CN117050215A - Polyethylene and chlorinated polyethylene thereof - Google Patents

Polyethylene and chlorinated polyethylene thereof Download PDF

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Publication number
CN117050215A
CN117050215A CN202311260736.8A CN202311260736A CN117050215A CN 117050215 A CN117050215 A CN 117050215A CN 202311260736 A CN202311260736 A CN 202311260736A CN 117050215 A CN117050215 A CN 117050215A
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polyethylene
temperature
chlorine
chlorinated
group
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Inventor
丁澈焕
李始贞
洪福基
朴城贤
金善美
崔二永
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020190163116A external-priority patent/KR102252430B1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Abstract

The present application relates to polyethylene and its chlorinated polyethylene. The polyethylene according to the present disclosure maintains a stable crystal structure at high temperature and ensures excellent uniformity of chlorine distribution, thereby preparing chlorinated polyethylene having excellent chlorination productivity and thermal stability by reacting with chlorine, and also preparing PVC blend having improved impact strength by including the chlorinated polyethylene.

Description

Polyethylene and chlorinated polyethylene thereof
The application relates to a divisional application, the international application number of the original application is PCT/KR2019/017398, the international application date is 2019, 12 months and 10 days, the Chinese national application number is 201980030754.2, the entering date of entering the Chinese national stage is 2020, 11 months and 06 days, and the application is named as polyethylene and chlorinated polyethylene thereof.
Technical Field
Cross Reference to Related Applications
The present application claims priority and rights to korean patent application No. 10-2018-0158328, filed in the korean intellectual property office at 10 of 12 th month of 2018, 10-2019-0007089, filed in 18 of 1 month of 2019, and 10-2019-0163116 filed in 9 of 12 months of 2019, the disclosures of which are incorporated herein by reference in their entirety.
The present disclosure relates to a polyethylene and a chlorinated polyethylene thereof, which can prepare a chlorinated polyethylene having excellent chlorination productivity and thermal stability, thereby improving impact strength of PVC blends by maintaining a stable crystal structure at high temperature and ensuring excellent uniformity of chlorine distribution.
Background
Chlorinated polyethylenes prepared by reacting polyethylene with chlorine are known to have better physical and mechanical properties than polyethylene, in particular they are resistant to harsh external environments and therefore can be used as packaging materials, for example various containers, fibres and pipes and heat transfer materials.
Chlorinated polyethylene is generally prepared by: the polyethylene is made into a suspension and then reacted with chlorine, or the polyethylene is placed in aqueous HCl and then reacted with chlorine, replacing the hydrogen of the polyethylene with chlorine.
In order to fully express the properties of chlorinated polyethylene, it is necessary to uniformly replace chlorine in the polyethylene, which is affected by the properties of the polyethylene reacted with chlorine. In particular, chlorinated Polyethylene (CPE) is widely used as impact reinforcement for pipes and window profiles by blending with PVC, and is generally prepared by reacting polyethylene with chlorine in suspension or with chlorine in aqueous HCl. The PVC blend product requires excellent impact strength, and the strength of the compound varies according to the physical properties of the chlorinated polyethylene. In particular, as the elongation of the CPE increases, the impact strength of the final product is excellent, and for this purpose it is preferred that the chlorine is uniformly distributed in the HDPE chains. In the case of the currently known general-purpose chlorinated polyethylene, since polyethylene prepared by Ziegler-Natta catalyst is used, uniformity of chlorine distribution in the polyethylene is lowered due to broad molecular weight distribution and high content of ultra-high molecular weight. Yet another disadvantage is insufficient impact strength when blended with PVC.
In addition, chlorination, deoxidation, dehydration and drying processes are performed to produce CPE. When the crystalline structure of HDPE cannot be kept stable, the crystalline structure may collapse and the pores of the Polyethylene (PE) particles may be blocked by chlorination reactions at high temperatures. After the deoxygenation process, a water wash is required to remove residual HCl in the PE particles. When the holes are blocked, the total production time is prolonged due to the prolonged deoxidizing time, and the productivity of chlorine may be lowered.
Thus, there is a need for excellent uniformity of chlorine distribution in chlorinated polyethylene to improve the impact strength of PVC blends. Accordingly, there is a continuing need to develop a process for preparing polyethylene that maintains a stable crystal structure to improve productivity in the chlorination process.
Disclosure of Invention
[ problem ]
The present disclosure provides a polyethylene and a chlorinated polyethylene thereof, which can prepare a chlorinated polyethylene having excellent chlorination productivity and thermal stability, thereby improving impact strength of PVC blends by maintaining a stable crystal structure at high temperature and ensuring excellent uniformity of chlorine distribution.
In addition, the present disclosure provides a method of preparing polyethylene.
[ technical solution ]
According to one embodiment of the present disclosure, there is provided a polyethylene having a high crystalline region ratio on a Temperature Rising Elution Fractionation (TREF) chart of 12.5% or less, wherein the high crystalline region ratio is obtained by dividing a pattern area having a high crystalline region above an elution temperature corresponding to a division point of a minimum peak between two highest peaks by a total pattern area in percent.
In addition, the present disclosure provides a method of preparing polyethylene.
The present disclosure also provides chlorinated polyethylene prepared by reacting polyethylene with chlorine.
[ beneficial effects ]
The polyethylene according to the present disclosure reacts with chlorine to produce chlorinated polyethylene having excellent chlorination productivity and thermal stability by maintaining a stable crystal structure at high temperature and ensuring excellent uniformity of chlorine distribution.
Drawings
Fig. 1 is a Temperature Rising Elution Fractionation (TREF) diagram of polyethylene of examples 1-2, showing high crystallization zones thereon, according to one embodiment of the present disclosure.
Detailed Description
In this disclosure, the terms "first," "second," and the like are used to describe different components, and these terms are used only to distinguish one component from another.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular forms also are intended to include plural forms unless the context clearly indicates otherwise. It will be further understood that the terms "comprises," "comprising," "includes," or "including" when used in this specification, specify the presence of stated features, integers, steps, components, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.
The terms "about" or "substantially" are intended to have a close numerical value or range of values where errors permit, and to prevent the exact or absolute numerical values disclosed for the understanding of the present invention from being used illegally or unfair to any unscrupulous third party.
For reference, "parts by weight" as used herein refers to the relative concept of the weight ratio of the remaining materials based on the weight of the particular material. For example, in a mixture containing 50g of material a, 20g of material B, and 30g of material C, the amounts of material B and C are 40 parts by weight and 60 parts by weight, respectively, based on 100 parts by weight of material a.
In addition, "wt% (wt%)" refers to the absolute concept of expressing the weight of a particular material in percent based on the total weight. In the above mixture, the contents of materials A, B and C were 50 wt%, 20 wt% and 30 wt%, respectively, based on the total weight of the mixture of 100%. At this time, the sum of the contents of the respective components does not exceed 100% by weight.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example and will herein be described in detail. It should be understood, however, that there is no intention to limit the invention to the specific forms disclosed, and it is to be understood that the invention includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Hereinafter, the present disclosure will be described in more detail.
According to one embodiment of the present disclosure, there is provided a polyethylene capable of preparing chlorinated polyethylene having excellent chlorination productivity and thermal stability, thereby improving impact strength of PVC blends by maintaining a stable crystal structure at high temperature and ensuring excellent uniformity of chlorine distribution.
The polyethylene is characterized in that the high crystallization region ratio on a Temperature Rising Elution Fractionation (TREF) chart is 12.5% or less, wherein the high crystallization region ratio is obtained by dividing a pattern area having a high crystallization region corresponding to an elution temperature or more at a division point of a minimum peak between two maximum peaks by a total pattern area in percentage.
