Note: Descriptions are shown in the official language in which they were submitted.
~ CH-2~24
This invention relates to mineral reinforced,
plasticized polyphenylene ether compositions. ~ore
particularly, it relates to -thermoplastic molding compositions
comprising a polyphenylene ether resin with or withou-t an
impact modifier, a plasticizing amount of a plasticizer, and
a mineral reinforcing agent which provides improved stif~ness
with unexpectedly signiEicant retention of ~uctility.
The polyphenylene ether resins are well known in
the art as a class of thermoplastics which possess a number
of outstan~ing physical properties. They can be prepared,
in general, by oxidative and non-oxidative methods, such
as are disclosed, for example, in Hay, U.SO 3,306,874 dated
; February 28, 1967 and 3,306,875 dated February 28, 1967 and
Stamatoff, U.S. 3,257,357 dated June 21, 1966 and 3,257,358
dated June 21, 1966.
: It is known that the polyphenylene ether resins
can be combined with impact modifiers to obtain improved
impact resistance and other mechanical properties. Suitable
impact modifiers for polyphenylene ether resins are disclosed
in Cizek, U.S. Patent 3,383,435 dated May 14, 1968.
` As employed herein the term "plasticized" is
.~ used to describe compositions having a sufficient amount of
plasticizer to reduce the temperature of optimum extrusion
by at least about 25F., and normally from about 25 t~
about 100~.
It has now been surprisingly discovered that
plasticized polyphenylene ether compositions comprising a
mineral reinforcing agent, possess enhanced stiffness, as
measured by flexural modulus and flexural strength, in
~ .
' ' ~ ' . ' ' '
L~ f~ ~CH-24~
comparison with corresponding compositions withou-t said
agent. Moreover, it was unexpected tha-t the improvements
in stiffness properties were to be obtained along with a
significant retention of ducti.lity, as measured by tensile
elongation and impact resistance.
In its broadest aspects, the present invention
comprises reinforced, plasticized thermoplastic compositions
suitable for molding or shaping, .i..e., by cornpression molding,
extrusion, calendering, and the li.ke, which posses enhanced
stiffness in comparison with the corresponding unreinforced
compositions, the compositions comprising:
(a) a polyphenylene ether resin alone or in
combination with an impact modifier;
(b) a plasticizer therefor in an amount at least
sufficient to raduce the temperature of
optimum extrusion at least about 25F.; and
(c) a mineral reinforcing agent in an amount at
least sufficient to provide enhanced stiffness
in comparison with a corresponding unreinforced
composition.
In general, the polyphenylene ether resins of the
compositions are of the family having structural units of the
formula:
\~ ~\Q /~
wherein the oxygen ether atom of one unit is connected to the
benzene nucleus of the next adjoining unit, n is a positive
.. : , ~ , . :- :
:. ~ - . ., . . .:
~ 8 CH 2~24
integer and is at least 50, and each Q is a monovalent
subs-tituent selected from the group consisting of hydrogen,
halogen, hydrocarbon radicals free of a tertiary alpha-
carbon atom, halohydrocarbon radicals having at least two
carbon atoms between the halogen atom and the phenyl nucleus,
hydrocarbonoxy radicals and halohydrocarbonoxy radicals
having at least two carbon atoms between the halogen atom
and the phenyl nucleus.
Preferably, the polyphenylene ether resins are
selected from those of the above formula wherein each Q is
alkyl, most preferably having from 1 to 4 carbon atoms.
Illustratively, members of this class include (poly(2,6-
dimethyl-1,4-phenylene) ether; poly(2,6-diethyl-1,
4-phenylene)ether; poly(2-methyl-6-ethyl-1,4-phenylene)ether;
poly(2-methyl-6~propyl-1,4-phenylene)ether; poly(2,6-dipropyl-
1,4-phenylene)ether; poly(2-ethyl-6propyl-1,4-phenylene)ether;
and the like.
Especially preferred is poly(2,6-dimethyl-1,4-
phenylene)ether, preferably having an intrinsic viscosity
of about 0.45 deciliters per gram (dl./g.) as measured in
chloroform at 30C.
The preparation of polyphenylene ether resins
corresponding to the above formula is described in the above-
mentioned patents of Hay and Stamatoff.
The choice of a plasticizer is not critical and
any of the conventional materials used for this purpose can
be employed. Preferably, component (b) will be selected from
among phthalate and phosphate plasticizing materials, and
especially phosphate plasticizers.
The phosphate plasticizer is preferably a compound
of the formula:
~ CH-2~24
OR P - ~R
OR
wherein Rl, R2 and R3 are the same or dif~erent and are alkyl,
haloalkyl, cycloalkyl, halocycloalkyl, aryl, haloaryl, alkyl
substituted aryl, haloalkyl substituted aryl, aryl substituted
alkyl, haloaryl substituted alkyl, hydroxyalkyl, hydroxyaryl,
hydroxyalkaryl, halogen and hydrogen.
Examples include cresyl diphenyl phosphate, 2-ethyl-
hexyl diphenyl phosphate, tricresyl phosphate, triiosopropyl-
phenyl phosphate, triphenyl phosphate, triethyl phosphate, di-
butyl phenyl phosphate, diethyl phosphate, cresyl diphenyl
phosphate, isooctyl diphenyl phosphate, tributyl phosphate,
2-ethylhexyl diphenyl phosphate, isodecyl diph~nyl phosphate,
isodecyl dicresyl phosphate, didecyl cresyl phosphate, tri-n-
hexyl phosphate, di-_-octyl phenyl phosphate, di-2-ethyl-hexyl
phenyl and tri-2-ethylhexyl phosphate or mixtures thereof.
