[0001] This application claims the benefit of Korean Patent
Application No. 2019-0105772, filed on August 28, 2019, in
10 the Korean Intellectual Property Office, the contents of
which are incorporated herein by reference.
Technical Field
[0002] The present invention relates to a polypropylene15
based composite material having improved physical properties
such as impact strength at low temperature and room
temperature, flexural strength, flexural modulus, etc., and a
method for preparing the same.
BACKGROUND ART
20 [0003] Generally, as compositions for car interior and
exterior material parts, polypropylene resin compositions
including polypropylene (PP) as a main component, an impact
reinforcing agent and an inorganic filler have been used.
[0004] Until the mid-1990s before developing ethylene/alpha25
olefin copolymers polymerized by applying a metallocene
2
catalyst, as car interior and exterior materials,
particularly, as materials for a bumper cover, ethylene
propylene rubber (EPR) or ethylene propylene diene rubber
(EDPM) has been mainly used in most polypropylene-based resin
5 compositions. However, after the appearance of
ethylene/alpha-olefin copolymers synthesized by a metallocene
catalyst, the ethylene/alpha-olefin copolymers have been used
as impact reinforcing agents, and at present, become the
mainstream. Because polypropylene-based composite materials
10 using thereof have advantages in having well-balanced
physical properties including impact strength, flexural
modulus, flexural strength, etc., having good moldability and
being cheap in price.
[0005] Since the molecular structure of polyolefin such as
15 ethylene/alpha-olefin copolymers synthesized by a metallocene
catalyst is more uniformly controlled than that by a Ziegler-
Natta catalyst, molecular weight distribution is narrow, and
mechanical properties are good overall. For a low-density
ethylene elastomer synthesized by the metallocene catalyst,
20 an alpha-olefin-based monomer is relatively uniformly
inserted in a polyethylene molecule when compared with a
Ziegler-Natta catalyst, and rubber properties of low-density
may be maintained while showing excellent properties of
mechanical properties.
25 [0006] However, the manufacture of even better products
3
having balanced physical properties and processability
according to diverse utilizing environments is consistently
required.
5 [0007] [Prior Art Documents]
[0008] [Patent Documents]
[0009] (Patent Document 1) US Registration Patent No.
5,064,802
[0010] (Patent Document 2) US Registration Patent No.
10 6,548,686
DISCLOSURE OF THE INVENTION
TECHNICAL PROBLEM
[0011] An object of the present invention is to provide a
15 polypropylene-based composite material having excellent
processability while showing excellent physical properties
including impact strength at low temperature and at room
temperature, flexural strength, flexural modulus, etc.
[0012] Another object of the present invention is to provide
20 a method for preparing the polypropylene-based composite
material.
TECHNICAL SOLUTION
[0013] The present invention provides a polypropylene-based
25 composite material including: polypropylene; and an olefin4
based copolymer satisfying conditions (a) to (c) below.
[0014] (a) A melt index (MI, 190°C, 2.16 kg load conditions)
is 10 to 100 g/10 min, (b) a soluble fraction (SF) at -20°C
measured by cross-fractionation chromatography (CFC) is 0.5
5 to 10 wt%, where a weight average molecular weight of the
soluble fraction (Mw(SF)) is 22,000 or more, and (c) a value
of Mw:Mw(SF), which is a ratio of a weight average molecular
weight of the olefin-based copolymer (Mw) and the weight
average molecular weight of the soluble fraction (Mw(SF), is
10 0.9:1 to 2:1.
[0015] In addition, the present invention provides a method
for preparing the polypropylene-based composite material of
claim 1, including: (S1) a step of preparing polypropylene;
15 (S2) a step of preparing an olefin-based copolymer by a
method including polymerizing an olefin-based monomer by
injecting hydrogen in 10 to 100 cc/min in the presence of a
catalyst composition including a transition metal compound
represented by the following Formula 1; and (S3) a step of
20 melting and kneading the polypropylene and the olefin-based
copolymer:
[0016] [Formula 1]
5
[0017] in Formula 1,
[0018] R1 is hydrogen; alkyl of 1 to 20 carbon atoms;
alkenyl of 2 to 20 carbon atoms; alkoxy of 1 to 20 carbon
5 atoms; aryl of 6 to 20 carbon atoms; arylalkoxy of 7 to 20
carbon atoms; alkylaryl of 7 to 20 carbon atoms; or arylalkyl
of 7 to 20 carbon atoms,
[0019] R2 and R3 are each independently hydrogen; halogen;
alkyl of 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon
10 atoms; arylalkyl of 7 to 20 carbon atoms; alkylamido of 1 to
20 carbon atoms; or arylamido of 6 to 20 carbon atoms,
[0020] R4 to R9 are each independently hydrogen; silyl;
alkyl of 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon
atoms; aryl of 6 to 20 carbon atoms; alkylaryl of 7 to 20
15 carbon atoms; arylalkyl of 7 to 20 carbon atoms; or a
metalloid radical of a metal in group 14, which is
substituted with hydrocarbyl of 1 to 20 carbon atoms,
6
[0021] adjacent two or more among the R2 to R9 may be
connected with each other to form a ring,
[0022] Q is Si; C; N; P; or S,
[0023] M is a transition metal in group 4, and
5 [0024] X1 and X2 are each independently hydrogen; halogen;
alkyl of 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon
atoms; aryl of 6 to 20 carbon atoms; alkylaryl of 7 to 20
carbon atoms; arylalkyl of 7 to 20 carbon atoms; alkylamino
of 1 to 20 carbon atoms; or arylamino of 6 to 20 carbon atoms.
10
ADVANTAGEOUS EFFECTS
[0025] The polypropylene-based composite material according
to the present invention includes an olefin-based copolymer
showing a higher weight average molecular weight value of a
15 soluble fraction at a low temperature in a low-crystallinity
region when compared with the conventional copolymer, and has
markedly improved impact strength at low temperature and at
room temperature while maintaining equivalent or better
tensile strength, and accordingly, shows effects of excellent
20 resistance against external impact.
BRIEF DESCRIPTION ON DRAWINGS
[0026] FIG. 1 is a graph showing the impact strength at low
temperature of polypropylene-based composite materials
25 according to an embodiment of the present invention and a
7
comparative embodiment.
[0027] FIG. 2 is a graph showing the physical properties of
polypropylene-based composite materials according to an
embodiment of the present invention and a comparative
5 embodiment.
BEST MODE FOR CARRYING OUT THE INVENTION
[0028] Hereinafter, the present invention will be described
in more detail to assist the understanding of the present
10 invention.
[0029] It will be understood that words or terms used in the
present disclosure and claims shall not be interpreted as the
meaning defined in commonly used dictionaries. It will be
further understood that the words or terms should be
15 interpreted as having a meaning that is consistent with their
meaning in the context of the relevant art and the technical
idea of the invention, based on the principle that an
inventor may properly define the meaning of the words or
terms to best explain the invention.
20 [0030] The term “polymer” used in the present invention
means a polymer compound prepared by polymerizing monomers
which are the same or different types. The common term,
“polymer” includes a term, “interpolymer” as well as
“homopolymer”, “copolymer” and “terpolymer”. The term
25 "interpolymer" means a polymer prepared by polymerizing two
8
or more different types of monomers. The common term
“interpolymer” includes a term “copolymer” (commonly used to
refer a polymer prepared from two different monomers) and a
term “terpolymer” (commonly used to refer a polymer prepared
5 from three different monomers). The term “interpolymer”
includes a polymer prepared by polymerizing four or more
types of monomers.
[0031] Hereinafter, the present invention will be explained
10 in detail.
[0032]
[0033] Generally, polypropylene is used as car interior and
15 exterior materials such as a car bumper, and to supplement
the low impact strength of polypropylene, a polyolefin-based
polymer is used together as an impact reinforcing material.
Above all, in order to show properties of impact resistance,
elastic modulus and tensile properties and to achieve high
20 impact strength properties according to various usage
environments, a low-density polyolefin-based polymer is used.
However, in this case, there are problems of deteriorating
the strength of polypropylene.
[0034] In this regard, in the present invention, an olefin25
based copolymer which has increased hardness and high
9
flowability, and may show improved physical properties of
tensile strength, flexural strength, flexural modulus, etc.
when compared with a copolymer having an equivalent degree of
density is used for preparing a polypropylene-based composite
5 material, and excellent mechanical strength and significantly
improved impact strength properties may be shown without
using a separate additive.
[0035] The polypropylene-based composite material of the
10 present invention is characterized in including:
polypropylene; and an olefin-based copolymer satisfying the
conditions of (a) to (c) below.
[0036] (a) A melt index (MI, 190°C, 2.16 kg load conditions)
is 10 to 100 g/10 min,
15 [0037] (b) a soluble fraction (SF) at -20°C measured by
cross-fractionation chromatography (CFC) is 0.5 to 10 wt%,
where a weight average molecular weight of the soluble
fraction (Mw(SF)) is 22,000 or more, and
[0038] (c) a value of Mw:Mw(SF), which is a ratio of a
20 weight average molecular weight of the olefin-based copolymer
(Mw) and the weight average molecular weight of the soluble
fraction (Mw(SF), is 0.9:1 to 2:1.
[0039] Polypropylene
25 [0040] In the polypropylene-based composite material of the
10
present invention, the “polypropylene” may particularly be a
homopolymer of polypropylene, or a copolymer of propylene and
an alpha-olefin-based monomer, and in this case, the
copolymer may be an alternating or random, or block copolymer.
5 However, the polypropylene which may be overlapped with the
olefin polymer is excluded, and the polypropylene is a
different compound from the olefin polymer.
[0041] The alpha-olefin-based monomer may particularly be an
aliphatic olefin of 2 to 12 carbon atoms, or 2 to 8 carbon
10 atoms. More particularly, ethylene, propylene, 1-butene, 1-
pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-
methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene, 4,4-
dimethyl-1-pentene, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-
15 hexene, etc., may be used, and any one among them or mixtures
of two or more thereof may be used.
[0042] More particularly, the polypropylene may be any one
selected from the group consisting of a polypropylene
copolymer, a propylene-alpha-olefin copolymer, and a
20 propylene-ethylene-alpha-olefin copolymer, or mixtures of two
or more thereof, and in this case, the copolymer may be a
random or block copolymer.
