Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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This invention relates to modified polyolefin
particles and process for preparation thereof. More
specifically, this invention relates to polyolefin
particles modified by monomers having a certain polar
group such as a carboxyl group, and to process for
preparation thereof.
Heretofore, methods for modifying a polyolefin
by giving it a polar group such as a carboxyl group have
been known.
For such modification of polyolefins there have
been adopted methods such as a method which comprises
compounding a modifier having a polar group and
extruding the mixture in a molten state to modify the
polyolefin at the high temperature and under the high
shearing force (the melting method) and a method which
comprises dissolving a polyolefin in a solvent and
compounding a modifier in the solution to carry out the
modification of the polyolefin (the solvent method).
On the other hand, Japanese Laid-Open Patent
Publication No. 77493/1975 discloses a method which
comprises contacting a particulate olefin polymer with
malefic anhydride in the presence of a radical intiator
and in the substantial absence of a liquid medium at a
temperature lower than the melting temperature of the
olefin to graft-polymerize malefic anhydride to the
particulate olefin polymer.
This Laid-Open Patent Publication emphasizes
that although when one of various polar monomers is
graft-polymerized to a particulate olefin polymer in the
substantial absence of a liquid medium, a polymer-adhered
film taking in the particulate olefin polymer is formed
on the inside wall of the polymerization vessel, such a
polymer-adhered film is not formed only when malefic
anhydride is used as the polar monomer.
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The Laid-Open Patent Publication also
discloses, in connection with the graft reaction
condition in the substantial absence of a liquid medium,
that it is possible to use a small amount of a solvent
becoming a gas at a relatively low temperature such as
acetone, methyl ethyl ketone, ether or chloroform in
order to prevent that malefic anhydride, which readily
sublimates, deposits as crystals at the low temperature
part of the reactor.
Japanese Laid-Open Patent Publication No.
32722/1980 discloses a method of preparing a modified
polyolefin composition having an improved adhesive
property by mixing polymer particles of an oC-oleffin of C2
to C10, a polymerizable compound represented by the
following formula
R2
CH2-CH-R1-OCO-C=CH2
(wherein Rl is a straight-chained lower alkylene group
and R2 is H or CH3), and an organic peroxide, and
reacting them at a temperature equal to or less than the
tacky point of the polymer and under an inert atmosphere.
The Laid-Open Patent Publication also discloses that the
above organic peroxide to be used is preferably in a
liquid state so that good dispersion is obtained in the
mixing stage, and that it is thus desirable that the
peroxide in a solid state is dissolved in an organic
solvent before use. The publication describes as such
organic solvents benzene, mineral spirit, toluene,
chlorobenzene, dichlorobenzene, acetone, dimethyl
phthalate, tertiary butyl alcohol, anisole, decalin and
xylene. The publication further discloses that a
modified polyolefin composition having a still further
increased adhesive property when 1 to 5 wt. parts of the
inert solvent is used per 100 wt. parts of the olefin
polymer particles in the reaction.
~~D35 s3
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Further, Japanese Laid-Open Patent Publication No.
174309/1982 discloses a gaseous phase graft polymerization
method which comprises previously adding a radical
polymerization initiator to a polymer having methyl groups,
methylene groups and methine groups (excluding polyphenylene
oxide) and adding a monomer to be grafted at the graft
polymerization temperature and at a pressure equal to or less
than the saturated vapor pressure to graft-polymerize the
monomer to the polymer. There are exemplified in the
publication polyethylene, polypropylene, etc. as the polymer,
and malefic anhydride as the monomer. Further, although it is
disclosed therein that a solvent which does not inhibit the
radical polymerization may be added in amount of 0 to 10 wt.
parts per 100 wt. parts of the polymer, no specific examples
of such a solvent is disclosed in the description and
examples.
According to the invention, there is provided a
process for preparation of modified polyolefin particles,
which comprises contacting and reacting;
(A) 100 wt. parts of polyolefin particles with
(B) 0.01 to 50 wt. parts of at least one ethylenic
unsaturated compound selected from the group consisting of
carboxyl group-containing ethylenic unsaturated compounds or
their carboxylic anhydrides or their carboxylic acid
derivatives, hydroxyl group-containing ethylenic unsaturated
compounds, amino-group-containing ethylenic unsaturated
compounds and glycidyl group-containing ethylenic unsaturated
compounds, in the presence of:
_~
67566-1180
..
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(C) more than 10 wt. parts to not more than 50 wt. parts
of a medium which is liquid at ordinary temperature, which has
a solubility in water at 20°C of 0.5 wt.% or less and which is
capable of swelling the polyolefin, and
(D) 0.01 to l0 wt. parts of a radical initiator.
The invention also provides modified polyolefin
particles which may be prepared by the above process of the
invention, have particular properties and are readily usable
for various uses.
The process for preparation of the modified
polyolefins of the invention is specifically described.
Polymers referred to in the invention include,
unless otherwise noted, both polymers and copolymers.
Polyolefin particles (A) used in the invention have
average particle sizes ranging preferably from 10 to 5,000
micrometers, more preferably from 100 to 4,000
67566-1180
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micrometers, particularly preferably from 300 to 3,000
micrometers.
Further, polyolefin particles (A) used in the
invention are polyolefin particles such that their
geometrical standard deviation, which indicates particle
size distribution, is in the range of preferably 1.0 to
2.0, more preferably 1.0 to 1.5, particularly preferably
1.0 to 1.3.
Further, polyolefin particles (A) used in the
invention are polyolefin particles such that their
apparent bulk density by natural drop is in the range of
preferably 0.2 g/ml or more, more preferably 0.30 to
0.70 g/ml, particularly preferably 0.35 to 0.60 g/ml.
A polyolefin composing the above polyolefin
particles may be obtained by polymerizing or copoly-
merizing, preferably alpha-olefins) having 2 to 20
carbon atoms.
Examples of such alpha-olefins include
ethylene, propylene, butene-1, pentene-1, 2-methyl-
butene-1, 3-methylbutene-1, hexene-1, 3-methylpentene-1,
4-methylpentene-1, 3,3-dimethylbutene-1, heptene-1,
methylhexene-1, dimethylpentene-1, trimethylbutene-1,
ethylpentene-1, octene-1, methylpentene-1, dimethyl-
hexene-1, trimethylpentene-1, ethylhexene-1, methyl-
ethylpentene-1, diethylbutene-1, propylpentene-l,
decene-l, methylnonene-l, dimethyloctene-1, tri-
methylheptene-1, ethyloctene-1, methylethylheptene-1,
diethylhexene-1, dodecene-l, hexadodecene-1, etc.
It is preferable to use, among them, alpha-
olefin(s) having 2 to 8 carbon atoms alone or in combina-
Lion.
There are used in the invention polymer
particles which contain a repeating unit derived from the
above alpha-olefins) in an amount of preferably 50 mole
% or more, more preferably 80 mole % or more, still more
Preferably 90 mole % or more, most preferably 100 mole %.
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Examples of other copolymerizable unsaturated
compounds, which may be used besides the above alpha-
olefins in the invention, include chain polyene com-
pounds, cyclic polyene compounds, cyclic monoene com-
pounds, styrene and substituted styrenes. Polyene com-
pounds having two or more of conjugated or non-conjugated
olefinic double bonds may preferably be used as such
polyene compounds, and include, for example, chain
polyene compound such as 1,4-hexadiene, 1,5-hexadiene,
1.7-octadiene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7-
octatriene, 1,5,9-decatriene and divinylbenzene; cyclic
polyene compounds such as 1,3-cyclopentadiene, 1,3-
cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cyclo-
heptadiene, dicyclopentadiene, dicyclohexadiene, 5-ethyl-
idene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-
2-norbornene, 5-isopropylidene-2-norbornene, methyl-
hydroindene, 2,3-diisopropylidene-5-norbornene, 2-ethyl-
idene-3-isopropylidene-5-norbornene and 2-propenyl-2,5-
norbornadiene; and the like. Further, there may also be
used as such a polyene compound a polyene compound ob-
tained by condensing a cyclopentadiene such as cyclo-
pentadiene with an alpha-olefin such as ethylene, pro-
pylene or butene-1 utilizing Diels-Alder reaction.