Especially preferred are aromatic phQsphates, e.g., triphenyl
phosphate.
Examples of phthalate plasticizers include dibenzyl
phthalate, phenyl cresyl phthalate, diethyl phthalate, dimethyl
2~ phthalate, phenyl benzyl phthalate, butyl benzyl phthalate,
butyl cyclohexyl phthalate, dibutyl phthalate, octyl cresyl -
phthalate, diphenyl phthalate, di-_hexyl phthalate, disohexyl
phthalate, butyl octyl phthalate, butyl decyl phthalate, di-
isooctyl phthalate~ di-2-ethylhexyl phthalatey di-n-octyl
phthalate, diisononyl phthalate, diisodecyl phthalate, di-2-
propyl heptyl phthalate, di-_-nonyl phthalate, di-n-decyl
phthalate and d:itridecyl phthalate.
The pLasticizer (b) is added in amounts which will
. .~l
- 4 -
- - , - .
~ CH 2~24
be sufficient -to provide a plasticized composition within the
meaning of the term described above. In general, the
plasticizer is present in amounts ranging from at leas-t
about 5 parts per hundred par-ts of resinous components
combined, preferably from about 5 to about 100 parts per
hundred parts of resin.
Illustratively, the mineral reinforcement is
selected from among talcs, aluminum silicate, e.g., clay,
hydrated, anhydrous or calcined clay, zinc oxide, titanium
dioxide, antimony oxide, barium sulfate, precipitated or
natural calcium carbonate, zinc sulfide, and the like,
Especially preferred is hydrated aluminum silicate.
Amounts of the mineral reinforcing agent will vary
depending on the formulation and needs of the particular
composition. In preferred compositions, however, the mineral
reinforcement will be present in at least about 5 parts per
hundred parts of resins combined. E~pecially preferred
embodiments will comprise anywhere from about 5 to about
150 parts of mineral reinforcement per hundred parts of resin
plus plasticizer.
The nature of the impact modifiers for the poly-
phenylene ether or polyphenylene ether/polystyrene resin is
not critical and any of the elastomeric polymers and copoly-
mers which are conventionally employed to improve impact
properties in thermoplastic compositions can be used.
Illustratively, the impact modifiers can be selected from
among elastomeric A B-Al block copolymers wherein terminal
blocks A and Al are the same or different and are derived
from a vinyl aromatic compound, e.g., styrene, ~ -methyl
styrene, vinyl toluene, vinyl xylene, vinyl naphthalene, and
the like, and center block B is derived from a conjugated
diene, e.g., butadlene, isoprene, 1,3-pentadiene, 2,3-dimethyl
::
- 5 -
8 CFL 2424
butadiene, and the like.
These can be made by an organometallic initiated
polymeri2ation process using, for example, sodium or l:ithium
metal or an organic derivative thereof. The diene monomers
can be polymerized with a monofunc-tional or difunctional
initiator, as is described in Kennedy et al, Interscience
Publishers, Vol. 23, Part II (lg69), pages 553-559. Other
methods of preparation are described in Zelinski, U.S.
3,~51,905 dated May 17, 1966 and Flolden et al, U.S.
3,231,635 dated January ~5, 1966.
The relative ratios of the polymer units in the
A-B-A block copolymers can vary broadly. It is preferred
that the center block B have a molecular weight greater than
that of the combined terminal blocks, however, to obtain
optimum impact strength and solvent resistance. In general,
the molecular weight of each of the respective terminal
blocks will range from about 2,000 to about 100,000 and the
molecular weight of the center block will range from about
65,000 to about 1,000,000.
20 A Examples include the Kraton~resins, commercially
available from Shell Chemical Co., Polymers Division, e.g.,
K-1101 (polystyrene-polybutadiene-polystyrene), K-110~ (poly
styrene-polybutadiene-polystyrene), and K-1107 (polystyrene-
polyisoprene~polystyrene).
The hydrogenated A-B-Al block copolymers are also
well known. In general, these are block copolymers of the
A-B-Al type in which terminal blocks A and Al are the same
or different and, prior to hydrogenation, comprise
homopolymers or copolymers derived from vinyl aromatic
hydrocarbons and, especially, vinyl aromatics wherein the
aromatic moiety can be either monocyclic or polycyclic.
Examples of the monomers are styrene, ~ - methyl styrene,
.
~ 3~ CH-242~
vinyl xylene, e-thyl vinyl xylene, vinyl naphthalene, and
the like. Center block B will always be derived from a
conjugated diene, e.g., butadiene, isoprene, 1,3-pentadiene,
and the like. Preferably, center block B wil be comprised
of polybutadiene or polyisoprene.
The preparation of hydrogenated A-B-A1 block copoly-
mers is described in Jones, U.S. Patent 3,431,323 dated
March 4, 1969.
Examples include the Kraton GTM resins, commercially
available from Shell Chemical Co., Polymers Division, e.g.,
G-GXT-0650, ~-GXT-0772, G-GXT-0782 and G-6521.
Radial teleblock copolymers of a vinyl aromatic
comound, a conjugated diene and a coupling are also suitable
impact modifiers for the compositions of this invention.
