technical field
[One]
[Correction with related applications]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0121151 dated September 30, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
The present invention relates to a polypropylene-based composite, and more particularly, to a polypropylene-based composite having improved impact strength and mechanical properties including a low-density olefin-based polymer having high mechanical rigidity introduced by a high crystallinity region.
background
[4]
In general, as a composition for automobile interior and exterior parts, a polypropylene-based resin composition containing polypropylene (PP) as a main component and an impact reinforcing material and an inorganic filler has been used.
[5]
Until the mid-1990s, before the development of ethylene-α-olefin copolymers polymerized by applying a metallocene catalyst, most polypropylene-based resin compositions were either EPR (Ethylene Propylene Rubber) or EPDM as materials for automobile interior and exterior materials, especially bumper covers. (ethylene propylene diene rubber) was mainly used as an impact reinforcing material. However, after the appearance of the ethylene-α-olefin copolymer synthesized by the metallocene catalyst, the ethylene-α-olefin copolymer has been used as an impact modifier and is now the mainstream. This is because the polypropylene-based composite material using this material has many advantages such as good formability and low price with balanced physical properties such as impact strength, elastic modulus, and flexural strength.
[6]
Polyolefins such as ethylene-α-olefin copolymer synthesized by a metallocene catalyst have a narrow molecular weight distribution and good mechanical properties because their molecular structure is more uniformly controlled than that of a Ziegler-Natta catalyst. Even in the low-density ethylene elastomer polymerized by the metallocene catalyst, since the α-olefin copolymer monomer is relatively uniformly intercalated into the polyethylene (PE) molecule than that by the Ziegler-Natta catalyst, other mechanical properties while maintaining the low-density rubber properties It also has good physical properties.
[7]
However, there is a limit to securing impact resistance according to various usage environments, and the development of a polypropylene-based composite that can overcome this limit is required.
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[8]
An object of the present invention is to provide a polypropylene-based composite that can exhibit significantly improved impact strength properties along with excellent mechanical strength.
means of solving the problem
[9]
In order to solve the above problems, the present invention provides a polypropylene-based composite including (A) polypropylene, and (B) an olefin-based polymer satisfying the requirements of (1) to (3) below.
[10]
(1) Melt Index (MI, 190°C, 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min, (2) Differential scanning calorimetry (DSC) measurement, the melting temperature is 20° C to 70 ℃, and (3) when measured by differential scanning calorimetry precision measurement (SSA), a high-temperature melting peak is confirmed at 75°C to 150°C, and the sum ΔH(75) of the melting enthalpy of the region is 1.0 J/g or more.
Effects of the Invention
[11]
The polypropylene-based composite according to the present invention includes an olefin-based polymer that exhibits high mechanical rigidity by introducing a high crystallinity region and can be uniformly dispersed in the composite with excellent compatibility with polypropylene. It is possible to exhibit significantly improved impact strength properties along with excellent mechanical strength without
Brief description of the drawing
[12]
1 is a graph showing the results of measuring the melting temperature of the polymer of Preparation Example 1 using a differential scanning calorimeter (DSC).
[13]
2 is a graph showing the results of measuring the melting temperature of the polymer of Comparative Preparation Example 1 using a differential scanning calorimeter (DSC).
[14]
3 is a graph showing the result of measuring the sum of enthalpy of melting ΔH (75) at 75° C. to 150° C. by differential scanning calorimetry precision measurement (SSA) for the polymer of Preparation Example 1;
[15]
4 is a graph showing the result of measuring the sum of enthalpy of melting ΔH (75) at 75° C. to 150° C. by differential scanning calorimetry precision measurement (SSA) for the polymer of Comparative Preparation Example 1.
Best mode for carrying out the invention
[16]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[17]
The terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[18]
As used herein, the term "polymer" means a polymer compound prepared by polymerization of monomers of the same or different types. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". Also, the term “interpolymer” refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term "copolymer" (which is commonly used to refer to polymers prepared from two different monomers), as well as the term "copolymer" (which is commonly used to refer to polymers prepared from three different types of monomers). used) the term "terpolymer". This includes polymers prepared by polymerization of four or more types of monomers.
[19]
[20]
In general, polypropylene is used as an interior and exterior material for automobiles such as automobile bumpers, and polyolefin-based polymers are also used as an impact reinforcing material to supplement the low impact strength of polypropylene. Among them, low-density polyolefin-based polymers are used to have high impact strength properties while exhibiting properties such as impact resistance, elastic modulus, and tensile properties according to various usage environments, but in this case, the problem of lowering the strength of polypropylene is rather there was.
[21]
[22]
In contrast, in the present invention, when the polypropylene-based composite is manufactured, an olefin-based polymer that exhibits an excellent impact strength improvement effect and can be uniformly dispersed in the composite with excellent compatibility with polypropylene is used, thereby providing excellent performance without using a separate additive. It can exhibit significantly improved impact strength properties along with mechanical strength.
[23]
[24]
The polypropylene-based composite material according to the present invention includes (A) polypropylene and (B) an olefin-based polymer satisfying the requirements of (1) to (3) below.
[25]
(1) Melt Index (MI, 190°C, 2.16 kg load condition) is 0.1 g/10 min to 10.0 g/10 min, (2) Differential scanning calorimetry (DSC) measurement, the melting temperature is 20° C to 70 ℃, and (3) when measured by differential scanning calorimetry precision measurement (SSA), a high-temperature melting peak is confirmed at 75°C to 150°C, and the sum ΔH(75) of the melting enthalpy of the region is 1.0 J/g or more.
[26]
[27]
Hereinafter, each component will be described in detail.
[28]
[29]
(A) polypropylene
[30]
In the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene may be specifically a polypropylene homopolymer or a copolymer of propylene and an alpha-olefin monomer, wherein the copolymer is alternately ( alternating) or random, or block copolymers. However, in the present invention, the polypropylene is a compound that may overlap with the olefin polymer, and is a different compound from the olefin polymer.
[31]
The alpha-olefin-based monomer may specifically be an aliphatic olefin having 2 to 12 carbon atoms, or 2 to 8 carbon atoms. More specifically, 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-aitocene, 4,4-dimethyl-1-pentene, 4,4- and diethyl-1-hexene or 3,4-dimethyl-1-hexene, and any one or a mixture of two or more thereof may be used.
[32]
More specifically, the polypropylene may be any one or a mixture of two or more selected from the group consisting of a polypropylene copolymer, a propylene-alpha-olefin copolymer, and a propylene-ethylene-alpha-olefin copolymer, wherein the public Copolymers may be random or block copolymers.
[33]
[34]
In addition, the polypropylene has a melt index (MI) of 0.5 g/10min to 100 g/10min measured at 230°C and a load of 2.16 kg, specifically, the melt index (MI) is 1 g/10min to 90 g/ It may be 10 min, and more specifically, it may be 10 g/10 min to 50 g/10 min. If the melt index of polypropylene is out of the above range, there is a possibility that a problem may occur during injection molding.
