Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
104V779
BACKaROUND OF THE INVENTION
. Fleld of the Inventlon
Thls lnventlon relates to rllled polymer~ and
more partlcularly to hlghly-rilled polyolefln compoeites,
and processe~ ror maklng these co~posltes and rormed ob~ecte
thererrom.
2. Deecrlptlon Or the Prlor Art
The utlllty Or organlc polymer~ has been broadened
ln reeent years to the degree that rlgld polymers such as the
nylons, A~S (acrylonltrlle/butadlene/styrene) and polyacetal
reslne have begun to replace the more conventlonal metal,
wood and eeramlc materlals. The lo~er cost Or polyolerlns
euch as polyethylene could make them candldates for a ~ider
range Or applleatlons lf certaln propertles such as heat
de neetlon te-perature, ~tlrrne-- and hardne-- eould be
lmprored.
Mueh reeeareh hae been dlreeted to~ard method~
; Or lmprorlng theee propertlee, moetly by fllllng polyolerlne
wlth rlnely-dlvlded sollds or ribrous ~lller. The addltl~n
ao Or rlllers to polyolerlns also serves to extend the use Or
,' polyolerlne.
One method Or preparlng a rllled polyole~ln 18 by
melt blendlng the polyolerln and ~lller. m le proeedure,
however, requlres that the polyolerln have a relatlvely low
moleeular welght, ror exa~ple, an lnherent vlseoslty Or
about ~ or less. Whlle the stlrrness Or the resultlng
prodUCtB 18 generally increased, these product6 typically
surrer from the disadvantQges of having a low elongation,
e.g., less than about 15~, and being brittle, e.g., havlng
a 0F Izod i~pact strength below about 0.75 ft lb/ln of notch.
t~'
i - 2 - ~
104~)779
Moreover, serlous problems are encountered durlng compound-
lng o~ these proaucts, includlng large po~er requirements
ror mixlng machlnery, degradatlon Or the polymer by heat,
nonunlformlty Or the rlller dlsperslon, and poor adheslon
of polymer to filler, even when "coupllng compounds" are
employed.
In order to avoid the problems encountered wlth these
melt blended products, varlous attempt~ have been ~ade to pre-
pare fllled polyoleflns wlthout compoundlng the polyolefln
L0 and the flller, the most wldely used such method belng poly-
merlzatlon of the olefin in the presence of selected flllers.
Most of the sugge~ted methods involve the use of coordina-
tlon catalysts. mese well-known catalysts are comblnatlons
of a compound Or a transltlon metal Or aroup IV A, V A or Vl A
Or the Perlodlc Table and a reduclng compound, for example,
an alkylalumlnum compound or, more broadly, an organo-
metalllc compound of a metal Or Group I, II or III of the
Perlodlc Table.
mese methods of formlng polyole~ln ln the
!0 presence Or flller, ln general ho~ever, have not provlded
the deslred toughness for hlghly-filled polyole~ln composl-
tlons. Although O-F Izod lmpact strengths a8 hlgh as about
1 ~t lb/ln of notch and elongations at break as hlgh a8
about 50% may be obtalned at 30~ flller in some cases,
these value~ drop off signiflcantly at hlgher flller con-
tents. For e~ample, at about 50~ flller the 0F Izod im-
~ I pact strength Or these ~ame compositlons ~ould be or the
;` order of only about 0.1 ft lb/ln of notch and the
elongatlon at break would be of the order of only about l~.
-- 3 --
1()4~79
SUMMARY OF THE INVENTION
The present lnventlon provldes a solld, homo-
geneous, partlculate, hlghly-rllled polyole~n composlte
~hlch can be molded to rormed artlcles Or superlor
toughness, stlrfness and hardness ~lthout any rurther com-
poundlng ~lth bulk polyolerln. me composlte comprlse~
(a) about 10-70% by ~eight Or polyolerln having an
lnherent vlscoslty Or at least about 4 selected
rom the group conslstlng Or homopolymers of l-
alkenes of 2 to about 10 carbon~ and copolymers
o~ l-alkenes o~ 2 to about lO carbons ~lth each
other, and
(b) about 30-90% by ~elght Or rlnely-dlvlded
lnorganic rlller compound havlng a neutral-to-
acldlc surrace and a ~elght-average equlvalent
spherlcal partlcle dlameter o~ about 0.1-50 ~,
and having lnteracted at lts surrace surrlclent
catalytlcally-actlve transltion metal compound to
provide about 0.000001-1.7 millimole o~ transi-
tion metal per gram o~ flller,
d d polyolefln being polymerized onto the surrace Or sald
flller, and sald composlte having a lO-~econd micronization
homogeneity Or at lesst about 50~ and a micronizatlon homo-
geneity lnde~ of at least about 20.
The composltes o~ thi~ invention are made by
varlouJ proccsses. One method ~hlch involves the u~e or
.` tltanla-contalnlng alumlnum sillcate clays comprises
(A) dehvdrating rlnely-dlvlded aluminum silicate clay
- selected rrom the group conslstlng Or kaolinlte~
~ 30 attapulglte, and ruller~s earth, and containing
.~0~077~
at least about 0 05% by ~elght Or tltania, sald clay
h-vlng a ~elght-average equivalent spherlcal partlcle
diameter Or about 0 1-50 ~, and belng free Or pro-
~- motion wlth added transltlon metal coordlnatlon
catalyst component, by heatlng at a temperature of
about 400-1400C to reduce the water Or hydration to
I less than one mole of ~ater per mole Or alumlnum
~llicate;
(B) dl~persing
(l) at least about l welght/volume percent Or rlnely-
~lvided lnorganlc Plller compound, sald rlller
belng
(a) about 70-lO0~ by ~elght o~ sald dehydrated
alumlnum slllcate clay, and
(b) 0 to about 30% by ~elght Or plgmentary oxlde
~elected ~rom the group conslstlng o~
tltanla, zinc o~lde, antlmony oxlde and
mlxtures thereor, sald plgmentary oxlde
havlng a ~elght-average egulvalent spherlcal
partlcle dlameter le~s than that Or the
clay, and
(2) bout 0.001-l 0 mllllmole, per gram Or filler,
Or organoalumlnum compound selected rrom the
group consl~tlng Or trlalkylalumlnums, dlalkyl-
aluminum hydrldes, dialkylalumlnum alkoxldes,
alkylalumlnum halides and polymerlc hydro-
carbylalumlnums ln ~hlch the alkyl groups,
allke or di~rerent, have l to about lO carbons
; each,
ln an lnert, llquld hydrocarbon dlluent;
-- 5 --
1()4~'779
(C) contactlng the resultlng dlsperslon wlth olefln
selected from the group conslstlng o~ l-alkenes
Or 2 to about 10 carbons and ml~tures thereo~ ~lth
agltation at a temperature Or about 0-250-C and a
pressure ~rom about atmospherlc to about 500 atmos-
pheres untll a composlte contalnlng about 10-70~ by
: ~elght, based on the polyole~ln and flller, Or
polyole~ln havlng an lnherent vlscoslty Or at
least about 4 is formed; and
(D) lsolating the re~ultlng po}yole n n/rlller composlte
as a ~ree-flowlng po~der.
Another method of preparlng the composltes Or this
lnventlon lnvolvlng the pretreatment or the ~lller wlth a
hydrolyzable titanlum compound comprlses
(A) contacting a ~lnely-dlvlded lnorganlc ~lller compound
havlng a neutral-~o-acldlc ourrace and a ~elght-
aver-ge equlvalent spherlcal particle dlameter Or
about 0.1-50 ~ ~lth surriclent hydrolyzable tltanlum
compound to provlde about 0.000001-1.7 mlllimole,
.20 per gram o~ flller, o~ tltanium lnteracted at the
surface Or the rlller;
(B) removlng unadsorbed tltanium compound ~rom the
~lller;
(C) hydrolyzlng the adsorbed titanlum compound;
(D) activatlng the tltanlum-treated flller by heatlng
at a temperature of at least about 100C to rorm a
. l tltania-modlfled flller;
(E) dl6perslng
(l) at lea~t about 1 ~elght/volume percent of flnely-
divlded lnorganlc flller compound, sald flller
104~779
belng
(~) about 70-lO0~ by welght Or sald tltanla-
modlrled nller, and
(b) 0 to about 30~ by weight Or pigmentary oxlde
~hlch is not tltanla-modirled, sald pigmentary
oxide belng selected ~rom the group confflsting
Or tltanla, zlnc oxide, antlmony oxide and
mlxtures thereof and having a ~elght-avera~e
equlvalent spherlcal partlcle dlameter less
than that of sald tltanla-modl~ied flller;
(2) about 0.001-1.0 mllllmole, per gram Or rlller,
or organoaluminum compound selected from the
group con~lsting Or trlalkyl~ m~num~, dlalkyl-
alumlnum hydrldes, dlalkylalu~inum alko~ides,
alkylalumlnum halldes and polymerlc hydro-
; carbylaluainums ln whlch the alk~l group~,
allke or dirrerent, have l to about lO carbons
each,
ln an lnert, llquid hydrocarbon dlluent;
20 (F) contactlng the resultlng dl~perslon wlth olerln
selected ~rom the group consistlng Or l-alkenes
. ~ Or 2 to about 10 carbons and mlxture~ thereor wlth
agltatlon at a temperature Or about 0-250-C and a
pre~sure rrom about atmo~pherlc to about 500 atmo~-
; phere~ untll a compo~ite containlng about 10-70
by welght, based on the polyole nn and rlller~
; o~ polyole~ln havlng an lnherent vlscoslty Or at
least about 4 1~ rormed; and
(~) lsolating the resultlng polyole~ln/~lller composlte
as a ~ree- nowlng powder.
-- 7 --
104~77g
Another method Or preparlng the composltes of
~ thls lnventlon involvlng the u~e Or a hydrocRrbon-soluble
- organic transltion metal compound ln whlch the organo-
alumlnum compound 18 prereacted wlth the flller comprlses
(A) dlsper~lng
(1) at least about 1 welght/volume percent Or
~-nely-d~vided lnorganic rlller compound
having a neutral-to-acld~c sur~ace and a
~elght-average equivalent spherlcal particle
dlameter Or about 0.1-50 ~, and
: (2) about 0.001-1.0 mllllmole, per gram Or rlller,
o~ organoalum~num compound selected rrom the
group conslsting Or trlalkylalu~$nums, dl-
alkylalumlnum hydrides, dlalkylalumlntlm
alkoxldes, alkylalumlnum halldes and polymerlc
hydrocarbylalumlnums ln whlch the alkyl groups,
allke or dlrrerent, have 1-10 carbons each,
in ~n lnert, llquia hydrocarbon dlluent;
(B) addln~ to the resultlng dlsperslon about 0.00001-
0.05 mllllmole, per gram Or flller, o~ catalytlcally
actlve, hydrocarbon-soluble organic transltlon
metal compound, sald transltlon metal compound being
present ln an amount su~rlclent to provlde a mole
ratlo of organoalumlnum compound to transitlon
metal ¢ompound Or about 1000 1 to about 4:1;
(C) contactlng the resulting dlspersion ~lth olerin
selected rrom the group consisting Or l-alkenes
Or 2 to about 10 carbons and mixtures thereo~ ~ith
agitatlon at a temperature Or about 0-100C and a
pressure ~rom about atmospherlc to about 500
- 8 -
10407~79
atmo~pheres until a composlte contalnlng about
: 10-70% by welght, based on the polyolefln and rlller,
Or polyolefln having an lnherent vlscoslty Or at
least about 4 is rormed; and
(D) isolatlng the resultlng polyolefln/riller composlte
a~ a ~ree- no~lng po~der.
Another method Or preparlng the composites Or thls
lnventlon lnvolving the use Or a hydrocarbon-soluble organlc
tr~nJltlon metal compound ln ~hlch the organoalumlnum compound
1~ prereacted ~lth the transltlon metal compound comprlses
(A) reactlng organoalumlnum compound selected from the
group conslstlng Or trlalkylalumlnums, dlalkyl-
alumlnum hydrldes, dlalk~lalumlnum alkoxldes,
alkylalumlnum halldes and polymerlc hydrocarbyl-
alumlnums ln ~hlch the alkyl groups, allke or
dlrrerent, have 1 to about 10 carbons each wlth
surficlent catalytlcally-actlve, hydrocarbon-soluble
organlc transltlon metal compound to provlde a mole
ratlo of organoalumlnum compound to transltlon
metal compound Or about 1000:1 to about 4 1 thereby
formlng a co~plex,
(B) dl8perslng
(1) at least about 1 welght/volume percent Or
finely-d~vlded inorganic flller compound havlng
a neutral-to-acidlc surrace and a welght-average
equlvalent spherlcal partlcle dlameter Or about
0.1-50 ~, and
(2) the organoalumlnum compound-transitlon metal
compound complex in an amount sufflclent to
~30 provlde about 0.001-1.0 mllllmole, per gram Or
_ g _
.. . ,. ~ . .
79
filler, of organoalumlnum compound and about
O.OOOOl-C.05 mllllmole, per gram of flller,
o~ transltion metal compound ..
ln an inert, llquld hydrocarbon dlluent;
(C) contactlng the resultlng dlsperslon wlth olefln
selected from the group conslstlng Or l-alkenes
'~ of 2 to about lO carbons and mixtures thereof wlthagltatlon at a temperature of about O-100C and a
pressure from atmospherlc to about 500 at~ospheres
untll a composlte contalnlng about 10-70% by welght,
: based on the polyolefln and flller, Or polyole~in
having an lnherent viscosity o~ at least about 4 i8
~ormed; and
(D) lsolatlng the re~ultlng polyolerln~lller composlte
as a rree-rlowlng powder.
BRIEF DESCRIPTION oF THE DRAWINoS
Flgure l shows a mlcronlzatlon graph for the
49/51 welght percent polyethylene/kaolin clay composite Or
Example l.
Flgure 2 shows a micronizatlon graph ror the
32/68 welght percent polyethylene/alumina trlhydrate
composlte of Example 2.
Flgure 3 shows a micronlzation graph ~or a
composltlon made by powder blendlng egual parts by welght
of polyethylene and kaolln clay ln accordance wlth the
prlor art.
DETAILED DESCRIPTION OF THE lNv~NTION
~; Unllke the rllled polyolerlns which have been
reported ln the prlor art, the fllled polyolefin composites
Or thls lnvention provlde formed ob~ects which are not
- 10 -
104~779
brlttle at higher flller contents, but retain the good
elongatlon, impact strength, and electrlcal propertles,
e.g., volume resistlvlty, whlch are characterlstlc Or
unfllled polyoleflns. For example, the composlte~ o~ thls
lnventlon, even at 50~ flller content, typlcally have O-F
Izod impact ~trengths o~ the order of about 20 rt lb/ln Or
notch and elongatlons at break of the order Or about 400~.
Surprlslngly, ln many cases, 0F Izod lmpact strengths Or
the order Or about 1 ft lb/ln Or notch and elongatlons at
break of the order of about 25% are obtalned wlth flller
contents as hlgh as about 90% ln accordance ~lth thls
lnventlon. Moreover, the rllled polyolerln composltes Or
thls lnventlon e~hlbit a range Or propertles lncludlng
lmproved modulus, higher hardnes~, lo~er creep, hlgher
heat de Mectlon temperature and lo~er materlal cost whlch,
~hen compared wlth un~llled polyole~lns, lndlcate a value-
ln-use not prevlously reallzed.
One of the lmportant reatures whlch dlstlngulshes
the rllled polyolerln composltes of thls lnventlon from the
rllled polyolefln composltlons o~ the prlor art 18 that they
are hlghly filled, that 18, they contaln at least about 30~,
and up to about 90%, by weight Or ~ ller. Thls lnventlon
provldes a reductlon ln the cost of polyolerln composltlons
by the addltlon Or large amounts of flller wlthout sacrl~lclng
essentlal physlcal propertles.
Another characterlstlc whlch dlstlngulshes the
hlghly-rllled polyolefln composltes of thls lnventlon ~rom
the fllled polyolefin composltlons Or the prlor art and
leads to the unusual combinatlon of physical properties
Or the composltes Or thls lnventlon 18 that the polyolefln le
104~779
polymerized onto the surface of the finely-dlvlded inorganlc
flller compound. In other ~ord~, each polymer chain 18
inltlated at, and grow~ from, the surface of the flller.
The term "surrace" includes all crevlce~, crack~, pores,
volds, and other lnterstices contributlng to the total sur-
face area Or the flller.
Stlll another characteristlc whlch dlstingulshes
the hlghly-rllled polyolefln composltes Or thls lnventlon
from the filled polyolefln compositlons of the prlor art
18 the hlgh molecular ~elght Or the polyolefln. me poly-
ole M n mu~t have sn lnherent viscosity of at least about 4
in order for the compo~ltes of thls lnventlon to exhlblt
the unusual comblnation or phy~ical propertles which charac-
terlze them. Prererably the polyolerln has an lnherent vl~-
coslty of at least about 8, and most preferably at least
about 12. The term "inherent vlscosity", a~ used hereln,
rerers to lnherent vlscoeltles determlned by the standard
procedure outllned belo~.
Another characteristic ~hich distingulshes the
highly-fllled polyolefln composltes Or thl~ lnventlon rrom
the fllled polyolefln compositlons Or the prlor art 18 that
they are homogeneous, that 18, substantlally rree Or polymer-
rree flller and filler-free polymer. me degree Or homo-
genelty Or the composite is determined by measuring lts
micronlzatlon homogenelty. The ~icronlzation homogenelty
determlnation 18 carried out by mlcronlzatlon and centrlnuga-
tion of the particulate composite using an alr micronizer.
This meas~rement lndicates the degree to which all of the
particles haYe the same polyolefin/filler content. Compositlons
whlch contain a signlrlcant amount of polyolefln-free flller
- 12 -
779
or flller-iree polyolefln do not possess thls characterls-
tlc homogeneity.
me composites of this lnventlon have a lO-~econd
mlcronlzatlon homogenelty Or at least about 50% and
prererably at least about 70%, and a mlcronlzatlon homogenelty
index Or at le-st about 20 and prererably at least about 50.
The terms "lO-second mlcronlzatlon homogenelty" and "microniza-
tlon homogenelty lndex", as used herein, refer to values
determlned by the standard procedures outllned below. These
procedures are used to obtaln mlcronlzatlon graphs of the
type lllustrated ln the drawings. m e mlcronlzation homo-
genelty values are calculated ~rom the data used to plot
thesc graphs.
The homogeneous composltes Or thl~ lnventlon are
prepared by a varlety of speclrlc proces~es whereby thc
olerln 18 polymerlzed onto rlller havlng the transl~lon
metal component o~ the coordlnatlon catalyst interacted at
lts surrace ln the presence Or ~n organoalumlnum compound.
The term "lnteracted" means bonded dlrectly, or lndlrectly
through the organoalumlnum compound, 80 that lt cannot be
washed Or~. The term "at lts surface" re~ers to the mono-
molecular layer o~ the flller whlch contain~ actlve polymerl-
zatlon sltes.
m ere are two lmportant concepts whlch must be
adhered to ln preparlng the composltes of thls lnventlon.
e rlrst concept 18 that substantlally all o~ the polymerlza-
tlon must occur on the surface Or the flller rather than ln
solutlon. For thls reason lt is preferred to use a transltion
metal compound whlch, ln comblnatlon wlth an organoaluminum
compound, 18 es~entlally inactive as an ole~ln polymerlzation
I - 13 -
104U7'79
catalyst in solutlon, but which, when adsorbed onto the
surface of the filler, is actlve as a polymerlzatlon cata-
lyst.
- I~ the transltlon metal is actlve ln ~olution,
the procedure has to be modlried 80 that all transltlon
metal present during polymerizatlon 18 irreversibly ~n the
surrace Or the riller. Thus, ln the case Or tltanlum tetra-
chloride, excess titanium tetrachlorlde not adsorbed by the
rlller must be removed and the adsorbed tltanium compound
hydrolyzed to tltanium oxlde. I~ the transition metal has
low or moderate actlvlty ln solutlon, but ls much more
active when adsorbed onto ~iller, for example 50 to 100
tlmes more active, then it can be used to rorm homogeneous
composites wlthout golng through this modlficatlon.
The second important concept whlch must be adhered
to ln these processes 18 that polymerlzatlon must take
~ place on substantlally all of the flller partlcles, Ir
-l the catalyst 18 very actlve and is readlly adsorbed by the
filler, such as ln the case of tetrabenzylzlrconium, care
must-be taken that the catalyst is not all adsorbed by only
part of the ~lller. m is problem may be overcome by flrst
reactlng the flller wlth excess organoalumlnum compound and
then adding the transltion metal compound. Another way Or
overcomlng thls problem may be to prereact an excess o~ the
organoalumlnum compound wlth the transltlon metal comFound
~ to ~orm a complex and then react this complex wlth the
j rlller. With some transltlon metal compounds such as
chromlum octoate lt is posslble to react the transltion
metal compound wlth the flller ~lrst wlth no deleterious
e~fect.
- 14
, . . .
.
1~4~779
m e compo~ites of this lnvention contain about
10-70~ by welght Or polyolefln, prererably about 15-60~,
and mos~ prerersbly about 20-55~. At least about
10~ by weight Or polyolefin is necessary to provide
~ufficlent blnder to rorm tough ob~ects. The mlnlmum amount
Or polyolerln necessary ln any speclfic case will depend
on the density, nature and partlcle slze of the flller.
Wlth larger partlcle slzes and higher denslties less poly~
olefln 18 needed.
; 10 The polyolerlns whlch are userul in accordance
wlth this lnvention are homopolymers Or l-alkenes Or 2 to
about 10 carbons and copolymers Or two or more such monomers
wlth each other. Suitable monomers include ethylene,
propylene, l-butene, l-pentene, 3-methylbutene-1, 4-methyl-
pcntene-l, l-hexene, l-octene, l-decene, and ml~tures thereor.
Partlcularly preferred are polyethylene, polypropglene and
copolymers Or ethylene wlth up to about 15% by welght Or
one or more l-~lkenes of 3 to about 10 carbons. Other monomers
known to be reactlve ln coordinatlon polymerizatlon reac-
tlons, ror example, llnear, nonconJugated dlole~lns such as
1,4-hexadlene, 1,6-octadlene, dlcyclopentadlene, norbornene
and norbornene derlvatlves such as ethylldene rbornene, may
also be added ln small amounts.
The composltes Or thls lnventlon al~o contaln
about 30-90~ by welght Or rlnely-dlvlded lnorganlc flller
compound, prererably about 40-85%, and most prererably about
45-80%. As the flller content Or the composlte is lncreased
as indicated by the mlnimu~ in the preferred and most pre-
ferred ranges, the ~ti~fness, hardness, and useful temperature
range increases wlthout degradlng other deslrable propertles
- 15 -
.
