Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO g6/00752 r ~ I/U~ .
7 ~
--1--
Compatibilized LCP Blends
F rhr~:n OF Tr~ n~V.F~TION
The present invenlion provides alloys compri~i ng Ih~ lu~upic liquid
crystali'ine polymers (LCPs) and poly~ .. t~... ' ' (PET) and at least
one
BACKGROUND
High p r~ ", V plastics are in wid~ dd use in many industries
and there is much interest in developing new plastics which are ecnm~
and recyclable, as well as high j~.ru~ di~ce~ The blending and ai'loying of
10 existing polymers is a cost effective way to pi~duce new high j~c.rulllldn~l, plastics which meet these criteria.
Polymer blends contidning IL~ lùLiulJ;c LCPs have received
increasing attention in the scientific and technical literaiture. The rainge of
high jJC~IÇUI111~ flexible polymers which have been blended
15 with TLCPs include polyimides, JJuly~lllide~ poly(~ ) (PES~,
poly(Pt~ ) (PEI), pol~ (PEEIC), poly~,dl; (PC),
polylethylene t~.l' ' ' ) (PET), poly(ethylene n~phth~l~t~), pùly, ' jL,..~,
sulfide (PPS), and POIJCU~Y~
TL~ llvLiu~, LCPs are a relatively new class of high p, ~
20 polymeric materials which combine the advantages of melt processability
and u~ .d;.~g m~. h~ properties. Because of their rigid backbone
sb-ucture with flexible spacer groups, commercially available Ih~ lullujJ;~
LCPs have far higher tensile strength and flexural moduli than cu~ l.Liulldl
polymers. However, Ill~,lllluLiujJ;~, LCPs are in many cases difficult to
25 process without specialized equipment and very costly as compared with
cu,.~, ' polymers when used alone.
Blending I~ lluLiujJic LCPs with other polymers has been shown to
improve julu~ dbiliily of the other polymers, particularly LCPs based on
wholly aromatic chain segments. r~ lllul~ blending with ~UII~
~I,.. ~pl~ polymers reduces costs, because less of the very cost1y LCP is
used. Also, because IL~.I.,uL.uJJ;c LCPs form an ordered phase in the melt
w0 96f007s2 P~ ~
~ ~ q~ 7 1 -2-
~hence, the narne Lh~ utlul ic), they have shetr viscosities far lower than
other polymers and thus, have potential importance as a processing aid in
mi~tures with other polymers by reducing the melt viscosity of the mi~ture.
uslus~;c LCP in blends with PET have been reported to act as
S 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 i5 disclosed that
blending a lL~-ullus~;-, LCP with other polyrners such as PET changes the
melt viscosity ûf PET. At lO~o loading (LCP) the viscosity of PET is
reduced to 25-50% of its original viscosity. O'Brien and Crosby (O'Brien,
10 G.S. and Crosby, J.M., P~ F~'.1i.,~i of COMPAT.I OY '91 Conference.
January 30-February 1, 1991, pp. 133-148) described LCPlPTFEblends to
improve the flow of PTFE in tshe melt.
The use of lh~ ùLIusJil_ LCPs in blends to provide "~c~nru-
~especially where the LCP has a very rigid structure has been reported.
15 XYDAR0 (Poly(ù~yl,~ jl co-bisphenyl t~.,, ' ' ' ), Amoco, and
VECTRA0 P.oly(u..yl,~,~vyl-co-w~ l,Ll,ùyl), lIoechst-Celatese, are
ih~,.lllVtlUIJiU LCPs which have been much studied as blend .v~
Crevecoeur, G. and Groeninckx, G., Polymer Eng. Science, 30, 532
(1990), reported that a ~ lllUt.U~ LCP can be used at 5-30~o levels in
20 polystyrene so that the LCP forms a disperse phase. In a 75:25
Polystyrene/VECTRA3 A950 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-
fbrillar morphology and to display a substantial increase in elastic modulus
25 over a ~ or in~ection-molded sample.
The use of LCPs in blends with lh. . "",l,t~l;, polymers, e.g., PC
and PET, to achieve improved mechanical properties over those of the
li" "",~ polymer alone was reported in 1989. See, Boslis, L.J.,
"Multilayer TI~e~U-UIJLI~ Advance Composites By ~'OPYtrLICi~ln", The
30 Polymer Processing Society Summer h~:eeting, Amherst, ~S~
August 16-17, 1989, Paper IOF. See, also Williams, D.J., P,u~.~di,.~;;, of
WO 9S/00752 r~
- 3 -
COMP~r ~ OY '91 Conference. January 30 - February 1, 1991, pp. 393-
408 which describes potential ~ ;t~t ~ for I~ ULlU~ . liquid crystal
polyester blends.
- Polymer molding Ct~ containing pol~L
5 ~ 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 poly~t~bl
may be used. Other blends are disclosed in, for e Lample, U.S. Patent Nos.
5,070,157 and 5,156,785.
A blend is a physical rnixture of two or more '.~ ~- '~ which
typically offers a Cu...l~lu..~S_ of properties and economies of the individual
-t~ It is well known that the nature and properties of the interface
of ~ , .,t~ in a blend frequently exert a limiting effect on the bulk
15 properties of a multi-phase blend material. In fact, the physical amd
m~orhgnit~l properties of a blend are very oRen inferior to the ., ~ I;nl~ _1
a~,erage of the properties of the original eU~ Blend ~ r
can be miscible or immiscible in their behavior toward each other.
Alloys are different from blends. Although they are also composed
20 of two or more t . ~ f ,~-, alloys exhibit strong ' ' forces
wherein; -~ bonding between the ~ of the blend is
provided by comr~tihili7f~rc This bonding in turn, creates new properties
different from those of the origina]: ~ and often exceeding those of
the average of the original il~ " The types of interaction or
25 "chemical bonding" between the ~ can include, for example, one
or more of the following .- ~ ionic; covalent; molecular inter-
pt~nPtrstion, hydrogen bonding; or associative.