[35]
Specifically, in the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene has a melt index (MI) of 0.5 g/10min to 100 g/10min, specifically measured at 230°C and a load of 2.16 kg. It may be an impact copolymer of 1 g/10min to 90 g/10min, and more specifically, it may be a propylene-ethylene impact copolymer, and the impact copolymer is 50 weight based on the total weight of the polypropylene-based composite material. % to 90% by weight, more specifically 80% to 90% by weight may be included. When the impact copolymer having such physical properties is included in the above-described content range as polypropylene, strength characteristics, particularly low temperature strength characteristics, may be improved.
[36]
The above-mentioned impact copolymer may be prepared to satisfy the above-mentioned physical property requirements using a conventional polymer manufacturing reaction, or may be commercially obtained and used. Specific examples include SEETE™ M1600 manufactured by LG Chem.
[37]
[38]
In addition In one embodiment, in the polypropylene-based composite material according to an embodiment of the present invention, the polypropylene has a DSC melting point in the range of 120° C. to 160° C., and 230° C. according to ASTM-D 1238, measured under load conditions of 2.16 kg , at least one random propylene copolymer having a melt flow rate (MFR) in the range of 5 g/10 min to 120 g/10 min, wherein the random propylene copolymer is 75 wt% to 97 wt% based on the total weight of the polypropylene-based composite , more specifically, may be included in an amount of 85 wt% to 91 wt%. When polypropylene having such physical properties is included in the above-described content range, mechanical strength of the polypropylene composite material such as hardness can be improved. The random propylene copolymer may be prepared to satisfy the above-mentioned physical property requirements using a conventional polymer preparation reaction, or may be commercially obtained and used. As a specific example, Braskem™ PP R7021-50RNA from Braskem America Inc. or Formolene™ 7320A from Formosa Plastics Corporation may be mentioned.
[39]
[40]
(B) Olefin-based polymer
[41]
The olefin-based polymer included in the polypropylene-based composite according to the present invention has an ultra-low density, and a high crystallinity region is introduced compared to a conventional olefin-based polymer, so that the same level of density and melt index (Melt Index, MI, 190° C.) , 2.16 kg load condition), indicating higher tensile strength and tear strength. The olefin-based polymer included in the polypropylene-based composite according to the present invention is prepared by a manufacturing method comprising the step of polymerizing an olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for polymerization, and hydrogen gas during polymerization A highly crystalline region is introduced according to the input, thereby exhibiting excellent mechanical rigidity.
[42]
[43]
The melt index (MI) can be adjusted by controlling the amount of the catalyst used in the process of polymerizing the olefin-based polymer for the comonomer, and affects the mechanical properties and impact strength, and moldability of the olefin-based polymer. In the present specification, the melt index is measured at 190 ° C., 2.16 kg load condition according to ASTM D1238 under low density conditions of 0.850 g / cc to 0.890 g / cc, 0.1 g / 10 minutes to 10 g / 10 minutes and specifically 0.3 g/10 min to 9 g/10 min, more specifically 0.4 g/10 min to 7 g/10 min.
[44]
When measured by differential scanning calorimetry (DSC), the melting point (Tm) may be 20°C to 70°C, specifically 20°C to 60°C, and more specifically 25°C to 50°C.
[45]
A high-temperature melting peak is confirmed at 75°C to 150°C during differential scanning calorimetry precision measurement (SSA), and specifically, the region may be 75°C to 145°C, and more specifically 75°C to 135°C. At this time, the total ΔH (75) of the melting enthalpy of the corresponding region may be 1.0 J/g or more, specifically 1.0 J/g to 3.0 J/g, and more specifically 1.0 J/g to 2.0 J/g. there is.
[46]
In general, the melting temperature (Tm) using a differential scanning calorimeter (DSC) is heated at a constant rate to a temperature approximately 30°C higher than the melting temperature (Tm), and then the temperature is approximately 30°C lower than the glass transition temperature (Tg). After the first cycle of cooling at a constant rate to The differential scanning calorimeter precision measurement (SSA) measurement is performed by heating and cooling to a temperature just before the peak of the melting temperature (Tm) after the first cycle using a differential scanning calorimeter (DSC). This is a method to obtain more precise crystal information by repeatedly performing heating and cooling processes (Eur. Polym. J. 2015, 65, 132).
[47]
When a small amount of highly crystalline region is introduced into the olefinic polymer, it does not appear when measuring the melting temperature using a general differential scanning calorimeter (DSC), and the high-temperature melting peak can be measured through the differential scanning calorimeter precision measurement (SSA).
[48]
In the olefin-based polymer, a high-temperature melting peak is confirmed in the above temperature range when measured by differential scanning calorimetry (SSA), and at this time, the melting enthalpy ΔH (75) of the corresponding region satisfies the above range, so that a conventional conventional olefin-based polymer When it has the same level of density and melt index values ​​as compared to , higher mechanical rigidity can be obtained.
[49]
On the other hand, the olefin-based polymer may further satisfy the requirement of (4) a density (d) of 0.850 g/cc to 0.890 g/cc, specifically, the density may be 0.850 g/cc to 0.880 g/cc, , more specifically 0.860 g/cc to 0.875 g/cc.
[50]
In general, the density of the olefin-based polymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like. The olefin-based polymer included in the polypropylene-based composite of the present invention is polymerized using a catalyst composition including a transition metal compound having a characteristic structure, and a large amount of comonomer can be introduced, so a low density in the range as described above can have
[51]
In addition, the olefin-based polymer may further satisfy the requirement (5) that the weight average molecular weight (Mw) is 10,000 g/mol to 500,000 g/mol, and specifically, the weight average molecular weight (Mw) is 30,000 g/mol to 30,000 g/mol 300,000 g/mol, more specifically 50,000 g/mol to 200,000 g/mol. In the present invention, the weight average molecular weight (Mw) is a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).
[52]
In addition, the olefin-based polymer additionally satisfies the requirement that the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (6) Molecular Weight Distribution (MWD) is 0.1 to 6.0. And, the molecular weight distribution (MWD) may be specifically 1.0 to 4.0, more specifically 2.0 to 3.0.
[53]
[54]
The olefin-based polymer is an olefin-based monomer, specifically, 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 It may be a copolymer of the above. More specifically, the olefin-based polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 12 carbon atoms or a copolymer of an alpha-olefin having 3 to 10 carbon atoms.
[55]
The alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5 - It may include any one or a mixture of two or more selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
[56]
More specifically, the olefin-based polymer may be a copolymer of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1-octene, and more specifically For example, the olefin-based polymer may be a copolymer of ethylene and 1-butene.
[57]
When the olefinic polymer is a copolymer of ethylene and alpha-olefin, the amount of the alpha-olefin is 90% by weight or less, more specifically 70% by weight or less, and even more specifically 5 to 60% by weight based on the total weight of the copolymer. It may be weight %, and more specifically, it may be 20 weight % to 50 weight %. When the alpha-olefin is included in the above range, it is easy to implement the above-described physical properties.