In general, chlorinated polyethylene is prepared by reacting polyethylene with chlorine, which means that a portion of the hydrogen in the polyethylene is replaced by chlorine. When the hydrogen of the polyethylene is replaced by chlorine, the properties of the polyethylene change because of the atomic volumes of hydrogen and chlorine. For example, the chlorination productivity and the thermal stability are further improved. In particular, the smaller and uniform the overall size of the chlorinated polyethylene particles, the easier the chlorine permeates into the center of the polyethylene particles, so that the degree of substitution of chlorine in the particles can be made uniform, thereby exhibiting excellent physical properties. For this reason, according to a Temperature Rising Elution Fractionation (TREF) analysis, the polyethylene according to the present disclosure can provide a chlorinated polyethylene having a high α -transition temperature and a low high crystalline region ratio, thereby exhibiting better chlorination productivity and thermal stability.
The polyethylene of the present disclosure is characterized by a low content of high crystalline regions in the molecular structure, which can increase the elongation of CPE by uniform chlorine substitution. In addition, the polyethylene of the present disclosure has a high α -transition temperature, so that a crystal structure can be stably maintained even at a high temperature. Accordingly, it is possible to shorten the deoxidizing time and improve the chlorination productivity by maintaining the crystal structure during the chlorination reaction at high temperature to prevent the pores of the polyethylene particles from being blocked. As a result, the polyethylene of the present disclosure can produce chlorinated polyethylene having excellent chlorination productivity and thermal stability, and can increase elongation of CPE by uniform chlorine substitution, thereby improving impact strength when used as an impact reinforcement material for PVC blends.
The polyethylene according to the present disclosure may be an ethylene homopolymer that does not comprise a separate copolymer.
The polyethylene may have an alpha transition temperature of about 120 ℃ or greater, or about 120 ℃ to about 145 ℃, about 122 ℃ or greater, or about 122 ℃ to about 145 ℃, or about 125 ℃ or greater, or about 125 ℃ to about 145 ℃. Here, the α -transition temperature refers to a temperature at which a change in crystal arrangement occurs while maintaining a layered structure in which crystals are formed, and can be measured by thermal analysis of polyethylene. Specifically, using a Dynamic Mechanical Analyzer (DMA), the αtransition temperature was measured by lowering the temperature to-60 ℃, holding at that temperature for 5 minutes, raising the temperature to 140 ℃, and then determining the top of the tan delta curve as the αtransition temperature. The crystal alignment change of polyethylene occurs near the alpha transition temperature. The polyethylene of the present disclosure has an alpha transition temperature of 120 ℃ or higher, which is close to the melting temperature, so that a change in crystal arrangement occurs at a higher temperature, and the morphology of polyethylene particles is difficult to change during chlorination. Thus, high chlorination productivity can be ensured.
As described above, the polyethylene of the present disclosure is characterized by a low proportion of high crystalline regions in a Temperature Rising Elution Fractionation (TREF) map having a high α transition temperature.
The polyethylene may have a low high crystalline fraction on a Temperature Rising Elution Fractionation (TREF) chart of less than about 12.5%, or from about 5% to about 12.5%. In particular, the high crystalline region ratio may be about 12% or less or about 5% to about 12%, or about 11.8% or less or about 5% to about 11.8%. Specifically, the lower the proportion of the high crystalline region, the easier the chlorine molecules penetrate into the crystal. Thus, for a homogeneous chlorination reaction, the high crystalline region ratio should be about 12% or less. When the high crystallization region ratio is too low, the α -transition temperature may also decrease, and thus the high crystallization region ratio may be preferably about 5% or more.
As shown in one embodiment of fig. 1, a high crystalline fraction can be obtained from a Temperature Rising Elution Fractionation (TREF) diagram of polyethylene. First, a Temperature Rising Elution Fractionation (TREF) chart of polyethylene is obtained, and an elution temperature, which is a division point corresponding to a minimum peak (minimum value) between two highest peaks among peaks appearing on the TREF chart, is used as a reference for a high crystallization region. The region having an elution temperature equal to or higher than the minimum value is referred to as a high crystallization region. Accordingly, a pattern area having a high crystallization region above the elution temperature is measured, and a high crystallization region ratio (%) is obtained by dividing the pattern area by the total pattern area by a percentage.
Specifically, a Temperature Rising Elution Fractionation (TREF) diagram of polyethylene can be obtained using Agilent Technologies 7890A manufactured by PolymerChar. For example, a sample was dissolved in 20mL of 1,2, 4-trichlorobenzene at a concentration of 1.5mg/mL, then dissolved by increasing the temperature from 30℃to 150℃at a rate of 40℃per minute, then recrystallized by decreasing the temperature to 35℃at a rate of 0.5℃per minute, and then eluted by increasing the temperature to 140℃at a rate of 1℃per minute to obtain a pattern.
As shown in one embodiment of fig. 1, the Temperature Rising Elution Fractionation (TREF) plot of polyethylene thus obtained has an elution temperature (c) on the X-axis and an elution amount (dW/dt) at that temperature on the Y-axis. The region having a temperature equal to or higher than the division point between two peaks on the TREF chart is referred to as a high crystallization region. That is, the elution temperature of the minimum value between two peaks is taken as the vertical axis, and a value obtained by integrating the areas of the graphs having the elution temperature equal to or higher than the elution temperature may be referred to as the area of the high crystallization region. The value of the percentage obtained by dividing the area of the high crystalline region by the total pattern area may be referred to as the high crystalline region ratio.
As described above, since polyethylene is prepared by optimizing a specific metallocene catalyst, the α -transition temperature is high and the high crystalline region ratio according to Temperature Rising Elution Fractionation (TREF) analysis is low. As a result, the polyethylene according to the present disclosure has characteristics that exhibit better chlorination productivity and thermal stability when preparing chlorinated polyethylene.
The polyethylene may have a Melt Index (MI) of about 0.1g/10min to about 1.5g/10min, about 0.15g/10min to about 1.2g/10min, about 0.18g/10min to about 1.0g/10min, or about 0.2g/10min to about 0.35g/10min, measured according to ASTM D1238 at a temperature of 190℃under a load of 5kg 5 ). Melt index MI for excellent thermal stability 5 May be about 1.5g/10minIn the lower, since the viscosity becomes higher as the MI is lower, and the PE particles change less in morphology in the high temperature slurry state for chlorination. Melt index MI for improved processability 5 May be 0.1g/10min or more because the viscosity is lower as MI is higher.
In addition, the polyethylene may have a Melt Flow Rate Ratio (MFRR) of about 10 to about 20, or about 11 to about 18 21 6/5 by dividing the melt index measured according to ASTM D1238 at 190 ℃,21.6kg load by the melt index measured at 190 ℃,5kg load).
The polyethylene may have about 0.947g/cm 3 To about 0.957g/cm 3 Or about 0.948g/cm 3 To 0.954g/cm 3 Is a density of (3). This means that the polyethylene has a high content of crystalline portions and is dense, and the crystalline structure of the polyethylene is difficult to change during chlorination.
The polyethylenes of the present disclosure can have a molecular weight distribution of 2 to 10, 3 to 7, or 3.5 to 6. This means that the molecular weight distribution of the polyethylene is narrow. When the molecular weight distribution is wide, the molecular weight difference between polyethylenes is large, so that the chlorine content of the polyethylene after the chlorination reaction may vary, and it is difficult to uniformly distribute the chlorine. In addition, when the low molecular weight component is melted, the fluidity becomes high, so that the pores of the polyethylene particles may be blocked, thereby reducing the chlorination productivity. However, since the polyethylene of the present disclosure has the molecular weight distribution as described above, the molecular weight difference between polyethylenes after the chlorination reaction is not large, and chlorine may be uniformly substituted.