Successful ct~nr~tihili7~tit~n by one or more of these; ~ ~ I;..,,~
gives rise to interfacial adhesion to provide the formation of cohesive multi-
30 phase co"lr~tihili7~d alloys with useful properties. To achievecompatibili_ation a number of strategies have emerged.
W096101)752 r.. ,.a,~s.
- 4 -
In one approach, suitable block or graft cu~O~ a are introduced to
serve as, ~ emulsifiers providing covalent bonds that traverse
and fortify f~he blend interface. Block and graft ~upûlyl~ may be
generated in-situ through reactive extrusion and blending to generate a
S rnmp~tihiii7P~i blend.
In another approach, polymers having ~ 'lir functional groups
are interacted with cl. ,~ containmg hydrogen to fonn hydrogen
bonding. Ionomers have also served as cnmp~l~;hili7Pr~ In some cases,
ionic or strong ~ are generated across the
10 interface, which in turn enhances rc~ r~tihili7~ti.~n
p-~ihili7!~finn can also result from the addition of a similar
functional group using the "like attract like" theory, such as the use of
chlorinated pul~ lunf to r~mr~tihili7pr poly~inyl chloride with
pul~.,lLyl~...,. This has been referred to as "associative" bonding.
FinaUy, ~ p ~ih;l;,.l;",l has even been ~ d by the
addition of a third immiscible phase component that exhibits relatively low
interfacial tension with each of the primary blend ~ , i.e., those
~ um~ intended to be ~u~ f l The ~.,...~UI..l.,;..v effects of
the mutuaUy miscible component may result from its presumed tendency to
20 become enriched in the vicinity of the blend interface.
Alloying provides a tool to lower the cost of h;gh performance resins
while at the same time retaining many of the desirable properties andlor
providing improved properties such as increased processabil;ty The most
successful alloying procedures result in a controlled and stable mu~h;)lo~,y
25 with a singular lh~rlllod~ profile. However, even when alloying is not
"complete" in the multi-component system useful cc~ l.u~ ., can resuit.
At present, there is no known direct , ' "ty between LCPs and
PEI .
Accordingly, approaches to comr~tihili7f LCPs with PEr and,
30 thereby, to provide LCP/PET alloys having properties which can be tailored
to meet end-use ~l :ri ~ .C are being sought.
W0 96/00752 P_ l l u.,,.. '
7 1 ,
-- 5 ~--
SUMMARY OF T~E INVENTION
The present invention provides alloys ~ g a Illcllllullu~ic
LCP, PET, and at least one compatibilizer. In one preferred e ~l,ofl; ~\- m
two cnn-p ~ihili~Pr~ are present.
Preferred c,.. ~ , include ~;u~,ol~lc. ~ , ethylene-
' ester cu~ol.y...~.~, such as ethylene-maleic anhydride
cu~ulJ ~ cu~ùl~ of ethylene and a carboxylic acid or acid
derivative, such as ethylene-methyl acrylate cu~,oly...~.~, puly~ Pll.~ or
ethylene-~ ,... S ~1 ester cu~ly~ grafted with functional m~m~nnPr.e
10 such as ethylene-methyl acrylate C~IJOIY---~ cul~ùlylllcl~ of ethylene and a
carboxylic acid or acid derivative, such as ethyL,..~ tllyl acrylate-maleic
anhydride t~.~ulylllcl~, t~ oly,-,c-~ of ethylene, I ' ester and a
carboxylic acid or acid derivative, such as ethylene-...rll.J; .,l.,lhal,lyli~- acid
t~ oly.l.~ , and acrylic pl~ctnmprc such as acrylic rubbers. A ~ ukuly
15 preferred cu~ulJ.~st~. elastomer is HYTRELrA HTR-6108; ethylene-maleic
anhydride copolymer is rolyl,ù..u 3009; ethylene-methyl acrylate copolymer
is SP 2205r"; ethylene-methyl acrylate copolymer grafted with maleic
anhydride is DS1328/6~; ethylene-methyl a,ly~ .aalcic anhydride
terpolymer is Lotadern' 2400; ethylene-methyl-~ ylic acid terpolymer
is EscorrA ATX-320, Escorr" ATX-325 or Escor~ XV-11.04; and acrylic
rubber is Vamacr~ G1.
Preferred ~ vllul~iC LCPs include wholly or partially aromatic
polyesters or ~o~,ol~c~ . A ~ icul,uly preferred copolyester is
XYDAR~ or VECTRAr~. Other preferred Ih~ ullu~;c liquid crystal
polymers include SUMIKOSUPER~ and EKONOL~ (Sumitomo Chemical),
DuPont HXn' and DuPont ZENITF" (E.l. duPont de Nemours), RODRUN~
(Unitika) and GRANLAR'Y (t'.r:~nfimcm~),
Preferred LCPs for use in the present invention include any such
resins with a melt l~ ,,c in the range of 250 to 320~C. rG-Ii~,ul.uly
preferred LCPs have a melt t,.~ IIulC in the range of 250 to 280~C.
One preferred alloy in accordance with the present invention
wo ~ 17~2
1 7 1 '~
comprises PET, a wholly aromatic LCP cu~ uly~Jt~. and an ethylene-methyl
acrylate-acrylic acid terpolymer t~ ul~;l; , for example, Escor'Y ATX-
320, Escorn' AlX-325, or EscoP' XV-I I.W.
Another preferred alloy comprises PET, a wholly aromatic LCP
S co~ . and an ethylene-maleic anhydride copolymer comr~tihili7~r such
as Polybondn' 30û9.