Further, examples of the cyclic monoene com-
pounds include monocycloalkenes such as cyclopropene,
cyclobutene, cyclopentene, cyclohexene, 3-methyl-
cyclohexene, cycloheptene, cyclooctene, cyclodecene,
cyclododecene, tetracyclodecene, octacyclodecene and
cycloeicosene; bicycloalkenes such as norbornene,
5-methyl-2-norbornene, 5-ethyl-2-norbornene,
5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene,
5,5,6-trimethyl-2-norbornene and 2-norbornene; tri-
cycloalkenes such as 2,3,3a,7a-tetrahydro-4,
7-methano-1H-indene and 3a,5,6,7a-tetrahydro-4,
7-methano-1H-indene; tetracycloalkenes such as 1,4,5,8-
dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,
~c~3ss3
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2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-
octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-
1,2.3,4,4a,5,8,8a-octahydronaphthalene, 2-propyl-
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,
2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octa-
hydronaphthalene, 2-stearyl-1,4,5,8-dimethano-
1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro-
naphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-
1.2,3,4,4a,5,8.8a-octahydronaphthalene, 2-chloro-
1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro-
naphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-
octahydronaphthalene, 2-fluoro-1.4,5,8-dimethano-
1,2,3,4,4a,5,8,8a-octahydronaphthalene and 2,3-
dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octa-
hydronaphthalene; polycycloalkenes such as hexacyclo
I6,6,1,13~6,110,13~02,7~09,14~ heptadecene-4,
pentacyclo I8,8,12'9,14'7~1~'1,18~0~
03,8~012,17~ heneicosene-5 and octacyclo (8,8,-
12'914'7,111,18~113,16~0~03,8~012,17~
docosene-5; and the like.
There may for example be used as the above
styrene and substituted styrenes those represented by the
following formula:
R1-C=CH2
(R2) n
wherein R1 is a hydrogen atom, lower alkyl group having
1 to 5 carbon atoms or halogen atom, and R2 is a
hydrogen atom, lower alkyl group having 1 to 5 carbon
atoms or vinyl group, and n is an integer of 1 to 5.
3o Specific examples of styrene and the substituted styrenes
;~~~3563
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include styrene, alpha-methylstyrene, vinyltoluene,
divinylbenzene, o-chlorostyrene,m-chlorostyrene and
p-chlorostyrene.
The above polyolefin particles (A) to be used
in the invention may be prepared by the method herein-
after detailedly described.
There may be used in the invention as the
ethylenic unsaturated compounds which are grafted to the
above polyolefin particles, carboxyl group-containing
ethylenic unsaturated compounds or their carboxylic
anhydride or their carboxylic acid derivatives, hydroxyl
group-containing ethylenic unsaturated compounds, amino
group-containing ethylenic unsaturated compounds and
glycidyl group-containing ethylenic unsaturated com-
pounds, as previously described. These ethylenic un-
saturated compounds may be used alone or in combination
of two or more of them.
There may, for example, preferably be used as
the carboxyl group-containing ethylenic unsaturated
compounds their carboxylic anhydrides and their carb-
oxylic acid derivatives those selected from the group
consisting of acrylic acid, methacrylic acid, malefic
acid, fumaric acid, tetrahydrophthalic acid, itaconic
acid, citraconic acid, crotonic acid and endo-cis-bicyclo
12,2,11 hept-5-ene-2,8-dicarboxylic acid, their caboxylic
anhydrides, and acid halides, amides, imides or esters of
these carboxylic acids.
Examples of the acid anhydrides, acid halides,
amides, imides and esters of the carboxylic acids include
malefic chloride, maleimide, malefic anhydride, citraconic an-
hydride, monomethyl maleate, dimethyl maleate, etc.
There may preferably be used among them unsaturated
dicarboxylic acids or their acid anhydrides, particularly
malefic acid or endo-cis-bicyclol2,2,llhept-5-ene-2,8-di-
carboxylic acid or their acid anhydrides.
Examples of the hydroxyl group-containing
2C~~35f 3
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ethylenic unsaturated compounds include hydroxyethyl
tmeth)acrylate, 2-hydroxypropyl tmeth)acrylate, 3-
hydroxypropyl tmeth)acrylate,2-hydroxy-3-phenoxypropyl-
tmeth)acrylate, 3-chloro-2-hydroxypropyl tmeth)acrylate,
glycerin monotmeth)acrylate, pentaerythritol mono-
tmeth)acrylate, trimethylolpropane monotmeth)acrylate,
tetramethylolethane monotmeth)acrylate, butanediol mono-
meth)acrylate, polyethylene glycol monotmeth)acrylate,
2-t6-hydroxyhexanoyloxy)ethyl acrylate, 10-undecen-1-ol,
1-octen-3-ol, 2-methanolnorbornene, hydroxystyrene,
hydroxyethyl vinyl ether, hydroxybutyl vinyl ether,
N-methylolacrylamide, 2-tmeth)acryloxyethyl acid
phosphate, glycerin monoallyl ether, allyl alcohol,
allyloxyethanol, 2-butene-1,4-diol, glycerin monoalcohol,
etc. It is particularly preferred to use 2-hydroxyethyl
tmeth)acrylate or 2-hydroxypropyl tmeth)acrylate as the
hydroxyl group-containing ethylenic unsaturated compound.
There may, for example, preferably be used as
the amino group-containing ethylenic unsaturated com-
Pounds those having an ethylenic unsaturated double bond
and at least one amino group in the molecule represented
by the following formula.
-NlR2
wherein Rl is a hydrogen atom, methyl group or ethyl
group, and R2 is a hydrogen atom, alkyl group having 1
to 12 carbon atoms or cycloalkyl group having 6 to 12
carbon atoms. The above alkyl group and cycloalkyl group
may have substituentts), respectively. Exmaples of these
amino group-containing ethylenic unsaturated compounds
include aminoethyl acrylate, propylaminoethyl acrylate,
dimethylaminoethyl methacrylate, aminopropyl acrylate,
phenylaminoethyl methacrylate, cyclohexylaminoethyl
methacrylate, methacryloxyethyl acid phosphate mono-
;~QS3ss3
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methanolamine half salt, N-vinyldiethylamine, N-acetyl-
vinylamine, allylamine, methallylamine, N-methyl-
acrylamine, N,N-dimethylacrylamide, N,N-dimethyl-
aminopropylacrylamide, acrylamide N-methylacrylamide.
p-aminostyrene, 6-aminohexylsuccinimide, 2-aminoethyl-
succinimide, etc. There may particularly preferably be
used as the amino group-containing ethylenic unsaturated
compounds acrylamine, amionoethyl methacrylate, amino-
propyl methacrylate, amino styrene, etc. among the above
examples thereof.
There may preferably be used as the glycidyl
group-containing ethylenic unsaturated compounds glycidyl
ethers such as allyl glycidel ether, 2-methylallyl
glycidyl ether and vinyl glycidyl ether. Allyl glycidyl
ether is particularly preferred among them. Such
glYcidyl ethers have a very high hydrolysis resistance
because they have no carboxyl group in the molecule and
thus there is no fear that the glycidyl group is
eliminated by hydrolysis. Glycidyl esters of conjugated
unsaturated dicarboxylic acids or other glycidyl com-
Pounds may be used so long as they are used in a small
ratio together with such glycidyl ether(s). Examples of
such glycidyl esters of conjugated unsaturated di-
carboxylic acids include diglycidyl maleate, methyl
glycidyl maleate, isopropyl glycidyl maleate, t-butyl
glYcidyl maleate, diglycidyl fumarate, methyl glycidyl
fumarate, isopropyl glycidyl fumarate, diglycidyl
itaconate, methyl glycidyl itaconate, isopropyl
glycidyl itaconate, diglycidyl 2-methyleneglutarate,
methyl glycidyl 2-methyleneglutarate, monoglycidyl ester
of butenedicarboxylic acid, etc. Examples of such other
glycidyl compounds include 3,4-epoxybutene, 3,4-
epoxy-3-methyl-1-butene, vinylcyclohexene monoxide,
p-glycidylstyrene, etc. Such glycidyl esterts) or other
glycidyl compoundts) is used desirably in a small ratio
of 0.1 mole or less per mole of the glycidyl ether(s).
%~~3ss 3
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Liquid media (C) used in the invention are
media of a liquid state at ordinary temperature whose
solubility in water at 20 °C is 0.5 wt. % or less,
preferably 0.4 wt. % or less and which are capable of
swelling the polyolefin. Examples of such liquid media
(C) include benzene (solubility: 0.09 wt. %), mineral
spirit (solubility: 0.00090 wt. %), toluene (solubility:
0.05 wt. %), chlorobenzene (solubility: 0.05 wt. %),
o-dichlorobenzene(solubility at 25 oC: 0.01 wt. %),
xylene (solubility: 0.02 wt. %), n-hexane (solubility:
0.014 wt. %), n-heptane (solubility: 0.005 wt. %),
n-octane (solubility at 25 oC: 0.002 wt. %), carbon-
tetrachloride (solubility: 0.44 wt. %), C1CH=C=CC12
(solubility: 0.11 wt. %), etc. These solvents may be
used alone or in combination in the invention.
According to the process of the invention
wherein modified polyolefin particles are prepared in the
presence of such a liquid medium (C), it is believed,
although the reason is not always clear, that the liquid
medium swells the polyolefin particles and as a result
the ethylenic unsaturated compound and radical initiator
may easily permeate into the polyolefin particles to
uniformly modify even the inside of the polyolefin
particles with the ethylenic unsaturated compound.
