Note: Descriptions are shown in the official language in which they were submitted.
2~39~3~ `
-- -2- 337-2181 ( BCT-4905 )
. . . ,
, . .
n~o ~ n_rrol~
Thi~ sention relate~ to thermoplastic resins
oomprising a polycarbonate re3in alone or polypha~ic
30 r~in mixture~ of polycarbona~ce re~in with a saturated
polye3ter re~in and/or an ela~to~er, comprl~ g a
poly ~ ethere3ter ) elasto~er or a poly t eth~r imide e~ter )
, ela~tomer or bo~h and/or a polyphenylene ether re~in,
and a modifier ~ompo~ition compri~ing two multi-~tage
35 graft polymer compo~ition~ in combina~ion.
. .
,
~ ,~
.
:: :
': ' ', .
.
;.
~03~
-3- 337-2181 (8CT-4905)
An-~O O' 1-- IW~-OII
Polycarbonate re~in compositions and blends
with other thermoplastic resins are widely used because
of their excellent properties.
There have been many attempts in the ar~ to
provide polyorganosiloxane-based graft polymers which
may be u eful as impac~ strength modifiers for
thermoplastic resinsO See, for example, U.S. Pa~ent No.
2,891,920 (J.F. ~yde, e~ al.); and O. Graiver, et al~,
Rubber Chem. Tech., 56 (5), 918 (1983).
U.S. Patent No. 3,898,300 states that a poly-
organosiloxane-based graft copolymer for improving the
impact strength of styrene ~S)/acrylonitrile (AN) resin
i3 formed by graftin~ S/AN comonomers in an emulsion
system on~o the vinylsiloxane or allylsiloxane containing
silicone substrate. ~S. Paten~ No. 4,071,577 describes
a similar approach by using a mercaptosiloxane in place
o~ vinyl-group containing siloxane3. ~uropean Patent
Application No7 0,166,900 reports further improvement of
polysiloxane~-based graft polymers and increased S/AN
impact strength by u3ing acryloxy-functionali~ed
siloxane as the graft-linking agent.
Relevant for its broad teachi~gs is BASF's
U.K. Patent No. 1,590,549 which describe~ the use of a
polyorganosiloxane-ba ed graft copolymer in various
t~ermopla~tic co~positions. Poor compatibility is
ob~erved with these composit~ons. Slmilarly, European
Patent Applicatlon No. 249,364 describes the use of a
polyorgano~iloxane-based gra~t copolymer in polycarbonate
re~in compo~itions and mixtures thPreof with~a saturated
polye~ter and/or a polyester ela~tomer. The modifier
therein ha~ relatively poor rubber integri~y aQd
incompatibility with the resin as well.
The use of a die~e or acrylic rubber-based
modifier in thermoplastic resin3 ha~ become a co~mon
.. . . . ..
~)39~3~
-4- 337-2181 (8CT-4905)
practice in the ar~. The selection of either material
depends largely on the end use purposes such as
weatherability or low temperature impac~ resistance.
Uniform color appearance of molded parts is a benefit
which is gained by using a diene-based modif ier over
acrylics. However, ~he unsaturated moieties of the
diene rubber restric~ i~s outdoor use to ~ome extent due
~o its tendency to oxidize and to yellow.
None of the references disclose the in-situ
co-homopolymerization o~ vinyl monomers in the presence
of siloxanes in an emulsion system, as described
hereinbelow. The present invention is also directed to
the use of graft polymers provided by subsequent graft
polymerization of vinyl monomers (eOg. polymethyl
(meth)acryla~e, polystyrene or styrene/acrylonitrile
copolymer~ in the presence of such a co-homopolymerized
polyorganosiloxane/vinyl-based substrate.
Surprisingly, i~ has been found ~hat partial
replacement of the oxidation or ozone sen~itive rubber
by a silicone-based rubber affect~ more improvements t
such a~ low temperature ductility, low glo~s, and impact
and discoloring re~is~anoe against thermal agins on the
blend~ described hereinafter. Unexpectedly, it is now
possible to prepare low gloss polycarbonate and
polyester blend.Q having both excellent low temperature
recistance and discoloration resistance by the addition
of an effective amount of a silicone-ba~ed impact
modifier to a diene-based modi~ier.
Mention i~ al~o made to European Patent
Application No. 0,260,558 which discloses a combination
of a silicone-based modif ier with an alkylacryla~e-based
modifier. The pa entee, however, make no mention of
the use of a diene-baced impact modifier.
Additionally, it is de~cribed in S.Y. Hobbs et
3S al, Polymer Bulletin, 17, 341 (19~7) and S.Y~ Hobbs et
~3~3~i
-5- 337 2181 (8CT-4905~
al, Jousnal of Material Science, 23, 1219 (198a) that in
polycarbonate/saturated polyester resin blends, typical
core-shell type modifiers such as Acryloid RM-330 (poly-
bu~ylacrylate core-methyl methacrylate shell, ~ohm and
~aas Company) or KM-653 (poly~utadiene core-styrene/methyl
methacrylate polymer shell~ Rohm and Haas Company) segre-
gate completely in the polycarbonate phase leaYing the
less ductile saturated polyester pha~e without any modifier.
There is evidence that in blends or mixtures
comprised of two different resin~, modification of both
phases can significantly improve low temperature toughne~s.
Van der Meer, in Dutch Patent Application Nos. 8600166 and
86202388O4 filed on January 12, 1986 and on December 30, 1986,
respectively, and Van der ~eer and ~obbs in commonly owned
copending U.S. Patent Application Serial NoO 07/007,268 filed
on JanuaLy 27~ 1987, attorney's docke no. 335-2019 (8CB-10,306)
have demonstrated this in polyphenylene ether (PPE)/polyamide
~nylon) blends where Kraton~ rubber (~tyrene butadiene-~tyrene
AB~ block copolym~r, Shell Chemi~al Co~pany) wa~ used ~o
modify the PPE pha~e and maleic anhydride func~ionalized
EPDM (ethylene-propylene-nonconjugated diene monomer
polymer) rubber wa used to modify the nylon phase.
~ ASF's 6erman Patent No. 3521956 discloses the
modificatian of the poly(butylene terephthalate) (P~T~ phase
of a PBT/PC polyphasic blend through the incorporation of
olefin polymers tha~ contain epoxy groups. The effectiveness
of this method, however, depends on the ability to establish
sufficient gra~ting of PBT o~ the epoxy groups of the ole~in
polymers during compounding in an extruder. The fact that
both mixing and grafting chemistry mu5t take place simulta-
neously places high demands on the compou~ding process, and
therefore, the succe3s of the 3ASF method has been limited.
It has been surprisingly found ~hat migration
of multi Rtage graft polymer modi~ier~ can be induced to
segregate different modi~ier~ into the di~erent phase~
~Q~9~3~a
-6- 337-21~1 [8CT-4905)
of polyphasic PC~PBT containing blends or mix~ures of
the same with poly(etherester) elastomer, poly(ether-
imide e~ter) elastomer and/or polyphenylene ether resins
by va~ying the amount of (me~h)acrylonitrile in the
S outermost stage of the modifiers. Therefore~ two or
more different modi~iers, each with a different amount
of (me~h)acryl~nitrile in th~ outelmost stage can be
combined to yield a desired distribution of modifier in
the PC phase and in th~ PBT phase resulting in optimum
toughness of the polyphasic blend. Such blends
particularly exhibit superior low tempera~ure toughnes.
when compared with those formulated with modifiers
residing in only one phase of the blend.
FIG. 1 i~ a trans~is3ion elPctron micrograph
of a polyphasic blend o~ PG, PaT, a polyorganosiloxane/-
polyvinyl-based graft copolymer mcdifier (CSi~)
(Silicone (Si)/Polystyrene (PS)Methyl methacrylate
(MMA) wt. ratio of 70:30, S1/PS wt. ratio o~ 95:5) and a
CSiM modifier (tSi~PS)-S/A~ wt. ratio of 70 30, Si/PS
wt. ratio of 95:5, S/AN wt. ra~io of 75:25, stained with
OSO4 and Ru04~ showing ~he complete segregation of CSiM
modifier ((Si/PS)-MMA) in the PC phase and CSiM modifier
(~Si/PS)-S/A~, S/A~ wt. ratio of 75:25) in the P~T
phase.
FIG. 2 is a transmisRion electron micrograph
of a polyphasic blend of PC, PBT, and CSiM modifi~r
((5i/PS)-S/AN wt. ratio of 70:30, Si/PS wt. ra~io of
95:5, S/AN wt. ratio of 75:25), stained with OsO4 and
Ru04, showing complete segregation of the modifier in
the PBT phase.
FIG. 3 is a transmission electron micrograph
of a polyphasic blend of PC, PBT, and CSiM modifier
((Si/PS)-MMA wt. ra~io of 70:30, Si/PS wt. ratio of
~2~3~3~35
-7- 337~2181 (8CT-4905
95~5), stained with OSO4 and RuO~, showing complete
segregation of the modifier in the PC phase.
FIG. 4 is a transmission electron micrograph
of a polyphasic blend of PC, P~T, and CSiM modifier
((Si/PS)-MMA/AN w~. ratio of 70030, 5i/P~ wt. ratio of
95:5, MMA/AN wt. ratio of 75:253, stained with OsO4 and
Ru04, showing complete cegregation of the modifier in
the P~T phase.
FIG. 5 is a ~ransmi~sion electron micrograph
o~ a polyphasic blend of PC, PBT, and CSi~ modifier
((Si/PS)-MMA/AN wt. ratio of 70:30, Si/PS wt. ratio of
95:5, MMA/AM wt. ratio of 95 5), stained with OSO4 and
Ru04, showiny the complete segreyation of the modifier
in the PC phase.
FIG. 6 is a tran~mis~ion electron ~icrograph
o~ a polyphasic blend of PC, PBT, butadiene rubber
sub~trate~S/MM~ outermo~t stage ~odifier, and high
rubber graf~ ABS modifier (A B-S wt. ra~io of 7.5:70:22.5),
~tained with OSO4 and Ru04, ehowing segregation of the
bu~adiene rubber subs~rate S~MMA outermo~t stage ~odifier
in th~ PC phase and the ABS modifier in the PBT phase.
~IG. 7 i~ a tran~missio~ electron micrograph
of a polyph~sic blend of PC, PBT and a butadie~e rubber
substrate-S/MMA outermost stage modifier, s~ained with
9S04 and Ru04, showing ~he segregation o~ the modifier
in the PC phaseO
S~n~R~ OF TEB I~YE~TIO~
A~cording to the pre~ent invention, there are
provided polyphasic resin compo~itions comprising a
mixture (A-l~ comprising (i) a polycarbonate resin phase
and (ii) a saturated polye~ter re~in phase~ a ~ixture
(A-2) compri~in~ (i) a polycarbonate re~in phase, (ii~ a
saturated polyester re~in phase, (iii) a poly(ether
imide) ela~tomer pha~e~ (iv~ a poly(etherimide ester~
elastom~r phase, (v) a polyphenylene ~ther re~in phase,
2t~3~5
-8- 337-2181 (3CT-4905)
or a mixkure of (i), (ii) and any o~ (iii), (iv) and
(v); or a mixture (A-3) o~ (A-lj and (A 2); and
an effec~ive amoun~ of a modi~ier composition (B)
comprising, in combination,
(1) a multi-stage graft polymer composition
comprising
(a) as a first stage,
(i) an organofiiloxane polymer, unitæ
derived from a cross-linking agent or ag~nts and
optionally units which serve a a grat-linking agent or
agents;
(ii) a polymeric substrate comprised of
units of a di~ne rubber and op~cionally units derived
from a cross-linking agent or agents; or
(iii) a polymeric co-homopolymerized
sub~trate comprising of, in combination, an organosiloxane
polymer; at lea t one vinyl-ba3ed polymer; and
optionally units derived from a cross~linking agent or
agent~, units which serve a~ a graft li~king agent or
agen~s, units derived from a cross-linking agen~ or
agents and unit~ from the same or d$fferent agent or
agents which serve as a graft-linking agent or agents or
a mixtur~ of any of the for~going; and
(b) at lea~t one subse~uent stage or stages
g~a~t polymerized in the presence of any previous stages
and which i3 comprised of a vinyl-based polymer or a
cro~-linked vinyl-ba ed polymer, the outermost stage o
which contains from zero to no ~ore than an amount of
polymerized or copolymerized ~eth)acrylonitrile unit~
3~ which will induce migration of multi-qtage composition
(1) into said polLycarbonate re~in phase; and
(2) a multi-~tage graft polymer composition
compr i5 ing
(a) as a first sta~e,
(i) an organosiloxane polymer, uni~s
~3~ 5
~9- 337-2181 (8CT-4905)
deriYed from a cross-linking agent or agent.~ and
optionally units which serve as a graf~-linking agent or
agents;
(ii) a polymeric substrate comprised of
units of a diene rubber and op~ionally unit3 derived
from a cross-linking agent or agents; or
~iii) a polymeric co-homopolymerized
substrate comprised of, in combination, an organosiloxane
polymer; at least one vinyl-based polym~r; and
optionally units derived fro~ a cross~linking agent or
agents, units which serve a-~ a graft-linking agent or
agents, units derived from a cross-linking agent or
agents and units from the same or different agent or
agents which serve as a gra~t-linking agent or agents or
a mix~ure of any of the foregoing; and
( b ) ak least one subsequen'c stage or stages
graft polymerized in the pre~ence of any previDus stage
and which is comprised of a vinyl-based polymer or a
cross-linked vinyl-based polym~r, the outermo$t staqa
having a content of a polymerized or copolymerized
(~eth~acrylonitrile units at lea~t sufficient to induce
migration of multi-stage composition (2) into said
saturated polye~ter re~in pha~e.