These are branched polymers having segments, or blocks,
; comprised of a conjugated diene polymer, and a vinyl aromatic
polymer, together with a coupling agent, wherein in the
copolymer structure chains of the diene polymer radiate
outwards from a coupling agent, each chain terminating at
its other end with a block of the vinyl aromatic polymer.
The radial teleblock copolymers are known in the
art. They are described in ADHESIVES AGE, December, 1971,
pages 15-20 and RUBBER WORLD, ~anuary, 1973, pages 27-32.
The preparation of these copolymers is described in
Zelinski et al, U.S. Patent 3,281,383 dated October 25,
1966.
~xamples of commercially available radial teleblock
copolymers are t:he SolpreneTM resins of Phillips Petroleum
Company designat:ed as Solprene 406 (containing about 60 parts
by welght of but:adiene units and about 40 parts by weight
of styrene unit~;), Solprene 411 (containing about 70 parts
by weight~ of butadiene units and about 30 parts by weight of
- 7 -
,~ ~ J
~ 5~ 8 C~ 2~2~
styrene units), Solprene ~14 (con-talning about 60 parts
by weight oE butadiene units and about 40 parts by weight
of styrene units), Solprene 417 (containing about 20 parts
by weight of butadiene units and about 80 parts by weight
of styrene units), and S411P (containing about 70 parts
by weight of butadiene units and about 30 parts by weight
of styrene units). These materials also include a relatively
minor amount of coupling agent, e.g., less than 1 part by
weight of coupling agent per 100 parts of polymer.
Also included are hydrogenated radial teleblock
copolymers of a vinyl aromatic compound, a conjugated diene
and a coupling agent, such as Solprene 512, commercially
available from Phillips Petroleum Co.
The impact modifier can also be selected from
acrylic resin modified diene rubber containing resins.
Preferably, these will be of the group consisting of a
resinous composition of a poly(alkylene methacrylate) grafted
on to a butadiene-styrene copolymer backbone or an acrylonitrile-
butadiene-styrene terpolymer backbone, or a resinous composition
of a mixture of a poly(alklmethacrylate) and a butadiene-
styrene copolymer or an acrylonitrile-butadiene-styrene
terpolymer.
A preferred commercially available impact modifier
A of this type is Acryloid KM611, sold by Rohm and Haas Co.,
which is an acrylic/styrene/styrene-butadiene terpolymer.
: The aforementioned acrylic resin modified
elastomers can be prepared by well known techniques, such as
those described in U.S. 2,943,074 dated June 28, 1960 and
U.S. 2,857,360 dated October 21, 1958.
The impact modifier can also be a graft .:
copolymer of a vinyl aromatic compound and a diene, prefer-
ably comprising from about 75 to about 10~ by weight of a
: -
- 8 -
'
~ 8 CH 2424
vinyl aromatic monomer and from about 25 to about 90%
by weight o-f a conjugated diene. By way of illustration,
the aromatic monomer can be selected from among styrene,
. ~3
-methyl styrene, vinyl toluene, vinyl xylene, and the likQ,
and the diene can be selected from among butadiene, iso~rene,
and the like. Graft copolymers of styrene and styrene-
butadiene are preferred.
An example of a preferred commercially available
~ graft copolymer is Blendex 525, sold by Marbon Chemical Co.
The compositions of this invention can be prepared
by conventional methods. Preferably, each of the ingredients
is added as part of a blend premix, and the blend is passed
through an extruder at an extrusion temperature of from
about 500 to about 625F., dependent on the needs of the
particular composition~ The strands emerging from the
extruder may be cooled, chopped into pellets, and molded or
other wise worked to any desired shape.
The following examples are illustrative of the
compositions of this invention. They are not to be
construed as limiting the invention to the particular
embodiments shown therein. All parts are by weight.
Units for the properties shown in the following
Examples are as follows, unless otherwise indicated:
Tensile yield, psi
- Tensile break, psi
Tensile elongation, %
Flexural modulus, psi
Flexural strength, psi
Melt viscosity, at 540 F., 1500 sec , poise
Gloss, 45 surface gloss, dimensionless units
~UL-94- Underwriters Laboratories Bulletin
~94, sec/sec.
_ g _
~ 8 C~I 2424
Izod Impact strength, ft.lbs./in.n.
Gardner Impact strength, in.lbs.
Heat distortion tempe:rature, F.
Coefficient of Linear Thermal Expansion (CLTE),
in/in F., measured f:rom -30C. to 65C.
EXM~PLES 1 - 4
Self-extinguishing, plasticized blends of 78 parts
of poly(2,6-dimethyl-1,4-phenylene ether) resin, intrinsic
viscosity about 0.45 deciliters/gram as measured in
chloroform at 30C., 22 parts of triphenyl phosphate flame
retardant plasticizer, 5 parts of styrene-butadiene-styrene
block copolymer (Kraton 1101, Shell Chemical Co., Polymers
Division), 1.5 parts of poly-ethylene and 20 parts of various
mineral reinforcing agents, as shown, are compounded and
extruded at a temperature of 580F. The extrudate is
.
chopped into pellets, molded into test bars at a temperature
of about 520 F., and evaluated for mechanical and flame
resistance properties. For purposes of comparison, a blend
of the same ingredients in the same amounts is prepared, but
without a filler. The mineral reinforcements and test
results are shown in Table 1.
'
~ .
