Note: Descriptions are shown in the official language in which they were submitted.
106~
The invention relates to the polymerization of alpha-
olefins having at least three carbon atoms, using catalysts
containing titanium,magnesium, aluminium and halogen. In the
process o~ the invention, it i9 possible to start from a
magnesium alcoholate and obtain a catalyst of high activity
and stereospeoificity.
The catalysts employed in the proce~s Or the invention
compri~e the reaction product of (A) an addition and/or
eubstitu~ion product of an electron-donor compound (~ewi3 bases)
with an aluminium alkyl, with (B) a compound and/or composition
containing magne~ium, titanium, aluminium and halogens in which
the atomic ratio of halogen : magnesium i~ at least 1:1, which
compound and/or composition is either (I) obtained by contacting
(al) a halogen-containing titanium compound with the product
of reaction between (a2) a magnesium alcoholate of the formula
XMgOR, where R is an alkyl, cycloalkyl or sryl radical containing
up to 20 carbon atoms snd X is a halogen atom or i9 radical R or OR,
or a magnesium alkyl or aryl of the formula RMgR in which R is as
defined above, or a magnesium salt of a eatursted or unsaturated
carboxylic acid, or a magnesium enolate, and (a3) aluminium
halides of the formula AlRnX3 n~ in which R and X are as defined
above, and _ is 0,1 or 2, or (II) a reaction product of (bl)
aluminium halides or alkylhalides or alkyls of the formula
AlRmX3 m~ in which R and X are as defined above, and _ is 0,1,2
or 3, with the product of reaction between a magnesium compound
89 defined above under (a2) or (b2) a halide or oxy-halide of
magnesium, with (b3) a titanium alcoholate. The titanium
alcoholate may be mixed with (b4) an aluminium alcoholate.
The term "addition and/or substitution product" of an
electron-donor compound means products consisting of or
including complexes of the electron-donor compound with an
sluminium alkyl and compounds re~ulting from the reaction of the
.~ -1- ~
i 1068446
aluminium trialkyl with an electron-donor compound cont~ining a
mobile hydrogen atom or atoms capable of reacting with the
aluminium trialkyl to bring about a substitution reaction such
~g:
3 2 ~ R2A~ AlR2 + 2R-H
R'
In such substitution product~, the aluminium atoms are bound
together by oxygen or nitrogen atoms. In the ~aid addition and/
or substitution products, the amount of aluminium combined is
generally from 0.01 to le~s than 1 mol per mol of that used as
starting material.
Among ~e~is base~ capable of appropriate addition and/
or substitution are amines, amides, ethers, esters, ketones,
nitriles, pho~phines, stibines, arsines, phosphoramide thioethers,
aldehyd~s, alcoholates, amides and salts of organic acids of
metals of the first four group~ of the Periodic Tsble. ~he most
interesting results, as regards both activity and stereo-
specificity, have been obtained using an ester or a diamine.
Typical e~amples of such compounds are ethyl benzoate, ethyl
~-methoxy-benzoate, diethyl carbonate, ethyl acetate, dimethyl
maleate, triethyl borate, ethyl o-chloro-benzoate, ethyl-
naphthenate, ethyl toluate, ethyl ~-butoxy-benzoate, ethyl
cyclohexanoate, ethyl pivalate, N,N,N',N'-tetramethylene-diamine,
1,2,4-trimethyl-piperazine, and 2,5-dimethyl-piperazine. The
preferred ~ewi~ base : aluminium alkyl ratio~is lower than
0.8:1; in the case of an ester or dismine, it i9 from 0.1:1 to
0.6:1 Generally, the catalyst activity and stereo~pecificity
are respectiYely lower a~d higher in proportion to the ~ewis
base : aluminium alkyl molar ratio~
Aluminium alkyls which can be used sccording to the
invention are preferably tho~e including alkyl groups having
a linear or branched chain cont~ining up to 20 carbon atoms,
--2--
~068446
or reaction products thereof with water, ammonia or a primary
amine, and consequently containing two or more aluminium atoms
bound to one another by an oxygen or nitrogen atom. Some typical
examples of such compounds are aluminium triethyl, aluminium
trimethyl, aluminium tri-n-butyl~ aluminium t~-n-propyl,
aluminium trii~ohexyl, aluminium triisooctyl, and those of the
formulae
Al (al2H25)3, (C2~5)2Al-o-Al(c2H5)~ (C2~5)2Al I ~1( 2 5)2
C6H5
and aluminium ispprenyl.
