Note: Descriptions are shown in the official language in which they were submitted.
WO 91/107l~X PCI`/US91/00'l30
2v~29~
THERMOPLASTIC COPOLYET~ERIMIDE ESTER ~ -
EI,ASTOMER-ACJ~Y~ATE RlJBBE}:t COMPOS TTION5
CROSS REFERENCE TO RELATEI:~ APPI.ICATI0N -.
The present application is a continuation-in-part of
copending United States Patent Application Serial No.
07/467,677, filed January 19, 1990.
FIELD OF THE INVENTIt:~N :
The present invention relates to blends of a
copolyetherimide ester elastomer and a rubbery ~rosslinkable
alkylacrylate elastomer.
BACXGROUND OF THF INVENTION
: ':
Thermoplastic elastomers of ~he type known as
. .
polyetherimide esters provide a variety of uniyue and
excellen~ properties and are particularly useful in extru~ion
and molding applications.
Polyetherim~de esters prepared from diols,
dicarboxylic aclds and polyoxyalkylene dlimide dlacids are
thermoplastic e}astomer~ havlng an excellent comb~nation of
- stress-s~rain propertles, low tensile ~et, high melting
temperaturec and excellent strength, toughne~s and flexibility
properties~ All of the~e proper~les are variou-~ly useful in
many elasto~er applications. Copoiyetherimide ester elastomers
also process well, due to their rapid crystallization rate and
excellent moldability characteristics. Elastomer~ with the low
flexural modulus of polyetherimide ester~ in combina~ion with
any of the afor~mentioned advantageous propertie3 have gained
wide acceptance in the field of elastomers.
Nonetheless, it has now b~en found that
polyetherimide esters can ~e improved or enhanced for certain
application~, especially with re~pect to improving the
"softne~s~ (lower durometer) of the el~s~omer, while retaining
satisfactory tensile properties. The improvements are
aecomplished by blendlng a rubbery ~ro~linkable alkylacrylate
elastomer wi~h the polyetherimide ester and dynamically
cros~linking ~he former.
Wor~ has been patented ~n which a rubber is mixed
~,
:~ '
. . ., . .,. ,, . ,-~ . ,;, : .. . ..
wo 91/10708 2 ~ '~ 9 ~. ~ 7 PCT/US91/00430
--2--
with a ~hermoplastic re~in and su~equently cro~slinked while
the ingredients are bein~ mixed. Thls is known in the art as
"dynamic curing" or "dynamic vulcanization". Ge~sler et al.,
United States Patent No. 3,037,954 demons~rated "dynamic
S curing~ of a butyl rubber/polypropylene blend. Fischex, Unlted
States Patent No. 3,758,643, partially cu:red EPDM rubber in
the presence of a polyolefin. Other polyolefin/rubber
vulcanizates in which the rubber is polybutadiene, natural
rubber, isoprene and EPDM are disclo~ed in United States
Patent Nos. 4,104,210; 4,130,535; a~d 4,311,628. In United
States Patent No. 4,594,390, a continuous proce~s ~or
preparing EPDM/polypropylene dynamic vulcanizates is reported.
The Monsanto Co~pany commercially produces an
EPDM/polypropylene dynamic vulcanizate under the rade name
"SANTOPRENE", and a nitrile rubb~r/polyole~in dynamic -: .
vulcanizate ~n~er the trad~ nam~ "GEOLAS~". Further, United
States Patent No. 4,801,647 disclo~e~ an EPDM/crystalline
polyolefin dynamic vulcanizato.
Dyna~lc vulcanization has also been disclosed
employing copolye~ters. Europ~ n patent, ~P O 293 821 A2,
discloses a ~ultiblock copolye~tar melt mLxed with
polychloroprene rubb~r wh~ch i~ then cro~311nked during
mixing. In Unlted State~ P~tent No. 4,739,012, a segmented
thermoplastic copolyQstar is bl~nd~d with a ~cond composition
2S which is`a blond of two partially cros~link~d polymers, such
as PVC or PVDC and a copolymer of ethylen~ and one or more
ethylenically unsaturated co~onom~r3 prepared by dynamic
vulcanlzatlon.
Acryllc rubber~ are al30 ~nown to bQ employed in
thermoplastic dynamic vulcanizat~ Coran ot al., Ru~ber Chem.
and Tech., 55, 116 (1982), disclo~e a m~trlx of polymers and
rubhers u~ed in the prep~ration of dyna~ic vulcanizate
compo it$on~ in which polyacrylate ru~ber w~ us~; however,
not with copolyetherlmide e~ters. Wolf~, Unlted 5tates Patent :
~5 No. 4,782,110 di3close~ dyn~mlcally vulcanizing
ethyle~e-al~ylacrylate copolymer r~bber~ wl~h crystalline
polyolefln3.
.
wosl/l0708 2 0 d 9 2 ~ 7 PCT/US91/~
Coran et al., United States Patent No.
4,3~7,199, disclose employing an ethylene-acrylic type
copolymer rubber containing free carboxylic moieties in blends
with polyesters such as PBT. A metal oxide is used as a source
of metal ions to neutralize the pendant acid groups, forming
an ionomeric network structure as distinguished from eo~alent
bond formation. In Coran et al., United States Patent Nos.
4,310,638 and 4,473,683 the ethylene ac:rylic copolymer is
blended with a nylon resin and a metal oxide; and amorphous
styrene ~ased resins and a metal oxide, re~pectively.