[58]
The olefin-based polymer included in the polypropylene-based composite according to an embodiment of the present invention having the above physical properties and structural characteristics is in the presence of a metallocene catalyst composition including one or more transition metal compounds in a single reactor. It may be prepared through a continuous solution polymerization reaction in which hydrogen gas is introduced and an olefinic monomer is polymerized. Accordingly, in the olefin-based polymer included in the polypropylene-based composite according to an embodiment of the present invention, a block is not formed in which two or more repeating units derived from any one of the monomers constituting the polymer in the polymer are linearly connected. . That is, the olefin-based polymer included in the polypropylene-based composite according to the present invention does not include a block copolymer, and a random copolymer, an alternating copolymer, and a graft copolymer. copolymer) may be selected from the group consisting of, and more specifically, may be a random copolymer.
[59]
In an example of the present invention, the amount of hydrogen gas added may be 0.35 to 3 parts by weight, specifically 0.4 to 2 parts by weight, and more specifically 0.45 to 1.5 parts by weight, based on 1 part by weight of the olefinic monomer added to the reaction system. can be negative In addition, in an example of the present invention, when the olefin-based polymer is polymerized by continuous solution polymerization, the hydrogen gas is 0.35 to 3 kg/h, specifically 0.4, based on 1 kg/h of the olefinic monomer introduced into the reaction system. to 2 kg/h, more specifically 0.45 to 1.5 kg/h.
[60]
In addition, in another example of the present invention, when the olefin-based polymer is a copolymer of ethylene and alpha-olefin, the hydrogen gas is 0.8 to 3 parts by weight based on 1 part by weight of ethylene.It may be added in an amount of parts, specifically 0.9 to 2.8 parts by weight, more specifically 1 to 2.7 parts by weight. In addition, in an example of the present invention, when the olefin-based polymer is a copolymer of ethylene and alpha-olefin, and polymerized by continuous solution polymerization, the hydrogen gas is 0.8 to 1 kg/h of ethylene introduced into the reaction system. 3 kg/h, specifically 0.9 to 2.8 kg/h, more specifically 1 to 2.7 kg/h.
[61]
When the polymerization is performed under the conditions in which the hydrogen gas is introduced in an amount within the above range, the olefin-based polymer of the present invention may satisfy the above-described physical properties.
[62]
Specifically, the olefin-based copolymer included in the polypropylene-based composite of the present invention is a step of polymerizing the olefin-based monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below It can be obtained by a manufacturing method comprising
[63]
However, in the preparation of the olefin-based polymer according to an embodiment of the present invention, the scope of the structure of the transition metal compound of Chemical Formula 1 is not limited to a specific disclosed form, and all items included in the spirit and technical scope of the present invention are not limited. It is to be understood as including modifications, equivalents and substitutions.
[64]
[Formula 1]
[65]

[66]
In Formula 1,
[67]
R 1 is the same as or different from each other, and each independently represents a Group 4 metal substituted with hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl, silyl, alkylaryl, arylalkyl, or hydrocarbyl. a metalloid radical, wherein the two R 1 may be connected to each other by an alkylidine radical including an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form a ring;
[68]
R 2 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; an amido radical, wherein two or more of R 2 may be connected to each other to form an aliphatic ring or an aromatic ring;
[69]
R 3 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen, substituted or unsubstituted with an aryl radical, and when the substituents are plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;
[70]
M is a Group 4 transition metal;
[71]
Q 1 and Q 2 are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or an alkylidene radical having 1 to 20 carbon atoms.
[72]
[73]
In addition, in another example of the present invention, in Formula 1, R 1 and R 2 are the same as or different from each other, and each independently hydrogen; alkyl having 1 to 20 carbon atoms; aryl; or silyl,
[74]
R 3 are the same as or different from each other, and alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl; alkylaryl; arylalkyl; alkoxy having 1 to 20 carbon atoms; aryloxy; or amido; At least two of R 6 may be connected to each other to form an aliphatic or aromatic ring;
[75]
The Q 1 and Q 2 are the same as or different from each other, and each independently halogen; alkyl having 1 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; may be arylamido,
[76]
M may be a Group 4 transition metal.
[77]
[78]
The transition metal compound represented by Formula 1 has a metal site connected by a cyclopentadienyl ligand into which tetrahydroquinoline is introduced, and thus the Cp-MN angle is structurally narrow, and Q 1-MQ 2 (Q 3 -MQ 4) The angle is kept wide. In addition, Cp, tetrahydroquinoline, nitrogen and metal sites are sequentially linked by a ring bond to form a more stable and rigid pentagonal ring structure. Therefore, when these compounds are activated by reacting them with a cocatalyst such as methylaluminoxane or B(C 6F 5) 3 and then applied to olefin polymerization, they have characteristics such as high activity, high molecular weight and high copolymerizability even at high polymerization temperatures. It is possible to polymerize olefinic polymers.
[79]
[80]
Each of the substituents defined in the present specification will be described in detail as follows.
[81]
As used herein, the term 'hydrocarbyl group' is, unless otherwise specified, the number of carbon atoms consisting of only carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl. It means a monovalent hydrocarbon group of 1 to 20.
[82]
As used herein, the term 'halogen' means fluorine, chlorine, bromine or iodine, unless otherwise specified.
[83]
The term 'alkyl' as used herein, unless otherwise specified, refers to a straight-chain or branched hydrocarbon residue.
[84]
As used herein, the term 'cycloalkyl' refers to cyclic alkyl including cyclopropyl and the like, unless otherwise specified.
[85]
As used herein, the term 'alkenyl' refers to a straight-chain or branched alkenyl group, unless otherwise specified.
[86]
The branched chain is alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
[87]
The term 'aryl' as used herein, unless otherwise specified, represents an aromatic group having 6 to 20 carbon atoms, specifically phenyl, naphthyl, anthryl, phenanthryl, chrysenyl, pyrenyl, anthracenyl, pyridyl, dimethyl anilinyl, anisolyl, and the like, but is not limited thereto.
[88]
The alkylaryl group means an aryl group substituted by the alkyl group.
[89]
The arylalkyl group means an alkyl group substituted by the aryl group.
[90]
The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 ring atoms and containing at least one hetero atom, and may be a single ring or a condensed ring of two or more rings. In addition, the heterocyclic group may be unsubstituted or substituted with an alkyl group. Examples thereof include indoline and tetrahydroquinoline, but the present invention is not limited thereto.
[91]
The alkyl amino group refers to an amino group substituted by the alkyl group, and includes, but is not limited to, a dimethylamino group and a diethylamino group.
[92]
According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is limited to these examples only. not.
[93]
In the present specification, silyl may be silyl unsubstituted or substituted with alkyl having 1 to 20 carbon atoms, for example, silyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl , triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris(trimethylsilyl)silyl, and the like, but are not limited thereto.
[94]
[95]
The compound of Formula 1 may be of Formula 1-1, but is not limited thereto.
[96]
[Formula 1-1]
[97]

[98]
In addition, it may be a compound having various structures within the range defined in Formula 1 above.