Component A) ~f the ¢ataly3t according to the invention
may be prepared by reacting the ~ewis base with the aluminium
alkyl in a suitable molar ratio. Alternatively the aluminium
trislkyl may be reacted with component B) and the ~ewis base
then added.
Some typical titanium compounds of type (al~ are
halides, oxyhalides and alkoxyhalides of titanium, and
particularly the tetrahalide.
Some typical magnesium compounds of type (a2) are
alcoholates having linear or branched alko~y groups preferably
containing up to 10 carbon atoms, halo-alcoholates and
psrticularly chloro-alcoholates having an alkoxy group o~ the
type ~pecified above, the acetylacetonate, methylglyoximate and
those of the formulae Mg(C2H5)2 or Mg(C6H5)2~
Some typical aluminium halides of type (a3) have X as
chlorine and R as defined and preferred above, and particularly
aluminium ethyl sesquichloride and ~luminium ethyl dichloride.
Some typical aluminium compounds of type (bl) are,
besides those mentioned for the compounds of type (a3),
trihalides and particularly the trichloride.
Some typical magnesium compounds of t~pe (b2) are
halides, anhydrous or hydrated, and particularly the chloride
1068446
and oxychloride.
Some typical titanium alcoholates of type (b3) are
tho9e of the formulae Ti(0-iC3H7)4, ~i(0-nC3H7)4~ Ti(0-iC4Hg)
Ti(0-nC H )4, Ti(Oa6H5)4 and ~i20(0-iC3H7)6.
compounds may optionally be utilised in admixture with s~aller
amounts of vanadium compound~ such as the oxytrichloride or the
tetrschloride.
Some typical aluminium alcoholatee of type (b4) are
s~mple alcoholate~, alkyl-alcoholates and halo-alcoholates, in
which the alkyl group contalns up to 10 carbon aton~, and the
halogen i9 chlorine, and particularly aluminium triisobutylate.
The final atomic ratios between the elements in
component B vary over w~de ranges. In ca~e (I) (reaction o~ a
with (a2 + a3)), particularly profitable result~ have been
achieved with Mg/~i ratios of from 0.5 to 30, preferably from 1
to 20, and with Mg/Al ratios of from 0.5 to 5, preferably from
0.8 to 3. In case (II) (reaction of bl with (b2 + b3 and
optionally b4~), particularly profitable results have been
attained with Mg/Ti ratios of from 0.5 to 30, preferably from
0.5 to ~0, with Mg/Al ratios of from 0.5 to 15, preferably from
0.8 to 10, and with Ti~Al (a~ b4) ratios of from 0.01 to 2,
preferably from 0.01 to 0.5. In case (II) (reaction of bl with
(a2 ~ b3)), psrticularly profitable results have been achieved
with Ng/Ti ratios of from 0.5 to 50, preferably from 1 to 30,
and with Mg/Al ratios of from 0.5 to 15, preferably of from 1
to 10. In all cases the Al/Ti ratio is hiBher than l; and
particularly advantageou8 results have been attained with Al/~i
ratios of from 10 to 10000.
~he alpha-olefins polymerized include propylene, butene-l
and 4-methylpentene-1. Propylene higher olefins may be
copolymerized with one another and/or with lower amounts of
ethylene. The polymerization cond~tions are well-known in the
--4--
1068446
art, and comprise temperatures of from -80C to ~150C,
preferably from 0C to 100C, the partial pressures of the
alpha-olefins being higher than atmospheric. Polymerization may
be conducted in a liquid phase, ~n the pre~ence or absencQ of
an inert hydro¢arbon diluent, or in ~ gas phase. In the poly-
merization of propylene, particularly satis*actory results have
been ~ttained operatin~ in the pre~ence of an aliphatic or
aromatic hydrocarbon diluent~ uid under thè polymerization
conditions, snd in liquid propylene as reaction medium.