~ lso to be mentioned are United States Patent
Nos. 4,116,914 (ethylene vinyl acetate rubber dynamical1y
vulcaniz~d with polyolefins); 4,480,074 (two step process for
dynamically vulcanizing an EPDM/PP vulcanizate with additional
EPDM); 4,226,953 (nitrile rubber dynamically vulcanized with
styrene-acrylonitrile re~ins); 4,207,407 ~chlorinated
polye~hylene dynamically vulcanized with nylon resins);
4,287,324 (ep ,nlorohydrin rubber dynamically vulcanized with
polye~ter~ such a~ P3T); and 4,593,062 (mixture of halogenated
butyl rubber and polychloroprene dynamically vulcanized with
polyolefins such a~ PP and PE). Special mention is made of EP0
327 010 A2, ~EP '010") which d~scloses blends of polyether
ester copoly~er with polyacrylate elastomers.
None of these howe~er di close a polyacrylate
rubber which ha3 been dynamically vulcanized with a
thermopla~tic copolyethorimide e~ter. It has now been
discovered and is shown in the examples hereinafter that
dynamically vulcanizlng a polyacrylate rubber with a
ther~opl~tlc copolyetherimide est~r provides an elastomer
compo~ition with improved softness whlle retaining excellent
tensile prop~rties. This is unexp~ctad because the
copolyether e~ters employed in EP '010 suffer from the loss of
tens1le properties to a much greater extent when mixed with
cros~}lnkable polyacryla~e rubbers and dynam1cally vuleanized.
,. ' ' .
. ' ' .
WO 91/10708 ~ 2 ~ ~ PCT/U891/00430
--4--
SUMMARY OF THE INVENTION
According to the pre~ent invention, there is
provided a ~hermoplastic elastomer composition comprising:
(A) a poly~therimide ~ster copolymer;
(B) a crosslinkable rubbery alkylacrylate, and
(C) a crosslinklng agent.
The polyetherimide ester copolymer can comprlse
the reaction product o~ (a) one or more low molecular weight
diols; (b) one or more dicarboxylic acids; and (c) one or more
polyoxyalkylene diimide diaclds. Preferably the dlol component
(a) comprises from about 60 to about 100 mole p~rcent
1,4-butanediol, th~ dicarboxylic acid component (b) comprises
from abou~ 60 to about 100 m~le percent dimethyl
terephthalate, and the polyoxyalkylene diimide diacid
component (c) is derived from tr~mellitic anhydride and a
polyoxyalkyl diamlne selec~ed from the group con~lsting of
polypropylene oxide dlamln0 and a copoly(ethylena
oxlde-propylene oxlde ) diamine h~ving pr~dominantly
polyethylene oxlde ln the backbone.
The pre~erred rubbery al~yl acrylate i9 based on
repeating u~its co~prising the ~ormula:
(CH2-CH) ; :
C-O
1 :
OC2~5
The pre~erred cros~linklng a~ent i~ sodlum stQarate. Also
contemplated are thermopla~tic elastoMer compo~l~ions further
comprising a f~ller such as a s~llca and a plasticizer. The
preferred compositions comprise component (A) ln an amount
: ranging from about 20 to about 99 par~s by weight and
: component (B) in an amoun~ ranging f rom abou~ 80 to abou~ l
part by welgh~ based upon 100 parts by weigh of (A) and (B)
together. ~ :
Al~o according to th~ pr~ent invent~on, there is
`~ provlded a proca~ for produc1ng a thermoplastlc elastomer
.
~ Pcr/ussl/ooq30 -
2~2~7
-5- :
composition somprising:
(Il mixing
(i) a polyetherimide ester copolymer, and
(ii) a crosslinXable rubbery alkylacrylate; and
(II) curing the mixture obtained in step (I) by addiny a
crosslinXing agent.
Preferably, step (II) of the procsss further
comprises adding an accelerator such as sulfur, sulfur donors,
magnesium oxide, tertiary amines and mixtures of any cf the
foregoing. Most preferred are quaternary ammonium compounds.
DETAILED DESCRIPTION OF THE INVENTION
The polyetherimide esters useful in the practice
of the present invention may be prepared from one 01- more
dlols, one or more dicarboxylic acids and one or more high
molecular weight polyoxyalkylene dlimide diac~ds.
They are generally comprised of recurring
polyether imide ester 3tructural units having the general
formula:
O O
t ~ / N- G -N R - C-O-R2~0 Jx ;
,t il
O O
wherein G i3 a divalent radical remaining a~er removal of the
amlno ~roups o~ a h~gh molecular we~ght polyalkylene ether
diamine; R i~ a trlvalent organic ra~ical; R2 is the divalent
radical r~m~ining ater the removal of the hydroxyl grou~s of
a diol; and x is a whole number having a value of from 2 to
about 40.
Pr~paration of such ma~eriAl~ is described in
dotail in U.S. Paten~ No. 4,556,705 of R.J. McCready, issued
Deca~ber 3, 1985 and hereby incorporated by reference.
The poly(etherimide e~ er3) u~ed herein may be
prep red by ~onv~ntional proces~e~, ~uch ~ e~terifica~lon and
con~nsation re~ctions far the prs~uction of poly~t;ers, to
'` ~
.~.
WO 91/10708 2 0 4 9 ~ ~ 7 PCT/US91/00430
--6 ~
provide random or block copolymers. Thus, polyetherimide
esters may be generally characterized as the reaction produc~
of the aforementioned diols and acids.
Preferred composition~ encompas~ed by the present
lnvention may be prepared from (a) one orrnore C2-C ; aliphatic
or cycloaliphatic diols, (b) one or more C4-C,6 aliphatic,
cycloaliphatic or aromatic dicarboxylic acids o-- ester
derivatives thereof and (c~ one or more polyoxyalkylene
diimide diacids. The amount of polyoxyalkylene diimide diacid
employed is generally dependent upon the deGiired properties of
the resultant polyetherimide ester. In general, the weight
ratio of polyoxyalkylene dilmide diacld (c~ to dicarboxylic
acid ~b) is from about 0.25 to 2.0, preferably from about 0.4
to about 1.4.
