27.2
+4.8%ATX320
6299-9 85.7%A150+9.5%A950 9.7 810
+4.8%ATX325
6299-10 8S.7%A150+9.5%A950 9.1 570 25.3
+4.8 %Chevron
8249-9 95%8006+4%A9507.1 209
+4%Hy~rel6108
TABLE B
LCP, thermoplastic aromatic polyester and a portion of ~e
total compatibilizer to be used are mixed and melt blended,
the rem~in~ler of the compatibilizer is added at a later time
and further melt blended.
R~ ~ HOPPER FEED VENT FEED TEN YLDTEN MOD OX-
ST MD MD BAR
(Kpsi) (Kpsi) RIER
6249-3 85.7%A150+ 2.4%ATX325 10.0 421 25.5
9.5 %A950
+ 2.4 %ATX325
6249-7 85.7%A150+ 2.4%BP3009 12.9 460 26.8
9.S %A950
+2.4%BP3009
8319-2 91 %8006+2% 1 %Fusabond226D6.9 320
Hyt}el6108 +7%A950
9085~ 86%7352+1% 10%A950+ 7.19 263 8.4
Hytrel6108 2%F~ )n~1'7~6D
2~i
SUBSTITUTE SHEET (RULE 263
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TABLE C
LCP, thermoplastic aromatic polyester and a first
compatibili~er are mixed and melt blended. A second
S comp~tt~lilizer is added to the melt blend at a later time and
further melt blended.
RUN # HOPPER FEED VENT FEED TEN YLD TEN MOD
ST MD(Kpsi) MD(Kpsi)
6249-8 85.7%Al50+ 2.4%Lotader7.2 233
9.5 %A950 2400
+2.4%ATX325
TABLE D
LCP and thermoplastic aromatic polyester are mixed and melt
blended and at least one compatibilizer is added at a later time
to the melt blend and further melt blended.
RUN # HOPPER FEED VENT TEN YLD TEN OX-
FElEDST MOD BARRIER
MD(Kpsi) MD(Kpsi)
6299-14 85.7%Al50+ 7.8% 9.1 530 26.6
9.5 %A950 ATX320
TABLE E
Thermoplastic aromatic polyester is melted under ~I ~r~ ial~
conditions in an extruder and at a later time LCP and at least
one compatibilizer are added to the PET and further melt
blended.
RUN # HOPPER FEED VENT FEED TEN YLD TEN
ST MOD
MD(Kpsi)MD(Kpsi)
6309-12 85.7%Al50 9.7%A950 7.1 460
+4.8 %ATX325
8249-4 94%8006 4%A950 7.16 233
+0.75 %SP2260
S~ TE SHEET(RULE 26)
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WO 97/24403 PCT/US95/17114
TABLE F
Thermoplastic aromatic polyester and a first compatibilizer are
melt blended and at a later time LCP and a second
cnmr~tibilizer are added to the melt blend and further mixed
and melt blended.
RUN #HOPPER FEEDVENT FEED TEN YLD TEN OX-
ST MOD RARR~.R
MD(Kpsi)MD(Kpsi)
7019-789%A150 9.3%A950 12.7 810 29.6
+4.7%ATX320 +2%BP3009
7069-889%A150 9.3 %A950 11.2 960 25.7
+4.7% +2%BP3009
ChevronDS
7069-989%A150 9.3%A950 9.6 740
+4.7%XV11.04 +2%BP3009
7069-1089%Al50 9.3 %A950 9.3 850 20.3
+4.7% +2%BP3009
Hyt~el6108
7079-189%A150 9.3%A950 14.8 840 29.8
+4.7% +2%BP3009
ChevronDS
8259-3939ta8006 4%A950 7.73 278
+2%Hytrel6108 + 1 %
Fusabond
226D
TABLE G
Thermoplastic aromatic polyester & LCP are mixed and melt
blended and two compatibilizers are added to the melt blended
and further melt blended.
RUN #HOPPER VENT FEED TEN YLD TEN OX-
FEED ST MOD l~ARRTF,R
MD(Kpsl)MD(Kpsi)
7069-685.7%A1502.4%Hyt}el6108 6.2 420 26.3
+9.5%A950 +2.4%BP3009
SuBsTlTuTE SHEFT (RULE 26
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- 29 -
TABLE H
Thermoplastic arom~tic polyester, LCP and two
S compa~ibilizers are mixed and .~iml-lt~nPously melt blended in
an extruder and extruded through a slot die.