Yet another preferred alloy in a~ ith this invention
comprises PET, a wholly aromatic LCP cuyuly~st~. and an ethylene-methyl
acrylate copolymer yrafted with maleic anhydride comp ~ihili7l~r~ such as
DSTY 1328/60, or a w yuly~t~ elastomer such as HYTRELn' HTR 6108.
Alloys comprising PET, LCP and at least two c~ ol,il:~ ~ are
~,~.,i ' 'y preferred in the practice of the present invention. The
y~ are preferably selected from a cuyoly~t~. elastomer,
ethylene-maleic 2nhydride copolymer, ethylcnc ..~ yl acrylate copolymer,
15 ethylene-methyl acrylate copolymer, ethylene-methyl acrylate-maleic
anhydride terpolymer, ethylene-methyl-l--ctL ~,yLc acid terpolymer or
acrylic rubber.
Preferred two ~ y~ alloys include: PET, a wllolly aromatic
LCP cuyOl~,aL , an ethylene-methyl acrylate-acrylic ac;d terpolymer and an
20 ethylene-maleic anhydride copolymer rnmp ~ihi1i7~r, Exemplary ethylene-
methyl acrylate-acrylic acid t~yOlyl~ include Escorn' ATX-32û, Escor'U
AIX-325, or Escor~ XV-11.04 and an exemplary ethylene-rnaleic
anhydride copolymer is Polybondn' 3ûû9.
In other preferred PLT/LCP alloys, the LCP comprises a wllolly
25 aromatic uuyulyeat.l amd the comr~ihili7~rs are an ethylene-methyl acrylate
copolymer and/or an ethylene-maleic anhydride copolymer. An exemplary
ra.yl~ a~yl acrylate copolymer is SP 2205~ and an exemplary ethylene-
maleic anhydride copolymer is Polybondn' 3ûû!'.
Another preferred LCP/PET alloy of the present invention comprises
30 a wholly aromatic LCP uuyol~ " and an ethylene-methyl acrylate
copolymer grafted with maleic anhydride and an ethylene-maleic anhydride
WOgC1007S2 ,~,~/u~
~ ~ bt ~i ! 7 ~
copolymer ' ' . Yet another preferreA alloy comprises PET,
wholly aromatic LCP cvpvlr~tel~ and cv~ul~ t~. elastomer such as
HYTRELff EITR 6108 and an ethylene-maleic anhydride copolymer such as
Polybondr" 3U09.
S The c l~ c .. ,ll-yl acrylate copolymer grafted with maleic
anitydride, DSff 1328/60, and the ethylene-maleic anhydride copolymer,
PolybondlY 3U09 are p~li~ ~l~ly preferreA when the LCP is VECTRAn'.
Also preferred when the LCP is VECTRAff is the cnmr~ihiii7Pr,
Polybondn' 3U09 and a second comr:ltihili7pr~ Fscor~ ATX-320, EscoP~
ATX-325, DS1328/60TY, Escorff XV-11.04, or HYTRELr'l6108.
The properties of the LCP and PET, as well as desired properties of
the resulting alloy, are all taken into c~ in selecting suitable
C,..,~ for use in the present invention. The properties of the
PET/LCP alloys of the present invention are adjusted by adjusting the
amvunt of . ' ' and, in some preferred I "l,oJ;~ ~ t', by the
manner in which the ~ are combineA.
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 of the c, ~ ;w~ as low as possible while achieving
the desired effect. Hence, in the present alloys the LCPs are useA as the
disperse phase, whereas PET is usPA as the ~ dUlll;llclllt or bulk phase.
When no comr~tihili7~ n exists between PET and LCP, such as
when no cnmp~ihili7Pr is present, the mechanical properties of the resulting
blend are low. For example, in films extruded from blends colnrricin~
10~ LCP I 9U~ PET (KODARIu A-]50) a machine direction (MD) tensile
strength of only about 6,000 psi and MD tensile modulus of only about
300,000 psi are obtaineA. Fu.~ .ul~:, the oxygen barrier properties are
poor, for example, around 35 to 40 cc/lUOin.2 It was unPYrP~ tPfily found
that when PET/LCP alloys were formed by adding suitable compatibilizers
in a~ulJ~e with the teachings of the present invention, improveA
mechanical properties and/or lower gas permeation (barrier) numbers were
W096/00752 r~,"~,,.,.. ,
2 l . ~ l 7
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obtained.
The present invention also provides methods of preparing the alloys
described above. These methods include:
i. LCP, PET and at least one comr~~ihili7P- are
S mixed and melt blended to form an alloy;
ii. LCP, PET and a portion of the tot~
cl~mpq~ihi1i7Pr to be used are mixed and melt
blended, the remainder of the ('( -'p q~ihili7Pr is
added at a later time and further melt blended;
iii. LCP, PET and a first c~ ,ili,. are mixed
and melt blended. A second comrqtihili7Pr is
added to the melt blend at a later time and
further melt blended;
iv. LCP and PET are mixed and melt blended and
at least one c~mr~tihili7P is added at a later
time to the melt blend and further melt
blended;
v. PEr is melted under .~ V~ t~ conditions in
an extruder and at a later time LCP and at lea t
one comFq~ihili7pr are added to the PLT and
further melt blended;
vi. PET and a first e~ li, are melt blended
and at a later time LCP and a second
it.ili,. . are added to the melt blend and
further mixed and melt blended;
Yii. PET and LCP are mixed and melt blended and
two comrqtihili7prc are added to the melt
blended and further melt blended; and
viii. PET, LCP and two c.o~ are mixed
and ~i .. ~ ~ . ~, ~Iy melt blended.