Suitable diols (a) for u~a in preparing the
compo~itions of the present inYention include saturated and
un~aturated aliphatic and cycloaliph~tlc dih~droxy compound~
as w~ll as aromat~c dihydroxy compound~ . These d~ ols are
prefer~bly of a low molecular weight, i.e. having a molecular
welght of about 250 or le~. When u~d herei~, the term
"d~ols" and "low molecular welght dlols" Yhould be const~ued
to include equivalent e8ter for~lng d~irlva~l~es thereof,
provi~ed, however, that the moLecul~r weight requirement
pertains to the diol only and not to i~ derivatives.
~5 Exemplary of est~r ~orming der1v~tive3 the~e m~y be given the
acstate~ of ~he dlol~ a well a~ for exampl~ ~thylene oxide or
ethylene c~bon~te for ethylene glycol.
Pre~erred satur~ted and unsaturated al~phatic and
cycloaliphatic dlol~ are tho~e havlng from 2 to 19 carbon
atoms. Exemplary of these diols thursi m~y ba glven ethylene
glycol; propane diol; butane dLol; pentan~ dlol; 2-methyl
propane diol; 2, 2-di~ethyl propan~ diol; hexaine diol; decane
diol; 2-octyl undecane diol; l, 2-, l, 3-, and 1, 4-~yclohexane
dlmethanol; 1,2-, 1,3-, and 1,4-dlhydroxy cycloh~xane; but2ne
dlol; and h~xene d~ol. E pecialiy pr~erred ar0 1,4-bu~ane
diol and mixture~ thereo~- wil:h hex~ne dlol or bu~ene diol,
mo~t p~Q~sr~bly l, 4-butanedio~l .
.
:' .. .~: ~
2 ~ 7 PCTtUS91/~30
_ 7 _
Aromatic diols suitable for use in the practice
of the present invention are generally those having from 6 to
a~out 19 carbon atoms. Included among the aromatic dihydroxy
compounds are resorcinol; hydroquinone; 1,5-dihydroxy
naphthalene; 4,4'-dihydroxy diphenyl bis(p-hydroxy
phenyl)methane and 2,2-bis(p-hydroxy phenyl)propane.
Especially preferred diols are the saturated
aliphatic diols, mixtures thereof and mixtures of a saturated
diol~s) with an unsaturated diolts), wherein each diol
contains from 2 to about 8 carbon atom~. Where more ~han one
diol is employed, it is preferred that at least about 60 mole
%, based on the total diol content, be the same diol) most
preferably at least 80 mole %. As mentioned above, the
preferred compositions are those in which 1,4-butanediol is
present in a predominant amount, mo~t preferably when
1,4-butanediol is the only diol.
Dicarboxylic acidsl(b) which are suitable for use
in the practice of the preqent ~nvent1on are aliphatic,
cycloaliphatic, and/or aromatic dicarboxyllc acids. These
aclds are preferably of a low molecular weight, i.e., having
a molecular weight of less than about 300; however, higher
molecular weigh~ dicarboxylic acids, especially dimer acids,
which are fully de~cribed in K~r~-Othmer,Encyclo~edia of
Chemical Technolo~y, 3rd Edition, vol. 7, John Wiley & Sons,
N.Y., pp. 768-782, m~y also be used. The term "di-arboxylic
aclds" as;used herein, includes equivalents of dicarboxylic
acldsi hav~ng two functional carboxyl groups which perform
subst~ntlally like dicarboxylic acids in reaction with glycols
and dlols in forming polyester polymers. These equivalents
include e~ters and ester-farmlng derivatives, such as acid
halides and anhydrides. The molecular weigh preference,
mentlo~ed abo , pertains to the acid and nc~ to its
equivalent e ter or es~er-~orming deriva~lve.
; Al~phatic dicarboxyl~c aclds, a ~he term is used
herein, re~ers to carboxylic acids havi~g two car~oxyl groups
each of whlch is attached ~o a satu~ted carbon atom. If the
carbon atom to whlch the carboxyl group is attached is
WO 91/10708 2 9 4 9 2 9 7 PCT~US91/00430
--8--
saturated and is in a ring, the acid is cy~loaliphatic.
Aromatic dicarboxylic acids, as the term is used
herein, are dicarboxylic acids having two carboxyl groups each
of which is a~tached to a carbon atom in an isolated or fused
benzene ring system. It ls no~ necessary that both earboxyl
groups be attached to the sa~e aromatic ring and where more
than one ring is present they can be joi.ned by aliphatic or
aromatic divalent radicals such as -O- or -SO2-.
Representative aliphatic and cycloalipha~ic acids
which can be used for this invention include se~acic acid,
1,2-cyclohexane dicarboxylic acid, 1,3-cyolohexane
dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic
acid, gLutaric acid, succinic acid, oxalic acid, azelaic acid,
diethylmalonic acid, allylmalonic ac~d, 4-cyclohexane-1,2-
dicarboxylic acid, 2-e~hylsuberic acid, tatramethylsuccinic :
acid, cyclopentanedlcarboxylic acid, decahydro-1,5-naphthalene
dlcarboxylic acid, 4,4'-bicyclohexyl dicarboxylic acid,
decahydro-2,6-naphthalen~ dicarboxylic acid, 4,4-
methylenebis(cyclohsxane carboxyllc acid), 3,4-furan
dicarboxyl~c acid, and l,l-cy~lobutane dlc~rboxyl$c acid.
Preferred aliphatic acid~ are cyclohexane dicarboxylic acids,
glutaric a~id, azelaic acid and adlplc ac~d.