Also conte~plat2d by the invention is a
~S composition as defined ahove, but where the modifier
composi~ion (8) additionally comprise~ a ~hird componen~
(3) which i3 different than both (1) and (2) and which
comprises
~a) a~ a first stage
~i) an organosiloxane polymer, units
derived from a cros3-linking agent or agents and
optionally unit.~ which ~erYe a~ a graft-linking agent or
agentst
(ii) a polymeric substrate comprised of
units of a diene rubber and optionally units derived
~C~39~5
-10- 337~2181 (8CT-4gO5)
frsm a cross-linking agent or agents, or
(iii) a polymeric co-homopolymerized
substrate compri~ed of, in combination/ an organosiloxane
polymer; at least one vinyl-ba~ed polymer; and
op~ionally units derived from a cross-linking agent or
agents~ units which serve a5 a graft-linking agen~ or
agents, units derived from a cross-linking agent or
agents and u~its from the same or different a~ent or
agen~Q which serve a-~ a graft-linking agent o~ agents or
a mixture o~ any of the foregoing; and
(b) at least one subsequent stage or stages
graft polymerized in the presence of any previous stages
and which is comprised of a vinyl-based polymer or a
cro~s-linked vinyl-based polymer.
lS Further conte~plated by the invention are
composition~ as abo~e defined wherein su,b~equent s~age-~
(l)(b) comprise (b)(i) a ~econd stage compri ing at
least one vinyl poly~er and optionally units derived
ro~ a cross-linking agen~ or agent~, units which ~erve
23 as a g~aft-linking agent or agents, unit~ derived from a
cros~-linking agent or agents and units from the sam2 or
different a~ent or agents which serve a~ a graft-linking
agent or agent~ or a mixture of any o the oregoing;
and (b)(ii) a third stage comprising at least one
~S vinyl-based polymer or cro~s-linked vinyl-based polymer
which is the ~ame or differen~ than (b)~i) and which
contains from zero ~o no more than n amount of
polymerized or copolymerized (meth)acrylonitrile which
will induce migration of the multi-~tage compo~ition (1)
into th~ polycarbonate re~in pha~e.
Additionally~ co~position~ wherein ~ubsequent
~tage~ ~2~(b) compri~e (b)(i~ a ~econd stage comprising
at least one vinyl-polymer and optionally unlt~ derived
fro~ a cross-linking agent or agent , units which serve
as a graf~-linking agent or agent , unit~ derived from a
... ... . . . .. ... . .. . . .. .....
~3~35
~ 337-2181 (8CT-4905)
cross-linking agent or agents and units from the ~ame or
different agent or agents which serve as a graft-linking
agent or agents, or a mixture of any of the foregoing;
and (b)(ii) a third seage comprising at le~8t one vinyl-
based polymer which is the sam~ as or different than
(b)(i), and which has a content of polymerized or
copolymeri~ed (meth)acrylonitrile uni~s at leas~
sufficient to induce migra~ion of multi-stage composition
(2) into the saturated polyester reQin phase; and
composition~ wherein both subsequent s~ages (l)(b) a~d
(2)(b) comprise two stages, (l)(b)(i) and (l)(b)(ii),
and (2)(b)(i) and (2)(b)(ii) correspondingly, as
described immediately above are proposed.
Another preferred embodiment of the present
1~ invention en~ompasse~ a polyphasic resin compo~ition
compri~ing a mixture (A-l) comprising ~i~ a polycarbonate
resin phas~ and (ii) a ~aturated polye~ter re~in phases
a~d an effective amount of a modifier compo~ition (B)
comprising, in combination, I
(13 a multi-stage polyorgano~iloxane/polyvinyl-
based graft polymer composition comprising
(a) a~ a first stage, a polymeric co-homo-
polymerized substrale compri~ed of, in combination, an
organosiloxane polymer; a~ lea~t one vinyl-based polymer
and optionally unit~ derived from a cross-linking agent
or agents, units which ~er~e a~ a graft-linking agen~ or
agents! units derived from a cros~-linking agent or
agents and units fro~ the same or different agent or
agene~ which serve as a graft-linkiny agent or agents,
or a mixture of any of the oregoiny7 and
(b) ae least one subsequent stage or stages
graft polymerized in the presence of any previou~ stage~
and which i~ comprised of a vi~yl-based polymer or a
cros~-linked vinyl-baqed polymar, the ou~er~ost ~tage of
-12- 337-2181 (8CT-4905)
which contains from zero to more ~han an a~ount of
polymerized or copolymerized ~meth)acrylonl~rlle uni~s
which will induce migration of multi-stage composition
(1) into the polycarbonate re in phase; and
(2) a multi-stage polyorganosiloxane/polyvinyl-
based graft poly~er composition comprising
(a) as a first s~age~ a polymeric co-homo-
polymerized substrate, wbich may be the same as or
di~ferent than (l~(a)~ comprised of, in combina~ion, an
organosiloxane polymer; a~ le~st one vinyl-based
polymer; and optionally uni~s derived from a cross-linking
agent or agents, units which serve as a graft-linking
agent or agents, units derived from a cro~s-linking
agent or agents and uni~s from the sam~ or di~ferent
lS agent or agent~ which serve a graf~-linking agent or
agents, or a mix~ure of any of ~h~ foregoing; and
~b) at least one sub~equent s~age or stages
graft polymerized in the presence of any previous stages
and which i8 comprised of a vinyl-ba~ed polymer or a
cross-linked vinyl-based polymer, the outermost stage
having a content of polymerized or copolymerized (meth)-
acrylonitrile units at lea~t suff$cient to induce
migration of multi-~tage compo~ition ~2) into the
saturated polye~ter resin phaseO
2S A preferred feature o~ the embodiment
contemplates subsequent stage (1) (b) comprising (b)(i) a
second stage comprising at least one vinyl polymer and
optionally unit~ derived rom a cros~-linking a~en~ or
ag~nt~, uni~s which serve as a graf~-linking agent or
agents, units derived from a cross-linking agent or
agents and units from the ~ame or differen~ agent or
agents which serve a~ a graft-linking agent or agents or
a mixture of any o~ the foregoing; and (b)~ii) a third
stage compri~ing at lea~t one vinyl-b~ed poly~er or
cros~linked vinyl-based polymer which is the ~ame a3 or
3~35
-13- 337-2181 (8CT-4905)
differen~ than (b)(i) and which contains from zero to no
more than an amount of polymerized or copolymerized
tmeth)acrylonitrile units which will induce migration of
multi-stage composition (1~ into the polycarbonate re~in
pha~e.
5ub~equent stage (2)(b) oomprising (b)(i) a
~econd stage comprising at least one vinyl polymer an~
optionally units derived ~rom A croq~-linking agent or
ayents, units which serve as a graft-linking agent or
agents, units derived from a cross-linking agent or
agents and units from the same or different agent or
agents which serve as a graft~linking agent or agents~
or a mixture of any of the foregoing; and (b)(ii~ a
third s~age comprising at least one vinyl-based polymer
or a cro~s~linked vinyl-based polymer which i~ the same
as or different than (b)(i) and which ha~ a content o~
polymerized or copolymerized ~me~h)acrylonitsile units
at lea~t suf~icient to induce migration of multi-stage
compo~ition (2) into ~he sa~urated palyester resin pha~e
i-~ also contemplated as are compo~ition~ wherein both
(l)(b) and (2)(b) comprise two ~tageg, (l~(b)(i) and
(l)(b)(ii), and (2)(b)(i) and (2)(b)(ii), corre~pondingly,
a-~ de~cribed immediately above.
The invention also provide~ a proce~s for
producing a polyphasic re in composition comprising the
s~ep3 of:
~ i) providing two first s~age substra~e~
independantly by the concurrent co-homopolymerization of
an organosiloxane, one or more vinyl-based monomers, and
optionally units derived from a cro~s-linking agent or
agents, uni~s which serve a~ a gra~t-linking agent or
agents, units derived fro~ a cro~3-linking agent or
agents and unit~ from the same or dlf~erent agen~ or
agents which serve a~ a yraft-linking agent or agents,
or a mixture of any of the foregoing;
~39~3~
-14- 337-2181 (8CT-4905)
tii) independently neutralizing each of the
two reaction masses of the foregoing polymerization step
to a pH of at leas~ about 6~5 to provide a neutralized
polyorganosiloxane/polyvinyl~based substrate latex;
(iii) graft polymerizing to one of the first
stage sub-strates at least one vinyl based monomer or a
vinyl-ba~ed monomer and a cross-linker, said monomers
being selected to provide that ~he outermos~ stage
contain~ from zero to no more than an amoun of
polymerized or copolymerized tmeth)acrylonitrile which
will induce migration of the resultant multi-stage
composition into the polycarbonate re~in phase of a
polycarbonate re~in phase/saturated polyester resin
phase mixture:
lS (iv) graft polymerizing to the remaining first
~tage substrate a vinyl-based monomer or a vinyl~based
monomer and a cross-linker, said monomers being selected
to provide that the ou~ermost stage ha~ a content of
polymerized or copolymerized (meth~acrylonitrile units
at least suf~icient to induce migration of th~ resultant
multistage composition into the sa~urated polyester
re3in phase of a polycarbonate re3in phas~/saturated
polyester re~in phase mixture;
(v) isolating the two multi-~tage organo-
siloxane/vinyl-based graft polymers to provide poly-
organosiloxane~polyvinyl-based modifiers for thermoplastic
resin.~;
(vi) combining independent modifying amoun~s
of the two polyorganosiloxane/polyvinyl-ba~ed modifiers
with a polypha~ic resin mixture.
Processes also are defined wherein in step (i)
only one first stage subs~rate i8 provided and that
substrate is subsequen~y divid0d into two poritions;
wherein graft polymerization s~ep (iii) is carried out
in two successive stages co~prising (l) graf~ polymerizing
,~, ,
,
~ O 3 ~
-15 337-2181 (8C~-4gO5)
at least one vinyl-based monomer; or vinyl-based monomer
in admixture with a cross-linker, a graft-linker, or a
cross- and graft-linker or a mixtuze of any o~ the
foregoing to produce a second stage polymer or cross-
linked polymer on the substra~e and ~hereafter, (2)graft polymerizing at least one vinyl-based monomer, or
a vinyl-based monomer and a cross-linker, which i5 the
same as or different ~han ~hat u ed in stage (l) to
produce a third stage of polymer on the second s age,
said monomers being selected to provide that the
outermost stage contains from zero ~o no more than an
amount of polymerized or copolymerized (meth)acrylonitrile
units which will induce migration of the resultant
multi-~tage composition into the polycarbonate re~in
phase of a polycarbonate resin pha~e/saturated polyester
resin phase mixtur~;
wherein step (iv~ is carried out in two
~uccessive stages comprising: (1) graft polymerizing at
least one vinyl-based monomer; or vinyl-ba~ed monomer in
admixture with a cross-linker, a graft-linker or a cross-
and graft-linker or a mix~ure of any o~ the foregoing to
produce a second stage polymer or cross-linked polymer
on said substrate; and therea~ter, (2~ graft polymerizing
at least one vinyl-based monomer or a vinyl-based
monomer and a cro~s-llnker which is the sa~e or
different than that used in stage (11 to produce a third
stage polymer on the second stage, said monomer being
selected to provide that the outermo~t stage has a
content of polymerized or copolymerized (meth)acrylonitrile
units at least ufficient to induce migration o~ the
resultant multi-~tage co~po~ition into the saturated
polye~ter re~in phase of a polycarbonate re~in
phase/saturated polyester resin phase mixture; and
wherein both step~ (iii~ and (iv) are carried5 out in two stages as de~cribed immediately above.