WO 96/00752 1 ~
~, t ~ 1 7 1
DI~TAll Fn D~S('RTPI~ON OF TI~E II~VENTION
The LCP/PET alloys of the present invention are formed by use of at
least one c(. ih.l;l.;i; ~ . In one preferred e..ll,o~li"..nt, two co~r:ltihili7~ c
are used to form the alloys.
The alloys of the present invention comprise from about 0.5 to about
10 weight percent Lh~ uLIu~i~ liquid crystalline polymer, from about 40 to
about 90 weight percent PE1, and from about I to about 50 weight percent
C~mp ihili7f~r.
The liquid crystalline polymer is preferably present in amounts from
about 5 to about 10 weight percent, PEI' is preferably present in amounts
from about 70 to about 93 weight percent and one or more co~np~ihili71~-s
are present in amounts from about 2 to about 20 weight percent.
In a ~J~Li~l~ly preferred ,I,o 1~", 1 the ~v",~ of the
present invention contain from about 9 to about 12 weight percent LCP,
from about 78 to about 86 weight percent PET, and from about 5 to about
10 weight percent c~
Suitable PET for use in the present invention is prepared by the
reaction of either terephthalic acid or dimethyl 1.l~, ' ' with ethylene
glycol. Other methods of making suitable PET are known to one of
ordinary skill in the art. Suitable PET is also available cu~ -lly from
a number of vendors, including KODAR'" A150, KODAR'' 9921, and
Eastman 13339 from Eastman Chemical and CPETn' from Goodyear.
KODAR~ A150 is one preferred cu.,.a.~ lly available PET for use in the
present invention.
Suitable LL~ llvLlul!;c LCPs for use in the present invention include
wholly and partially aromatic polyesters and co-polyesters such as those
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. Preferred lh~llllvlruJ~;c LCPs for use
in the present invention include wholly aromatic co-polyester. Vectran'
A950, sold by Celanese Research Corporation, Summit, New lersey is one
such wholly aromatic ~;v~ùl~ ~t~l. This polymer has been reported to
Wo 961007S~ /u~!"t
~ ~ q ~
- 10 -
consist wsentially of about 25-27 percent of 6-oxy-2-naphthoyl moieties and
about 73-75 percent of P-U1~Y~ LVYI moieties, as described in exarnple 4 of
U.S. Patent No. 4,468,364 and in G. W. Calundann et al., "Anisotropic
Polymers, Their Synthesis and Properties~, reprinted from P~u~ of
S the Robert A. Welch f'fnff-rPnri~c on Chemical Research, XXVI Synthetic
Polymers, November 15-17, 1982, Houston, Texas, pp. 247-291 (see
especially pp. 263-265).
Preferred lh~l~vllu~ic LCPs include wholly or partially aromatic
polyesters or .~,vlyw~,~. A particularly preferred ~uf,ùl~est~l is
10 XYDARTY or VECTRAlY. Other preferred LL~ uLlul~iC liquid crystal
polymers include SUM[KOSUPER0 and EKONOLD' (Sumitomo Chemical),
DuPont HXrY and DuPont ZENIT~ (E.I. duPont de Nemours), RODRUN~
(Unitika) and GRANLARn~ (~rsfnnmnnf).
In ' ' v the f~ of the alloys of the present invention
15 a number of variables including, the properties of the polymers to be
blended, properties of the ff mF~fibili7f-rs and the amount and ratio of the
cu ,, ~ 1~ are talcen into cnnr~ r~fi~n These variables are tailored and
optimized in accordance with the present teachings to provide alloys to meet
a particular end use ~ ; -, For example, if high gas barrier
20 properties are desirecl, then polymers having high individual gas barrier
properties are preferably selected.
The amount of: I ' ' is adjusted to provide i~U~ t~
bonding arnong the c r ' of the alloy to enhance properties and at the
same time, to avoid the formation of a quasi- or pseudo-cross linked
25 network which is not readily ~J-uc~.~'ulc.
The CO.~ b;~ for use in the present invention are either
miscible with each of the LCP and the PET through, e.g., covaient, ionic,
molecular inter-pf-nf~trz~finn, hydrogen bonding or associative ;.~t~ A- I;r..~c as
mentioned above, or have interactive miscibility when the LCP and PET are
30 present in a common phase. In other ~vords, the functional groups of the
ff,mp~fihili7f~r, LCP, and PET for use in the alloys are also chemically
~ W0 96/0(\752 1~
~ ~ j 4 1 7 1 ' '~
rnmr~fihlr For example, if the LCP to be alloyed with PET has an
aliphatic type of polyester f ~ n~lily~ such as acrylate or ~ lha~lylaLr;~ or
an aromatic r~ ly~ such as a benzoate or phthalate ester linkage, then
preferred Cf~ ;;l ;li ?. will have a r" . I;.~ ;ly, such as a polyester
S functional group or a maleic anhyciride functional group, that is capable of
reacting with the polyester group.
C~ il,;l;,. . for use in the present invention are also l, u~ h1r
in the melting and processing rangP of PET and the LCP and exhibit
u."- stability at the intended processing t~.,.,...~alllr By
10 t. ..~ UIlra stabiiity is meant that a component of the alloy essentially
retains its chemicai filnr tinn~lity and, hence, its interfacial interaction with
the other , of the ailoy with which it interacts. If one of the
were not thermally stable, it is possible that the
cnnnr~ihilirltinn achieved could fail on subsequent processing.
Preferred alloys of the present invention comprise at least one
LL~l.luL~ulJ;c LCP, PET, and at least one romr~tihili7Pr. PalLi~u;ally
preferred ~ ~ ' include two or mûre r., .,l.~;l.;l;,. .~, wherein at
least one ~ l~lnr''~ interacts with the LCP and at least one interacts
with the PET. The ratios of cnmr~tihili7r~rs to each other and in the total
20 ~ o~ are adjusted to achieve alloys having the desired properties as
is shown in the examples which follow.