R~presentative aromati~ dicarboxyl~c acid~ which
can be u~ed include terephth~lic acid, isoph~halic acid,
phthal~c acld, bi-benzoic acid, ~ub~tituted dicarboxy
compounds wlth two benzene nuclei such a2 bis(p- :
ca~boxyphenyl)me~hane~ oxybi3~benzoic ~cld), ethylena 1,2-bis-
(p-oxybenzolc acld), l,S-naphthylene dlca~oxyllc acid, 2,6-
naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic
acid, phananthr~ne dic~rboxylic acid, anthracene dicarboxylic
acid, 4,4'-sulfonyl dlbenzoic acid, and halo and C1-C,2 alkyl,
alkoxy, and aryl ring substitution deri~tiv~ thereof.
Hydroxy acids such ~ p-(beta-hydroxy0thoxy~banzoic acid can
al~o b~ u~ed provided an arcmatlc dicarboxy1ic acid is also .:
pre~ent. .-
Preferred dicarboxylic ~cid~ for the prep~ration ~. .
of the polyetherimlde e3ters of the pre~e~t lnvention ase the
. . .
WO9l/10708 2 0 ~ 3 ~ ~ 7 P~TtUS9l/~30
_g_
aromatic dicarboxylic acids, mixtures thereof and mixtures of
one or more dicarboxylic acids with an allphatic or
cycloaliphatic dicarboxylic acid, mos~ preferably the aromatlc
dicarboxylic acids. Among the aromatic acLds, those with 8-16
S carbon atoms are preferred, partic~].arly the benzene
dicarboxylic acids, i.e., phthalic, terephthalic and
isophthalic acids and their dimethyl derivatives. Especially
preferred is dimethyl terephthalate.
Finally, where mixtures of dicarboxylic acids are
employed in the practice of the present inven~ion, it is
preferred that at least about 60 mole %, preferably at least
about 80 mole %, based on 100 mole ~ of dicarboxylic acid (b)
be of the same dicarboxylic acid or ester derivative thereof.
A5 mentioned above, the preferred compositions are those in
lS which dimethyl terephthalate is the predominant dicarboxylic
a~id, most preferably when dimethyl terephthalate is the only
dicarboxylic acid.
Polyoxyalkylene dlimide dlacids (c) suitable for
u~e h~reln are high molecular weight diim1de diacids wherein
the average molecular weight i~ greater than about 700, most
preferably greater than about gO0. They may be prep~red by the
imidization reaction of one or more tricarboxyllc acid
compounds containing two vicinal carboxyl groups or an
anhydrlde group and an additional carboxyl group which must be
es~erifiable and preferably is nonimidizable with a high
molecular weight polyox~alkylene diamine. The polyoxyalkylene
diimide diacid~ and proces3es for their preparatisn are more
fully dt~closed in McCready, European Patent No. 180,149,
published May 7, 1986, and entltled "~lgh Molecular Weight
Dilmide-Diacid Compounds Ucieful in the Preparation of
Polyether Imide E~ter(s) and Amide~s)~, incorporated herein ~y ~ :
reference.
WO 91~10708 ~ 7 PCT/US91/00430
-la-
.
In general, the polyoxyalkylene dlimide diacids
useful herein may be characterized by the following formula:
' .
O O
~C~ ~C~ ;
}~ ' OOC R N-G-N R-COOR '
C \ C
11 11
O Q :.
wherein each R is independently a ~rivalen~ organic radical,
preferably a C2 to C20 aliphatic~ aro~ati~ or.cycloa;Liphatic
trivalent organic radical; each R' is lndapandently hydrogen
or a monovalent organic radical pre~erably s~lected ~rom the
group con~lsting of Cl to C6 aliphatic and cycloaliphatic
radicalq and C6 to C12 aromatlc radlcals, e.g. phenyl, mo~t
p~eferably hydrogen; and G is the r~dic~l re~ining aft~r the
r~moval of tho terminal (or as nearly teEmlnal as po~sible)
hydroxy groups of a long chaln ether glyco~ having an average :.
molecular weigh~ of ~rom about 600 to about 12000, prefer~bly
from abou~ 900 to abou~ 4000, and a carbon-to-oxygan ratlo of
about l.8 to about 4.3. .
Represen~a~ive long chAin ether glycols from
which the polyoxyal~ylsne diam~n~ i~ prep~red include
poly(ethylene ether)glycol; poly(propylene e~her) glycol;
poly(tetramethylene ether)glycol; rando~ o~ block copolymers
of ethylene oxide and propylene ox~do, lncludlng propylene
oxide termlnated poly(ethylene ether)glycol; and random or
: ~0 block copolymer~ of tetrahydrofuran wlth ~inor amoun~ of a . --
second monomer such as methyl tetrahydrofuran (u~ed in
propor~ion such that the carbon-to-oxyg~n mol~ ratio in ~he
glycol does not ~x~eed a~out 4.3)~ Especially preferred
poly(alkylene ether)qlycols are poly(propylene ether)glycol : .-
35 and poly(ethylene ether)glycoLs en~ c~pped with paly(propylene
ether)~lycol or propylene oxide.
In general, the polyoxyalkyl~C~C6~ne dla~ne
. "'
.
wo 91/10708 2 3 4 ;~ 2 ~ 7 PC~/US91/00430
-11-
useful within the scope of the present inventlon will have an
average molecular weight of from about 600 to 12000,
pre~erabiy from about 900 to 4000. These may be characterized
by the following general formula:
H2N-G-NH2
wherein G is the radical remaining after the removal of the
amino groups of a lony chain alkylene et:her diamine. These
polyether diprimary diamines are availab.le commercially from
Texaco Chemical Company under the trademl3rk "JEFFAMINE". In
general they are prepared by known procesC~es for the amination
of glycols. For example, they may be prepared by aminating
the glycol in the presence of ammonia, Raney nlckel catalyst t
and hydrogen as set forth in Be~ium Patent No. 634,741.
Alternatively, they may be prepared by treating the glycol
1~ with a~monia and hydrogen over a nlckel-copper-chromium
catalyst as taught by United Statec Patent No. 3,654,370.