X~3~35
-16- 337-2181 (8CT-4905)
Also contemplated in another a~pect of the
invention are compositions comprising a polycarbonate
resin (A); a mix~ure (A-l) comprising (i) a polycarbonate
re~in and (ii) a sa~ura~ed polyester re~in; a mixture
(A-2) compri~ing (i) a polycarbonate resin, and (iii) a
poly(etheres~er) elastomer or (iv) a poly(etherimide
e~t~r) elastom2r or a mixture of (iii) and liv); a
mix~ure (A 3) comprising li) a polycarbonate resin, (ii)
a saturated polyester resin and (iii) a poly(etherester)
elastomer, (iv) a poly(etheri~ide) elastomer or a
mix~ure of (iii~ and (iv); or a mix~ure (A 4) of any of
the foregoiing; and
an ef ective amount of a modifier composition (B)
comprising, in combina~ion,
~1) a multi-stage polyorganosiloxane-based
g~aft polymer composition (GSim) comprising
~a) as a first stage, a~ organociloxane
polymer r units derived frum a cross-linking agent or
agents and optionally uni~s which serve a~ a graf~-linking
agent or agents; and
(b) at least one subsequent stage or stages
graft polymerized in the presence of any previous stages
and which is comprised of a vinyl-based polymer or a
cross~ ked vinyl-ba~ed polymer and
~2) a diene rubber-based graft copolymer
composition compri~in~
~a~ as a first stage, a polymer substrate
comprised of units of a diene rubber and optionally
unit~ derived from a cross-linking agent or agents; and
(b) at lea.~ o~e ~ubsequent stage graf~
polymerized in the presence of any previous stages and
which is comprised of a vinyl-based polymer or a cross~
linked vinyl-ba~ed polymer, the weight ratio of (1) to
(2) being from 1 to 9:9 to 1.
~3~3~
-17- 337-2181 (8CT-49053
Also contemplated in the preferred feature is
a composi~ion wherein first stage (l)(a) is replaced by
first stage (l)~a) which comprises a polymeric
co-homopolymerized substrate comprised o , in co~bination,
an organosiloxane polymer; a~ least one vinyl-based
polymer; and optionally units derived from a cro~-
linking agent or agents, unit~ which serve as a
graft-linking agent or agents, units derived from a
cross-linking agent or agents and units from the same or
different agent or agents which serve as a yraf~-linking
agent or agents or a mixture of any of the foregoing.
Additionally, envisioned in thi~ preferred
feature are subsequen~ stages in components (1) and ( 2
comprisiny:
(b)(i) a second stage comprising at least one
vinyl polymer and optionally unit~ derived from a cro~s-
linking agent or agents, unit~ which s~rve as a graft-
linking agent or agents, units derived from a
cross-linking agent or agents a~d u~it~ fro~ the same
agent or agen~s which serve as a graf~-linking agent or
agents, or a mix~ure of any of the foregoing; and
(b)~ii) a third stage co~prising at least one
vinyl-based polymer or a cross linked vinyl~based
eolymer which is the same or d~fferent tha~ (b)(i).
Polycarbona~e resins (A) or (i), sui~able for
use in thi~ invention, can comprise non-aromatic a~ well
as aromatic form~. With respect to aromatic polycarbonate
resins, the~e can be made by those skilled in thi~ art
or can be obtained from a va~ie~y of comm~rcial sources.
They may be prepared by reacting a dihydro~y compound
such a~ a dihydric phenol and/or a polyhydroxy compound
with a carbonate precursor, such a~ phosgene, a
haloformate or a carbonate e~ter such as a diester of
~)3~35
~ 337-2181 (~CT-4905)
carbonic acid. Typically, they will have recurring
structural units of the formula:
11 ~
~ O - A - O - C ~
wherein A is a divalent aromatic radical of the dihydric
phenol e~ployed in the polymer produc~ng reaction.
Preferably, ~he aromatic carbonate polymers have an
intrinsic viscosity ranging from 0.30 to 1~0 dl/g
~easured in me~hylene chloride at 25C~. 8y dihydric
phenols is mean~ mononuclear or polynuclear aromatic
compounds containing ~wo hydroxy radicals, each of which
is attached to a carbon atom of an aromatic nucleus.
Typically, dihydric phenols include 2~2-bis-(4 hydroxy-
phenyl)propane; 2,2-bi~-(3,5-dimethyl 4 hydroxyphenyl)-
propanes 4,4'-di hydroxydiphenyl ether; bis(2-hydroxy-
phenyl1methane, mixture3 thereof and the like. The
preferred aroma~ic carbonate polymer for component (A)
or (i) i~ a homopolymer derived from 2,2-bi~(4-hydroxy-
phenyl~propane(bisphenol-A~.
Poly(ester carbonates) for use in the
inveneion are known and can be obtained commercially.
Generally, they ar~ copolyester~ comprising recurring
carbonate group~:
~ O - C - O
carboxylate groups
~ C ~
and aromatic carbocyclic group~ in the linear polymer
.. .. . . . .
2~ L35
-19 337W21al (8CT-4905)
chain, in which a~ least some o~ the carboxylate groups
and at lea3t some of the carbona~e groups are bonded
directly to ring carbon atoms of the aromatic carbocyclic
groups. The~e poly(ester carbonate~ in general, are
prepared by reacting a difunctional carboxylic acid
such as phthalic acid, issphthalic acid, terephthalic
acid~ homophthalic acid, o-, m-, and p-phenylenediacetic
acid the polynuclear aromatic acids~ such a~ diphenic
acid, l,4-naph~halic acid; mixture~ o~ any of the
foregoing, and the like, with a dihydric phenol and a
carbonate precursor, of the types deQcribed above. ~ ~
particularly useful poly(ester carbonate) i~ derived fro~
bisphenol-A, isophthalic acid, terephthalic acid, or a
mixture of isophthalic acid and terephthalic acid, or
the reactive derivatives of ~hese acids such as
terephthaloyl dichloride, or a mixture thereof, and
phosgene. The molar proportion~ o dihydroxy diaryl
unit~ to benzenedicarboxylate units to carbonate unit~
can range from 1 0.30-0.80 0O70O0.20 and the molar range
of terephthalate units to i~ophthalate units can ran~e
from 9:1 to 2:8 in this preferred family of resins.
The aromatic dihydric phenol sulfone polymer
re-nins useful in component~ (A) and (i) are a family of
resins which can be made by those skilled in this art.
For example, homopolymer~ o~ dihydric phenol, and a
dihydroxydiphenyl sulfone and a carbonate precursor can
be prepared a~ well a~ copolymers of a dihydric phenol
and a carbonate precursor can be made accordinq to the
description in Schnell, et al~, U.S. Patent No.
3,271,367. A preferred ~aterial is made by polymerizing
bis-~3,5-dimethyl-4-hydroxyphenyl) 5ul fone, alone, or
especially in combination with bisphenol-A with phosgene
or a phosgene precursor, in accordance with the
de~cription in Fox, U.S. Patent No. 3,737,409.
E~pecially preferred is a copolymer made by reactin~ 40
~33~
-20- 337-2181 (8CT-4905)
to 99 wei~ht percen~ of ~he sulfone, 1 to 60 weight
percent of the bisphenol with pho~gene.
Polyesters (iii) suitable for use herein may
be saturated or unsa~urated or polyester ela~tomers and
S are generally derived from an aliphatic or cycloaliphatic
diol, or mix~ures thereof, containing fro~ 2 to about 10
carbon atom~ and at lea~t one aromatic dicarboxylic
acid. Preferred saturated polye~ter resins comprise the
reaction produc~ of a dicarboxylic acid or a chemical
equivalent thereof and a diol. Preferred polyesters are
derived from an aliphatic diol and an aromatic
dicarboxylic acid and have repeated units of the
following general formulas
~ t CH2 ~ O - C ~ ,C -
wherein n i~ an integer of from 2 to 4~
The most preferred poly~ter~ ar~ poly~ethylene
terephthalate~ and poly(l,4-butylene ~erephthalate).
Also contemplated herein are ~he abov~
polyesters with minor amounts, e.g., from 0.5 to about 2
percent by weight, of units d~rived from aliph3tic acid
and/or aliphatic polyol~ to form copolye~ters. The
aliphatic polyol~ include glycol~, ~uch as poly(ethylene
glycol). All such polye ters can be made ~ollowing the
teaching3 of, for example, U.S. Patent Nos. 2,465,319
and 3,047,539.
The polye~ters which are derived from a
cycloaliphatic diol and an aro~atic dicarboxylic acid
aee prepared, for example, by conden~inq either the cis-
or trans-isomer (or mix ure3 thereof) of, for example,
1,4-cyclohexanedimethanol with an aromatic dicarboxylic
~339~.3.~
-21- 337-2181 (8CT-4905)
ac~d as to produce a polye~ter having recurring units of
~he following formula:
r~ o o
11 il
~ ~ C~2 ~ - C~2 ~ - C - R - C -
wherein the cyclohexane ring is selected from the cis-
and tran~-isomers thereof and R represents an aryl
radical containing 6 to 20 carbon atom~ and which is the
decarboxylated re~idue derived from an aromatic
dicarboxylic acid.
~xamples of aro~atic dicarboxylic acids
represen~ed by the decarboxylated residue R are
isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl)
ethane, 4,4'-dicarboxydiphenyl ether, etc., and mixture~
of these. All o~ the~e acids contain at least one
aromatic nucleus. Acids containing fu~ed ring~ can al~o
be pre ent, ~uch as in 1~4- or 1,5-naphthalenedicarboxylic
acid-q. The preferred dicarboxylic acid~ are terephthalic
acid or a mixture of terephthalic and isophthalic acid~.
Another pre~erred polye~ter may be derived
from the reaction of either the cis- or trans-i~omer (or
a mixture thereof1 of 1,4-cyclchexanedimethanol with a
~ixture of isophthalic and terephthalic acids. Such a
polye~ter would have repeating units of the formula:
~ - C~ 2 ~ ~ C~
Still another preerred polye~ter i~ a copoly-
e ter derived from a cyclohexanedimethanol, an alkylene
glycol and an aroma~ic dicarboxylic acid. The e
copolye~ters are prepared by condensing eithe the Ci3-
or trans-isomer (or mixture~ thereo~) o~, for example,
~391~5
-22- 337-2181 (8CT-4905)
1~4-cyclohexanedime~hanol and an alkylene glycol with an
aromatic dica boxylic acid so as to produce a copolyes~er
having units of ~he following formula:
~ 0 - CH~ ~ C~2 ~ C - R - C
11 \
t ~ C~2~ - c ~ ct
Y
wherein the cyclohexane ring is selec~ed from the cis-
and trans-isomers th~reof, R is as previously defined, n
is an integer of 2 to 4, the x units comprise from about
10 to about 90 percent by weight and the y uni~s
comprise from abou~ 90 to ahou~ 10 pe~cen~ by weight.
Such a preferred copolyestPr may be derived
from the reaction of either the ci~- or trans-isomer (or
mixture8 thereof3 of 1,4-cyclohexaQedime~hanol and
ethylene glycol with terephthalic acid in a molar ratio
of 1:2:~. These copolyesters have repeating units of
the following formula:
~ ~ C~2~} C~2 ~ ~ 11 ~11 ~
x
~O~C~2~0 - 11~" ~
wherein x and y are as previously defined.
The polye~ter~ de~cribed herein are either
commercially available or can be produced by methods
;~0~3~
-23- 337-2181 (8CT-4905)
well known in ~he art, such as those set forth in, for
example, U~S. Patent No. 2,901,466.
The polyesters used herein have an intrinsic
viscosity of from about 0.4 to abou~ 2.0 dl/g as
measured in a 60:40 phenol:te~rachloroethane mix~ure or
similar solvent at 23~-30C.
Polyester elastomers preferably comprise a
block copolymer consisting of (1) polyester segments and
(2) polyether or poly~etherimide) segmen~q~ Preferred
are polyester segmen~s comprising poly(l,4-butylene
terephthalate) and polyether or poly(etherimide)
segments comprising a polyalkylene ether glyool, or an
imide acid capped polyalkylene ether diamine, or a
mixture o~ such segments.
The poly(etherester) elastomer (iii) for use
aq a component in the invention i~ a block copolymer
consisting o~ polyester cegments and polyether segments
having molecular weights of 400 to 20,000. The
polyester segment con~ists o~ a polye~ter obtained by
condensation of an aromatic dicarboxylic acid with an
alkylene glycol. Examples of this segment are as cited
above in the case of the saturated polyester~ Preferred
examples of this segment are poly(l,4-butylene
terephthalate) and poly(ethylene terephthalate). On the
other hand, the polyether segment consists of a
polyalkylene ether glycol, e.g. poly(ethylene oxide~
glycol, poly(tetramethylene oxide) glycol, poly(propylene
oxide) glycol, or a mixture thereof; an alipha~ic
polye~ter, e.g. a polya~ter re~ul~ing from the reac~ion
of an aliphatic dicarboxylic acid of 2 to 12 carbon
atoms with an aliphatic glycol of 2 ~o 10 carbon atom ,
more specifically, polyethylene adipate, polyte~ra-
methylene adipate, polyethylene sebacate, polyneopentyl
sebacate, polyhexamethylene azelate, or poly-~-caprolactone.
The content of the polyether segment in the poly(ether-
~1~39~3~
-24- 337-2181 ~aCT-~905)
e~er~ elas~omer is pre~erably from 2 to 80 percent by
weightO
The poly(etherimide ester) ela~tomers (iv)
used herein may be prepared from one or more diols, one
or more dicarboxylic aoids and one or more high
molecular weigh~c polyoxyalkylene dlimide diacids.