[99]
[100]
Since the transition metal compound of Formula 1 can introduce a large amount of alpha-olefin as well as low-density polyethylene due to the structural characteristics of the catalyst, it is possible to prepare a low-density polyolefin copolymer of 0.850 g/cc to 0.890 g/cc. .
[101]
The transition metal compound of Formula 1 may be prepared by the following method as an example.
[102]
[Scheme 1]
[103]

[104]
[105]
In Scheme 1, R 1 to R 3, M, Q 1 and Q 2 are as defined in Formula 1 above.
[106]
Formula 1 may be prepared according to the method described in Korean Patent Publication No. 2007-0003071, and the entire contents of the patent document are included in the present specification.
[107]
[108]
The transition metal compound of Formula 1 may be used as a catalyst for polymerization in the form of a composition further comprising at least one of the cocatalyst compounds represented by Formula 2, Formula 3, and Formula 4 in addition to the above.
[109]
[Formula 2]
[110]
-[Al(R 4)-O] a-
[111]
[Formula 3]
[112]
A(R 4) 3
[113]
[Formula 4]
[114]
[L-H] +[W(D) 4] - or [L] +[W(D) 4] -
[115]
In Formulas 2 to 3,
[116]
R 4 may be the same as or different from each other, and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[117]
A is aluminum or boron,
[118]
D is each independently aryl having 6 to 20 carbons or alkyl having 1 to 20 carbons in which one or more hydrogen atoms may be substituted with a substituent, wherein the substituents are halogen, hydrocarbyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons and at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,
[119]
H is a hydrogen atom,
[120]
L is a neutral or cationic Lewis base,
[121]
W is a group 13 element,
[122]
a is an integer greater than or equal to 2;
[123]
Examples of the compound represented by Formula 2 include alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and two or more of the alkylaluminoxanes are mixed and modified alkylaluminoxane, and specifically may be methylaluminoxane and modified methylaluminoxane (MMAO).
[124]
represented by the above formula (3) Examples of compounds to be used include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, Triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron , triisobutyl boron, tripropyl boron, tributyl boron, and the like, and specifically, may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.
[125]
Examples of the compound represented by Formula 4 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, and trimethylammoniumtetra (o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N -Diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, dimethyl Anilinium tetrakis(pentafluorophenyl)borate, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tri Propylammonium tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum , tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammoniumtetrapentafluorophenylaluminum, triphenyl Phosphonium tetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl) ) boron or triphenylcarboniumtetrapentafluorophenylboron.
[126]
The catalyst composition, as a first method, 1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 2 or Formula 3 to obtain a mixture; and 2) adding the compound represented by Formula 4 to the mixture.
[127]
In addition, the catalyst composition may be prepared by contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 4 as a second method.
[128]
In the case of the first method among the methods for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 to the compound represented by Formula 2 or Formula 3 is 1/ It may be 5,000 to 1/2, specifically 1/1,000 to 1/10, and more specifically 1/500 to 1/20. When the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 2 or Formula 3 exceeds 1/2, the amount of the alkylating agent is very small, and there is a problem that the alkylation of the metal compound cannot proceed completely, , when the molar ratio is less than 1/5,000, the metal compound is alkylated, but due to a side reaction between the remaining excess alkylating agent and the activator, which is the compound of Formula 4, there is a problem in that the activation of the alkylated metal compound cannot be completed. . In addition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 may be 1/25 to 1, specifically 1/10 to 1, and more specifically 1/5 to can be 1. When the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 exceeds 1, the amount of the activator is relatively small, so the activation of the metal compound is not completely achieved, and thus the activity of the catalyst composition may fall, and if the molar ratio is less than 1/25, the metal compound is fully activated, but the unit price of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with an excess of the remaining activator.
[129]
In the case of the second method among the methods for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 may be 1/10,000 to 1/10, and specifically 1/5,000 It may be from 1/100 to 1/100, and more specifically, from 1/3,000 to 1/500. When the molar ratio is greater than 1/10, the amount of the activator is relatively small, so the activation of the metal compound may not be completely achieved, and thus the activity of the resulting catalyst composition may be reduced. If it is less than 1/10,000, the activation of the metal compound is completely achieved, but the cost of the catalyst composition may not be economical or the purity of the resulting polymer may be deteriorated with the remaining excess activator.
[130]
In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene or toluene may be used as the reaction solvent.
[131]
In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a supported form on a carrier.
[132]
The carrier may be used without any particular limitation as long as it is used as a carrier in a metallocene-based catalyst. Specifically, the carrier may be silica, silica-alumina or silica-magnesia, and any one or a mixture of two or more thereof may be used.
[133]
Among them, when the carrier is silica, since the functional group of the silica carrier and the metallocene compound of Formula 1 chemically forms a bond, there is almost no catalyst released from the surface during olefin polymerization. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall surface or polymer particles are agglomerated during the manufacturing process of the olefin-based polymer. In addition, the olefin-based polymer prepared in the presence of the catalyst including the silica carrier has excellent particle shape and apparent density of the polymer.
[134]
More specifically, the carrier may be high-temperature dried silica or silica-alumina containing a siloxane group having high reactivity on the surface through a method such as high-temperature drying.
[135]
The carrier may further include an oxide, carbonate, sulfate or nitrate component such as Na 2O, K 2CO 3, BaSO 4 or Mg(NO 3) 2 .
[136]
The polymerization reaction for polymerizing the olefinic monomer may be accomplished by a conventional process applied to polymerization of the olefinic monomer, such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.
[137]
The polymerization reaction of the olefin monomer may be performed under an inert solvent, and examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, but not limited thereto.
[138]
Polymerization of the olefin-based polymer may be made at a temperature of about 25 °C to about 500 °C, specifically 80 °C to 250 °C, more preferably at a temperature of 100 °C to 200 °C. In addition, the reaction pressure during polymerization is 1 kgf/cm 2 to 150 kgf/cm 2 , preferably 1 kgf/cm 2 to 120 kgf/cm 2 , more preferably 5 kgf/cm 2 to 100 kgf/cm 2 can be
[139]
Modes for carrying out the invention
[140]
Example
[141]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.
[142]
[143]
Catalyst Preparation Example 1: Preparation of transition metal compound A
[144]

[145]
(1) 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8-(2,3,4,5- Preparation of tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline)
[146]
(i) Preparation of lithium carbamate
[147]
1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a shlenk flask. The Schlenk flask was immersed in a -78°C low-temperature bath made of dry ice and acetone and stirred for 30 minutes. Then, n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into a syringe under a nitrogen atmosphere, and a pale yellow slurry was formed. Then, after stirring the flask for 2 hours, the temperature of the flask was raised to room temperature while removing the butane gas produced. The flask was again immersed in a low temperature bath at -78° C. to lower the temperature, and then CO 2 gas was introduced. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler and the temperature was raised to room temperature while removing carbon dioxide gas. After that, excess CO 2 gas and solvent were removed under vacuum. After moving the flask to a dry box, pentane was added, stirred vigorously, and filtered to obtain lithium carbamate, a white solid compound. The white solid compound is coordinated with diethyl ether. In this case, the yield is 100%.