[0043] In addition, the melt index (MI) measured at 230°C
25 and a load of 2.16 kg of the polypropylene may be 0.5 g/10
11
min to 200 g/10 min, and particularly, the melt index (MI)
may be 1 g/10 min to 150 g/10 min, more particularly, 10 g/10
min to 120 g/10 min. If the melt index of the polypropylene
is deviated from the range, it is apprehended that defects
5 may be generated during injection molding, but polypropylene
having suitable melt index to a person skilled in the art may
be used considering the types and amounts of materials mixed
with the polypropylene-based composite material and the usage
of the polypropylene-based composite material.
10 [0044] Particularly, in the polypropylene-based composite
material according to an embodiment of the present invention,
the polypropylene may be an impact copolymer having a melt
index measured at 230°C and a load of 2.16 kg of 0.5 g/10 min
to 150 g/10 min, particularly, 1 g/10 min to 120 g/10 min,
15 more particularly, a propylene-ethylene impact copolymer.
The impact copolymer may be included in 30 wt% to 90 wt%,
more particularly, 30 wt% to 80 wt% with respect to the total
weight of the polypropylene-based composite material. In
case of including the impact copolymer having such physical
20 properties as polypropylene in the above-described amount
range, particularly strength properties at low temperature
may be improved.
[0045] The impact copolymer may be prepared so as to satisfy
the above-described physical property conditions by using a
25 general preparation reaction of a polymer, or may be obtained
12
commercially. Particular examples may include Moplen CB5230
of DAELIM Industrial Co., Ltd., Moplen CB5290 of DAELIM
Industrial Co., Ltd., SEETETM M1600 of LG Chem, Co., etc.
5 [0046] In addition, in the polypropylene-based composite
material of the present invention, the polypropylene may
particularly be one or more random propylene copolymers
having a DSC melting point in a range of 120°C to 160°C, and
a melting flow rate (MFR) measured at 230°C and a load of
10 2.16 kg according to ASTM-D 1238 in a range of 5 g/10 min to
120 g/10 min, and the random propylene copolymer may be
included in 30 wt% to 90 wt%, more particularly, 30 wt% to 80
wt% with respect to the total weight of the polypropylenebased
composite material. If the polypropylene having such
15 physical properties is included in the above-described amount
range, the mechanical strength of the polypropylene-based
composite material including hardness, etc. may be improved.
[0047] The random propylene copolymer may be prepared so as
to satisfy the above-described physical property conditions
20 by using the common preparation reaction of a polymer, or may
be obtained commercially. Particular examples may include
BraskemTM PP R7021-50RNA of Braskem America Inc., FormoleneTM
7320A of Formosa Plastics Corporation in America, etc.
25 [0048] Olefin-based copolymer
13
[0049] In the polypropylene-based composite material of the
present invention, the “olefin-based copolymer” satisfies the
conditions of (a) to (c) below, particularly, satisfying
conditions on a melt index, the amount and weight average
5 molecular weight of a soluble fraction at -20°C, and a ratio
of a weight average molecular weight of the olefin-based
copolymer and the weight average molecular weight of the
soluble fraction, at the same time.
[0050] (a) A melt index (MI, 190°C, 2.16 kg load conditions)
10 is 10 to 100 g/10 min,
[0051] (b) a soluble fraction (SF) at -20°C measured by
cross-fractionation chromatography (CFC) is 0.5 to 10 wt%,
where a weight average molecular weight of the soluble
fraction (Mw(SF)) is 22,000 or more, and
15 [0052] (c) a value of Mw:Mw(SF), which is a ratio of a
weight average molecular weight of the olefin-based copolymer
(Mw) and the weight average molecular weight of the soluble
fraction (Mw(SF), is 0.9:1 to 2:1.
[0053] According to the condition (a), the melt index (MI,
20 190°C, 2.16 kg load conditions) of the olefin-based copolymer
according to the present invention is 10 to 100 g/10 min.
[0054] The melt index (MI) may be controlled by controlling
the amount used of a catalyst with respect to a comonomer in
a process of polymerizing an olefin-based copolymer, and
25 influences the mechanical properties, impact strength of the
14
olefin-based copolymer, and moldability. The melt index is
measured in low-density conditions, and measured under 190°C
and 2.16 kg load conditions according to ASTM D1238, and may
be 10 to 100 g/10 min, particularly, 10 g/10 min or more, 11
5 g/10 min or more, 11.5 g/10 min or more, or 12 g/10 min or
more, and 100 g/10 min or less, 50 g/10 min or less, 40 g/10
min or less, or 36 g/10 min or less.
[0055] If the melt index of the olefin-based copolymer is
less than 10 g/10 min, the preparation of a polypropylene10
based composite material using the same may be difficult, and
the polypropylene-based composite material thus prepared may
also show a low melt index, and accordingly, it would be
unfavorable in view of processability, and application to
various uses may become difficult.
15
[0056] According to the condition (b), the olefin-based
copolymer according to the present invention has the soluble
fraction (SF) at -20°C measured by cross-fractionation
chromatography (CFC) of 0.5 to 10 wt%, where a weight average
20 molecular weight of the soluble fraction (Mw(SF)) is 22,000
or more.
[0057] The cross-fractionation chromatography (CFC) is a
combined method of temperature rising elution fractionation
(TREF) and gel filtration chromatography (GPC), and the
25 crystallinity distribution and molecular weight distribution
15
of the olefin-based copolymer may be found simultaneously.
[0058] Particularly, a specimen solution with a high
temperature in which an olefin-based copolymer is completely
dissolved in a solvent, is injected into a column filled with
5 an inert carrier, and the temperature of the column is
decreased so as to attach the specimen to the surface of a
filler. Then, the temperature of the column is slowly
increased while flowing o-dichlorobenzene in the column. The
concentration of the olefin-based copolymer eluted at each
10 temperature is detected, and at the same time, the component
eluted at each temperature is sent fraction by fraction via
on-line to GPC to obtain chromatogram, and from the
chromatogram, the molecular weight distribution of each
component is calculated.
15 [0059] In addition, since the elution temperature increases
with the increase of the crystallinity of the eluted
component, the crystallinity distribution of the olefin-based
copolymer may be found by obtaining the relation of the
elution temperature and the elution amount (wt%) of the
20 olefin-based copolymer.
[0060] The olefin-based copolymer of the present invention
may have a soluble fraction at -20°C measured by CFC of 0.5
to 10 wt%, particularly, 0.5 wt% or more, 1 wt% or more, 2
wt% or more, or 2.5 wt% or more, and 10 wt% or less, 8 wt% or
25 less, 7 wt% or less, 6 wt% or less.
16
[0061] In addition, while satisfying the soluble fraction
content at -20°C, the weight average molecular weight of the
soluble fraction (Mw(SF)) may be 22,000 g/mol or more,
5 particularly, 23,000 g/mol or more, 24,000 g/mol or more,
25,000 g/mol or more, and 100,000 g/mol or less, less than
60,000 g/mol, 60,000 g/mol or less, 50,000 g/mol or less,
45,000 g/mol or less, 40,000 g/mol or less.
10 [0062] It is known that the olefin-based copolymer eluted at
a low elution temperature is a low-crystallinity copolymer
having low stereoregularity, high comonomer content and low
density. Particularly, as measured in the present invention,
the soluble fraction at -20°C includes components having
15 extremely very low crystallinity and has strong amorphous
properties, and is expressed as an ultralow crystallinity
region. In general polymerization, if copolymerization
properties are extremely increased, the molecular weight of a
polymer decreases in inverse proportion. As a result, the
20 ultralow crystallinity soluble fraction which is eluted at -
20°C or less generally has a very low molecular weight when
compared with the whole olefin-based copolymer.
[0063] Meanwhile, the soluble fraction of -20°C has ultralow
crystallinity, and has a very low density and excellent
25 elasticity, and if prepared into a polypropylene-based
17
composite material, effects of improving impact strength are
achieved. On the contrary, considering the molecular weight,
the molecular weight is markedly low in contrast to the
molecular weight of the whole olefin-based copolymer, and the
5 soluble fraction causes the decrease of mechanical strength
such as tensile strength, and accordingly, there are problems
of showing weak impact strength at low temperature and at
high temperature.
[0064] On the contrary, in the olefin-based copolymer of the
10 present invention, the content of the soluble fraction at -
20°C measured by CFC as described above is 0.5 to 20 wt%, but
various physical properties such as flexural strength and
hardness as well as tearing strength and tensile strength are
excellent. This is achieved because the weight average
15 molecular weight of the soluble fraction shows a high value
of 22,000 g/mol or more.
[0065] According to the condition (c), the value of
Mw:Mw(SF), which is a ratio of a weight average molecular
20 weight of the olefin-based copolymer (Mw) according to the
present invention and the weight average molecular weight of
the soluble fraction (Mw(SF), is 0.9:1 to 2:1.
[0066] As described above, the olefin-based copolymer of the
25 present invention has a high weight average molecular weight
18
value of the soluble fraction at -20°C measured by CFC. In
addition, the molecular weight distribution is considered
uniformed irrespective of crystallinity when compared with
the conventional copolymer such that, even though compared
5 with the total weight average molecular weight (Mw) of the
olefin-based copolymer, the value of Mw:Mw(SF) satisfies
0.9:1 to 2:1. As described above, because the molecular
weight in the ultralow crystalline region which is the
soluble fraction at -20°C maintains a similar level in
10 contrast to the total molecular weight, mechanical properties
such as tensile strength are excellent while having the
similar level of impact strength with respect to the
conventional olefin-based copolymer.
[0067] The value of Mw:Mw(SF) may be 0.9:1 to 2:1, 1:1 to
15 2:1, 1,5:1 to 2:1, or 1.7:1 to 2:1, and if the ratio of
Mw(SF) with respect to Mw increases, the impact strength of
the olefin-based copolymer at low temperature and at high
temperature may also be improved.
20 [0068] In addition, the olefin-based copolymer of the
present invention shows a low density of 0.85 g/cc to 0.89
g/cc, particularly, 0.8500 g/cc or more, 0.8550 g/cc or more,
0.8600 g/cc or more, and 0.8900 g/cc or less, 0.8800 g/cc or
less, if measured according to ASTM D-792. That is, the
25 olefin-based copolymer according to the present invention may
19
be an olefin-based copolymer with a low density, which
satisfies the conditions of (a) to (c) as described above and
has a low density in the above-described range at the same
time, but the density value is not limited thereto.