Preparation of such mateeial~ is described in de~ail in
UOS. Patent No. 4,556,705 o R.J. McCready, i~sued
December 3, 1985 and hereby incorporated by reference.
The poly(etherimide ester) elastomer~ used
herein may be prepared by conventional processes, such
a~ esterification and condensation reac~ions for the
production of polyesters, to provide rando~ or block
copolymers. Thus, poly(etherimide e~ers) may be
15 generally charac:terized as the reaction product of the
aforementioned diols and acids~
~ he polyphenylene ether resin (v) in the
invention i-~ a hamopoly~er or copolymer repre~ented by
the formula
~ ~
wherein Ql through Q4 are selec~ed independently of each
other ~rom the group con~isting of hydrogen and
hydrocarbon radical.~ and m denotes a num~er of 30 or
more.
Examples of such polyphenylene ether re~ins
include poly~2,6-dimethyl-1,4-phenylene~ether, poly(2,6-
diethyl-1,4 phenylene)ether, poly(2~6-dipropyl~1,4-
phenylene)e~her, poly(2-methyl-6-ethyl-1,4-phenylene)~
ether~ poly(2-methyl 6-propyl-1j4 phenylene)ether,
3913~
-25- 337-2181 (8CT-4905)
poly(2-ethyl-6-propy~ 4-phenylene)ether~ copolymer of
(2,6-dimethyl~1,4-phenylene)ether with (2~3,6-trimethyl-
1,4~phenylene)ether, copolymer of (2,6-diethy1-1,4-
phenylene)ether with (2,3,6-trimethyl~1,4-phenylene)ether,
and copolymer of (2,6-dimethyl-1,4-phenylene)ether with
(2,3,6-triethyl-1~4-phenylene)ether~ Of these polymers,
preferred are poly(2,6-dimethyl-1,4-phenylene)ether and
a copolymer of (2,6-dimethyl-1,4-phenylene)ether with
(2,3,6-trimethyl-1,4-phenylene)e~her. Particularly
preferred is a poly(2,6 dimethyl-1,4-phenylene)ether
resin. There is no particular restriction on the
polymerization degree of the polyphenylene ether resin
used in the invention, but it is preferable to use the
re~in having a reduced viscosity of 0.3 to 0.7 dl/g
measured in chloroform at 25C. Resins having a les
reduced viscosity than 0.3 dl/g tend to exhibit low heat
stability while reqin having a reduced viscosity
exceeding 0.7 dl/g ~end to have inferior moldabilityO
A preferred composition comprises a mixture
(A-l~ comprising (i) a polyca bonate resin and (ii~ a
sa~urated polyester resin.
The multi-stage polyorganosiloxane-based gra~t
polymers may be prepared with or without the incorporation
of a vinyl-based polymer. Where incorporation of the
vinyl-based polymer is desired, the process is generally
described hereinbelow by a co-ho~opolymerization
proce~s.
Co-homopolymerization reer~ to a polymerization
step where two distinct polymerization mechani~ms are
effected concurrently, including simultaneously. In
particular, the first stage co-hompolymerization may
encompa3s a siloxane polymerization (e.g., ring opening
and condensation mechanism) in conjunction with a
concurren vinyl polymerization. The discrete
mechanism-~ are not seen as competing with each o~her,
~ 3 S
-~6- 337-2181 (8CT-4905)
but rather, two homopolymer~ are concurrently produced
each retaining its own structure.
The co-homopolymerization process may provide
two discrete networks rather than a random copolymer.
While not intending to be bound by any theory, it is
possible that the network(s~ comprises two or more
distinct interpenetrating polymer phases, which provide
the additional strength needed in the polyorganosiloxane~
This is evidenced by the two distinct glas~ transition
temperatures which can be detected by differential
scanning calorimetry. Preferably, the product of the
co-homopolymerization process is rubbery instead of a
resin-like powder.
Subsequen~ to the co-homopolymerization of the
siloxanes and vinyl-based monomers of the first step, at
least one additional graft polymeri~ation proces~ is
utilized to achieve the multi-stage polyorgano~iloxane~-
polyvinyl-based graft polymers of the pre3ent invention.
The subsequent graf~ polymeriza~ion is
pre~erably of at lea~t one vinyl~based type monomer~ It
has been found that a styrene/acrylonitrile copolymer,
an alkyl(meth)acrylate polymer or alkyl(meth)acrylate/
acrylonitrile copolymer is particularly ef~ective
as the se~ond s~age graft polymer or copolymer, or as
the outermost stage when in~ermediary stages are
optionally utilized, and when two modifier compositions
are utilized in combina~ion.
The foregoing polyorganosiloxane/polyvinyl-based
graft poly~er can be isolated and utilized, for example,
as an impact i~proving agent for thermoplasti~ resins as `-
will be discusssd in detail below~
~ dditional cross-linking and/or graft-linking
agent can be utilized in this initial stage to provide
co-homopolymerized network~ f rom both polymeric
con3tituent5 which provide greater rubber integrity.
-
20391;~5
-27- 337-2181 (8CT-4905)
The firs~ stage rubbery subs~rake is provided
by a series of sequential pzocessing stepsO In a
premixing step the ingredients required for the reaction
of the organosiloxane(s~ and optional vinyl-ba~ed
monomer(s) aEe premixed with water and suitable cross-
linker(s), graft-linker(s), initia~or(s) and surfactant(s).
The premixed ingredients are homogenized by conventional
means. The reactions may begin a~ this early s~age o~
the process but these reactions are generally slow at
room temperature. The homogenized reactants may be
directed to a reaotor vessel, typically stainless steel
or glass flasks, under a nitrogen blanket. ~eat is
applied to facilitate the reaction. For typical 5 to S0
gallon stainles~ steel reactors, a 3 to 6 hour residence
time at 75 to 90 degree~ centigrada is adequate to
complete the co-homopolymeriza~ion. Cooling for 2 to 6
hours will typically reduce ~he temperature to at least
room temperature where the reaction mas~ can be held for
3 ~o 72 hours. Cooling to lower temperatures ~e.g~ 5
degrees centigrade) may sometime~ be pre~erred ~ince
this may enhance the properties of the newly formed
polyorganosiloxane/polyvinyl-ba~ed substrate.
Cooling to room tempera~ure or lower allows
the polyorganosiloxane portion ~o build molecular
weight, thereby miniMizing the ex~ractable silicone
rubber fragmen~s and optimizing physical properties of
the product for certain application~. Generally, lower
temperature~ are pre~erred when it is desired ~o
optimize the elasticity of the formed polyorganosiloxane/
polyvinyl-based sub~trate.
The initiator for the siloxane componen~ can
be any ionic ring opening type initiator when cyclic
siloxanes are utilized, such a3 alkylarylsul~onic acids,
alkyldiaryldisulfonic acids, alkyl~ulfonic acids, and the
like. The best suited example is dodecylben2enesulfonic
;~1)3~3~
2~- 337-2181 (8CT-4905)
acid which can act as an initiator and at the same time
as an emulsifier. In some cases, ~he joint use of a
metal salt of an a~orementioned sulfonic acid is also
preferred.
The initiator for the optional styrenic or
other vinyl-based monomers in ~he co-homopolymerization
proce~s can be any organic soluble radical initia~or,
such as azobisisobutyronitrile ~AIBN) and the organic
peroxides, e.g. benzoyl peroxide, dichlorobenzoyl
peroxide, and tert-butyl perbenzoate~ Also suitable are
water-soluble radical initiators such as the persulfates.
Although it is possible to charge this type of initia~or
at the beginning of the process, it is preferred that it
be charged continuously or incremen~ally during the
co-homopolymerization period. Since persulfate is less
stable in the acid conditions of the siloxane
polymerization, it is preferred that the persulfate be
added over time to keep the vinyl polymerization
running. Particle size, p~ and total solids measurements
can be readily monitored at this stage of the process.
A latex rubber emulsion prepared as described above will
generally contain particle~ having an average diameter
of lO0 to 800 nanometers and preferably lS0 ts 400
nanometers. The particle size is particularly
influenced by the homogenization pressure (and the
number of passes through the homogenizer~ and the
composition of the reaction ingredients. A pressure
range of 2000 to 12000 psi i~ typical, and 3000 to 9000
psi is preferred~ Multiple passes through the
homogenizer may be preferred, but on a large scale, a
~ingle pass may be mo t practical.
The foregoing reaceion steps mus~ be followed
by a suitable neutralization process to provide the
products of the invention. The main object of the
neu~ralization is to quench the siloxane polymerization.
3~
29~ 337-2181 (8CT-4905)
This is accomplished by adding a caustic solution such
as sodium hydroxide, potassium hydroxide, pota~ium or
sodium carbona~e, sodium hydrogen carbonate, triethanol-
amine or triethylamine. The p~ of the reaction solution
may be raised ~rom a level o~ 1 ~o 3 to a p~ of at least
6.5, and preferably 7 to 9.
It is often de~irable to add addi ional soap
or sur~actant to the emulsion formed at the end of the
firs~ stage, prior to the neutralization step.
Additional ~urfac~ant tend~ to facilitate avoidance o~
premature agglomeration or flocculation of the
co-homopolymerized rubber in the quench step.
The foregoing co-homopolymerization proce~s
provides a rubbery network composed o~ a polyorgano
siloxane/polyvinyl-based sub~trate. Thi~ substrate is
the fir~t stage of ~he gzaft polymer of the present
invention. Optionally, a fir~t ~tage comprising an
organosiloxane polymer with units derived from a cross-
linking aqent or agents and optionally units which serve
as a graft-linking a~en~ or agen~s may be employed. Th~
organosiloxane polymer can be prepared in a manner
according to th~ prior art, e.g. European Patent
Application NoO 0,166,900. Also contemplated are
mixture~ of the co-ho~opolymerized sub3trate with
silicone sub~rates.
~he next stage involves the graft polymeri~ation
o addi~ional vinyl-func~ional moietie~ onto graft ~i$e~
provided by the rubbery subs rate particles on the latex
ormed in the first s~age.
The grafted polymers will preferably be the
product o~ a vinyl polymerization process. Suitable
vinyl monomers for qraft polymerization include, withou~
limita~ion, alkenyl aromatic compounds such a~ styrene,
divinylbenzene, alpha-methylstyrene, vinyl toluene,
halogenated styrene and the like~ methacrylates such as
~33~
-30- 337-2181 (8CT-4905)
methyl methacrylate and 2-ethylhexyl methacrylate;
acrylates such as acrylic acid, methyl acrylate, ethyl
acrylate and butyl acrylate; vinyl cyanide compounds
such as acrylonitrile and methacrylonitrile; 012fins
such as ethylene, propylene, butadiene, isoprene, and
ehloroprene; other vinyl compounds such as acrylamide~,
N-(mono or di-substitutedjalkyl acrylamide~, vinyl
acetate, vinyl chloride, vinyl alkyl ethers, allyl
(meth)acrylate, triallyl isocyannurate~ ethylene
dimethacrylate, diallyl maleate, maleic a~hydride;
maleimide compounds such as maleimide, and N-phenyl (or
alkyl) maleimide; and mixture of these monomersO
Preferred vinyl based polymers of subsequent
stages (l)(b) and (2)(b) in the organosiloxane-based or
the organosiloxane/vinyl-based poly~ers comprise at
lea~t one selected from the group consis~ing of alkenyl
aromatic compounds, (meth)acryla~e co~pound~, vinyl
cyanide compounds, maleimide compound~ and acrylamide
compounds. ~specially preferred are polystyrene,
poly~me~hyl methacryla~e), styrene/acryloni~rile
copolymer, styrene/methyl methacrylate copolymer and
methyl methacrylate/acrylonitrile copolymer.
The vinyl polymerization is accomplished in an
emulsion; therefore, water-soluble initiators are
suitable, e.g. potas~ium persulfate, sodium persulfate
and ammonium persulfateO It i~ practical to add the
initiator at the beginning of this step, prior to
charging the vinyl monomer for the second s~age
polymerization. Other Redox initiator sy~tems, such a~
cumene hydroperoxide/~errous sulfa~e/glucose/sodiu~
pyrophosphate, can also be utilized at thi~ stage as
well a~ other organic peroxides.
Sequential multi-stage polymerization
proces~eq Oe this type are someti~es referred to as
core-shell processe~. rt i~ preferred, however, to
-31- 337-2181 (8CT-4905)
describe them as multi-stage graft polymerization
processes wherein the ini~ial stage provides a
co-homopolymerized organosiloxane/vinyl-based substrateO
This substrate may have sufficient grafting site~ for a
second or subsequent stage to be grafted thereto.
Grafted polystyrene, poly(me~h)acrylate, styrene/-
acrylonitrile copolymer, methyl me~hacrylate/-
acrylonitrile copolymer or styrene/divinylbenzene
copolymer as the outermost stage is preferred, yet many
other intermediary stage~ such as a butyl acrylate stage
are also contemplated. Furthermore, the grafting of
additional stages of the same or different kinds is also
possible.