~he following Examplee illustrate the in~ention; the
physical properties measured being d~termined as follows:
melt-flow index (MI~) AS~M D_1238/73; flexural rigidity ASTM
D_747/70 on specimens prepared by moulding with 8 plate pre~s at
200C and annealing at 140C for 2 hours.
~AMPIE 1
a) Prearation of comPonent B
25.4 g of Mg~OC2H5)2 were treated with 140 ml of a
s~lution containing 60 g of Al(C2H5)C12 in 91 ml of n-hexane
(Cl/~g atomic ratio = 1.6), at 25C for 2 hours. The reaction
w~s exothermic snd 90 cooled. At the conclusion, the solid
resction product was repeatedly washed by decantation with
n-hexane and then dried under vacuum at 45C. The collected
solid product (23.9 g) uas sub~ected to elemental analysis snd
yielded the following results;
Mg = 20.9 g/100 g
Al = 5 g/100 g
Cl = 44.95 g/100 g.
This product ~as treated with TiC14 in excess for 1 hour at 136C,
then repeatedly washed with _-hexane, to remove every trace of
free TiC14, and finally dried under vacuum at 50C. The ~olid
product obtained, sub~ected to elemental analysis, yielded the
followlng results
1068446
Mg = 16.95 g/100 g ~i = 7.75 g/100 g
Al = 3.5 g/100 g Cl = 65.5 g/100 g.
~he 3ur~ace area was 160 m2/g.
b) Polymerization of Pro~Ylene in a ~olvent
310 mg of the solid product o~ Example la, were
introduced lnto a ~tainless steel, 2.5 litre autoclave, containing
1 litre of heptane and 1.135 g of Al(C2H5)3, mixed with 572 mg
o~ ethyl anis~te. Polymeri~ation was ~onducted at 60C, at a
pres~ure of 5 kg/cm2 gauge~ with propylene and hydrogen (1.5%
by volume of the gas phase) for 5 hours. ~he pressure wa~ kept
con~tant by continuous feeding of propylene. At the conclusion,
the solvent was removed by stripping with steam, 263 g of dry
polymer were obtained. ~he yield was 10,950 g of polypropylene/g
of ~ he polymer had a residue after e~traction in boiling
heptane of 81~, and a bulk density of 0.33 kg/litre.
c) Pol~merization of ~ro~lene in liquid monomer
~ ~tainless steel, 30 litre autoclave wa~ fed with 10 kg
of propylene, 12.5 g of Al(C2H5)3 in 90 ml of n-heptane, 7.20 g
of ethyl anisate in 120 ml of n-heptane, 900 mg of the solid
product of E~ample la in 130 ml of n-heptane and 15 N~ (normsl
litres) of hydrogen. ~he polymerization temperature was brought
to 65C and the pressure ad~usted to 26.5 kg/cm2 gauge. After 5
hours polymerization, the excess propylene was removed and 2.95
kg of polypropylene were obtained. ~he yield was 42 9 300 g of
polymer/g of ~i. The polymer had a residue to extraction with
boiling n-heptane of 78.5% and a bulk density of 0.32 kg/l.
EXAMP~E 2
a) Pre~aration of component B.
20.4 g of Ti(O_Bu)4 (titanium tetra-n-butylate) were
mixed with 11.4 g of anhydroua MgC12 powder and kept at 165C
for 3 hours. A semi-fluid product was obtained, in which a
portion of the magne~ium chloride was dissolved. In cold
~06a446
condition~, the reaction product was sdded to 240 ml of n-hexane,
and thoroughly broken up by stirring. The suspension was mixed
with 38.2 g of AlC2H5C12 in n-heptane salution at a concentration
of 478 g/l~ ~he mixture temperature wa~ brought to 70C and
kept at this value for 1 h~ After cooling, the solid pre¢ipitate
~a9 dacanted until the e~ce~s aluminium alkyl disappeared. The
sQlid product was dried under vacuum at 50C. Its elemental
analy~i~ was:
Mg ~ 11.45 ~/100 g ~i 5 12.1 g/100 g
Al 3.45 g/100 g Cl = 63.75 g/100 g.