0 ~ 9
the composite. Filler contents ~re determined by ash
analy~l8~ that is, rrOm the ash eontent on combu~tion. Slnee
combustion removes all water of hydration, the filler content
18 ealeulated from the a~h content by accounting ~or this 1Q~6
Or water during combustion.
Any lnorganie riller compound ean be used in aeeord-
anee ~lth this inventlon provided it ~eets the criterla de-
serlbed below. By "inorganie f~ller eompound" iB meant a solid
eompound ~hieh does not eontain earbon exeept in th rorm Or
earbonate. Suitable rillers inelud mineral~, for examplo,
all-ml~a hydrat-s such as alumin~ trihydrate and the like,
metal phosphates and sulrates sueh as in601uble caleium
pho~phates, ealetum sulfate, and barium ~ulrate; ~ilieas
(SiO2) ~ueh as sand, diatom~eeous earth and pumice; metal
earbonates sueh as barlum earbonate, calcium carbonato and
~;! zlnc earbonate; metal osido~ ~ueh a~ tltanla (e.g., rutlle
! and anatase), zinc oxide, antimeny oxide, Ana iron oxide
(e.g., m~gnetlte FeO-Fe203); and water-in~oluble sllieate~
~ueh a~ alumlnum s~lieate ela~s; a~d ~tural mlxture~ Or the~e 20 eo~pounas sueh as slate. Other suitable inorganie flllers in-
elude ~ynthetic silieas~ sgnthetie earbonates; glass powder
and rlbers; synthetic ~illcates ~uch as SILENE* L, a pre-
cipltated, hgdrated calclwm sllicate; and ~nthetlc tltanates
; ~uch as FYBEX*, an acicular potas~ium titanate.
By U~lum~na hydrateB~ iB mcant al~m1na~ o~ the
~ormNla A1203-~H20 in which x is about 1.5-3Ø By "alumlna
trihydrates" is meant alumina~ Or the ~ormula A1203-~H20
in which x i~ abou~ 2.5-3Ø
By "water-insoluble silicates" i~ meant silicates
which are either completely insoluble or ~o clo~e to being
* denotcs trade mark ~~`
- 16 -
k
-
~040779
completely insoluble that the small amount of solubllity
does not prevent the advantages Or thls inventlon from belng
reallzed. Typlcal water-insoluble slllcates include calcium
sllicate6 (CaS103) such as wollastonlte; magnesium slllcates
such as talc; magneslum calclum alumlnum sllicates
-Ca)O.A1203 5S102 nH207 such as montmorillonlte and
serpentlne; lithlum alumlnum sillcates ~uch as spodumene
Li,Na) ~12Si4012~; potassium aluminum 611icates such as
~eldspar (K20-A1203~6SiO2) and mica (K20-3A1203-6Sl02-2H2o);
magnesium lron slllcates such as ollvlne ~ ,Fe)2S104 ~ ;
alumlnum slllcates (A1203-S102) such as sllllmanlte and
kyanlte; and alumlnum sllicate clays.
A partlcularly pre~erred class of rlllers 18
alumlnum slllcate clays Or the rormula A1203-xS102-nH20
; where x 18 1 to 5 and n is 0 to 4. Sultable alumlnum alll-
cate clays lnclude kaollnlte, attapulglte, ~uller~ earth
and bentonlte. The prererred clay 18 kaollnite.
Another prererred class o~ ~illersls alumlna trl-
hydrate~. When at least about 30% by weight o~ the flller
ln the composlte 18 alumlna trlhydrate, the resulting ~ormed
ob~ects exhibit ~lame-retardant characteristlcs.
The riller used in accordance with this inventlon
should have a neutral-to-acldlc surface. Many rlllers such
as alumlna hydrates, silicas, water-insoluble sillcates,
lnsoluble calclum phosphates, tltania, zlnc oxide, lron oxlde,
antimony oxide and mixtures thereof naturally have neutral-
; to-acldic sur~aces. Other filler~ such as calcium sulfate,
calclum carbonate, barlum sulfate and zinc carbonate are basic
in nature and thereby lnhiblt polymerizatlon. Stlll other
mlnerals such as mlca, silicas which contaln alkali or alkaline
- 17 -
104~779
earth metal, and wollagtonlte give variable polymerlzatlon
behavior.
In those cQse~ where the ~iller i8 not neutral-
to-acldlc, lt has been found that polymerizatlon lnhlbltlon
; dlrrlcultles can be overcome by n rst coatlng the filler wlth about 0.01 to 2%, based on the flller, of an acldlc oxlde
such as sllica, alumlna or acld phosphate thereby givlng the
flller an acldlc surrace. More could be added but ~ould serve
no useful purpose. me ~mount of acldic oxlde at the sur~ace
of the flller can vary ~rom about 0.001 to about 0.5 mllllmole
per gram of ~iller, and pre~erably about 0.01-0.05 mllllmole.
m ese acldlc oxlde coatlngs are obtQlned by
treatlng the ~lller wlth a compound whlch 18 hydrolyzed to
an acldic oxide. For example, carbonate ~lllers are coated
by slmply mlxlng an aqueous suspenslon conta~nln4 about
10-50~ by welght o~ the solid ~lller wlth an aqueous 801u-
tlon contalnlng about 1-10% by welght o~ an alumlnum salt
4CaCo3 + 2AlC13 ~ A1203/cac03 + 3caC12 + 3C02
Other mlnerals can be coated by t~ atlng wlth an aqueous
salt solutlon and ammonla:
CaS04 + 2AlC13 ~ A1203/CaSo4 + 6NH4Cl
Acld phosphate coatlng~ can be obtalned by treatlng the
flller with phosphorlc acld:
2CaC03 + H3P04~ CaHP04/CaC03 + H20 + C02
Slllca coatlngs can be obtalned, for e~ample, by treatlng
calcium carbonflte wlth slllcon tetrachlorlde:
SiC14 + CaS04 > S102/CaS04 + 4NH4Cl
The flllers used ln accordance wlth thls lnven-
tlon should have a welght-average equlvalent spherlcal
3 dlameter of about 0.1-50 ~. The term "equivalent
- 18 -
104~779
spherlcal partlcle dlameter" 18 used because not all o~ the
use~ul ~illers are ~pherical ln shape and thus do not hsve
simple diameter~. Thls ter~ means that the particle ha~ a
diameter equivalent to the dlameter o~ a sphere havlng the
same volume. Pre~ersbly the welght-average equivalent
spherlcal particle diameter i8 less than about 45 ~, and
most pre~erably i8 about l to 25 ~. If the average particle
slze 18 smaller than about 0.1 ~, then the advantageous impact
strength and elongatlon obtalned in accordance wlth thls
lnventlon wlll not be reallzed. If the average partlcle
dlameter 18 larger than about 50 ~, then the lmpact
reslstance wlll be less than deslred especlally at hlgher
flller contents. Also composltes contalnlng such lsrge Plller
partlcles result in rormed ob~ects having rough surfaces in
areas whlch undergo stretchlng durlng formation.
The ~lllers used in accordance wlth thls lnventlon
pre~erably al~o have a surface area o~ about 0.01-lO0 m2/g.
Most pre~erably the surface area 18 ln the range Or sbout
0.5-50 m2/g. Ir the surface area 18 too small, then the
product may not have the requlslte homogenelty. I~ the sur-
face area 18 too great, the advantageous comblnatlon of
lmpact strength, elongatlon and stlfPness obtalned ln accord-
ance wlth thls inventlon may not be reallzed.
me composltes Or thls lnventlon are prepared uslng
an lnorganlc ~lller havlng lnteracted at lts surfaee a
catalytlcally actlve transltion metal compound. By
"transltion metal" 18 meant a metal o~ Group IV A, V A or
VI A of the Perlodic Chart o~ the Elements published in
Advanced Inorganic Chemlstry by F. A. Cotton and G. Wllklnson,
~o Intersclence Publlshers (1972). These metals are tltsnium,
- 19 -
)779
zlrconium, harnlum, vanadlum, nioblum, fantalum, chromium,
molybdenum and tungsten.
Any Or the transltlon metal components of coordlna-
tlon cataly~t systems dlsclosed in the prlor Qrt as belng
sultable for olefln polymerlzatlon are sultable for use ln
accordance with thls lnventlon. Preferably the transltion metal
compound, at the stage that lt comes in contact wlth the olefln
ln the polymerlzatlon process, contalns substantlally no halo-
gen bonded to the transitlon metal. The ~lller should contaln
sufricient transitlon metal compound to provlde about 0.000001-
1.7 millimole, per gram Or filler, of transltlon metal, and
prererably about 0.00001-0.8.
The upper limlt Or 1.7 millimoles, per gram Or
flller, Or tran~ltion metal lnteracted at the surrace Or the
rlller represents saturatlon oP the monomolecular layer at the
~ur~ace Or the ~lller with transitlon metal ln the close~t
posslble packlng conflguration. Although more transition
metal can be adsorbed as an added layer, no more than 1.7
mlllimoles Or transitlon metal can lnteract at the surrace.
The processes used to prepare the composites o~
thls invention also include as part Or the coordinatlon cata-
lyst system an organoalumlnum compound selected rrom the group
conslstlng Or trlalkylaluminums (RlR2R3Al), dialkylalumlnum
hydrldes (RlR2AlH), dlalkylalumlnum alkoxides (RlR2AlOR3),
alkylalumlnum halideE (RlR2AlX and RlAlX2) and polymerlc
, .,
hydrocarbylaluminums ln whlch the alkyl groups, allke or
; dlfrerent, have 1 to about lO carbons each. Sultable com-
pounds lnclude the commerclally available trlmethylalumlnum,
triethylalumlnum, trl-n-propylalumlnum, trilsobutylaluminum,
tri-n-hexylalumlnum, tri-n-octylaluminum, trl-n-decylalumlnum,
- 20 -
1~)4~;'7~
dlethylaluminum hydrlde, dilsobutylalumlnum hydrlde, diethyl-
alumlnum ethoxlde, dllsobutylaluminum ethoxlde, and the llke.
Polymerlc hydrocarbylalumlnums such as alumlnum-lsoprene
polymer~ are descrlbed ln U.S. Patent 3,149,136. me trl-
alkylalumlnums and dialkylalumlnum hydrldes are preferred.
me alkylalumlnum halides are not preferred slnce the final
polymer is corroslve to metal in many applicatlons Preferably
the composlte~ of thls inventlon are rree Or resldual halogen
and thus noncorroslve. me organoalumlnum compound should be
pre8ent ln the amount Or about 0.001-l.O mlllimole,`per gram
o~ ~lller, and prererably about 0.002-0.2 mlllimole.
One approach to preparlng these products lnvolves
technlques for pretreatlng the ~iller to contaln about
0.00001-1.7, and preferably about O.OOl-O.ô millimole, per
gram o~ ~lller, Or certain transltlon metals ln the ~orm Or
a catalytically-actlve transltion metal compound lnteracted
at lts surrace, unless lt already has such a metal component
lnteracted at its ~urface in lts natural occurrlng state,
and lsolating the transitlon metal compound-contalnlng rlller
rrom any transltlon metal compound not attached to the
lller. The polymerlzatlon 18 then carried out by dlspers-
lng the pretreated filler ln an lnert, llquld hydrocarbon
along with the organoaluminum compound and the olerin.
When the filler 18 an aluminum slllcate clay
contalnlng at least about 0.05% and pre~erably at least about
0.5% by weight Or tltanla and being selected rrom the group
consisting Or kaollnite, attapulglte and ruller's earth, lt
contains a sur-iclent amount o~ tltanla ln actlve form at
its sur~ace that polymerlzatlon 1~ promoted ln the presence
Or an alumlnum compound wlthout addltlon of catalytlcally-
104~ ,9active transit$on metal compound belng necessary. A
typical aluminum silicate clay of this type contains, for
example, about 0~5-2.0% titania. me composites of this
lnventlon are prepared by this method using about 0.01-
2% by weight of an alkylaluminum compound, based on the flller.
When w ing these tltania-containing clays without
added tran~ition metal, homogeneous compositos are pre-
pared by rir~t dehydrating the clay to reduce lts ~ater of
hydration content to les~ than one mole of water per mole Or
- 10 aluminum silicate (A1203-xSiO2) in accordance with the
egu~tion:
A1203.XSl02-nH20 -;~ AL203-XS102-YH20 + (n~Y)H20
where x i~ 1 to 5, n is 0 to 4, and y i~ le88 than 1. me
dehydratlon i8 carrled out by heating the clay in a dry
at sphere at a temperature o~ about 400-1400C ror up to
about 18 hours.
It 1B pre~erred in most cases that the atmos-
phere used durlng this dehydration be an oxldlzing atmDephere.
~y "oxldlzing atmosphere" i8 meant an atmosphere containlng
at least about 0.5% oxygen. It 18 bellevod that the
pres-nce Or a nominal amount Or oxygen in the atmosphere
durlng the dehydration prevents 1088 o~ chemically combined
";
ox~gen by the clay. ln the ca~e Or certaln clays such as
tho~e having a low lron content, the dehydration can be
carried out in a nonoxldizing atmo~phere. The polymerlzatlon
lc then carried out by dispersing the dehydrated clay in a
hydrocarbon dlluent and adding the organoaluminum compound and
the olefln.
- 22 -
1~q0779
When the filler does not contain sufricient titania
ln actlve rorm~ it can be pretreated to contain active
titanium ~ites. It has been found that any neutral-to-
acidic filler can be pretreated by thls process. In accord-
ance with this proce~s, the rlller is tirst contacted with
a hydrolyzable titanium compound, the adsorbed titanium
species i~ hydrolyzed, and the tltanium-treated filler 18
activated.
Suitable hydro}yzable tlt~nium compound6 include
titanlum tetrachlorlde, tetraalkyl titanates and mixture~
thereor ~herein the alkyl groups, alike or dir~erent, have 1-6
carbon atoms. In the ca~e of titanium tetrachloride, the
filler can be espo~ed to titanium totrachloride vapor until
the surrsce 1~ saturated. In the ease of the titanat-
ester~, the rlllor i~ milled with a ~olutlon o~ titanate
e~ter. Sinco the titanium compound i~ adsorbed rrom
the ~olutlon by the riller, the conc~ntration of
tltanium in the ~olutlon may vary ov~r ~ide limits pro-
~ided the solutlon at least contains the minimum a unt of
titanium that i~ de~ir~d at the ~urrace of the
flller. Suitable totraalkyl titunates include tetramethyl
tltanat-, tetraethyl titanate, tetrapropyl titan~te, tetra-
lsopropyl titanate, and the like. Contacting Or the ~iller
~lth tltanium tetrachloride or a titanate e~ter i~ belleved
to result in bonding a tltanium-containing group to the sur-
face Or the substrate riller. The tltanlum containlng-
- 23 -
I
- .. . . ..
~4~7~79
flller 18 then freed of unadsorbed tltanium compound by
washlng or by vaporizatlon such as by sweeplng with hot
nltrogen.
m e adsorbed titanium compound 18 then hydrolyzed
to what 18 believed to be a derivative of tltanlc acld
/~l(OH)4_7 chemlcally bound to the surrace of the particle.
When the tltanlum compound ls tltanlum tetrachlorlde, thls
is accompllshed by contactlng the tltanium-treated flller
~lth aqueous or molst gaseous ammonla to ensure that all
of the chlorlne 18 removed. In the case of a titanate
ester, hydrolysls or the tltanlum compound can be
accomplished by exposlng the titanlum-treated flller to
molst alr.
The tltanium-treated flller is then activated by
heating at a temperature of at least about 100C. Although
the ~orm of the tltanlum compound on the surface Or the
actlvated flller 18 not known wlth certalnty, it 18 belleved
to be closely related to titanla. Accordingly, the hydro-
lyzed and activated tltanium-treated flller is referred to
hereln as titanla-modified filler. In the case of alumlna
trihydrate the activation temperature should not exceed about
200C and preferably is about 100-180C. In the case of
titanla-modlfled clay, further actlvatlon can be obtalned,
if deslred, by dehydratlng the clay to reduce the water of
hydration to less than that of the monohydrate. This de-
hydration i8 carrled out at a temperature of about 400-1400C
for up to about 18 hours.
In the case of tltania-modified clay, the effects
oP thi~ activatlon and/or dehydration step can advantageously
3o be maximized by precedlng, accompanying or followlng it wl~h
!
- 24 -
~04V779
a hydrogenation ~tep. This 18 accomplished by heQting the
ClRy at a temperature o~ about lOo -1400C ~or about 0.5-
20 hours under hydrogen flow. me change effected ln the
clay 18 retained on storage in air or on air-oxidatlon of
the clay at elevated temperatures. The actual state of oxl-
dation or reduction Or the clay is o~ no consequence when
this hydrogenat~on i8 carried out. After activation, the
polymerlzation is carried out by contacting the pretrested
; ~iller wlth an organoalumlnum compound and olefin.
~o Any of the neutral-to-acidic Pillers descrlbed
herein can be pretreated to provide a chromlum compound
; interacted at the surrace. me chromium treating Rtep i~
carried out by treatlng the filler wlth a solution o~ a
chromlum(III) compound ln a suitable solvent. me solvent
u~ed to prepare thls ~olutlon may be ~ater or any organlc
liquid in ~hich the chromlum(III) compound 18 soluble.
A prererred clas~ of solvents includes polar ~olvents such
as ~ater and alcohols, especlally alkanols ~uch as
methanol. Sultable water-soluble or organic solvent-soluble
chromlum compounds lnclude chromium nltrate; chromium halides
such as chromlum fluoride, chloride, bromide and iodide;
Cl to C12 organic acid salts of chromlum such as chromlum
acetate, chromium oxalate, chromium octoate, and chromium
naphthenate; chromlum ~ulfate; fumaratochromium(III) nltrate;
methacrylato~hromium hydroxlde; methacrylato~hromium
chloride; and the like; and mlxtures thereof. The chromlum
compound 18 pre~erably halogen-rree.
m e chromium-modlrled filler i8 activated by
drylng at a temperature Or about 25-400C, pre~erably about
150-250C, and most preferably about 175-200C. At tempera-
,1
- 25 -
.
~ ~ ,
lO~ g
tures below the boillng point o~ the solvent belng removed,
the drying proce~s may be asslsted by u~e Or vacuum.
Although lt 1~ not understood exactly what takes place
during this activation ~tep, lt 1~ belleved that more than
a slmple drylng 18 lnvolved. me terms "dry" and "drylng",
when used throughout the ~peclflcatlon and clalms ln ref-
erence to the flller, means dry to the extent that resldual
volatiles no longer adversely e~fect polymerlzatlon. After
actlvatlon, the polymerlzatlon 1~ carried out by contacting
the pretreated flller wlth an organoalumlnum compound and
ole~ln.
In carrylng out the polymerlæation reactlon, part
Or the pretreated rlller may be replaced by one or more
oP certain inorganlc plgmentary oxldes not havlng cata-
lytlcally-actlve transltlon metal compound lnteracted at
thelr sur~ace. These pigments, whlch can comprlse up to
about 30% by weight of the particulate filler, include plg-
mentary titanla, zlnc oxide, antlmony oxlde and ml~ture~
; thereo~. Although plgmentary titania will catalyze some 20 ole~ln polymerlzatlon, lt i8 not consldered to be cata-
lytically actlve in the sense of the catalytlcally-actlve
transltlon metal compounds used hereln. When plgmentary
oxlde 18 present, the flller preferably contalns about
5-25% by welght o~ plgmentary oxide. m e plgmentary oxlde
may be activated, i~ desired, by heating at a temperature
o~ at least about 100C. The pigmentary oxlde should hare
a welght-average equlvalent spherlcal partlcle dlameter less
than that Or the flller havlng catalytically-actlve transi-
tlon metal compound lnteracted at lts sur~ace. Preferably
the plgmentary oxide has a welght-average equlvalent
- 26 -
104~)7 79
spherlcal particle dlameter of not more than half that Or
the flller having catalytlcally-actlve transitlon metal com-
pound interacted at lts surface.
A substrate contalnlng plgmentary oxlde Or the
specified particle size in addltlon to the transltlon metal-
contalnlng ~lller yields whlter products and generally per-
mits even hlgher filler loadlng than otherwlse posslble
wlthout any 1088 in the propertles of the products. me
comblnatlon Or physlcal propertles of these polyolefln/
flller/plgment composites ls ln the range of the expen-
slve AES copolymer reslns and thereby provldes an
economlcally superlor product for uses requlrlng toughness,
rlgidlty and hlgh lmpact strength as compared wlth a slmilar
composlte contalnlng no plgment.
When the lnorganlc rlller 18 a mlxture of two or
more o~ the above solld components, the mlxture 18
generally mllled, e.g., ln A p81nt mlll, ball mlll, collold
mlll, sand grlnder or rod mlll, untll all components are
unlformly dlspersed. Thls process usually requlres about
0.1-24 hours. The mllllng can be perrormed on the dry
components, but is preferably done ln a slurry of the
flller ln an lnert dlluent such as the one to be used ln
the polymerlzatlon step.
Before the flller can be used in the polymerlza-
tlon reactlon, lt must flrst be freed or gaseous oxygen,
water and other polar lmpurltle~ that interfere wlth the
polymerlzatlon reactlon. This ls readlly accompllshed by
sweeping the filler wlth an inert gas such as nltrogen wlth
heatlng.
~0 me polymerlzatlon i8 carrled out by dispersing
.
.
-
~040~9
- at least about 1 weight/volume percent and preferably about
5 weight/volume percent Or the pretreatod riller in an inert,
liquld hydrocarbon, along with the organoaluminum compound.
mO olefin i~ then added and the polymerization is carried
out untll a composite containlng about 10-70% by weight,
ba~ed on the polyolerin and ~iller, Or polyolefin is formed.
Weight/volume percent, as used throughout the speclrlcation
and claims, rerers to grams Or solid added to 100 milli-
liters o~ liguid.
Another approach to preparing the homogeneous
composites Or this invention involves the adsorption Or
a hydroearbon-soluble, organic transition metal compound
at the ~urrace Or the filler in the polymerization medium.
By "hydroesrbon-soluble" i~ meant an organic transition
metal eompound whieh i6 soluble in at least one hydro-
earbon ~ol~ent or ean be solubilized in ~ueh solvent by
the pre~onee Or an organoaluminum eompound. The polymeri-
zation 1B earrled out under eonditions whereby the tran~i-
tion metal eompound is relatively re aetive as a cataly~t
~hen adsorbed at the sur~aee Or the filler, for exsmple at
least 50 times more aetive, than when in solution.