[148]
1H NMR(C 6D 6 , C 5D 5N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH 2), 2.34 (br s, 2H, quin-CH 2), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH 2), 6.76 (brd, J = 5.6 Hz, 1H, quin-CH) ppm
[149]
13 C NMR (C 6D 6): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C=O) ppm
[150]
(ii) Preparation of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline
[151]

[152]
The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were sequentially added. The Schlenk flask was immersed in a low temperature bath at -20°C made with acetone and a small amount of dry ice and stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture changed to red. Stirring was continued for 6 hours while maintaining -20°C. CeCl 3·2LiCl solution (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentynone (5.89 g, 42.60 mmol) were mixed in a syringe, and then put into a flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature, and after 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Then, after adding water (15 mL) to the flask, ethyl acetate was added thereto and filtered to obtain a filtrate. After the filtrate was transferred to a separatory funnel, hydrochloric acid (2 N, 80 mL) was added, and the mixture was shaken for 12 minutes. Then, after neutralization by adding a saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, filtered, and the filtrate was taken to remove the solvent. The obtained filtrate was purified by column chromatography using a solvent of hexane and ethyl acetate (v/v, 10:1) to obtain a yellow oil. The yield was 40%.
[153]
1H NMR(C 6D 6 ): δ 1.00 (br d, 3H, Cp-CH 3 ), 1.63 - 1.73 (m, 2H, quin-CH 2 ), 1.80 (s, 3H, Cp-CH 3 ), 1.81 ( s, 3H, Cp-CH 3), 1.85 (s, 3H, Cp-CH 3), 2.64 (t, J = 6.0 Hz, 2H, quin-CH 2), 2.84 - 2.90 (br, 2H, quin-CH 2), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm
[154]
[155]
(2) [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl- η 5 , κ -N] titanium dimethyl ([(1,2,3,4-Tetrahydroquinolin- Preparation of 8-yl)tetramethylcyclopentadienyl-eta5,kapa-N]titanium dimethyl)
[156]

[157]
(i) Preparation of [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-η 5, κ-N]dilithium compound
[158]
8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline (8.07 g) prepared through step (1) in a dry box , 32.0 mmol) and 140 mL of diethyl ether were placed in a round flask, the temperature was lowered to -30°C, and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added with stirring. The reaction was carried out for 6 hours while raising the temperature to room temperature. After that, it was filtered while washing with diethyl ether several times to obtain a solid. A vacuum was applied to remove the remaining solvent to obtain a dilithium compound (9.83 g) as a yellow solid. The yield was 95%.
[159]
1H NMR (C 6D 6, C 5D 5N): δ 2.38 (br s, 2H, quin-CH 2), 2.53 (br s, 12H, Cp-CH 3), 3.48 (br s, 2H, quin-CH 2 ) ), 4.19 (br s, 2H, quin-CH 2), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs, 1H, quin -CH) ppm
[160]
[161]
(ii) (1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η 5, κ-N] preparation of titanium dimethyl
[162]
In a dry box, TiCl 4·DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round flask, and while stirring at -30°C, MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added thereto. After stirring for 15 minutes, the [(1,2,3,4-tetrahydroquinolin-8-yl)tetramethylcyclopentadienyl-ηη 5, κ-N]dilithium compound prepared in step (i) ( 5.30 g, 15.76 mmol) was placed in a flask. The mixture was stirred for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. When the pentane was removed by vacuum, a dark brown compound (3.70 g) was obtained. The yield was 71.3%.
[163]
1H NMR(C 6D 6 ): δ 0.59 (s, 6H, Ti-CH 3 ), 1.66 (s, 6H, Cp-CH 3 ), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH 2 ) , 2.05 (s, 6H, Cp-CH 3), 2.47 (t, J = 6.0 Hz, 2H, quin-CH 2), 4.53 (m, 2H, quin-CH 2), 6.84 (t, J = 7.2 Hz) , 1H, quin-CH), 6.93 (d, J =7.6 Hz, quin-CH), 7.01 (d, J =6.8 Hz, quin-CH) ppm
[164]
13C NMR (C 6D 6 ): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm
[165]
[166]
Catalyst Preparation Example 2: Preparation of transition metal compound B
[167]

[168]
(1) Preparation of 2-methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline
[169]
Through the same method as (1) of Preparation Example 1, except that 2-methyl indoline was used instead of 1,2,3,4-tetrahydroquinoline in (1) of Preparation Example 1, 2 -Methyl-7-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)indoline was prepared. The yield was 19%.
[170]
1H NMR (C 6D 6): δ 6.97 (d, J=7.2 Hz, 1H, CH), δ 6.78 (d, J=8 Hz, 1H, CH), δ 6.67 (t, J=7.4 Hz, 1H, CH) ), δ 3.94 (m, 1H, quinoline-CH), δ 3.51 (br s, 1H, NH), δ 3.24-3.08 (m, 2H, quinoline-CH 2, Cp-CH), δ 2.65 (m, 1H) , quinoline-CH 2), δ 1.89(s, 3H, Cp-CH 3), δ 1.84(s, 3H, Cp-CH 3), δ 1.82(s, 3H, Cp-CH 3), δ 1.13(d , J=6Hz, 3H, quinoline-CH 3), δ 0.93 (3H, Cp-CH 3) ppm.
[171]
[172]
(2) [(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kappa-N]titanium dimethyl ([(2-Methylindolin-7-yl)tetramethylcyclopentadienyl-eta5,kapa-N] production of titanium dimethyl)
[173]
(i) 2-methyl-7-(2,3 in place of 8-(2,3,4,5-tetramethyl-1,3-cyclopentadienyl)-1,2,3,4-tetrahydroquinoline ,4,5-tetramethyl-1,3-cyclopentadienyl)-indoline (2.25 g, 8.88 mmol) through the same method as (2) (i) of Preparation Example 1, except that A dilithium salt compound (compound 4 g) coordinated with 0.58 equivalents of diethyl ether was obtained (1.37 g, 50 %).
[174]
1H NMR (Pyridine-d8): δ 7.22 (br s, 1H, CH), δ 7.18 (d, J=6Hz, 1H, CH), δ 6.32 (t, 1H, CH), δ 4.61 (brs, 1H, CH), δ 3.54 (m, 1H, CH), δ 3.00 (m, 1H, CH), δ 2.35-2.12 (m , 13H, CH, Cp-CH3), δ 1.39 (d, indoline-CH3) ppm.
[175]
[176]
(ii) A titanium compound was prepared in the same manner as in (2)(ii) of Preparation Example 1 with the dilithium salt compound (compound 4g) (1.37 g, 4.44 mmol) prepared in (i) above.
[177]
1H NMR (C 6D 6 ): δ 7.01-6.96 (m, 2H, CH), δ 6.82 (t, J=7.4 Hz, 1H, CH), δ
[178]
4.96(m, 1H, CH), δ 2.88(m, 1H, CH), δ 2.40(m, 1H, CH), δ 2.02(s, 3H, Cp-CH 3), δ 2.01(s, 3H, Cp -CH 3), δ 1.70(s, 3H, Cp-CH 3), δ 1.69(s, 3H, Cp-CH 3), δ 1.65 (d, J=6.4Hz, 3H, indoline-CH 3), δ 0.71 (d, J=10 Hz, 6H, TiMe 2-CH 3) ppm.