The organosiloxanes useful in the first stage
of the composition are any of those known to produce
silicone elastomers and may include those which are
hydroxy-, vinyl-, hydride- or mercapto- end capped
linear organosiloxane oligomersO
The polyorganosiloxanes will be comprise~
primarily of units o~ the forNula
nsio(4-n~/2
wherein R is hydrogen or a monovalent hydrocarbon radical
of about 1 to 16 carbon atoms and n is 0, 1 or 2.
Preferred among the organosiloxanes are those
in cyclic form having three or more siloxane units, and
most preferred are those having three ~o six units.
Such organosiloxanes include, without limitation, for
example, hexamethylcyclotrisilo~ane, octame~hylcyclo-
tetrasiloxane, decamethylcyclopentasiloxane, dodeca-
methylcyclohexa~iloxane, trimethyltriphenylcyclotri-
siloxane, tetramethyltetraphenylcyclotetrasilaxane,
tetramethyltetravinylcyclotetrasiloxane and
octaphenylcyclotetrasiloxaneO These or similar
organosiloxane~ may be used alone or in combina~ion.
9~35
-32~ 337-2181 (8CT-4905)
The vinyl-based monomers useful in conjunction
with the co-homopolymerization of organosiloxanes in the
first stage are preferred to be alkenyl aromatic
compound~ such a~ styrene, divinylbenzene, alpha-methyl-
styrene, vinyl toluene, vinyl naphthalene, vinyl anthracene,and halogenated styrene or its derivatives. Other
suitable vinyl-based monomers include acrylic acids and
acrylate~ such as methyl~, ethyl-, alkyl-, or bu~yl-
acrylate; methacrylate~ such a3 methyl methacrylate, or
2-ethylhexyl methacrylate; vinyl cyanide3 such as acrylo-
nitrile, and methacrylonitrile, olefin~ such a~ ethylene,
propylene, butadiene, isoprene, and chloroprene; and
other vinyl compounds su~h as vinyl imidazole, 5-vinyl-
2-norbornene, vinyl pyridine, vinyl pyrrolidinone, vinyl
acetate, vinyl alkyl ethers, vinyl chloridei vinyl
furan, N-vinylcarbazole, allyl (me~h)acrylate, triallyl
isocyanurate, ethylene di(m~th)arylate, butylene
di(meth)acrylate, diallyl maleate, and maleic anhydride;
maleimide compounds such a~ maleimide, and N-phenyl (or
alkyl) maleimide~; acrylamides; N-(mono or disubstituted)
acrylamides, and mixtures of any of these monomers. In
general, any rubbery or glassy vinyl type monomer may be
used which can be mixable with the organosiloxane.
. Preferred vinyl-ba ed polymer components of
the first stage substrate of the polyorganosiloxane/-
polyvinyl-based graft copoly~er compri~e pri~arily
alkenyl aromatic units, (meth)acrylate units or mix~ures
thereof. E~pecially preferred i~ poly~tyrene.
Typically, the vinyl-ba~ed component of the
first stage co-homopolymer will be present in an amount
of approximately 3 to 97 weight percent and
correspondingly the organosiloxane component will be
present in an amount of approximately 97 to 3 weight
percent. Preferably, the vinyl-ba~ed component will
~3~ 5
-33- 337-2181 (8CT-4905)
comprise approximately S to 45 weight percent of ~he
first stage of the co-homopolymerized substrate.
The cros -linker composition u~ed in
conjunc~ion with ~he organosiloxane component of the
presen~ compositions can have the general formula:
R n ~ Si(ORl)4 n
wherein n is 0, 1 or 2, preferably 0 or 1, and each
independently represents hydrogen sr a monovalent
hydrocarbon radical selected from among alkyl or aryl
radicals having 1 to 1~ carbon atom~ preferably methyl,
ethyl and phenyl. R~ can be the same as Rl or can be a
vinyl, alkenyl, thio, or (meth)acrylo~y alkyl functional
radical. When R2 is a vinyl, alkenyl, thio or acryloxy
alkyl radical and n i 1, the cro~s-linker compound can
also act as a graft-linker.
A preferred cross linker compound is te~ra-
ethoxysilane. A co~bination cross~linking and graft-
linking compound is vinyltriethoxysilane. Another
suitable choice is gamma-me~hacryloxypropyl~rimethoxy-
silane.
The multi-stage polyorganosiloxane/polyvinyl-
based graft product of the present invention can be
isolated by conventional mean~ such as hot solution
coagulation. For exampl~, an electrolytic solution of
about O.S to 5 percent aluminum sulfate or magnesium
sulfate in water can be prepared and heated to about 75
to 95C. When the latex is added, with agi~ation, the
graft product will precipitate and can be held at an
elevated temperature for about 10 minutes whereupon it
may be filter washed. Commerical latex isolation
technique3 such as spray dryers may also be utilized.
The diene rubber-based graft polymer
compositions comprise a first stage subs~rate of units
9135
-3~- 337-2181 (8CT-4905)
derived from a diene rubber and optionally units derived
from a cross-linking agent or agents. Diene~ are
generally classified as hydrocarbon-based molecules
having at least two conjugated double bond~. Other
examples of diene rubbers are styrene/butadiene rubber,
acrylonitrile~butadien~, isoprene rubber, chloroprene
rubber or 1,3-dimethylbutadiene rubber~
Vinyl-based polymers useful in the subsequent
stage~ of the diene rubber-based graft copolymer are
selected ~rom alkenyl aromatic compound-~, (meth)acrylate
compounds, vinyl cyanide compounds and acrylamide
compounds.
Alkenyl aromatic polymer re~ins useful as
component tb) are, in general~ those having at least 25
percent o~ their units derived fro~ a mono~er having the
formula
CRl =C~R2
R5 ~
wherein Rl and R2 are selected from the group consisting
of lower alkyl or alkenyl groups of fro~ 1 to 6 carbon
atom~ and hydrogen; R3 and R4 are selested from the
group consisting of chloro; bromo, hydrog~n and lower
alkyl of from 1 to 6 carbon atom~; R5 and R6 ire
selected from the group consisting of hydrogen and lower
alkyl and alkenyl groups of from 1 to 6 carbon~ or RS
2S and R6 may be concatenated together with hydrocarbyl
group~ to ~or~ a naphthyl group.
Materials that may be copolymeri~ed with ~he
units of the alkenyl aromatic monomer include tho~e
having the general formula:
,
~6~3~3~L35
-35 337-2181 (8CT-4905)
R7 - C~ = C-~ C~2~ R
wherein R7 and R8 represent a subs~ituent selec~ed from
the group consisting of hydrogen, halogen, an alkyl
group of 1-4 carbon atom~ carboalkoxy or R7 and R8
taken together represent an anhydride linkage (-COOOC-),
and R is hydrogen, vinyl, an alkyl or alkenyl group
having 1 to 12 carbon atom~, cycloalkyl, carboalkoxy,
alkoxy-alkyl, alkyl carboxyl, ketoxy, halogen~ carboxy,
cyano or pyridyl and n is 0 or a whole number between 1
and 9.
~ Meth)acrylates are generally produced in a
two-~ep proce~3 wherein an acetone is reacted with a
hydrogen cyanide to form an acetone cyanohydrin which is
then heated in the presence of an alcohol to produce the
(meth)acrylate. Preferred (meth~acrylates are methyl
acrylate, ethyl acrylate, butyl acrylate and methyl
me~hacrylate.
Vinyl cya~ides useful ln the practice of th0
present inventio~ are comprised of the following general
formula
CN
C~2 ' CRl
wherein Rl is an alkyl group o~ from 1 to 6 carbon
atom~.
Acrylamide~ are well known in the art and
generally comrpise hydrocarbon3 having a group
comprising the following general formula
C~2 = C~ - C ~ ~2
~ .; ., . .,, ~ . . . .
.
~)3~
-36- 337-2188 (8CT-4905)
Preferred embodiments of the diene rubber-
based graft poly~er are a first stage ~a)(ii) compri~ing
units of a polybutadiene rubber and subsequent stage or
stages (b) comprising poly(methyl methacrylate), me~hyl
methacrylate/styrene copolymer or methyl methacrylate/
acrylonitrile copolymer.
The thermoplastic resin composition may also
contain an effective amount of any suitable additives
such as addition rubbers, polymers, fillers, pigments,
waxes, lubricants, proces~ing assis~ant~, dyes,
antioxidan~s, heat stabilizers, ultraviolet light
absorber and mold release agents.
The reinforcing filler can be comprised of any
organic or inorganic filler in~luding but not limited to
~lass fiber, carbon fiber, aramid fiber, metallic fiber~
whisker, glass beads, glas~ flakes, calcium carbonate,
talc, mica, aluminum oxide, magnesium hydroxide, boron
extrude, beryllium oxide, calcium silicate, clay or
metal powder.
Platinum compounds are often utilized in
conjunction wi~h polyorganosiloxane Gompositions in
order to enhance the flame re~ardance of the latter.
Platinum complexes are also used a~ cataly~ts in certain
hydrosilation processes although such catalysts are not
necessary for the practice o~ the prese~t invention. A~
flame retarding additive~, however, there may be
utilized the reaction product of chloroplatinic acid and
organosilicon compounds a~ described in U.S. Patent No.
3,220,972. Another platinum compound is seen in U.S.
Patent No. 3 "75,452 de~cribing platinum-containing
polyorganosiloxanes. Other fire retardants are
compounds based on elemen~ary red phosphorous compounds,
other phosphorou~ compounds, halogen~, antimony oxide~,
iron oxides, zinc oxides and the likeO
~)39~
37- 337-2181 (8CT-490~)
Preferably, component A, A-l, A~2, A-3 or A-4
comprise3 from 1 to 99 parts by weight and component B
co~prises from 99 to 1 part by weight per 100 parts by
weight of A, A-l, A-2, A 3 or A-4 and B combined.
S Modifier composition (B) is comprised of from 1 to 99
part~ by weight of componen~ (1) and from 99 to 1 part
by weight of component (2) based upon 100 parts by
weight of tB).
When the polyphasic resin composition
comprises the preferred embodi~en~ of mixture (~
comprising (i) a polycarbonate resin phase and (ii) a
saturated polyester re3i~ pha~e and modifier composition
(B) compri5ing two polyorganosiloxane/polyvinyl-based
graft polymers, in combination, component (Aol)
pre~erably co~prise~ from about 99 to about 37 parts by
weight and component (B) comprises from about 1 to about
63 part~ by weight per 100 parts by weight of (A-l) and
(B) tog~the~.
In general, the first stage comprising the
polyorganosiloxane-based polymer subs~rate, ~he diene
rubber-ba~ed polymer subctrate or the co-homopolymerized
polyorganosiloxane/polyvinyl-ba~ed substrate each will
independently comprise approximately 5 to 95 weight
percent of the correponding to~al graft polymer ba~ed
upon the weight of the first stage and the subsequent
stage or stages taken together. Pr~ferably the first
stage will comprise approximately 30 to 90 weight
percent on the same ba~is. Correspondingly, the
subsequent stage~, comprising the additional grafted
vinyl polymers, will comprise approximately 95 to 5
weight percent and preferably approximately 70 to 10
weight percent on the same basis. In the multi-stage
systems, preferably9 the ratio o~ fir~t s~age substrate
(l)(a) and/or (2)(a) to second stage polymer (b)~
10:90 to 90:10 and the amoun~ of third stage polymer
3~3~
-38- 337-2181 (8CT-4905)
(b)(ii) co~prises ~rom about 10 to about 90 parts by
weight of (l)(a) and/or (2)~a), (b)(i) and (b)(iij
combined~
Subsequent stages (l)(b) and 12)(b) may differ
in the selection of monomeric units which comprise the
polymers or may di~fer in the ratio of ~he same
monomeric units in each of ~he sub~equent stages to each
other which comprise the polymer~.
The amount of polymerized or copolymerized
(meth3acrylonitrile units in the outermost stage of each
of the component~, (1) and (2) of modifier composition
(B) based upon the weight o~ the corresponding outermost
stage will determine into which phase of the resin blend
the particular graft polymer will be induced to migrate
lS and finally to segregate. For example, in a modified
(PC)/(PBT) blend, it is believed that such segregation
i3 dictated by the interfacial energy variation~ ~etween
the modifiers and the resins comprising the blend, with
~he co~ponents having outermo~t stages wi~h higher
levels of polymerized or copolymerized (meth)acrylonitrile
migrating to the more brit~le PBT ph~se and the
components havins outermost stages with either no or low
levels of tmeth)acrylonitrile migrating to the PC phase.