Aceordingl~, this approaeh does not require re val Or exce~s
transition metal eompound from the polymerization reaetion
medium.
The~e organie transition metal eompounds may
be w ed in an olef~n polymerization involving any
neutral-to-acidic riller. In accordance with this
- 28 -
~ ~ 7
A
.,9
' ::
,
. ' "
i~)4~
method the polymer1zation i~ carrled out by dl~perslng
the rlller ln an lnert, llquid hydroc~rbon along wlth about
0.00001-0.5 mllllmole, per gram Or filler, and prererably
about 0.0001-0.01 milllmole of tran~ition metal ln the form
Or a hydrocarbon-soluble organic transltlon metal co~pound,
and about 0.001-l.0 millimole, per gram of flller, of an
organoaluminum compound and preferably about 0.002-0.2 milll-
mole.m e org~nlc tran~itlon metal compounds used ln
this approach are Or the rormula
LnMXp
~hereln L 18 an organlc llgand bonded to M by carbon,
oxygen, or nltrogen; M 18 a transitlon metal; X 18 a non-
organlc llgand, preferably halogen; n 18 an lnteger rrOm l
to the hlghest valence or M, and p 1B an lnteger ~rom 0 to
l less than the hlghest valence Or M. Sultable L groups
~nclude hydrocarbyl such as alkyl and alkenyl, substltuted
hydrocarbyl such a8 substltuted alkyl and substltuted alkengl,
hydrocarbyloxy, hydrocarboncarbonylo~y, hydrocarbylsllyl-
hydrocarbyl, dlhydrocarbylamino, ~-dlketonato, and the llke.
Illustratlve classes o~ suitable organlc transl-
tlon metal compound~ lnclude tetrabenzylzlrconium and
related tetrabenzyl, tetrakis(substltuted benzyl), and tetra-
naphthyl derlvatlves or tltanlum, zirconlum, and harnium
dlsclosed by long in U.S. 3,635,935, Ploll et al. in U.S.
3,681,317, and Candlln et al. ln U.S. 3,738,944; tetrakls-
(trlmethylsllylmethyl)zirconlum and related compounds dls-
¦; closed by Candlln et al. in U.S. 3,738,944; and tetraneo-
phylchromlum and the related tetrahydrocarbylchromiums dis-
o closed by Kruse in U.S. 3,798,250.
,
- 29 -
~, ,
'
104~}779
A prererred class Or hydrocarbon-soluble organic
transltlon metal compounds are those in which some or all
of the L groups are substituted alkyl groups of the rormula
-CH2y
ln l~hlch Y represents an atom or group capable of lnter-
actlon l~lth the vacant d-orbltals o~ the metal ~. Sultable
Y group~ lnclude aromatlc groups such as phenyl, naphthyl,
substltuted phenyl and substltuted naphthyl groups, and
groups of the rormula
M'(R)3
ln ~hich M~ 18 carbon or sllicon, and R, allke or dlrrerent~
1~ hydrocarbyl such as alkyl or aryl.
Bpeclflc hydrocarbon-soluble transltlon metal com-
pounds lnclude tetrabenzylzlrconium, tetrabenzyltltan~um,
tetrabenzylhafnium, tetraneophylzlrconlum, tetranoophyl-
chromlum, tetrQneophyltltanlum, tetrakls(p-lsopropylbenzyl)-
tltanlum, tetratolyltltanlum, tetrakls(tetraethylbenzyl)-
tltanlum, tetramethyltltanlum, tetraneopentylzlrconlum,
tetraneopentyltltanlum, tetraneopentylhafnlum, tetrakls(p-
methylbenzyl)zirconium, tetrakls(l-naphthylm~thyl)tltanlum,
tetrakls(trimethylsllylmethyl)zlrconium, trlbenzylzlrconium
chlorlde, trls(~-allyl)zlrconlum bromlde, tris(7~-methallyl)-
tltanlum chlorlde, tetrakls(i~-allyl)hafnlum, tetrakls(~r-
allyl)chromium, tetrakis(~-allyl)nloblum, chromium octoate,
chromium naphthenate, tetrakls(2,4-pentanedlonato)zlrconlum,
tetrskis(2,4-pentanedionato)titanium, tetrakls(dlmethyl-
amlno)tltanium, tetrakls(dlethylamino)vanadlum, and the llke.
Preferably the organlc transltlon metal compound contalns no
j halogen bonded to metal.
3o The amount o~ hydrocarbon-soluble organic transi-
- 3 -
.. . .
104~)779
tlon metal compound added to the polymerization reactlon
should be sufficient to provlde about 0.00001-0.05 millimole
of transition metal per gram of filler and prererably about
0.0001-0.01 milllmole. mls amount wlll provlde flller
havlng interacted at lts surface sufflclent organic transl-
tion metal compound to provlde about 0.000001-0.05 mllll-
mole Or transltlon metal per gram of fll~er and preferably
about 0.00001-0.01 mllllmole.
m e preferred hydrocarbon-soluble organic transl-
tlon metal compounds are the zirconium compounds. Preferably
the polymerizatlon reactlon 18 carried out ln the presence
Or sufflclent zlrconlum compound to provide about 0.0005-
0.005 mlllimole of zlrconlum per gram of fil7er. m is
amount ~ill provlde flller havlng interacted at its sur-
face suf~icient organic transition metal compound to pro-
vide about 0.0001-0.001 mlllimole Or zlrconlum per gram or
filler.
The most actlve of the hydrocarbon-soluble
organlc transltion metal compounds are the zlrconlum com-
pounds. In order to provide homogeneous composltes uslng
hydrocarbon-soluble organic zlrconium compounds, it has
been found that the order in ~hich the ingredlents are con-
tacted 18 very lmportant. mese same rules are adYantageously
followed ln the case of less actlve transltion metal com-
pounds, with the posslble exception or chromlum compounds of
lo~ activlty where satlsfactory results are obtalned by con-
tactlng the filler and the transition metal compound directly.
m e most important rule relatlng to order o~ addl-
tion ls that the initial contact for the flller and the
transition metal compound must not be between each other.
:
- 31 -
1040779
Inltial contact between the flller and the transltion metal
compound leads to a heterogeneous product and should be
avolded.
In preparing homogeneou~ products by this approach,
lnltlal contact between the filler and the transition metal
compound can be avoided by proceedlng in one Or two ways.
In accordance wlth one method, the ~lller is first reacted
wlth a large excess of the organoalumlnum compound. me
mcle ratio o~ organoaluminum compound to transitlon metal
compound should be in the range Or about lO00:1 to about
4 1 and preferably about 40:1 to about lO:l.
It 18 believed that thls excess organoalumlnum
compound reacts ~lth many of the hydroxyl groups on the
surrace Or the rlller, thus limiting the adsorptlon sltes
avallable to thc transltlon metal compound. The transltlon
metal compound no~ reacts unirormly with all Or the nller
partlcles as lt seeks the liDited number o~ avallable sites.
In accordance with another and preferred method Or
avoldlng initlal contact between the ~iller and the transitlon
metal compound, the transltlon metal compound is ~lrst reacted
wlth a large excess o~ the organoalumlnum compound ln amounts
which provide a mole ratio of organoaluminum compound to
transition metal compound of about lO00:1 to about 4:1 thereby
rorming a complex. The dispersion of n ller ln the hydrocar-
; bon diluent i~ then contacted with the complex in an amount
su~ficient to provide about 0.001-l.0 mlllimole and pref-
erably about 0.002-0.2 milllmole, per gram o~ filler, o~
organoaluminum compound and about 0.00001-0.05 mllllmole,
and preferably about 0.0001-0.01 milllmole, per gram o~
~iller, of transitlon metal compound.
- 32 -
104~779
Sultable inert, llquld hydrocarbon diluent6 for
use as the polymerlzatlon medium include aromatlc, saturated
aliphatic and saturated alicyclic hydrocarbons. While the
llquld cycllc and acyclic hydrocarbons of about 5-lO carbons
such as pentane, hexane, heptane, octane, decane, cyc-
lohe~ane, benzene, toluene, xylene and tetralin are pre-
ferred, the lower boillng propanes and butane~ can also be
used.
The dlluent should be anhydrous and preferably i~
made 80 by passlng lt through hiB~ly absorptive alumina such
a8 a Woelm acld alumlna column lmmediately prior to use.
The llquid dlluents can also be freed Or contamlnants such
as oxygen and water by treatment ~ith traces, e.g., about
0.50%, based on the welght of dlluent, of the organoalumlnum
compound to be used as a cataly~t component ln the polymeri-
zatlon. m 18, along wlth the acid alumlna treatment, ensures
maxlmum avoldance Or molsture and other impurities.
me slurry o~ the flller ln the dlluent can be
qulte vlscous, especially in the case of hlgh-sollds slurrles.
Additlon of the organoalumlnum compound to these slurries
with vlgorous stlrring dramatlcally reduces the vlscosity.
For example, the vlscoslty Or a typlcal system might be
reduced ~rom about 5,000 centlpoises to about 300 centlpolses.
m e polymerlzatlon reactlon can be carried out at
temperatures of about 0-250C. Polymerization temperatures
below that at ~hich the dlluent swells the polyole~in
are preferred since swelllng greatly increases the vlscosity
; of the reactlon mlxture and makes agitation dlfficult or
; imposslble unless low concentrations o~ materials are uEed.
For practical reasons, polymerlzations should be run at
- 33 -
104V~779
temperatures not ln excess of about 100C when pure
alkanes or cycloalkane~ are used. When a stron4 polyole-
fin solvent such ~ benzene, toluene, tetrslln or xylene
18 used, even lower temperature~ such as about 60C or
below should be used. Preferably temperatures of about
25-100C ~re used, and most preferably about 50-
90-C.
Polymerlzatlon 18 readlly carrled out at pressures
~rom about atmospherlc to about 500 atmospheres. Pressures
ln the lower range are generally preferred, and about 3_
70 atmosphere8 are most satlsractory. The course oY the
polymerlzation reaction 18 followed by notlng the change in
welght of the supply vessel containlng the olefin. The
eupply vessel 18 normally used to malntain the pressure ln
the reaction ve~el. Reactlon t-me~ m~y vary over ~ ~idc
range, ror example, from a few seconds to about 24 hours.
When comblnationc o~ particulatc Pl~lers ~re
used, lntlmate ml~lng 18 crltic-l to provlde Plnely_dlvlded
unlrorm compo~ites. Agltatlon during polymerization con-
trola both particle size and unirormity Or compositlon.
Strong agltation, a8 achieved with very rflpid stlrrlng,
gives a fine-grained, free-flowlng product. m 18 is best
achieved by use of an autoclave equipped wlth an efficlent
stirrer. me resultlng polyolefin/filler compo8ite is
lsolated as a ~ree-flowlng, homogeneous powder
by means Or conventional steps such as flltering, washing
and drying.
me ~illed polyolefln composltes Or thls lnrention
are essentlally static-free. By "statlc-free" it is meant
that the powder compositions flow freely through a glass
'
- 34 -
104~779
funnel havlng an inslde stem diameter of 1 centimeter.
m e weight-average equlvalent spherlcal partlcle
dlameter Or the filled polyolerln composite can vary over
the range of about 0.1 ~ to about 5 mm depending on the
particle diameter or the rlller and the amount Or aggrega-
tlon ln the product. Aggregates are readlly broken up.
Prererably the particle dlameter 18 ln the range Or about
1-500 ~.
In these composltes lt 18 believed that the
polyolePin coats and penetrates the filler. Ho~ever, the
polyole~ln does not completely encapsulate the flller par-
tlcles as evidenced bythe e~tractlon Or alumlna from
polyole~ln/clay composltes by treatment wlth mlneral acld.
It 1B nurther believed that the deposlted polyole~ln 18
intimately bonded to the Plller. The composites Or thls
lnventlon, consequently, run no danger Or mechanlcal separa-
tlon lnto thelr components durlng agltatlon or mechanical
operations. This is the basis ror uslng alr mlcronization to
determlne the homogenelty o~ these composltes.
T~o or more composltes Or thls lnventlon harlng
difrerent propertles can be readily blended together to
glve a new composlte hav$ng propertles lntermedlate to
those Or the lndlvldual component composltes. For example,
a rlame-retardant composlte based on alumlna trlhydrate can
be blended with a composlte havlng a hlgh modulus and a
high heat deflection temperature based on kaolln clay to
glve a new composlte havlng propertle~ intermediate bet~een
those of the component composites. Such blends can be pre-
pared by blending techniques lnvolving temperatures below
the sortening point Or the composite. For e~ample, the
''
- 35 -
1~)4~779
composites can be blended by dry-blending techniques or by
high-speed stirring of the component composites in a suitable
liquid medium. When a liquid medium is used, it has been
found that the use of a 8mall amount of a conventional
wetting agent i8 helpful.
~ A wide variety of additives can be readily
a blended with the polyolefin/filler composites without the
necessity of melting the polymer. For example, the
composites can be stabilized against ultraviolet and thermal
10 oxidative exposure by the addition of conventional stabili-
zcrs and conventlonal antioxidants. Suitable ultravlolet light
adsorber~ include substituted benzophenones such as 2-hydroxy-
~-n-heptyloxybenzophenone, benzotriazoles such a~ sub~tituted
hydroxybenootriazoles, salicylates such a~ phenyl salicylate,
metal chelate~ such as CYASORB*W 1084 and CYASONB W 2548,
and carbon black.
Suitable antioxidants for addition to the composites
; o~ thi~ invention include alkylated phenols and bi~-
ph~nols ~uch a~ GOOD-RITE* 3114, a butylated hydroxytoluene;
20 alkylidene bi~-, trls-, and polyphenols ~uch as IR~ANOX*
; 1010 and SANIOWHITE* powder; thio and dithio bis-, tris-,
and polyalkylated phe~ols such as SANIONOX*; phenol con-
den~atlon product~ ~uch a~ TOPONOL* CA, amines such a~
CARSTAB* 601; e~ter~ ~uch a~ dllauryl thiodlpropionate; and
organic pho~phite~ and pho~phate~ ~uah as trldodecyl phos-
phlte and tri~(nonylphenyl) phosphites. Fire retardants
~uch a~ chlorinated polyethylene, zinc pho~phate~ and
tri~t2,3-dlbromopropyl) phosphate can al~o be added.
The compo~ites of this invention can al~o be
,
formulated with convention~l orgPn~c and inorganic pigment~
* denotes trade mark
- 36 -
., . .. , . .... ~ . ..
104g779
to provlde colored systems. Sultable pigments lnclude
quinacrldone red, anthraqulnone red, diarylide yellow-HR,
bis-azo red, bls-azo orange, bis-azo yellow, ~oindolinone
orange, isolndollnone yellow, lsolndollnone red, phthalo-
cyanine blue, pthalocyanine green, carbon black, iron oxide,
ultramarine blue, ultramarine green, pigmentary oxides such as
plgmentary tit~nia, zinc oxide and antimony o~lde, and the
llke. mese pigments should have a weight-average efrective
~pherical particle diameter less than that Or the flller con-
talnlng the actlve polymerizatlon sltes.
e composite~ Or this lnvention are formed into
userul artlcles by various rormlng techniques$ some Or ~hich
have been used heretofore wlth polyole~ins and other resins
and other~ which have been used heretorore rOr metal rorming
but whlch have not been previously used ror reslns. m ese
technique~ generally lnvolve subJecting the compo~ite to a
temperature at which the composite sortens in the range Or
about 105-250C and a posltlve pressure Or about 10-100,000
psi or more. me temperature selccted ln any speciflc case
will depend on the partlcular rlller u~ed. For example,
composites contalnlng alumina trlhydrate are preferably not
proce~sed above about 200C. In general, temperatures of
about 150-225C and pressures o~ about 10-15,000 psi are
preferred .
i A userul means Or formlng articles ~rom these
polyolerin/flller composltes 18 by compresslon moldlng,
which lnvolves the simult&neou~ application of heat and
pressure. mis operatlon can be carrled out by ~illing a
mold with the composite powder, and pressing the powder
in the mold with application of heat ~urficient to ral~e
- 37 -
,. ~
104~779
the temperature above the ~oftening point of the composlte.
Temper~tures of about 150 -225C and positive pres~ures of
about 10-5000 psi, and pre~erably o~ at least lO00 psl, are
; suitable. When the formed article has cooled below the
meltlng polnt of the polymer, the mold i8 opened and the
article 18 removed.
Sheets may be formed ~rom these polyolefin/flller
composltes uslng sultable sheetlng equlpment by passing the
composlte along a continuous belt, sub~ecting the composite
to a softenlng te~perature ln the range Or about 150-250C
~hlle it passes through a restricted space whlch compresses
the composlte against the belt at a pressure of about
50-5000 psi without subJecting the composlte to shearlng
forces, and remo~lng the reeulting sheet from the continuous
; belt arter it passes through the restricted space.
one suitable plece of equipment ~or formlng
these sheets 18 a contlnuous vulcanlzer. Uslng thls
equipment the polyole~ln/filler powder 18 placed on a
continuous belt ~hlch passes through shear-free compres-
sion rolls. The powder is heated to a softening tempera-
ture in the range of about 150-225C ~hile it is compressed
through the compresslon rolls at a pressure o~ about 50-
lO0 psi. me composite can be heated in any sultable
manner such as by passing the belt containing the composite
through a heatlng zone prlor to passing through the compres-
slon rolls or by use o~ a heated compresslon roll.
Sheets can al60 be ~ormed using sheeting equlp-
ment of the type described ln U.S. 3,286,008. By this method
the composlte is heated to a softenlng temperature of about
150-250C as it 18 compressed between t~o contlnuous belts
38
104~779
~hlch, a8 they progress, move closer together thereby
developlng a pressure of about 1000-5000 psl. me result-
lng sheet is then cooled to a temperature below the meltlng
point of the polyolefin and removed from between the belts.
Userul articles can be prepared from these sheets
by suitable rerorming techniques. For e~ample, formed ob-
~ects Or a wide variety of shapes can be prepared by heat-
lng a piece of compression molded sheet and then pressing
the hot sheet between a male die and a pad of elastomerlc
material. The temperature to whlch the sheet 1~ heated cQn
rary from about 105 toabout 225C. The male dle can be
made of any solld material such as metal, wood, resin, and
the llke. Sultable elastomerlc materials lnclude silicone
rubber, urethane rubber, and the llke. m e elastomeric pad
can be of ~n~ sultable thickness, ~or e~ample, it can be a
block oP elastomeric materlal havlng rlgld backlng. The hot
sheet 18 allowed to cool as lt 18 pressed between the die
and the pad, and thus can be removed from the dle alnost
immedlately. In some cases it is desirable to sub~ect the
~'20 die to internal cooling.
e re~orming of these compression molded sheets
can also be carried out by controlled hydraulic ~orming in
whlch the elastomerlc pad is a rubber diaphragm backed by a
hydraulic fluld. Stlll another method of reforming ls by
hot or cold, matched-metal mold ~ormlng, that is, pressing
or stamplng the sheet bet~een male and female metal dies.
The composites Or this invention can also be
formed lnto filmæ. These films may be obtained by stretching
a sheet or film for;med by any of the above compression mold-
ing techniques, such as the above sheetlng techniques or
I - 39 -
104~)779
presslng between platens and heating. The stretchlng can
be carried out at temperatures irom room temperature to
temperatures above the melting point of the polyolefin. me
sheet or fllm may be stretched either ln one direction or ln
more thsn one direction either sequentially or ~imultaneously.
me degree o~ volds developed during stretchlng wlll vary
dependlng on the stretching technique, filler, and slze of
~lller partlcle used.
In the case Or pull stretching, an opaque, paper-
llke fllm having an lncreased degree Or volds 18 obtalned.
Thls technlque reduces the thlckness Or the iilm, but does
not necessarll~ change lts ~trength. Stretchlng by rolllng
the sheet or fllm under pressure results ln a fllm which is
stronger than the orlginal and has a relatively lower void
content than a slmllar ~lLm formed by pull-stretchlng. In
thls rolllng technique, temperatures above or belo~ the
normal meltlng temperature Or the polyolefln may be used.
Because Or the partlculate nature Or the
composltes Or thls lnventlon they are amenable to another
method Or rormlng obJects, based on powder technology,
whlch lnvolves cold compresslng in a mold rollowed by
slnterlng. The po~der 18 placed ln a mold and compre~sed
at a pressure of about 100-100,000 psl, prererably at
least about 1000 psl, and most pre~erably, at least about
5,000 psl, at a temperature below the meltlng polnt or the
polymer to form selr-supportlng artlcles. The artlcle i8
then removed from the mold and den~lfied by heatlng at a
te~perature sbove the so~tenlng polnt Or the composlte,
e.g., about 105-225C, to form the rlnished artlcle.
m e composltes o~ this lnventlon are al~o u~eful
- 40 -
104Q779
rOr coatlng a wlde varlety of substrate~ by conventlonal
powder-coatlng technlques. In accordance wlth these tech-
nlques, for example, a substrate can be heated and then
dlpped lnto Q rluidlzed bed of the composite powder. me
powder wlll adhere to the hot substrate because of the ad-
heslve character o~ the ~oftened composlte. The powder
coatlng 18 then coalesced by slnterlng. mis technlque 18
userul ~or wlre coatlng and the like.
DETERMINATION OF INHERERT VISCOSITY
Inherent viscoslty is measured by the followlng
procedure A sample of the compo~ite powder calculated to
contaln 0.025 g Or polyolefln 18 placed ln a closed rlask
containlng a magnetlc stlrrlng bar and adapted rOr lnsertion
a thermometer and a condenser contalnlng a nitrogen purge
tube. Into thls rlask 18 plpetted 50 ml Or 1,2,4-
trlchlorobenzene contalning 1.33 g/l Or butylated hydroxy-
toluene antioxldant to glve a 0.05 weight/volume percent
solutlon or polyolerin.
Wlth the thermometer and condenser ln place,
nltrogen 18 slowly passed over the contents of the rlask,
the magnetlc stlrrer 18 started, and the contents o~ the
flask are heated to 180C. m e solutlon 18 stirred at thls
temperature for 2 hours. At the completlon oP thls time,
the condenser unlt and the thermometer are removed from
the flask. A ground glass stopper 18 lnserted lnto the
thermometer-well, a tube to support a capillary viscometer
is inserted in the condenser-well, and the entire unit 1B
transrerred to an oil bath and malntained at 130C. A
capillary viscometer having three scratch marks, one near
the bottom, one above the bulb and one below the bulb is
- 41 -
~ 1040~779
inserted in the support tube.