[179]
[180]
Example Preparation Example 1
[181]
After charging a 1.5 L continuous process reactor with hexane solvent (5 kg/h) and 1-butene (0.95 kg/h), the temperature at the top of the reactor was preheated to 140.7°C. Triisobutylaluminum compound (0.06 mmol/min), transition metal compound B obtained in Catalyst Preparation Example 2 (0.40 μmol/min), and dimethylanilinium tetrakis (pentafluorophenyl) borate promoter (1.20 μmol/min) ) were simultaneously introduced into the reactor. Then, hydrogen gas (15 cc/min) and ethylene (0.87 kg/h) were introduced into the reactor.was added and maintained at 141° C. for at least 30 minutes in a continuous process at a pressure of 89 bar to proceed with a copolymerization reaction to obtain a copolymer. After drying in a vacuum oven for more than 12 hours, physical properties were measured.
[182]
[183]
Examples Preparation Examples 2 to 5
[184]
The copolymerization reaction was carried out in the same manner as in Preparation Example 1, and the amount of transition metal compound, the amount of catalyst and co-catalyst, and the reaction temperature, hydrogen input, and amount of comonomer were respectively changed as shown in Table 1 below to proceed with the copolymerization reaction. A copolymer was obtained.
[185]
[186]
Comparative Preparation Example 1
[187]
DF610 from Mitsui Chemicals was purchased and used.
[188]
[189]
Comparative Preparation Examples 2 to 4
[190]
The copolymerization reaction was carried out in the same manner as in Preparation Example 1, and the type of transition metal compound, the amount of the transition metal compound, the amount of catalyst and co-catalyst, and the reaction temperature, the amount of hydrogen input, and the amount of comonomer were measured in Table 1 below, respectively. It changed and the copolymerization reaction was advanced, and the copolymer was obtained.
[191]
[192]
Comparative Preparation Example 5
[193]
DF710 from Mitsui Chemicals was purchased and used.
[194]
[195]
Comparative Preparation Example 6
[196]
DF640 from Mitsui Chemicals was purchased and used.
[197]
[198]
Comparative Preparation Example 7
[199]
Dow's EG7447 was purchased and used.
[200]
[Table 1]
Catalyst Type Catalyst
usage
(μmol
/min) cocatalyst
(μmol
/min) TiBAl
(mmol
/min) ethylene
(kg/h) hexane
(Kg/h) 1-butene
(kg/h) hydrogen
(cc/min) reaction temperature
(℃
Example Preparation Example 1 Transition metal compound B 0.40 1.20 0.06 0.87 5 0.95 15 141
Example Preparation Example 2 Transition metal compound B 0.60 1.80 0.05 0.87 7 0.93 32 145
Example Preparation Example 3 Transition metal compound B 0.45 1.35 0.04 0.87 7 0.75 15 145
Example Preparation Example 4 Transition metal compound B 0.74 2.22 0.05 0.87 7 0.93 25 150
Example Preparation Example 5 Transition metal compound B 0.55 1.65 0.04 0.87 7 0.84 38 148
Comparative Preparation Example 2 Transition metal compound B 0.78 2.34 0.06 0.87 5 1.15 - 161
Comparative Preparation Example 3 Transition metal compound A 0.32 0.96 0.05 0.87 5 0.62 - 145
Comparative Preparation Example 4 Transition metal compound B 0.50 1.50 0.06 0.87 5 1.15 10 161
Additional Comparative Preparation Examples
8 overuse
[201]
Experimental Example 1: Evaluation of physical properties of olefin-based polymers The copolymers of Preparation Examples 1 to 5 and Comparative Preparation Examples 1 to 4 were evaluated for physical properties according to the following method, and are shown in Tables 2 and 3 below.
[202]
1) Density of the polymer
[203]
Measured by ASTM D-792.
[204]
2) Polymer Melt Index (MI)
[205]
It was measured by ASTM D-1238 (Condition E, 190°C, 2.16 kg load).
[206]
3) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (MWD)
[207]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured using gel permeation chromatography (GPC), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.
[208]
- Column: PL Olexis
[209]
- Solvent: TCB (Trichlorobenzene)
[210]
- Flow rate: 1.0 ml/min
[211]
- Sample concentration: 1.0 mg/ml
[212]
- Injection volume: 200 μl
[213]
- Column temperature: 160℃
[214]
- Detector: Agilent High Temperature RI detector
[215]
- Standard: Polystyrene (corrected by cubic function)
[216]
4) Melting point of polymer (Tm)
[217]
It was obtained using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments. That is, after increasing the temperature to 150° C., maintaining it at that temperature for 1 minute, then lowering it to -100° C., and increasing the temperature again, the top of the DSC curve was used as the melting point. At this time, the rate of temperature rise and fall is 10° C./min, and the melting point is obtained while the second temperature rises.
[218]
The DSC graph of the polymer of Preparation Example 1 is shown in FIG. 1, and the DSC graph of the polymer of Comparative Preparation Example 1 is shown in FIG. 2, respectively.
[219]
5) Sum of the high-temperature melting peak of the polymer and the melting enthalpy at 75°C or higher ΔH(75)
[220]
The differential scanning calorimeter (DSC: Differential Scanning Calorimeter 250) manufactured by TA Instruments was obtained by SSA (Successive self-nucleation/annealing) measurement method.
[221]
Specifically, in the first cycle, the temperature was increased to 150°C, held at that temperature for 1 minute, and then cooled to -100°C. In the second cycle, the temperature was increased to 120 °C, held at that temperature for 30 minutes and then cooled to -100 °C. In the third cycle, the temperature was increased to 110 °C, held at that temperature for 30 minutes and then cooled to -100 °C. In this way, the process of raising the temperature at 10°C intervals and cooling to -100°C was repeated until -60°C so that crystallization was performed for each temperature section.
[222]
In the last cycle, the heat capacity was specified while increasing the temperature to 150°C. Then, ΔH(75) was obtained by summing the enthalpy of melting at 75°C or higher.
[223]
3 shows the SSA graph of the polymer of Preparation Example 1, and FIG. 4 shows the SSA graph of the polymer of Comparative Preparation Example 1, respectively.
[224]
6) Hardness (shore A)
[225]
Hardness was measured according to ASTM D2240 standard using TECLOCK's GC610 STAND for Durometer and Mitutoyo's Shore Durometer Type A.
[226]
7) Polymer tensile strength and tear strength
[227]
The olefinic copolymers of Preparation Example 1 and Comparative Preparation Examples 1 to 3 were each extruded to prepare pellets, and then tensile strength and tear strength at breakage were measured according to ASTM D638 (50 mm/min).