Whether the above conjecture is true or not, modified
Polyolefin particles, which is excellent in granular
material characteristics, may be obtained by the inven-
tion wherein the graft polymerization is carried out in
the presence of liquid medium (C).
There may be used as radical initiator (D) to
be used in the invention e~ r se known an organic
peroxide, azo compound or the like. Examples of the
organic peroxides include dicumyl peroxide, di-tert-butyl
peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane,
2,5-dimethyi-2,5-bis(tert-butylperoxy)hexyne-3, 1,3-bis
(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-
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butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl 4,4-bis
(tert-butylperoxy) valerate, dibenzoyl peroxide, tert-
butyl peroxybenzoate, acetyl peroxide, isobutyryl
peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl
peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-
dichlorobenzoyl peroxide, m-toluoyl peroxide, etc.
Further , there may be used as the azo compounds,
azobisisobutyronitrile, etc. Such radical initiators may
be used alone or in combination. Dibenzoyl peroxide is
Particularly preferred among such radical initiators.
The process of the invention is carried out by
contacting and reacting the above polyolefin particles
(A), ethylenic unsaturated compound (B), liquid medium
(C) and radical initiator (D) using, per 100 wt. parts of
the polyolefin particles, 0.01 to 50 wt. parts,
preferably 0.1 to 40 wt. parts of the ethylenic
unsaturated compound, more than 10 wt. parts to not more
than 50 wt. parts, preferably 12 to 40 wt. parts of the
liquid medium, and 0.01 to 10 wt. parts, preferably 0.05
to 8 wt. parts of the radical initiator.
There is no particular restriction about the
method and order of contact of the above components (A),
(B), (C) and (D), and the following methods may for
example be adopted:
A method which comprises preparing a solution of the
ethylenic unsaturated compound and radical initiator in
the liquid medium, dispersing the polyolefin particles
therein and carrying out the reaction. A method which
comprises preparing a solution of the radical initiator
in the liquid medium, dispersing the polyolefin particles
therein, leading the polyolefin particles to a sub-
stantially reactive state, for example, by heating, and
thereafter adding the ethylenic unsaturated compound to
carry out the reaction. A method which comprises leading
the polyolefin particles to a substantially reactive
state, for example, by heating, and dispersing the
2C~~3af 3
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resulting polyolefin particles in a solution of the
ethylenic unsaturated compound and radical initiator in
the liquid medium to carry out the reaction. A method
which comprises dispersing the polyolefin particles in a
solution of the radical initiator in the liquid medium,
and contacting the dispersion with the ethylenic un-
saturated compound in a gaseous state under heating to
carry out the reaction.
It is preferred that the contact of the
Polyolefin particles with the ethylenic unsaturated
compound is carried out at a temperature at which the
polyolefin particles can substantially hold their shape,
namely at a temperature lower than the temperature at
which the polyolefin particles begin to mutually fuse.
Suitable temperature for the contact is varied depending
on the polyolefin particles and radical initiator to be
used, but is usually, for example, in the range of 0 to
150 °C. In case of the polyolefin particles being, for
example, polyolefin particles mainly composed of poly-
propylene, the temperature of upper limit is about
150 °C, in case of polyolefin particles mainly composed
of high density polyethylene the upper limit temperature
is about 120 °C, and in case of polyolefin particles
mainly composed of low density polyethylene the upper
limit temperature is about 90 °C.
The reaction time for modification in the
invention may appropriately be determined taking the
conditions such as the reaction temperature into account,
but is usually 1/60 to 20 hours, preferably 0.5 to 10 hours.
Any apparatus may be used for the above
reaction without particular restrictions so long as it is
an apparatus capable of mixing and heating of the poly-
olefin particles, and for example, any reactor of
vertical type or horizontal type may be used. Specifi-
cally, fluid beds, moving beds, loop reactors, horizontal
reactors with agitating blade, rotating drums, vertical
20~35f 3
- 14 -
reactors with agitating blade, etc. may be used.
Thus, there may be prepared according to the
process of the invention modified polyolefin particles
of the invention characterized in that
, (a) their average particle size is in the
range of 100 to 5,000 micrometers,
(b) their geometrical standard deviation is
between 1 and 2,
(c) the content of the particles having a
Particle size of 100 micrometer or less is 20 wt. % or
less, and
(d) they are modified by polar groups
selected from the group consisting of carboxyl groups or
their anhydride groups or their derivative groups,
hydroxyl groups, amino groups, and glycidyl groups.
The modified polyolefin particles of the
invention are those whose average particle size is
preferably in the range of 200 to 4,000 micrometers,
particularly preferably in the range of 300 to 3,000
micrometers.
Further, the geometrical standard deviation of
the modified polyolefin particles of the invention is in
the range of preferably 1.0 to 1.5, particularly pre-
ferably 1.0 to 1.3. Further, the content of fine par-
ticles of 100 micrometer or less is in the range of
Preferably 0 to 10 wt. %, particularly preferably 0 to
2 wt. % .
Further, the apparent specific gravity of the
modified polyolefin particles of the invention is in the
range of preferably 0.25 to 0.7, more preferably 0.30 to
0.60 and partuclarly preferably 0.35 to 0.50. Further,
the average value of the major axis length/minor axis
length ratio of the particles composing the above
particle group is in the range of preferably 1.0 to 3.0,
more preferably 1.0 to 2.0, and particularly preferably
1.0 to 1.5.
~O~D3563
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The modified polyolefin particles of the
invention have polarity, and thus may advantageously be
used, for example, as a raw material of fine particle
coatings.
Suitable processes of preparation of the poly-
olefin particles to be used in the process of the
invention are described below.
The polyolefin particles obtained by adopting
these processes contain in their ash the transition
metals only in an amount of usually 100 ppm or less,
preferably 10 ppm or less and particularly preferably
5 ppm or less, and the halogens only in an amount of
usually 300 ppm or less, preferably 100 ppm or less and
particularly preferably 50 ppm or less.
The polyolefin particles to be used in the
invention may be obtained by polymerizing or
copolymerizing at least the above alpha-olefin in the
presence of a catalyst. The above polymerization
reaction or copolymerization reaction may be carried out
either in gaseous phase (gaseous phase method) or in
liquid phase (liquid phase method).
The polymerization or copolymerization reaction
by the liquid phase method is preferably carried out in a
suspended state so that the formed polyolefin particles
may be obtained in a solid state.
It is desirable in preparation of the poly-
olefin particles to adopt either of a method wherein the
crystalline olefin polymer part and amorphous olefin
polymer part are simultaneously formed by supplying two
or more kinds of monomers into a reactor, or of a
method wherein the synthesis of the crystalline olefin
polymer part and the synthesis of the amorphous olefin
polymer part are separately and serially carried out
using at least two or more of polymerizers. The latter
method is preferred from the viewpoint that the molecular
weight, composition and amount of the amorphous olefin
~0~3563
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polymer part may freely be varied.
The most desirable method is a method which
comprises synthesizing the crystalline olefin polymer
part by gaseous polymerization and then synthesizing the
amorphous olefin polymer part by gaseous polymerization,
or a method which comprises synthesizing the crystalline
olefin polymer part using the monomer as a solvent and
then synthesizing the amorphous olefin polymer part by
gaseous polymerization.
There may be used as a solvent to be used in
this polymerization or copolymerization reaction an inert
hydrocarbon or an alpha-olefin as a raw material.
There may usually be used as a catalyst to be
used in the above polymerization or copolymerization
reaction a catalyst comprising a catalyst component (A>
containing a transition metal of the IV A, V A, VI A, VII
A or VIII group of the periodic table of elements, and a
catalyst component (B) of an organic metal compound
containing a metal of the I, II or III group of the
periodic table of elements.
As the above catalyst components (A) are
preferred catalyst components each containing a transi-
tion metal atom of the IV A or V A group of the periodic
table of elements, and among them are further preferred
catalyst components each containing at least one atom
selected from the group consisting of titanium,
zirconium, hafnium and vanadium.
Further, other preferred catalyst components
(A) include catalyst components each containing a halogen
atom and magnesium atom besides the above transition
metal atom, and catalyst components each containing a
compound wherein a group having a conjugated pi election
is coordinated to a transition metal atom of the IV A or
V A group of the periodic table.
It is preferred to use as catalyst component
(A) in the invention a catalyst which is prepared so that
203563
- 17 -
it can exist either ear se in a solid state or in a solid
state by being carried on a carrier in the reaction
system in the above polymerization or copolymerization
reaction.
The above catalyst component (A) is further
detailedly described taking as an example solid catalyst
component (A) which contains the above transition metal,
a halogen atom and a magnesium atom.