RUN # HOPPER FEED TEN YLD T~N MOD OX-
ST ~DD~Kpsi) BARRUER
h1D(Kpsi)
7169-3 80%A150+10%A950 7.9 370 25.3
+~.5%Hytrel6108+~.5%BP3009
TABLE J
Thermoplastic aromatic polyester, LCP and two
co~ )aLil)ilizers are mixed and ~imlllt~nPously melt blended
and extruded through a circular, counter-rotating die.
RUN # HOPPER FEED TEN YLD TEN MOD
ST ~DD(Kpsi) ~DD(Kpsi)
1199~3 83%A150+10%A950+5%ATX320 6.2 440
+2%BP3009
H99-4 81%A150+10%A950+5%SP2205 5.9 370
+4 %BP3009
1199-5 81%A150+10%A950+5%SP2205 7.2 440
+4%Hysrel6108
SUBSTITUTE S~IEET (RULE 26
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- 30 -
TABLE K
Thermoplastic aromatic polyester and a first co~ a~ibilizer are
S melt blended and, at a later time, LCP and a second
comp~tihlizer are added to the melt and fur~er mixed and
melt blended and extruded using a circular rotating trimodal
die.
RUN # HOPPER FEED VENT FEED TEN YLD TEN
ST MOD
MD(Kpsi) MD(Kpsi)
3249-2 83.6%A150 10%A950+2%BP3009 9.0 290
+ 4.4 %ATX320
3249-5 83.6%A150 10%A950+2%BP3009 6.5 220
+4.4%ChevronDS
TABLE L
Control thermoplastic aloll~Lic polyester
RUN # HOPPER FEEDTEN YLD TEN OX-
ST MOD RARV~R
MD(Kpsi)MD(Kpsi)
6249-1 100%A150 5.5 162
5269-0 100%A150 5.4 190
5119-0 100%A150 5.8 169
4239-1 100%A150 6.2 176 31.5
6299-1 100%A150 5.2 320
7069-1 100%A150 5.3 320 29.9
3189-1 100%A150 6.2 200
SlJ3~ 111 ulTE SHEET (RULE 26
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TABLE M
Control thermoplastic aromatic polyester & LCP, No Com?atibilizer
RUN #HOPPER FEED l~:N YLD TEN OX-
ST MOD B,~RRni.R
MD(Kpsi)MD(Kpsi)
3189-2 90%A150+10%A950 6.9 290
3189-5 90%A150+10%A950 5.5 210 22.7
3189-9 90%A150+ 10%A950 5.8 231
6249-2 90%A150+ 10%A950 7.4 251
7069-2 90%A150+10%A950 6.1 420 24.9
7019-5 90%A150+10%A950 6.1 440
TABLE N - Ma~ lJa~ch
RUN # HOPPER FEED VENT TEN YLD TEN OX-
FEED ST MOD BARR
MD~Kpsi) ~DD(Kpsi
)
8129-1 83%A150 10%A950 8.0 550 20.6
+5%Hytrel6108 +2%BP3009
8129-5 78%A150 10%A950 7.8 230 19.6
+10%Hytrel6108 +2%BP3009
8129-10 83%A150 10%A950 5.6 430 22.1
+5%Hytrel6108 +2%BP3009
8129-16 78%A150 10%A950 5.9 420 18.5
+ 10%Hytrel6108 +2%Hytrel6108
8129-17 78%A150 10%A950 5.8 430 18.4
+ 10%Hytrel6108 +2%Hytrel6108
8129-18 78%A150 10%A950 7.4 600 19.5
+ 10%Hytrel6108 +2%BP3009
8129-19 78%A150 10%A950 7.6 710 18.0
+ 10%Hytrel6108 +2%BP3009
8289-5 94~o7352 1 %A950 7.37 268
+2%Hytrel6108 +3 %Fusabond
226D
SuBsTlTuTE SHEET (RULE 26
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W O 97/24403 PCTrUS95/17114
TABLE O
In some runs, LCP, thermoplastic aromatic polyester and one
S co~ libilizer are added to the hopper feed and melt blended to form
an alloy. In other runs, thermoplastic aromatic polyester and one
comr~tihilzer are added to the hopper feed and LCP and Fusabond
226 are added at the vent feed and melt blended to form an alloy.