- -- 10 --
~ o ~ s~
8 CH 2424
I ~ ~ I I o
~ ~ . I
:~ ~ ,-
U CO~
o U~
U
C~
U o o
~ o o
~ ,~
~1 ~ ~ ~1
hU~
Xtl~ O . O
L~ ~ O o
00 1 1 ~
O C~l O
~1
,
S~C~
~ C~
H~1 ~ 0~
N O ~I t~ 1
~1 C
~3 ~ o
O ~D ~ U~ r~ , ....
O
,o, C) o ~ rl O O
a ~ o
E~ ~ ~
5~ h
~ U O O
a) .
; E~ ~ r~ t ~ ~5 n tJ
~ . ~
~ ~ ~ ' ~
;
~5~
` 8 C~ 2~24
EXAMPLES 5 - LO
Self-extinguish:ing, plasti.cized compositons of
78 parts of poly(2,6-dimethyl-1,4-phenylene ether), 22
parts of triphenyl phosphate flame retardant plasticizer,
5 parts of styrene-butadiene-styrene block copolymer
(Shell's Kraton 1101), 1.'; parts of polyethylene and a clay
~iller (Al-Sil Ate NCF, Freeport Kaolin CoO) in the amounts
shown are prepared and molded as in Examples 1-4. The
_ 10 physical properties are summarized in Table 2.
', .
,~ -
.: . .
. ~.-` .
: .
: I
: i
.~j ' .
. . . :: . .
: . : .. -- - ' :
.- - - - .
- , . . . -: . :
, . . . , : . . :, . :
-. , , .:, - :
. . .: . . ,.
,.,,. .:: . - . .. :: . .. :: . : .: .
8 CH 242 4
C) o C~ o
,~
X X I X I I ~C
~) o ~ o~ ~o
I~
. ~ o
U~
n
~D ~ I~ ~J r~
. ~
o o o ~ o o
o o o o o o
)J O ~D ~ ~ 0
~a u~ ~ u~
~:1 ~
:~ o o o o o o
o o o o o o
ro o C~ o o o o
o
C`J ~ ~ r~
O G~ I` ~ ~ h
1:: N
al , ,,, .c u
C~ O
U~ C~l O ~U~ U) ~ ~ U~
N C`l C`l r I
V C~) r~
~ ~ .'
~ ~J OU~ ~ ~ 1` 0
1~ N O 1~C~ o 1 3
H r-l ~
C~
c o ul ~ o ct~ ~ oo c`l o
E~ ri ~ ~
w v)
,~ h c
~) o o o C~ o o o U~
u~ Q) ~ C~
c
~ ~ ~ a~ o c~
E-~ r~ r-l ~:1 X
C ~
:: ~ O O ~ O O O O C r-l
r-J O O O O O O O ~U
a~ ~ I r-l t~1 1~ C~ 4
0~ t:~ O O r-l C~ 00
r-l r-l r~ 5:
' ~E-~
r~ ~
U ~d
~o~
rl ~ ~ ~ U~ ~
~ ~ ~ 0 01.'~ C O ^ ~- ~
: ~: ,~ ~ u~ ~ h o
,~ ' U~ ` o ~;~, ):4
~ ~ D O U~ QJ :
_ r~ r~
~ r-l rl ~1 U
~ ~ ~ : C O ~ r~ :
~ C 4
: ~:
~ : ~ O ~r~ O
~ ,
. u~ ~ r~ cx:) cr~ o ¢
:~: ~ r-l r~
: ~ ` . .. -. .: - . ` : ' :
8 CH 2424
It is shown that even with amounts of reinforcement
as high as 67 phr (40%), in Example 9, a signi~icant amount
of ductility, as measured by tensile elongation and impact
strength, is retained as compared with the unreinforced
control (lOA ).
EXAMPLES~ 13
Blends of poly(2,6~di:methyl-1,4 phenylene ether)
resin, mineral oil, styrene-butadiene-styrene block
copolymer (Kraton 1101), polyethylene and a clay reinforcing
~iller are compounded, extruded and molded as in Examples
1-4. The formulations and physical properties are
summarized in Table 3.
TABLE 3
EXAMPLE 11 ll_* 12 13 13A*
Ingredients (parts by weight)
poly(2,6-dimethyl-1,4-
phenylene ether) 78 78 78 85 85
mineral oil (Kaydol) 22 22 22 15 15
styrene-butadiene-styrene
block copolymer
(Kraton 1101) 5 5 5 5 5 ' ''
polyethylene 1.5 1.5 1.5 1.5 1.5
~ clay reinforcing agent
: (NCF, Freeport Kaolin) 25 -- 43 43 --
~ -- _______ ____ ________
,~ * control
~ EXAMPLE 11 llA* 12 13 13A*
'~ Proper'ties
Tensile yield 8,500 9,100 8,500 11,400 10,900
Tensile strength
at break ~ 8,400 8,000 8,400 11,400 9,700
Tensile elongation 39 52 24 71 60
3a
Izod impact : 3.5 7.4 2.4 2.0 5.8 '
Gardner impact 163 282 I22 42 272
'
~ : 14
.~
, . .
. . : . . :. . - :
8 CH 2424
TABLE 3 continued
EXMAPLE 11 llA* 12 13 13A*
Flexural modulus 457l000 312,000 547,000 608,000 350,000
Flexural strength 13l600 12,50014,30018,00014,700
Heat Distortion Temp. 232 230 241 267 253
_ _
* control
EXAMPLES 14 - 19
.