The following ~.".,l~.l;l,;l;, ~ are pLuli~ulauly preferred in the
practice of the present invention wherein c~.."l.".,. ,l~ of the alloy comprise
PEP and wholly aromatic esters and ~upùl~st.~ Iiquid crystal polymers,
such as VECTRAn' and XYDAR~:
i. Copolyester elastomers such as H~rRELn'
HTR-6108 from DuPont;
ii. Etbylene-maLeic anhydride CUIJOIYI~ (HDPE
grafted with maleic anhydride), such as
Polybond~ 3009 from BP Chemirals;
iii. LLIIyl.~ yl acrylate cupoly.. l~, such as
wos6/007s2 r~ u., ~ ~
~1 ~ 41 7 1 12 -
SP 2205 from Chevron;
iY. Ethylene-methyl acrylate cu~oly~ grafted
with maleic anhydride, such as DS 1328/60
from Chevron;
v. Ethylene-methyl acrylate-maleic anhydride
terpolymers, such as Lotader~ 2400 from
Atochem;
vi. Etnylene-methyl-,.,ih~ , acid t~ ~l uly
(ethylene-methyl acrylate-acrylic acid
h~ ) such as Escorr" ATX-320, EscofY
ATX-325, and Escor~ XY-11.04; and
vii. Acrylic rubber such as YAMACn' from
DuPont.
The alloys of the present invention can be extruded to form various
articles of ...~._r~L.~.c such as films and tubes useful, e.g., in food
packaging, electronic circuit substrates and structural A~ The
films can be ll~ fv~ d to provide, e.g., trays, blow molded to, e.g.,
form containers, and otherwise processed by known methods. In some
20 rll.l~.l;- - .l~, articles of ,., -- ..r~ U~e comprismg the alloys of the present
invention are provided with a thin coating of, e.g., glass, metal or another
polymer both to protect the article and to provide suitable means to aff1x
labels and the like.
To illustrate the improved properties of the alloys of the present
25 invention, various alloys were prepared as taught herein and extruded to
form films having improved tensile strength, tensile modulus andJor oxygen
barrier properties oYer films extruded from PET or LCP and PET blends
without cnmr~Rtihili7~r~ In some films, tensile strength was increased by up
to more than 2 times and tensile modulus was increased up to more than 3
30 times over that of the blend without ~n npo~ihili7~r. In many instances,
values above 10,000 psi and tensile strength and~or above 500,000 psi and
~ W0 96/00752 r~ s
2 T ~ 4 T 7 7
- 13 -
tensile modulus were obtained.
Films extruded from zlloys compricing PET, and an anhydride-
grafted ea~ , methyl acrylate copolymer, ~ v~ LCP whoay
~ aromatic cvpul~ t~. and an elhgl~.. ~.l.ale;c amhydride copolymer showed
gre_t improved ' ~ ' properties.
Films extruded from three component alloys ~ u 'l'~ c PET, wholly
aromatic ~u~.vl~t.,, and an cL;.~l~uc mcthyl-metha acrylic acid terpolymer,
e.g., EscoP' ATX-320 or -325, had superior m~l-~nir~l properties. Also,
thrce component blends comprising PET, wholly aromatic co~ol~t~l and a
CUIJOI~ elastomer such as HYl'RELm HTR-6108 were extruded to
produce films having superior mrrl~nira~ properties.
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/100in.2 expected for PET.
Films extruded from alloys c~mpriQ~ng PET, a wholly aromatic
~u~yOlJ. LCP and a co~ol~ ,. elastomer such as HYTREL~ 6108 had
excellent barrier properties. Also, films extruded from alloys con rri~;ng
PET, a ~iu~Jol~ elastomer, such as HYTRELr" 6108, a wholly aromatic
co~vl~ ., and ethylene-malc-ic anhydride copolymer, such as Polybond~
3009 had excellcnt oxygen barrier properties, e.g., from about 21 to 23
cc/lOOin2.
OptionaL ~ , well known to the skilled artisan may be added
to alloys of the present invention provided that they do not interfere with
formation or with the desired final properties of an alloy. Such additives
25 includes fillers and pigments, lubricants, mold release agents, pl.
ultravioJet stabilizers and so forth.
In the methods of the present invention, romp~ihili7f rc are used
eitber alone or in various ~ vith LCP and PET to achieve the
desired results. They are also used in single step and sequential
30 rnmpafihi1i7~ n methods as described below.
The following methods have been found to provide alloys having
WO g61007S2 ~ J ~
21 a41 71
- 14 -
improved properties which can be used, e.g., to provide films having
improYed properties over fiims of LCP and PET blends. These methods
include:
i. LCP, PET and at least one ~v.,.~
S are mixed amd melt blended to form an
alloy;
ii. LCP, PET and a portion of the total
comrqtihili7P~ to be used are mixed and
melt blended, the remainder of the
.... "I.. I;l.;li,~ . is added at a later time and
further melt blended;
iii. LCP, PET and a first c~ are
mixed and melt blended. A second
comrqtihili7Pr is added to the melt blend
l'i at a later time and further melt blended,
iv. LCP and PET are mixed and melt
blended and at least one cnmrq~ihili7Pr is
added at a iater time to the melt blend
and further melt blended;
v. PET is melted under d~JIJlU~
conditions in an extruder and at a later
time LCP and at least one comrq.~ihiii7Pr
are added to the PET and further melt
blended;
25 Yi. PET and a first compatibilizer are melt
blended and at a later time LCP and a
second comrqtihili7er are added to the
melt blend and further mi~ed and melt
blended;
30vii. PET and LCP are mixed and melt
blended and two cnmrqtihili7Prs are
~ wos6/no7s2 ~ a~ -
4 1 7 ~ ~ ~
- 15 -
added to the melt blended and further
melt blended; and
viii. PET, LCP and two enmr~tihili7~t~ are
mixed and c;mllltzmPo~ y melt blended.
s
By controlling the order in which the ~n~n~ of the alloys are mixed
and melt blended the properties of the alloy are controlled to enable the
production of articles of In~ulur~iulc~ e.g., films, which have improved
properties over the properties of a similar article of ~ .ur~ctulc composed
10 solely of PET or of LCP and PE~'.