After 1 hour at 130C in the oil bath, the vls-
cometer 18 ad~usted 80 that the tip is immersed ln the solu-
tlon to the depth indlcated by the bottom scratch. Vacuum
is gently applied to the top of the vlscometer until the
solutlon has rlsen to a level above the top scratch on the
viscometer. The vacuum 18 removed and the solutlon 1~
allo~ed to ~all. m e flo~ o~ the solutlon between the
~cratch above the bulb cnd the scratch below the bulb 18
times. Thls flow time measurement lB repeated untll three
values whlch check within + 0.3 second are obtalned. The
flow tlme o~ the pure solvent 18 also measured at 130C in
the same way.
The inherent vlscoslty 18 calculated uslng the
followlng equatlons
Relatlve Vl8coBlty = Time o~ 801utlon
Tlme or solvent rlow
Inherent Visco81ty = natural%lo~ of relative vlscoslty
w/ polymer concentratlon
DETERMINATION OF 10-SECOND MICRONIZATION
HO~OGENEITY
m e 10-second mlcronlzatlon homogeneltles of the
composites o~ thls lnventlon are determlned using an 8-lnch,
stalnless steel Jet Pulverizer Model 08-505 micronlzer made
by the Jet Pulverlzer Co., Palmyra, N.J. This mlcronlzer
contains a grinding chamber, pneumatlc ~eeder and a product
dlscharge tube. me grlnding is performed by 6 air ~ets
placed tangent to a 5-lnch circle at the perlpheral ~all Or
the grlnding chamber. The pneumatic feeder conslsts o~ a
funnel ~eedlng into a venturi tube connected at one end to
an alr Jet and dlscharglng at the other end lnto the top
~o of the grlndlng chamber tangent to the perlpheral w~ll.
- 42 -
1~)4~779
The product dl~charge tube is a central chamber into whlch
the product drops and through whlch lt i8 dl~charged.
e procedure rOr determinlng 10-second mlcro-
nlzatlon homogenelty 18 as follows: The alr ~ets o~ the
mlcronlzer are turned on and the alr pressure is ad~usted
to 75 psl. A 10-gram sample of the polyolefln/flller
composlte 1~ added all at once dlrectly to the raw-feed
Punnel. Ten seconds a~ter the sample 18 added, the alr
; ~ets are turned orf and the 10-second mlcronlzation product
rractlon 18 recovered from the discharge tube. The percent
~lller content of thi~ product 18 determlned by measurlng
lts ash content by combustlon. The filler content of this
fractlon 1~ then compared wlth the flller content of the
feed composite to get an absolute difrerence in filler con-
tent. me 10-second mlcronlzation homogenelty (MH) per-
centage iB determined in accordance with the equatlon:
MH - 100 _ absolute dirrerence in filler content x 100
filler contcnt of feed
DETER~INATION OF ~ICRONIZATION HO~OGENEITY INDEX
me micronlzation homogeneity lndex i~ determlned
by restarting the air micronizer and taklng additlonal
product rractlons from the dlscharge tube of the mlcronlzer
wlthout adding any more sample. The micronizer 18 operated
at 75 psl air-pre~sure for periods found suitable to glve
at least three more reasonably slzed fractlons, wlth the
resldue, i~ any, considered to be the last fraction. The
last fraction must contaln 5-15~ by welght Or the recovered
product with the provlso that the percentage of the total
recovered product in the last fraction must not e~ceed the
percentage of polyolefin ln the feed composlte.
The flller content of each of the fractions, lnclud-
- 43 -
~O~V779
lng the first 10-second fractlon, i8 determined. The mlcronl-
zatlon homogeneity index (MHI) i8 then calculated by subtract-
ing the difrerence ( ~ ) between the filler content of the
hlghest flller fraction and the filler content of the lowest
flller fractlon from the 10-second micronizatlon homogenelty
(MH) percentage ln accordance with the following equation:
MHI = MH - ~
The results of these homogeneity tests correlate
very well with the physical properties of the composites,
especlally wlth the elongation at break and 0F Izod lmpact
~trength. When the flller content of the composition 18
below about 67~ the 10-second micronization homogeneity
alone serves to differentiate between homogeneous and
heterogeneous compo8ition8. For example, a typlcal
partially heterogeneous 50% clay composltion of the prior
art prepared by polymerlzlng olefin in the presence of
tltanlum trlchloride and clay had a 10-second mlcronlza-
tlon homogenetty o~ about 42%. In an extreme case Or
heterogenelty,a typical prlor art 50/50 blend of clay and
polyethylene,having the homogeneity graph lllustrated in
Figure 3, ha~ a 10-second mlcronlzatlon homogenelty of
about 2%.
When the flller content of the composltlon 18
above about 67%, the 10-second test becomes less reliable
by itself as an indlcator of homogeneity. For example,
a 11/89 blend of polyethylene and clay which glve~ a microni-
zstlon graph simllar to that of Figure 3 was found to have a
10-second micronizatlon homogeneity of 91~. However, the
mlcronizatlon homogeneity lndex was -3.
3o
- 44 -
1(~4V'779
E~ES OF q~E ~r~iTlON
T!he ~ollolring ~les illustr~te the inventlon~
1~11 parts and percentage~ are by ~ ht ~11e88 other~ise
8p ci~led.
Ia the~e ~ples ph~ic~l propertie~ are de-
ter~i~a b~r the rollo~ ~ te~t dedg~tio~.
t S~cl~le~tion~
Tens~le ~tre~ , ~xl~ (T) A8q!~1 D-638-71A
131oag tio~ at break tBb) ASDI D-638-7Lq
llod~ in ta~loa, initlal (~,) J~DI D-638-71A
od l~t ~tre~gth ASDI D-256-721~.
~hrd~r l~t ~trlgth SPI~ TS-159
art)
B~t d ~lection te~perature (~DT) ASq~l D-648-56
:, Fl~r-l ~treDgth ~1 D-790-7~
~loxur~l Ddulu~ J~DI D-790-n
Rocl~ll h~e~ ASq!ll D-785~65
o~ s~ ~a~ ~ D-2863
Ia t~ to~llo, elon~ation ~a ~a~w te~t~, to~t b~ Or
~pe I ~a ~ ~ 0~ ~s~ to~t ~tlaod 638-72 ~Id b~r~ pre-
~area accor~ to ~8~1 te~t ~tho~ 638-44T ~re wed.
o~yB~n ~dos (OI) i~ a ~a~we of tbo rr~ctloDal
part b3r ~rolu~ o~ o~r~ i~ a~a o~rgen-nltrogon ~i~ure
ee~ up~ort co~bwtlon Or the ~a~ple. Accordi~lgly,
a~ ~lue i~ ~ce~8 o~ 0.21 l~dlc~ l~e ret~rda~
alr.
s!hl~ ~pl- w-s EU~ICX~ ~ (~lck Sta~dard
GhOllliCal 00~) Bor't kl~Olia ela~ l~hieh ~a~ a ~urra¢e area o~
9.3 ~2/g, in llhi;ch 53,~ Or the partlcle~ c a ~eight-
* dalote~ tradc ~rk
.~
10~ 9
average equl~ralent spherical partl¢le di~ter Or le~s th~n
2 ~, ana ~ch ha~ a tot~ tlt~nlum cont~nt o~ 0.25 ~l
Or T~02 per gro~. A 4Q-g portion oP the above cl~ ~Ihlch
h~ been drl~d at 25QC rOr 18 hr i~ a 30-lltl~rh~r ~trca~
o~ nitr~g~n ~ added to 600 ~1 Or dr~, deo~ge~ted cg~clo-
he~ae in a blender eup to l~hich h~q alread~ been aaaed
4 1_l (0.8 g) o~ trllsobut3rl~u~i~m~ ~nd 0.2 l of totra-
beazylzlrconlum at~solvea in 2 ~l o~ toluene.
q!hs pol~r~zatlQn llac carrled out at 50C under
100 p~l et~rlene pre8~ure ~or 25 Dli~utes la produced 78 e
po~der that p s~ed a 28-mo~h ~creen.
me pro~uct ~aB round to contain 51.02~ clay by
ash analysls. The 10-second mlcronizatlon homDgenelty ~as
80 and the mlcronlzatiDn ho g~neity lnde~ ~as 56. Test
bars ¢ompre~slon molded at 175-C and 2000 psl had the
rollo~ing phyJlcal properties:
Tenslle (T): 2577 psi
Elongatlon (E~): 263%
Mbdul w (Mi) 823,000 pgl
O F Izod lmpact: 17.4 ~tib/in of notch
E~AMæLE 2
Thi~ ~ample uses GHA* 332 (Great Lakes
PCundry and Sand Co.) A1203-3H20 ~hich has a ~elght-average
equivalent spherical partlcle diameter o~ 4 ~. The
alumina trlhydrato wa~ dried at 180-190C ror 12.5 hr under
a 700-llter/hr flo~ o~ nitrogen.
The re~ction ml~ture ~a~ prepared in a dry Binks
tank fitted with a stirrer under nitrogen pressure. The
following ingredlents were added to the tank in the speci~ied
order.
* denotes trade mark
-- 46 --
~04077g
2.5 gal of dry, deo~ygenated hexane
30.0 mmol Or trii~obutylaluminum
1.2 mm~l Or tetrabenzylzirconium in 12 ml
o~ toluene
The mlxture ~a~ ~tirred ror 0.5 hr and then 1900 g Or the
alum~na hydrate ~a~ added. Stirring Nas continued ror an
addltlonal 0.5 hr and the entire content~ o~ the tank wa~
pu~ped und~r nitrogen blanXet into a 5-gal, ~tirred autocla~e.
; The tank ~as rin~ed ~ith an addltional gallon o~ hexane and
the rinse liquid wa~ also added to the autocla~e. me poly-
merization Wa8 carrled out at 50C under 100 p~i ethylene
pressure ~or 29.5 min.
me product uas round to contain 68.3~ A1203~3~20
by ash analJ~ig. The 10-secQnd mlcronlzation homogeneity
~a~ 93% and the micronization homogonelty indes wa~ 79.
Te~t bar~ compre~slon molded at 175-C and 3000 p~i had the
~ollo~ing phy~ical properties~
0~ Izod impact: 6.9 rt lb/in Or notch
; 74F Gardner i ~ t: 140 in lb (125 mil samplq~
-40F Gardner impact: 160 ln lb (125 mll sample)
EXAMPLE 3
Tb~ esample illu~trate~ tho preparation Or a
composite rrOm a kaolinite clay without the additlon Or a
tran~ition metal coordination catalyst component.
~ batch of HARWICK GE kaolin cl~y (Example 1)
wa~ driod (calclned) at 600C under a flow Or dry 4:1
nitrogen~osygen mi~ture at 30 liter~/hour for 13 hour~ and
', cooled under nitrogen to a~bient temperature. The calcined
clay had a ~urrace area Or 7.4 m2/g.
A 500-ml batch Or deo~ygenated cyclohe~ane was
- 47 -
..~,
:
iO40779
pa~scd through a bed Or Woelm acid alumina und transrerred
under a nltrogen blankct to a closed blender. The ~olvent
wa~ ~tirred and 0.5 mmol (0.1 g) o~ trii~obutylaluminum
and 40 g of the above clay wa~ added in turn follo~ed by
0.15 e Or additional trli~obutylalu~lnum.
me resulting clay sw pen~ion was transrerred to
a l-llter, ~tainles~ steel autoclave fltted with a m~gnetically
driven ~tirror. Eth~lene ~a~ added and the mlxture stirred
and heated at 70-C and an ethylene pr-s~ure Or 100 p8i for
1 hour and 27 mlnute8. The ~utocla~e was cooled, unrcacted
ethylene vented, and the reactlo~-mixture riltered to recover
76.5 g Or polyethylene/clay composlte.
Ash analy~l8 chowed that the product co~tained
48.3% clay. The polyetbylene h~d an inherent viscosity Or
12.88. Tho compo dte had a 10-~econd mlcronization home-
genelty Or 80~. A strlp Or f~lmJ h~t-pres~ed rrom thi~
product, ~a~ orlented by drawlng 5.5 dlameters at 150C.
T~t bars ~ere prepar-d by heatlng the compo~lte
at 175-C ~or 3 minute~, rollowed by compre~lon at 2000 p~l
rOr 1 mlnute. The~e bar~ had the following propertie~;
Tcn~ile (T): 3134, 3028 psi
Elongatlon (Eb): 471%, 422%
~o~ul w (Ml) 4Ç3,100, 409,500 p~l
0F Izod impact: 4.9 ft lb/in Or notch
264-p~l Heat derlection: 56C
EXAMæLE 4
Thi~ example ill w trate~ the formatlon Or
~heet~ rrom a pQlyolerin/filler composite and the rerorming
Or the~e ~heet~ lnto formed obJects.
(A) HARWICK GK ksolin clay (Example 1) was
- 48 -
,,} ...,~
1~)4~79
drled at 600C for 18 hours under a 100 l/hr flow of a
4:1 N2 2 mixture and cooled under nltrogen flow. A batch
of 2.5 gallon~ of deoxggenated, dr~ cyclohexane containing
5 g of tril~obutylaluminum wa~ placed in a dry, oxygen-
~ree, 5-gallon, gla~-lined kettle under nitrogen purge.
After ~tirring this æolutlon ror 10 minute~, a low-~i~co~ity
suspen~ion of 1500 g Or the abo~e clay ln 1 gallon of dry,
oxygen-rree cyclohexane containing 10 g of tril~obutyl-
all'm~num ~8 added to the glas~-lined kettle. The polymeri-
z~tlon ~a~ carrled out at 70C for 12 hour~ under an ethylenepre~8Ure 0~ 100 p8i. The product w~ ~tabillzed by adding
20 g~o~ IRGA~OX 1010 antloxldant dl~sol~ea in 300 ml of
other to the ~lurry, collected by filtration and dried in air.
The product ~elghed 3142 g a~ter ~io~ing through a
16-me~h ~creon and haa a clay contont Or 43.41% by a~h
anAly~i~. Te~t bar~ were prepared by preheating the compo~lte
in a id at 175C ~or 3 mlnute~, ~ollowed by compre~lon at
2000 p~i ~or 1 mlnute. The~e bar~ had the following propertle~:
TenJ~e ~T): 2886, 2795 psl
Elongatlon (Eb): 336%, 408%
Mod~l w (Mi): 248,000, 295,000 pal
0F Izod lmp~et: 21 ~t lb/in Or noteh
(ga~e a hinge break)
(B) Part (A) ~a~ repeated. The produet ~elghed
2778 g and had a elay eontent o~ 48.05~ by a~h analy~
The 10-~eeond micronization ho~ogeneity o~ thi~ product wa~
84% and the mlcronlzation ho geneity lnde~ w~ 52. Te~t bar~
~ere prepared by preheating the eompo~ite in a mold at 175C for
3 minutes, rollowed by eQmpre~lon at 20Q0 p~i for i minute.
me~e b r~ had the following propertie~:
10 4~'77 9
Tenslle (T): 3206, 2276 p8i
Elongatlon (Eb): 461~, 230%
Modulus (Ml): 370,000, 311,000 p8i
O-F Izod lmpact: 18 rt lb/ln Or notch
thlnge break)
(C) m e products of Parts (A) and (B) were placed
ln a large contalner and the contalner was rolled to mlx the
po~ders before uslng. m e mlxture was put through a 24-ln
~lde contlnuous vulcanlzer made by Adamson unlted Company
(sub~ldlary Or United Englneerlng and Fbundry Co.). The
vulcanlzer has rolls, one o~ whlch 1B heated, ~olned by
a contlnuous stalnle~s steel belt.
In this procedure, the composite powder was fed
onto the stainless steel belt, sgueezed between the rolls
wlthout shear, and carried around the heated roll at 400F
and a speed of 1.8 ~t/~in. m e sheet was manually removed
~rom the roll. m e physical properties Or the composlte
sheet, measured ln t~o directlons, werc as shown in
Table I. Test bars were prepared by preheating the composite
ln a mold at 175C ~or 3 mlnutes, ~ollowed by compression
at 2000 psi for 1 minute. These bars had the propertles
given in Table I.
TABLE I
0F Izod
T Mi Eb (ft lb/-
(p8i) (k~ (%) in of notch)a
Machine ?940310 157 13
Directlon
Transverse 2570354 205 13
Dlrection
Compres~lon 2790305 357 19
Molded
2740340 345 18
a - no clean break, values approximate
- 50-
,
1040779
(D) me composite sheet prepared above was
heated on a hot plate and its temperature ~as monltored
~ith a surrace pyrometer. When it reached the deslred
temper~ure, lt wa~ tran~ferred to a male dio in the shape
Or a truncated pyramid and pressed between the die and a
block Or ~ilicone rubber. me rubber assumed the shape
Or the mass that was pressed into it aad thus acted as a
~e~le die. Arter the sheet cooled, the mold wa~ opened
and the ~ormed pyramld was removed. An Izod ~mpact te~t
at room temperature was performed on pieces cut rrom the
slde of the rormed plece. me data obtained are glven
in Table II.
TAELE II
Formlng O-F Izod lmpact,
Temperature, G rt lb/in o~ notch
130 15.4
145 11.4
160 12.5
Uhrormed ~heet 17.2
EXAHoeIES 5-lg
~ h~ e~ample illustrates the preparation Or
compo~ites ~rom kaolln clay and pigmentary oxide using
tltanium tetrachlorlde as the transition metal compound.-
(A) A 500-g portion Or HARWICK 50-R kaolin clay
(~eight-average e~uivalent spherical partlcle dlameter Or
0.59~) ~a~ layered bet~een gla~s wool in a 3-llter beaker,
and drled at 600C uhile purglng with nitrogen. Arter 18
hours, the clay was cooled to 160C and lO-~l, lO-ml, and
5-ml portlons o~ t~tanium tetrachlorlde were vaporlzed
through the clay at 3-hour intervals. The clay waB coolea
.
- 51 -
' , ~ ' .
104~779
under nitrogen purge ~nd oxpo~ed to air l~r 4 da~.
A ~i~orm mlxture o~ 160 g Or the above/~di~ied
clay and 40 g Or TI-PU~* R-lQl rutile (titanium dio~cide
pigment, E.I. du Pont de ~iremour~ and aO., ~eight-average
equlvalent ~pherical particle dlameter of 0.18 ~) ln 200 ml
Or cyclohe~e was mtlled l ith glass rod~ for 1 aa~.
me rtller misture wa~ collected by riltration, and drled
at 600-C under a 4:1 nitrogen:o~ggen mixture rlOw Or 30
llter~hlour for 18 hours and cooled under nitrogen from
400C.
Deo~rgenated cyclohe~ane ~500 D~l) wa~ pas~ed
through a bed Or Woelm acid alumina into an enclo~ed
blender cup under constant nltrogen purge. The solvent
tlrred and 50 g of` the above rtller mi~cture was added.
During stirrint, 0.79 g Or trlisobutylaluminum was added to
glve a very low rl~coslty fluid suspension of inorganic
m~terials in the cyclohe~ane.
Polymerlzatlon ~as carried out in a m~gnetically
~tlrred autoclave that had been drled under nitr0gen pur,ge
~hile heating at 150C. The above sw penslon was ~orced
by nltrogen pressure ~rom the blender cup through a poly-
ethylene tube lnto the autoclave. The polymerlzatlon ~as
carrled out at an ethylene pressure Or lO0 psi and a 70C
temperature.
Ih 57 minutes, 75 g oP po~der haring a rlller content
o~ 59.0 calculated rrom the carbon analy~i8 was formed.
Test bars compression molded at 175-C had the ~ollo~ing
phy~lcal properties reported ln Table III. A strip of r~lm
hot-~res~ed ~rom this product, wa~ hot draNn 2.5 dlameters
at 25-C and 4.5 dlameter~ at 130-C.
''~ * denote~ trade mar~
-52-
~'~
~e ~ ~ ,
1~4~77g
f
(B) Variations in preparing the filled polyethylene
compQsite~ of Part (A) are aleo given in Table III. ASP*
400 (Engelhard Mlnerals Co.) kaolin clay has a weight-average
equivalent ~pherical particle diameter of 4.8 ~. HYDRITE*
MP kaolln clay (Georgia Kaolin Co.) ha~ a weight-average
equiv~lent spherical particle diameter Or 9 ~ and a range of
1.5-35 ~. A strip Or ~ilm hot-pres~ed from the product Or
E~ample 8 ~as oriented at room temperature. A strip of fllm
hot-pre~sed from the product Or Example 9 was grey in color,
tough and orientable ~t room temperature.
* denote~ trade mark
; - 53 -
104~779
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w~ ~c~ ~ ~-- m-- w-- ~-- m~ ~ ;
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14 P; P~ ~~ P; ~ n
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*
~k
- 54 -
.
104~779 ~;
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h¦ , ~i CU .~ O p, 0
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cl o ~. o ~ dl
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~ ~ ol ~ ~1 u~ ~ 0 N
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1~O Hl ~) C~0 ~I N ~1~ CU ~ N 0 Ir~ o
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E~l ~ ~ ~ C~ ~ ~ O ~ ~ O
W-- N ~ ~rl ~I N H CU N N ~ 8
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a-
104(~77
EXA~E 15
Thi~ example lllu6trates the preparation o~ a
composite containing polypro wlenc.
A mixture o~ 1200 g o~ HARWICK 50-R kaolin clay
(Example 5) and 100 ml of tetraisopropyl titanate in enough
cyclohe~ane to make the mixture fluid was rod milled at room
temp~rature over a weekend. The clay wa~ collected by
filtratlon, washed with cyclohexane, air-dricd and pulverized
ln a blender. me clay was then dried ror 18 hour~ at 600C
unaer a 30 llters/hour streamo~a~:l N2:02 mixture, and
then cooled under nitrogen.
A ~lurry was made ~rom 70 g of the tita~la-coated
clay, 500 ml of dry, deo~ygenated cyclohexaneJ ~nd 0.79 g o~
trii~obutylaluminum. The slurry was tran~ferred to an auto-
clave, 150 g o~ propylone added, ~nd the mixture heated at
70C rOr 12 hours.
The gro~ product ~as precipitatod by ~tlrring
~lgorously ~ith acetone in a blender. me mixture was
allowed to soparate by otandingJ the solvent decantedJ and
the stirring ~ith acetone and decantatlon repeated t~ice.
The ~olid polypropylene/P~ller compos~te wa~ a free-flowing
powder.
The product by carbon and hydrogen analysl~ ~as
Pound to contain 76% clay. me polypropylene had an lnherent
vlscoslty Or 6.8 mea~ured ln decalln at a concentratlon oP
0.1 ~/v%. A Pilm pressed at 160C and 3000 p~i could be bent
but not crea~ed. Compresslon molded test bars ~d the ~ollow-
lng propertle~:
Ten~ile (T): 813 p~l
Elongatlon (Eb): 2.3%
- 55 -
.~ ,i,
~ 7 7 ~
Modulus (Mi): 235,000 p8i.