Blends of 78 parts of poly(2,6-dimethyl-1,4-phenylene
ether) resin, 22 parts of triphenyl phosphate flame retardant
plasticizer, 1.5 parts of polyethylene, 0.5 parts of tridecyl
phosphite, 0.15 parts of ~inc sulfide, 0.15 parts of zinc
oxide, 43 parts of a clay reinforcing filler (NCF, Freeport
Kaolin) and various impact modifiers and amounts, as shown,
- ~ I are compounded, extruded and molded as in Examples 1-4.
The physical properties are_summarized in Table 4.
.
' '
;~
.~ .,
,,.., ,~ ,1
~ ~'', , ,
, . . .
, ' ,
".,~1
.
-:
- -, .: ~:
-. :' :, :. ., .. . : , .:
.. . .. -,: , . , , , . , ~ .
. .
., , ~ , . .
., ~
.:
- .. ., : :
- :, .. , , ~ ., :
- .- .: , :. , . ~ ,,
,, . -:, ,
-. ~- ' . , :
:: : : ,
~g~ 7~ ~C~1~242~
o o o o o o
o o o o o o
o 1~ In
u~
Ln Ln
~1 ~ ~ ~ ~ ~
o o o o o o
. o o o o o o
o o o o o o
~ O
h :~~~o o In ~ n
n n n In In ~
L~ O In In
o ~ oo cn ~ cs~
h
~ ~ 0
H N ~ 1 tN ~1 ~i
~ ~ ~ O ~ ~9
O ~In In ~ ~ ~
a) x O O O O O O
~1 0 o o o o o o
.,1Q~ g ~ ~ co
h
~r ~a: ~ ~ O cO O~ cS
E~
~ ~ o o o
~q ~ o o o o o o
~C ~ n oo ~ o o o . -
E~ " ~ ~ ~ o m
O ~ O
,I cr~ o o ~ ~
h
~n a) .
~ ~ O
a~ ~c)
e~ -
~ 0 U~ O
a) ~ I ~I o
au ~rl h0~ h O o O Sl !
rl (~ Drl tl) Ut a) 1 ~ ~I CJ a) ~ E~
~ e ~ e r~ - 0 RS a)
h rd :~ ~ ~ 0 :~ ra a) ~ a) ~ o ~ V
0 ~ r-l~ r l~ r l ~ 1 ~ ~I r l ~i O e
rl ~ O Q O ~ O Y ~1 ~ O ~ V ~
~1 Q ~ e o ~
~1 I Oa, o I o ~ O ~ . ~ ~ o
r~ a~ 1 0 0 t) e ~ Q
o ~ rl ~rl rd a~ V ~ S-l
) ~ o s:~ ~r-l ~ ~1 ~ ,5:~ r~
S~ O ~ ~ h G) >~ L~ ~ V --1 r 1
~) ~1 0 ~ O ~ O r~ ~rl r-¦~1 ~ tCi r~
U ~ r-l1q r l~ r~ ~ O ~ r~
tCiU~ Q QU~ ~ ~al Q~ a) r~ Lt)
~ u, ~ o I (L) ~ a) u~
1-1 ~ r~ ~ d
,L~ ~d r-l ~rl ~C
O f~ ) r-l Ln r-l r~
~O ~) ~O r l ~) a) L~ ~1 O ~D ~ .C~
Ln ~ r~Lf`) IR Ln ~ Q L~ tQ e Lt~ O Q r-l S-l O
r-l ~ ~) r-l
~ ~ ~ m
a)
r-l ~D ~I t5~ ,S:~ .
~ ~ Ln ~ I~ CO ~
1~ r I--I r-l r I r-l r-l
X
~, - 16 -
.
. ~ .
8 CH 2424
EX~MPLES 20 - 38
Blends of 78 parts of poly (2,6-dimethyl-1,
4-phenylene ether), 22 parts of triphenyl phosphate, 5
parts of acrylic-styrene-styrene-butadiene terpolymer
(Acryloid KM 611, Rohm & ~aas Co.), 1.5 parts of
- polyethylene, 0.5 parts of tridecyl phosphite, 0.15 parts
of zinc sulfide, 0.15 parts of zinc oxide and 43 parts of
various mineral reinforcin.g agents are compounded, extruded
. and molded as in Examples 1-4. The mineral reinforcements
and test results are summarized in Tables 5, 5A and 5B.
.~ I
~. .
- .
. . j .
, :
:?
'`"`':` '
. I
., '~ , .
:' - ,, .' . , ,' `', ' ' . . ,, . ' ~ ' ~ '
- - .
. ,- ' - ~ ~ , ' . , : ' ' :
: . . : . : : .
: ~
- ~ ~ .......... , . : .
- . . :- .
, ' . '. : . ~ ~:
: ~ . . .. '
- . : ~ : -: ' , ',
: .
- : : . . . .