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 containing two comr:~tihi1i7rr~ sequentiai Cu~ ;h;li~
15 according to methods (iii) and (vi~ above are preferred l..cl,., ~ . methods. It was .,..~ .ily discovered that these unique methods of combining two
or more cnmr~tihili7~ r.c provided alloys having improved properties.
While not wishing to be bound by theory, it is believed that in this novel
process, two comr~tihili7~rs interact sequentiaily to provide the desired
comp~ihi1i7tltion and in some cases also interact with each other. In the
case of PET-LCP blends of the present invention, the interaction is between
the PET and a first rnmr~ihili7~-, and the LCP interacts with a second
comp~'ihili7~. The products of dlese two ;"1~ , then sequentially
react with one another to form an alloy.
The methods of the present invention provide a great deal of
flexibility to achieve the desired rnmr~fihili7~tinn through the wide array of
p~c~ c for the ,~ to interact with the major c~" 1~ of
the ailoy, which is the object of the mnmr~tihili7~tinn The method of the
present invention is an innovative yet efficient way to achieve the desired
end results.
In one preferred ~ nl.û~ ,1 of the present invention, Chevron DS
w096/007~2 r_~u~
~. ~ 'J ~ 1 7
- 16 -
1328/60, an ~Lydl;d. grafted ethylene-methyl acrylate copolymer, was
melt b}ended with PET and then Polybond'Y 3009, an ethylene-maleic
anhydride copolymer, tnd VECTRA~ A950 were added to the mixture and
further melt blended to produce alloys which were extruded to produce
5 films having greatly improved mechanical properties. For example, a
tensile strength of 14,800 psi was obtained in one film extruded from an
alloy made by feeding 5~o of the Chevron DS 1328/60 in the hopper with
the PET, and then by feeding 2% PolybondlU 3009 with the LCP
VECTRA~ A950 into the vent feed port.
In anottter preferred e.. l" ' t, Escor~ ATX-325, an ethylene-
methyl-ll..,.h~,~ ylic acid terpolymer, was melt blended with PF,T and then
Polybondn' 3009 and Vectra"' A950 were added to the mixture and further
melt blended. A tensile modulus value of 1.09 rnillion psi was obtained in a
film extruded from an alloy made by feeding 5% of Exxon AlXn' 320 in
the hopper with the PET, and then feeding 2% Polybondn' 3009 witll the
LCP VECTRATY A950 into the vent feed port.
Accordingly, it can be seen that films produced trom the alloys of
the present invention have ~u~ ,ly improved properties over f lms of
LCP and PET blends or of PET alone.
Conventional extrusion equipment was used to produce the alloys of
the present invention and to extrude films from these alloys. Mixing and
melt blending of cu~ to form the alloys of tlte present invention is
carried out using Cu~ ...u~ l single or double screw extruders. It is
preferred that the extruder system has not less than 25~1 LID ratio and not
25 smaller than 2". Extrusion conditions such as processing t ~ l.r,An..r~
rotation speed of the screw, feed Mte and through put were optimized for
the particular alloy by taking into c~ the properties of the
polymers being melt blended to form the alloy, including resulting viscosity
of the melt blend. Typically, higher shear screw ~ ir~ .\, were found
3û to give better dispersions of the LCP and better c~mr~ihili7~ir.n resulting
in alloys that could be used to produce filllls having improved properties.
wo g6~007~2 r~
Typical (r~ ullr~ employed for the processing were 525 to 580~F. The
rotation rate of the screw was, typically between 50 to 200 rpm.
The alloy cc,".~ are ~ uL ~ l~, c,.".l;l,.. .l, e.g., dried and
then fed to the extruder using cunv~ iullcll u-- II.o~ For example,
S the ~o i~p~ can be melt hlended and extruded to form pellets. The
pellets can then be extruded or injection molded to form the desired article
of ...cu.uL.. tu-~. Alternatively, the dry ~v~ o~ can be blended in a
hopper and extruded, e.g., to a filrn directly.
The Ill~tull,l-.~dil-g or IllclaL,.bdl~l-il-g technique in which typically, a
10 blend of two , is processed into pellets to form the "~"~ct~.l~l~..rl"
can also be used. The ~c~t Ibl-nd can be run through an extruder a second
time with additional cu~ added in a~.ulJcu~.~ with the teachings of
the present invention. This is a convenient method of ." ",rS.. I.,.~, because
an inventory of, - '~ 1,1 .,.i material can be made and then combined with
15 different ~u~ as desired. One advantage to the m~ct~rhl~n~ v
process is that small and very controlled amounts of additional ~
can be added to the ,...~Ct. .hl' ~ For example, if the Illcl.~i ' has 105~o
LCI', the Illc~ll,clt-h can be passed through the extruder again with, for
example, 10% of the ' ' ' and 90% of the other polymers, providing
20 a, ~ that is 1% in LCP.
Through ,~ .,g controlled low ~ ,,u;., of a
component in the alloy can be obtained; and additional mixing and shearing
through multi-passes in the extruder can be achieved, if desired.