5 [0069] In addition, the olefin-based copolymer of the
present invention may satisfy a weight average molecular
weight (Mw) of 10,000 to 100,000 g/mol, particularly, 20,000
to 80,000 g/mol, more particularly, 20,000 g/mol or more,
30,000 g/mol or more, 40,000 g/mol or more, 80,000 g/mol or
10 less, 70,000 g/mol or less. The weight average molecular
weight (Mw) is a polystyrene conversion molecular weight
analyzed by gel permeation chromatography (GPC).
[0070] In addition, the olefin-based copolymer of the
present invention may have a ratio (Mw/Mn) of a weight
15 average molecular weight (Mw) and a number average molecular
weight (Mn), i.e., molecular weight distribution (MWD) of 1.5
to 3.0, particularly, 1.5 or more, 1.8 or more, 3.0 or less,
2.8 or less, 2.5 or less, 2.4 or less.
[0071] The olefin-based copolymer of the present invention
20 may have hardness (shore A) of 30 to 80, particularly, 40 to
80, more particularly, 50 to 80. The olefin-based copolymer
may show higher hardness (shore A) with the equivalent
degrees of density and melt index values when compared with a
commonly used conventional olefin-based copolymer, and
25 accordingly, may have improved tearing strength, tensile
20
strength, elongation rate and flexural strength.
[0072] As described later, the olefin-based copolymer of the
present invention may be an olefin-based copolymer prepared
by carrying out polymerization reaction using a transition
5 metal compound represented by Formula 1 as a catalyst and
injecting a specific amount of hydrogen, and by preparing by
such a preparation method, the olefin-based copolymer of the
present invention shows a higher weight average molecular
weight value of a soluble fraction at -20°C and improved
10 physical properties of tearing strength, tensile strength,
elongation rate and flexural strength when compared with the
conventional olefin-based copolymer.
[0073] The olefin-based copolymer of the present invention
15 may be a copolymer of two or more selected from olefin-based
monomers, particularly, an alpha-olefin-based monomer, a
cyclic olefin-based monomer, a diene olefin-based monomer, a
triene olefin-based monomer and a styrene-based monomer, and
particularly, a copolymer of ethylene and an alpha-olefin20
based monomer of 3 to 12 carbon atoms, or a copolymer of
ethylene and an alpha-olefin-based monomer of 3 to 10 carbon
atoms. Particularly, the olefin-based copolymer of the
present invention may be a copolymer of ethylene with
propylene, ethylene with 1-butene, ethylene with 1-hexene,
25 ethylene with 4-methyl-1-pentene or ethylene with 1-octene.
21
[0074] The alpha-olefin-based monomer may include one or
more selected from the group consisting of propylene, 1-
butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene,
1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-
5 hexadecene, 1-eicocene, norbornene, norbornadiene, ethylidene
norbornene, phenyl norbornene, vinyl norbornene,
dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-
hexadiene, styrene, alpha-methylstyrene, divinylbenzene and
3-chloromethylstyrene, without limitation.
10
[0075] The olefin-based copolymer of the present invention
may be prepared by continuous solution polymerization
reaction by which an olefin-based monomer is polymerized
while continuously injecting hydrogen in the presence of a
15 metallocene catalyst composition including one or more
transition metal compounds in a single reactor.
[0076] The olefin-based copolymer according to the present
invention may be selected from the group consisting of a
random copolymer, an alternating copolymer and a graft
20 copolymer, and more particularly, may be a random copolymer.
[0077] The olefin-based copolymer may be prepared by a
method including a step of polymerizing an olefin-based
monomer by injecting hydrogen in 10 to 100 cc/min in the
presence of a catalyst composition including a transition
25 metal compound represented by Formula 1, which will be
22
explained later. This will be explained in detail below
referring to the preparation method of a polypropylene-based
composite material.
5 [0078] Meanwhile, the polypropylene-based composite material
of the present invention, if applied to a rubber composition,
may include each constituent component in a suitable amount
according to the use of the rubber composition and to satisfy
the physical properties thus required.
10 [0079] Particularly, the polypropylene-based composite
material may include the olefin-based copolymer in 5 to 70
wt%, particularly, 5 to 50 wt%, more particularly, 5 to 40
wt%, more particularly, 10 to 40 wt%.
[0080] If the amount of the olefin-based copolymer is less
15 than the mixing ratio, impact strength may decrease, and if
the amount is greater than the mixing ratio, tensile strength
and hardness may decrease. The significance of improving
effects according to the control of the mixing ratio of the
polypropylene and olefin-based copolymer may be considered.
20 [0081] The polypropylene-based composite material according
to an embodiment of the present invention may selectively
further include an inorganic filler to improve the mechanical
properties of the polypropylene-based composite material
together with the polypropylene and olefin-based copolymer.
25 [0082] The inorganic filler may be a powder-type filler, a
23
flake-type filler, a fiber-type filler, or a balloon-type
filler, and any one among them or mixtures of two or more
thereof may be used. Particularly, the powder-type filler
may include: natural silicic acid or silicate such as fine
5 powder talc, kaolinite, plastic clay, and sericite; carbonate
such as settleable calcium carbonate, heavy calcium carbonate
and magnesium carbonate; hydroxide such as aluminum hydroxide
and magnesium hydroxide; oxide such as zinc oxide, magnesium
oxide and titanium oxide; synthetic silicic acid or silicate
10 such as hydrated calcium silicate, hydrated aluminum silicate,
hydrated silicic acid and anhydrous silicic acid. In
addition, as the flake-type filler, mica, etc. may be
included. In addition, as the fiber-type filler, basic
magnesium sulfate whisker, calcium titanate whisker, aluminum
15 borate whisker, sepiolite, processed mineral fiber (PMF),
potassium titanate, etc. may be included. As the balloontype
filler, glass balloon, etc. may be included. Among them,
talc may be used.
20 [0083] In addition, the inorganic filler may be surface
treated to improve the strength properties and molding
processability of the polypropylene-based composite material.
[0084] Particularly, the inorganic filler may be physically
or chemically surface treated using a surface treating agent
25 such as a silane coupling agent, a higher fatty acid, a fatty
24
acid metal salt, an unsaturated organic acid, an organic
titanate, a resin acid and polyethylene glycol.
[0085] In addition, the inorganic filler may have an average
particle diameter (D50) of 1 μm to 20 μm, more particularly,
5 7 μm to 15 μm. If the average particle diameter of the
inorganic filler is less than 1 μm, when mixing the
polypropylene and the olefin-based copolymer, uniform
dispersion is difficult due to the agglomeration of inorganic
filler particles, and as a result, the improving effects of
10 the mechanical properties of the polypropylene-based
composite material may become insignificant. In addition, if
the average particle diameter of the inorganic filler is
greater than 20 μm, it is apprehended that the physical
properties of a rubber composition may be deteriorated due to
15 the deterioration of the dispersibility of the inorganic
filler itself.
[0086] In the present invention, the average particle
diameter (D50) of the inorganic filler may be defined as a
particle diameter based on 50% of particle diameter
20 distribution. In the present invention, the average particle
diameter (D50) of the inorganic filler may be measured by,
for example, observing electron microscope using scanning
electron microscopy (SEM), field emission scanning electron
microscopy (FE-SEM), etc., or by a laser diffraction method.
25 In case of measuring by the laser diffraction method, more
25
particularly, the inorganic filler particles are dispersed in
a dispersion medium and introduced into a commercially
available laser diffraction particle size measurement
apparatus (for example, Microtrac MT 3000), and then, an
5 average particle diameter (D50) based on 50% of particle
diameter distribution in the measurement apparatus may be
computed.
[0087] The inorganic filler may be included in 0.1 parts by
10 weight to 40 parts by weight with respect to 100 parts by
weight of polypropylene. If the amount of the inorganic
filler in the polypropylene-based composite material is less
than 0.1 parts by weight with respect to 100 parts by weight
of polypropylene, improving effects according to the
15 inclusion of the inorganic filler is insignificant, and if
the amount is greater than 40 parts by weight, the
processability of the polypropylene-based composite material
may be deteriorated. More particularly, the inorganic filler
may be included in 0.1 wt% to 20 wt% with respect to the
20 total weight of the polypropylene-based composite material.
[0088] The polypropylene-based composite material according
to an embodiment of the present invention, satisfying the
above-described configuration and amount conditions, may be
prepared by adding polypropylene and selectively an inorganic
25 filler to an olefin-based copolymer and then heating. In
26
this case, the type and amount of the polypropylene are the
same as explained above.
[0089] A mixing process may be performed by a common method.
Particularly, the mixing may be performed using a super mixer
5 or a ribbon mixer.
[0090] In addition, during the mixing process, an additive
such as an antioxidant, a thermal stabilizer, an ultraviolet
stabilizer, and an antistatic agent may be further included,
and to improve coatability, a small amount of an adhesive
10 resin or an additive having a polar group may be selectively
further used in a suitable amount range.
[0091] In addition, the heating process may be performed at
the melting point of polypropylene or higher to a temperature
of 210°C or less. The heating process may be performed using
15 various compounding and processing apparatus such as a twinscrew
extruder, a single-screw extruder, a roll-mill, a
kneader and a banbury mixer.
[0092] The polypropylene-based composite material according
to an embodiment of the present invention, prepared by the
20 above-described preparation method may further improve the
dispersibility of polypropylene by using optimum two types of
olefin-based copolymers combined to improved the impact
strength of the polypropylene-based composite material, and
as a result, the impact strength may be improved without
25 degrading the mechanical properties such as the tensile
27
strength of the polypropylene-based composite material.
[0093] Accordingly, the polypropylene-based composite
material according to an embodiment of the present invention
is useful for hollow molding, injection molding or extrusion
5 molding in various fields and usages including wrapping,
building or daily supplies like materials for cars, wires,
toys, fibers or medicine, and has excellent toughness and
impact strength at a low temperature as well as at room
temperature and very excellent physical properties including
10 heat resistance, rigidity, etc., and accordingly, may be
usefully used in the interior or exterior parts of cars.