.: - ' - ' . ' :
8CH-242D,
~ ~t_
E~ o
~ N ~) u~
C5~ aJ \ ~ \ ~ \ \ \
. ~ . . .
r~,
OOOOOOoo
O O O O O O OO
S-l ~ 0~ o~I oCO
U:~ ~ ~ ~ ~ L~lL' ) W ~1
r~ r~ r~ ~r~
X O O O O O O OO
tl) OOOOOOOO
,_1 ~ OOOOOOOO
I~J O
r-l r-l O ~D 00 0 t`l~`
L~ r l 1~~9 ~rr-l
~ ~t~L') IS~L'~ ~D(`')
O O
r-l r-l O
S~
~ ~S ~ O OO rC~ ~
,~ r ~ o O A
s~ ~ ,~ `3 ~ Q
dUl
u~
u a) a~
~ ,~
~1 O ~ o ~ ~ o,,~
N . . . . . . . ~) r~l
H O r l 1` r-l ~r-lr~ 1 0 r-l ~
Lr~ ~ (1~ C)
~ rd
~ ~ ~ D O $ ~
~ o
r~ ~ rl
~ rl Q~
~1 rl
~I) ~ U
,~ ~ oooooooo a)s~
rl ~ OOOOOOOO S~ ~
ul a) 0~ ~9 ,-, ,-1 ~g ~ ~ co Q, O -
~ S~ ~ O C~ O
a) 1~ ~ ~` co C5~ co~;o ~ oo ~ O C) ~)
E~ 0
O ~ ~ rl
~-rlr~.~
oooooooo ,~IO~1
r-l OOOOOOOO ~Ur~lO(~O
a)~ ~ o ~ C) O O (~ K 11~
,1 `` ` ` ` ` ` ` O S~ ~ ~ K
t~ oo o o o ,~ ~ ~ ~3 K
o ~
~ ~n s~ o ~ o
,1 r~ U~ O ~ a~
S~
td ~ O ~
s~ ~ ~ a) 0 ~ 14 h
,~ A
,~ s~ ~ X ,1 ~ ` o O ~
~ U ~ n S~Z
~ ~ o~
rl rl El ~ r l ~3
,) rl ~ ~ ~ 1 O _5 ~r~lr~
,1 ~1 ~) (d a~ (~ rd ~Z; S-l^rl-rl rl rl rl-rl
O ~) R A u~
O
U o
a~ ~
rt I'C
o ~1 ~ 9
~C
- 1 8
. ~ . . .
~ ~ ~ 8 CH 2424
i~ ~ ~
O ~ O
C,) ~ o ~
C~ ,C) o
' s~a
D N~ E3
IC ~d ~1
O ~D ~ C~l C`l C`l C~ ~ a i3
.~ o o o o o o
.,~ ~ o o o o o o o~ o ~ .
C O ~ ;b h
~ ~:q ~
¢ ' ~ V C~ o
~1 O O O O O O O N
~sl r-l O O O O O O
Q~ ~ co a~ o ~ C~
.. ^ ^ 5-1 ~ N N Q)
~ ~ P~
- G o ~ ~ c,~ ,C ~ ~ a
- ~ ~ C~ h ~ ~
cd td ~ $
: ~ ~ ~ C) t.) U
,( E3 E E e ~ a) ~ u~
5~ ~ Z
c) ~ o ~ e
~1 ~1~1 ~ ~ td ~ O O O
~ ~d ~ rl ~r~
, ~
C~ J C~ ~ ~ o ~ ~:
X'
~: ~: ~ ~ :
k~
:
.
.
:
. .
-- 19 --
. : :
. . .
. : . . . ~
$~ 8 CH 2424
.
o o o c o o o
o o O o c~
I n ~ ~ r~ a~
o
O o o o o c~ O
~C O o O O o C~ o
a~ o o o o o c~ o
O u~ ~ ~ ~ o
c~ r~ oo
C
a) u
C
~3 ~ o o o o c~ o~
u~
c~ a
u
e N C`~ O ~1 0
0~
C
O U~ O ~ I~ ~ C`l C`~
~1 ~ U) C~ l O
~ . ~ .
,_1 ,~ O ~ O O O O O
~rl t~ O O O O O O O
O~ ~ ~ r~
C h
~CJ ~ r~ ~0 1~ C~ c.~ c~ r~ O
u~ E~ c7
o o o o o o o ,~ ''' '
~ ~ O o o o o o O
¢ a) u~ o c~ r~ o O O O
E~ ~r~
a~ co a~ a~ ~ o r~
~J O
u~ O
. ~ . ,~
a~ o 0
5~ U
O H
S'l ~1 ^ U bl)
aJ ~ ~ ~ ~ 0
,_1 ~ ~; ~ (~ r ,~.
h ~ ,, ¢ ~I c~ 0
~l ~ ~ ~ ~ ~ o ~~
r~ J ~ 0 ~ ~ o 5~ A O ~ u~
'~: O~
~ : : '
~L ~
E~ ~ ~ ~ ul ~ r~ r~ ~ u ~ 3
~` - 0 ~ ~ ~ ~ ~ ~ ~ ~.
:
~: :
: ~
~ :: : :
:
- 20
: ' ' ~ ' : ~' '` ` ' ''
8 CH 2424
EXAMPLES_38 - 43
Molded compositions of poly(2,6-dimethyl-1,
4-phenylene ether) resin, triphenyl phosphate and various
mineral reinforcing agents, as shown, are prepared as in
Examples 1-4 and evaluated for physical properties. The
Formulations and physical properties are summarized in
Tables 6 and 6A, respectively.
;
.
- .,, ~ .
~, . .... , :: : - .
.
''
,
8 CH 2424
o
'~1 ~ ,~ o
~1 ~ r~ o
o~ o
CJ`I In U~ O ~ ` ~
:
o
~D ~ ~ ~ ~ I I
.
.
': :
~,~
a) . ~ .