The present invention will be further illustrated with reference to the
25 following exarnple which is intended to aid in the lIn~f.~ J- ~1;ng of the
present invention, but which is not to be construed as a limitation thereof.
~X ~IvlPLE
The alloy ..,...1,~ should be ~I,u~J~u,u~i~t~ly treated, e.g., dried,
30 before processing as would be readily apparent to the skilled artisan.
The work described in the following example was carried out using a
WO 96100752 1 ~ I/V~,S~
~ ! q4 1 7 1 1'8 -
conventional 25 mm or 40 mm co-rotating, non-i.it~ g twin screw
extruder, ~ nl by Berstorff Corpomtion. Mixing and kneading
elements for the screw ~V l;Y.~AI;~ were varied according to converltiollal
wisdom to achie~e the desired degree of mixing
Films were extruded from a slot die, approximately 8 inches wide
with die gap of t.~ 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 comprising one or more alloys of
the present invention. Since the degree of uniaxial orientation produced in
the extruded film has an impact on the propenies, films having similar
extrusion conditions were compared in the work discussed below.
A universal testing machine was used for testing the tensile
propenies based on ASTM standard tests, e.g., ASTM #0882.
The LCP used was Vectra~ A-950 from Hoechst-Celanese
Corporation. PET purchased from Eastman Chemicals under the tradename
KODAR~ A150 was used in the following work. The c~mr:~tihili7Prs used
included: Hytrel'Y HTR-6108 from DuPont (Copolyester elastomer);
Polybond~ 3009 from BP Chemicals (HDPE grafted with maleic
anhydride); SP 2205 from Chevron ~Lh~le..~ mcthyl acrylate cu~olyl~
DS 1328/60 from Chevron (ethylene-methyl acrylate copolymer grafted with
maleic anhydride); Lotader'" 2400 from Atochem (ethylene-methyl acrylate-
maleic anhydride t~.~ol~..,e.), Escor~ ATX-320 from Exxon Chemicals
(~LJI~,.c l..~,li.~l acrylate acr~ilic acid ~ ulyll~ ; Escor~ ATX-325 from
E~xon Chemicals (ethylene-methyl acrylate-acrylic acid Lt ~?ly~ ); Escor~
25 XV-11.04 from Exxon Chemicals (ethylene-methyl acrylate-acrylic acid
terpolymer); and Vamac"' Gl Acrylic rubber from DuPont.
The run conditions and results are shown in Tables I-~rll. In the
Tablesl the PLT used is indicated as "A150" or "9921" the VECTRAT~ LCP
is indicated as "A950.n "Ten Yld St." indicates Tensile Yield Strength; and
30 "Ten. Mod." indicates Tensile Modulus Values. In the Tables,
compatibilizers listed are identifed as follows: HYTREL~ HTR-6108 as
wo 96100752 r .,~
71 :
- 19 -
Hytrel 6108; PolybondTY 3009 as "BP3009"; SP 2205'Y as "SP2205"; DS
~ 1328/60 as ~Chev DS-; Lotader'" 2400 as "Lotader 2400"; Escor~ ATX-
32(), ATX-325 and XV11.04 as "ATX320", "ATX325" and "XV11.04"
TABLE A
LCP, PEr and at least one c~lmr~fihili7~ are mixed and melt
blended to form an alloy
RUIY I }IOPI'ER PEEDVL~rll~D ~ YLD IEI~ blOD OX.
Sl' MD~;pi)MD(lipi) BARRIER
IS 6299-7 85.7%A150195%A950+4.8*A3X320 10.6 800 27.2
6299-9 85.711A150+9.5~U 950+4.8~A7X325 - 9.7 810
6299 10 85.7%A150+9.5%A950+4.8%Cbevl 1 ~ 9.1 570 25.3
I'ABLE B
LCP, PET and a portion of the total cc ~nrqtihili7l~r to be used
are mixed and melt blended, the remainder of the
c~mrqtihili7~-r is added at a later time and furhter melt
blended.
RIUR' I IlOm~R l EEDn~r rr~D~N YLD l'EN MOD OX-
Sl'MWiPI)b4D(E;Ihi) RAlliUFR
6249 3 85.7'11A150+9.5~A950+2.4~AI'X325 2.4%AIX325 10.0 421 25.5
62497 85.7~1A150+9.5~A950~2.4~BP3009 2.45~BP3009 12.9 450 26.8
W0 96/0075~ r~
1 7 7
- 20 -
TABLE C
LCP, PET and a first ~ mrtihili7~r are mixed and m_lt
S blended. A second ~ ';17~ is added to the melt blend
at a later time and filrther melt blended.
R~f li103.~3nED n~NT~7 TENYLD ~NM(3~ ox-ST MD~ MD~Rpi3 sARR~R
62Js-a 2s.7%AIsu+s.s*Asso+2.41lA7x325 2 4*~00 7 2 233
TABLE~ D
LCP and PET are mixed and melt blended and at least one
~nm~tihiii7l!r is added at a later time to t'he melt blend and
further melt blended.
2~'
R7JN r 13OPP~R F~D v~r EED n~; YLD 7.1iN MOD ox.
ST ~4Dff~d3 ~ID~l;pi3 r4~RRlFR
6299-14 aS.7*AlSC+9.5~Aff~ 7.a*ATX320 9.1 s3a 26.6
TABLE E
PET is melted under a~ r ~1 ' conditions in an e~ctr~uder
and at a later time LCP and at least one c.omp~tihili7i~r are
added to the PET and further melt blended.