For example, the molecular weight distribution (MWD, polydispersity index) may be measured using gel permeation chromatography (GPC, manufactured by Water). The MWD may be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn), and then dividing the weight average molecular weight by the number average molecular weight.
Specifically, PL-GPC220 manufactured by Waters can be used as a Gel Permeation Chromatography (GPC) instrument, and a column of Polymer Laboratories PLgel MIX-B300 mm length can be used. The evaluation temperature may be 160℃and 1,2, 4-trichlorobenzene may be used for the solvent at a flow rate of 1 mL/min. Each polyethylene sample may be pretreated by dissolving it in 1,2, 4-trichlorobenzene containing 0.0125% BHT for 10 hours using a GPC analyzer (PL-GP 220) and feeding the sample at a concentration of 10mg/10mL in an amount of 200 microliters (μl). Mw and Mn can be derived using calibration curves formed from polystyrene standards. 9 polystyrene standards having a molecular weight of 2000g/mol, 10000g/mol, 30000g/mol, 70000g/mol, 200000g/mol, 700000g/mol, 2000000g/mol, 4000000g/mol, 10000000g/mol were used.
The polyethylene may have a weight average molecular weight of from about 160000g/mol to about 260000g/mol, from about 170000g/mol to about 250000g/mol, or from about 180000g/mol to about 240000 g/mol. This means that polyethylene has a high molecular weight and a high content of a high molecular weight component, which results in an effect of increasing the content of a linking molecule described later.
According to another embodiment of the present disclosure, there is provided a process for preparing the polyethylene described above.
The method of preparing polyethylene according to the present disclosure may include the steps of: at least one first metallocene compound represented by the following chemical formula 1; and polymerizing ethylene in the presence of at least one second metallocene compound selected from the compounds represented by the following chemical formula 2:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
R 1 to R 8 At least one of (C) is- (CH) 2 ) n -OR, wherein R is C 1-6 A linear or branched alkyl group, and n is an integer from 2 to 6;
R 1 to R 8 The remainder of (2) being the same or different from each other and each being independently selected from hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, C 7-40 Alkylaryl, and C 7-40 Arylalkyl, or two or more substituents adjacent to each other may be linked to each other to form an unsubstituted or C-substituted 1-10 Hydrocarbyl-substituted C 6-20 Aliphatic or aromatic rings;
Q 1 and Q 2 Are identical or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkylaryl or C 7-40 An arylalkyl group;
A 1 carbon (C), silicon (Si) or germanium (Ge);
M 1 is a group 4 transition metal;
X 1 and X 2 Are identical or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, amino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 A sulfonate group; and
m is an integer of 0 or 1,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
Q 3 and Q 4 Are identical or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkylaryl or C 7-40 An arylalkyl group;
A 2 carbon (C), silicon (Si) or germanium (Ge);
M 2 is a group 4 transition metal;
X 3 and X 4 Are identical or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, amino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 Sulfonate groups (sulfonate groups); and
C 1 and C 2 One of (3) is composed ofThe following chemical formula 3a or 3b, the other is represented by the following chemical formula 3c, 3d or 3 e;
[ chemical formula 3a ]
[ chemical formula 3b ]
[ chemical formula 3c ]
[ chemical formula 3d ]
[ chemical formula 3e ]
In chemical formulas 3a, 3b, 3c, 3d and 3e, R 9 To R 39 And R is 17' To R 21' Are identical or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Silylalkyl, C 1-20 Alkoxysilyl group, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkylaryl or C 7-40 Arylalkyl, provided that R 17 To R 21 And R is 17' To R 21' At least one of (C) 1-20 A haloalkyl group, a halogen atom,
R 22 to R 39 More than two substituents adjacent to each other may be linked to each other to form an unsubstitutedSubstituted or covered C 1-10 Hydrocarbyl-substituted C 6-20 Aliphatic or aromatic rings; and
* Representation and A 1 And M 1 Binding sites.
In this document, the following terms may be defined as follows, unless otherwise indicated.
The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The hydrocarbyl group is a monovalent functional group in which a hydrogen atom is removed from the hydrocarbon, and may include alkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkylaryl, alkenylaryl, alkynylaryl, and the like. In addition, C 1-30 The hydrocarbon radical may be C 1-20 Hydrocarbon or C 1-10 A hydrocarbon group. For example, the hydrocarbyl group may be a straight chain, branched or cyclic alkyl group. More specifically, C 1-30 The hydrocarbon group may be a straight-chain, branched or cyclic alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl and cyclohexyl; or aryl, such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, or fluorenyl. Furthermore, it may be alkylaryl groups such as methylphenyl, ethylphenyl, methylbiphenyl, and methylnaphthyl, or arylalkyl groups such as benzyl, phenethyl, biphenylmethyl, and naphthylmethyl. It may also be alkenyl, such as allyl, vinyl, propenyl, butenyl, and pentenyl.
In addition, C 1-20 The alkyl group may be a linear, branched or cyclic alkyl group. Specifically, the C 1-20 The alkyl group may be C 1-20 A linear alkyl group; c (C) 1-15 A linear alkyl group; c (C) 1-5 A linear alkyl group; c (C) 3-20 Branched or cyclic alkyl; c (C) 3-15 Branched or cyclic alkyl; or C 3-10 Branched or cyclic alkyl groups. For example, the C 1-20 Alkyl groups may include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like, but the disclosure is not limited thereto.
The C is 2-20 Alkenyl includes straight-chain or branched alkenyl groups,and may specifically include allyl, vinyl, propenyl, butenyl, pentenyl, and the like, but the disclosure is not limited thereto.
The C is 1-20 Alkoxy groups may include methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, cyclohexyloxy, and the like, but the disclosure is not limited thereto.
The C is 2-20 Alkoxyalkyl groups are functional groups in which at least one hydrogen of the above alkyl groups is substituted with an alkoxy group, and may include methoxymethyl, methoxyethyl, ethoxymethyl, isopropoxymethyl, isopropoxyethyl, isopropoxypropyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, tert-butoxyhexyl, and the like, but the present disclosure is not limited thereto.
The C is 6-40 Aryloxy groups may include phenoxy, diphenoxy, naphthoxy, and the like, but the disclosure is not limited thereto.
The C is 7-40 An aryloxyalkyl group is a functional group in which at least one hydrogen in the above alkyl group is substituted with an aryloxy group, and it may include phenoxymethyl, phenoxyethyl, phenoxyhexyl, and the like, but the present disclosure is not limited thereto.
The C is 1-20 Alkylsilyl or C 1-20 Alkoxysilyl groups are wherein-SiH 3 A functional group in which 1 to 3 hydrogens are substituted with 1 to 3 of the above alkyl groups or alkoxy groups, and which may include an alkylsilyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group, or a dimethylpropylsilyl group; alkoxysilyl groups such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl; or an alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, or a dimethoxypropylsilyl group, etc., but the present disclosure is not limited thereto.
The C is 1-20 Silylalkyl is a functional group in which at least one hydrogen in the above alkyl group is replaced with a silyl group, and it may include-CH 2 -SiH 3 Methyl silylmethyl or dimethyl ethoxysilylpropyl, etc., but the disclosure is not limited thereto.
In addition, other than divalent substituents, C 1-20 The alkylene group is the same as the above-mentioned alkyl group, and it may include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and the like, but the present disclosure is not limited thereto.