Therefore, by varying the a~ount of polymerized or
copolymerized (meth)acrylonitrile in the outermost ~tage
of the components of a multi-component modifier,
portions of the modifier can be distributed in each
phase of the blend re~ulting in two or more phases of
the blend being simultaneously modified. As a result,
improved impact modi~cation and particularly superior
low temperature toughness and lower ductile/brittle
transition of multi-phase blends is aocompli~hed by this
dual-phase modifica~ion aR compared to blends having
modifiers in only one resin phase. Additionally, the
X~3~35
_39- 337-2181 (8CT-49n5)
proce~sing difficultie~ associated with melt gra~ing
chemistry are eliminated.
Preferably, the content of polymerized or
copolymerized (meth)acrylonitrile units in ~he outermost
stage of multi-stage composition (1) range~ from 0 ~o
les~ than about 20 percent by weight of that outermost
stage, and the content of polymerized or copolymerized
(meth)acrylonitrile uni~s in the outermost stage of
multi-stage compositlon (2) range~ upwardly from greater
than abou~ 20 percent by weight of that outermost stage.
Most preferably, the conten~ of polymerized or
copolymerized (meth)acrylonitrile units in the outermost
stage of multi-stage oomposition (1) rangas from 0 to
about 5 percent by weight of that outermost stage, and
the content of polymerized or copolymeri~ed (me~h)-
acrylonitrile units in the outermost ~tage of mul~i-
stage composition (2) ranges upwardly from greater than
about 25 percent by weight of that outermo~t stage.
It is believed that in a polypha~ic re~in
composition comprised of (A~ i) a polycarbona~e resin
phase and (ii) a saturated polye~ter resin phase,
incorporation of a major fraction of the modi~ier in the
more brittle PBT phase is important in aehieving maxi~um
low temperature toughness.
D~SCRIPT~O~ OF T~ PREF2RR~D ~BODI~ENTS
~he following examples illustrate the
invention without-limita~ion. All part~ are given by
weight unle~s otherwise indicated. Impact strengths are
reported as notched Izod (NI) according to ASTM D-256 at
room temperature (23C) unle~s otherwise ~pecifled and
as Charpy NI in a falling weight test~ Weld line
strenqth (DG) i~ measured on one-eighth inch unno~ched
Izod bars molded in a double-ga~ed mold. Ten~ile
propertie~ are measured by ~STM D-638 as Tensile Yield
Strength, Tensile Break Strength, Tensile Modulus,
~39~ 5
-40- 337-2181 ~8CT-4905)
Elongation at Yield and Elongation at Break. 5urface
gloss, 60, is measured by ASTM D-523 7 and Delta
Yellowness Index is measuced by yellowne s index
increase after aging for 96 hours at 125C.
A single slash is used between monomers of a
single stage, and a double slash or a hyphen is used as
a shorthand method of indicating separa~ion between
stages. The first stage to be polymerized is written
first before the double slash or hyphen, and subsequent
~tages are written subsequently.
~A~PLX 1
A well mixed dry blend of 50 parts of
polycarbona~e (Lexan~ 141), 40 par~ of saturated
polye~ter (Valox- 315), 0.9 part of a s~abilizer
package, 2.5 parts of a CSiM modifier ((~i/P5)-MMA wt.
ratio of 70:30, 5i/PS wt. ra~io of 95:5) and 7,5 parts
o~ a C5iM modifier ((Si/PS)-S/AN w~. ra~io of 70:30,
Si/PS wt. ratio of ~5:5, S/A~ w~. ratio o~ 75:25) is
extruded on a Welding Engineers twin screw extruder
operating at 400 rpm (65 gm/min) with barrel zones se~
at 250, 375, 510 r 510 ~ 510 and 510Fo Tensile and
notched Izod bars are molded in a Boy injection molding
machine at 280C. A sample is also thermally aged at
120C for 168 ho~rs. Tests on both aged and non-aged
sample~ are conducted according to the above methods.
Segregation o the two CSiM modi~ier~ i~ illustrated in
FIG. 1. The C9iM modi~ier ((Si/PS)-MMA wt. ratio of
70:30~ S~PS wt. ratio of 95:5~ (5) appears a~ separate
particles in the polycarbonate (1) phase of the
PC(l)/PBT(3) blend, and the CSiM modifier ((8i/PS)-S/AN
wt. ratio of 70~30, SijPS wt. ra'~io of 95:5, S~AN wt.
ratio of 75:25) (7) appears in the PBT (3) phase o~ the
PC(l)/P8T~3) blend of the non-aged sample. Properties
are summarized in Table 1.
~3~3~35
-41- 337-2181 (8CT 4905)
CO~ARA~
The procedure of Example 1 i~ followed
substituting a dry blend of 50 parts of polycarbonate
(Lexan 1~13, 40 parts of sa~urated polyester (Yalox
315), 0.9 part o~ a stabilizer package and 10 par~s of
a CSiM modifier ((Si/PS~-S/AN wt. ratio of 70~30 7 Si/PS
Wto ratio o~ 95.5, S~A~ Wto ratio of 75:253. FI~. 2
illustrates the complete segr~gation of the CSiM
modifier ((Si/PS)-S/AN wt. ratio of 70 30, Si/PS wt.
ratio of 95:5, S/AN wt. ratio of 7S:25) t7) in the
PBT(3) phase of the PC(1)/PBT(3) blend of the non-aged
sample. Properties are summarized in Table 1.
co~
The procedure of Example 1 i~ followed
substituting a dry blend of 50 parts of polycarbo~ate
(hexan- 141), 40 parts of sa~urated polyester (Valox
315), 0.9 part of a stabilizer packa~e, and 10 parts of
a CSi~ modifier ((Si/PS)-~A wt. ratio of 70:30, Si/P5
wt. ratio of 95:5). Thermal aging is carried out at
~0 90C for 96 hours. FIG~ 3 illustrate3 the compl~te
seqregation of the CSiM modi~ier ((Si/PS~-M~A, wt. ratio
of 70:30, Si/PS wt. ratio of 95:5) (5) in the PC(l)
phase of the PC~l)/PBT(31 blend of the non-aged sampl2.
Properties are summarized in Table 1.
ISD~LI~ 2
T~e procedure of Example 1 i5 followed
substi~uting a dry blend of 50 parts of polycarbonate
(Lexan 141), 40 part~ of ~aturated polyester (Valox
315), 0.9 part of a stabilizer package, 7.5 parts of a
CSiM modifier ((Si/PS)-MM~/A~ wt. ratio of 70:30, SiJP5
wt. ratio of 95:5, M~A/AN wt. ratio of 75:25) and 2.5
parts of a CSiM modifier ((Si/PS)~MMA Wto ratio o
70:30, Si/PS wt. ratio of 95:5~. Properties are
summarized in Table 1.
3~
-42- 337~2181 (8CT-4905)
~PAaATrV~ ~a~P~ 2~*
__ ~__
The procedure of Example 1 is followed
sub~tituting a dry blend of 50 parts of polycarbonate
(Lexan~ 141), 40 parts of satura~ed polyester (Valox-
315), Q.9 par~ of a stabilizez package, and 10 parts of
a CSiM ((Si/PS)-M~A/AN Wto ratio of 70:30, Si/PS wt.
ratio of 9;:5, MMA/AN wt. ratio of 75:25). FIG. 4
illustrates ~he comple~e segregation of the CSiM
modifier ((5i/P~)MMA/AN wt. ratio of 70:30, Si/PS w~
ratio of 95:5, MMA/AN wt. ratio of 75:25) i~ the PBT(3)
phase of the PC(l)/PB~(3) blend of the non-aged sa~ple.
Propertie~ are summarized in ~able 1.
~ ~ L~ 3
The procedure of ~xample 1 is followed
substituting a dry blend of 50 parts of polycarbonate
(Lexan~ 141), 40 parts of saturat~d polye~er (Yalo~
315), 0.9 part of a stabilizer package, 7.5 parts of a
CSiM modifier ((Si/PS)-M~A/~N wt. ratio of 7n:30, Si/PS
wt. ratio of 95:5, MMA/~N wt- ratio of 75:25) and 2O5
parts of a CSiM modifier ~(S1/PS)-M~/AN wt. ratio of
70:30, Si/PS wt. ratio of 95:5, M~A/A~ wt. ratio of
95:5). Prop~rtie~ are su~marized in Table 1.
CO ARATIVB ~ PL~ 3A*
The procedure of Example 1 i~ followed
substituting a dry blend of 50 parts of polycarbonate
lLexan 141), 40 parts of saturated polyester (Valox-
315), 0.9 part of a stabilizer package, and 10 parts of
a CSiN (~Si/PS)-M~h/~N wt. ratio of 70:30~ Si~PS wt.
ratio o~ 95:5, MMA/AN wt. ratio of 95:5). FIG. 5
illustrate~ the co~plete segregation of the CSiM
~odifier ((Si/PS)MMA/AN wt. ratio of 70:30, Si/P~ wt.
ratio of 95:5, M~A~l wt. ratio of 95:5~ (ll) in the
PC~l) phase of the PC(l)/PBT(3) blend of ~he non-aged
sample. Properties are sum~arized in Table 1.
':
3~5
-43- 337-2181 (8CT-4905)
Inspection of Table 1 below shows that the
polyphasic resin blends of Examples 1, 2 and 3, which
have CSiM modifier in both re~in phases, have
significantly lower ductile/bri~tle transition, i.e.
-~5C, than Comparative Examples lA*, 1~*, 2A* and 3~*
which have modifier in only one resin phase. The dual-
phase modified blend~ achieve optimum levels of
toughening, particularly at low temperature , as is seen
by the impact s~rengths of Example~ 1, 2 and 3 when
compared wi~h the Comparative Examples a~ ~30C and
lowerO The incorporation of a major portion of the
impact modifier in the more brittle P8T phase appears to
be ~mportant in achieving maximum low temperature
toughness, again as illustrated by E~amples 1, 2 and 3.
Figure~ 1, 3 and 5 show that when li~tle or no (meth)-
acrylonitrile units are present in the ou~ermost stage
of a component tha~ the modifier compon*nt segregates in
the polycarbonate pha~e of the PC/PBT blend~ Figures 1,
2 and 4 show that when higher amounts, such as at least
25 percent by weight, of (me~h)acrylonitrile units are
pre~ent in the outermost stage of the modifier
component, the modifier component segregates in the PBT
phase of the PC/P3T blend.
~1[33~35
_~4_ 337-2181 (8C~-490S)
1 o c~ a~ o 0 ^ r~ ~ O
~1 o cn u~ ~ o o
U~ ~ I I s ~ n o I 1~ a~ c o ~ I
_, _
t~
. ~ 1 o o ~ o a~ ~ o u~
æ
z
u~ ~
ml o o ~ O ~ o
_ _ _
t- _ ~
~~ o o al o '~
Z ~ u~ ~r . ,~ I I I ~ I ~ ~ I ~ u~ I r~ 1` ~ o
~2 O ~ _ U~
~e
o
P~
r~ O O a~
u u c~
a. -- O ~ O .~ _ O ~ _ O
- ~ o u o ~ o ~ ~ c~ o
~ o ~ ~ ~ ~ 9 0 ~ ~ ~ ~ 9 r~7
.C ~ o ~ o ~ _I ~ ~ o ~ o ~ ~
c ~ ~ ~ 0
.8 ~U N e ~
ILI ~ ~ 0 J Ll ~ ~3 i V ~ U U U ~ Ll aa
U ~ s ,~ ~ ~n o In ~ U~
~1 O O ~ U~
P~U t.~ U i'~
~1)3~35
-45~ 337-2181 (8CT-4905)
TABLE 1 (Cont'd)
:~ r
A - Lexan~ 141, poly(bisphenol-~ carbonate), General
Electric Company
B - Valox~ 315, poly(l,4-butylene ~erephthalate),
General Electric Company
C - (Si/PS)-S/AN wt. ratio of 70:30, Si/PS wt~ ratio o~
95:5, 5/AN wt. ratio of 75:25
D - (Si~PS)-M~A wt. ratio of 70:30, Si/PS wt. ratio of
9s:5
- (Si/PS~-MMA/AN wt. ratio of 70:30, 5i/PS wt. ratio
of 95:5, MMA/AN wt. ratio of 95:5
F - (Si/PS)-MMA/AN wt. ratio o~ 70O30~ Si/PS wt. ratio
of 95.5, M~A/AN w~. ratio o 75~25
;~3~3~
46- 337-2181 (8CT-4905)
~r~KP~B ~
A dry blend of 50 par~s of polycarbo~a~e
(Lexan~ 141), 40 parts of saturate~ polye~ter .(Valox
315), 0.9 part of a stabilizer package, 5 parts of a
butadiene rubber substrate~S~MMA outermost stage
modifier (Acryloid ~-653) and 5 parts of a high rubber
graft ABS modifier (A-B-S wt. ratio of 7.5:70:~2.5 - U.S.
Pa~ent No. 4,753,986) i5 compounded via a ~ingle pas~
extrusion process at 500F on a Welding Engineers twin
screw e~truder, pelletized, and molded. Segregation of
these two modifiers is illustrated in FIG. 6. The
~M-653 (13) modifier with no acrylonitrile in the
outermost stage appears in the PC(l) phase and the ABS
modifier (15) appears in the PBT ~3) phase of the
PC(l)/PBT(3) blend.