R7~ J ~0PP3~ 3.~EED VE~T 3.~EED ~ 71~ ~7D ox.
aT ~Da~Pil .7~Da~, d) sA~RIFR
6309-12 as.7s Al.~70 9.7~A950+4.~A7X325 7.1 ~o
~ ~.'096/0~7s2 P~
. . "~
~ 4171 ~ ~
-21-
TABLE F
PET and a first cn~r~ihiii7Pr are melt blended and at a later
time LCP and a second rn~lr~ hili7Pr are added to ~ie melt
blend and further mixed and melt blended.
RUN r 330P7RR FEEDVE~'TrTEDTEN YLD Tl~i MOD OX-
ST MD(lipi)MD(I~pi) RMRIER
70t9.7 39%A150+4.7%A7X3209.3%A950+2%B~G09 12.7 810 29.6
7069.5 59~A1511+4.7%~v~DS9.3%A950+2%B~009 11.2 Y611 25.7
70699 89aA150+4.7%XVII.049.3$AY5(1+2%BP3009 Y.6 740
h769 10 8Y%A15(1+4.7%H3~,16108Y.3%AY50+2~Ri'3G09 Y,3 550 20.3
7079 1 39%A150+4.7%Ctevm~DS9.3%A950+2%BP3009 14.8 W0 29.5
TABLE G
PET & LCP are mi.xed and melt blended and two
~omr~ihili7Prs are added to the melt blended and further melt
blended.
UUN iT BOPP3'~ RTEDvr~T iTEDTi N YLD TF.N MOD OX-
ST MDa~il. D(i';pi) BARRIER
70696 85.79iA150+9.5*A9502.4%Hybrl6103+2.49BP.3i09 6.2 420 26.3
TABLE H
PET, LCP and two compatibili7ers are mixed and
~j""~U~ J~ y melt blended in an extruder and extruded
through a slot die.
RU~ 310PlliR PFED Tl:N YLD TG~I M(3D OX-
S~i' MD:Bplii3~iD(lip-iJ BARR13J'R
7169 3 80*A150+10%695G+7.5~H3~16105+2.5%i3P3009 7,9 370 25.3
4C3
SUBSTITUTE SHEET (RULE 26)
~0 961007~2 ~ sa~
- 22 -
S TABLE J
PET, LCP and two compatibilizers are mixed and
~ .. Iy melt blended and extruded through a circular,
counter-rotating die.
R11~ OI'PER rEED VFJ~T TEN YlD TE~i ~IOD OX-
BEEI) STMD(I~p~il b~)(llplii BARRIE~
1199-3 83~A150~iO*A950+5*A1~320+211iBP3009 - 0.2 UO
11994 81~.'.150910*A950+5*$P2205+4$1BnO09 - 59 320
1199-5 811tA150+10*A950+51l~ n 22 44ll
TABLF. K
PET and a first l'U"'LJ I~ are melt blended and, at a later
time, LCP and a second ~ are added to the melt
and further mixed and melt blended and extruded using a
circular rotating trimodal die.
RUN 4 BOPPI;R r~D vsNrTEN Yl,D lEN MOI) OX-
I~EDST Mlilfil.dllUl~(Ep0 BARRI.I~
32~192 33.611A15d+~.4*ATX32U lOXA9N+2%3nO09 9.0 290
3249 5 83.65A150+4.4*Chev~~lD9 IO~A950+2%BP3003 6.5 22d
SUBSTITUTE SHEET ~RULE 26)
~ WO 9(i/00752 r~
~ ~ Y '~ 1 7 1
TABLE L - Control PET
}~1.11'1 t IlOI lli:R F~D V~T I lED IE~ YLD IllN blOD OX-
Sl MDI~sl) MD~I~p3 BARRIER
6249-1 IN~IA150 - 5~5 162
5269-0 IN5A150 5 4 190
5119.0 IN1iA150 - 5.8 169
4239-1 IN~A150 6 2 176 31.5
62991 IN5A150 5.2 320
7059-1 IN5A150 - 5.3 320 29.9
3189-1 1005At50 62 2N
TABLE M - Con~rol PET & LCP~ No C~'".,.-~;l.;l;,. .
RU~; r IlOlql;R ~EDVE3~TFliED 1~ YLD TEN MOD OX-
8T MK6pd~MD~pl~ 13ARRIER
3189-2 905A150+10SA950 - 6.9 290
3189-5 9051A150+1011A950 - 5.5 210 22.7
3189-9 901AI50+10*A950 - 5.8 231
6249-2 909iA150+10*A950 . 74 251
7069 2 905A150+10SA950 - 6.1 420 24.9
7019 5 90*A150+10ilAff0 - 6.1 440
Wo s~ 7s2
't ~ f ~
- 24 -
TA~sr ~; N
UUN~ lilOl?~ERFEED VEIYT~D ~YLII TENMOD OX.
STMD(I;~I)UD~p j~ IIA~RRER
8129-1 8391A150+5*Hyll~5108IOI~A950~21111~009 8.0 550 20.6
8129-5 781tAlS ' 1:IC*A950+20BP3009 7.8 230 19 5
8129-10 8311A150 I S~IO~A950+2*DI3009 5.5 430 22 1
8129-16 78~1A150+101BHylld6103 lO*A950+2%HyarlS103 5.9 420 18.5
8129-17 7811A150+10*Hy~5108lO~A950+211~Hytlel6105 5.8 430 18.4
0 8129 IB 78~A150+10*Hy~el610BlObA950+8*0~009 7.4 600 19.5
8129 19 78SlA150+101~Hyll~lSlOB lOBlA950+2~1il3~009 7.6 710 18.0
The present invention has been described in detail including the
preferred 1 .,.1.~1;.,. .,~ thereof. However, it would be ..~ t~d that
those skilled in the art, upon ~ ;u~ Or the present disclosure, may
make mn~ifi~innc andlor i~ u~ b on this invention and still be
20 ~Yithin the scope and spirit of this invention as set forth in the following
claims.