::
~: ,Q
{n I ~
~1 U ~ _~ 0
h .C aJ
1~ t~ .C O
~ P ~.~
`'1: _ ~J ~ O
: X ~ ~ ~ O
~ Cl~ .,~ p, ~,1
. ~ ro a~
I S~
~rl ~ C
C`J ?~ O
'~ ~ aJ 0 ~ 0 C~
~: O ~ h ~
~: : p, `~ ~ u ~ N
' ~ : ` ` :
:: : i
:
22
: :
J1~ 8 CH 2424
C
t~ o o o o o o
,cn u~ u~ CO ~ ~ C
~,~ ~"
U~ U~ U~ ~ I~
V~
O o I C~l I ;t
C~
o o o o o o
o o o o o o
h G~ O C~ ~ i` oo
,-i U
X O O O' o O C)
a~ o o o o o o
O O O O O O
O .~
.~ ~; ~ oo o Ln r~ o
~3 h
~ ~ O O C ~ C O
¢ S~ r-~ ~ O C~ O ~J
E-l ~ C~)
t~
o ~ o ~ o
O O O r-i o ,-i
'.
::
- ,~ ~ ~ ~ ~ r~
: ,~
,,~ .Y
U) ~ O O O O O O
, ~ ~ ~ O O O O O O
o s~ r~ 1~
oo ), o~a~ oo co
;: ~ O O O O O O
~ O O O O O O
O O ~ O O O
: ~
n
~ c~) G~ O ~ CN
:: ~ W ~ ~ ~ `~ ~ ~ . -
:~ ~ : ' , ~,
. .
- 2 3 - .
:
: :
,, . . , , . .. . -
:
~ ~5174 ~ CH 2424
EXAMPLES 44-48
_
Molded compositions of poly(2,6-dimethyl-1,
4-phenylene ether), triphenyl phosphate, mineral reinforcing
agents and impact modiflerc; are prepared as in Examples 1-4.
The formulations and physical properties are shown in
Tables 7 and 7A, respectively.
~.. ".. , . :, - : , -
, : ~
. .
:., ::
~ ; ,: ,, , : ~
':
8 CH ~. ~ 2 '1
.
col o~ r-l O Ln
t~ r-l I Ln
:
. .
r~l ~ ~ o Ln
.:
~ l Ln Ln O Ln
~t I Ln r~
.
L~ Ln Ln
Ln r-~ I O Ln
~ . ~ l Ln n o Ln
~ ` I~ ~ I Ln ~I r~
'. ~ .
~1
~: r,l~
. 3
7~ ~ ~ r~
r,~l i ~ 1 ~ 3
r~ r,~ r
rl~ ~; o p- ~a.) ~ r~ r~
~ P J_~ C L~ C Cl O ~r-l ~I r,~
cr ~ a) IJ O Xa~
~ E3 Q~ .C O
W u~ ~ r~ r,~ r,/~ L) U
JJ ~ ~ ~.L) O ~ rl) ~ ¢
C ~ r ~ rJl Q 1-1 .. 0 ~~ E;
~ O ~ l ~
^ ~C) rJ Ln C) ~ ~ O
'a ~ ~ r,,, C~l ~r~
~U _~ ~ ,L~ r~ 0 Q) Lr~ r--J Cl E3
~i >~ r~ p,~' r,~
, ~ O P~ SJ ~ rl ~\ ~r~ a) O t~ U O r--l
H p~ a ~ ~ r,~
' "'
~:` '': '
, ' : '
' ~:
.
-- 25 --
:, ::
.,
,~, ....... , . . , .`. . . ..
:,
- : : :, : : .
,, : . .
.gJ~'7.~-~
8CH-2424
~r
~ ooooo
,1
~ . ~
4~ ooIoo
~ ~ N N N N
a u
~E~
U~
u~ oIn u~
o
~I ~IO o [` o
C~ ~ ~
oO O O O
OO O U~ O
5-1 ~r`CO N n
~1 ~ ~ ~ ~ ~ ~
ooooo
a) ooooo
~1 ~ ooooo
o
u~
~ s~
~1 rd ~ N N N ~)
E-~ ~ ~1 ~ N N r-l
O
td
H o l ~ Ou~co
N
H ~Ir~r~
:
: ~
~ In O ~ Ul
O
,~ : .
: :
~: ooooO
~: ooooo
~1 O N ~ r~ ~ N
~: rl~ I
u~ m co ~
~ o o o o o
~I 0 0 0 0 0
a~ ~ ~ ~ ,~ ,_ ,,
rl ~ ~ ~ ~ ~
: ~ ~ ~ 0~ CO OD 00
.-
Q
X
:
-- 2 6
~:
~: . . . .. :: . , . : -
~i4 8 CFL 2424
EXAMPLES 49 - 50
Blends of poly (2,6-dimethyl-1, 4-phenylene ether)
resin, triphenyl phosphate, clay (NCF, Freeport Kaolin),
a styrene-butadiene-styrene block copolymer (Kraton 1101),
polyethylene, tridecyl phosphite, zinc sulfide and zinc oxide
are compounded, extruded and molded as in Rxamples 1-4. The
molded compositions are evaluated for physical properties,
initially, after heat aging and after water immersion. The
10 formulations and test results are summarized in Tables
8, 8A, 8B and 8C.