Oth~r method~ for the productlon thereof lnclude those taught
in Unlt~d Stat9~ patQnt No~. 3,155,728 and 3,236,~95 and
French Patent No~. 1,551,605 and 1,446,708. A11 of the
foregoing patent~ ar~ incorpor~ted her~in by reference.
Th~ tricar~oxylic co~ponent mAy be almost any
car~oxylic acid anhydr~de conta~ning an additional carboxylic
group or the corra~ponding acid ~h~reof containing ~wo
imide-forming vicinal car~oxyl groups ln Lieu of the anhydride . -.
group. Mlxture~ thereof are al~o suita~le. The addi~ional
carboxylic groùp must be esterlfiable and pr~ferably is
sub~tantlally nonlmidlzable.
~he tricarboxylic acid material~ can be
characterazed by the followlng formula:
O
Il
/C\ ~ .
R ' OOC-R 0
~ \ C / .
Iï .
O
where R i3 a triv~len~ oryanic radical, prefarably a C2 to C~0
aliphatlc, aro~'c~c, or cycloaliphatic trlvAlent organic
Wo 91/10708 2 ~ 4 ~ PCT/US91/0043
-12-
radical and R' is preferably hydrogen or a monovalent organic
radical prefexably selected from the group consisting of C to
C6 aliphatic or cyc)oaliphatic radicals and C6 to C12 aromatic
radicals, e.g. phenyl; most preferably hydrogen. A preferred
tricarboxylic component is trimellitic anhydrlde.
~ riefly, these polyoxyalkylene diimide dlacids
may be prepared by known imidiz~ation react1ons including melt
synthesis or by synthesizing in a solvent system. Such
reactions will generally occur at temperatures of from 100
degrees C to 300 degrees C, preferably at fro~ about 150
degrees C to about 250 degrees C while drawing off water or in
a solvent system at the reflux te~perature of the solvent or
azeetropic ~solvent) mixture.
Although the weight ratlo of the above
in~redients is not crit1cal, it is preferred that the diol be
present in at lea~ a molar equivalent amount, preferably a
molar exc~Ys, most preferably at lea~t 150 mole % b~ed on the
mole~ of dicarboxylic acid (b) and polyoxyalkylene diimide
diacld (c) comblned. Such molar exce3~ of diol will allow for
optim~l yLeld~, based on the amount of acld~, while accounting
for the los~ of diol during e3~eri~icatlon~0ndensation.
Further, while the welght ratio of dicaEboxylic
acid (b) to polyoxy~lkylenQ dlimide di~cid (c~ i~ not critical
to form the polye~herimide e~ters used in the present
invention, preferred compesitions are tho~e in which the
weight ratio of the polyoxyalkylene diimide dlac~d (c) to
dlcarboxylic acld (b) is ~ro~ about 0.25 to about 2,
pre~erably from about 0.4 to about 1.4. ~he actual weight
r2tio e~ployed will be dependent upon the specific
polyoxyalkylene diimide diacld used and more importantly, the
desired physical and chemic~l propertie~ o~ the resultant
polyetherimide e ter. In general, the low~r the ratio of
polyoxyalkylene diimlde diester to d~car~oxylic acid the
better strength, crystallization and he2~ dlstortion
propertie~ o~ the polymer. Alternatively, the higher the
r~tio, the bet~er the ~lexibllity, ten~ile se~ and low
temperature lmpact ~hAracteristicS.
, . ,:
.. , .. ,.~ .. , .. . .... , . ~ .. , ;.. ,.. .... . ; :.. . .. ., ., . .. - .. ... . . . . . . . .. .. ..
wosl/10708 2 ~ PCT/US91/~30
In preferred embodiments, the poly~therimide
ester product will comprise the reaction product of dimethyl
terephthalaset most preferably, with up to 40 mole % of
another dicarboxylic acid; 1,4-butanediol, optionally with up
5 to 40 mole % of another saturated or unsaturated aliphatic or
cycloaliphatic dioli and a polyoxyalkylE!ne diimide dihcid
prepared from a polyoxyalkylene diimine of ~olecular wei~ht of
from about 600 to about 12000, preferably from about 900 to ~:
4000, and trimellitic anhydride. In its most preferred
embodiments, the diol will be 100 mole ~ 1,4-butanediol and
the dicarboxylic acid 100 mole ~ dimethyl terephthalate.
The polyetherimide esters described herein may be
prepared by conventional esterification/condensation reac~ions
for the production of polyes~ers. Exemplary of the proce~ses
that may be practiced are as set forth in, for examp~e, U.S.
Pat. Nos. 3,023,192, 3,763,109, 3,651,014, 3,663,653 and
3,801,547, herein incorporated by reference. Additionally,
the~e compositions may be prepared by such processe~ and other
known proces~es to effect random copclymers, block copolymers
or hybrids thereof wherein bo~h random and block unit~ are
present.
It is customary and preferred to utilize a
catalyst in the process for the prsduction of the
polyetherimide esters of the present invention~ In general,
any of the known e~ter-interchange and polycondenc~tion
cataly~ts may be used. Although two sep~rate catalya~s or
cataly~t sy~tem~ may bo used, one for e3ter interchange and
one for polycon~ensatlon, it ls preferred, where appropriate,
to u~e one catalyst or catalyst system for both. In those
in~tances where two separate catalysts are used, it is
preferred and advantageous to render the ester-interchange
~atalyst inaffective followin~ the completion of the
precondensation reaction ~y means of known catalyst inhibitors
or quenchers, in particular, phosphorus compounds such as
phosphoric acid, phosphenic acit, phosphonic acld and the
a}kyl or aryl e~ers of salts thereof, in order ~o increase
the thermal stability of the resultant polymer.