[0094] The polypropylene-based composite material of the
present invention may be used for manufacturing molded
articles or car parts.
15 [0095] The molded article may particularly include a blow
molding molded article, an inflation molded article, a cast
molded article, an extrusion laminate molded article, an
extrusion molded article, a foam molded article, an injection
molded article, a sheet, a film, a fiber, a monofilament, or
20 a non-woven fabric.
[0096] In addition, the car part may be for the interior or
exterior material of cars.
[0097]
28
[0098] The method for preparing the polypropylene-based
composite material of the present invention is characterized
in including: (S1) a step of preparing polypropylene; (S2) a
5 step of preparing an olefin-based copolymer by a method
including a step of polymerizing an olefin-based monomer by
injecting hydrogen in 10 to 100 cc/min in the presence of a
catalyst composition including a transition metal compound
represented by the following Formula 1: and (S3) a step of
10 melting and kneading the polypropylene and the olefin-based
copolymer:
[0099] [Formula 1]
[00100] in Formula 1,
15 [00101] R1 is hydrogen; alkyl of 1 to 20 carbon atoms;
alkenyl of 2 to 20 carbon atoms; alkoxy of 1 to 20 carbon
atoms; aryl of 6 to 20 carbon atoms; arylalkoxy of 7 to 20
29
carbon atoms; alkylaryl of 7 to 20 carbon atoms; or arylalkyl
of 7 to 20 carbon atoms,
[00102] R2 and R3 are each independently hydrogen; halogen;
alkyl of 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon
5 atoms; arylalkyl of 7 to 20 carbon atoms; alkylamido of 1 to
20 carbon atoms; or arylamido of 6 to 20 carbon atoms,
[00103] R4 to R9 are each independently hydrogen; silyl;
alkyl of 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon
atoms; aryl of 6 to 20 carbon atoms; alkylaryl of 7 to 20
10 carbon atoms; arylalkyl of 7 to 20 carbon atoms; or a
metalloid radical of a metal in group 14, which is
substituted with hydrocarbyl of 1 to 20 carbon atoms,
[00104] two or more adjacent groups among R2 to R9 are
connected with each other to form a ring,
15 [00105] Q is Si; C; N; P; or S,
[00106] M is a transition metal in group 4, and
[00107] X1 and X2 are each independently hydrogen; halogen;
alkyl of 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon
atoms; aryl of 6 to 20 carbon atoms; alkylaryl of 7 to 20
20 carbon atoms; arylalkyl of 7 to 20 carbon atoms; alkylamino
of 1 to 20 carbon atoms; or arylamino of 6 to 20 carbon atoms.
[00108] In the transition metal compound of Formula 1,
described in the present disclosure, cyclopentadiene to which
25 benzothiophene is fused by ring-type bonding, and an amido
30
group (N-R1) are stably crosslinked by Q (Si; C; N; or P),
and a structure where a transition metal in group 4 makes
coordination bonds is formed.
[00109] If the catalyst composition is applied to the
5 polymerization reaction of the olefin-based monomer, the
production of a copolymer having high activity, high
molecular weight and high copolymerization properties at a
high polymerization temperature may be achieved.
Particularly, the transition metal compound of Formula 1 may
10 introduce a large amount of alpha-olefin as well as linear
low-density polyethylene with a level of 0.85 g/cc to 0.93
g/cc due to its structural characteristics, and the
preparation of a polymer (elastomer) in a ultralow density
region of a density of less than 0.910 g/cc is also possible.
15 [00110] In addition, in the present invention, the olefinbased
copolymer is prepared by polymerizing an olefin-based
monomer by using the catalyst of the transition metal
compound represented by Formula 1 and injecting hydrogen in
10 to 100 cc/min, and an olefin-based copolymer having a high
20 weight average molecular weight of a soluble fraction at a
low temperature and showing excellent physical properties
including tearing strength, tensile strength and elongation
rate may be prepared as described above when compared with an
olefin-based copolymer prepared by polymerizing a monomer
25 using a transition metal compound not corresponding to
31
Formula 1 or not injecting hydrogen.
[00111] In Formula 1, R1 may be hydrogen; alkyl of 1 to 20
carbon atoms; alkoxy of 1 to 20 carbon atoms; aryl of 6 to 20
5 carbon atoms; arylalkoxy of 7 to 20 carbon atoms; alkylaryl
of 7 to 20 carbon atoms; or arylalkyl of 7 to 20 carbon atoms.
Preferably, R1 may be alkyl of 1 to 20 carbon atoms; aryl of
6 to 20 carbon atoms; arylalkoxy of 7 to 20 carbon atoms; or
arylalkyl of 7 to 20 carbon atoms, and more preferably, may
10 be methyl, ethyl, propyl, butyl, isobutyl, tert-butyl,
isopropyl, cyclohexyl, benzyl, phenyl, methoxyphenyl,
ethoxyphenyl, fluorophenyl, bromophenyl, chlorophenyl,
dimethylphenyl or diethylphenyl.
[00112] In Formula 1, R2 and R3 may be each independently
15 hydrogen; alkyl of 1 to 20 carbon atoms; aryl of 6 to 20
carbon atoms; or alkylaryl of 6 to 20 carbon atoms, and
preferably, R2 and R3 may be each independently hydrogen;
alkyl of 1 to 20 carbon atoms; or aryl of 6 to 20 carbon
atoms.
20 [00113] In Formula 1, R4 to R9 may be each independently
hydrogen; alkyl of 1 to 20 carbon atoms; aryl of 6 to 20
carbon atoms; alkylaryl of 7 to 20 carbon atoms; or arylalkyl
of 7 to 20 carbon atoms.
[00114] In Formula 1, R4 and R5 may be the same or different,
25 and may be each independently alkyl of 1 to 20 carbon atoms;
32
or aryl of 6 to 20 carbon atoms.
[00115] In Formula 1, R4 and R5 may be the same or different,
and may be each independently alkyl of 1 to 6 carbon atoms.
[00116] In Formula 1, R4 and R5 may be methyl, ethyl or
5 propyl.
[00117] In Formula 1, R6 to R9 may be the same or different
and may be each independently hydrogen; alkyl of 1 to 20
carbon atoms; aryl of 6 to 20 carbon atoms; alkylaryl of 7 to
20 carbon atoms, or arylalkyl of 7 to 20 carbon atoms.
10 [00118] In Formula 1, R6 to R9 may be the same or different
and may be each independently hydrogen; or alkyl of 1 to 20
carbon atoms.
[00119] In Formula 1, R6 to R9 may be the same or different
and may be each independently hydrogen or methyl.
15 [00120] In Formula 1, M may be Ti, Hf or Zr.
[00121] In Formula 1, X1 and X2 may be the same or different
and may be each independently hydrogen, halogen, alkyl of 1
to 20 carbon atoms, or alkenyl of 2 to 20 carbon atoms.
20 [00122] Preferably, R1 is hydrogen; alkyl of 1 to 20 carbon
atoms; alkoxy of 1 to 20 carbon atoms; aryl of 6 to 20 carbon
atoms; arylalkoxy of 7 to 20 carbon atoms; alkylaryl of 7 to
20 carbon atoms; or arylalkyl of 7 to 20 carbon atoms, R2 and
R3 are each independently hydrogen; alkyl of 1 to 20 carbon
25 atoms; aryl of 6 to 20 carbon atoms; or alkylaryl of 6 to 20
33
carbon atoms, R4 to R9 are each independently hydrogen; alkyl
of 1 to 20 carbon atoms; aryl of 6 to 20 carbon atoms;
alkylaryl of 7 to 20 carbon atoms; or arylalkyl of 7 to 20
carbon atoms, where adjacent two or more among R2 to R9 may
5 be connected with each other to form an aliphatic ring of 5
to 20 carbon atoms or an aromatic ring of 6 to 20 carbon
atoms; the aliphatic ring or aromatic ring may be substituted
with halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to
20 carbon atoms, or aryl of 6 to 20 carbon atoms, and Q may
10 be Si; C; N; or P.
[00123] More preferably, R1 may be alkyl of 1 to 20 carbon
atoms; aryl of 6 to 20 carbon atoms; arylalkoxy of 7 to 20
carbon atoms; or arylalkyl of 7 to 20 carbon atoms, R2 and R3
may be each independently hydrogen; alkyl of 1 to 20 carbon
15 atoms; or aryl of 6 to 20 carbon atoms, R4 to R9 may be each
independently hydrogen; alkyl of 1 to 20 carbon atoms; or
aryl of 6 to 20 carbon atoms, and Q may be Si.
[00124] In addition, the transition metal compound
20 represented by Formula 1 may be selected from the group
consisting of the following Formula 1-1 to Formula 1-6, but
an embodiment is not limited thereto and various compounds
within the defined range by Formula 1 may be applied in the
present invention:
25 [00125] [Formula 1-1] [Formula 1-2] [Formula 1-3]
34
[00126] [Formula 1-4] [Formula 1-5] [Formula 1-6]
[00127] Each substituent used in this disclosure will be
5 explained in detail as follows.
[00128] In the present invention, the term “halogen” means
fluorine, chlorine, bromine or iodine.
[00129] In the present invention, the term “alkyl” means a
linear chain or branch chain of a hydrocarbon residual group.
10 [00130] In the present invention, the term “alkenyl” means a
linear chain or branch chain of an alkenyl group. The
branched chain may be alkyl of 1 to 20 carbon atoms; alkenyl
of 2 to 20 carbon atoms; aryl of 6 to 20 carbon atoms;
35
alkylaryl of 7 to 20 carbon atoms; or arylalkyl of 7 to 20
carbon atoms.
[00131] In the present invention, the term “aryl” may
preferably have 6 to 20 carbon atoms, and may particularly be
5 phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl,
anisolyl, etc., without limitation.
[00132] In the present invention, the term “silyl” may be
silyl substituted with alkyl of 1 to 20 carbon atoms, and may
be, for example, trimethylsilyl or triethylsilyl.
10 [00133] In the present invention, the term “alkylaryl” means
an aryl group substituted with the alkyl group.
[00134] In the present invention, the term “arylalkyl” means
an alkyl group substituted with the aryl group.