The average particle size of the above solid
catalyst component (A) is in the range of preferably 1 to
200 micrometers, more preferably 5 to 100 micrometers and
particularly preferably 10 to 80 micrometers. Further,
the geometrical standard deviation (crg) of solid catalyst
(A) as a measure for the particle size distribution of
solid catalyst (A) is in the range of preferably 1.0 to
3.0, more preferably 1.0 to 2.1 and particularly pre-
ferably 1.0 to 1.7.
The average particle size and particle size
distribution of catalyst component (A) may be measured as
follows by the light transmission method:
The particle size distribution is measured by taking in a
cell for measurement a dispersion prepared by adding a
catalyst component (A) to a solvent which does not
dissolve catalyst component (A) to a concentration
(content) of 0.1 to about 0.5 wt. %, preferably
0.1 wt. %, and applying a light and continuously
measuring the intensity of the light passing through the
liquid in a state wherein the particles are sedimenting.
The standard deviation (~g) is determined from the
logarithmic normal distribution function based on this
particle size distribution. More specifically, the
standard deviation (~g) is determined as the ratio
(e50/el6) of the average particle size (B50) to a
particle size (816) between which and the smallest
particle size 16 wt. % of the total particles are con-
tained. In this connection, the average particle size of
~Ot~3563
- 1B -
the catalyst is weight average particle size.
Further, catalyst component tA) has a shape
such as, preferably a true spherical, ellipsoidal or
granular shape, and the aspect ratio of the particle is
preferably 3 or less, more preferably 2 or less,
particularly preferably 1.5 or less.
Further, when this catalyst component tA)
contains magnesium atom, titanium atom, a halogen atom
and an electron donor, the magnesium/titanium ratio (atom
ratio) is preferably larger than 1 and is usually in the
range of 2 to 50, preferably 6 to 30. Further, the
halogen/titanium ratio (atom ratio) is in the range of
usually 4 to 100, preferably 6 to 40, and the election
donor/titanium ratio (atom ratio) is in the range of
usually 0.1 to 10, preferably 0.2 to 6. Further, the
specific surface area of this catalyst component tA) is
in the range of usually 3 m2/g or more, preferably
40 m2/g or more, more preferably 100 to 800 m2/g~
The titanium compound in such a catalyst com-
ponent tA) is not generally eliminated by a simple
procedure such as washing with hexane at ordinary
temperature.
Further, catalyst component tA) may contain
other atoms or metals besides the above ingredients, or
may be diluted with an organic or inorganic diluent.
Further, functional groupts) or the like may be in-
troduced into this catalyst component tA).
The above catalyst component tA) may be
prepared by adopting, for example, a method which
comprises forming a magnesium compound whose average
particle size and particle size distribution fall within
the above ranges and whose shape is the above-described
shape, and then making a preparation of the catalyst, or
a method which comprises contacting the magnesium com-
pound in a liquid state with the titanium compound in a
liquid state, and then forming a solid catalyst so that
20~D3563
- 19 -
it may have the above particle properties.
Such a catalyst component (A) may be used as
such. Further, it is also possible to use as catalyst
component (A) a catalyst component obtained by carrying
on a carrier of uniform shape the magnesium compound,
titanium compound and, if necessary, the electron donor.
Further, it is also possible to previously prepare a
finely powdery catalyst and then granulate it into the
above preferred shape.
Such catalyst components (A) are disclosed in
Japanese Laid-Open Patent Publications Nos. 135102/1980,
135103/1980, 811/1981 and 67311/1981 and Japanese Patent
Applications Nos. 181019/1981 and 21109/1986.
Some examples of processes for preparation of
catalyst component (A) are described below:
(1) A solid complex of the magnesium compound
and the electron donor having the average particle size
of 1 to 200 micrometers and the geometrical standard
deviation (~g) of particle size distribution of 3.0 or
less is reacted with a liquid titanium halide compound,
Preferably titanium tetrachloride under the reaction
conditions, either after preliminary treatment of the
complex with a reaction assistant such as an electron
donor and/or an organoaluminum compound or a halogen-
containing silicon compound, or without any preliminary
treatment.
(2) A liquid magnesium compound having no
reducing ability is reacted with a liquid titanium com-
pound preferably in the presence of an electron donor to
deposit a solid component whose average particle size is
1 to 200 micrometers and geometrical standard deviation
(~g) is 3.0 or less. If necessary, the solid component
is further reacted with a liquid titanium compound,
preferably titanium tetrachloride, or with a liquid
titanium compound and an electron donor.
(3) A liquid magnesium compound having a
~0~3563
- 20 -
reacting ability is previously contacted with a reaction
assistant capable of making the magnesium compound lose
its reducing ability, for example, a polysiloxane or a
halogen-containing silicon compound to deposit a solid
component having an average particle size of 1 to 200
micrometers and the geometrical standard deviation of
particle size distribution (gg) of 3.0 or less. This
solid component is then reacted with a liquid titanium
compound, preferably titanium tetrachloride, or a
titanium compound and an electron donor.
(4) A magnesium compound having a reducing
ability is contacted with an inorganic carrier such as
silica or an organic carrier. The resulting carrier,
after being contacted with a halogen-containing compound
or without such a contact, is contacted with a liquid
titanium compound, preferably titanium tetrachloride, or
with a titanium compound and an electron donor to react
the magnesium compound carried on the carrier with the
titanium compound and the like.
Such a solid catalyst component (A) has an
ability capable of preparing a polymer having a high
streoregularity at a high catalyst efficiency. For
example, when the homopolymerization of propylene is
carried out under the same conditions, the solid catalyst
component (A) has an ability capable of preparing a
Polypropylene having an isotacticity index (insoluble
matters in boiling n-heptane) of 92 % or more,
particularly 96 % or more in an amount of usually 3,000 g
or more, preferably 5,000 g or more, particularly
preferably 10,000 g or more per millimole of titanium.
There are described below examples of magnesium
compounds, halogen-containing silicon compounds, titanium
compounds and electron donors which may be used for
preparation of the above catalyst components (A).
Further, aluminium ingredients used for preparation of
these catalyst components (A) are compounds exemplified
;~oo35s3
- 21 -
in case of the later-mentioned organometal compound
catalyst component tB).
Examples of the magnesium compounds include
inorganic magnesium compounds such as magnesium oxide,
magnesium hydroxide and hydrotalcite; and organic
magnesium compounds such as magnesium carboxylates,
alkoxymagnesiums, allyloxymagnesium, alkoxymagnesium
halides, allyloxymagnesium halides and magnesium di-
halides and further dialkylmagnesiums and diaryl-
magnesiums.
Examples of the titanium compounds include
titanium halides such as titanium tetrachloride; alkoxy-
titanium halides, allyloxytitanium halides, alkoxy-
titaniums, allyloxytitanium, etc. Titanium tetrahalides
are preferred among them, and titanium tetrachloride is
particularly preferred.
Examples of the electron donors include oxygen-
containing electron donors such as alcohols, phenols,
ketones, aldehydes, carboxylic acids, esters of organic
acids or inorganic acids, ethers, acid amides, acid
anhydrides, and alkoxysilanes; and nitrogen-containing
electron donors such as ammonia, amines, nitrites and
isocyanates.
Specific examples of compounds which may be
used as such electron donors include alcohols having 1 to
18 carbon atoms such as methanol, ethanol, propanol,
pentanol, hexanol, octanol, dodecanol, octadecyl alcohol,
oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
isopropyl alcohol, cumyl alcohol and isopropylbenzyl
alcohol;
phenols having 6 to 20 carbon atoms (these phenols may
have lower alkyl groups) as substituentts)) such as
phenol, cresol, xylenol, ethylphenol, propylphenol,
nonylphenol, cumylphenol and naphthol;
ketones having 3 to 15 carbon atoms such as acetone,
methyl ethyl ketone, methyl isobutyl ketone, aceto-
2G~35f 3
- 22 -
phenone, benzophenone and benzoquinone;
aldehydes having 2 to 15 carbon atoms such as acet-
aldehyde, propionaldehyde, octylaldehyde, benzaldehyde,
tolylaldehyde and naphthoaldehyde;
organic acid esters having 2 to 30 carbon atoms such as
methyl formate, methyl acetate, ethyl acetate, vinyl
acetate, propyl acetate, octyl acetate, cyclohexyl
acetate, ethyl propionate, methyl butyrate, ethyl
valerate, methyl chloroacetate, ethyl dichloroacetate,
methyl methacrylate, ethyl dichloroacetate, methyl meth-
acrylate, ethyl crotonate, ethyl cyclohexanecarboxylate,
methylbenzoate, ethyl benzoate, propyl benzoate, butyl
benzoate, octyl benzoate, cyclohexyl benzoate, phenyl
benzoate, benzyl benzoate, methyl toluate, ethyl toluate,
amyl toluate, ethyl ethylbenzoate, methyl anisate, n-
butyl maleate, diisobutyl methylmalonate, di-n-hexyl-
1,2-cyclohexane dicarboxylate, diethyl endo-cis-
bicyclol2,2,llhept-5-ene-2,8-dicarboxylate,diisopropyl
tetrahydrophthalate, diethyl phthalate, diisobutyl
phthalate, di-n-butyl phthalate, di-2-ethylhexyl
Phthalate, ~~-butyrolactone, ~ -valerolactone, coumarin,
phthalide and ethylene carbonate;
acid halides having 2 to 15 carbon atoms such as acetyl
chloride, benzoyl chloride, toluyl chloride and anisyl
chloride; ethers having 2 to 20 carbon atoms such as
methyl ether, ethyl ether, isopropyl ether, butyl ether,
amyl ether, tetrahydrofuran and anisole and diphenyl
ether; acid amides such as acetamide, benzamide and
toluamide;
amines such as methylamine, ethylamine, diethylamine,
tributylamine, piperidine, tribenzylamine, aniline,
pyridine, picoline and tetramethylenediamine; nitriles
such as acetonitrile, benzonitrile and tolunitrile;
orgnophosphorus compounds having the P-O-P bond such as
trimethyl phosphite and triethyl phosphite;
alkoxysilanes such as ethyl silicate and diphenyl-
dimethoxysilane; etc.