b) PolYmerization oi ~rop~ene in liquid monomer
10 kg of propylene, 12.5 g of Al(C2H5)3 in 90
ml of _-heptane, 6.36 ~ of ethyl anisate in 120 ml of n-heptane,
860 mg Or the solid product of Example 2a in 130 ml of _-heptsne
and 15 Nl of hydrogen were introduced into a ~tainless ~teel,
30 litre autoclave. The temperature was brought to 65C and
the pressure ad~usted at 26.5 kg/cm2 gauge After 5 hour~
polymerization and removing the exce~s propylene 0.6 kg of
polypropylene were obtained (yield - 5,770 g of polymer/g of Ti),
having a residue to extraction with boiling n-heptane of 68.6%
and a bulk density of 0.20 kg/l.
EXAMPIE 3
a~ Pre~ar~ion of comPonent ~
11.65 g of anhydrous MgC12 in powder form were mixed
with 29.55 g of Al(Osec.~u)3 (aluminium secondary tributylate)
and 4.08 g of Ti(On.~u)4 at 165C for 6 hours. A pa~te, semi-
~olid in hot conditions and solid in cold conditions9 wa~ thus
obtained. This was broken up by stirring in 240 ml _-hexane in
cold conditions. At 20C, the suspencion wa9 mixed uith 38.15 g
of AlC2H5C12 in a _-heptane solution at a concentration of 478 g/l,
The temperature was brought to 70C and kept at this vslue for
1 hour. After cooling, the solid product was decanted, and
~068446
repeatedly washed with n-hexane by decantation to remove the
excess aluminium alkyl. ~he solid product wa~ dried under vacuum
at 50C Its elemental analysis ~as
Mg - 16.15 ghoo g Ti = 3 g/100 g
Al = 7.05 g/100 g Cl = 57.45 g/100 g.
Its surfa¢e area was 46 m2/g,
b) PAol~rization of ro~lene ~n a solvent
119 mg o~ the eolld product of Example 3a were
introduced into a ~tainless steel, 2.5 litre autoolave containing
1 litre of n-heptane and 1.35 g of Al~C2H5)3 mixed ~ith 447 mg
of ethyl anisste. Polymeri~stion was conducted at 60C at
5 kg/cm2 gauge with propylene and hydrogen (1.5% by volume of
the gss phsse) for 5 hours. Thc pressure was kept constant by
continuous feeding of propylene. At the conclusion, after
removal of the esolvent by stripping with steam, 74 g of dry
polypropylene were obtained, ha~ing a residue to extraction with
boiling a-heptane of 77.6%, in a yield of 20,700 g of polymer/g
of ~i.
c) Pol~merization of ~ro~Ylene in liquid monomer.
A stainless steel 30 litre autoclave was fed with 10 kg
of propylene, 12.5 g of Al(C2H5)3 in 90 ml of n-heptane, 6.36 g
of ethyl anisate in 120 1 of n-heptane, 856 mg of the solid
product of ~xample 3a in 130 ml of n=heptane and 15 Nl of hydrogen.
~he temperature was brought to 65C and the pressure to 26.5 kg/
cm2 gauge. After 5 hours polymer$zation, the exce~ propylene
wa8 removed, and 1~61 kg of polypropylene were obtained (yield:
62,600 g of polymer/g ~f Ti), which had a residue to extraction
with boiling n~heptane of 78.5%, a bulk density of 0.29 kg/l, an
intrin~ic viscosity of 2 dl/g, a melt-flow index of 3.7 g/10' and
a flexural rigidity of 10310 kg/cm2.
E~AMPIE 4
a ) Preparation of com~onent B.