25~ Izod impact: 0.3 ~t lb/in o~ notch
EXAMP$E 16
ml8 example lllustrates the preparation Or a
compo~lte contalning an ethylene/propylene copolymer.
A 400-g portion Or ~ARWICE 50-R kaolin clay
(Examplo 5) wa~ placet in a 2-liter be~ker between layers
Or glass wool. The mixture was heated to 300C and nltrogen
was passed up through the bed by means o~ a dlp stick. After
8 houre, the clay temperature ~as ad~usted to 160C and
threo 10 ml portions Or TiC14 ~er~ inJected at 2-hour inter-
vals lnto the lower glass wool layer. men nltrogen Wa8
again pa~sed through the clay at 160C to remove excess
TlC14. me materlal at 25C was exposed to air at 25C
to hydrolyze ad~orbed TiC14. The tltania-modifled clay was
then dried at ~00C for 18 hour~ under a 30 l/hr rlow Or a
3:1 N2:02 gas mixturo and cooled in a nitrogen rlow.
A 400-ml, dry~ oxygon-rree, shakRr tube was
charged with a suspenslon of ~0 g o~ the above dried, titania-
modiried clsy in 150 ~1 Or dry, deoxygenated cyclohexane con-
talning 1 g Or triisobutylalu~inum. me reactor Wa8 closed,
charged with 150 g Or propylene, and heated to 80C. The
propylene developed a pressure Or 300 psi. The pressure was
increa~ed by 100 pBi with ethylene. Arter 6 hour~, 35 g Or
ethylene wa8 con~umed.
The ethylene-propylene copolymer/rlller composition
~oighed 72 g and contalned 55% clay. The polymer had an
inherent vlscoslty Or 9.80. A rilm pressed at 150C ~rom the
product was rubbery and could be cool drawn. The drawn part
wa~ ~180 rubbery.
- 56 -
~)4~779
E~E l7
ml~ example illustratea the preparation of a
compo~ite from a hydrogenated and titanated clay.
A mixture of 500 g of HARWICK GK kaolin clay
(Example 1), 500 ml of cyclohexane and 75 ml o~ tetralso-
propyl tltanate was rod milled for 1 day and the 5011~
collected on a filter. The filter cake was washed with
cyclohexane, air-drled and pulvcrlzed in a blender. me
titanla-modlrlcd clay W~B calcined at 600C under a 30-liter/
hour Plow o* hydrogcn Por 18 hour~ and exposed to air. A 70-g
port~on o~ the hydrogenated product wa~ oxidlzcd by heatlng
at 600C Por 18 hours under a 30-litcr~hour flow o~ a 4:1
J22 mi~ture.
The oxygenated clay was charged into an auto-
cla~e with 650 ml of cyclohexane and 0.792 g o~ txli~obutyl-
alumlnum, and polymcrization carried out at 70C and an
ethyleno pre~sure of 100 psi for 40 minuto~. This ylelded
93 g o~ a powdered product that was ~ound to contain 69.66%
clay by Ash analysis and had a 10-second micronizatlon homo-
genelty oP 88%.
me ph~81cal properties of test bars compres~lon
molded at 175C and 2000 p~i were:
Tensllo (T): 3401, 3469 psl
Elongation (Eb): 178% 200%
Modulu~ (Mi) 965,500, 837,100 p8i
0F Izod impact: 1 Pt lb/ln of notch
264-psl Heat deflection: 90C
Rockwell hardnes~ (R ~cale): 85
(B) A repetltlon of the above polymerlzation
ylelded 85 g of powder in 23 minute~ reaction tlme. The
- 57 -
.~
104(~ 9
p~oduct was found by ash analysis to have a clay content o~
71.86%. me polymer had an inherent viscosity o~ 14.77. The
physical properties of test b~rs compression molded at 175C
and 2000 psl were as follows:
Tensile tT): 3439, 3421 psi
Elongation (Eb): 44%, 10%
Modulus (Mi): 1,280,000, 1,111,000 p~i
0F Izod impact: 1.5 ft lb/ln Or notch
264-psi Heat derlectlon: 98C
EXAMPLE 18
:
This example illustrates the preparation of a
composite uslng a water-soluble chromium salt as the
transltion metal compound.
HARWICK GK kaolln clay (Example 1) was calcined
at 600C to remove essentially all water of hydration, and
then cooled. A 1000-g portlon Or the clay was made into a
slurry wlth 1100 ml of distilled water containing 1.24 g
of chrominum(III) acetate monohydrate. The slurry wa~ tumbled
in a rod mill ~or 2 hours. The pH remained essentially con-
stant at 5.5-6. Finally, the solid was isolated, and the
aqueou~ solution was noted to be lighter in oolor than the
original solution. The treated clay was dried at 180C in a
~tream o~ nitrogen.
A l-gal autoclave was dried at 150C under nitrogen
purge and charged under nitrogen purge with 1000 ml of dried
cyclohexane and 2 ml of a 1.6 molar solution of triethylaluminum.
Next, a slurry wa~ added, comprislng 180 g of the above
treated kaolin clay and 800 g o~ dried heptane containing
4 ml of a 1.6 molar solut~on of triethylaluminum. The auto-
clave was closed and heated to 60C. me polymerization was
- 58 -
104~)779
carried out under an ethylene pressure of 150 p~i during
2.16 hours. mc product (370 g) was isolated, a~ter rinsing
with methanol and drying, as a fine, white powder.
The compo~ite was found by ash analysis to contain
46.2% clay, and had a 10-second micronization homogeneity of
89%. me polymer had an inherent viscosity of 11.60. A
~ample o~ thls composition was compression molded at 175C
into test b~rs that had the following propertic6:
Tensile (T): 3300 psl
Elongation (Eb): 5%
Modulus (Mi): 433,000 psi
73F Izod impact: 15 ft lb/in of notch
EXAMP~ 19
Thls examplo lllustrAtes the importance o~ not con-
tacting the ~lller ln~tially with a zirconlum compound.
(A) A l-l~tcr, magnetically driven autoclave wa~
dried at 150C by flr~t evacuating to a pres~ure o~ 0.5 mm
o~ Hg ~or 2 hrs ~nd then purging for 3 hours at 150C with
nitrogen. HARWICK GE k~olin clay (Example 1) was dried at
600C ~or 18 hours under a 30-liter/hour flou of 4:1
N2:02 mlxture and allowed to cool in nltrogen. me resulting
cl~y h~d a surface area of 7.4 m ~g. The reaction mixture
W~8 prepared a~ a low-vi~co~ity su~pension by adding 50 g of
the dry cl y to a dry enclosed blender cup under nltrogen
purge containing 500 ml of dry, deo~ygenated cyclohexane and
3 mmol oP triisobutylaluminum. After stirring the afore-
mentioned lngredients, 0.22 g (0.01 mmol/g of clay) of tetra-
benzylzlrconlum was added. The pale pink-orange mixture was
transferred through polyethylene tubing into the autoclave by
a 1-2 p8ig nltrogen pressure applied to the blender cup.
- 59 -
A
104~77~
The polymerization was carried out at 70c under an
ethylene pressure of 100 p5i for 2 hours and 3 minutes.
The powdery product, 98 g, wa~ found by ~sh
analy~i~ to have a clay content Or 46.45%, ana a lO-
second micronization hom~geneity of 75%. Thc polymor had an
inherent vlscoslty Or 15.01. Compre~sion molded test bars
had the following physlcal properties:
Tensile (T): 3108, 3532 p8i
Elongation (Eb): 353%, 448%
Modulus (Mi): 360,700, 403,800 psi
0F Izod impact: l9 rt lb/in of notch
(B) For comparleon, the above procedure was re-
peated, except that no clay ua~ added and 0.050 g of tetra-
benzylzirconium ~a~ used. When etbylene was processed uith
the re~ulting mlxture at 60C nd 100 p~l for 3 hr and 14
min, oa~y 0.1 g Or polymer waJ rormed.
(C) For ~urther comparison, the procedure of thi~
example ~J repeated except ~or the rollouing change~:
1. The flller was 70 g of ALCOA C-30BP A1203.3H20, drled
at 150C for 18 hr under a 30-1/hr ~low Or nitrogen.
2. Tho ~m~unt of tetrabenzylzirconlum wa8 0.050 g
(0.0014 mmol p~r gram of riller).
3. me tetrabenzylzirconium WaB added before the triisobutyl-
aluminum~
4. The reaction uith ethylene was carried out for 3 hr and
36 min at 60C.
During the 3 hr and 36 mln perlod, only 21 g o~ ethylene
wa~ taken up~ and only 2 g in the last 58 min. The 21 g
correspond~ to a compositlon contalning only 23% polyethylene
(53.5% in the product o~ Part A). The product was lumpy and
* denote~ trade mark
- 60 -
104~ 9
heterogenoous in appearance. Compression m~lded te~t bars
had the following phy~lcal properties.
Tensile (T): 1236, 1400 psi
Elongation (Eb): 7.4% 1.1%
Modulu8 (M1): 575,700, 576,700 p~i
0F Izod Impact: o.86, 0.85 ~t lb/in of notch
(D) For still further compari~on, the procedure
Or the immediately preceding comparative example was repeated
except that O.lg(0.0028 mmol per gram Or filler) Or tetra-
benzylzirconium and no trii~obutylaluminum was added. Only a
tracc of polymerlzation took place after 3 hours.
EXAMPLE 20
ThiB example illu~trates the preparation o~
composite from diatomaceou~ earth.
A 247-g portion Or CE~ITE* diatomacoous earth
tsilica) having a surface area of 10-20 m2/g was placed betwoen
two layer~ Or glass wool in a 2-1 beaker, the system was
heatod to 160C, and nitrogen wa~ pas~ed through the mineral
bed for 18 hours. The nltrogen wa8 stopped, and three 8-g
portlQns Or tltanlum tetrachloride were placed in the bottom
o~ the beaker through a syringe at 2-hr intervals with the
temperature still at 160C. The system wa~ then purged with
nltrogen for t~o hOUrB. me mlneral was stirred overnight
with water containing enough ammonlum hydroxide to make the
mixture sllghtly basic. The mixture was flltered, and the
solid on the ~llter wag washed wlth water unt$1 the ~resh
~ashlngs were ~ree of chloride ion. me wct 601id wa~ sus-
pended in ~ater, the suspension was put through an 80-mesh
screen, and the solid was separated by ~iltration and dried
at 100C~ It conta~ned 0.38% Ti (0.08 mmol of TiO2/~ of
* denote~ trade mark
_ 61 -
. . .
10~779
mineral). A portion of the product wa~ further dried at
500C for 18 hours ln a stream of 4:1 N202 mlxture flowlng
at 30 l/hr and cooled ln a stream of nitrogen.
Deoxygenated cyclohexane (500 ml) wa~ passed
through Q bed of Woelm acid alumina into an enclosed blender
cup under constant nltrogen pressure. Stlrring was started,
and 1 mmol of triisobutylaluminum was added, followed by
so g ~r drled filler and an additional 2 mmol of triisobutyl-
aluminum. The low-vlscoslty dlspersion thus obtalned was
transferred wlth nltrogen pressure through polyethylene
tubing to a stirrer-equlpped, stainle~s steel autoclave that
had been dried under a nitrogen purge at 150C. The auto-
clave was closed, stirrlng was started, the mlxture was
heated to 70C, ethylene was admitted to 100 psi, and these
condltions were continued Por 10 hours. After cooling, the
solld wa~ separated by filtration and air-dried.
The product was 103 g of ~ polyethylene/
dlatomaceous earth composlte that was found by ash analysls
to contain 38.92~ filler, and had a 10-second micronization
homogeneity or 83%. The polymer had an inherent vlscosity
of 23.33. Compre~sion molded bars had the following physlcal
properties
Tensile (T); 4245, 4196 psi
Elongation (Eb): 301%, 295%
Modulus (Mi): 514,000, 535,000 psl
0F Izod lmpact: 4.8, 5.4 ft lb/in of notch
EXAMPLE 21
This example lllu~trates the preparation of a
composlte from slate flour.
Slate flour (powdered ~late, 200 g), 50 ml of
- 62 -
1(~4~)779
tetraisopropyl titanate, add 400 cc Or cyclohex~ne were
mixed in a rod~mill rOr one hour, aft¢r which the ~late
~lour wae sepaxated by filtration, washed wlth cyclohexane
and air-dried. It contalned 0.93% Ti (0.2 mmol of T102/g
Or mineral).
Firty gram~ Or the titania-trcated slate (~ur-
ther dried a~ in Examplc 20), 600 ml of deoxygenated cyclo-
hexane, and a total of 0.4 mmol Or trii~obutylaluminum
were mixed and procesaed with ~thylene at 70C and 100 psi
by eo~entially tho procedure Or Example 20. The polymeri--
~zat1on was otopp~d after 50 g Or ethylene had reacted (4 hr
and 21 min).
The product ~n the liquid pha~e w~ 68 g Or a pow-
dery polyethylene/slate compo~ite th~t wa~ found by ~h
~nalysi~ to have a riller content Or 51.85%. A hot-pres~ed
sheet formed rrom the composite wa~ brown and ~ery unirorm.
Compreo~ion molded bar~ had the following propertie~:
T~nslle (T): 3427 p~i
Elon4ation (Eb): 472%
M~dulus (Mi): 286,000 pBi
0F Izod impact: 14.2, 15.9 rt lb/in Or
notch
264-poi Heat deflection 55.5, 57.5C
EXAMælE 22
m is example tllustrates the formation Or ob~ects
from a compo ite by cold compre~sing ~nd ~intering.
A 1500-g batch Or AICOA C-333 A1203 3 ~0 having
~creen an~lysi~ Or 99% through 325 me~h, 94-99% le~ than
30 ~, 85-93% le88 th~n 20 ~, 56-67~ le~s than 10 ~, 20-40%
le~ than 5 ~, and a median partlcle ~ize Or 6.5 to 9.5 ~,
30 wa~ placed between l-in layers of gla6~ wool in a 3-liter
- 63 -
.,i
104~79
beaker ln a heatlng mantle. Dry nitrogen was pas~ed
through the bed for 2 hours at 160C. Then the nltrogen
flOW was stopped and 3 successlve 15-ml portlons of
TlC14 spaced 2 hr apart were vaporlzed through the alumlna
hydrate. The mass was cooled under nltrogen flow and 6tlrred
for 14 hour~ with 2 llters of distllled water containing
100 ml of concentrated aqueous ammonla. The solid was
collected by ~lltratlon, washed wlth dl~tllled water until
the ~lltrate was free of chloride ion, and alr drled
(analysls Tl, 0.53% or 0.11 mmol of T102/g of ~lller).
The flller was drled at 175C for 16 hours under a 30-llter
per hour flow of nitrogen before using.
A charge oP 400 g of the titanated alumina trlhy-
drate su~pended ln 1845 ml of cyclohexane contalnlng 18 mmol
of trilsobutylaluminum was transferred to a 2-gal autoclave
which already contalned 0.7 gal o~ cyclohexane. Polymeriza-
tlon was carried out at 70C and an ethylene pressure Or
100 psl ~or 2 hours and 9 minutes and gave 592 g of powder.
The product was found to contain 63.6% A1203-3H20
by ash analysls. A melt pressed film from the product was
easily orlented while cold. The physlcal properties of
test bars compres~lon molded at 175C and 3000 psi were
Tensile (T): 3402, 3330 psl
Elongatlon (Eb): 408~, 395~
Modulus (Ml): 415,017, 421,765 psi
0F Izod impact: 11.5 ft lb/in of notch (no break)
Oxygen lndex .305
The powdery composite was fabricated by cold com-
pacting and sintering as follows. The powder was pressed
at ambient temperature to green forms having enough strength
- 64 _
104111779
to be handled wlthout special techniques followed by a
heat-treatment above the meltlng point of the polymer. m e
hot piece was cooled unlformly to prevent warpage.
me data in Table IV demonstrate the effect of
pressure variations ln preparing the green sheets on the
physical properties of the f~nal product. me green sheets
were sintered between brass plates in a circulatlng air
oven and cooled slowly by wrapping the sheets and bras~
plates ln glass wool lnsulation.
mis procedure i8 a versatile method for prepar-
ing compllcated shapes and slzes. Because the green forms
shrlnk durlng sintering, lt 18 necessary to make the green
form larger than the deslred ob~ect.
- 65 -
I0407~9
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- 66 -
~4~779
EXAMP$E 23
This example illustrates the preparation Or a
composite containing zinc oxlde a~ the filler.
A mixture Or 300 g of KADOX 15 zinc oxide
(Example 14), 60 g Or tetraisopropyl tit~nate, and 400 ml of
dry cyclohexane was ~haken occa~ionally and allowed to ~tand
for 7 hour~. Tho solld was ~eparated by riltration, washed
with dry cyclohexano, snd air-dried. A portion Or the product
wa~ driod at 500C ~or 18 hour~ undcr A strcam Or 4:1 N202
mi~ture flowing at 30 l/hr and cooled undor nitrogen.
By e~entlally the proce~ Or E~ mple 20, a poly-
merlzation modium wa~ m~de up rrom 250 ml Or deoxygenated, dry
cyclohexane, 0.5 mmol Or trii~obutylaluminum, 40 g Or the
dried, coated zinc oxlde, a~d an addltlonal 2.5 mmol of trl-
loobutylalumlnu~, and th mlxture WaJ proce~sed with ethylene
at 70C and 50-100 p~i in a ~hakor tube untll 28 g Or ethyleno
rcacted (8 hr).
The polyethglene/zinc oxide compo~lte thu~ obtained
weighed 64 g ~hlch indicated that the compo~ite contained about
62~ zinc oxlde. Test bar~ werc propared by preheating the
compo~ite in a mold at 175C rOr 3 minute~, followed by
compre~ion at 2000 p~i ~or 1 minute. These bar~ had the
~ollowing propcrtie~:
Ten~ile (T): 2820, 2799 p~i
Elongation (Eb): 126%, 145%
Modulus (Mi): 275,000 241,000 p~i
0F Izod impact: 19 rt lb/in Or notch
EXANEIE 24
Thls examplc illu~trate~ the preparatlon Or a
compo~ite from calcium hydro~en phosph~te.
- 67 -
1040779
A batch of calcium hydrogen pho3phate, CaHP04
(J.T. Baker Co.) wa~ dxied by heatlng at 250C ~or 18 hours
under a stream of nitrogen flowing at 30 l/hr By essentially
the method of Example l9, 60 g of th~ dri~d mineral Wa~
mixed with 600 ml of dry, deoxygenated cyclohexane, 4 mmol
of trii~obutylaluminum, and a ~olution of 0 100 g of tetra-
benzylzlrconium (0.2 mmol) in 2 ml of toluene, and the mix-
ture was processed with ethylene at 50C and lO0 psi until
40 g of ethylene had reacted (3 hr and 43 mln).
me polyethylene/CaHP04 compo~ite thus produced
consl~ted o~ 18 g of powder add 63 g oP larger picce~ of
~olld. Both gave ~trong hot-pre~ed ~ilm~. The larger
p~-ce~ were pulv-rized in a blender, after which the solid
pas~od a 16-me~h screen. The product wa~ ~ound by a~h
analy~i~ to h~ve a fill-r content o~ 58.60%. Plaque~
(3 5 x 6.5 in) were prepar-d by preheatlng the composite
in & mold at 180C for 3 min, followed by compre~ion at
3000 p~i for 2 m~n. Test bar~ cut from the~e plAques had
t~e ~ollowing properties
Ten~le (T) 2231, 2202 p6i
Elongation (Eb) 418%, 395%
Modul w (Mi) 327,000 373,000 p~l -
0F Izod impact 8.7, 8.6 ft lb/in of notch
(hinge bre~k)
Oxygen index 0.227
EXAMPLE 25
ml8 example illu~trates thc preparation Or a
compoaite ~rom calcium carbonate which has been coated with
- alumina
(A) A 1200-g portion of GAMMA SPERSE* 80 calcium
* denote~ trade mark
_ 68 -
,. ...
1040779
carbonate (Georgia~Marble Co.), having a surface area of 3.6
~2/g and a welght-average effective spherical particle
dlameter o~ 2.2 ~, was suspended in 2 1 of water by stlrrlng
at 25C for 10 min~tes. A solution of 57 g of AlC13 6H20in
400 ml of water was added dropwise wlth stirrlng over 15
minutes, and the mlxture wa~ stlrred ~or one hour and
dlvlded into two equal parts. One part was flltered, and
the solld on the filter was washed with water untll the
fresh washlngs were free of chlorlde ion and then dried.
It contained 1.3% Al by X ray fluorescence. The product
was dried additionally at 250C for 18 hours under nitrogen
flowlng at 100 l/hr.
A 2-gal, stalnless steel autoclave with a mag-
netically drlven stirrer was dried and deoxygenated by
purging three tlmes at 150C wlth ethylene at 50 psl,
purglng ~t 150C for three hour~ wlth nltrogen, and cool-
lng under nltrogen. It was charged wlth 0.65 gal of dry,
deoxygenated hexane at 25C.
Flve hundred grams of the dried, alumina-coated
calclum carbonate was charged under nltrogen to a creased,
5-1, round-bottom flask fitted with a ~ood blender blade
assembly and containing 18 mmol of triisobutylaluminum added
as a 1 M solution in heptane and 0.7 gal o~ dry, deoxygenated
cyclohexane. m e mixture was stirred briefly to give a low-
vlscosity dls~ersion, and o~ g (0.00011 mmol/g of calclum
carbonate) of tetrabenzylzlrconium waæ added. The mlxture
changed rapidly from yellow to orange. The dispersion was
transferred under nltrogen pressure through a polyethylene
tube to the autoclave, and the system was heated to 70C and
pressured with ethylene at a maximum pressure of 69 psi with
- 69 -
104~)'7~9
stirring until 410 g of ethylene had reacted (24 min). me
solid polyethylene/calcium carbonate composition thus formed
was isolated by riltration, washed with cyclohexane, a~d
dried.
The product consisted o~ 1000 g of a powder that
pa~sed a 12-me~h screen, plu8 ~0 g of coarser particles.
The powder was found by ash analy~i~ to contain 49.5% CaC03.