[228]
[Table 2]
density
(g/mL) MI
(g/10min) Mw
(g/mol) MWD DSC SSA
Tm
(℃) High-temperature melting peak presence ΔH(75)
(J/g)
Example Preparation Example 1 0.862 1.20 106,000 2.01 32.1 Yes 1.04
Example Preparation 2 0.866 4.39 69,070 2.07 33.0 Yes 1.61
Example Preparation 3 0.872 1.22 99,068 2.05 45.9 Yes 1.11
Example Preparation 4 0.866 3.30 70,000 2.11 37.8 Yes 1.05
Example Preparation 5 0.865 5.10 75,388 2.09 37.2 Yes 1.12
Comparative Preparation Example 1 0.861 1.32 105,000 1.98 39.7 None 0
Comparative Preparation Example 2 0.861 1.12 102,000 2.11 28.6 Yes 0.71
Comparative Preparation Example 3 0.862 1.20 91,419 2.18 28.5 Yes 0.56
Comparative Preparation Example 4 0.862 1.23 100,423 2.185 29.9 Yes 0.61
Comparative Preparation Example 5 0.869 1.20 92,000 2.04 49.3 None 0
Comparative Preparation Example 6 0.865 3.40 71,000 2.04 43.8 None 0
Comparative Preparation Example 7 0.868 5.10 76,735 2.14 44.2 None 0.48
Additional Comparative Preparation Example 8
[229]
[Table 3]
density
(g/mL) MI
(g/10min) MWD DSC SSA Tensile strength Tear strength Hardness
(Shore A)
Tm
(°C) ΔH(75)
(J/g)
Example Preparation 1 0.862 1.20 2.01 32.1 1.04 2.2 29.5 55.0
Comparative Preparation Example 1 0.861 1.32 1.98 39.7 0 2.1 25.6 56.7
Comparative Preparation Example 2 0.861 1.12 2.11 28.6 0.71 1.6 22.4 52.9
Comparative Preparation Example 3 0.862 1.20 2.18 28.5 0.56 1.3 16.7 51.6
[230]
When the olefin-based polymer of Preparation Example 1 and the olefin-based polymer of Comparative Preparation Example 1 having an equivalent level of density and MI were compared, FIGS. 1 and 2 measured by DSC show a similar trend and show a similar graph form, showing a significant difference is not confirmed, but it can be seen that there is a large difference in the high temperature region of 75° C. or higher in FIGS. 3 and 4 measured by SSA. Specifically, in Preparation Example 1, a peak appears at 75° C. or higher, whereas Comparative Preparation Example does not. Comparative Preparation Example 2 and Comparative Preparation Example 3 had a peak in the corresponding region, but the size was smaller than that of Preparation Example. Due to the difference in the high-temperature melting peak measured by SSA, Example 1 had ΔH(75) of 1.0 Although it showed a value of J/g or more, in the comparative example, ΔH(75) showed a value of less than 1.0 J/g, or there was no peak in the corresponding region.
[231]
Through Table 3, the mechanical strength of Preparation Example 1 and Comparative Preparation Examples 1, 2, and 3 having an equivalent level of density and MI can be compared. It can be seen that in Preparation Example 1, a polymer melted at a high temperature was introduced to increase mechanical rigidity, and thus tensile strength and tear strength were increased compared to Comparative Examples 1 to 3.
[232]
[233]
Examples Preparation Examples 1 to 5 are polymers obtained by polymerizing an olefinic monomer while introducing hydrogen gas, and a high crystallinity region was introduced to exhibit a high-temperature melting peak, and thus ΔH(75) exhibited a value of 1.0 J/g or more. and showed high mechanical rigidity. Through comparison with Comparative Preparation Example 2 and Comparative Preparation Example 4, whether or not ΔH(75) satisfies a value of 1.0 J/g or more depends on whether hydrogen gas is added during polymerization and the amount thereof, and the mechanical stiffness is also changed was able to confirm
[234]
[235]Example 1: Preparation of polypropylene-based composites
[236]
To 20 parts by weight of the olefin copolymer prepared in Example 1, 60 parts by weight of a high crystallinity impact copolymer polypropylene (CB5230, manufactured by Daehan Petrochemical) having a melt index (230° C., 2.16 kg) of 30 g/10 min and 20 parts by weight of talc (KCNAP-400™, Kotsu Corporation) (average particle diameter (D 50) = 11.0 μm) was added, and 0.1 parts by weight of AO1010 (Irganox 1010, Ciba Specialty Chemicals) as an antioxidant, tris(2,4-di) -tert-butylphenyl)phosphite (A0168) 0.1 parts by weight and calcium stearate (Ca-st) 0.3 parts by weight were added, and then melt-kneaded using a twin-screw extruder to obtain a pellet-form polypropylene-based composite compound. prepared. At this time, the twin screw extruder had a diameter of 25Φ, a ratio of diameter to length of 40, a barrel temperature of 200° C. to 230° C., a screw rotation speed of 250 rpm, and an extrusion amount of 25 kr/hr.
[237]
[238]
Examples 2 to 5: Preparation of polypropylene-based composites
[239]
A polypropylene-based composite was prepared in the same manner as in Example 1, except that the olefin copolymer as shown in Table 4 was used instead of the olefin copolymer prepared in Preparation Example 1. In this case, in Example 5, the type of polypropylene and the ratio of the olefin copolymer to the polypropylene were different.
[240]
The polypropylene represented by CB5290 in Table 4 below is a high crystalline impact copolymer polypropylene (CB5290, manufactured by Daehan Petrochemical Co., Ltd.) having a melt index (230° C., 2.16 kg) of 90 g/10 min.
[241]
[242]
Comparative Examples 1 to 7: Preparation of polypropylene-based composites
[243]
A polypropylene-based composite was prepared in the same manner as in Example 1, except that the olefin copolymer as shown in Table 4 was used instead of the olefin copolymer prepared in Preparation Example 1. In this case, in Comparative Example 7, the type of polypropylene and the ratio of the olefin copolymer to the polypropylene were different.
[244]
The polypropylene represented by CB5290 in Table 4 below is a high crystalline impact copolymer polypropylene (CB5290, manufactured by Daehan Petrochemical Co., Ltd.) having a melt index (230° C., 2.16 kg) of 90 g/10 min.
[245]
[Table 4]
olefinic
Polymer Polypropylene Blending Ratio
Olefin polymer
(wt%) PP
(wt%) talc
(weight%)
Example 1 Example Preparation Example 1 CB5230 20 60 20
Example 2 Example Preparation Example 3 CB5230 20 60 20
Example 3 Example Preparation Example 4 CB5230 20 60 20
Example 4 Example Preparation 5 CB5230 20 60 20
Example 5 Example Preparation Example 3 CB5290 30 50 20
Comparative Example 1 Comparative Preparation Example 1 CB5230 20 60 20
Comparative Example 2 Comparative Preparation Example 2 CB5230 20 60 20
Comparative Example 3 Comparative Preparation Example 3 CB5230 20 60 20
Comparative Example 4 Comparative Preparation Example 5 CB5230 20 60 20
Comparative Example 5 Comparative Preparation Example 6 CB5230 20 60 20
Comparative Example 6 Comparative Preparation Example 7 CB5230 20 60 20
Comparative Example 7 Comparative Preparation Example 5 CB5290 30 50 20
[246]
Experimental Example 2: Evaluation of physical properties of polypropylene-based composites
[247]
In order to confirm the physical properties of the polypropylene-based composites prepared in Examples 1 to 5 and Comparative Examples 1 to 7, the polypropylene-based composite was prepared by injection molding at a temperature of 230° C. using an injection machine, and a constant temperature After standing in a humidity room for 1 day, the specific gravity of the polymer, the melt index of the polymer, tensile strength, flexural strength and flexural modulus, low and room temperature impact strength, and shrinkage were measured. The physical properties of the prepared specimens are shown in Table 5 below.