The C is 6-20 Aryl groups may be monocyclic, bicyclic or tricyclic aromatic hydrocarbons. For example, the C 6-20 Aryl groups may include phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, and the like, but the disclosure is not limited thereto.
The C is 7-20 Alkylaryl may refer to a substituent in which at least one hydrogen of an aromatic ring is substituted with an alkyl group as described above. For example, the C 7-20 Alkylaryl groups can include methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, and the like, but the disclosure is not limited thereto.
The C is 7-20 Arylalkyl may refer to a substituent in which at least one hydrogen of the alkyl group is substituted with the aryl group described above. For example, the C 7-20 Arylalkyl groups can include benzyl, phenethyl, biphenylmethyl, naphthylmethyl, and the like, but the disclosure is not limited thereto.
In addition, other than divalent substituents, C 6-20 Arylene is the same as aryl described above, and may include phenylene, biphenylene, naphthylene, anthrylene, phenanthrylene, fluorenylene, and the like, although the disclosure is not limited thereto.
The group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or (Rf), and more specifically, may be titanium (Ti), zirconium (Zr), or hafnium (Hf). More specifically, it may be zirconium (Zr) or hafnium (Hf), but the present disclosure is not limited thereto.
Further, the group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and more specifically, may be boron (B) or aluminum (Al), but the disclosure is not limited thereto.
The first metallocene compound may be represented by any one of the following chemical formulas 1-1 to 1-4.
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1-4]
In chemical formulas 1-1 to 1-4, Q 1 、Q 2 、A 1 、M 1 、X 1 、X 2 R is as follows 1 To R 8 As defined in chemical formula 1, and R' are the same or different from each other and are each independently C 1-10 A hydrocarbon group.
Specifically, Q 1 And Q 2 May each be C 1-3 Alkyl, and preferably methyl.
Specifically, X 1 And X 2 Each may be halogen, and preferably chlorine.
Specifically, A 1 May be silicon (Si).
Specifically, M 1 May be zirconium (Zr) or hafnium (Hf).
Specifically, R 1 To R 8 Can each be hydrogen, or C 1-20 Alkyl, or C 1-10 Alkyl, or C 1-6 Alkyl, or C 1-6 Alkoxy substituted C 2-6 Alkyl, or C 1-4 Alkoxy substituted C 4-6 An alkyl group. Alternatively, R 32 To R 39 More than two substituents adjacent to each other may be linked to each other to form a group C 1-3 Alkyl substituted C 6-20 Aliphatic or aromatic rings.
Preferably, R 3 And R is 6 May each be C 1-6 Alkyl, or C 1-6 Alkoxy substituted C 2-6 Alkyl, or C 4-6 Alkyl, or C 1-4 Alkoxy substituted C 4-6 An alkyl group. For example, R 3 And R is 6 May each be n-butyl, n-pentyl, n-hexyl, t-butoxybutyl or t-butoxyhexyl.
And R is 1 、R 2 、R 4 、R 5 、R 7 And R is 8 May be hydrogen.
The compound represented by chemical formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
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The first metallocene compound represented by the above structural formula can be synthesized by applying a known reaction, and reference may be made to examples for a detailed synthesis method.
In the method for producing polyethylene according to the present disclosure, at least one first metallocene compound represented by chemical formula 1, chemical formula 1-2, chemical formula 1-3, or chemical formula 1-4 as described above is used together with at least one second metallocene compound as described below. Thus, by optimizing the high crystalline region ratio according to Temperature Rising Elution Fractionation (TREF) analysis while increasing the alpha transition temperature of the polyethylene, high productivity and excellent impact strength can be achieved during PVC blend processing in the CPE process described below.
Meanwhile, the second metallocene compound may be represented by the following chemical formula 2-1.
[ chemical formula 2-1]
In chemical formula 2-1, Q 3 、Q 4 、A 2 、M 2 、X 3 、X 24 、R 11 And R is 17 To R 29 The same definition as in chemical formula 2.
Specifically, Q 3 And Q 4 May each be C 1-3 Alkyl, or C 2-12 Alkoxyalkyl groups, and preferably methyl or tert-butoxyhexyl.
Specifically, X 3 And X 4 Each may be halogen, and preferably is chlorine.
Specifically, A 2 May be silicon (Si).
Specifically, M 2 May be zirconium (Zr) or hafnium (Hf), and is preferably zirconium (Zr).
Specifically, R 17 To R 21 And R is 17’ To R 21’ Can each be hydrogen or C 1-6 Haloalkyl, and is preferably hydrogen or C 1-3 A haloalkyl group. For example, R 17 To R 20 Or R is 17' To R 20' May be hydrogen, and R 21 Or R is 21' Can be a trihalomethyl group, preferably a trifluoromethyl group.
Specifically, R 11 And R is 11 ' may each be C 1-6 Straight-chain or branched alkyl, or C 1-3 A linear or branched alkyl group, and preferably a methyl group.
Specifically, R 22 To R 29 Can each be hydrogen, or C 1-20 Alkyl, or C 1-10 Alkyl, or C 1-6 Alkyl, or C 1-3 An alkyl group. Alternatively, R 22 To R 29 More than two substituents adjacent to each other may be linked to each other to form a group C 1-3 Alkyl substituted C 6-20 Aliphatic or aromatic rings.
Specifically, R 30 To R 35 Can each be hydrogen, or C 1-20 Alkyl, or C 1-10 Alkyl, or C 1-6 Alkyl, or C 1-3 An alkyl group.
Specifically, R 26 To R 29 Can each be hydrogen, or C 1-20 Alkyl, or C 1-10 Alkyl, or C 1-6 Alkyl, or C 1-3 An alkyl group.
The compound represented by chemical formula 2 may be, for example, a compound represented by the following structural formula, but is not limited thereto.
The second metallocene compound represented by the above structural formula can be synthesized by applying a known reaction, and reference may be made to examples for a detailed synthesis method.
The preparation of the metallocene compound is specifically described in examples described later.
The metallocene catalysts used in the present disclosure may be supported on a carrier together with a cocatalyst compound.
In the supported metallocene catalyst according to the present disclosure, the cocatalyst for activating the metallocene compound supported on the carrier is an organometallic compound containing a group 13 metal, and is not particularly limited as long as it can be used in olefin polymerization in the presence of a general metallocene catalyst.
The cocatalyst is an organometallic compound containing a group 13 metal and is not particularly limited as long as it can be used in ethylene polymerization in the presence of a general metallocene catalyst.
Specifically, the cocatalyst may be at least one selected from compounds represented by the following chemical formulas 4 to 6:
[ chemical formula 4]
-[Al(R 40 )-O] c -
In the chemical formula 4, the chemical formula is shown in the drawing,
R 40 each independently is halogen, C 1-20 Alkyl or C 1-20 Haloalkyl, and
c is an integer of 2 or more;
[ chemical formula 5]
D(R 41 ) 3
In the chemical formula 5, the chemical formula is shown in the drawing,
d is aluminum or boron, and
R 41 each independently is hydrogen, halogen, C 1-20 C substituted by hydrocarbon or halogen 1-20 A hydrocarbon group,
[ chemical formula 6]
[L-H] + [Q(E) 4 ] - Or [ L ]] + [Q(E) 4 ] -
In the chemical formula 6, the chemical formula is shown in the drawing,
l is a neutral or cationic lewis base;
[L-H] + is a Bronsted acid, and is preferably a Bronsted acid,
q is Br 3+ Or Al 3+ A kind of electronic device
E is each independently unsubstituted or is selected from halogen, C 1-20 Alkyl, C 1-20 Alkoxy and phenoxy substituted C 6-20 Aryl or C 1-20 An alkyl group.