;~pp3563
- 23 -
These electron donors may be used alone or in
combination.
Among these electron donors preferred ones are
compounds having no active hydrogen, for example, esters
of organic acids or inorganic acids, alkoxy (aryloxy)
silane compounds, ethers, ketones, tertiary amines, acid
nalides and acid anhydrides; further preferred ones are
organic acid esters and alkoxy (aryloxy) silane compound;
and particuarly preferred ones are esters of aromatic
monocarboxylic acids with alcohols having 1 to 8 carbon
atoms, esters of dicarboxylic acids such as malonic acid,
substituted malonic acids, substituted succinic acids,
malefic acid, substituted malefic acids, 1,2-cyclohexane-
dicarboxylic acid or phthalic acid with alcohols having 2
or more carbon atoms, etc. It may of course be possible
to directly add such an electron donor in preparation of
the catalyst. Further, it is also possible that the
electron donor is not added as a raw material in pre-
paration of catalyst component (A), but, for example a
compound capable of being converted to such an electron
donor is compounded in the reaction system and the com-
pound is converted to the electron donor in the step of
preparation of the catalyst.
The thus prepared catalyst component (A) may be
purified by adequate washing with a liquid inert hydro-
carbon. Examples of the hydrocarbons which may be used
in the washing include
aliphatic hydrocarbon compounds such as n-pentane, iso-
pentane, n-hexane, isohexane, n-heptane, n-octane, iso-
octane, n-decane, n-dodecane, kerosene and liquid
Paraffin;
alicyclic hydrocarbon compounds such as cyclopentane,
methylcyclopentane, cyclohexane and methylcyclohexane;
aromatic hydrocarbon compounds such as benzen, toluene,
xylene and cymene; and
halogenated hydrocarbon compounds such as chlorobenzene
20~3~63
- 24 -
and dichloroethane.
These compounds may be used alone or in com-
bination.
There may preferably be used as organometal
compound catalyst components (B) organoaluminum compounds
having at least one A1-carbon bond in the molecule.
Examples of these organoaluminum compounds
include, for example,
(i) organoaluminum compounds represented by
the formula
RlmA1(OR2)nHpXq
(wherein R1 and R2 are hydrocarbon groups having
usually 1 to 15, preferably 1 to 4 carbon atoms and may
be the same or different with each other, X is a halogen
atom, m, n, p and q are numbers of 0<m<3, 0<n<3, 0~<3
and 0<q<3 and m+n+p+q=3), and
ii) complex alkylated compounds of a metal of
the I group of the periodic table and aluminum re-
presented by the formula
M1A1R14
(wherein Ml is Li, Na or K, and Rl is as defined
above).
The following compounds may specifically be
included in the organoaluminum compounds of the above
formula (i):
Compounds represented by the formula
RlmA1 (OR2) 3-m
(wherein R1 and R2 are as defined above, and m is
preferably a number of 1.5_<m<3)
Compounds represented by the formula
2(jt~3563
- 25 -
RlmAlX3-m
(where Rl is as defined above, X is a halogen, and m is
preferably a number of 0<m<3)
Compounds represented by the formula
RlmAlH3-m
(wherein Rl is as defined above, and m is preferably a
number of 2<m<3)
s
Compounds represented by the formula
RlmA1 (OR2) nXq
(wherein Rl and R2 are as defined above, X is a
halogen, and m, n and q are numbers of 0<m<3, 0<n<3 and
s s
0<q<3 and m+n+1=3).
s
Specific examples of the organoaluminum com-
pounds represented by the above formula (i) include
trialkylaluminums such as triethylaluminum, tri-
butylaluminum and triisopropylaluminum;
trialkenylaluminums such as triisoprenylaluminum;
dialkylaluminum alkoxides such as diethylaluminum
ethoxide and dibutylaluminum butoxide;
alkylaluminum sesquialkoxides such as ethylaluminum
sesquiethoxide and butylaluminum sesquibutoxide;
partially alkoxylated alkylaluminums such as those having
the average composition represented by the formula
R12.5A1(OR2)0.5'
dialkylaluminum halides such as diethylaluminum chloride,
dibutylaluminum chloride and diethylaluminum bromide;
alkylaluminum sesquihalides such as ethylaluminum
sesquichloride, butylaluminum sesquichloride and ethyl-
aluminum sesquibromide;
~0~3563
- 26 -
partially halogenated alkylaluminums, for example alkyl-
aluminum dihalide such as ethylaluminum dichloride,
propylaluminum dichloride and butylaluminum dibromide;
dialkylaluminum hydrides such as diethylaluminum hydride
and dibutylaluminum hydride;
partially hydrogenated alkylaluminums, for example,
alkylaluminum dihydrides such as ethylaluminum dihydride
and propylaluminum dihydride; and
partially alkoxylated and halogenated alkylaluminums such
as ethylaluminum ethoxide chloride, butylaluminum
butoxide chloride and ethylaluminum ethoxide bromide.
Further, the organoaluminum compounds may be
compounds analogous to those represented by the formula
(i), for example, organoaluminum compounds wherein two or
more of aluminum atoms are linked via an oxygen or
nitrogen atom. Specific examples of such compounds
include
(C2H5) 2AlOA1 (C2H5) 2'
(C4H9) 2AlOA1 (C4H9) 2'
~C2H5)2A1NA1(C2H5)2 and the like.
C6H5
Further, exmaples of the organoaluminum com-
pounds represented by the above formula (ii) include
LiAl (C2H5) 4, LiAl (C~Hl5) 4' etc.
It is particularly preferred to use among the
above various organoaluminum compounds trialkylaluminums,
mixtures of a trialkylaluminum and an alkylaluminum
halide, or mixtures of a trialkylaluminum and an aluminum
halide.
;~G~~3563
- 27 -
Further, it is preferred to use an electron
donor tC) together with the catalyst component tA) and
the organometal compound catalyst component tB).
Examples of usable electron donors tC) include
amines, amides, ethers, ketones, nitriles, phosphines,
stibines, arsines, phosphamides, esters, thioethers,
thioesters, acid anhydrides, acid halides, aldehydes,
alcoholates, alkoxytaryloxy)silanes, organic acids, and
amides of metals belonging to the I, II, III or IV group
of the periodic table, and acceptable salts of the above
compounds. The salt may also be formed in the reaction
system by reaction of the organic acid with the organo-
metal compound as catalyst component tB).
There may be mentioned as specific examples of
these electron donors compounds previously exemplified as
such in catalyst components tA). Particularly preferred
electron donors among such electron donors are organic
acid esters, alkoxytaryloxy)silane compounds, ethers,
ketones, acid anhydrides, amides, etc. When the electron
donor in catalyst component tA) is a monocarboxylic acid
ester. an aromatic carboxylic acid alkyl ester is
particularly preferred as the electron donor. Further,
when the electron donor in catalyst component tA) fs an
ester of a dicarboxylic acid and an alcohol having 2 or
more carbon atoms, an alkoxytaryloxy)silane compound
represented by the formula
RnSitORl)4-n
(wherein R and R1 are hydrocarbon groups and n is a
number of 0<n<4) or an amine having a large steric
s
hindrance is preferably used as electron donor tC).