--8--
1068446
23 g of anhydrous MgC12 in powder form wers mixed with
59 g of Al(Osec.Bu)3 and ~ith 4.08 g of ~i(OnBu)4 at 165C for
6 hours. A semi-solid paste wa~ thus obtained, which was cold-
dispersed by stirring in 180 ml of n~he~ane. At 20C, 76.2 g of
AlC2H5C12 in a n-heptane solution at a concentration o~ 478 g/l
were mixed with the suspen~ion. The tempersture was brought to
70¢ ~ith int~n~e stirrin~ for 1 hour. After ¢ooling, the solid
product was d~canted and repeatedly washed with n-hexane by
decantation in order to remove the excess aluminium alkyl. The
solid product was dried under vacuu~ at 50C. Elemental analysis
showed:
Mg - 19.5 g h g ~i = 1.95 g/100 g
Al = 4.2 g/100 g Cl = 65.10 g/100 g
The ~urface area was 70 m2/g.
b) Polymerization of ~roP~lene in a solvent.
234 mg of the solid product of E~ample 4a were
introduced into a stainless steel, 2.5 litre autocla~e containing
1 litre of n-heptane and 1.135 g of Al(C2H5)3 mixed with 571 mg
of ethyl anisate. Polymerization was conducted at 60C, st a
pre3sure of 5 kg/cm2 gauge with propylene and hydrogen (1.5% by
volume of the gas phase) for 5 hour~. The pres~ure was kept
constant by the continuous feeding of propylene. After removing
the ~olvent by stripping with steam, 95 g of polymer were
obtained. The yield was 20,800 g of polypropylene/g of ~i. The
product left a residue to extraction with boiling n-heptane of
80.5% and a bulk density of 0.355 kg/l.
c) Polymeri2ation of ~ lene in li~uid monomer,
10 kg of propylene, 12,5 g of Al(C2H5)3 in 90 ml of
= heptane, 7.75 g of ethyl-ani~ate in 120 ml of n-heptane, 1.1 g
of the ~olid product of ~xample 4a in 130 ml of = heptane and 15
Nl of hydrogen were introduced into a 30 litre 3tai~1e~ ~teel
autoclave. The temper~ture was brought to 65C and the pre~ure
_g_
1068446
to 26.5 kg/cm gauge. After 5 hours polymerization, the excess
propylene was removed, and 1.5 kg of polypropylene, having a
residue to extraction with boiling n-heptane of 81,5%, were
obtained. The yield wa~ 70,000 ~ of polymer/g of ~i, and the
polymer e~hibited the follo~ing ¢haracteristics:
bulk density 0.21 kg/l
viscos~ty 1.5 dl/g
melt-~ow ind~x 1.34 g/10~
~lexural rig~dity 11,830 kg/cm2
10 EXAMPIE ~
a) Preparation of com~onent ~.
18-12 g of Mg(002H5)2 were mixed with 5.~ g of
Ti(On.C4Hg)4 (titanium-tetra-n-butylate) in 240 ml of n-hexane
at about 70C for 45'. ~his mixture ~as added to 90 g of
Al(C2H5)C12 in a n-heptane solution at a concentration of 478 g/l.
The temperature was brought to 75C and kept at th~ value for
1 hour. After cooling, the solia preclpitate wa~ decanted and
repeatedly waYhed with _-hexane by decantation to remove the
excess sluminium alkyl. The solid product was dried under
vacuum at 45C. Elemental analysis showed:
Ng ~ 12.25 g/100 g `~i - 3.6 g/100 g
Al = 8.0 g/100 g Cl =`6.8 g~100 g
The surface area was 179 m2/g.
b) P~la~erization Or pro~ylene in a ~olvent.
189 mg of the solid product of Exsmple 5a ~ere
introduced into a 2.5 litre stainless steel autoclave containing
1 litre of _-heptane and 1.135 g of Al(C2H5)3, mixed ~ith 447 mg
of ethyl anisate. Polymerization was conducted at 60C, at a
pressure of 5 kg/cm2 gsuge with propylene and hydrogen (1.5% ~y
~0 ~olum~ of the gas pha~e) for 5 hours. ~he pres~ure wa~ kept
constant ~y continuous feeding Or propylene. After removing the
~olvent by stripping with ~team, 290 g of polypropylene having a
--10--
iO68446
residue to e~traction ~ith boiling n-heptane o~ 71% were obtained;
the yield being 42,600 g o~ polymer/g of ~i.
c) Polymerization of ~ro~lene in_a liquid monomei.