[00135] In the present invention, the term “alkyl amino”
15 means an amino group substituted with the alkyl group, and
includes a dimethylamino group, a diethylamino group, etc.,
without limitation.
[00136] In the present invention, the term “hydrocarbyl
group” means a monovalent hydrocarbon group of 1 to 20 carbon
20 atoms, which is composed of only carbon and hydrogen
irrespective of its structure, such as alkyl, aryl, alkenyl,
alkynyl, cycloalkyl, alkylaryl and arylalkyl, unless
otherwise referred to.
25 [00137] The transition metal compound represented by Formula
36
1 may be used solely, or as a composition type including one
or more promoter compounds represented by Formula 2 to
Formula 4 below in addition to the transition metal compound
of Formula 1, as a catalyst of the polymerization reaction of
5 an olefin-based monomer. The promoter compound may assist
the activation of the transition metal compound of Formula 1
above.
[00138] [Formula 2]
-[Al(R10)-O]a-
10 [00139] [Formula 3]
A(R10)3
[00140] [Formula 4]
[L-H]+[W(D)4]- or [L]+[W(D)4]-
[00141] In Formulae 2 to 4,
15 [00142] R10 groups may be the same or different from each
other and each independently selected from the group
consisting of halogen, hydrocarbyl of 1 to 20 carbon atoms,
and halogen-substituted hydrocarbyl of 1 to 20 carbon atoms,
[00143] A is aluminum or boron,
20 [00144] each D is independently aryl of 6 to 20 carbon atoms
or alkyl of 1 to 20 carbon atoms, of which one or more
hydrogen atoms may be substituted with substituents, wherein
the substituent is at least any one selected from the group
consisting of halogen, hydrocarbyl of 1 to 20 carbon atoms,
25 alkoxy of 1 to 20 carbon atoms and aryloxy of 6 to 20 carbon
37
atoms,
[00145] H is a hydrogen atom,
[00146] L is a neutral or cationic Lewis acid,
[00147] W is an element in group 13, and
5 [00148] a is an integer of 2 or more.
[00149] The compound represented by Formula 2 may include
alkylaluminoxane such as methylaluminoxane (MAO),
ethylaluminoxane, isobutylaluminoxane and butylalminoxane,
10 and a modified alkylaluminoxane obtained by mixing two or
more types of the alkylaluminoxane, particularly,
methylaluminoxane, modified methylaluminoxane (MMAO), without
limitation.
[00150] The compound represented by Formula 3 may include
15 trimethylaluminum, triethylaluminum, triisobutylaluminum,
tripropylaluminum, tributylaluminum, dimethylchloroaluminum,
triisopropylaluminum, tri-s-butylaluminum,
tricyclopentylaluminum, tripentylaluminum,
triisopentylaluminum, trihexylaluminum, trioctylaluminum,
20 ethyldimethylaluminum, methyldiethylaluminum,
triphenylaluminum, tri-p-tolylaluminum,
dimethylaluminummethoxide, dimethylaluminumethoxide,
trimethylboron, triethylboron, triisobutylboron,
tripropylboron, tributylboron, etc. and particularly, may be
25 selected from trimethylaluminum, triethylaluminum and
38
triisobutylaluminum, without limitation.
[00151] The compound represented by Formula 4 may include
triethylammoniumtetraphenylboron,
tributylammoniumtetraphenylboron,
5 trimethylammoniumtetraphenylboron,
tripropylammoniumtetraphenylboron, trimethylammoniumtetra(ptolyl)
boron, trimethylammoniumtetra(o,p-dimethylphenyl)boron,
tributylammoniumtetra(p-trifluoromethylphenyl)boron,
trimethylammoniumtetra(p-trifluoromethylphenyl)boron,
10 tributylammoniumtetrapentafluorophenylboron, N,Ndiethylaniliumtetraphenylboron,
N,Ndiethylaniliumtetrapentafluorophenylboron,
diethylammoniumtetrapentafluorophenylboron,
triphenylphosphoniumtetraphenylboron,
15 trimethylphosphoniumtetraphenylboron, dimethylanilium
tetrakis(pentafluorophenyl) borate,
triethylammoniumtetraphenylaluminum,
tributylammoniumtetraphenylaluminum,
trimethylammoniumtetraphenylaluminum,
20 tripropylammoniumtetraphenylaluminum,
trimethylammoniumtetra(p-tolyl)aluminum,
tripropylammoniumtetra(p-tolyl)aluminum,
triethylammoniumtetra(o,p-dimethylphenyl)aluminum,
tributylammoniumtetra(p-trifluoromethylphenyl)aluminum,
25 trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum,
39
tributylammoniumtetrapentafluorophenylaluminum, N,Ndiethylaniliniumtetraphenylaluminum,
N,Ndiethylaniliumtetrapentafluorophenylaluminum,
diethylammoniumtetrapentatetraphenylaluminum,
5 triphenylphosphoniumtetraphenylaluminum,
trimethylphosphoniumtetraphenylaluminum,
tripropylammoniumtetra(p-tolyl)boron,
triethylammoniumtetra(o,p-dimethylphenyl)boron,
triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, or
10 triphenylcarboniumtetrapentafluorophenylboron, without
limitation.
[00152] The catalyst composition may be prepared by, as a
first method, a preparation method including a step of
15 obtaining a mixture by contacting the transition metal
compound represented by Formula 1 with the compound
represented by Formula 2 or Formula 3; and a step of adding
the compound represented by Formula 4 to the mixture.
[00153] In this case, the molar ratio of the transition metal
20 compound represented by Formula 1 and the compound
represented by Formula 2 or Formula 3 may be 1:2 to 1:5,000,
particularly, 1:10 to 1:1,000, more particularly, 1:2 to
1:500.
[00154] If the molar ratio of the transition metal compound
25 represented by Formula 1 and the compound represented by
40
Formula 2 or Formula 3 is less than 1:2, the amount of an
alkylating agent is too small, and the alkylation of a metal
compound may be incompletely carried out, and if the molar
ratio is greater than 1:5,000, the alkylation of the metal
5 compound may be achieved, but the activation of the alkylated
metal compound may be incompletely carried out due to the
side reactions between an excessive amount of the alkylating
agent remained and an activating agent of the compound of
Formula 4.
10 [00155] In addition, the molar ratio of the transition metal
compound represented by Formula 1 and the compound
represented by Formula 4 may be 1:1 to 1:25, particularly,
1:1 to 1:10, more particularly, 1:1 to 1:5. If the molar
ratio of the transition metal compound represented by Formula
15 1 and the compound represented by Formula 4 is less than 1:1,
the amount of an activating agent is relatively small, and
the activation of the metal compound may be incompletely
carried out, and thus, the activity of the catalyst
composition may be deteriorated. If the molar ratio is
20 greater than 1:25, the activation of the metal compound may
be completely carried out, but due to the excessive amount of
the activating agent remained, it would not be economical
considering the unit cost of the catalyst composition, or the
purity of a polymer produced may be degraded.
25 [00156] In addition, the catalyst composition may be prepared
41
by, as a second method, a method of contacting the transition
metal compound represented by Formula 1 with the compound
represented by Formula 2.
[00157] In this case, the molar ratio of the transition metal
5 compound represented by Formula 1 and the compound
represented by Formula 2 may be 1:10 to 1:10,000,
particularly, 1:100 to 1:5,000, more particularly, 1:500 to
1:3,000. If the molar ratio is less than 1:10, the amount of
an activating agent is relatively small, and the activation
10 of a metal compound may be incompletely carried out, and the
activity of the catalyst composition thus produced may be
degraded. If the molar ratio is greater than 1:10,000, the
activation of the metal compound may be completely carried
out, but due to the excessive amount of the activating agent
15 remained, it would not be economical considering the unit
cost of the catalyst composition, or the purity of a polymer
produced may be degraded.
[00158] As the reaction solvent during preparing the catalyst
composition, a hydrocarbon-based solvent such as pentane,
20 hexane, and heptane, or an aromatic solvent such as benzene
and toluene may be used, without limitation.
[00159] In addition, the catalyst composition may include the
transition metal compound and the promoter compound in a
supported type on a support. Any supports used in a
25 metallocene-based catalyst may be used as the support without
42
specific limitation. Particularly, the support may be silica,
silica-alumina or silica-magnesia, and any one among them or
mixtures of two or more thereof may be used.
[00160] In case where the support is silica among them, since
5 a silica support and the functional group of the metallocene
compound of Formula 1 form a chemical bond, there is no
catalyst separated from the surface during an olefin
polymerization process. As a result, the generation of
fouling, by which polymer particles are agglomerated on the
10 wall side of a reactor or from each other during the
preparation process of an olefin-based copolymer, may be
prevented. In addition, the particle shape and apparent
density of a polymer of the olefin-based copolymer prepared
in the presence of a catalyst including the silica support
15 are excellent.
[00161] More particularly, the support may be silica or
silica-alumina, including a highly reactive siloxane group
and dried at a high temperature through a method of drying at
a high temperature, etc.
20 [00162] The support may further include an oxide, a carbonate,
a sulfate, or a nitrate component such as Na2O, K2CO3, BaSO4
and Mg(NO3)2.
[00163] The drying temperature of the support is preferably,
from 200 to 800°C, more preferably, from 300 to 600°C, most
25 preferably, from 300 to 400°C. If the drying temperature of
43
the support is less than 200°C, humidity is too high and
water at the surface may react with the promoter, and if the
temperature is greater than 800°C, the pores at the surface
of the support may be combined to decrease the surface area,
5 and a large amount of the hydroxyl groups at the surface may
be removed to remain only siloxane groups to decrease
reaction sites with the promoter, undesirably.
[00164] In addition, the amount of the hydroxyl group at the
surface of the support may preferably be 0.1 to 10 mmol/g,
10 and more preferably, 0.5 to 5 mmol/g. The amount of the
hydroxyl group at the surface of the support may be
controlled by the preparation method and conditions of the
support, or drying conditions such as temperature, time,
vacuum and spray drying.
15
[00165] The polymerization of the olefin-based copolymer may
be performed at about 50 to 200°C, 50°C or higher, 70°C or
higher, 100°C or higher, 200°C or less, 180°C or less, 160°C
or less, 150or less.