Preferred specific examples of these
alkoxytaryloxy)silane compounds include trimethyl-
methoxysilane, trimethoxyethoxysilane, dimethyl-
dimethoxysilane, dimethylethoxysilane, diisopropyl-
zoa3SS3
- 28 -
dimethoxysilane, t-butylmethyldimethoxysilane, t-butyl-
methyldiethoxysilane, t-amylmethyldiethoxysilane, di-
phenyldimethoxysilane, phenylmethyldimethoxysilane,
diphenyldiethoxysilane, bis-o-tolydimethoxysilane, bis-
m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane,
bis-p-tolyldiethoxysilane, bis(ethylphenyl)dimethoxy-
silane, dicyclohexyldimethoxysilane, cyclohexylmethyldi-
methoxysilane, cyclohexylmethyldiethoxysilane, ethyltri-
methoxysilane, ethyltriethoxysilane, vinyltrimethoxy-
silane, n-propyltriethoxysilane, decyltrimethoxysilane,
decyltriethoxysilane, phenyltrimethoxysilane, gamma-
chloropropyltrimethoxysilane, methyltriethoxysilane,
vinyltriethoxysilane, t-butyltriethoxysilane, n-butyl-
triethoxysilane, isobutyltriethoxysilane, phenyltri-
ethoxysilane, gamma-aminopropyltriethoxysilane, chloro-
triethoxysilane, ethyltriisopropoxysilane, vinyltri-
butoxysilane, cyclohexyltrimethoxysilane, cyclohexyltri-
ethoxysilane, 2-norbornanetrimethoxysilane, 2-
norbornanetriethoxysilane, 2-norbornanemethyldimethoxy-
silane, ethyl silicate, butyl silicate, trimethyl-
phenoxysilane, methyltriallyloxysilane, vinyltris(beta-
methoxyethoxy)silane, dimethyltetraethoxydisiloxane,
etc. Among them are particularly preferred ethyltri-
ethoxysilane, n-propyltriethoxysilane, t-butyltri-
ethoxysilane, vinyltriethoxysilane, phenyltriethoxy-
silane, vinyltributoxysilane, diphenyldimethoxysilane,
phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane,
p-tolylmethyldimethoxysilane, dicyclohexyldimethoxy-
silane, cyclohexylmethyldimethoxysilane, 2-
norbornanetriethoxysilane, 2-norbornanemethyldimethoxy-
silane, diphenyldiethoxysilane, ethyl silicate, etc.
Further, as the above amines having a large
steric hindrance are particularly preferred 2,2,6,6-
tetramethylpyperidine, and 2,2,5,5-tetramethylpyrrolidine,
derivatives of these amines, tetramethylmethylenediamine,
etc.
2G~3S63
- 29
Alkoxytaryloxy)silane compounds are
particularly preferred among the above various electron
donors used as catalyst components.
Further, there may preferably be used in the
above process a catalyst comprising a catalyst component
(A) which contains a transition metal atom compound of
the IV A or V A group of the periodic table of elements
having as ligand(s) groups) having conjugated pi-
electrons, and an organometal compound catalyst component
(B)
Examples of the transition metals of the IV A
and V A groups of the periodic table include ziroconium,
titanium, hafnium, chromium, vanadium, etc.
Further, examples of the ligands having groups
having conjugated pi-electrons include unsubstituted or
alkyl-substituted cyclopentadienyl groups such as cyclo-
petadienyl, methylcyclopentadienyl, ethylcyclo-
pentadienyl, t-butylcyclopentadienyl, dimethylcyclo-
pentadienyl and pentamethylcyclopentadienyl groups, an
indenyl group, an fluorenyl group, etc.
Further, there may be mentioned as preferred
examples of the ligands wherein at least two of the above
ligands having the cycloalkadienyl skeleton are linked
via a lower alkyl group or group containing silicon,
phosphorus, oxygen or nitrogen. Examples of such groups
include ethylenebisindenyl and isopropyl(cyclo-
pentadienyl-1-fluorenyl) groups, etc.
One or more or preferably two of such ligands
having the cycloalkadienyl skeleton are coordinated to
the transition metal.
Other ligands than the ligands having the
cycloalkadienyi skeleton include hydrocarbon groups
having 1 to 12 carbon atoms, alkoxy groups, aryloxy
groups, halogens and hydrogen.
There may be exemplified as the hydrocarbon
groups having 1 to 12 carbon atoms alkyl groups,
203563
- 30 -
cycloalkyl groups, aryl groups, aralkyl groups, etc.
Specifically, examples of the alkyl groups include methyl
ethyl, propyl, isopropyl and butyl groups, etc., exmaples
of the cycloalkyl groups include cyclopentyl and cyclo-
hexyl groups, etc., examples of the aryl groups include
phenyl and tolyl groups, etc., and examples of the
aralkyl groups include benzyl and neophyl groups, etc.
Examples of the alkoxy groups include methoxy,
ethoxy and butoxy groups, etc., the examples of the
aryloxy groups include a phenoxy group, etc., and
halogens include fluorine, chlorine, bromine and iodine.
Such transition metal compounds containing
ligandts) having the cycloalkadienyl skeleton to be used
in the invention are more specifically represented, for
example in case of the valence of the transition metal
being 4, by the formula
R2kR31R4mR5nM
(wherein M is ziroconium, titanium, hafnium, vanadium or
the like, R2 is a group having the cycloalkadienyl
2p skeleton, R3, R4 and R5 are groups having the cyclo-
alkadienyl skeleton, alkyl groups, cycloalkyl groups,
aryl groups, aralkyl groups, alkoxy groups, aryloxy
groups, halogen atoms or hydrogens, k is an integer of
one or more, and k, 1, m and n are numbers of k+1+m+n=4).
Particularly preferred compounds among the compounds of
the above formula are those wherein R2 and R3 are
groups having the cycloalkadienyl skeleton and the two
groups having the cycloalkadienyl skeleton are linked via
a group containing silicon, phosphorus, oxygen or
nitrogen.
Specific examples of the transition metal
compounds wherein M is ziroconium and which contain
ligandsts) having the cycloalkadienyl skeleton are
indicated below:
2~3563
- 31 -
bis(cyclopentadienyl)ziroconium monochloride monohydride,
bis(cyclopentadienyl)ziroconium monobromide monohydride,
bis(cyclopentadienyl)methylzirconium hydride,
bistcyclopentadienyl)ethylzirconium hydride,
bis(cyclopentadienyl)phenylzirconium hydride,
bistcyclopentadienyl)benzylzirconium hydride,
bis(cyclopentadienyl)neopentylzirconium hydride,
bis(methylcyclopentadienyl)zirconium monochloride hydride,
bistindenyl)zirconium monochloride monohydride,
bis(cyclopentadienyl)zirconium dichloride,
bis(cyclopentadienyl)zirconium dibromide,
bistcyclopentadienyl)methylzirconium monochloride,
bis(cyclopentadienyl)ethylzirconium monochloride,
bis(cyclopentadienyl)cyclohexylzirconium monochloride,
bis(cyclopentadienyl)phenylzirconium monochloride,
bistcyclopentadienyl)benzylzirconium monochloride,
bis(methylcyclopentadienyl)zirconium dichloride,
bis(t-butylcyclopentadienyl)zirconium dichloride,
bis(indenyl)zirconium dichloride,
bis(indenyl)zirconium dibromide,
bis(cyclopentadienyl)zirconiumdimethyl,
bis(cyclopentadienyl)zirconiumdiphenyl,
bis(cyclopentadienyl)zirconiumdibenzyl,
bis(cyclopentadienyl)zirconiummethoxy chloride,
bis(cyclopentadienyl)zirconiumethoxy chloride,
bistmethylcyclopentadienyl)zirconiumethoxy chloride,
bis(cyclopentadienyl)zirconiumphenoxy chloride,
bis(fluorenyl)zirconium dichloride,
ethylenebis(indenyl)diethylzirconium,
ethylenebis(indenyl)diphenylzirconium,
ethylenebis(indenyl)dimethylzirconium,
ethylenebis(indenyl)ethylzirconium monochloride,
ethylenebis(indenyl)zirconium dichloride,
isopropylidenebis(indenyl)zirconium dichloride,
isopropylidine(cyclopentadienyl)-1-fluorenylzirconium
chloride,
;~G~3563
- 32 -
ethylenebis(indenyl)zirconium dibromide,
ethylenebis(indenyl)zirconiummethoxy monochloride,
ethylenebis(indenyl)zirconiumethoxy monochloride,
ethylenebis(indenyl)zirconiumphenoxy monochloride,
ethylenebis(cyclopentadienyl)zirconium dichloride,
propylenebis(cyclopentadienyl)zirconium dichloride,
ethylenebis(t-butylcyclopentadienyl)zirconium dichloride,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium
monochloride,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium
dichloride,
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium
dibromide,
ethylenebis(4-methyl-1-indenyl)zirconium dichloride,
ethylenebis(5-methyl-1-indenyl)zirconium dichloride,
ethylenebis(6-methyl-1-indenyl)zirconium dichloride,
ethylenebis(7-methyl-1-indenyl)zirconium dichloride,
ethylenebis(5-methoxy-1-indenyl)zirconium dichloride,
ethylenebist2,3-dimethyl-1-indenyl)zirconium dichloride,
ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride,
ethylene bis(4,7-dimethoxy-1-indenyl)zirconium dichloride.