A 1/8-in sheet compressionmOlded at 175C and 2000 psi was
cut into test bars which had the following properties:
Ten~ile t T): 3498, 3229 psi
Ten~ile (T) at 70C: 3784 p8i
Elongation (Eb): 38~%, 309%
Elongatlon (Eb) at 70C 890%
ModulUs (Mi) 227,000 262,000 psi
0F Izod impact: 13.4. 13.6 ~t lb/in of
notch
264-psl Heat derlection: 54~5~ 55C
(B) in contrast, when 425 g o~ calcium carbonate
that had not been coated with aluminum Nas treated with
ethylene with the same catalyst s~stem, at 60C and 100 p~i,
only 50 g o~ ethylene reacted in two hours.
EXAMP$E 26
mi8 example illustrates the preparation of a
composite rrom calcium carbonate coated with ~ilica.
A solutlon Or monomeric silicic acid wa~ prepared
by adding 28 g Or silicon tetrachloride to 200 g Or ice with
strong stirring in a blender. The re~ulting clear ~olution
~as added immediately, dropwise with stirring, to a ~uspen-
~ion Or 1000 g Or GAM~A SPERSE 80 calcium carbonate
(Example 25) in 2 1 of water. me mixture wa~ filtered,
- 70 -
104~779
and the solld on the filter was wa~hed free of chloride ion
with water, drled, and pulverized. It was further dried at
300C under a stream of nitrogen flowing at 30 l/hr.
Cyclohexane (600 ml) was passed through a bed of
Woelm acid alumina into an enclosed blender cup under nitro-
gen. Triisobutylaluminum (4 mmol) was added, followed by
70 g of t~e silica-coated calcium carbonate described above
and 0.10 g of tetrabenzylzirconlum (0.001 mmol/g Or calclum
carbonate), all wlth ~tlrring. me flnal mlxture was plnk-
orange. The dlsperslon was transferred through a poly-
ethylene tube under nltrogen pres~ure to a one-llter, stain-
less steel autoclave equlpped wlth a magnetic stlrrer,
whlch autoclave had been dried at 150'C and 0.5 mm vacuum
~or two hours, followed by purglng ~lth nltrogen at 150C.
The system was heated to 60C, ethylene was admitted to 100
p8i, and the reactlon mlxture was held at 60C and 100 psl
untll 37 g of ethylene had reacted (45 mln).
Flltratlon and drylng gave 93 g of polyethylene/
calclum carbonate composite as a powder that passed
through a 28-mesh screen. The product was found by
ash analysis to contain 66.7% calclum carbonate.
Compression molded test bars had the followlng propertles
Tensile (T): 2791, 2666 psl
Elongatlon (Eb): 354~, 288~
Modulus (Ni): 301,000, 401,000 psl
0F Izod impact 12.5, 12.4 ft lb/in of notch
EXAMPLE 27
This example illustrates the preparatlon of a
composlte from calclum carbonate coated with acld pho~phate.
A solutlon of 45 g of 85% phosphorlc acid in 200 ml
lV4~)77~
o~ water was added dropwise with stirring to a suspension of
600 g of GAMMA SPERSE 80 calcium carbonate (Example 25).
The sw pension was ~lltered, and the solid on the ~ilter was
washed with water and dried. It contained 1.98% phosphorus.
The solid was further dried at 250C for 18 hours in a stream
o~ nitrogen.
By e~sentially the method Or Example 19, 70 g o~
the dried calcium carbonate was mixed with 600 g o~ cyclo-
hexane, 4 mmol o~ triisobutylaluminum, and a ~olution of
0.100 g o~ tetrabenzylzirconium in 5 ml of toluene, and the
mixture was processed with ethylene at 50C and 100 psi ~or
1 hr and 2 m~n to give 7Z g o~ polyethylene/calc~um car-
bonate composition as a powder.
The product was found by ash anaiysis to contain
63.5% calcium carbonate. A hot-pressed rilm prepared ~rom this
composlte was tough and cold drawable. Plaques (3.5 x 6.5 in)
were prepared by preheating the composite in a mold at 180C
for 3 mln, followed by compre~sion at 3000 psi for 2 min~ Test
bars cut from these plaques had the ~ollowing properties:
Tenslle (T): 2685, 2506 psi
Elongation (Eb): 421%, 357%
ModulW (Mi) 647,ooo, 625,000
0F Izod impact: 9.6, 9.7 ft lb/in of notch
(hlnge break)
EXAMPLES 28-33
The#e examples illustrate the preparation Or com-
posltes using a variety o~ hydrocarbon-~oluble organic transi-
tion metal compoundæ.
Up to the start of the polymerization, all
operations were carried out under dry nitrogen. Two liters
.
..
104~7~g
of reagent-grade cyclohexane was pas~ed through a 3-inch
bed Or Woelm acld alumina into a 5-1, round-bottom flask
~ltted with a blender in lts base. Stirring wa~ started,
and 7.5 mmol Or trlisobut~lall~m~num was added from a
~yringe, followed 10-15 ~econd~ later by 185 g of HARWICK GK
kaoli~ clay (Example 1) that had becn dried at 265-275C
~or 16 hr in a 6tream Or nitrogen and cooled under
nitrogen. Arter ~tirring for one minute, a ~olution Or
0.2 mmol (90 mg) o~ tetrabenzyltitanium in 6 ml of toluene
wa~ added from a ~yringe and the ~uspension wa~ stirred
vigorously for rive minute~.
The ~u~pen~ion was then transrerred through poly-
ethylene tubl~g under nitrogen pre~sure to a dry, oxygen-
free, ordinary-steel autoclave equipped with a ~tlrrer.
The stirrer wa~ run at 1000 rpm during the addltion and
thc aubsequent polymerization. me autoclave was heated to
60C, the nltrogen wa~ replaced by surricient ethylene
(45 g) to reach a pre~ure Or 100 p8i, and the sy~tem was
heated at 60C ~nd malntalned at 100 p~i until an addltlonal
90 g Or ethylene had been added. The aim was to form an
approximately 67/33 clay/polyethylene composlte. The time
required was 1.12 hr. The autoclave wa8 immedlately vented
to atmospheric pre~ure and cooled, and the solld composite
was separated b~ flltration and alr-dried to givc 261.9 g Or
powder that pa~sed a 28-mesh screen.
A portion of the product was added to a CHBr3:CC14
mixturo (1:1)3 all the powder ~loated, lndicating that no
unattached clay partlcle~ were pre~ent, l.e., all the clay
particles had been coated with polyethylene. In a s~mllar
teBt with CC}4:n-C3H70H ~3:2 by volume), all the powder
- 73 ~
~04(~779
sank, lndicatlng that no clay-free polyethylene was pre~ent.
The product was found on ash analysls to have a clay content
of 64.o%.
By essentlally the foregoing procedure, polyethylene/
clay composltes were made with other catalysts in place Or
tetrabenzyltltanium. m ese runs, together wlth the propertie~
o~ the products, are summarized ln Table V. m e Gardner
lmpact strength data were obtalned on compression molded
samples havlng the mil thicknesses indicated in parenthesls
ln the table.
- 74 -
N 1040779
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1-~ 0
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U~ ~0 U~
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o ~ h ~d ~U ~U N
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- 75 -
1~4~t~79
EXAMPLE 34
This example illustrates the preparation of
a composite using tetraneophylzirconium as the hydrocarbon
~oluble transitlon metal compound.
All operation3 up to the start o~ the polymerization
were carried out under dry nitrogen. me apparatus was
similar to that o~ Example 28. To a æolution of ll mmol
Or diisobutylaluminum hydride in 2.5 1 Or dry, deoxygenated
cyclohexane waæ added 0.31 g (0.5 mmol) o~ tetraneophyl-
zirconium Ltetrakiæ(2-methyl-2-phenylpropyl)zirconium~ .
Arter brief stirring the m~xture was allowed to stand for
one hour. The æolution became orange during the rirst half
hour; not much color change occurred thereafter. Five hundred
grams of G~A 431 alumina trihydrate (Great Lake~ Foundr~ &
Sand Co., weight average equlvalent spherlcal partlcle diameter
3.5 ~), that had been dried over a weekend at 180C under a
~tre~m Or nltrogen and cooled, waæ added, and the mlxture was
stlrred for about five minutes to give a uniform s wpension.
The suspension wa~ transrerred to an autoclave
containing 0.63 gal of cyclohexane and processed with
ethylene at 40C and llO psl, with stirring at 450 rpm,
untll 200 g of ethylene had reacted (77 min). The autoclave
was vented, the mixture was cooled, a~d the polyethylene/-
alumlna trlhydrate composition was separated ~ flltration,
washed with cyclohexane, and air-dried.
me product was a powder, 9~6% Or which pa~ed a 16-
me~h screen, On a~h analysiæ the product wa~ found to
have an alumina trihydrate content of 63.6%. me inherent
vi~cosity Or the polymer was 26.57. Compression molded
test ~amples had the rollowing physical propertieæ:
- 76 -
1()40779
Tensile (T): 3028 2906 psi
Elongation (Eb): 440% 45%
Modulus (Mi): 383,000 473,000 pæi
0F Izod impact: 6.9, 7.6 ft lb/in of notch
Gardner impact: 240 in lb (128 mil)
264-psi Heat de~lection: 67C 77C
~lexural modulus: 406,500, ~01,500 psl
EXAMPLE 35
This example illustrate~ the preparation of a
composite using tetraneophylchromium as the hydrocarbon-
soluble transition metal cQmpound.
A one-gallon autoclave was dried at 150C under
nitrogen purge, cooled and charged ~ith 0.3 gal of dried
hexane and 1 ml of a 1.6 molar solutlon o~ trlethylaluminum
in hex~ne. Next wa~ introduced under nitrogen purge a slurry
prepared Prom 700 ml of dried heptane ~o ~hich had been
added, with stirring, in order: 115 g Or SATINIONE* No. 1
dehydrated kaolin clay (Engelhard Mineral Co.) havlng a
weight~averAge e~fective spherlcal partlcle diameter o~ 2
microns and a surface area of 8.2 m2/g, 0.007 mmol of tetra-
neophylcXromium in he~ane solution and 2 ml of a 1.6 1ar
solution of trlethylaluminum in hexane. The autoclave was
closed and the polymerlzation was carried out at 50C for
15.5 hr ~nder 100 psi ethylene pre~sure.
The product, 188 g,-~as isolated on a filter a~
a rlne, nearly white powder, and wa~ found to contain
59.08% clay by ash analysis. The inherent visco~ity of the
polymer was 19.22 and the composition had a 10-second
micronization homogeneity of 90. Specimens lded from the
compo~itlon at 175 and 2000 psi pressure had the following
* denotes trade mark
- 77 -
. ..~.
,~. .~
104~)~779
properties:
Tenæile (T): 3019 p8i
Elongation (Eb): 304%
ModulUS (Mi?: s88,000 psi
0F Izod impact: 6.8 ~t lb/in of notch
EXAMPLE 36
This example illustrates the preparation o~ a
composlte uæing chromium octoate as the hydrocarbon-soluble
tranæition metal compound.
A one-gallon autocalve waæ dried at 150C under
nltrogen purge, cooled and charged with 0.3 gal of dried
hexane and 1 ml of a 1.6 molar solution of triethylalumlnum
in hexane. Next was introduced under nitrogen purge a
slurry prepared from 700 ml Or heptane to which had been
added ln turn, wlth stlrrlng, the following:
1 ml Or a 0.01 molar solutlon of chromium octoate
ln heptane; 146 g o~ SATINTONE No. 1 kaolin clay (Example 35),
drled at 190C; a second 1 ~1 of the 0.01 molar solutlon o~
chromlum octoate in heptane; and 1.5 ml o~ a 1.6 molar solu-
tlon o~ trlethylaluminum ln hexane. me autoclave was closed
and the polymerlzation was carrled out at 50C for 7.3 houræ
under 100 p~l ethylene pressure.
me product, 285.3 g, ~as isolated on a fllter as
a mostly ~ine, nearly white powder. It contained 49.35%
clay by ash analy~is and had a 10-second micronization homo-
genelty Or 84%. The inherent vlscoslty Or the polymer was
24.28. Specimen~ molded from this composition at 175C and
2000 psi pressure had the following phys~cal propertles:
Tensile (T): 2809 pæi
Elongation (Eb): 358~
- 78 -
i..~
10~0`~79
Modulu~ (Mi): 371,000 p~i
0F Izod impact: 8.9 ft lb/in of notch
EXAM~IE 37
This example illustrates the preparation of a
composite u~ing tetramethyl tltanate in the polymerization
reaction.
The fnllowing operations were all carried out in
a nitrogen atmo~phere. To 2 1 Or cyclohexane in 5-1.
gla~Q pot ~ltted wlth a Waring Blender was added 5.1 mmol
Or (C2H5)3Al as 1.6 molar solution in heptane, followed
by 200 g of ALCOA C-30BF A1203-3~20 (All~m~num Co. of
America), having a screen analysis of 1-3% on 200 mesh,
15-20% on 325 mesh and 80-85% throu~h 325 mesh, and a sur-
~ace area of 1.6 m2/g, heated at 152C ~or 16 hr in a
nitrogen stream and cooled in nitrogen. Thie mi~ture wa~
~tirred vigorously ror 1 minute. mere was then added
0.3 mmol o~ Ti(OCH3)4 as a ~olid, followed by vigorous
stirring ~or 8 minutes. This suspension was tra~s~erred to
a l-gal steel autoclave under nltrogen pressure; the stirrer
in the autoclave was rotated at 1,000 rpm during the transfer
and during the resulting polymerlzatlon. The polym~rization
wa~ carried out at 250 p8i ethylene pres~ure ~or 3.25 hrs.
The autoclave was then vented and cooled, and the solids
~iltered and air-dried. me total welght o~ the product re-
covered was 287.9 g; 156 g o~ this passed through a 20-me~h
~creen and 52.3 g only through a 14-mesh ~creen.
me material pa~sing through the 20-mesh screen
w 8 ~ound by abh analysis to contain 67.8% A1203-3H20. The
polymer had an inherent viscoslty o~ 16.25. The product
was pressed at 180C ~nd 2000 psi into a 129-130 mil plaque.
- 79 -
1040'~9
Test bars ~rom thi~ plaque had the following properties:
Ten~ile (T): 2069 psi
Elongation (Eb): 313%
Modulus (Mi): 474,000 p~i
0F Izo~ lmpact: 11.0 rt lb/in of notch
25C Gardner lmpact: 115 in/lb
SUPELEMEJlAR~ MSCLOSURE
It has now been found that in preferred embodiments
of the pre~ent invention the polyolefins are polyethylene and
copolymers Or ethylene containing up to about 15% by uelght Or
units derived from one or more l-alkenes o~ 3 to lO carbong, ~uch
polyolerin~ h~ing an inherent vl~coslty of at lea~t about 2,
Sultable co~onomers include propylone, l-butene, l-pentene,
3-methyl-1-butene, 4-methyl-l-butene, l-hexcne, l-octene, l-docene,
and mixture~ thereo~.
The polyole~lns must have an lnherent ~l~oosity Or at
lea~ about 2 in order rOr the composltes of this invention to
e~hlblt the unw u~l co~bination Or physical propertles which
characterize them. All Or the composites Or this inventlon are
compres~ion moldable. For optimum properties of the composite,
the polyolerin should havo an inherent vi~cosity of at least
about 4, pro~erably at least about 8 and more preferably at
loast about 12. For ln~ection molding, the polyolerln should
have an inhe~ent viscosity Or about 2 to about 6, and preferably
about 3 to about 5.
The composlte~ of this invention al~o contain about
30 to about 90% by weight of flnely divided, inorganlc filler
compound. The compres~ion ldable composite~ preferably con-
tain about 40 to about 85~ by weight of inorg~nic riller com-
pound, and st preferably about 45 to about 80%. me in~ectionmoldable composites preferably contain abo~t 30 to about 70%
-- 80 --
; ~
104V77~3
by weight of inorganic filler compound, and mo~t preferably
about 30 to about 50%.
me composi~es o~ th¢ pre~ent invention may be
obtaiacd by the proce~ses de~crlbed hereinbefore.
The compo~ites of the prc~ent invention, especially
tho~e composlte~ in which the polyolerin ha~ an inherent
vl~co~ity o~ about 2 to about 6, may be formed into w e~ul
article~ by conventional in~ection lding techniques. mese
technique~ generally involve r-m or screw ln~ectlon o~ the com-
pQsite into a mold and ~ubJectlon of the composite in the mold
to a temperature at which lt ~o~tens in the range of about 150
to about 250~C and a po~itlve pressure of at least about l,000
p8i. In general, temperature~ Or about 210 to about 240~ and
pre~surc~ Or about lO,000 to about 15,000 p8i are prererred.
The temperature ~elected in any ~peclfic ca~e, however, ~ill
depend on the particular riller w ed. For examplc, compo~ites
containing all~mtra trihydrate ~hould not be proce~ed above
about 200C. Prererably the~e composlte~ are proce~ed at
temper~ture~ o~ about 170 to about 190C. For in~ection
lding the polyolefin preferably ha~ an inherent vi~cosity Or
about 3 to about 5.
me present inventlon 1~ illw trated further by the
rollowing o~ample~
EXAMPIE 38
Thi~ example illu~trate~ the preparation of a
composite ~rom a kaolinite clay without the addition o~ ~
transition metal coordination catalyst component using diiso-
butylaluminum chloride a~ the organoall~m~num compound.
A batch o~ ~ARWICK GK kaolinite clay (ExAmple 3)
was dried (calcined) at 600C under a 30 liters/hour flow o~
4:1 N2:02 mixture for 18 hour~ and cooled under nitrogen. A
- 81 -
10 4 ~7 7~
l-llter autocla~e was charged with a mobile sw pension of
60 g of the above clay in 600 ml o~ cyclohcxane and 0.8 g o~
diiæobutyl~luminum chloride. Polym~rizatlon w~s carried out
at 70C aad an ethylene pressure of 100 p~i for 2 hours and
46 minute~.
me product, a powder, amounted to 106 g. Ash
analy~is ~howed that the compo~ite had a clay content of 57.1~.
The 10-second micronlzation homGgeneity wa~ 79%. The poly-
ethylene had an inherent visco~lty o~ 30.67. A film pre~eed
from the powder at 180C was ~trong and ~lesible.
Compres~ion molded test b~rs had the ~ollownng
properties:
Ten~ile (T): 2772, 2784 p~i
Elongation (Eb): 272, 372%
ModulW (Mi) 442,ooo, 44s,ooo p~i
0F Izod impact: 1.4, 1.4 ~t lb/in o~ notch
EXAMPLE 39
Alumina h~drate, ALCOA HYDRAL* no. having a
~urrace area o~ 6-8 m2/g and a ueight-average equivalent
spherical particle diameter o~ 1 ~, wa~ placed between l-in
layer~ of gl-~ wool in a 3-llter beaker ln a heating m~ntle.
Dry nitrogen wa~ pa~sed through the bed ~or 2 hour~ at 160C.
Then the nitrogen flow was ~toppod and 3 succes~ive 10-ml
portlon~ o~ TlC14 were vaporized through the alumina hydratc.
The m~ wa~ cooled under nitrogen flow and stirred ror 2
hour~ with 500 ml of dlstilled water containing 21 ml of
concentrated aqueous amm~nia. me solid was collected by
filtration and washed wlth water. me abæorbed TiC14 wa~
converted to TiO2 by exposing the product to moist air ror
2 days. Berore u8ing, the filler was dried at 150C for 18
hours under a ~low of 30 l/hr Or dry ~itrogen.
* denotes trade mark
- 82 -
,~
10~779
A slurry of 50 g of the above alumina, 1 g Or
antimony trloxide, 500 ml of cyclohexane and o.6 g of triiso-
butylaluminum was tran~f~rred to a l-liter autoclave. The
polymerization was carrlcd out ~t 70C and an ethylene
pressure of 100 p~i for 1 hour and 16 min.
me product, 88 g o~ powder, had an ash content of
38.07%, which iB equivalent to 57.8% ~iller. The polymer had
an inh~rcnt visco~ity o~ 17.29. The compo~ite had a 10-æecond
micronization homogeneity of 98%. The physical propertie~ of
comprc~sion molded test bars were as ~ollows:
Ten~lle (T): 3154, 3010 psi
Elongation (Eb): 498, 464~
Modulus (Mi): 317,000, 322,000 psi
0F Izod lmpact: 15.2 rt lb/in Or notch
Rockwcll hardne8~: 66
Oxygcn lndex: 0.325
EXAMPLE 40
(A) A 200-g batch Or ALCOA C-30BF A1203-3H20
ha~ing a ~urrAce area Or 1.6 m2/g and a screcn analy d~ of
1-3% on 200 ~h, 15-20% on 325 mc~h and 80-85% through 325
me~h wa~ placcd bctwcen l-in layers of gla~ wool in a
3-llter beaker in a heating mantle. Dry nitrogen was
pas~ed through the bed for 2 hour~ at 160C. Thcn the
nitrogen Mow was stopped and 3 successive 10-ml portion~
of TiC14 were vaporized through the alumina hydrate. Thc
m~B~ wa~ coolcd under nitrogen ~low (anal~ls: Cl, 0.54%; Tl,
o.60% or 0.13 milllgram-atom Or Ti per gram Or filler), and
stirred ~0r 2 hours with 500 ml of di~tilled water contain-
ing 21 ml Or concentrated aqueous ammonia. me solld was
collected by ~lltrat~on and wa~hcd with water (analy~
-83-
.~
10407'7~
Cl, 140 ppm; Ti, o.60%). The ~iller was drlcd at 170C for
18 hour~ und~r a 30-liter per hour ~low of nitrogen before
w lng.
A 2-gallon, ~tirred autoclave, previou~ly dried ~d
deoxygenated with nitrogen, W8~ charged with 0.7 gallon of dry,
deoxygenated cyclohex~ne and a bile ~uspension of 500 g o~
TiO2-modified ALCOA C-30BF alumina trihydrate in 1895 ml
o~ dry, deoxygenated cyclohexane containing 3.6 g o~ tril~o-
butylalumlnum. The polymerlzation wa~ carried out at 70C
undcr an ethylene pre~ure o~ 100 p~i ~or 1 hr and 41 min.
me product wa~ collected by filtration and air dried.
~ he a~h content of thc product wa~ 43.11%, whlch
1~ equivalènt to 66% al~ na trihydrate. me physical proper-
tie~ Or compression lded te~t bars were a~ ~ollows:
Tenslle (T): 2813, 2814 p~i
Elongation (Eb): 337%, 295%
ModUlu~ (Mi) 424,ooo, 425,000 psi
0F Izod impact: 9.3 ~t lb/in o~ notch (no break)
Flcxural modul w : 379,000, 386,000 p~i
Oxygen ~ndex: 0.342, 0.342
To a ~u~penslon of appro~im tely 700 g o~ this
protuct ln 1.5 1 o~ cyclohexane was added 2.1 g of IRGANOX
1010 di~solved i~ 50 ml of ether. The mlxture wa~ ~tirred
for several mlnutes before the solid was collected by
vacuum ~iltration and air dried.