0 RIJN # HOPPER ~ED VENT FEEDTEN YLD TEN
ST MD MOD
~Kpsi~MD(Kpsi)
9259-1 100%A150 - 5.5 180
9259-2 90%A150+10%A950 - 7.3 560
9259-3 85%A150+10%A950 - 8.7 740
+ 5 %ATX325
9269-1 100%7352 - 5.8 250
9269-2 90%7352+10%A950 - 6.2 290
9269-3 85%7352+10%A950 - 7.0 290
+5 %ATX325
9269-4 88%7352+10%A950 - 6.7 300
+2%Escor325
9269-5 86%7352+ 10%A950 - 7.3 300
+4%Escor325
9269-6 86%7352 10%A950 7.3 320
+2%Escor325 +2%Fusabond226
9269-7 84%7352 10%A950 7.2 310
+4%Escor325 +2%Fusabond226
9269-8 86%7352 10%A950 7.2 310
+2%Hytrel6108 +2%Fusabond226
9269-9 84%7352 10%A950 6.5 260
+4%Hytrel6108 +2%Fusabond226
9269-lOA 85 %7352 10 %A950 6.7 280
+4%Hytrel6108 + 1 %Fltr ~hont~ 6
SUBSTITUTE SHEET (RULE 21;~
CA 02241860 1998-06-26
W O 97t24403 PCT~US95/17114
TABLE O - cont'd
RUN # HOPPER Fl~;ED VENT FEED TEN YLD TE;N
ST MD MOD
(Kpsi)MD(Kpsi)
5 9269-lOB85%7352 10%A950 7.0 340
+4%Hytrel6108 +1%r~ 6
9269-11 82%7352 10%A950 7.0 320
+5%Hytrel6108 +3%F~ h-n~ 6
9269-1286%7352+10%A950 - 6.4 310
+4%Hytrel6108
9269-1387%7352+10%A950 - 7.3 340
+3 %Hytrel6108
9269-1488%7352+ 10%A950 - 6.9 330
+2%Hyt~el6108
109269-1589%7352+10%A950 - 7.3 320
+ 1 %Hytrel6108
TABLE P
LCP, thermoplastic aromatic polyester and comp~tihilizer are
added to the hopper feed and melt blended to form an alloy.
20 RUN # HOPPER FEED TEN YLD TEN MOD
ST MD (Kpsi)
MD (Kpsi)
04059-1 90%CPET+10%950 10 610
04059-2 86~h%CPET+10%A950+31h%ATX320 11 640
04059-3 85 %CPET + 10 %A950 + 5 %ATX32011.7 620
S~J~a 1 l l UTE SHEET (RULE 26)
CA 02241860 1998-06-26
W O 97124403 PCTAUS95/17114
- 34 -
TABLE Q
s
LCP, thermoplastic aromatic polyester and cc ...p;1lihilizer are
added to the hopper feed and melt blended to form an alloy
RUN # HOPPER FEED OXYGEN-
pF,Rl~lAR~ ,lTY
cc-milllOOin2-d ,.'
11169-1 100%7352 28
9269-3 85 %7352 + 5 %ATX325 + 10 %A950 9
92694 88%7352+2%ATX325+10%A9S0 9
9269-S 86%7352+4%ATX325+10%A9S0 9
9269-12 86%7352+4%Hytrel6108+109t0A9S0 21
9269-13 87%7352+3%Hyt~el6108+ 10%A950 8
9269-14 88%7352+2%Hytrel6108+10%A950 20
9269-15 89%7352+1%Hytrel+10%A95022
The present invention has been described in detail inr~ ing the
p,~;re,led embotlim~nt~ thereof. EIowever, it would be a~pl~.;idled that those
2~ skilled in the art, upon c~m~ider~tion of the present disclosure, may ~ke
modifif ~tinns and/or improvements on this invention and still be within the
scope and spirit of ~is invention as set for~ in the following claims.
SUBSTITUTE SHEET (RULE 26~