[248]
1) Specific gravity
[249]
Measured according to ASTM D792.
[250]
2) Polymer Melt Index (MI)
[251]
The melt index (MI) of the polymer was measured by ASTM D-1238 (Condition E, 230°C, 2.16 kg load).
[252]
3) Tensile strength, and flexural strength
[253]
Measurements were made according to ASTM D790 using an INSTRON 3365 instrument.
[254]
4) Low and room temperature impact strength
[255]
It was carried out according to ASTM D256, the impact strength was measured at room temperature under the conditions of room temperature (23 ℃), and the low temperature impact strength was measured after standing in a low temperature chamber (-30 ℃) for more than 12 hours.
[256]
[Table 5]
specific gravity MI
(g/10min) Tensile strength Flexural strength Low temperature impact strength Room temperature impact strength
Example 1 1.033 14.3 211 341 4.7 42.1
Comparative Example 1 1.041 14.6 211 336 4.7 43.9
Comparative Example 2 1.030 13.9 206 334 4.8 42.5
Comparative Example 3 1.038 13.9 205 327 4.7 40.9
Example 2 1.037 14.6 219 344 3.6 34.5
Comparative Example 4 1.03 15.0 216 340 3.8 37.3
Example 3 1.032 17.0 239 336 3.8 34.8
Comparative Example 5 1.032 17.4 238 334 3.8 34.5
Example 4 1.036 17.7 217 336 4.3 32.9
Comparative Example 6 1.031 17.8 217 333 4.4 33.1
Example 5 1.031 16.2 171 246 8.4 53.7
Comparative Example 7 1.033 16.7 168 241 9.0 52.8
[257]
Referring to Table 5, when comparing the polypropylene-based composites including the olefin-based copolymer having the same level of density and MI value, the polypropylene-based composite of the Example was lower than the polypropylene-based composite of Comparative Example at a similar level of low temperature It can be seen that the mechanical strength such as tensile strength and flexural strength was improved while maintaining the impact strength and the impact strength at room temperature. Through this, it could be confirmed that the polypropylene-based composite of Example includes an olefin-based copolymer having high mechanical rigidity in which a high crystallinity region is introduced, thereby increasing the mechanical rigidity of the polypropylene-based composite.
Claims
[Claim 1]
(A) polypropylene, and (B) a polypropylene-based composite comprising an olefin-based polymer satisfying the requirements of (1) to (3) below: (1) Melt Index (MI, 190°C, 2.16 kg) load condition) is 0.1 g/10 min to 10.0 g/10 min, (2) a melting temperature of 20° C. to 70° C. when measured by differential scanning calorimetry (DSC), and (3) when measured by differential scanning calorimetry (SSA). A high-temperature melting peak is observed at 75°C to 150°C, and the sum ΔH(75) of the melting enthalpy of the region is 1.0 J/g or more.
[Claim 2]
The polypropylene-based composite material according to claim 1, wherein the polypropylene (A) has a melt index of 0.5 g/10 min to 100 g/10 min measured at 230°C and a load of 2.16 kg.
[Claim 3]
The polypropylene-based composite according to claim 1, wherein the polypropylene (A) is an impact copolymer having a melt index of 0.5 g/10 min to 100 g/10 min measured at 230°C and a load of 2.16 kg.
[Claim 4]
The polypropylene-based composite according to claim 1, wherein the (B) olefin-based polymer further satisfies the requirement (4) having a density (d) of 0.850 g/cc to 0.890 g/cc.
[Claim 5]
[Claim 2] The polypropylene-based composite material according to claim 1, wherein (B) the olefin-based polymer further satisfies (5) a weight average molecular weight (Mw) of 10,000 g/mol to 500,000 g/mol.
[Claim 6]
The polypropylene-based composite material according to claim 1, wherein the (B) olefin-based polymer further satisfies (6) a molecular weight distribution (MWD) of 0.1 to 6.0.
[Claim 7]
The polypropylene-based composite according to claim 1, wherein (B) the olefin-based polymer is a copolymer of ethylene and an alpha-olefin comonomer having 3 to 12 carbon atoms.
[Claim 8]
8. The method of claim 7, wherein the alpha-olefin comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-unde. Sene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4 - Polypropylene comprising any one or a mixture of two or more selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene based composites.
[Claim 9]
The polypropylene-based composite material according to claim 1, wherein the (B) olefin-based polymer is a copolymer of ethylene and 1-hexene.
[Claim 10]
The method according to claim 1, wherein the (B) olefin-based polymer comprises the step of polymerizing the olefinic monomer by introducing hydrogen gas in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 below. A polypropylene-based composite obtained by A metalloid radical of a Group 4 metal substituted with silyl, alkylaryl, arylalkyl, or hydrocarbyl, wherein the two R 1 are alkylidine radicals including an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms. may be linked to each other to form a ring; R 2 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; aryl; alkoxy; aryloxy; an amido radical, wherein two or more of R 2 may be connected to each other to form an aliphatic ring or an aromatic ring; R 3 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen, substituted or unsubstituted with an aryl radical, and when the substituents are plural, two or more substituents among the substituents are connected to each other may form an aliphatic or aromatic ring; M is a Group 4 transition metal; Q 1 and Q 2 are each independently halogen; alkyl having 1 to 20 carbon atoms; alkenyl; aryl; alkylaryl; arylalkyl; alkyl amido having 1 to 20 carbon atoms; aryl amido; or an alkylidene radical having 1 to 20 carbon atoms.
[Claim 11]
According to claim 1, wherein the (B) olefin-based polymer is prepared by a continuous solution polymerization reaction using a continuous stirred reactor (Continuous Stirred Tank Reactor) by introducing hydrogen gas in the presence of the catalyst composition for olefin polymerization, poly Propylene-based composites.
[Claim 12]
The polypropylene-based composite according to claim 1, wherein the polypropylene-based composite comprises 5 to 40% by weight of the (B) olefin-based polymer.
[Claim 13]
The polypropylene-based composite according to claim 1, wherein the polypropylene-based composite further comprises an inorganic filler.
[Claim 14]
14. The method of claim 13, wherein the polypropylene-based composite (A) contains the inorganic filler in an amount of 0.1 parts by weight to 40 parts by weight based on 100 parts by weight of polypropylene, and the inorganic filler has an average particle diameter (D 50) of 1 ㎛ to 20㎛ polypropylene-based composite material.