C} ~
The procedure of Example 4 i~ followed
substituting a dry blend of 15 part~ of polycarbonate
(Lexan- 141), 70 parts of saturated polyester (Valox~
315), 0.9 part of a ~tabilizer packag~, a~d 15 parts of
a butadiene rubber substrate-S/MMA outer~o~t stage
modi~ier (Acryloid~ 653). FIG. 7 illustrates the
segregation of the modifier (13) in th~ PC(ll of the
PC(l)/PBT(3) blend.
~SA~L~ 5
.
The procedure of Example 1 is followed
~ub~tituting a dry blend of 5U parts of polycarbonate
resin tLex~n- 141~ 40 part~ of saturat~d polye~ter
re~in (Valox~ 315), 2.5 parS~ of a CSiM modifier
(tSi/PS)-MMA wt. ra~io of 70:30 7 Si/PS wt. ratio of
95:5) and 7.5 parts of a CSiM modifier ((Si/PS)-S/AN wt.
ratio of 70:30, Si/PS wt. ra~io of g5:5, 9/AN wt. ratio
of 75:25). A composi~ion will be formed in accordance
with the appended claims.
,
;~ ' ,
-47- 337-2181 (8CT-4905
~A~P~ 6
The procedure of Example 1 i~ followed
substituting a dry blend of 50 parts of polycarbonate
re3in (Lexan~ 141), 40 parts of sa~urated polye~ter
resin (Valox~ 315), 7.5 parts of a CSiM modifier
((Si/P5)-MMA/AN wt. ratio of 70:30, Si/PS wt. ratio of
95:5, MMA/~ wt. ratio of 75:25) and 2~5 parts of a CSi~
modifier ((Si/PS)-MMA w~. ratio of 70:30, Si/PS wt.
ratio of 95:5). A co~position will be for~ed in
accordance with the appended claim~.
e~anPLe 7
The procedure of Example 1 is followed
~ubstituting a dry blend of 50 parts of polycarbonate
resin (Lexan- 141), 40 part3 of saturated polyester
lS resin (Valox 315), 7.5 parts of a CSiM modifier
((Si/PS)-MM~/~N wt. ratio of 70:30, Si/PS wt. ratio of
95:5, MMA/A~ wt. ratio of 75:25) and 2.5 parts of a CSiM
modifier ~(Si/PS)-M~A/~N w~. ratio of 70:30, Si/PS w~.
ra~io of 95:5~ MMA/A~ wt. ratio of 9S:5). A co~position
will be formed in accordance with the append~d claims.
The procedure of Example 1 is followed
substitu~ing a dry blend of 45 parts of saturated
polye~ter re~in (Valox~ 315), 30 parts of polyphenylene
ether resin (PPE) (vacuum vented, 14 parts of poly-
carbonate re~in (HILEX~, poly~bi~phenol-A carbonate),
General Electric Company), 2.5 parts of a CSiM modifier
~(Sl/PS)-MMA wt. ratio of 70:30, Si~PS wt~ ratio of
95:5) and 7.5 parts of a CSi~ modifier ~(Si/~5)-S/~N wt.
ratio of 70:30, Si/PS wto ratio of 95:5, S/AN wt. ratio
of 75:25). A composition will be ~or~ed in accordance
with th~ appended claimQ.
~3~ 5
-~8- 337 2181 (8CT-4905
ex~e 9
The procedure of ~xample 1 is followed
substituting a dry blend of 46 parts o saturated
polyester resin (Valox 315) 9 30 parts of polyphenylene
ether re~in (vacuum vented), 14 parts of polycarbonate
resin (~I~EXQ), 7.5 parts of a C~i~ modifier ((Si/PS)-
MMA/AN wt. ratio of 70:30, Si/PS wt~ ratio of 95:5,
MMA/AN wto ratio of 75:25) and 2.5 parts of CSiM
modifier ((Si/P~)-MMA wt. ratio of 70:30, Si/PS wt.
ratio of 95:5). A composition will be formed in
accordance with the appended claim~. -
~a~pL~ 10
The procedure of Example 1 i~ followed
substituting a dry blend of 46 parts of saturated
polye~ter re~in (Valox~ 315), 30 parts of polyphenylene
ether resin (vacuum vented~, 14 parts of polycarbonate
resin (~ILEX~)~ 7.5 parts of a CSiM modifier ((Si/PS)-
M~A/AN wt. ratio of 70:30, Si/P5 Wto ratio of 95:5,
MMA/AN w~. ratio o~ 75:25) and 2.5 pa~tR of a CSiM
modifier ((Si/PS)-MMA/AN wt. ra~io of 70~30, Si/PS wt.
ratio of 95:5, MMA/AN w~. ratio of 95:5). A composition
will be formed in accordance wi~h the appended claims.
PROCED~R~ A
Genera~ Procedure ~or Sili~one
Graft Copolymer (GSiM) Synthesis
(Si-S~AN wt. ratio of 72:28, S/AN wt. r~tio of 75:25)
To deionized water, 400 par~s, containing 1.33
parts of dodecylbenzenesulfonic acid dissolved therein,
i~ added a mixture comprising 90 parts o~ octamethyl-
cyclote~rasiloxane, 5 part~ of tetravinyltetramethyl-
cyclotetrasiloxane, 5.5 parts of vinyltriethoxy3ilane,
1.7 parts of tetrae~hoxysilane, 1043 parts of gamma-
methacryloxypropyltrimethoxysila~e, 0.67 part of
divinylbenzene and 0.093 part of a platinum catalyst
;;
.
3~
-49- 337-2181 (8C~-~905)
(Silicone Product No. 88034). The emulsion is
homogenized by passing twice through a homogenizer at a
pressure of 7600 to 8600 psi. The emulsion is then
stored for 5 hours at 75C and cooled for 13 hours
overnight. The silicone emulsion is then neutralized to
p~ 7.S by adding 5 parts of 15 percent aqueous potassium
carbonate solution. The silicone rubber ha~ a yield of
about 83.5 percen~, a gel content of about 71.3 percent
and a 14.6 degree of swelling. The ~ol fraction
possesses a Mw/Mn of 48,600/19,700 mea~ured by gel
permeation chromatography against polystyrene standards.
To the core latex is then graft polymerized a 75/25
mixture of styrene/acrylonitrile for 6 hours at 75C
which is persulfate initiated. The polymer~ are then
lS isolated by coagulation and vacuum dried at 65C
resulting in a silicone-3tyrene/acrylonitrile weight
ratio of 72:28 ba~ed on ~inal conversion. The S/A~
graft efficiency is 25 percent~
P~DC8DoR~ B
General Procedure for Silioone/Polys~yrene
Gr a f t Copolymer (CSiM) Synthesis
((Sl/PS)-S/AN wt. ratio of 70:30,
5/AN wt ratio of 75 25)
To 40Q parts of deionized water containing
1.33 parts o~ dodecylbenzene~ulfonic acid dissolved
~harein is admixed an organic mixture comprising 90
parts of oc~amethylcyclotetrasiloxane, 10 parts of
tetravinyltetramethylcyclotetra~iloxane, 1.7 part~ of
tetraethoxy~ilane, 1.43 par~s of gamma~methacryloxypropyl-
trimethoxy~ilane, O.C97 part o~ a platinum catalyst
301ution, 33.3 parts of styrene and 0.67 part of
divinylbenzene. The mixture is stirred and ~hen
homogenized twice under an impinging pre~sure of about
8000 psi. ~he crude emul~ion is then polymerized at
75C for 6 hours followed by overnight cooling down to
~039~
-50- 337 2181 (8CT-4905)
room temperature. A potassium persulfate solution (0.17
part in 8.17 parts deionized waterJ i~ added over the
first four hours at 75C as a styrene polymerization
initiator. The silicone/polystyrene substrate emulsion
is then quenched by neutralization from p~ 1.7 to 8.1
_ following an optional addition of 0.67 part of GAFAC
RE610 which is predissolved in 6 parts o~ deionized
water. The silicone/polystyrene rubber ha~ a
polymerization yield of 87.3 percent, a mean diameter of
230 nm, a gel content of 78 percent and 13.6 degree of
swelling. To the substra~e latex is grafted polymerized
a 75/25 S~AN mixture for a total of 6 hours at 75C
u~ing potassium persulfate a~ the initiator. The
substrate to S/AN weight ratio is 70:30, and the second
stage graft efficiency is measured at 60 percent usin~
methyl ethyl ketone Soxhlet extraction.
PRCClCDaR~ C
CSiM ((Si/BA)-S/AN wt. ratio of 70:30,
S/AN wt. ratio of 75lZ5~ Slo~he~i~
Procedure B i~ ~ollowed substituting butyl
acrylate (3A~ for styrene a^~ the vinyl-based polymer
component of the substrate latex.
PROC~D~ D
General Procedure for Sllicone/Polystyrene-
BA-S/AN Grat Copolymer (CSiM) Synthe~is
((Si/PS)-BA-S/AN wt. ratio of 35:3~:30,
S/AN wt. ratio of 75:25)
rhe procedure of Procedure B i3 repeated to
produce the silicone/polystyrene first stage substrate.
~owever, at the second stage, to the silicone/polystyrene
latex is added one stream containing butyl acrylate,
butylene glycol diacrylate, diallyl maleate, deionized
water and sodiu~ dodecylbenzene sulfonate concurrently
with another aqueous strea~ consi~ting of a water-soluble
X [)3~35
-51- 337-2181 (8GT-4905)
initiator over a period o~ 1 to 3 hours at 75C. The
butyl acrylate to ~he dry silicone/polystyrene subs~rate
weight ratio is aimed a~ 35s35. The S/AN graf~ing
procedure of Procedure B is then repeated as are the
isolation steps.
PROCZ W R~ ~
Procedure ~ i5 followed substituting poly-
styrene for ~tyrene/acrylonitrile copolym~r a~ the graft
stage.
PPOC~DU B ~
Procedure B i~ followed sub~tituting poly-
(~ethyl methacrylatej for styrene/acrylonitrile
copolymer as th~ grat stage.
A dry blend of 39 parts of a ~aturated
polyester resin (poly(1,4-butylene ~erephthalate), P~,
Yalox 315, General ~lectric Company), 45O75 parts o~ a
polycarbonate re~in (poly(bisphenoloA carbonate~, Lexan~
141, General Blectric Company), 7 parts o~ a GSiM
modifier (Si-S/AN wt. ratio of 72:2B, 5/AN wt. ratio of
7S:25) prepared by the method of Procedure A, 7 parts of
a butadiene rubber subs~rate-S/M~A outermo~t stage
modifier ~Acryloid- RH-653, Rohm and ~aa~ Company) and
1.25 par~s of a stabilizer package are tumble mixed to
give a homogeneous powdsr dispersion within the pellets.
The blend is then fed into a Werner Pfleiderer 30 mm
twin screw extruder und~r the following conditionss
2~33~ 5
-5~- 337-2181 (8CT-4905)
Screw Speed 200 ~pm
Throughput Rate 20 lb/hr
zone 1 195C
zone 2 210C
zone 3-5, die 230-250G.
The extrudate is pelletized, dried at 140F
and then Lnjection molded on a 75 ton Newbury molding
mashine. A sample is then ~hermally aged at 125C for
96 hours. ~ests on both aged a~d non-aged samples are
conducted~ Propertie~ are summarized in Table 2.
conpA2~TIv~ E~A~PL~ llA~
The procedure of Example 11 i5 followed
substituting a dry blend of 39 parts of ~aturated
polyester (Valox 315), 45.75 parts of polycarbonate
(Le~an~ 141), 14 parts of a butadiene rubber subs~ra~e-
S/M~A outermost stage modifier (Acryloid R~ 653), and
1.25 parts o~ a stabilizer package. Propertie~ are
summarized in Table 2.
co~pa~ATIvE B8aNpL~ llB~
The procedure of Example 11 i~ followed
substituting a dry blend of 39 parts of saturated
polye~ter (Valox0 315~, 45.75 par~s of polycarbonate
(Lexan~ 141), 14 parts of a GSiM modifier (~i-S/AN wt.
ratio of 72:28, S/AN wt. ratio o 75:25) prepared by the
method of Procedure A and 1.25 parts of a stabilizer
package. Properties are summarized in Table 2.
~ clearly demon~trated fro~ Table 2 below,
only the example containing bo~h the diene-ba~ed
modifier and the G5iM modifier in combination ~Example
11) exhibit~ uniformly good phy~ical propertie ,
possessing good impact re~istance, low temperature
- . :
;. .
~3~
-53- 337-2181 (8CT-4905)
ductility, tensile strength, de~irably low gloss, and
re~istance ~o yellowing and property 108~ because of
thermal aging. The blend containing only the diene-based
modifier (Comparative Example 11~*) while exhibiting
good strength related characteristics, exhibits poor
resistance to yellowing and ha~ a high gloss. The blend
containing only the GSiM modifier, (ComparatiYe Example
llB*) doe~ not exhibit good low temperature ductility in
the blends, ha~ poor thermal stability, and is inferior
to the blend combina~ion (Example 111 in most other
respects a-~ well.