(B) Part (A) wa6 repeated using a polymerlzation
time Or 1 hour and 57 mlnutes. me ash content was 43.33%,
which is equivalent to 66.2% A1203-3H20. Compression m~lded
test bars had the followin6 properties:
.~
1041}7~79
Tenslle (T): 2845, 2742 p8i
Elongation (Eb): 287%, 289%
Modulus (Mi): 479,000, 448,000 pBi
~lexural modulus: 366,ooo, 349,000 p i
Oxygen index: 0.325, 0.342
(C) Part (A) was repeated w ing a polymcrization
tlme of 2 hours and 27 minute~. me ash content wa~ 43~53%,
which i~ cqui~alent to 66.6% A1203-3H20. The physlcal
properties o~ compro~ion molded test bars were:
Ten~ (T): 2434, 2603 p~i
E~ongation (Eb): 171%, 260%
Modul w (Mi): 4~8,ooo, 451,000 psi
0F Izod impact: 9.2 ft lb/in of notch (no break)
Flexural modulus: 388,~00, 353,000 p~l
O~gen index: 0.342, 0.342
(D) The thre~ stabilized composlte~ propared in
(A), (B) and (C) above ~ere mixed in a rolling drum and
the mlxture wa~ put through the contlnuou~ vulcanlzer Or
Ex~mple 5. In thi~ procedure, the powdor was red onto the
~talnles~ steel belt, ~queezed between the rolls without
~hear, and carried around the heated belt at 400F and a
speed o~ 1.8 ~t/min. The ~heet was manually removed
~ro~ the roll. The phy~lcal propertles Or the compo~ltion
~heot mea~ured in two direction~ were a~ shown in Table VI
The propertio~ Or test bar~ compre~lon molded at 175C and
a pre~sure o~ 2000 p~l ~re al80 given.
TABIE ~I
T Mi Eh
(P8i) (kpsi')
30 Machine
Directions 2564 429 137
Transver~e
Direction~ 2534 434 135
Co~pre~ion
, ~ ded 2537 454 215
~,.s
- 85 -
~04~17~9
me sheet was molded into pyramidal obJects
by the method o~ Example 5. An ~zod impact te~t at room
temporature wa~ performed on ~ample~ cut from the ~ide of the
~ormed piece~.
Forming 0F Izod Impact,
Temperature, ~C rt lb/ln of notch
125 8.2
140 9-7
150 7.5
Unrormed ~heet 8.3
EXAMPLE 41
Thi8 example shows the u~e o~ dehydrated kaolinite
and Cr(OAc)3 at low polymerization temæerature.
A ~lurry wa~ made from 1000 g of SATINT~NE No. 1
dehydrated kaolinitc clay (Engelhard Mineral Co.), h~ving a
welght-average ef~ective ~pherical particle diameter o~ 2
micron~ and a ~urface area o~ 8.2 m2~g, and 1.2 liter~ o~ a
~olution containing 1.24 g o~ chromium (III) acet~te mono-
hydrate. The ~lurry ~a8 mlxed in a rod mill ror 20 hours,
and then 30 ml Or ~ 1% ammoniu~ hydroxide ~olution wa~ added
to rai~e the p~ o~ the slurry to 5. Arter a total or 50
hours in the mill, the slurry WaB filtered to i~olate the
~olid. The aqueous solution wa~ noted to be llghter in
color th~n the origin~l chromium(III) acetate ~olution.
The collected solid was wa~hed with ~00 ml Or acetone and
dried at 170-190C in a ~tream of nitrogen.
A l-gal autocla~e Wa8 dried at 150C under nltro-
gen purge and charged under nitrogen purge with 0.35 gal
of dried cyclohexane ~nd 2 ml o~ a 1.6 molar ~olution o~
triethyl~luminum in hexane. To this wa~ added a 51urry
~ompri~lng 159 g Or the above treated kaolinite, 750 ml
- 86 -
iO4077~
Or dried heptane and 4 ml of a 1.6 lar solution Or tri-
ethylaluminum in hexane. me autoclave was closed and the
polymerization was carrled out during 3 hours and gO mlnutes
at 35C under an ethylene pressure of 100 p5i.
The product (334 g), isolated as a rine, white
powder a~ter rinsing with methanol and drying, wa~ de-
termlned to contain 53.5% by weight of clay by ash analysls.
The polymor had an inherent viscoæity of 16.05. The composite
had a 10-second micronization homogeneity Or 87% and a microni-
zation hom~geneity index of 65.
Bars, compres~ion molded at 175C and 1500-2Q00 pæi,
had tho rOllOwing properties:
Tensile (T): 3232 psi
Elongation (Eb): 346%
ModUlu8 (Mi) 577- psi
73F Izod lmpact: 14.8 rt lb/in Or notch
EXAMPLE 42
This oxample show~ the use Or wollastonlbe as
the rlller.
A ælurry was prepared rrOm 800 g of CAB-0-LITE* Fl
wollastonite (calcium silicate, Cabot Corporation, particle size
distribution by sedimentation, cumNlative percent, 55% greater
than 55 ~, ~5% le~s than 20 ~, 22% less than 10 ~, 13% less than
5 ~, 9% less than 3 ~, 7% lesæ than 1 ~, fiber length~ average
13-15 times diameter) in 1400 ml Or di~tilled water containing
1 g Or chromium (III) acetate monohydrate and 5 ml o~ isopropyl
alcoho~. The lnitial pH wa# 4, but gradually rose to 6.5
during 4 days as the slurry was mixed in a rod mill. The
solid was iæolated by filtration and dried in a ~tream of
nltrogen at 170C. For each gram of wolla~tonite 0.0026
D le Or chromium acetate wa~ used.
* denotes trade mark
- 87 -
iO407'7~
A l-gal autoclave was dried at 150C under nltro-
gen purge, cooled and charged, in order, with 1.5 liter~ of
dried heptane, 2 ml of a 1.6 molar Rolutlon of trietbyl-
aluminum, 200 g of the wollastonlte prepared above, and
finally~ an additional 3 ml of the 1.6 molar solution of
triethylaluminum. The a~toclave was closed and the mix-
ture was stirred for 10 minutes under nitrogen. The poly-
merization was then carried out at 65C for 38 hours under
an etbylene pressure of 350 p5i.
me product (276 g) was isolated as a fine, white
powder after rlnsing with methanol and drying. Ash analy-
6i~ indicated that it contained 70.6% filler. me polymer
had an inherent vi~coslty of 10.06. me composite had a 10-
second micronization homogeneity of 76% and a micronization
hom~geneity index of 52%. Bars, compression molded at 175C
and 2000-3000 p~i, had the following propertles:
Tensile (T): 2647 psi
Elongation (Eb); 8.3%
Modulus (Mi): 1,064,000 psi
73F Izod impact: 1.4 ft lb/in Or notch
EXAMPLE 43
This e~ample shows the use of chromium- dified
talc as the filler.
A slurry was prepared from 1000 g o~ undried talc
in 1250 ml of distilled water containing 5 ml o~ 1% NH40H
solution and 10 ml of VOLAN* L ~E.I. du Pont de Nemours
and Company, a solution containing 6% C~(III) as methacrylato-
chromium chloride, special low-chloride composition~ To
this slurry was added 100 ~1 of isopropyl alcohol. The pR
of the glurry was 5.0 and remained constant during 24 hours
of mixing of the ælurry in a ball m~ll with stones. The slurry
* denotes trade mark
- ~8 -
104~)779
wa8 separated ~rom the stones and the ~olid was isolated by
filtrations, washed with about 500 ml o~ acetone, and dried in
alr and then ~n a stream of nitrogen at 190C. For each gram
of talc, 0.01 milligram-atom o~ Cr(III) was used.
A l-gal autoclave waB dried at 150C under nitrogen
purge, cooled, and charged with 1.3 liter~ of dried heptane
and 2 ml of a 1.6 molar solution of trimethylaluminum in
hexane. Next, 194 g of the talc prepared above was made into
a slurry in 750 ml of dried heptane containing 5 ml o~ a 1.6
molar solution of trimethylalumlnum hexane, and the whole
slurry was transfe~red to the autoclave. me autoclave was
closed and the polymerization was carried out at 55C for about
10 hours under an ethylene pressure o~ 150 psi.
me product (299.5 g) was a fine, white granular
powder, arter rlnsing with methanol and drying. It waæ cal-
culated to contain 58.6% talc based on the materials used. me
compo#ite had a 10-second micronization homogeneity o~ 91%
and a micronizatlon homogoneity lndex of 82. Bars moldod ~rom
this compositlon at 175C and 2000 psi pres~ure had the follow-
ing physical properties:
Tenælle (T): 2644 psi
Elongation (Eb): 150%
Modulus (Mi): 631,500 p~i
0F Izod impact: 3.4 ft lb/ln o~ notch
EXAMPIE 4~
A 2-gallon autoclave ~ltted wlth a magnetically
drl~en stirrer was prepared for the polymerlzatlon by pres-
8uring to 20 psi Or ethylene and ~enting 3 times at 150C
rollowed b~ 3 hours o~ nitrogen purging at 150C. The auto-
clave was charged with 0.7 gal of deoxygenated, dry hexane.
- 89 -
,. ~
1040779
me reaction mixture was prepared in a dry, nitrogen-
purged, l-gallon, round bottom ~laæk Pitted with Pood-blender
blades in the bottom. The flask was charged with 500 g of
ALCOA ~-30BF A1203-3H20 (Example 13), dried at 160C under
a 60-1/hr stream of nitrogen for 18 hours and having a surPace
area of about 1.6 m2/g, 0.6 gallon o~ dry, deoxygenated cyclo-
hexane, and 1~ mm~l o~ triisobutylalumlnum. The mixture wa6
blended to a low-viscosity unifo~m ~uspension. men 0.22 g of
tetrabenzylzirconlum, a~ a freshl~ made solution in 5 ml of
toluene, was added to the stirred su~penslon. Thl8 pale orange
mixture was tran~ferred by a 1-2 psig nitrogen pressure in
the Pla~k through polyethylene tubing into the autoclave. The
polymerization was carried out at 60C and an ethylene pressure
o~ 100 p~l wlth the stirrer at 500 rpm. The reaction was ~topped
after 220 g oP ethylene was consumed, which took 25 minutes.
The alumlna trihydrate contained approxlmately 0.005 milligram-
atom Or Zr per gram.
me product wa~ collected by filtration and air
dried, glving 682 g oP powder which pa~sed a 28-mesh screen,
and contained 74.0% A1203.3H2~ (ash, 48.49%). Tost bars com-
pression lded from the' powder at 170C and 2000 psi had the
~ollowing propertles:
Tensile (T): 2507, 2545 psi
Elongation (Eb): 309~, 323%
Modulus (M13: 541,600, 501,300 psi
0F Izod impact: 4.9 ft lb/in of notch
EXAMPLE 45
A mixture Or 200 g of bentonite clay, 80 ml of
tetraisopropyl titanate, and ~00 ml of dry cyclohexane
was sh~ken briePly and allowed to stand ror one day. The
solld was separated by Piltration, washed with dry cyclo-
-- 90 --
, ,,
. .~ 1
1040~7~79hexane, and air drled. A portion of the product was drled
at 600C for 18 hours under a ætream of 4:1 N2:02 mixture
rlowing at 30 l/hr.
Deoxygenated cyclohexane (6Qo mll was pas~ed through
a bed of Woelm acld alumina lnto an enclosed blender cup
under constant nitrogen pressure. Stirring Wa8 ~tarted, and
0.1 1 Or triisobutylaluminum wa~ added, rollowed by 60 g Or
dried product and an addltlonal 0.3 1 of trilsobutyl-
aluminum. me low-viscoslty dlsperslon thus obtalned was
trans~erred with nltrogen pressure through polyethylene
tublng to a ~tlrrer-equlpped, stainless steel autoclave
that had been dried under a nltrogen purge at 150C. The
autoclave wa~ closed, stlrring was st~ted, the mixture
was heated to 70C, ethylene was admitted to 100 psi, and
these condltions were continued until 45 g Or ethylene
had roacted (1 hour and 15 min). Arter cooling, the solld
was separated by filtration and air drled.
mere ~as thus obtained 93 g Or polyethylene/bentonlte
composlte a8 a powder that gave on a~h analysl~ by combustlon
a rlller content Or 48.55%. me polymer had àn inherent
~iscosity Or 14.74. me composite had a 10-second microniza-
tlon homogenelty Or 99% and a micronlzatlon homogene~ty index
Or 90.
A hot-pressed film prepared from thi~ compo~ite
was ~trong and flexlble and creased without cracking.
Compres6ion molded bars had the ~ollowing properties:
Tensile (T): 3994, 4598 p8i
Elongatlon (Eb): 196%, 334%
Modul w (Mi) 399,000, 293,000 pBi
0F Izod impact: 7.2, 7.4 ft lb~in of notch
- 91 -
1040'~'79
EXAM~I,E 46
HARWICK GK kaollnite clay (Example 3) that had been
calcined overnight at 1~00C ln air to give a surface area of
4.5 square meters per gram wa8 redried by heating at 500C for
18 hour~ in a stream o~ 4:1 N2:02 mixture flowing at 30 l/hr
and cooled in a stream of nitrogen.
Deoxygenated cyclohexane (600 ml), 70 g of the
dried clay, and a total of 0.4 mmol of triisobutylal~m~um
~ere mixed and processed with ethylene at 50C and 100 psi
by es~entially the procedure of Example 20. The polymerization
wa~ stopped a~ter 27 g o~ ethylene had reacted (25 min).
me product was 77 g o~ a polyethylene/cl~y compo~ite
which passed through a 28-mesh ~creen, plus 6 g o~ coarser
materlal, which was aiscarded. Ash analysis by combustion
indicated that the compo~ite had a 69.40% clay content. me
polymer had an inherent ~iscoslty of 23.50. Compression molded
ba~s had the following properties:
Ten~ile (T): 2435, 2284 psi
Elongatlon (~ ): 315%, 314~
Modulus (Mi): 567,ooo, 720,000 p~i
0F Izod impact: 9.3 ft lb/in Or notch
264-psl Hcat
de~loctlon: 85 87C
EXAMPLE ~7
A mlxture o~ 300 g of Concord mica and a solutlon of
50 g of tetral~opropyl tltanate in 600 ml of cyclohexane was
~haken briefly and allowed to stand for one day. The ~olld
wa~ separated by ~iltratlon, washed wlth dry cyclohexane, and
air dried. A portion o~ the coated mica was dried at 300C
~or 18 hour~ under nitrogen. The dried mica contained 0.05
milligram-atom o~ Ti per gram.
- 92 -
1040779
Forty gram~ of the dried mica was mixed with
250 ml of deoxygenated cyclohexane and a total of 0.4 mmol
of trllsobutylaluminum, and the mixture was proce~sed wlth
ethylene at 70C and 300 psi, all by essentially the pro-
cedure of Example 21, until 27 g of ethy~ene had reacted (8 hr).
me polyethylene/mica compo~lte was obtained aæ
small, fluffy partlcle~ (71 g). It was found by aæh analysis
to contain about 56% mica. me polymcr had an inherent Vi8-
coslty Or 27.77. me composite had a 10-second micronization
homogeneity of 86% and a mlcronization homogeneity index of 72.
Compre~sion molded bar~ had the following propertie~:
Tensile (T): 1808, 1805 psi
Elongation (Eb): 22%, 20%
Modulus (Mi): 491,000, 753,000 pBi
0F Izod impact: 1.8 ft lb/in o~ notch
264-psi Heat deflection: 80C
EXAMPLES 48-52
Using the procedure of Example 28, a ~ariety of
hydrocarbon-soluble organic transition metal compound cataly~t
components wero u~ed to make polyethylene/alumina trihydrate
compo~ltes. Two hundred grams of ALCOA C-30BF alumina
trihydratc (Example 13) wa~ used in each run, the obJecti~e
belng to make an approximately 69/31 alumlna trihydrate/polyethylene
composltc. Wlth~the exception of Example 34, each run wa~ con-
tinued untll 90 g of ethylene had reacted. In Example 34 the
polymerlza~lon was stopped after 46 g of ethylene had reactcd.
The re~ults are ~ummarized in Table VII.
- 93 -
04(~9
.~ ~ ~ ~ C~ 0 ~
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,1 ~ CU ,1 C~
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h .. ~ u~ ~) o 1~ 0
P~ ' E~
. . * *
~ e~ ~l ~ ~ ~O CU
~ ~-~1 O c~
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1040779
EXAMPLE 53
LU330* Feldæpar (Lawson-Unlted Products, mean
particle ~lze 5 ~, sur~ace area 1.4-1.5 m2/g was coated with
A1203 by adding a ~olution o~ 24 g of AlC13.6H20
in 400 ml o~ water to a suspension Or 500 g of the mineral
in 2 1 Or water. A~ter stirring 30 minutes, the mixture
was neutralized with 5% aqueous a D nia followed by an
additional hour o~ stirring. The product wa~ collected
by filtratlon, and washed wlth distilled water until the
riltrate wag neutral. me alumina-coated feldspar was
dried at 200C ror 18 hours hnder the purge.
A suspension was prepared b~ adding 60 g of the above
reld~par to 600 ml Or deoxygenated, dry cyclohexane containing 4
mmol o~ triisobutyl~luminum and 0.2 mm~l of tetrabenzylzirconium
(0.003 milli~ram-atom Or Zr per gram o~ feldspar). m is suspen3ion
wa~ trans~erred to a l-liter stirred autoclave. The polymerl-
ation wa~ carried out at 50C under an ethylene pre~sure Or
100 psi ~or 5 minutes at which time 25 g Or ethylene had been
consu~d.,
me resulting composite had an ash content by
combu8tion Or 61.44%. The polymer had an inherent ~i~cosity Or
22.09. Compres~ion molded bar~ had the ~ollowing properties:
Tensile (T): 2946, 2600 p~i
Elongation (Eb): 431%, 357%
Modulu~ (Mi): 583,000, 565,ooo p~i
0F Izod impact: 10.1, 9.9 ft lb/in Or notch
EXAMPLE 54
A 1200-g portlon Or BaS04 powder in 2500 ml Or
water was coated with A1203 as de~cribed for CaC03 ~n
E~ample 27.
* denote~ trade mark
- 96 -
.~ .
~04S~7~9
A~ter adding a solutiQn oP 57 g o~ AlC13.6H20 in
400 ml of water, the mixture was neutralized ~th dropwise
additlon of 5% aqueous ammonia. The solid wa~ collected
by filtration and washed with distilled water. One-half
of the molst product was resuspended ln 1500 ml o~ water
and treated with a solution of TiOC12 made by adding 9 ml
o~ Tial4 dropwise to 200 g of ~ce. The re~ulting mixture
was neutralized by the dropwi~e addition of 5% aqueous
ammonia. The solid was collected by riltration and washed
with water. Based on the amounts of materials used, the
BaS04 contained 1.0% A1203 and 1.08% TiO2 ~.14 milligram-atom
of Ti per gram of BaSO~) at the surface. The BaS04 was dried at
300C for 18 hrs under a nitrogen flow of 30 l/hr be~ore use.
me reaction mixture was prepared in a blender cup
~rom 600 ml of deo~ygenated, dry cyclohexane, 100 g of
the abo~e coated BaS04, and 5 mmol of trii~obutylaluminum.
Tho polymerization was carrled out in a l-liter stirred auto-
clave ~t 70C under an ethylene pressure of 100 psi rOr
14 minutes during which time 18 g Or ethylene was consumed.
The product (117 g Or powder) had an ash content
Or 80.21%. Compression molded tcst bArs had the following
propertie~:
Ten~ile (T): 2366, 2304 psi
Elongation (Eb): 177%- 211%
Modulus (Mi): 745,000, 694,ooo psi
0F Izod impact: 4.4, 4.3 ft lb/in of notch
EXAMPLE 55
This example illustrate~ the use of a mixture of
fuller~ earth and titanium dioxide as the filler.
The reaction m~xture wa~ prepared by addlng 60 g
of a 90% ~uller~s earth: 10% TI-PURE R-101 rutile (Example
7) mixture, which had been dried by heating for 13 hour~ at
300C under a 30-liter/hr nitrogen flow, to 600 ml o~ dry and
- 97 -
~. ....... .
104~'7'7~
oxygen-~ree cyclohexane contalning 4 mmol (0.8 g) of
triisobutylaluminum and 0.2 mmol o~ tetrabenzylzirconium
~n 2 ml o~ toluene ~n an enclosed blender cup under nitrogen
purge. After stirring, the mixture was trans~erred to a
dry and oxygen-~ree, l-liter autoclave. The polymerizatlon
was carried out at ~0C under 100 p5i ~r ethylene in 19
minutes. mere resulted 97 g Or composite powder that
passed a 20 mesh sieve.
When the composite wag pyrolyzed in air, it had
an a~h content of 46.94%. The polymer had an inherent
viscoslty Or 14.98 (0.025 w/Y %). me 10-second micronization
homogeneitg was 99%, and the micronization homogeneity
index wa~ 77.
Te~t bar~ were prepared by heatlng the composlte
at 180C for 1 min, rollowed by compression at 3000 psi ror
3 min at 180C. The~e bars had the following properties:
Tensile (T): 3645, 3499 psi
Elongation (Eb): 43%, 29%
ModulU8 (M1): 483,000, 451,000 pBi
0F Izod impact: 2.4, 2.2 ~t lb/in o~ notch
EXAMPIE 56
Thi~ esample illustrates the use of a titania
costed mlxture of kaolinite clay and alumina trlhydrate ag
the riller.
A 60-g portion Or tetraisopropyl titanate was
added to a stirred sugpension Or 150 g o~ uncalcined
HARWICK GK kaolinite clay (Example 1) and 150 g of
ALCOA C-30BF A1203.3H20(~ample 13) in ~00 ml of cyclo-
hexane, and the visco~ity dropped to that of the solvent.
The mlxture wa~ milled with glas~ rods ~or 1 day. The
solid was collected by filtration, washed with cyclohexane,
- 98 -
' 040779
expo~ed to alr, and dried by heating for 18 hours at 170C
under a 30-liter per hour flow of nitrogen.