TABLE 8
EXAMPLE _ 5
Ingredients (parts by weight)
poly(2,6-dimethyl-1,4-
phenylene ether) 55 67
triphenyl phosphate 15 13
styrene-butadiene-styrene,~
block copolymer (B~e~/~ilOl) 5 5
t~ra~
~ clay 30 20
polyethylene 1.5 1.5
tridecyl phosphate 0.5 0.5
zinc sulfide 0.15 0.15
zinc oxide 0.15 0.15
:
27 -
- ~ 4 8 CH 2424
TABLE 8A. Initial Physical Properties
EXAMPLE 49 50
Properties
Tensile yield, psi 73 F 9,360 9,120
150F. 6,770 6,370
Elongation, ~73 F. 41 68
150 F. 39 58
Flexural Strength, psi73 F. 13,900 12,700
150F. 8,400 8,200
Flexural Modulus, psi73 F. 558,900 419,600
150 F.446,000 353,000
Notched Izod impact, O
ft.lbs./in. 73 F. 3.3 8.6
-40 F. 0.8 1.1
Gardner impact, in.lbs. 73F. 83 252
-40 F~ 10 45
~ - 28 -
8CH 2424
_ _ _ __
o ~ ~ ~ ~r
~; ~n ~r o
. ~ ~ ~ I CO ~D CO 0
~ O
'n . o
~ ;- ~1 ~ OO OOOO
5~n ~ ra o o o o o o
~~ ~ ~ ~r co I r~ c~ o cr
. E~
O ~
n
o o o o o o
oo oooo
0 ~ ~r ~ I o~ oo o
,1
tJ ~ o~ ~ o
~:
~ ~ 0~
~~d o~ooo~o
~1. ~; ~ ~
s~ _ . .
~ . ~ u~In cn ~ r~ o
~U~ I ~ In r~1 ~ cn ~ N
. H ~
O ~ ,~
:
~ :
,~ . a
u~ ~? .,1 ~ ooooooo
o U~ ~ ooooooo
: 'n ~ a) ~ ~ ~ I~ o
P~~D a~ s~ ~
~ E~ ~ co oo co co ~ ., ,; -.
ai
o~
. . ~ ooooooo
. ~ ooooooo
~ a) ~r In O ~O t~
E~ ~ ~ 1
4~ :: '
~ ~d O ~ o o ~ o o
~;~ ~ . ~ -~
a
; ~ ~ : : :,
.... . ..
: '
29 - .
.
-: ~ . `, , - , ~ . . ,
. .
8 CH 2424
_____ _
.
c~ I~ ~ c~
W ~ 00o~ 00 '
H ~O `J ~ ~ C~lC`l C`l
C
O ~ ~ C`~
r-l ~D ~ I C~l C~l r~ ~i
_ aJ ,~ O O C~ O O O
n ~1 ~ o o o o o o
~ u~ ~ r~ n c~ ~
C:
~~:q CO oo ~ o cr~ C~l
~ E~ ~
o o o o o o
o o o o o o
a3 ~ o c~l ~o
,~
~ ~ a~ o ~ ,~ ~c~l
.
C ou~ .
o . ~ o ~ o o t~ C~ o
_, Z
~ ~ . -
:, CJ I~ O ~ ~ ~ O 0~
w ~ ~-1 o c~ '
E ~17 ~ ~ ~o u~ In In
.
. ~
: o o~ o ~ ~J ~ o In
~ ~ n u~ ~
~: ~
: C.~ - ~ V o o o o o o o
r~ _ O O ~ O O O O
n u~ a. I ~ ~ o ~ ,1 In
~o C~ ~ ..
,GJ ~ C~
U
~ o o o o o o o
i~ o o ~o o o o o
~1 ~D CO 1~ ~ ~ ,-1
: ?~ o~ c~ O ,_~
'
: O
. r ~ ~ O
~ ~ ~ ~ ~ C~ CO
_ ~.. _ . __ _.
~ Ln ~ ":
: ~ ~ W~
`:: :
-- 3 0 -- ` i
::
,, ~ ':: .. ...... . ..... . . . . .
.
r~.~f~L 8 C~T 2~2al
'
;
O
N , , , ,
u ~ E
~ b~
~r c ~ o ~ ~ I~
,~: .
1~
E ~
a ,~ ~ O O O O O O O O
,, ~ O O O O O O O O
~n ~ ~ a~ - I` co ~ ~ ~ a~
. ,
~ ~~ 00 1~1~ 1~ CO CO ~ r~
~ C
~ O OO O O O O O
a~ ~ o oo o o o c) o
~1 ~ ~ O
U ~ ~
O
. ~
. ~ P,, ~
. ~ ~ . '
~rl ~ O OO O O O ~ O
o ~
~' I ~
. X
~:~ ' ~ : . ':'
_ ,
:. .. .
.,
:: :
- 31 -
~L 3l~ 8 CH 2424
~ l
.
o
N CL ~ ~/ ~cO , ,
-~ E oo ~ ~ ~~ ~ ~ ~
. .
0~ ~ ) ~ ~ 'O ct~ r~
'~
a~ v O O O O O O O O
O.,1 aJ r~ u~ o ~-1 ~ ~
C~ p:~ oo^ CO^ CO~ ^ CO ''
C~ o o o o o o o o
: ~ ~ o o o o o o, o o
~ . ~ ~ ~
O~ o o .'
' .
. :~
~ : , .
.~ O O O o O o ~ C~ O
'~ ~ . .
Z;
o _ , .... __.
e
W
:
~: . :
.
:
- 3 2 -
~ 7~ 8 CH 2~2~
Obviously, other modifications and variations
of the present invention are possible in the light of the
above teachings. It is therefore, to be understood that
changes may be made in the particular embodiments described
above which are within the full intended scope of the
invention as defined in the appended c].aims.
. .
- 33 - :
:
,' ' ', ' .~ -. ' ' :' ' ' -, ~ , ,. . :