10 kg o$ propylene, 12.5 g of Al~C2H5)3 i~ 90 ml of
_-heptane, 6,36 g o~ ethyl anisate in 120 ml o~ n-heptane~ 790
m~ of the solid product Or Example 5a in 130 ml of n-heptane and
15 Nl of hydrogen were introduced into a stsinless ste~l 30
litre autoclave, Polymeri~ation t~mper~ture was performed at
65C and 26.5 kg/om2 gauge. A~ter 5 hour3, the ex¢ess propylene
wae removed, and 3.05 kg of polypropylene were obtained (yield =
107,000 g of polymer/g of Ti). ~he polymer left a residue to
extraotion with boiling heptane o~ 74~, a bulk density of 0.29
kg/l, a melt-flow index of 2.5 g/lOt and a flexural r~gidity of
8730 kg/cm2.
EXAMPIE 6
-
a) Pre~aration of com~onent B.
39.6 g of Mg(OC2H5)2 were mixed with 5.62 g of ~i(OnC4Hg)
(titanium-tetra-n-butylate) in 240 ml o~ n-hexane at about 70C
for 45 minutes. 183 g o~ Al(C2H5)C12 in solution in _-heptane
at a concentration of 478 g/l were added. Polymerization was
effect~d at 75C ~or 1 hour. After cooling, the solid precipitate
wae decanted and repeatedly ~ashed by decantation with n-hexane
to remove the excess alumin~um alkyl. The solid product wa~
dried under ~acuum at 45C. ~he elemental analysis was:
~g - 19.55 g/100 g ~i = 2 g/100 g
Al = 6.30 g/100 g Cl = 68.35 g/100 g
The surface area ~as 79 m2/g.
b) Pol~merization of ~ro~lene in a ~olvent.
173 mg of the solid product of Example 6a w~re
introduced into a 2.5 litre ~tainle~s steel autoclsve containing
1 litre of n-heptane and 1.135 g of Al(C2H5)3 mixed with 571 mg
of ethyl anisate~ Polymerization was conducted at 60C, at a
io68~46
pressure of 5 kg/¢m2 gauge with propylene and hydrogen (1.5% by
volume Or the gas pha~e) for 5 hour~. ~he pressure was kept
constant by continuous feeding of propylene. After removal
of the solvent by stripping with ste~m, 150 g of polypropylene,
having a re~idue to extraction with boiling n-heptane o~ 72.6%
and a bulk density of 0.353 kg/l, w~re obtained in a yield of
43,300 g Or polymer/g of ~i,
c) Polym~ris ~ ~ in l~Quid monomer,
10 g Or propylene, 12.5 g of ~l(C2H5)3 in 90 ml of
n-heptane, 8.75 g of ethyl ani~ate in 120 ml o~ n-heptane, 1.05
g o~ the solid product Or Example 69 in 130 ml of n-heptane and
15 Nl of hydrogen ~ere introdu¢ed into a 30 litre stainless
steel autoclave. Polymeri~stion Wa8 effected to 65C and 26.5
kg/cm2 gauge. After 5 hours, the excess propylene was remo~ed,
and 1.13 kg Or polypropylene, ha~ing a residue to extraction with
boiling n-heptane of 80.5%, ~ere obtained in a yield of 5~,800 g
of polymer/g of Ti. ~he polymer e~hibited the following
propertie~:
bulk density 0.~3 kg/l
20 melt-flow index 5.1 g/10'
flexural rigidity 11,500 gtcm2
3~A~PIæ 7
~) Pol~meri~ation o~ pro~lene in a solvent.