The reaction mixture wa~ prepared by add~ng 70 g
of the above frcshly prepared titania coated 1:1 HARMICK GK
kaolinite clay: ALCOA C-30BF mlxture to 600 ml of dry and
oxygen-free cyclohexane containing 4 mmol (0.8 g) of trl-
isobutylaluminum in an enclosed blender cup under nitrogen
purge. After stirring, the mixture wa~ transferred to a
dry and o~gen-free, l-liter autoclave. The polymerization
was carried out at 60C under 100 psi of ethylene for 1 hour
and 11 minuteæ. The product was 89 g of compo~ite powder
that passed a 20 mesh sleve.
me compo~ite was found by a~h analysis to contain
67.5% mineral. The polymer had an inherent ~lscoslty of
27.47 ~0.025 w/v 0 . The 10-second mic~onization homogenelty
wa~ 86% and the mlcronlzatlon homogeneity index was 68
Test bars ~hich were prepared by heating thc
compo~ite in a mold at 180C for 1 minute and then co~pressing
at 3000 psl at 180C for 3 minutes had the following properties:
Ten~ile (T): 3025, 2826 p8i
Elongatlon (Eb): 301%
Modulus (Mi): 955,000 psi
0F Izod Impact: 8.1. 8.3 ft lb/in of notch
EXAMPLE 57
This example illustrate~ the w e of bentonite clay
wlth a hydrocarbon-soluble organic tran~ition metal catalyst.
The reaction mixture wa~ prepared by adding 70 g of bentonite
(Fisher Scientific), which had been dried by heating for
18 hours at 300C under a 30-liter/hr nitrogen flow,
to 600 ml of clay and o~ygen-free cyclohexane containing
4 mmol (0.8 g) trii~obutylaluminum and 0.2 mmol of
tetrabenzylzirconium, 2 ml of toluene in an enclosed blender
cup with nitrogen purge. After stirring, the mixture was
_ 99
~0~7~,'9
transferred to a dry and oxygen-free, l-liter autoclave.
me polymerization was carried out at 50C under 100 psi of
ethylene in 9 minutes. There resulted 115 g of compo~ite
powder that passed a 20-mesh sieve.
When the composite was pyrolyzed in air, it had
an a~h content of 52.65%. me polymer had an inherent
viscosity oP 11.26 (0.025 w/v %). The 10-~eoond micronization
hom~geneity was 79% and the micronization homogeneity index
was 66.
Test bars were prepared by heating the composite
at 180C Por 1 minute, rollowed by compression at 3000 psi
for 3 minutes at 180C. me test bars had the following
properties:
Ten~lle (T): 3214, 3202 psi
Elongation 'Eb' 32~, 19%
Modulus (Ml): 495,000, 399,000 psi
0F Izod Impact: 1.2; 1.2 ft lb/in of notch
EXAMPLE 58
m is example illustrates the use Or tricalcium
phosphate as the Piller.
The reaction mixture was prepared by adding 60 g
oP Ca3(P04)2 (J.T. Baker Co.), which ha~ been ~ried by
heating Por 13 hours at 300C under a 30-liter/hr nitrogen
flow, to 600 ml Or dry and oxygen-free cyc~ohexane containing
4 mmol (0.8 g) of triisobutylaluminum and 0.2 mmol o~
tetrabenzylzirconium in 2 ml of toluene in an enclosed blender
cup under nitrogen purge. A~ter stirring, the mlxture was
transferred to a dry and oxygen-free autoclave. me
polymerization was carried out at 50C under 100 p~i of
ethylene in 18 m1nutes. There resulted 100 g o~ compo6ite
powder that pa~sed a 28-mesh sie~e.
- 100 -
,~
1040779
When the composite was pyrol~zed in air, it had
an a~h content of 48.95%. The polymer had an inherent
viscosity of 8.49 (0.025 w/v %). The 10-~econd mlcronization
homogeneity was 74% and the micronlzation homogeneity index
waæ 41.
Test bars were prepared by heat~ng the composite
at 180C for 1 mlnute, followed by compression at 3000 pBi
ror 3 minutes at 180C. The baræ had the following
properties:
Tensile (T): 3128, 3133 psl
Elongation (Eb): 28~, 16%
Modulu~ (Mi): 555,000, 599,000 p~i
0F Izod Impact: 1.8, 2.0 ft lb/in of notch
EXAMPLE 59
This example illustrate~ the preparation of a
compo~ite ~rom calcium carbonate coated with ~ ilica.
A solution Or monomeric silicic acid wa~ prepared
by adding 28 g of silicon tetrachloride to 200 g of ice with
~trong ~tirring in a blender. The r~ulting clear solution
wa6 added immedlately, dropwise with ~tirring, to a
suspen~ion of 1000 g Or GAMMA SPERSE 80 calcium carbonate
(Example 27) in 2 liters of water. The mlxture wa~ filtered,
and the ~olid on the filter ~a~ wa~hed free of chloride ion
with water, dried, and pulverized. It was further dried
for 18 hours at 300C under a stream of nitrogen flowing at
30 l/hr.
The reaction mlxture was prepared by adding
70 g or the above SiO2 coated CaC03 to 600 ml of dry and
oxygen-free cyclohexane oontaining 4 mmol (0.8 g) of
triisobutylaluminum and 0.2 1 of tetrabenzylzirconlum in
- 101 -
1040779
2 ml of toluene ln an enclosed blendcr cup under nitroge~
purge. After stirring, the mixture Was transferred to a
dry and oxygen-free autoclave. me polymerization was
carried out at 50C under 100 p8i of ethylene in 21 minutes.
There re~ulted 95 g of composite powder that passed a 16-mesh
sievc.
me composite was found by ash analysis to contain
72.2% CaC03. The polymer had an lhherent viscosity of
25.02 (0.025 w/v %). me 10-second micronization homogeneity
wa~ 98% and the micronization hom~genelty index was 85.
Te#t bars were prepared by heating the composite at
180C for 1 minute, followed by compression at 3000 psi for
3 minutes at 180C. These bars had the ~ollowing properties:
Tensile (T): 2716, 2663 psi
Elongation (Eb): 279%, 270%
ModUlu~ (Mi) 889,000, 748,ooo psi
0F Izod Impact: 6.2, 7.1 ft lb/in Or notch
EXAMPLE 60
ThlB example illustrate~ the preparation o~ a
composite ~rom c~lcium carbon~te coated with acid phosphate.
A solutlon Or 45 g Or 85% phosphoric acid in 200 ml
of water was added dropwise *ith stirring to a suspension of
600 g Or GAMMA SPERSE 80 calcium carbonate (Example 27).
The suspension wa~ filtered, and thc solid on the filter was
washed with water and drled. The solid was further dried
at 250C ror 18 hour~ ln a 30-liter/hr stream o~ nltrogen.
The reaction mixture was prepared by adding 70 g of H3P04
treated CaC03 to 600 ml of dry and oxygen-free cyclohexane
containing 4 mmol (0.8 g) of triisobutylaluminum and 0.2
mmol of tetrabenzylzirconium in 2 ml of toluene in an
enclosed blender cup under nitrogen purge. After stirring,
the mixture was transferred to a dry and o~ygen-free auto-
- 102 -
,.: i~.
~ . .
1040779
clave. me polymerizat~on was carried out at 50C under 100
psi of eth~lene in 9 minute~. There resulted 97 g of
composite powder ~hat passed a 16-mesh sieve.
The composite was found by ash analysis to
contain 71% CaC03. The poly~er had a~ inherent viscosity
Or 24.96 (0.025 w/v %). The 10-second micronization
homogeneity was 98% and the micronization homogeneity ~ndex
wa~ 81.
Test bars were prepared by heating the compoYite
at 180C ror 1 min, followed by compression at 3000 psi for
3 min at 180C. mese bar~ had the following propert~es:
Ten~ile (T): 2692~ 2637 p8i
Elongation (Eb): 244%, 255%
Modulus (Mi): 573,000, 600,000 psi
0F Izod Impact: 8.2, 11.0 ft lb/in of notch
EXAMPLE 61
Thi~ example illw trates the w e o~ alumina coatod
CaF2 a~ the rlller.
me CaF2 wa~ coated with A1203 by suspending 390 g
o~ CaF2 in approximately 1500 cc Or distilled water and
adding dropwise a ~olution of 25 g o~ AlC13.6H20 in ~00 ml
Or water while stirring. The mixture wa~ neutralized with
5% aqueous ammonia whlch at the same time preclpitated A1203.
The m1~ture was stlrred for one hour and the ~olld was
collected by flltration and wa~hed with di~tilled water~
The solld wa~ dried at 150C for 18 hour~ under a 30-llter/hr
flow Or nltrogen.
Analysis: Al 1.18%, 1.25%
me polymerization wa~ carrled out in a dry and
oxygen-rree, l-liter autocla~e. The reaction mixture was
- 103 -
. .
104~7~9
prepared by adding 80 g of the above A1203 coated CaF~
to 600 ml of dry and oxygen-free ~yclohexane containing
4 mmol (0.8 g) of triisobutylaluminum and 0.2 mmol
of te~rabenzylzirconium. The vigorow ly stirrred mixture
wa~ tran~erred to the autoclave. The polymerization was
carried out at 50C undor 100 psi Or ethylene ~or 8 minutes.
The product wa~ 82 g of composite which passed through a 16-
me~h ~leve and 27 g Or larger particles hhlch were discarded.
When the compo6ite wa~ pyrolyzed in air, it had
an a~h content of 55.85%. The 10-sccond micronization
homogeneity was 72% and the micronlzation homogeneity index
wa~ 52. Test bars, prepared by lding at 180C for 1 minute
followed by compre~sion at 3000 p~i for 3 minutes, had the
following properti-~:
Ten~ile (T): 3294, 3314 pBi
Modulus (Mi): 407,000, 464, ooo p~i
Elongation (Eb): 221%, 216%
0F Izod Impact: 13.8, 12.4 ~t lb/in o~ notch
EXAMPIE 62
~0 Thi~ example illustrate~ the use of dawsonite a~
the ~iller.
(A) To a stirred ~uspenslon of 500 g of ground
daw~onite tALCOA, Lot No. P1746-3) in 2 ~b of ether was
added dropwise over 1 hour a solution of 10 g of 85% phosphoric
acid in 300 ml of ether. After being stirred for 3 hour~ re,
the mixture wa~ ~iltered under nitrogen pre~sure, and the
solid on the filter was dried in a ~tream o~ nitrogen. me
acid-pho~phate-coated daw~onite thus obtained weighed 493 g.
Analy~ P 1.01%, 0.98%
(B) Dry, deoxygenated cyclohexane (600 ml) was
passed through a bed of Woelm acid alumlna into an enclosed
- 104 -
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1040'779
blender cup under nitrogen. There were then added 0.3 mmol
o~ triisobutylaluminum, a solution o~ 0.3 mmol of tetra-
benzylzirconium in 3 ml of toluene, and 60 g of the phosphoric
acid-treated dawsonite o~ part (A), which had been dried ~urther
at 125C for 18 hours in a stream o~ nitrogen at 30 l~hr.
The re~ulting dispersion was trans~erred through polyethylene
tubing under nitrogen pressure to a l-liter stainles~-steel
autocla~e equipped with a stirrer. The autoclave had prev-
iou~ly been dried by heatlng at 150C under 0.5 mm vacuum
ror 2 hours, purging with nitrogen at 150C for 3 hours~ and
cooling under nitrogen. Stirring was started, the system was
heated to 50C, thc autoclave was pre~sured with ethylene
to 60 psi, and the mixture was heated at 50C and 60 p8i,
wlth rcpressuring as necessary, until 40 g of ethylene had
been consumed in addition to that required for the initial
pressuring (3 hr). The autoclave was cooled and vented, and
the solld product was separated by filtration and dried. me
rocovcred product ~onsisted Or 77 g of powder that passed
through a 28-me~h screeDhand 16 g of larger particles. The
powder gave 36.40% ash on combustion, corre~ponding to a
36/64 polyethylene/daw~onite composition. me inherent vls-
cosity df the polymer Wa8 20.11 determined usi~g a 0.025 w/v %
solution. me composite had a 10-~econd micronization homo-
geneity of 96% and a micronization homogenelty index of 82.
The powder w~s compression molded to a plaque by
heating in a ld at 185C for 3 minutes, followed by heating
at 185C and 3000 p~i for 2 minutes. Test bars cut from the
plaque had the following properties:
Tensile (T): 2748, 2686 p5i
3o Elongation (Eb): 26%, 4.7%
Modulus (Mi): 647 592 kpsi
0F Izod Impact: 5.2, 4.3 ft lb/in of notch
(hinge break)
- 105 -
~040~779
264-psi Heat Deflection: 71.5C, 77.5C
EXAMPLE 63
Thi~ example shows that composlte~ containing
dawsonite as ~iller ha~e some M ame-retardant prop~rties.
Example 52 wa~ repeated, with the ~ollowing change~:
The pho phoric acid-treated qaw~onlte WAB air-micronized
before the ~inal drying, to m~nimize the pre~ence of aggre-
gates, and the polymerization was carried out at 100 psi until
38 g oP ethylene had been cQnsumed tl hr, 54 min). The prod-
uct wag 89 g of a powder that passed through a 16-mesh screen.
It gave 33.66% a~h on combustion, corresponding to a poly-
ethylene/daw80nlte compo~ition of 40.8/59.2.
Bars cut from a plaque compression molded at
180C and 3000 psi had the following properti~:
Tensile (T): 2562, 2568 psi
Elongatlon 'Eb' 386%, 103%
Modulus (Mi): 454, 472 kpsi
0F Izod Impact: 7.~, 6.2 ft lb/in of notch
(partial break)
Oxygen Index: 0.269
EXAMPIE 64
This example ill w trates the use of a mixture Or
alumin~ trihydrate and daw~onite as the filler.
(A) A mixture of 200 g of GHA 431 alumina tri-
hydrate (Example 39), 50 g of the acid-phosphate treated
dawsonlte described ln Example 52 (A), 3 ml of tetraisopropyl
tltanate, and 500 ml of cyclohexane was rod-milled for 5
hour~. The product was separated by ~iltration, wa~hed with
cyclohexune, and dried under nitrogen. It was then air-
micronized.
(B) ~y essentially the procedure of Examplc 52 (B)3,a dispersion containing 55 g of the 4/1 alumina trihydrate/
daw~onite prepared in part (A) above which had been dried
- 106 -
, ,
iO4t)7~
~urther at 170C for 18 hours in a stream of nitrogen at30 l/hr, 4 mmol Or triisobutylaluminum 0.2 mmol of tetra-
benzylzirconium, and 600 ml of cyclohexane was processed
with ethylene at 50C and 100 p8i until 43 g of ethylene
had been consumed (3 hr, 17 min). The recovered product
was 91 g Or a powder that pa~sed through a 16-mesh æcreen.
It gave 38.71% ash on combustion, corresponding to a poly-
ethylene/mineral compoæition of 39.2/60.8, the mineral being
4/1 alumina trihydrate/dawsonite. The composite had a 10-
second micronizatlon homogeneity Or ~6% and a micronizationhomogenelty index of 87.
Test bars cut from a plaque compression molded
at 180C and 3000 p31 had the following properties:
Tensile (T): 2233, 2298 psi
Elongation (Eb): 353%~ 298%
Modulus (M1): 396, 45 kpsl
0F Izod Impact: 13-3, 13.5 rt lb/in o~ notch
(partlal break)
Oxygen lndex: 0.276
EXAMPIE 65
This exa~ple lllustrates an in~ection moldable
composite containing kaolinite clay.
Up to the ~tart of the polymerization and during
addltlon Or antioxidant to the product, all operation~ were
carried out under nitrogen.
(A) Cyclohexane (2.5 1) was sparged with nitrogen
and passed through Woelm acid alumina into a blender equipped
with a high-æpeed stirrer. Triisobutylall~m~num (12.2 mmol)
was added, followed by 0.53 mmol Or tetrabenzylzirconium a~
a 5% solutinn in toluene. The resulting solution waæ allowed
to stand for about 0.5 minute. A 500-g portion of HARWICK
- 107 -
~.
. . ~.
i04(~ 9
GK soft kaolinite clay (Example 1) that had been dried at
150C for 24 hour~ was then added. The mixture was stirred
at high speed for one minute. The resulting slurry wa6
transferred through polyethylene tubing under nitrogen
pressure to a 5-gal stainless steel autoclave containing
3 gal of dry, deoxygenated hexane. Before the hexane was
charged, the autoclave had been heated at 150C and 0.5 mm
vacuum for two hours, purged with nitrogen at 150C for
three hours, and cooled under nitrogen. Stirring at 500 rpm
was started, the mi~ture wa~ hcated to 50~ and the system
wa~ pres3ured with hydrogen to 500 psi. Ethylene was
admitted to the ~ystem at 100 psi, and thc polymerization
was continued, with reprcsæuring of ethylene aæ necessary,
untll 850 g of ethylene had been consumed (46.82 min). The
autoclave was cooled, excesæ prc6sure was bled down, a
solutlon of 0.085 g (0.01% of the expected amount of
polyethylene) of IRGANOX 1010 antioxidant in toluene was
stlrred in, and the product was separated by filtration
and dried.
The ~inely powdered composite gave 29.38% ash on
combustion, corresponding to a polyethylene/clay composition
o~ 65.8/34.2. The inherent viscosity of the polymer waæ
2.54.
Hot-compression molded tc~t bars had the following
properties:
Tens~le (T): 2750 p~i
Elongation: (Eb): 77%
ModulU8 (Mi) 309 kpsi
0F Izod Impact: 1.2 ft lb/in of notch
73F Izod Impact: 2.6 rt lb/in of notch
FlexNral modulus: 264 kpsi
_ 108 -
.: ,..
104~779
In addition, tensile bars, plaques, and combs were
made by in~ection molding in a-Newberry ram-in~ection molder
(Model HI-30-T). The composite was heated in the in~ector
at 230C rOr about 20 seconds, then ram in~ected at 6,ooo
psi ror 20 seconds into the mold, which was heated at 100C,
and cooled ln the mold for 20 seconds.
(B) For the formation of molded objects by screw-
ln~ection molding, a blend was prepared by combining the
product o~ part (A) above with the products of four other
runs. These runs were carried out by the general method
described ln part (A) above, with some variation in the amounts
of clay, ethylene, triisobutylaluminum, and tetrabenzylzir-
conlum. Their clay contents ranged from 31.7% to 40.4%, and
the lnherent vlscosities of the polymers ranged ~rom 2.54 to
5.15. ~he clay content of the overall blend was 35.3%, and
the lnherent vlscosity of the polyethylene was 3.92.
The blend waæ in~ection molded to 4-oz tumblers
and 2 5/8 in dlameter Mlchlgan gears in a 6-oz Van Dorn
8crew-ln~ectlon molder. The blended composite was heated
and melted at 400F and ln~ected at 16,000 psi through a
nozzle heated at 450F lnto a mold heated at 165-170F. The
total cycle was 23 seconds, with a 10-second heatlng, a
5-second ln~ectlon, and an 8-second hold.
(C) A sample was prepared by the method of part
(A) above, except that 13.0 mmol of triisobutylaluminum
and 0.56 mmol Or tetrabenzylzirconium were used, the clay
had been dried at 170C ~or 2.0 hours, stirring was at 400
rpm, the reaction temperature was 54C, and 930 g o~ ethylene
was consumed (38;35 min). The solid product gave 26.7%
ash on combustlon, corresponding to a polyethylene/clay
-- 109 --
. .
1040779
composltlon of 69.0/31Ø The inherent viscosity of the
polymer was 3.96. The composite had a 10-second micronization
homogeneity of 64% and a micronization homogeneity index of
37. Oniy 3.33 g o~ the composite was available for use in
this determination.
Hot-compression molded test bars had the following
properties:
Tensile tT): 3027 psi
Elongation (Eb): 399%
Modulus (M1): 300 kpsi
0F Izod impact: 1.4 ft lb/in Or notch
73F Izod impact: 4.2 ft lb/in of notch
Fiexural modulus: 301 kpsi
tD) A blend of two samples prepared in two
different runs by essentially the method of part (C) above
except that in each run stirring was at 450 rpm, the poly-
merlzation temperature was 53C, and 100 g of ethylene was
consumed (37.88 min, 42.24 min). The blend of the two runs
gave 28.2% ash on combustion, corresponding to an overall
polyethylene/clay composition of 67.2/32.8. The inherent
viscosity Or the polymer was 3.13. The composite had a-
10-second mlcronizatlon homogeneity of 64% and a microniza-
tion homogeneity index of 40.
Hot-compression molded test bars had the following
properties:
Tensile (T): 3086 psi
Elongation (Eb): 436%
Modulus (Mi): 331 kpsi
0F Izod lmpact: 0.98 ft lb/in Or notch
73F Izod impact: 2.22 ft lb/in Or notch
Flexural modulus: 297 kpsi
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1040779
EXAMPIE 66
This ex~mple illustrates an in~ection moldable
composite containing titanium dioxide pigment.
(A) By essentially the method o~ Example 55 (A),
600 g of TI-PURE R 101 rutile (Example 7) that had been
dried at 400C ~or 24 hours in a stream o~ nitrogen at 30-40
l/hr, 8.0 mmol of triisobutylaluminum, and 0.40 mmol o~
tetrabenzylzirconium were processed with hydrogen at 600 psi
and ethyléne at 35 psi at 44-51C until 800 g of eth~lene
~0 had been con~umed (40.85 min). The solid product thuæ
produced gave 45.82% ash on combustlon, corresponding to a
polyethylene/ tltania composition o~ 54.2/45.8. The inherent
viscosity of the polymer was 4.13.
Test bar6 made by hot-compression molding had the
following properties:
Tensile (T): 347 p~i
Elongation (Eb): 188%
Modulw (Mi): 442 kpsi
0F Izod Impact: 2.4 ~t lb/in of notch
264-psl Heat De~lectlon: 57C
Flexural Modulus: 309 kpsi
Test bars, plaques, and combs were prepared by
ram-in~ection lding. Tumbleræ and gears were made by
sciew-in~ectlon molding.
(B) Homogenelty determinatlons were run on a
sample prepared by the method of Part (A) above, except that
700 g o~ tltanium dioxide was used and the polymerizatlon
was carried out at 30 p8i ethylene pressure and 40-47C until
850 g o~ ethylene had been consumed (60.02 min). The solid
product gave 46.49% ash on combustlon, corresponding to a
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1040779
polyethylene/tltania composition of 53.5/46.5. The inherent
viscosity of the polymer was 4.04. The composite had a
10-second micronization homogeneity of 75~ and a microniza-
tlon homogeneity lndex of 57.
Test bars made by hot-compression molding had
the ~ollowlng properties:
Tenslle (T): 3200 psi
Elongation (Eb): 7.2%
Modulus tMi): 465 kpsl
. 0F Izod lmpact: 1.14 ft lb/ln o~ notch
264-psl Heat Deflection: 55.5C
Flexural Modulus: 308 kpsi
112 -
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