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WO 91/10708 2~ 9 7 PC~/US91/00430
-14-
Exemplary of the suitable known catalysts th~re
may be given the acetates, carboxylates, hydroxides, oxides,
alcoholates or organic complex compounds of zinc, manganese,
antimony, cobalt, lead, calcium and the alkall metals insofar
as these compounds are soluble in the reaction mixture.
Specific examples include, zinc acetate, c~Lcium acetate and
combinations thereof with antimony tri-oxide and the like. ~-:
These catalysts as well as additional useful catalysts are
described in U.S. Pat. Nos. 2,465,319; 2,534,023; 2,850,483;
2,892,871; 2,937,160; 2,998,412; 3,047,539; 3,110,693 and
3,385,830, among others, incorporated herein by re~erenc~. -.
Where the reactants and reactions allow, it is prefer.red to
us~ the titanium catalysts including th~ inorganlc and organic
titanium containing catalysts, such a tho~e descrlbed in, for
lS example, U.S. Pat. Nos. 2,720,502; 2,727,8~1; 2,729,619;
2,822,34a; 2,906,737; 3,047,515; 3,056,817, 3,056,818; and ...
3,075,952 among others, incorporated herein by reference.
Especlally preferred are tha organic tltanate~ such as
tetra-butyl titana~e, tetra-i~opropyl tltanata and tetra-octyl
tltanate and the co~plex titan8t~3 derlvod rom alkali or
alkaline earth metal alkoxides and titan~te esters, most
preferably the organlc titan~tss. Thcse too may be used alone
or in combin~tion wi~h other cat~ly~t~ such a3 for example,
zinc acetate, mangano~e acetate or antimony rioxide, and/or
with a ca~alyst quencher a~ d~scribed abov~.
Although the~e polyetherimide esters pos~e~s many
de~l~abl~ propertie , it i5 often preferred to stabllize the
compoRitlon~ tO h~at, oxldatlon, radiation by W light and the
like, a8 de~cribed in the afore~ntioned U.S. Patent No.
4,556,705.
: The polyacrylate ela8~0m~r~ or rubbery
a}kylacxylates are generally copolymer~ h~ving two major
components: the b~ckbone, compri~ing from about 95 to about 99 ..
welght percent of tha polymer; and t~e react1ve cure site,
compri3in~ fro~ abou~ 1 to abou~ 5 weight percent of the
:poLymer. Preferably the copolym~rs have h~gh ~olecular
weights, typ~cally arcund 100,000 MY (Yi~cos~ty average
: , '
Wo 91/10708 2B4~ 7 PC~/US91/00430
-15-
molecular weight). The backbones are made from mo~omeric acid
esters to form repeating units of primarily two types:
(CH2-CH) or (CH~-CHi
C=~ C=0
O-CnH2n+l O-cnH2noc~H2tn+l
where n is 2 or 4 and m is 1 or 2. The most common cure site
monomers ar~ described in the below referenced Starmer et al.
ar~icle. Especially preferred are 2-chloroethyl vinyl ether
and allyl gly~idyl ether. Physically, polyacrylate elastomexs
are inherently sof and tacky. ~hey commonly have relatively
low Mooney viscosities ~ML-1+4 @ 100 C) in the 2S to 60 ~ -
ranqe. These elastomers are more fully de cribed in P.H.
Starmer and F.R. ~olf, Encyclopedia of Polymer Sci~nce and
Engineering, 2d Ed., 306-325 (1985), incorporated herein by
reference.
The mixing o~ the polyeth~rim~de e~ters and
polyacrylate elastomer~ may be carried out ln any device known
to those skilled in the art. Prefe~bly the components are
melt mixed in a compoundlng device ~ueh a~ an internal mix~r
: (Brabender or Banbury typ~) and extru~er~ ~twln screw or
kneading). The polyetheri~ide ~ter~ and polyacrylate ~.
elasto~ers arQ typically combin~ble in proportlons ranging
from ab~u~ 20 to about 99 parts by w~igh~ polyeth~rimide ester
and ~ro~ about 80 to a~out 1 part by w~igh~ polya~rylate
ela8tomer based upon lO0 parts by welght of the two reRins
comblned. P~ferably, the polyetherimlde e~ter lS pres~nt in
an amount xanginq from 20 to about 80 partS by weight, most
pr~erably from abo~t 40 to about 60 p~r~s by wo~ght; and
corre~pondingly the~polyacryla~e ela~tomer i9 pre~ent in an
~: amount~ranging fro~ about:80 to a~out 20 part~ by weight, most
preferably f~om about 60 to abou~ 40 parts by weight. In
another preferr~d e~bodiment the co~po~ltions of the present
35 ~ invention compri3e about 50~p r~ by welght polyetherimide ;~
e~ter and about 50 p~rts by we~gh~ poly~cryl~t~ elastomer.
.,
- .:
~ /107U~ 2 ~ ~ ~ 2 .3 ~ PCT/US91/~
-16-
The mixing compositions may also contain, Ln
addition to resin and rubber, various additives known t.o those
skilled in the art for use in compounding of thermoplastics,
rubbers, and their blends, to modify the properties thereof,
such as, - but not limited to fillers, stabilizers,
antidegradents, processing aids, plastic:izers, pigments and
the like. Typical fillers would include carbon blacks,
silicas, clays, minerals or mixtures threof. Both low an~ high
molecular weight plasticizers are contemplated.
In a typical composition, the thermoplastic
copolyetherimide ester resin, rubber and additives are mixed
in the appropriate device at a temperature high enough to
soften and~or melt the materials such that an intimate mixture
is obtained. Once an intimate mixture is obtained, the rubber
material is cured by the add~tion of crosslinking agents, and
optionally accelerators and heating, e.g., at from about 200
C to about 250 C, for from about 30 min. ~o about 30 sec.,
preferably from 5 min. to about 30 sec.