It is also possible to use transition metal
compounds wherein titanium metal, hafnium metal, chromium
metal, vanadium metal or the like is substituted for the
zirconium in the above zirconium compounds.
It is preferred to use as the organometal
compounds catalyst component (B) in the situation an
organoaluminum compound obtained either preferably by
reaction of an organoaluminum compound with water or by
reaction of a solution of an aluminooxane in a solvent
such as hydrocarbon with water or an active hydrogen-
containing compound.
Such organoaluminum compounds are insoluble or
sparingly soluble in benzene at 60 °C.
The amount of the catalyst to be used is varied
~~~3563
- 33 -
depending on the kind of the used catalyst, etc. For
instance, when the above catalyst component (A), organo-
metal compound catalyst component (B) and electron donor
(C) are used, the catalyst component (A) is used in an
amount within the range of usually 0.001 to 0.5 millimole,
preferably 0.005 to 0.5 millimole in terms of the transi-
tion metal per liter of the polymerization volume.
Further, the organometal compound catalyst (B) is used in
an amount such that the amount of the metal atom of the
organometal compound catalyst (B> becomes an amount
within usually 1 to 10,000 moles, preferably 5 to
500 moles per mole of the transition metal atom of the
catalyst component (A) in the polymerization system.
Further, when electron donor (C) is used, it is used in
an amount within the range of 100 moles or less, pre-
ferably 1 to 50 moles, particularly preferably 3 to
moles per mole of the transition metal of the catalyst
component (A) in the polymerization system.
It is preferred to carry out a preliminary
polymerization before the main polymerization using the
20 above catalyst. Such a preliminary polymerization is
carried out using as the catalyst prepared by combining
at least catalyst component (A) and organometal compound
catalyst component (B).
The polymerization amount in the preliminary
Polymerization is, when titanium is used as the
transition metal, usually 1 to 2,000 g, preferably 3 to
1,000 g, particularly preferably 10 to 500 g per gram of
the titanium catalyst component.
It is preferred to use an inert hydrocarbon
solvent in carrying out the preliminary polymerization.
Examples of such inert hydrocarbon solvents include
aliphatic hydrocarbons such as propane, butane, n-
pentane, i-pentane, n-hexane, i-hexane, n-heptane, n-
octane, i-octane, n-decane, n-dodecane and kerosene;
alicyclic hydrocarbons such cyclopentane, methylcyclo-
203563
- 34 -
pentane, cyclohexane and methylcyclohexane; aromatic
hydrocarbones such as benzene, toluene and xylene; and
halogenated hydrocarbons such as methylene chloride,
ethyl chloride, ethylene chloride and chlorobenzene.
Among these inert hydrocarbon solvents aliphatic hydro-
carbons are preferred and aliphatic hydrocarbons having 4
to 10 carbon atoms are particularly preferred. Further,
it is also possible to use as the solvent the monomer to
be used in the reaction.
Suitable examples of alpha-olefin to be used in
this preliminary polymerization include alpha-olefin
having 10 or less carbon atoms such as ethylene, pro-
pylene, 1-butene, 1-pentene, 4-methyl-1-pentene,
3-methyl-1-pentene, 1-heptene, 1-octene and 1-decene, and
alpha-olefines having 3 to 6 carbon atoms are further
preferred and propylene is particularly preferred. These
alpha-olefins may be used either alone, or in combination
of two or more of them so long as a crystalline polymer
is prepared.
The polymerization temperature in the pre-
liminary polymerization is varied depending on the alpha-
olefin to be used and use of the inert solvent and cannot
unconditionally be determined, but the temperature is in
the range of generally -40 to 80 °C, preferably -20 to
40 °C, particularly preferably -10 to 30 °C. For
example, the temperature is arranged in the range of -40
to 70 oC in case of propylene being used as the alpha-
olefin, -40 to 40 °C in case of 1-butene being used, or
-40 to 70 oC in case of 3-methyl-1-pentene being used.
It is also possible to make hydrogen gas coexist in the
reaction system of this preliminary polymerization.
Polyolefin particles may be prepared by
carrying out a polymerization reaction (main poly-
merization~ introducing the above monomer in the reaction
system, either after the preliminary polymerization was
carried out in the above manner or without carrying out
-35- ~~~~53
preliminary polymerization.
'fhe monorner to be used in the main polymeri-
zation may be identical to or different from the monomer
used in the preliminary polymerization.
The polymerization temperature in main poly-
merization of the olefin is in the range of usually -50
to 200 °C, preferably 0 to 150 °C. The polymerization
pressure is in the range of usually atmospheric pressure
to 100 kg/cm2, preferably atmospheric pressure to
50 kg/cm2. The polymerization reaction may be carried
out by any of the batch, semi-continuous and continuous
methods.
'fire molecular weight of the olefin polymer to
be obtained may be adjusted by hydrogen and/or the poly-
merization temperature.
In the invention, the thus obtained polyolefin
particles are usually then used as such for the modifica-
tion reaction without subjecting the particles to a
pulverization or granulation step.
'fire present invention is further described by
the following examples, but the invention should not be
limited therto.
Examples 1 to 10
(a) Preparation of catalyst component (A)
After a High speed stirring apparatus having an
inner volume of 21 (made by Tokushu Kika Kogyo Co.) was
throughly nitrogen-purged, 700 ml of purified kerosene,
10 g of commercially available MgCl2, 24.2 g of ethanol
and 3 g of Emazol 32U (trade-mark of sorbitan distearate
made by Kao-Atlas Co., Ltd.) were placed therein, and the
3U system was heated with stirring and stirred at 120 oC
and 800 rpm for 30 minutes. The mixture was transferred,
with high speed stirring using a Teflon tube having an
inner diameter of 5 mm, to a 2-liter glass flask (with a
stirrer) previously containing 11 of purified kerosene
cooled to -10 °C. The resulting solid was collected by
filtration, and washed thoroughly with hexane to obtain a
Trade-mark
i
67566-1180
2Ga3~63
- 36 -
carrier.
7.5 g of the carrier was suspended in 150 ml of
titanium tetrachloride at rom temperature, 1.3 ml of
diisobutyl phthalate was added, and the system was heated
to 120 oC. After stirring and mixing at 120 oC for 2
hours, the solid part was collected by filtration and
resuspended in 150 ml of titanium tetrachloride, and
stirring and mixing at 130 °C for 2 hours were carried
out again. The reaction solid was collected from the
reaction mixture by filtration and washed with an
adequate amount of purified hexane to obtain a solid
catalyst component (A). The component contained in terms
of atom 2.2 wt. % of titanium, 63 wt. % of chlorine and
wt. % of magnesium, and 5.5 wt. % of diisobutyl
phthalate. A true spherical catalyst was obtained whose
15 average particle size was 64 micrometers and geometrical
standard deviation (~g) of particle size distribution is
1.5.
(b) Preliminary polymerization
The following preliminary polymerization was
20 carried out on the catalyst component (A).
200 ml of purified hexane was placed in a
400-ml glass reactor which had been nitrogen-purged, and
then 20mmo1 of triethylaluminum, 4 mmol of diphenyl-
dimethoxysilane and 2 mmol, in terms of titanium atom, of
the above Ti catalyst component (A) were placed therein.
Propylene was then supplied at a speed of 5.9 Nl/hour
over a period of one hour, whereby 2.8.g of propylene was
polymerized per gram of the Ti catalyst component (A).
After the preliminary polymerization, the liquid part was
removed by filtration and the separated solid part was
resuspended in decane.
(c) Polymerization
(I) Homopolymerization (1)
5 kg of propylene was placed in a 17-1 poly-
merizer at room temperature and heated, and then 8 mmol of
~oa3ss3
- 37 -
triethylaluminum, 8 mmol of diphenyldimethoxysilane and
0.08 mmol, in terms of titanium atom, of the preliminary
polymerization-treated catalyst component (A) were added
thereto at 50 °C. The temperature inside the poly-
merizer was maintained at 70 °C for 2 hours, and then
the remaining propylene was purged to recover a polymer.
The obtained polymer had I~l of 6.97 dl/g and an apparent
bulk density of 0.45 g/ml, and the yield was 3.1 kg.
Further, the average particle size of the
P°lymer was 1.8 mm and the geometrical standard deviation
thereof was 1.3, and the content of fine particles having
a particle size of 100 micrometers or less contained in
the polymer was 0.1 wt. %.
Homopolymerization (2)
The same procedure as in homopolymerization (1)
was carried out except that 1.5 N liters of hydrogen was
added after the addition of 5 kg of prop twenty minutes
was adopted. 3.3 kg of a polymer having f~l of 3.5 dl/g
and an apparent bulk density of 0.46g/ml was obtained.
Further, the average particle size of the
Polymer was 1.7 mm and the geometrical standard
deviation thereof was 1.3, and the content of fine
particles of 100 micrometers or less contained in the
polymer was 0.2 wt. %.