20 [00166] In addition, the polymerization of the olefin-based
copolymer may be performed at a pressure of 1 kgf/cm2 to 150
kgf/cm2, preferably, 1 kgf/cm2 to 120 kgf/cm2, more preferably,
5 kgf/cm2 to 100 kgf/cm2.
[00167] The polymerization reaction of the olefin monomer may
25 be performed in an inert solvent, and as the inert solvent,
44
benzene, toluene, xylene, cumene, heptane, cyclohexane,
methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene,
and 1-octene may be used, without limitation.
5 [00168] Examples
[00169] Hereinafter, the present invention will be explained
in more detail referring to embodiments. However, the
embodiments are provided only for illustration, and the scope
of the present invention is not limited thereto.
10
[00170] [Preparation of transition metal compound]
[00171] Synthetic Example 1
[00172]
[00173] Synthesis of N-tert-butyl-1-(1,2-dimethyl-3H15
benzo[b]cyclopenta[d]thiophene-3-yl)-1,1-dimethylsilaneamine
[00174]
[00175] To a 100 ml schlenk flask, 4.65 g (15.88 mmol) of
chloro(1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene-3-
45
yl)dimethylsilane was weighed and added, and 80 ml of THF was
put thereto. At room temperature, tBuNH2 (4 eq, 6.68 ml) was
put thereto, followed by reacting at room temperature for 3
days. After finishing the reaction, THF was removed and the
5 resultant reaction product was filtered with hexane. After
drying solvents, 4.50 g (86%) of a yellow liquid was obtained.
[00176] 1H-NMR (in CDCl3, 500 MHz): 7.99 (d, 1H), 7.83 (d,
1H), 7.35 (dd, 1H), 7.24 (dd, 1H), 3.49 (s, 1H), 2.37 (s, 3H),
2.17 (s, 3H), 1.27 (s, 9H), 0.19 (s, 3H), -0.17 (s, 3H).
10 [00177]
[00178]
[00179] To a 50 ml schlenk flask, the ligand compound (1.06 g,
3.22 mmol/1.0 eq) and MTBE 16.0 ml (0.2 M) were put and
stirred first. n-BuLi (2.64 ml, 6.60 mmol/2.05 eq, 2.5 M in
15 THF) was added thereto at -40°C, followed by reacting at room
temperature overnight. After that, MeMgBr (2.68 ml, 8.05
mmol/2.5 eq, 3.0 M in diethyl ether) was slowly added thereto
dropwisely at -40°C, and TiCl4 (2.68 ml, 3.22 mmol/1.0 eq,
46
1.0 M in toluene) was put in order, followed by reacting at
room temperature overnight. After that, the reaction mixture
was passed through celite for filtration using hexane. After
dying the solvents, 1.07 g (82%) of a brown solid was
5 obtained.
[00180] 1H-NMR (in CDCl3, 500 MHz): 7.99 (d, 1H), 7.68 (d,
1H), 7.40 (dd, 1H), 7.30 (dd, 1H), 3.22 (s, 1H), 2.67 (s, 3H),
2.05 (s, 3H), 1.54 (s, 9H), 0.58 (s, 3H), 0.57 (s, 3H), 0.40
(s, 3H), -0.45 (s, 3H).
10
[00181] Comparative Synthetic Example 1
[00182]
[00183] Synthesis of N-tert-butyl-1-(1,2-dimetyl-3Hbenzo[
b]cyclopenta[d]thiophene-3-yl)-1,1-
15 (methyl)(phenyl)silaneamine
[00184]
[00185] (i) Preparation of chloro-1-(1,2-dimethyl-3Hbenzo[
b]cyclopenta[d]thiophene-3-yl)-1,1-
47
(methyl)(phenyl)silane
[00186] To a 250 ml schlenk flask, 10 g (1.0 eq, 49.925 mmol)
of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene and 100 ml
of THF were put, and 22 ml (1.1 eq, 54.918 mmol, 2.5 M in
5 hexane) of n-BuLi was added thereto dropwisely at -30°C,
followed by stirring at room temperature for 3 hours. A
stirred Li-complex THF solution was cannulated into a schlenk
flask containing 8.1 ml (1.0 eq, 49.925 mmol) of
dichloro(methyl)(phenyl)silane and 70 ml of THF at -78°C,
10 followed by stirring at room temperature overnight. After
stirring, drying in vacuum was carried out and extraction
with 100 ml of hexane was carried out.
[00187] (ii) Preparation of N-tert-butyl-1-(1,2-dimethyl-3Hbenzo[
b]cyclopenta[d]thiophene-3-yl)-1,1-
15 (methyl)(phenyl)silaneamine
[00188] To 100 ml of an extracted chloro-1-(1,2-dimethyl-3Hbenzo[
b]cyclopenta[d]thiophene-3-yl)-1,1-
(methyl)(phenyl)silane hexane solution, 42 ml (8 eq, 399.4
mmol) of t-BuNH2 was put at room temperature, followed by
20 stirring at room temperature overnight. After stirring,
drying in vacuum was carried out and extraction with 150 ml
of hexane was carried out. After drying the solvents, 13.36
g (68%, dr = 1:1) of a yellow solid was obtained.
[00189] 1H NMR (CDCl3, 500 MHz): δ 7.93 (t, 2H), 7.79 (d,1H),
25 7.71 (d,1H), 7.60 (d, 2H), 7.48 (d, 2H), 7.40-7.10 (m, 10H,
48
aromatic), 3.62 (s, 1H), 3.60 (s, 1H), 2.28 (s, 6H), 2.09 (s,
3H), 1.76 (s, 3H), 1.12 (s, 18H), 0.23 (s, 3H), 0.13 (s, 3H).
[00190]
[00191]
5 [00192] To a 100 ml schlenk flask, 4.93 g (12.575 mmol, 1.0
eq) of a ligand compound and 50 ml (0.2 M) of toluene were
put and 10.3 ml (25.779 mmol, 2.05 eq, 2.5M in hexane) of n-
BuLi was added thereto dropwisely at -30°C, followed by
stirring at room temperature overnight. After stirring, 12.6
10 ml (37.725 mmol, 3.0 eq, 3.0 M in diethyl ether) of MeMgBr
was added thereto dropwisely, 13.2 ml (13.204 mmol, 1.05 eq,
1.0 M in toluene) of TiCl4 was put in order, followed by
stirring at room temperature overnight. After stirring,
drying in vacuum and extraction with 150 ml of hexane were
15 carried out, the solvent was removed to 50 ml, and 4 ml
(37.725 mmol, 3.0 eq) of DME was added dropwisely, followed
by stirring at room temperature overnight. Again, drying in
vacuum and extraction with 150 ml of hexane were carried out.
49
After dying the solvents, 2.23 g (38%, dr = 1:0.5) of a brown
solid was obtained.
[00193] 1H NMR (CDCl3, 500 MHz): δ 7.98 (d, 1H), 7.94 (d, 1H),
7.71 (t, 6H), 7.50-7.30 (10H), 2.66 (s, 3H), 2.61 (s, 3H),
5 2.15 (s, 3H), 1.62 (s, 9H), 1.56 (s, 9H), 1.53 (s, 3H), 0.93
(s, 3H), 0.31 (s, 3H), 0.58 (s, 3H), 0.51 (s, 3H), -0.26 (s,
3H), -0.39 (s, 3H).
[00194] [Preparation of olefin-based copolymer]
10 [00195] Preparation Example 1
[00196] In a 1.5 L autoclave continuous process reactor, a
hexane solvent (7 kg/h) and 1-butene (0.95 kg/h) were charged,
and the top of the reactor was pre-heated to a temperature of
141°C. A triisobutylaluminum compound (0.05 mmol/min), the
15 transition metal compound (0.17 μmol/min) obtained in
Synthetic Example 1 as a catalyst, and a dimethylanilium
tetrakis(pentafluorophenyl) borate promoter (0.51 μmol/min)
were put into the reactor at the same time. Then, into the
autoclave reactor, ethylene (0.87 kg/h) and a hydrogen gas
20 (12 cc/min) were injected and a copolymerization reaction was
continuously carried out while maintaining a pressure of 89
bar and 141°C for 30 minutes or more to prepare a copolymer.
After drying for 12 hours or more, physical properties were
measured.
25
50
[00197] Preparation Example 2
[00198] An olefin-based copolymer was prepared by carrying
out the same method as in Preparation Example 1 except for
changing reaction conditions as shown in Table 1 below.
5
[00199] Comparative Preparation Example 1
[00200] DF7350 (Mitsui Co.) was purchased and used.
[00201] Comparative Preparation Example 2
10 [00202] EG8137 (Dow Co.) was purchased and used.
[00203] Comparative Preparation Examples 3 and 4: Preparation
of olefin-based copolymers
[00204] Copolymers were prepared by carrying out the same
15 method as in Preparation Example 1 except for using the
catalyst of Synthetic Example 1, not injecting a hydrogen gas,
and changing the amounts of other materials as shown in Table
1 below for Comparative Example 3, and using the catalyst of
Comparative Synthetic Example 1, and changing the amounts of
20 other materials as shown in Table 1 below as Comparative
Example 4.
[00205] Comparative Preparation Example 5
[00206] EG8842 (Dow Co.) was purchased and used.
25 [00207] [Table 1]
51
Catalyst
type
Catalyst
content
(μmol/mi
n)
Promot
er
(μmol/
min)
TiBAl
(mmol
/min)
Ethyle
ne
(kg/h)
Hydro
gen
(cc/m
in)
Hexan
e
(kg/h
)
Alpha olefin
monomer
Reaction
temperat
ure
(°C)
1-butene
(kg/h)
1-octene
(kg/h)
Preparation
Example 1
Synthetic
Example 1
0.17 0.51 0.05 0.87 12 7 0.95 - 141
Preparation
Example 2
Synthetic
Example 1
0.48 1.44 0.10 0.87 8 7 - 1.87 140
Comparative
Preparation
Example 1
DF7350
Comparative
Preparation
Example 2
EG8137
Comparative
Preparation
Example 3
Synthetic
Example 1
0.38 1.14 0.05 0.87 - 5 1 - 150
Comparative
Preparation
Example 4
Comparati
ve
Synthetic
Example 1
0.235 0.705 0.05 0.87 23 7 0.85 - 141
Comparative
Preparation
Example 5
EG8842
[00208] [Evaluation of physical properties of olefin-based
copolymer]
[00209] Experimental Example 1
5 [00210] With respect to the olefin-based copolymers of
Preparation Examples 1 and 2, and Comparative Preparation
Examples 1 to 5, physical properties were evaluated according
to the methods below and are shown in Table 2 below.