328 mg of the solid product prepared of Example 4a
were introduced into a 2.5 litre stainless ~teel autoclave
containing 1 litre of _-heptane and 1.135 g of Al(C2H5)3 mixed
with 450 mg of ethyl para-toluste. Polymerization W~3 conducted
at 60C and 5 kg/cm2 gsuge with propylene and hydrogen (1~5% by
volume of the gas pha~e) for 5 hours. The pre~sure W~9 kept
constant by continuous feeding of propylene. After removing
the solvent by stripping with steam, 296 g o~ polymer having a
residue to extraction wlth boiling n-heptane of 78.6~, ~ bulk
-12-
t 1o68446
density of 0.38 kg/l and an intrinsic viscosity of 2 dl/g were
obtained in a yield of 46,~00 g of polypropylene/g of ~i.
b) Pol~meri~ation of pro~lene in liàùid monomer
10 k~ o~ propylene along with 12.5 g of Al(C2H5)3 in
90 ml of n-heptane, 6 g Or ethyl para-toluate in 120 ml of
n-heptane~ 1.05 ~ of the solid produ¢t of Example 4a in 130 ml
on ~-heptsne and 15 Nl o~ hydrogen ~are introduced into a 30
litre ~tainles~ steel autoclave. Polymeri~ation Wa9 e~fected
at 65C and 26.5 kg/cm2 gauge. After 5 hours, the e~cess
propylene W~9 removed, 1.9 kg of polypropylene were obtained in
~ yield of 97,500 g of polymer/g of ~i, ha~ing a residue to
extraction with boiling a-heptane of 80.5%. The polymer was
characterised by the following properties:
bulk density 0.21 kg h
intrinsic viscosity 2 dl/g
melt-flow index 3.1 g/10'
fle~ural rigidity 10,750 g/cm2
EXAMPIE 8
Polymerization of pr~o~ ene in a solvent
240 mg of the solid product of ~xample 4a were
introduced into a 2.5 litre stainless steel autoclave contai~ing
1 litr~ of n= heptane and 1.1~5 g of Al(iC4Hg)3 mixed with 329 mg
of ethyl anieate. Polymerization wa9 conducted at 60C and
5 kg/cm2 gauge with propylene and hydrogen (1.5% by volume of
the gae phase) for 5 hours. The pres~ure wa~ kept constant by
continuous feeding of propylene. After removing the eolvent by
~tripping with ~team, 137 g of polymer in a yield of 29,400 g of
polypropylene/g of ~i were obtained leaving a res~due to
extraction in boiling n-heptane of 72.5%.
Polvmerization of ~ropylene in liauid monomer~
10 kg of propylene, 12.5 g o~ Al(i~4Hg)3 in 90 ml of
n-heptane, 4.15 g of ethyl ani~ste in 120 ml of n heptane, 1 g
~068446
of the solid product of E~ample 4a in 130 ml of n-heptane and 15
Nl of hydrogen were introduced i~to 8 30 litre ~talnless ~teel
autoclave. Polymeri~ation was performed at 65C and 26.5 kg/cm2
gauge, After S hours the e2cQss prop~lene was removed a~d 1.55
kg of polypropylene in a yield of 79,500 g of polymer/g of Ti,
~re obtained. ~his left ~ residue to extraction in boiling
n-heptane of 76%, a bulk density Or 0.3 kg/l, an intrin~ic
viscosity o~ 2 dl/g and a flexural rigidity of 8850 kg/cm2.
EXAMPIE_2
PQl~meri~ation Or ~ro~lcne in liauid monomer.
10 kg Or propylene, 12.5 g of Al(iC4~9)3 in 90 ml of
a-heptsne, 3.45 g of ethyl para-toluate in 120 ml of n-heptane,
1.06 g of the solid product of Example 4a in 130 ml of
n-heptane and 15 Nl of hydrogen were introduced into a 30 litre
stainless steel autoclave. Polymerization ~as performed at
65C and 26.5 kg/cm2 gauge. After 5 hours the exces~ propylene
was removed, 1.4 kg Or polypropylene in a yield of 67,600 g of
polymer/g of Ti, w~re obtained. This exhibited a re~idue to
extraction with boiling n-heptane of 80.5%, a bulk density o~
0.32 kg/l, an intrinsic viscosity of 2dl/g ànd a flexural
rigidity o~ 10,200 kg/cm2.
E~AMPIE 10
Polymerization of propylene in a ~olvent.