Crosslinking agents are any agents which promote
vulcanization of the acrylic elastomer. The cure system
employed varies with type of cure-site monomer present in the
acrylic elastomer. Pref~rred crosslinkiny agents are soaps
including metallic carboxylates such as sodium or potassium
stearate. Optionally the cure system may also comprise an
accelerator as well as a crosslin~ing agent. PreEerred
accelerators include sulfur; sulfur donors such as
tetrame~hylthiouram; or bases such as magnesium oxide or
tertiary amines. Ammonium benzoate, ammonium adipate, and
soap/quaternary amine systems are also known to be effective
cure systems, as are red lead/ethylene ~hlourea and diamines
and polyamines. ~ost preferred is a soap/quaternary ammonium
system. These and others are more extensively discussed in the
above-ref~renced Starmer et al. article.
Mixing ti~e is determined by ~he temperature
and/or amounts of crosslinking agents added. The materials
thus produced are processable by common thenmoplastic
processing techniques, such as injection and oompression
WO91/107~X 2 ~ 7 PCTlUSg~ 30
molding techniques and yield flexible, elastomeric parts.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following examples illustrate the present
invention. They are not tO be construed to limit the claims in
any manner whatsoever.
EXAMPLES ~ AND lA*
To a ~anbury mixer are added a crosslinXable
polyacrylate elastomer comprisin~ alkyl halide vinyl ether
cure sites ("H'--EMP" 4451CG, Zeon Chemical Co.), a
polyetherimide esler resin ~"LO-MOD" J-1013, GE Plastics,
Pittsfield, MA, MeCready, U.S. Patent No. 4,456,705), a
hindered phenolic antioxidant stab~lizer ~ GANOX l0l0",
CIBA-Geigy), a plasticizer ("PARAPLEX" G-62, C. P. Hall Co.,
Chicago, IL, U.S.A.), and a phosphite/thioes~er secondary
stabilizer t"MARX" 5117, Argus Div., Witco Co., ~.Y., U.S.A.).
The mixture is mixed to form an intLmate blend. Once an
intimate blend is obtained, a crosslinker (sodium stearate)
and an acce}erator (quate~nary ammonium complex, "~PC-50",
Zeon Chemical Co., Japan) are added. The m~xtu~e is then
dynamically cured by mixing for 3 to 4 minutes a~ a
temperature o~ 200 to 220 C. The composition is injection
molded into test spe~imens and te~ted for tensile strength
properties. For comparative purposes, a back-to-back sample
is prepared, except that a copolyether ester resin simiLar to
those described in EPO 0 327 0l0 A2 ("HYTREL" G-4078) is
employed as the thermoplastic elastomerinstead of the
polyetherimlde e~ter resin. The ~o~mulations used and the
physical properties obtained are ~et forth in Table l.
:
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WO 91/10708 2 a ~ ~ 2 ~ ~ PCT/US91/00430
1~
TABLE_ l
ExamDle lA~ 1
In~redientstParts/wt)
Polyetherimide ester
resina _- 763.6
Polyether ester reslnb 76:3.6 --
Polyacrylate elastomerC 763.6 763.6
Sodium stearate crosslinker 39.5 30.5
Quaternary ammonium acceleratord 15.3 . 15.3
Hindered phenol antioxidante 3.8 3. a
Plasticizerf 7.6 7.6
Secondary antioxidant5 3.8 3.8
Processing aidh 7.6 7.6
Properties .
Tensile break strength, psi 889 1063
Elongation break, % 182 156 .
....................................... ..... ..... ........ ... ................ ... ... ..
_ _ _ _ _
a--''LOMODI~ J1013, GE Plastics, Pittsfield, MA 01201, U.S.A.
b--"HYTREL" G-4078, DuPont Company, Wilmington, DE, U.S.A.
c--"HYTE~P" 4451CG, Zeon Chemica} Co., Japan :
d--"NPC-50", Zeon Chemical Co., Japan ~ :
e--"IRGANOX"1010, CIB~-Geigy Co., Ardsley, NY, U.S.A. .
f--"PARAPLEX" G-62, C.P. HALL Co., Chicago, IL, U.S.A.
g--"MARX" 5117, Witco Chemical Co., N.Y. U.S.A. ~:
h--"STRUKTOL" ~S-280, Struktol Co., U.S.A.
The foregoing results demonstrate that a
compocition prepared by dynamically vulcanizing a
crosslinkab}e polyacrylate rubber with a thermoplastic
copolyetherimlde ester resin unexpectedly provides better
retention of tensile properties t-han a composition prepared by
dynamically vulcanizing a polyacrylate rubber with a .
th~rmoplastic copolyether ester resin, as ~au~ht Ln the prior :~
art EPO 0 327 010.
This is especially surprising in light of the
be~ter tensile.properties of the copolyether eqter alone when
compared with the copolyetherimide ester alone, tensile
. : : . . .. . , . ~ . ,: ..
WO91/1070h 2 ~ ~ v~ 2 ~ 7 PCT/US91/~30
-19-
breaking strengths being typically 2359 psi and 2159 psi,
respectively, and elongations at break of 532 % and 215 %,
respectively.
Thus, by employing a copolyetherimide ester as
the thermoplastic resin dynamically vulcanized with a
crosslinkable rubbery alkylacrylate there is observed a 49.2
percent retention in tensile break strength and a 72.6 percent
retention in elongation at break, as compared to a 37.7
percent retention in tensile break strength and 34.2 percent
retention in elongation at break with the copolyether ester of
the prior art.
EXAMPLES 2-4
To a Brabender mixer are added 42.6 g of a
polyacrylate elastomer (l00 phr), 28.4 g of a polyetherimide
lS ester (66.7 phr) and 0.43 g (l phr) of an antioxidant
("IRGANOX" l0l0). The mixture is mlxed and heated at 220 C to
form an intimate blend. Once an ~timate blend is obtained,
1.70 g (4 phr) of a crosslinker ~sodium 3tearate) and 0.85
(2 phr) of an accelerator ("NPC-50") are added. The mixture is
dynamica~ly cured by mixing for 2 to 3 minutes at 220 C and
the composition is compression molded into test specimens and
tested ~or tensile strength properti~s according to ASTM
D-412. For comparative purposes, tests are run wLthout curing.