[00211] (1) Density
10 [00212] Measurement was conducted according to ASTM D-792.
[00213] (2) Melt index (MI)
[00214] Measurement was conducted according to ASTM D-1238
(condition E, 190°C, 2.16 kg load).
[00215] (3) Weight average molecular weight (g/mol) and
15 molecular weight distribution (MWD)
52
[00216] Number average molecular weight (Mn) and weight
average molecular weight (Mw) were measured respectively,
using gel permeation chromatography (GPC), and molecular
weight distribution was calculated through dividing the
5 weight average molecular weight by the number average
molecular weight. The weight average molecular weight (Mw)
thus measured and molecular weight distribution (MWD) show
values for the total fraction of the polymer prepared.
[00217] - column: PL Olexis
10 [00218] - solvent: trichlorobenzene (TCB)
[00219] - flow rate: 1.0 ml/min
[00220] - specimen concentration: 1.0 mg/ml
[00221] - injection amount: 200 μl
[00222] - column temperature: 160°C
15 [00223] - Detector: Agilent High Temperature RI detector
[00224] - Standard: Polystyrene (calibrated by cubic
function)
[00225] (4) Melting temperature (Tm)
[00226] The melting temperature was obtained using a
20 differential scanning calorimeter (DSC 6000) manufactured by
PerKinElmer Co. That is, the temperature was elevated to
200°C, kept for 1 minute, and decreased to -100°C, and then,
the temperature was elevated again. The apex of a DSC curve
was set to the melting point. In this case, the elevating
25 rate and decreasing rate of the temperature were controlled
53
to 10°C/min, and the melting point was obtained during the
second elevation of the temperature.
[00227] (5) Elution temperature (Te)
[00228] CFC of PolymerChar Co. was used as a measurement
5 apparatus. First, the polymer solution was completely
dissolved using o-dichlorobenzene as a solvent at 130°C for
60 minutes in an oven in a CFC analyzer, and then the
solution was introduced into a TREF column controlled to
130°C. Then, the column was cooled to 95°C and stabilized
10 for 45 minutes. Then, the temperature of the TREF column was
decreased to -20°C in a rate of 0.5°C/min, and was kept at -
20°C for 10 minutes. After that, an elution amount (mass%)
was measured using an infrared spectrophotometer. Then, the
temperature of the TREF column was increased in a rate of
15 20°C/min to a preset temperature and at the reached
temperature, the temperature was maintained for a preset time
(that is, about 27 minutes), and this work was repeated until
the temperature of the TREF reached 130°C, and the amount
(mass%) of an eluted fraction in each temperature range was
20 measured. In addition, a weight average molecular weight
(Mw) was measured by the same measurement principle of GPC
except for sending the eluted fraction at each temperature to
a GPC column and using o-dichlorobenzene as a solvent.
[00229] The elution temperature (Te) means a temperature
25 corresponding to the apex among peaks present after -20°C on
54
a graph of temperature vs. elution fraction.
[00230] (6) Measurement of soluble fraction (SF) content
[00231] The soluble fraction (SF) content means the amount of
a fraction eluted at -20°C or less, and the weight average
5 molecular weight of the soluble fraction (Mw(SF)) was
measured using a GPC column of CFC.
[00232] (7) Weight average molecular weight of soluble
fraction (Mw(SF)) and Mw:Mw(SF)
[00233] Mw:Mw(SF) was calculated as a ratio of the weight
10 average molecular weight (Mw) measured by GPC and the weight
average molecular weight of a soluble fraction (Mw(SF))
measured by CFC.
[00234] [Table 2]
Density
(g/cc)
MI
(g/10 min)
Mw MWD Tm (°C) Te (°C) SF (%) Mw (SF)
Mw:Mw
(SF)
Preparation
Example 1
0.8698 29.9 44043 2.03 55.6 17.0 5.0 25092 1.8:1
Preparation
Example 2
0.8674 12.6 65269 2.14 57.4 19.9 2.9 34750 1.9:1
Comparative
Preparation
Example 1
0.8700 29.5 44489 1.91 53.9 18.2 4.4 9877 4.5:1
Comparative
Preparation
Example 2
0.8700 30.3 47495 2.12 53.6 17.6 4.6 10481 4.5:1
Comparative
Preparation
Example 3
0.8702 28.3 45016 1.96 55.9 17.3 4.8 5587 8.1:1
Comparative
Preparation
Example 4
0.8690 12.5 63581 2.04 61.1 23.3 3.3 20800 3.1:1
Comparative
Preparation
Example 5
0.8590 0.95 132023 2.02 43.1 7.7 5.3 135552 0.97:1
[00235] As shown in Table 2, in Preparation Examples 1 and 2,
15 by which the olefin-based copolymers prepared by using the
transition metal compound of Formula 1 and injecting hydrogen,
55
the soluble fractions showed high values of a molecular
weight of 22,000 or more, and at the same time, ratios with
respect to the total weight average molecular weight of the
olefin-based copolymer were included in 0.9:1 to 2:1 and the
5 weight average molecular weights of the soluble fractions
showed similar levels as the total weight average molecular
weight.
[00236] In contrast, in Comparative Preparation Examples 1
and 2, which are commercially available, Comparative
10 Preparation Example 3 by which polymerization was conducted
without injecting hydrogen, and Comparative Preparation
Example 4 using the catalyst of Comparative Synthetic Example
1 which does not correspond to Formula 1, the weight average
molecular weights of soluble fractions were less than 22,000
15 g/mol, and ratios with respect to the weight average
molecular weight of the total olefin-based copolymer were
3.1:1 to 8.1:1, showing a large difference.
[00237] Particularly, as in Comparative Preparation Example 5,
it was confirmed that if the ratio of the weight average
20 molecular weight of the soluble fraction with respect to the
total weight average molecular weight was increased, the
maintenance of the melt index high and to 10 g/10 min or more,
at the same time, was difficult.
25 [00238] Example 1: Preparation of polypropylene-based
56
composite material
[00239] To 20 parts by weight of the olefin-based copolymer
prepared in Preparation Example 1, 60 parts by weight of
high-crystallinity impact copolymer polypropylene (CB5230,
5 DAELIM Industrial Co., Ltd.) having a melt index of 30 g/10
min, and 20 parts by weight of talc (KCNAP-400TM, Coats Co.)
(average particle diameter (D50) = 11.0 μm) were added, and
then, 0.01 parts by weight of AO1010 as an antioxidant, 0.01
parts by weight of tris(2,4-di-tert-butylphenyl)phosphite
10 (A0168), and 0.3 parts by weight of Ca-St as a slip agent
were added. Then, the resultant mixture was melted and
kneaded using a twin screw extruder to prepare a
polypropylene-based composite material compound in a pellet
shape. In this case, the twin screw extruder has a diameter
15 of 25 Φ and a ratio of length to diameter of 40, and
conditions were set to a barrel temperature of 160°C to 210°C,
a screw rotation velocity of 250 rpm, and an extrusion rate
of 25 kr/hr.
20 [00240] Examples 2 to 5, and Comparative Examples 1 to 11
[00241] Polypropylene-based composite materials were prepared
by the same method as in Example 1 except for changing the
type of olefin-based copolymers used, and the amount of each
material as in the table below.
25 [00242] [Table 3]
57
Olefin-based copolymer Polypropylene (parts by weight) Talc
(parts by
weight)
Type Parts by
weight
CB5230 (melt index
of 30 g/10 min)
CB5290 (melt index
of 90 g/10 min)
Example 1 Preparation
Example 1
20 60 0 20
Example 2 Preparation
Example 1
20 0 65 15
Example 3 Preparation
Example 1
20 0 60 20
Example 4 Preparation
Example 2
20 60 0 20
Example 5 Preparation
Example 2
30 0 50 20
Comparative
Example 1
Comparative
Preparation
Example 1
20 60 0 20
Comparative
Example 2
Comparative
Preparation
Example 2
20 60 0 20
Comparative
Example 3
Comparative
Preparation
Example 5
20 60 0 20
Comparative
Example 4
Comparative
Preparation
Example 1
20 0 65 15
Comparative
Example 5
Comparative
Preparation
Example 2
20 0 65 15
Comparative
Example 6
Comparative
Preparation
Example 1
20 0 60 20
Comparative
Example 7
Comparative
Preparation
Example 2
20 0 60 20
Comparative
Example 8
Comparative
Preparation
Example 3
20 0 60 20
Comparative
Example 9
Comparative
Preparation
Example 3
20 60 0 20
Comparative
Example 10
Comparative
Preparation
Example 4
20 60 0 20
Comparative
Example 11
Comparative
Preparation
Example 4
30 0 50 20
[00243] However, in Comparative Example 3, since the melt
index of a copolymer was very low and processability was bad,
the successful preparation of a polypropylene-based composite
material by the above-described preparation method was very
5 difficult.
58
[00244] Experimental Example 2: Evaluation of physical
properties of polypropylene-based composite material
[00245] With respect to the polypropylene-based copolymers of
5 the Examples and Comparative Examples, specimens were
manufactured by injection molding using an injection machine
at a temperature of 200°C and stood in a constant temperature
and humidity room for 1 day, and physical properties were
measured according to the methods below.
10 [00246] (1) Density
[00247] Measurement was conducted according to ASTM D-792.
[00248] (2) Melt index (M1)
[00249] Measurement was conducted according to ASTM D-1238
(condition E, 230°C, 2.16 kg load).
15 [00250] (3) Tensile strength
[00251] Measurement was conducted using INSTRON 3365
apparatus according to ASTM D638.
[00252] (4) Flexural strength and flexural modulus
[00253] Measurement was conducted using INSTRON 3365
20 apparatus according to ASTM D790.
[00254] (5) Impact strength at low temperature and at room
temperature
[00255] Measurement was conducted according to ASTM D256,
impact strength at low temperature was measured at -30°C
25 after 12 hours, and impact strength at room temperature was
59
measured at 23°C after 48 hours.