287 ~g of the solid product of Example 6a were
introduced into a 2.5 litre stainless steel autoclave containing
1 litre Or n-heptane and 1.135 g of Al(C2H5)3 mixed with 533 mg
of ethyl para-toluate. Polymeri~ation was conducted at 60C
and 5 kg/cm2 gauge with propylene and hydrogen (1.5% by volume
of the ga~ phase) for 5 hours. The pres~ure wa9 kept constant
by continuou~ feeding of propylene. After removing the ~olvent
by stripping with steam, 180 g of polymer in ~ yield of 31,400 g
of polypropylene/g of Ti were obtained, and left a residue to
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extraction with boiling n-heptane o~ 80~ and a bulk density of
0.253 kg/l.
Polymerization of pro~lene in liaùid monomer.
10 k3 of propylene, 12.5 g Or AltC2H5)3 in 90 ml of
n-heptane~ 6~45 g of ethyl para-toluate in 120 ml of n-heptane
1 g of the solid product o~ Exsmple 6a, in 130 ml of n-heptane
and 15 Nl o~ hydrogen wer~ introduced into a 30 litre stainle~s
steel autocla~e. Polymerization was performed a~ 65C and
26.5 kg/cm2 gauge. A~ter 5 hours~ the excesg propylene was
removed and 1.3 kg of polypropylene, in a yield of 65~000 g of
polymer/g Or Ti ~ere obtained~ and left 8 residue to estraction
with boiling n-heptane Or 84%~ a bulk density of 0.27 kg/l, an
intrinsi¢ viscosity of 2.4 dl/g, a melt-flow inde~ of 3.2 g/10
and a fle~ural rigidity of 13520 k~/cm2.
EXA~PIE 11
PolYmerisation of pro~Ylene_in a solvent.
204 mg of the solid product of Example 6a were
introduced into a 2.5 litre stainle~ steel autoclave containing
1 litre of n-heptane and 1.135 g of Al(i~C4~9)3 mixed with 215
~g of ethyl para-toluate Polymeri~ation wa~ conducted at 60C
and 5 kg/cm2 gauge with propylene and hydrogen (1.5% by volume
Or the gas phase) for 5 hours. ~he pressure was kept constant
by continuous feed$ng of propylene After removing the ~olvent
by ~tripping with steam~ 196 g of polymer in a yield of 19,400 g
Or polypropylene/g of ~i were obtained~ and left a residue to
e~traction in boiling n-heptane of 69 5%,
Pol~merization of ~ro~lene in liguid monomer.
10 kg of propylene, 12.5 g of Al(iC4Hg)3 in 90 ml of
n-heptane~ 3.45 g of ethyl para-toluate in 120 ml of _~heptane,
1.04 g of the solid product of Example 6a ~n 90 ml of n-heptane
and 15 Nl of hydrogen were introduced into a 30 litre ~tainles~
steel autoclave. Polymerization was performed at 65C and
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26.5 kg/cm2 gauge. After 5 hour~, the escess propylene wa~
removed, and 1.15 kg of polypropylene in a yield of 55,300 g
of polymsr /~ of Ti w~re obtained and left a re~idue to
extraction in boiling n-heptane o~ 76.5%, a bulk density of
0.30 kgh~ an intrin~ic vi~cosity of 1.8 dl/g, a melt-flow index
of 4 g/10' and a flexural rigidity of 10,460 kg/cm2.
EXAMPIE 12
Pol~merization of ~ro~,~le~e ln a ~olvent~
246 mg of the solid product of Example 6a were
introduced into a 2.5 litre st~inle~s ~teel autoclave containing
1 litre of n-heptane and 1.135 g of Al(~2H5)3 mixed ~ith 329 mg
of ethyl ani~ate. Polymerisation ~as ¢onducted at 60C and
5 kg/cm2 gauge with propylene and hydrogen (1.5% by volume of
the ga~ ph~se) for 5 hours. ~fter remo~ing the 301vent by
stripping with steam, 200 g of polymer in 8 yield of 41,700 g
of polypropylene/g of Ti were obtained and left a res~due to
e~traction in boiling n-heptane of 71.5%.
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