The compound represented by chemical formula 4 may be an alkylaluminoxane such as Modified Methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc.
The alkyl metal compound represented by chemical formula 5 may be trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, dimethylaluminum isobutyl aluminum, dimethylaluminum, diethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylmethoxyaluminum, dimethylethoxyaluminum, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like.
The compound represented by chemical formula 6 may be triethylammonium tetraphenyl boron, tributylammonium tetraphenyl boron, trimethylammonium tetraphenyl boron, tripropylammonium tetraphenyl boron, trimethylammonium tetrakis (p-tolyl) boron, tripropylammonium tetrakis (p-tolyl) boron, triethylammonium tetrakis (o, p-dimethylphenyl) boron, trimethylammonium tetrakis (o, p-dimethylphenyl) boron, tributylammonium tetrakis (p-trifluoromethylphenyl) boron, trimethylammonium tetrakis (p-trifluoromethylphenyl) boron, tributylammonium tetrakis (pentafluorophenyl) boron, N-diethylanilinium tetraphenyl boron, N, N-diethylanilinium tetrakis (pentafluorophenyl) boron, diethylammonium tetrakis (pentafluorophenyl) boron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetrakis (p-tolyl) aluminum, tripropylammonium tetrakis (p-tolyl) aluminum, triethylammonium tetrakis (o, p-dimethylphenyl) aluminum, tributylammonium tetrakis (p-trifluoromethylphenyl) aluminum, trimethylammonium tetrakis (p-trifluoromethylphenyl) aluminum, tributylammonium tetrakis (pentafluorophenyl) aluminum, N-diethylanilinium tetraphenylaluminum, N-diethylanilinium tetrakis (pentafluorophenyl) aluminum, diethylammonium tetrakis (pentafluorophenyl) aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylanilinium tetraphenylaluminum, triethylammonium tetraphenylaluminum, triphenylcarbonium tetraphenyl boron, triphenylcarbonium tetraphenyl aluminum, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrakis (pentafluorophenyl) boron, and the like.
The cocatalyst can be supported in an amount of about 5mmol to about 20mmol based on 1g of the carrier.
In the supported metallocene catalyst according to the present disclosure, a support having hydroxyl groups on the surface may be used. Preferably, a carrier containing highly reactive hydroxyl groups or siloxane groups that is dried to remove moisture on the surface can be used.
For example, the support may be silica, silica-alumina, or silica-magnesia, dried at high temperature, and typically contains oxides, carbonates, sulfates, and nitrates, such as Na 2 O、K 2 CO 3 、BaSO 4 、Mg(NO 3 ) 2 Etc.
The drying temperature of the support may preferably be about 200 ℃ to 800 ℃, more preferably about 300 ℃ to 600 ℃, and most preferably about 300 ℃ to 400 ℃. When the drying temperature of the support is less than about 200 ℃, surface moisture may react with the cocatalyst due to excessive moisture. When it is greater than about 800 ℃, the pores on the support surface may combine to reduce the surface area, and a large number of hydroxyl groups may be lost on the surface, and only siloxane groups may remain, thereby reducing the reaction sites with the cocatalyst, which is not preferred.
The amount of hydroxyl groups on the surface of the support may preferably be from about 0.1mmol/g to about 10mmol/g, more preferably from about 0.5mmol/g to about 5mmol/g. The amount of hydroxyl groups on the surface of the support may be controlled according to the preparation method and conditions of the support, or drying conditions (e.g., temperature, time, vacuum, spray drying, etc.).
When the amount of hydroxyl groups is less than about 0.1mmol/g, the reaction sites with the cocatalyst are small, whereas when it exceeds about 10mmol/g, it is likely to originate from moisture on the surface of the carrier particles instead of hydroxyl groups, which is not preferable.
In the supported metallocene catalysts of the present disclosure, the weight ratio of total transition metals to support included in the metallocene catalysts may be about 1:10 to 1:1000. When the support and the metallocene compound are contained in the above weight ratio, an optimal shape can be exhibited. In addition, the weight ratio of promoter compound to carrier may be from 1:1 to 1:100.
The ethylene polymerization may be carried out using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.
In particular, the polyethylene according to the present disclosure may be prepared by the following steps: at least one first metallocene compound represented by chemical formula 1; and at least one second metallocene compound selected from the compounds represented by chemical formula 2.
The weight ratio of the first metallocene compound to the second metallocene compound (first metallocene compound: second metallocene compound) may be about 40:60 to 75:25, or about 42:58 to about 65:35. The weight ratio of the catalyst precursor may be in the above range in terms of achieving a molecular structure having a narrow particle distribution and a low content of ultra-high molecular weight to improve the impact strength of PVC blends and to produce chlorinated polyethylene having excellent chlorination productivity and thermal stability.
In addition, the polyethylene may be prepared under the metallocene catalyst as described above while introducing hydrogen. Here, the hydrogen may be introduced in an amount of about 30ppm to about 60ppm, about 30ppm to about 45ppm, or about 30ppm to about 40ppm with respect to the ethylene.
In addition, the polymerization may be carried out at a temperature of from about 25 ℃ to about 500 ℃, preferably from about 25 ℃ to about 200 ℃, more preferably from about 50 ℃ to about 150 ℃. In addition, the ratio of the pressure to the flow rate can be about 1kgf/cm 2 To about 100kgf/cm 2 Preferably about 1kgf/cm 2 To about 50kgf/cm 2 More preferably about 5kgf/cm 2 To about 30kgf/cm 2 Is polymerized under pressure.
In addition, the supported metallocene catalyst may be in a C5 to C12 aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane and isomers thereof; aromatic hydrocarbon solvents such as toluene and benzene, or hydrocarbon solvents substituted with chlorine such as methylene chloride and chlorobenzene. The solvent used herein is preferably used after treating with a small amount of aluminum alkyl to remove a small amount of water or air as a catalyst poison. It is also possible to use further cocatalysts.
According to another embodiment of the present disclosure, there is provided Chlorinated Polyethylene (CPE) using the above polyethylene.
The chlorinated polyethylene according to the present disclosure may be prepared by polymerizing ethylene in the presence of the above-described supported metallocene catalyst, and then reacting the polyethylene with chlorine.
The reaction with chlorine may be carried out by dispersing the prepared polyethylene with water, an emulsifier and a dispersant, and then adding a catalyst and chlorine to react.
As the emulsifier, polyether or polyalkylene oxide may be used. The dispersant may be a polymeric salt or an organic acid polymeric salt, and the organic acid may be methacrylic acid or acrylic acid.
The catalyst may be a chlorination catalyst used in the art, and benzoyl peroxide may be used. The chlorine may be used alone or may be used after being mixed with an inert gas.
The chlorination reaction may be conducted at about 60 ℃ to about 150 ℃, about 70 ℃ to about 145 ℃, or about 80 ℃ to about 140 ℃ for about 10 minutes to about 10 hours, about 1 hour to about 9 hours, or about 2 hours to about 8 hours.
The chlorinated polyethylene prepared by the above reaction may be further subjected to a neutralization process, a washing process and/or a drying process, and thus may be obtained in the form of powder.