[00256] [Table 4]
Specific
gravity
(g/ml)
Melt
index
(g/10
min)
Tensile
strength
(kgf/cm2)
Flexural
strength
(kgf/cm2)
Flexural
modulus
(kgf/cm2)
Impact
strength at
low
temperature
(kgf·m/m)
Impact
strength at
high
temperature
(kgf·m/m)
Example 1 1.026 23.0 225 341 19861 3.7 22.8
Comparative
Example 1
1.032 23.1 223 338 19614 3.5 21.5
Comparative
Example 2
1.033 23.6 215 325 19613 3.4 21.6
[00257] [Table 5]
Specific
gravity
(g/ml)
Melt
index
(g/10
min)
Tensile
strength
(kgf/cm2)
Flexural
strength
(kgf/cm2)
Flexural
modulus
(kgf/cm2)
Impact
strength at
low
temperature
(kgf·m/m)
Impact
strength at
high
temperature
(kgf·m/m)
Example 2 0.993 38.4 217 330 18915 4.1 22.4
Comparative
Example 4
0.999 37.0 217 329 18511 3.8 22.3
Comparative
Example 5
0.999 36.7 208 318 18715 3.8 20.8
[00258] [Table 6]
Specific
gravity
(g/ml)
Melt
index
(g/10
min)
Tensile
strength
(kgf/cm2)
Flexural
strength
(kgf/cm2)
Flexural
modulus
(kgf/cm2)
Impact
strength at
low
temperature
(kgf·m/m)
Impact
strength at
high
temperature
(kgf·m/m)
Example 3 1.039 34.9 214 327 19840 3.8 22.9
Comparative
Example 6
1.033 34.7 212 327 19500 3.6 22.3
Comparative
Example 7
1.025 32.3 210 317 19231 3.6 22.6
Comparative
Example 8
1.032 33.9 201 309 19104 3.4 20.2
5 [00259] [Table 7]
Specific
gravity
(g/ml)
Melt
index
(g/10
min)
Tensile
strength
(kgf/cm2)
Flexural
strength
(kgf/cm2)
Flexural
modulus
(kgf/cm2)
Impact
strength at
low
temperature
(kgf·m/m)
Impact
strength at
high
temperature
(kgf·m/m)
Example 4 1.030 22.5 221 344 19998 3.7 33.8
Comparative
Example 9
1.028 22.7 205 315 19556 3.2 30.5
Comparative
Example 10
1.037 21.2 221 343 19990 3.5 33.1
[00260] [Table 8]
Specific
gravity
Melt
index
Tensile
strength
Flexural
strength
Flexural
modulus
Impact
strength at
Impact
strength at
60
(g/ml) (g/10
min)
(kgf/cm2) (kgf/cm2) (kgf/cm2) low
temperature
(kgf·m/m)
high
temperature
(kgf·m/m)
Example 5 1.019 29.2 171 236 13489 8.8 54.1
Comparative
Example 11
1.022 26.5 170 235 13477 8.3 53.1
[00261] In Tables 4 to 8 above, the Examples and the
Comparative Examples are correspondingly summarized, in which
the type of the olefin-based copolymer was changed but the
composition formulation was the same.
5 [00262] As described above, the polypropylene-based composite
material of Comparative Example 3 was intended to prepare by
using Comparative Preparation Example 5 having a very low
melt index of 0.95 g/10 min, processability was very inferior,
and successful preparation of a polypropylene-based composite
10 material was difficult, because a copolymer having a very low
melt index was used.
[00263] Meanwhile, as shown in the Tables, all the
polypropylene-based composite materials of the Examples
prepared by using the olefin-based copolymers of the
15 Preparation Examples according to the present invention were
confirmed to show improved physical properties including the
impact strength at low temperature and at high temperature
when compared with the Comparative Examples.
[00264] As described above, by preparing a polypropylene20
based composite material using an olefin-based copolymer
satisfying all the conditions defined in the present
invention, a polypropylene-based composite material may be
61
easily prepared with excellent processability. Also, it is
confirmed that since high impact strength at low temperature
and at high temperature is achieved, and processability is
excellent, a polypropylene-based composite material
5 applicable to various usages may be prepared.

CLAIMS

1. A polypropylene-based composite material comprising
polypropylene; and
5 an olefin-based copolymer satisfying the following
conditions (a) to (c):
(a) a melt index (MI, 190°C, 2.16 kg load conditions)
is 10 to 100 g/10 min,
(b) a soluble fraction (SF) at -20°C measured by cross10
fractionation chromatography (CFC) is 0.5 to 10 wt%, where a
weight average molecular weight of the soluble fraction
(Mw(SF)) is 22,000 or more, and
(c) a value of Mw:Mw(SF), which is a ratio of a weight
average molecular weight of the olefin-based copolymer (Mw)
15 and the weight average molecular weight of the soluble
fraction (Mw(SF), is 0.9:1 to 2:1.
2. The polypropylene-based composite material according to
claim 1, wherein the polypropylene is an impact copolymer
20 having a melt index (230°C, 2.16 kg load conditions) of 0.5
to 150 g/10 min.
3. The polypropylene-based composite material according to
claim 1, wherein the weight average molecular weight of the
25 olefin-based copolymer is from 10,000 to 100,000 g/mol.
63
4. The polypropylene-based composite material according to
claim 1, wherein molecular weight distribution of the olefinbased
copolymer is from 1.5 to 3.0.
5
5. The polypropylene-based composite material according to
claim 1, wherein the polypropylene-based composite material
comprises the olefin-based copolymer in 5 to 70 wt%.
10 6. The polypropylene-based composite material according to
claim 1, wherein the olefin-based copolymer is a copolymer of
ethylene and an alpha-olefin-based comonomer of 3 to 12
carbon atoms.
15 7. A method for preparing the polypropylene-based
composite material of claim 1, the method comprising
(S1) a step of preparing polypropylene;
(S2) a step of preparing an olefin-based copolymer by a
method comprising polymerizing an olefin-based monomer by
20 injecting hydrogen in 10 to 100 cc/min in the presence of a
catalyst composition comprising a transition metal compound
represented by the following Formula 1; and
(S3) a step of melting and kneading the polypropylene
and the olefin-based copolymer:
25 [Formula 1]
64
in Formula 1,
R1 is hydrogen; alkyl of 1 to 20 carbon atoms; alkenyl
of 2 to 20 carbon atoms; alkoxy of 1 to 20 carbon atoms; aryl
5 of 6 to 20 carbon atoms; arylalkoxy of 7 to 20 carbon atoms;
alkylaryl of 7 to 20 carbon atoms; or arylalkyl of 7 to 20
carbon atoms,
R2 and R3 are each independently hydrogen; halogen;
alkyl of 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon
10 atoms; arylalkyl of 7 to 20 carbon atoms; alkylamido of 1 to
20 carbon atoms; or arylamido of 6 to 20 carbon atoms,
R4 to R9 are each independently hydrogen; silyl; alkyl
of 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon atoms;
aryl of 6 to 20 carbon atoms; alkylaryl of 7 to 20 carbon
15 atoms; arylalkyl of 7 to 20 carbon atoms; or a metalloid
radical of a metal in group 14, which is substituted with
hydrocarbyl of 1 to 20 carbon atoms,
65
adjacent two or more among the R2 to R9 are optionally
connected with each other to form a ring,
Q is Si; C; N; P; or S,
M is a transition metal in group 4, and
5 X1 and X2 are each independently hydrogen; halogen;
alkyl of 1 to 20 carbon atoms; alkenyl of 2 to 20 carbon
atoms; aryl of 6 to 20 carbon atoms; alkylaryl of 7 to 20
carbon atoms; arylalkyl of 7 to 20 carbon atoms; alkylamino
of 1 to 20 carbon atoms; or arylamino of 6 to 20 carbon atoms.
10
8. The method for preparing the polypropylene-based
composite material according to claim 7, wherein
R1 is hydrogen; alkyl of 1 to 20 carbon atoms; alkoxy
of 1 to 20 carbon atoms; aryl of 6 to 20 carbon atoms;
15 arylalkoxy of 7 to 20 carbon atoms; alkylaryl of 7 to 20
carbon atoms; or arylalkyl of 7 to 20 carbon atoms,
R2 and R3 are each independently hydrogen; alkyl of 1 to
20 carbon atoms; aryl of 6 to 20 carbon atoms; or alkylaryl
of 6 to 20 carbon atoms,
20 R4 to R9 are each independently hydrogen; alkyl of 1 to
20 carbon atoms; aryl of 6 to 20 carbon atoms; alkylaryl of 7
to 20 carbon atoms; or arylalkyl of 7 to 20 carbon atoms,
adjacent two or more among the R2 to R9 are optionally
connected with each other to form an aliphatic ring of 5 to
25 20 carbon atoms or an aromatic ring of 6 to 20 carbon atoms,
66
the aliphatic ring or the aromatic ring are optionally
substituted with halogen, alkyl of 1 to 20 carbon atoms,
alkenyl of 2 to 20 carbon atoms, or aryl of 6 to 20 carbon
atoms, and
5 Q is Si; C; N; or P.
9. The method for preparing the polypropylene-based
composite material according to claim 7, wherein
R1 is alkyl of 1 to 20 carbon atoms; aryl of 6 to 20
10 carbon atoms; arylalkoxy of 7 to 20 carbon atoms; or
arylalkyl of 7 to 20 carbon atoms,
R2 and R3 are each independently hydrogen; alkyl of 1 to
20 carbon atoms; or aryl of 6 to 20 carbon atoms,
R4 to R9 are each independently hydrogen; alkyl of 1 to
15 20 carbon atoms; or aryl of 6 to 20 carbon atoms, and
Q is Si.
10. The method for preparing the polypropylene-based
composite material according to claim 7, wherein the
20 transition metal compound represented by Formula 1 is
selected from the group consisting of compounds of the
following Formula 1-1 to Formula 1-6.
[Formula 1-1] [Formula 1-2] [Formula 1-3]
[Formula 1-4] [Formula 1-5] [Formula 1-6]
5
11. The method for preparing the polypropylene-based
composite material according to claim 7, wherein the
polymerization is carried out at 50 to 200°C.