~03913~
~54 337-2181 (8CT-4905)
~BLB 2
POLY~ST~/POLYCARBO~T~ G5i~ ~ODIFI~ BL~DS
~a~ple 11 11~ llB~
C01a~08itio!1
Polyester Resin A 39 39 39
Polycarbonate Resin B 45.75 45.754S.75
~-653 C 7 14
GSiM D 7 _ 14
Stabilizess 1~25 1.251~25
Propertie~
60 Gloss, ~ 62.3 96.0 68.3
NI @ R.T. (ft-lbs/in)
.125~
Non-Aged Sample 12.6 12.1 11,4
Thermally Aged Sample 11-0 10.8 3O0
Retention, % 87~3 89.3 26.3
Delta Yellow Index 5.5 18~9 4.9
Cbarpy NI, (ft-lbs/in)
R.~. - 8.1
10C - - 6.1
0C ~.1 8.8 2.8
-10C 7.6 8.0 2.9
-20C 5.1 3.1
-30C 2.7 2.9 2.0
Tensile Strength
Yield, Kpsi 6.7 8.1 6.9
Break 5.6 6.6 6.1
Tensile Modulus
Rpsi 14.9 15.5 14.4
Elongation, %
Yield 7.3 8.6 7.9
Break 42 169 ~9
A - Valox- 315, poly(l,4-butylene terephthalate),
General Electric Company
B - Lexan- 141, poly(bisphenol-A carbonate), General
Electric Company
C - Acryloid- KM-653, butadiene rubber substrate-S/MMA
outermost stage, Roh~ and Haas Co~pany
D - 5i-S/~N wt. ra~io of 72:28, S/AN wt. ratio o 75:25,
Procedure A
~ 3 5
-55- 337-2181 (8CT 49053
~ P~ 12
The procedure of Example 11 is followed
sub~tituti~g a dry blend of 39 parts (780 gram~) of
saturated polye~tel (Valox9 315), 44.75 par~s (895
gram~) of polycarbonate (Lexan9 141)~ 1 part (20 grams)
of polycarbonate (Lexan M~4545, poly(bisphenol-A
carbonate), General Elec~ric Company), 3.5 par~s (70
grams) of a butadiene rubber substrate-S~MMA outermost
stage modifi~r (Acryloid~ RM-653), 10~5 parts (21U
grams) of a CSi~ modifier ((Si/PS)-S/AN w~. ratio o
70s30, S/AN wt- ratio of 75:25~ prepared by the method
of Procedure B, 1 part (20 gram~ of red coloran (Red
624) and 1025 parts (25 gram~) of a stabilizer package.
Properties are ~ummarized in Table 3.
CO~ ~
The procedure of Example 11 i~ followed
substitu~ing a dry blend of 39 par~s (780 gram~) o~
saturated polyestar (Valoxa 315~, 4~.75 parts (895
grams) of polycarbonate (Le~an~ 141), 1 part (20 grams)
of polycarbonate (Lexan~ ML4545), 14 parts (280 gram~) I
of a butadiene rubber substrate-S~MMA outer~o~t stage
modifier (acryloid ~M-653), 1 part (20 gram~) of red
colorant ~Red 624) and 1.25 parts (25 gram~) of a
stabilizer package. Properties are summarized i~ Table
3.
CO~PaR~IY~ ~AXP~ 12B~
The procedure of Example 11 is followed
~ub~tituting a dry blend of 39 part (780 grams) of
saturated polyester (Valox~ 315~, 4~75 par~s (895
grams) of polycarbonate (Lexan4 141), 1 part (20 gram )
of polycarbonate (Lexan~ ML4545), 14 part3 (280 gram~)
of a CSi~ modifier ((Si/PS)-S/AN wt. ratio of 70:30,
S/AN wt. ratio of 75:25) prepared by the method of
Procedure B, 1 part (20 gram~) of red colorant (Red
21~39~35
~56- 337-2181 (8CT-4905)
624) and 1~25 parts (25 gram~1 o~ a stabilizer paekage.
Proper~ies are summarized in Table 3.
~ PLe 13
The procedure of Example 11 is followed
substituting a dry blend of 39 par~ (780 grams) of
saturated polye~ter (Valox~ 315), 44.75 parts (895
grams) of polycarbonate (Lexan~ 141), 1 part (2C grams)
of polycarbonate (Lexan~ M~4545), 7 parts (140 grams) of
a butadiene rubber substrate-S/~M~ outermost stage modi~iar
(Acryloid- RM-653], 7 parts (140 gram~) of a CSiM modifier
~(Si/PS)-S/AN wt. ratio of 70:30, S/AN wt. ratio of
75:25) prepared by the method of Procedure B, 1 part (20
grams) of red colorant (Red 624) and 1.25 parts (25
grams) of a ~tabilizer package. Properties ar~
sum~arized in Table 3.
~PIi~
The procedure of Example ll i8 followe~
substituting a dry blend of 39 parts ( 780 grams ) of
saturated polyester (Valox- 315); 44.75 parts (895
grams) of polycarbonate (Lexan- 141), 1 part (20 grams)
of polycarbo~ate (Lexan~ M~4545), 10~5 parts (210 grams)
of a butadiene rubber substrate-5/MMA outermost stage
modifier (Acryloid~ K~-653), 3.5 parts (70 grams) of a
CSiM modifier ((Si/PS)-S/~N wt~ ratio of 70:30, S/A~ wt.
ra~io of 75:25) prepared by the method of Procedure B, 1
part (20 gra~) of red colorant (Red 624) and 1.25 parts
(25 gra~) of a stabilizer package. Properties are
summarized in Table 3.
A~ can be ~een from Table 3 below, the samples
containing the combi~ed modi~iers exhibit good impac~
resi~tance, appearance and low gloss characteris~cic~.
Comparative Example 12A* containing no C5~1~t, while
Z~3~5
-57- 337-2181 ( 8CT-4905 ~
exhibiting good strength characteris~ics, is glo~sy and
thu~ not useful in de~3ired losq gloss applications.
.
~,
: . . .
.
5~- 337-2181 (8CT-4905)
T~BL~ 3
RED PI~ T~D BL~DS
__ __
Esa~ples 1~ 12A~ 12B~ 13 1~
Polyester A 3~ 39 3~ 39 39
wt% (gms) (780) (780) (780) (780) (780~
Polycarbonate B 44O7S 44.75 44 75 44.75 44.75
w~ (gms) (895) (895) ~895) (~95) (~95)
Polycarbonate C
wt~ (gms~ (20) (20) (20) (20) (20)
RM-65~ D 3 5 14 7 10.5
wt~ (gms) (70) (280) (140~ (21n)
CSiM E 10.5 - 14 7 3,5~
wt~ (gms) (210) (280) (140) (7o)
Red Colorant F
wt~ (gms) (20) (20) (20) (20) (20)
S~abilizers 1.25 1.25 1O25 1.25 1.25
wt~ (g~s) ~25) (25) (~5) (25) ~2~)
ProFerties
DG, ft-lbs/in 20.0 32.2 13.7 24.3 28.6
NI @ R.T.,
ft-lb3/in .125~
Non-Aged Sample13.9 14.1 12.2 13.3 14.4
Thermally Aged
Sample 9.8 12.0 2O9 lI.1 12.3
% Retention 70.5 85~1 23.8 83.5 85.4
Color AppearanceDull Good Dull Good Good
60 Gloss 3593 94.2 27.2 50.7 70r7
A - Valox- 315t poly(l,4-bu~ylene terephthalate), General Electric
Company
a - Lexan- 141, polytbisphenol-A c~rbonate), General Electric
Company
C - Lexan- M~454S, poly(b~sphenol-A carbonate), General Elec~ric
Company
D - Acryloid- KM-653, butadiene rubber substrate-S/MM~ outermos~
stage, Rohm and ~aa3 Company
E - tSi/PS)-S/AN wt. ra~io of 70:33, S/~N wt. ra~io of 75:~5,
Procedure 3
F - Red 624
-59- 337-2181 (8CT-4905)
s
The procedure of Example 12 is followed
sub~ti~uting the CSiM modifier ((5i/BA~-S/AN wt. ratio
Of 70 30 ~ S/AN wto ratio o~ 75O25) prepared by the
method of Procedure C ~or ~he CSiM modifier prepared by
the method o~ Procedure B. A composition will be formed
in accordance with the appended claims,
e~pL~ 1~
The procedure of ~xample 12 is follow~d
substituting the CSiM modifier ((Si/P5~-~A-S/~N wt.
ratio of 35:35:30, S/AN wt~ ratio of 75:25) prepared by
the method of Procedure D for the CSi~ modifier prepa~ed
by the method o~ Procedure B~ A compo~ition will be
formed in accordance with the appended claims.
~ A~L~S 17-19
Example 12 i~ repeat~d three time~ adding
- re~pectively an effective amount of red pho~phorous
flame retardant, an effectiv~ amount of glas~ fiber and
an effective amount o~ both red pho~phorous and glas~
fiber. Compositions will be ~ormed in accordance with
the appended claims.
~PI.~ 20
The procedure of ~xample 12 i8 ~ollowed
sub3tituting the CSiM modi~ier ((Si/PS)-PS wt. ratio of
70:30) prepared by the method of Procedu~e ~ for the
CSiM modifi~r prepared by the method of Procedure B.
composition will b~ formed i~ accordanc~ with the
appended claims.
~S~P~ 2l
The procedure of Example 12 i8 followed
substituting the C5i~ modifier (Si/PS-MMA wt. ratio of
70:30) prepared by the method of Procedure F for the
~3~35
-60- 337-2181 (8CT-4905)
C5iM prepared by the me~hod of Procedure s. A
composition will be formed in accordance wi~h the
appended claim~.
~A~PL~ 22
~he procedure of 2xample 11 is followed,
except dry blending is performed with no polye~ter
re~in. A composition will be formed in accordance with
the appended claims.
In the foregoing examples, the degree o~ ~
swelling can be determined in the ~ollowing fashion:
A prepared polyorganosiloxane ba ed latex i5 '
coagulated by adding it to about four times it~ volume
of methanol and water (lsl volume ratio) containing 1
wt. percent MgSO4. ~he precipita~ed rubber i~ washed
and vacuum-dried a~ 70C overnight. ~pproximately 1 g
of the dry silicone-based rubber i~ immer~ed in 100 ml
of toluene for 20 ~o 24 hour~ at ambient temperature and
allowed to swell. The exce3~ tolu~ne is separated by
decantation. The swelled polymer i~ vacuum-dried at
60C overnight, and the re8ulting polymer i~ weighedO
The degree o swelling is calculated a~: DS ~ ((weight
of swelled polymer) - (weight of dry polymer)) divided
by (weight of dry polymer).
Graft Efficiency can be determined by weighing
dry multi-stage polyorgano~ilo~ane-~a~ed graft polymer
in a weighed thimble which i~ Soxhlet extracted by
acetone for 20 to 22 hours. After vacuu~ drying, the
re~idue of the extraction is weighed. The graft
efficiency is calculated a~: G~ (~) = t(weight of
grafted monomer(s) x 100) divided by ~weigh~ of total
monomer( 8 ) polymerized).
All patent~, applications, publications and
t~st method~ mentioned above are hereby incorporated by
ref~rence.
.
~ ~t~
-61- 337-2181 (8CT-4905)
Many variations of the present invention will
~ugge~t them~elves to those skilled in this art in light
of ~he above, detailed description. For example, the
aromatic polycarbonate can be replaced in whole or in
part wi~h a polye~ter carbonate containing units derived
from bisphenol-~, phosgene and t~rephthaloyl chloride
and/or isophthaloyl chloride. The aromatic polycarbonate
can be replaced in whole or in part by a polycarbonate
containing units of bis(3,5-dimethyl-4-hydroxy
phenyl~-~ulfone, alone or combined with bi~phenol-A. ~he
poly(ethylene terephthalate) can be replaced in whole or
in part by poly(l,4-bu~ylene terephthalate~ or by a
polyester derived from 1,4 cyclohexanedimethanol alone
or combined with ethylene glycol and terephthalic acid
and/or isophthalic acid. Pla inum complexes may be
employed as catalysts in the hydro~ilation process.
Additionally, modifiers tB) compriQi~g four or
more component co~bination~ can be designed such a-q two
different CSiM's, a GSi~ and a diene rubber-based graft
copolymer; two diffe~ent CSiM's and two differen~ diene
rubber-based graft copolymers; two different CSiM9s and
two different GSiM'ss three differen~ CSiM's a~d a
GSiMt three different GSiM's and a CSiM two different
diene rubber-ba~ed graft copolymers, a GSiM and a CSi~;
and the like. All such modifications are within t~e
ull intended scope of the appended claims.