Chlorinated polyethylene has excellent uniformity of chlorine distribution and exhibits high elongation because polyethylene maintains a stable crystal structure at high temperature and has a low content of high crystalline regions. For example, the chlorinated polyethylene may have an elongation of about 1000% or more, or about 1100% or more, when measured according to ASTM D-412. In addition, the elongation of the chlorinated polyethylene can be measured at 500 mm/min. Specifically, after preparing chlorinated polyethylene by reacting polyethylene with chlorine in a slurry (water or aqueous HCl solution) at about 60 ℃ to about 150 ℃, the elongation measured at 500mm/min according to ASTM D-412 may be about 1000% or more. Specifically, the elongation of CPE can be a value measured for chlorinated polyethylene obtained by: about 500kg to about 600kg of polyethylene (water or aqueous HCl) in the slurry state is heated from about 75 ℃ to about 85 ℃ to a final temperature of about 120 ℃ to about 140 ℃ at a rate of about 15 ℃/hr to about 18.5 ℃/hr, and then subjected to a chlorination reaction with gaseous chlorine at a final temperature of about 120 ℃ to about 140 ℃ for about 2 hours to about 5 hours. At this time, the chlorination reaction may be performed by injecting chlorine in a gaseous state while raising the temperature while maintaining the pressure in the reactor at about 0.2Mpa to about 0.4Mpa, and the total amount of injected chlorine is about 550kg to about 650kg.
For example, the chlorinated polyethylene may have a chlorine content of about 20wt% to about 45wt%, about 31wt% to about 40wt%, or about 33wt% to about 38 wt%. The chlorine content of chlorinated polyethylene can be measured using combustion ion chromatography. For example, combustion ion chromatography uses a combustion IC (ICS-5000/AQF-2100H) device equipped with an IonPac AS18 (4X 250 mm) column. The chlorine content can be measured at an inlet temperature of 900 ℃ and an outlet temperature of 1000 ℃ using KOH (30.5 mM) as eluent at a flow rate of 1 mL/min. The apparatus conditions and measurement conditions for measuring chlorine content are described in test example 2 described later, and detailed description thereof is omitted.
The chlorinated polyethylene may be, for example, a randomly chlorinated polyethylene.
The chlorinated polyethylene prepared according to the present disclosure is excellent in chemical resistance, weather resistance, flame retardancy, processability and impact strength reinforcing effect, and is widely used as an impact reinforcing agent for PVC pipes and window profiles.
In addition, the chlorinated polyethylene according to the present disclosure may be produced into PVC shaped products by conventional methods in the art. For example, a molded article can be produced by roll-milling and extruding chlorinated polyethylene.
Hereinafter, preferred embodiments are provided to aid in understanding the present invention. However, these examples are for illustrative purposes only and the present invention is not intended to be limited by these examples.
[ preparation of catalyst precursor ]
Synthesis example 1: preparation of the first metallocene Compound
Preparation of tert-butyl-O- (CH) using 6-chlorohexanol by the method shown in Tetrahedron letters 2951 (1988) 2 ) 6 -Cl and reacting it with sodium cyclopentadienyl (Cp sodium salt, naCp) to obtain tert-butyl-O- (CH) 2 ) 6 -C 5 H 5 (yield: 60%, boiling point (b.p.) 80 ℃ C./0.1 mmHg).
In addition, tert-butyl-O- (CH) is reacted at-78deg.C 2 ) 6 -C 5 H 5 Dissolved in THF and n-butyllithium (n-BuLi) was slowly added thereto. After this time, it was warmed to room temperature and reacted for 8 hours. The lithium salt solution synthesized as described above was slowly added to ZrCl at-78 ℃ 4 (THF) 2 (170g,4.50 mmol)/THF (30 mL) and further reacted at room temperature for about 6 hours. All volatiles were dried in vacuo and the resulting oily liquid material was filtered by addition of hexane solvent. The filtered solution was dried under vacuum and hexane was added to obtain a precipitate at low temperature (-20 ℃). The precipitate obtained was filtered off at low temperature to obtain [ tBu-O- (CH) as a white solid 2 ) 6 -C 5 H 4 ] 2 ZrCl 2 (yield 92%).
1 H-NMR(300MHz,CDCl 3 ):6.28(t,J＝2.6Hz,2H),6.19(t,J＝2.6Hz,2H),3.31(t,6.6Hz,2H),2.62(t,J＝8Hz),1.7–1.3(m,8H),1.17(s,9H).
13 C-NMR(CDCl 3 ):135.09,116.66,112.28,72.42,61.52,30.66,30.31,30.14,29.18,27.58,26.00.
Synthesis example 2: preparation of the second metallocene Compound
Preparation of 2-1 ligand compounds
2.9g (7.4 mmol) of 8-methyl-5- (2- (trifluoromethyl) benzyl) -5, 10-indano [1,2-b ] indole are dissolved in 100mL of hexane and 2mL (16.8 mmol) of MTBE (methyl tert-butyl ether) and 3.2mL (8.1 mmol) of a 2.5M solution of n-butyllithium in hexane are added dropwise to a dry ice/acetone bath and stirred at room temperature overnight. In another 250mL schlenk flask, 2g (7.4 mmol) of (6-t-butoxyhexyl) dichloro (methyl) silane was dissolved in 50mL of hexane and added dropwise to a dry ice/acetone bath. Then, a lithiated slurry of 8-methyl-5- (2- (trifluoromethyl) benzyl) -5, 10-indano [1,2-b ] indole was added dropwise via cannula. After injection, the mixture was slowly warmed to room temperature and then stirred at room temperature overnight. At the same time, 1.2g (7.4 mmol) of fluorene was also dissolved in 100mL of Tetrahydrofuran (THF), and 3.2mL (8.1 mmol) of 2.5M n-BuLi hexane solution was added dropwise to the dry ice/acetone bath, followed by stirring overnight at room temperature.
The reaction solution (Si solution) of 8-methyl-5- (2- (trifluoromethyl) benzyl) -5, 10-indano [1,2-b ] indole and (6- (t-butoxy) hexyl) dichloro (methyl) silane was confirmed by NMR sampling.
1 H NMR(500MHz,CDCl 3 ):7.74-6.49(11H,m),5.87(2H,s),4.05(1H,d),3.32(2H,m),3.49(3H,s),1.50-1.25(8H,m),1.15(9H,s),0.50(2H,m),0.17(3H,d).
After confirmation of the synthesis, the lithiated solution of fluorene was slowly added dropwise to the Si solution in a dry ice/acetone bath and stirred at room temperature overnight. After the reaction, it was extracted with diethyl ether/water, and the residual water of the organic layer was extracted with MgSO 4 And (5) removing. Then, the solvent was removed under reduced pressure in vacuo to give 5.5g (7.4 mmol) of the oily ligand compound, which was confirmed by 1H-NMR.
1 H NMR(500MHz,CDCl 3 ):7.89-6.53(19H,m),5.82(2H,s),4.26(1H,d),4.14-4.10(1H,m),3.19(3H,s),2.40(3H,m),1.35-1.21(6H,m),1.14(9H,s),0.97-0.9(4H,m),-0.34(3H,t).
Preparation of 2-2 metallocene compounds
5.4g (Mw 742.00,7.4 mmol) of the ligand compound synthesized in 2-1 above was dissolved in 80mL of toluene and 3mL (25.2 mmol) of MTBE, and 7.1mL (17.8 mmol) of a 2.5M solution of n-BuLi in hexane was added dropwise to the dry ice/acetone bath, followed by stirring at room temperature overnight. 3.0g (8.0 mmol) of ZrCl was added to 80mL of toluene 4 (THF) 2 To prepare a slurry. 80mL of ZrCl 4 (THF) 2 Is transferred to a ligand-Li solution in a dry ice/acetone bath and stirred at room temperature overnight.