(II) Copolymer
2.5 kg of propylene and 20 N liters of hydrogen
were placed in a 17-1 polymerizes at room temperature and
heated, and 15 mmol of triethylaluminum, 1.5 mmol of di-
phenyldimethoxysilane and 0.05 mmol in terms of titanium
atom of the preliminary polymerization-treated catalyst
component (A) were added at 50 °C, and the temperature
inside the polymerizes was maintained at 70 °C. 14
minutes after the temperature had reached 70 °C, the
vent valve was opened and the propylene was purged until
the pressure of the inside of the polymerizes became
atmospheric pressure. After the purge, a copoly-
2G~~3563
- 38 -
merization was carried out. Namely, ethylene, propylene
and hydrogen were supplied to the polymerizes at
velocities of 480 Nl/hr, 720 N1/hr and 12 N1/hr, res-
pectively. Vent opening was adjusted so that the pres-
s sure of the inside of the polymerizes became
kg/cm2.G. The temperature during the copolymeriza-
tion was maintained at 70 °C. After 60 minutes of
polymerization time, the inside of the polymerizes was
depressurized to obtain 3.2 kg of a polymer. MI of the
10 polymer at 230 °C under a load of 2 kg was 10 g/lOmin.,
the ethylene content thereof was 25 mol % and the ap-
parent bulk density thereof was 0.42 g/ml. Further, the
content of the components soluble in n-decane at 23 °C
in the polymer was 25 wt. %, and the ethylene content of
the soluble components was 50 mol %.
Further, the average particle size of the
obtained polymer was 1.9 mm, the geometrical standard
deviation thereof was 1.3, and the content of fine par-
ticles of 100 micrometers or less container in the
polymer was 0.0 wt. %.
(d) 100 wt. parts of the polypropylene (PP)
Indicated in Table 1 was charged in a stainless
autoclave equipped with an agitating blade having a
spiral type Bobble ribbon, and the inside of the auto-
clave was throughly nitrogen-purged. A solution
consisting of malefic anhydride (MAH), benzoyl peroxide
(BPO) and the solvent in the mutual ratio indicated in
Table 1 was dropwise added to the polypropylene over a
period of 10 minutes while the polypropylene was stirred
at room temperature, and thereafter the mixture was
further stirred at room temperature for additional 30
minutes.
Then, the temperature of the system was raised
to 100 °C and the reaction was carried out for 4 hours.
The polymer after the reaction was dissolved in
P-xYlane of 130 °C, the solution was allowed to cool,
~G~35f~3
- 39 -
and the polymer was deposited with acetone, whereby the
polymer became free of the unreacted matter and thus was
purified.
The results are shown in Table 1.
2003Sf 3
- 40 -
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~0~3563
- 41 -
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2~~3563
- 42 -
Comparative example 1
100 wt. parts of polypropylene thomocopolymer
(2). 2.27 wt. parts of MAH and 0.17 wt. parts of 2,5-di-
methyl-2,5-di(t-butylperoxy)hexyne-3 (made by Nippon
Yushi Co., Ltd.) were mixed in Henschel mixer, supplied
to a biaxial extruder (made by Plastic Kagaku Co., Ltd.,
PLABOR 40L/D-40 set to 200 oC, and molten and kneaded.
The graft amount of the thus obtained modified product
was 0.18 wt. $ and MFR thereof was 30.
Examples 11 to 13
(a) Polymerization
tI) Homopolymer
5 kg of propylene was added to a 17-1 poly-
merizer at room temperature, followed by addition of 1.51
of hydrogen. The mixture was heated, and at 50 °C were
added 8 mmol of triethylaluminum, 8 mmol of diphenyldi-
methoxysilane and 0.08 mmol in terms of titanium atom of
the preliminary polymerization-treated catalyst component
(A) obtained in tb) of Example 1. The inside of the
polymerizer was maintained at 70 oC for one hour and 20
minutes. The remaining propylene was then purged and the
polymer was collected. The polymer had I~l of 3.5 dl/g
and an apparent bulk density of 0.46 g/ml, and the yield
thereof was 3.3 kg
(b) 100 wt. parts of the polypropylene (PP)
indicated in Table 2 was charged into a stainless auto-
clave equipped with an agitating blade having a spiral
type double ribbon, and the inside of the system was
throughly nitrogen-purged. A solution consisting of
allyl glycidyl ether, benzonyl peroxide (BPO) and toluene
in the mutual ratio descirbed in Table 2 was dropwise
added to the polypropylene over a period of 10 minutes
while the polypropylene was stirred at room temperature,
and after the dropwise addition the mixture was further
stirred at room temperature for additional 30 minutes.
Thereafter, the temperature of the inside of
;~C~035f'3
- 43 -
the system was raised to 100 oC, and the reaction was
carried out for 4 hours.
The polymer after the reaction was dissolved in
p-xylene of 130 oC, and after natural cooling of the
mixture deposited with acetone, whereby the unreacted
matters were removed to purify the polymer.
Table 2
Exam.ll Exam. Exam.
l2 l3
Homopolymer t2) twt. part) 100 100 100
Monomer
tkind) Allyl Glycidyl
ether
twt. parts) 1.0 2.5 5.0
BPO twt. parts) 0.4 0.17 0.17
Toluene twt. parts) 17.4 17.4 17.4
Graft amount twt. parts) 0.51 0.20 0.18
Graft efficiency t%) 51 8 3.6
MFR 230oC. 2160g 0.81 0.99 0.96
tg/10 min.>
Characteristics of the
modified polyolefin
particles
Average particle size ~(m) 1.7 1.7 1.7
Geometrical standard 1.3 1.3 1.3
deviation
Content of fine particles 0.2 0.2 0.2
of 100 micrometers or less
twt. %)
Apparent bulk density 0.46 0.46 0.46
tg/ml )
203563
- 44 -
Examples 14 to 16
The monomer, benzoyl peroxide (BPO) and toluene
in the respective amounts indicated in Table 3 were added
to 100 wt. parts of the copolymer obtained in (c) of
Example 1, followed by mixing at room temperature. 10 g
of this mixture was weighed and placed in a test tube
having a diameter of 25 mm, cooled with liquid nitrogen
to freeze it. Then, the inside of the system was nitrogen-
purged, the temperture of the system was brought back to
room temperature, the test tube was placed in an oil bath
of 100 °C, and the reaction was carried out for 4
hours.
The polyolefin particles after the reaction was
dissolved in p-xylene at 130 °C, and after allowing the
mixture to cool, was deposited with methanol to carry out
a purification.
The graft amount was determined by IR using the
previously prepared calibration curve.
203563
- 45 -
Table 3
Exam. Exam. Exam.
l4 l5 l6
Copolymer (wt. part) 100 100 100
Monomer HEMA1) HEA2) HPA3)
(kind)
(wt. part) 3.03 2.71 3.03
BPO (wt. part) 0.17 0.17 0.17
Toluene (wt, parts) 17.4 17.4 17.4
Graft amount (wt. parts) 0.23 0.27 0.22
Graft efficiency (%) 7.6 10 7.3
MFR 230C, 21608 10.1 7.2 7.2
(8/10 min.)
Characteristics of the
modif ied polyolef in
particles
Average particle size ~A4m) 1.9 1.9 1.9
Geometrical standard 1.3 1.3 1.3
deviation
Content of fine particles 0.0 0.0 0.0
of 100 micrometers or less
(wt. %)
Apparent bulk density 0.42 0.42 0.42
(g/ml)
1) HEMA: 2-hydroxyethyl methacrylate
2) HEA : 2-hydroxyethyl acrylate
3) HPA : 2-hydroxypropyl acrylate
Example 17
3008 of the homopolymer (2) obtained by (c) of
Example 1 was charged in a 1-1 glass reactor equipped
with a spiral type double ribbon agitating blade and a
dropping funnel, and the inside of the system was
thoroughly nitrogen-purged. Then, a solution consisting
of 528 of toluene, 9.18 of N,N-dimethylamino methacrylate
2~~3563
- 46 -
and 0.51 g of BPO was placed in the dropping funnel. The
solution was dropwise added to the PP at room temperature
for 10 minutes while the latter was stirred, and the
mixture was further stirred at that temperature for
additional 30 minutes. The temperature inside the system
was then raised to 100 °C and the reaction was carried
out for 4 hours.
After the reaction, the polyolefin particles
were dissolved in xylene of 130 oC, and after allowing
the solution to cool, deposited with acetone to carry out
the purification thereof. Measurement of graft amount of
the particles revealed that 0.25 wt. ~ of N,N-dimethyl-
amino methacrylate was grafted. MFR of the graft polymer
was 1.1 g/10 minutes.
The average particle size of these modified
polyolefin particles was 1.7 mm and the geometrical
standard deviation thereof was 1.3, and the content of
fine particles of 100 micrometers or less contained in
this polymer was 0.2 wt. $.