The results along with compositional data are set forth below
in Table 2.
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WO 91/10708 ~2Q ~ V 2 ~ ~ PCI'/US91/0~
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wos1/1070x '~ 2 9 7 PCT/US9~ 30
-21-
It can be seen from. Table 2 above that
dynamically curing the polyetherimide ester vastly improves
the tensile break streng~h with a minimal decrease in .
elongation break. (Example 3 vs. 3A*). In the copolyetherimide
ester examples, curing improved the tensile break strength.
EXAMPLES ~8
.
The procedure of Examples 2-4 is repeated except
employing a Banbury mixer and various other addit~es and the
concen~ration of a filler is variedO The compositions are
then injection molded into ASTM D-412 Type } bars. The results
along with compositional data are set forth in Table 3 below.
'~
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--22--
WO 91/10708 PCT/US91/00430
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wogl/10708 7.a49~7 PCT/US91/~30
-23-
EXAMPLES 9-l3 .
The procedure of Examples 5-8 is repeated except various other
additives are employed and two different plasticizers are
employed at two concentration levels (2.5 and 5.0 phr). The
results are set forth in Table 4 below.
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WO 91/10708 -24- PCq~/US91/00430
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WO9~10708 ~ 2 3 7 PCT/U~g~ 30
-25-
TABLE 4 (continued !
'
= Polyacrylate elastomer (Zeon ChemicaLs Co., footnote a
Table 2)
= Polyetherimide ester (General Elec~ric Co., footnote b
Table 23
A = Failed du~ing initial straining at 100
B = Failed during hold at 100% strain
c = according to ASTM D395-B for 22 hours, avera~e values of
four runs.
EXAMPLES_14-18
The procedure of Exa~ples 5-8 is repeated except
various other additives are employed and the rubber/res in
wei~ht ratio ~s varied at 20/80, 40/60, 50/50, 60/40 and
80/20. The re~ults along with compo81tlonal data are ~et forth
below in Table 5.
~ . .
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2 ~ 7
WO 91/1070EI PCT/US91/00430
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WO 91/10708 2 ~3 4 ~ ~ ~ 7 PCT/IJS91/00430
--28-- -
From the above Tables 1-5 it can be seen that the
physical properties of a typical composition containing 60
parts by weight rubber and 40 parts by weight crystalline
thermoplastic polyetherimide ester and a suitable additives
package are: Tension Set (ASTM D412) typically 15 to 25
percent; Compression Set (ASTM D395 Method ~-plied sample)
approximately 16 percent at 23 C/22 hours and 45 percent at
100 C/22 hours. Hardness values (Shor~ A durometer) of 55 to
80+ points can be achieved by suitable choice o~ components
and additives.
The compositions of the present invention are
placed under Dynamic Mechanical Thermal Analysis (DMTA) to
produce DMTA curves. Typical thermoplastic materials, such as
th~ thermoplastic elastomer~ u~ed herein, exhibit storage
modulus versus temperature DMTA curves whLch can be described
as posse~sing a glas3y plaiteau which ~g generally constant in
magnitude, followed by a glass transition region which is
characterized by a two to three order o~ magnituda drop in the
storage modulus to the ~o-called rubb2ry plateau. The rubbery
plateau-storage modulus va~ue is then u~ually ob~srved to
decrease with increasing temperature in thermoplastics (i.e.
- viscous flow~. In semi-cry~alllne thermopla3tic~ the rubbery
plateau is then followed by a large drop of~ at the
crystallin~ melting point of the polymer.
In the compositions of the present invention, the
drop o~f of modulus associated with the melting of the
polyetherimide ester is observed to be followed by what may be
termed a ~econd rubbery plateau which wa~ ~oundi to be of
es~entially constant magnitude to the extent of the
~temperature tested ~250 C). The presence of this second
rubbery plateau was ~ound ~o be dependent on ~he ratio of
rubber to thermoplastic with compo~it$on~ having below 50
weight percen~ ~rubber not exh~bL~ing the ~econd rubbery
plateau. In a thermoset rubber ma erial, the ~torage modulus
would be essentially constant in the rubbery plateau region
and would not drop of~ with ~increa~ing ta~perature (until
. ~ . . , . , , . ~ . ~ , . . ..
WO Yl/1071J~ 2 ~ ~ ~ 7. 9 7 PCI/US91/0~430
--29--
degradation occurs), due to crosslinking of the ~ystem.
To test the thermoplasticity of the compositions
a typical material which exhibits the second rubbery plateau
was prepared, molded and then heated for 75 minutes at 200 C
in an air circulating oven. The material is then charged into
a Brabender mixer and mixed ~o a molten state in which the
consistency was observed to be constant as a function of time
over a ten minute test period.
Thus, the materials are thermoplastics. If the
materials were becoming thermoset above the melting point of
the crystalline thermoplastic polyetherimide ester, they would
have shear degraded when reprocessed as does a true thermoset
material.
The above patents, pa~ent applications,
publicatlons and test methods are hereby incorporated by
reference.
Many variations of the present invention wLll
suggest ~hemselves to those skilled in the art in light of the
above~detailed descriptLon. For example, any copolyetherimide
ester resin and cros~linkable alkylacrylate elastomer may be
employed. Other suitable crosslinkers and accelerators are
also contemplated. Additives such as flame re~ardants, light
stabilizers and the like may be employed in the compositions
of the present invention. All such obvious modifications are
within the full in~ended scope of the appended clalms.