After the reaction mixture was filtered to remove LiCl, toluene in the filtrate was removed by vacuum drying, and 100mL of hexane was then added thereto, followed by sonication for 1 hour. It was filtered to obtain 3.5g (yield 52 mol%) of a purple metallocene compound as a filtered solid.
1 H NMR(500MHz,CDCl 3 ):7.90-6.69(9H,m),5.67(2H,s),3.37(2H,m),2.56(3H,s),2.13-1.51(11H,m),1.17(9H,s).
Synthesis example 3: preparation of the second metallocene Compound
Preparation of 3-1 ligand compounds
6.3g (20 mmol) of 1, 8-bis (bromomethyl) naphthalene and 8.3g (40 mmol) of methyl TMS-indene lithium salt were each dissolved in 80mL of THF, then added dropwise in a dry ice/acetone bath, followed by stirring overnight at room temperature. After stirring was completed, the reaction product was extracted with diethyl ether/water and was extracted with MgSO 4 Residual moisture of the organic layer was removed. Then, the solvent was removed under reduced pressure in vacuo to give 11.1g (20mmol,Mw 556.93g/mol) of a liquid ligand compound.
Preparation of 3-2 metallocene compounds
11g of the ligand compound synthesized in 3-1 was dissolved in a mixed solvent of 80mL of toluene and 5mL of methyl tert-butyl ether (MTBE), and 16.7mL (41.6 mmol) of a 2.5M hexane solution of n-butyllithium was added dropwise, followed by stirring at room temperature. 7.5g (19.8 mmol) of ZrCl 4 (THF) 2 80mL of toluene was added to make a slurry, and the slurry was transferred to a dry ice/acetone bath and stirred at room temperature overnight.
After completion of stirring, the slurry was filtered to remove LiCl, toluene of the filtrate was removed by vacuum drying, and then 100mL of hexane was added thereto, followed by sonication for 1 hour. Thereafter, the slurry was filtered to obtain 4.5g (yield 62.3mol%, yellow solid) of the metallocene compound as a filtered solid.
1 H NMR(500MHz,CDCl 3 ):8.16-6.95(14H,m),5.99(2H,d),3.99(2H,m),3.83(2H,m),3.39(2H,m),0.15(18H,d).
Synthesis example 4: preparation of the second metallocene Compound
Preparation of 4-1 ligand compounds
3g (10 mmol) of the indenoindole derivative are dissolved in 100mL of hexane, and 4.4mL (11 mmol) of a 2.5M solution of n-butyllithium in hexane are added dropwise thereto, followed by stirring at room temperature overnight. Another 250mL schlenk flask was prepared and placed in a glove box. Then, 2.7g (10 mmol) of (6-t-butoxyhexyl) dichloro (methyl) silane was weighed and taken out in a glove box, dissolved in 50mL of hexane, and then a lithiated slurry was added dropwise thereto. The mixture was slowly warmed to room temperature and stirred overnight. 10mmol of Cp sodium salt was dissolved in 100mL of THF, then added dropwise to the mixture, followed by stirring overnight at room temperature. After the reaction, the reaction mixture was purified by using MgSO 4 The residual moisture in the organic layer was removed by extraction, and the solvent was removed under reduced pressure in vacuo to obtain the ligand compound as an oil. By means of 1 H NMR was confirmed.
Preparation of 4-2 metallocene compounds
7.9mmol of the ligand compound synthesized in 4-1 was dissolved in 80mL of toluene, and 6.6mL (16.6 mmol) of a 2.5M solution of n-butyllithium hexane was added dropwise thereto, followed by stirring at room temperature overnight. Preparation of 7.9mmol of ZrCl in 80mL of toluene 4 (THF) 2 Is a slurry and, the ligand lithium solution is transferred and stirred.
The reaction mixture was filtered to remove LiCl, and toluene of the filtrate was dried in vacuo to obtain 1.5g of a liquid catalyst in a yield of 23mol%.
[ preparation of Supported catalyst ]
Preparation example 1: preparation of Supported catalysts
5.0kg of toluene solution was charged into a 20L stainless steel (sus) high-pressure reactor, and the reactor temperature was maintained at 40 ℃. After 1000g of silica (SP 948, manufactured by Grace Davison Co.) dehydrated in vacuo at a temperature of 600℃for 12 hours was added to the reactor and the silica was sufficiently dispersed, 84g of the metallocene compound of Synthesis example 1 was dissolved in toluene, added thereto, and then reacted for 2 hours while stirring at 200rpm at 40 ℃. After this time, stirring was stopped, followed by settling for 30 minutes, and then the reaction solution was decanted.
To the reactor was added 2.5kg of toluene, and 9.4kg of a 10wt% Methylaluminoxane (MAO)/toluene solution was added thereto, and then the solution was stirred at 200rpm at 40℃for 12 hours. After this time, stirring was stopped, followed by settling for 30 minutes, and then the reaction solution was decanted. After adding 3.0kg of toluene and stirring for 10 minutes, stirring was stopped, followed by settling for 30 minutes, and then the toluene solution was decanted.
After adding 3.0kg of toluene to the reactor, 116g of the metallocene compound of Synthesis example 2 was dissolved in 1L of toluene solution, and added thereto, followed by stirring at 200rpm at 40℃for 2 hours. At this time, the weight ratio of the metallocene compound of Synthesis example 1 to the metallocene compound of Synthesis example 2 was 42:58. After the reactor temperature was lowered to room temperature, stirring was stopped, followed by settling for 30 minutes, and then the reaction solution was decanted.
2.0kg of toluene was added to the reactor and stirred for 10 minutes. Then, stirring was stopped, followed by settling for 30 minutes, and then the reaction solution was decanted.
3.0kg of hexane was added to the reactor, and the hexane slurry was sent to a filter dryer, and the hexane solution was filtered. Preparation of 1kg-SiO by drying under reduced pressure at 40℃for 4 hours 2 Supported hybrid catalysts.
Comparative preparation example 1 preparation of Supported catalyst
A supported hybrid catalyst was prepared in the same manner as in preparation example 1, except that the metallocene compound of synthesis example 3 was used instead of the metallocene compound of synthesis example 2.
Comparative preparation example 2 preparation of Supported catalyst
A supported hybrid catalyst was prepared in the same manner as in preparation example 1, except that the metallocene compound of synthesis example 4 was used instead of the metallocene compound of synthesis example 2.
[ preparation of polyethylene ]
Example 1-1
The supported catalyst prepared in preparation example 1 was added to a single slurry polymerization process to prepare high density polyethylene.
First, 100m was filled with 25 tons/hr of hexane, 10 tons/hr of ethylene, 30ppm of hydrogen (relative to ethylene), and 10 kg/hr of Triethylaluminum (TEAL) at a flow rate 3 The reactor was charged with 0.5kg/hr of the supported hybrid metallocene catalyst of preparation example 1. Thereafter, ethylene was fed at a reactor temperature of 82℃and 7.0kg/cm 2 To 7.5kg/cm 2 The reaction was continued in the hexane slurry state under the pressure of (2). Then, it is subjected to solvent removal and drying to prepare high-density polyethylene in the form of powder.
Examples 1 to 2
A high-density polyethylene having a powder form was produced in the same manner as in example 1-1, except that the input amount of hydrogen was changed to 40 ppm.
Examples 1 to 3
A high-density polyethylene having a powder form was produced in the same manner as in example 1-1, except that the input amount of hydrogen was changed to 35 ppm.
Comparative example 1-1
Preparation for preparation using Ziegler-Natta (Z/N) catalyst and having a Melt Index (MI) of 0.45g/10min 5 A commercial product of High Density Polyethylene (HDPE) (CE 604K, manufactured by LG chemistry) at 190℃of 5kg was used for comparative example 1-1.
Comparative examples 1 to 2
High density polyethylene in the form of powder was prepared in the same manner as in examples 1-2, except that the supported catalyst prepared in comparative preparation example 1 was used instead of the supported catalyst prepared in preparation example 1.
Comparative examples 1 to 3
High-density polyethylene having a powder form was prepared in the same manner as in comparative examples 1-2, except that the input amount of hydrogen was changed to 70 ppm.
Comparative examples 1 to 4
High-density polyethylene having a powder form was produced in the same manner as in comparative examples 1-2, except that the input amount of hydrogen was changed to 50 ppm.
Comparative examples 1 to 5
High density polyethylene having a powder form was prepared in the same manner as in example 1-1, except that the supported catalyst prepared in comparative preparation example 2 was used instead of the supported catalyst prepared in preparation example 1.
Test example 1
Physical properties of the polyethylenes prepared in examples and comparative examples were measured using the following methods, and the results are shown in table 1 below.
1) Melt index (MI, g/10 min)
Melt Index (MI) was measured according to ASTM D1238 at 190℃under a load of 5kg and 21.6kg, respectively 2.16 ，MI 5 ，MI 21.6 ). The weight (g) of the 10 minute molten polymer was recorded as melt index.
2) Melt flow Rate ratio (MFRR, MI 21.6/5 )
The melt flow rate ratio (MFRR ) is obtained by dividing the melt index measured according to ASTM D1238 at 190℃under a load of 21.6kg by the melt index measured at 190℃under a load of 5kg 21.6/5 )。
3) Density of
Density (g/cm) was measured according to ASTM D1505 3 )。
4) High crystalline region ratio (%)
A Temperature Rising Elution Fractionation (TREF) plot of polyethylene is obtained and an elution temperature, which is a division point (minimum) between two highest peaks among peaks appearing on the TREF plot, is used as a reference for the vertical axis at which the high crystallization zone starts. Then, the pattern area of the high crystallization region having a temperature equal to or higher than the elution temperature of the minimum value is measured, and the value of the percentage obtained by dividing the pattern area by the total pattern area is expressed as the high crystallization region ratio (%). A Temperature Rising Elution Fractionation (TREF) plot of polyethylene was obtained using Agilent Technologies 7890A manufactured by polymer char. For example, a sample was dissolved in 20mL of 1,2, 4-trichlorobenzene at a concentration of 1.5mg/mL, then dissolved by increasing the temperature from 30℃to 150℃at a rate of 40℃per minute, then recrystallized by decreasing the temperature to 35℃at a rate of 0.5℃per minute, and then eluted by increasing the temperature to 140℃at a rate of 1℃per minute to obtain a pattern.
5) Alpha transition temperature (. Degree. C.)
The alpha transition temperature was measured using a Dynamic Mechanical Analyzer (DMA) by lowering the temperature to-60 ℃ for 5 minutes at which the temperature was raised to 140 ℃ and then determining the top of the tan delta curve as the alpha transition temperature.
[ Table 1 ]
In Table 1, polymerization period H 2 Is the hydrogen content based on the ethylene input.
As shown in table 1, it can be confirmed that the examples show a high α -transformation temperature of about 125 ℃ to about 145 ℃ higher than 120 ℃ and a low high crystalline region ratio of 11.8% or less, as compared with the comparative examples.
Test example 2
The polyethylene prepared in examples and comparative examples was used to prepare chlorinated polyethylene.
[ preparation of chlorinated polyethylene ]
5000L of water and 550kg of the high-density polyethylene prepared in example 1-1 were charged into a reactor, followed by sodium polymethacrylate as a dispersing agent, propylene oxide and ethylene oxide copolyethers as an emulsifier, and benzoyl peroxide as a catalyst. Then, the temperature was raised from 80℃to 132℃at a rate of 17.3℃per hr, and chlorination was carried out at a final temperature of 132℃for 3 hours by injecting gaseous chlorine. At this time, gaseous chlorine was injected while raising the temperature and maintaining the reactor pressure at 0.3Mpa, and the total input of chlorine was 610kg. The chlorinated reaction was neutralized with NaOH for 4 hours, washed again with running water for 4 hours, and finally dried at 120 ℃ to prepare chlorinated polyethylene in powder form.
In addition, the polyethylenes prepared in examples 1-2 to 1-3 and comparative examples 1-1 to 1-5 were also used to prepare chlorinated polyethylenes having a powder form in the same manner as described above.
As described above, the physical properties of the chlorinated polyethylenes of examples 2-1 to 2-3 and comparative examples 2-1 to 2-5 prepared using the polyethylenes of examples 1-1 to 1-3 and comparative examples 1-1 to 1-5 were measured by the following methods, and the results are shown in table 2 below.
1) Elongation of CPE (%)
Elongation of CPE was measured at 500mm/min according to ASTM D-2240.
2) Deoxygenation time of CPE (min)
The deoxidation process was performed by adding water until the pH of the solution reached 6.0 or more in the preparation of chlorinated polyethylene, and the time taken until the pH of the solution became 6.0 or more was measured as the deoxidation time. In this case, the deoxidization time of the CPE is preferably 550 minutes or less. When it exceeds 550 minutes, the entire chlorination process is delayed, which may cause a problem of reduced CPE productivity.
[ Table 2 ]
As shown in table 2, it can be confirmed that the examples were very effective in improving impact strength during the preparation of PVC blends not only with excellent CPE productivity due to significantly reduced deoxidizing time, but also by achieving high elongation of greater than 1123% after chlorination, as compared to the comparative examples.

Claims (9)

1. A polyethylene having an alpha transition temperature of 120 ℃ or higher, wherein the alpha transition temperature is measured by thermal analysis of the polyethylene by a method using a dynamic mechanical analyzer by lowering the temperature to-60 ℃, holding at that temperature for 5 minutes, raising the temperature to 140 ℃, then determining the top of the tan delta curve as the alpha transition temperature, and
a high crystallization region ratio on a temperature rising elution fractionation chart of 12.5% or less, wherein the high crystallization region ratio is obtained by dividing a pattern area having a high crystallization region corresponding to an elution temperature or more at a division point of a minimum peak between two maximum peaks in a TREF chart by a total pattern area in percentage.
2. The polyethylene according to claim 1, wherein the polyethylene is an ethylene homopolymer.
3. The polyethylene of claim 1, wherein the polyethylene has an alpha transition temperature of 120 ℃ to 145 ℃.
4. The polyethylene according to claim 1, wherein the polyethylene has a high crystalline fraction on a temperature rising elution fractionation chart of 5% to 12.5%.
5. The polyethylene of claim 1, wherein the polyethylene has a melt index MI of 0.1g/10min to 1.5g/10min 5 。
6. The polyethylene of claim 1, wherein the polyethylene has a melt flow rate ratio MFRR of 10 to 20 21.6/5 Is a value obtained by dividing the melt index measured according to ASTM D1238 at 190 ℃,21.6kg load by the melt index measured at 190 ℃,5kg load.
7. The polyethylene of claim 1, wherein the polyethylene has 0.947g/cm 3 To 0.957g/cm 3 Is a density of (3).
8. A chlorinated polyethylene prepared by reacting the polyethylene according to any one of claims 1 to 7 with chlorine.
9. The chlorinated polyethylene of claim 8, wherein the chlorinated polyethylene has an elongation of 1000% or more when measured according to ASTM D-412.
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