WO2002053622A1 - Addition copolymers of cyclic olefins containing sulfur - Google Patents
Addition copolymers of cyclic olefins containing sulfur Download PDFInfo
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- WO2002053622A1 WO2002053622A1 PCT/KR2001/002291 KR0102291W WO02053622A1 WO 2002053622 A1 WO2002053622 A1 WO 2002053622A1 KR 0102291 W KR0102291 W KR 0102291W WO 02053622 A1 WO02053622 A1 WO 02053622A1
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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
- C08F228/00—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 bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—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 bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
Definitions
- the present invention relates to addition copolymers of cyclic olefins.
- the present invention relates to cyclic olefin copolymers of norbornene type compounds containing sulfur to provide excellent adhesiveness to metal, and methods for using the same.
- Silicon oxides and silicon nitrides have been widely used as inorganic compounds in the electronic material industry. However, due to the increasing need for smaller and more effective devices, the demand for high performance material has increased.
- Typically considered features for polymers include low dielectric constant, and moisture absorption, excellent adhesiveness to metal, mechanical strength, thermal stability, transparency and high glass transition temperature (T g >200°C). These polymers can be applied to semiconductors, TFT-LCD insulating films, multi-chip modules, integrated circuit (IC), packaging for an electronic element, low dielectric coating agent or film for optical use, e.g., flat panel display.
- Polymers such as polyimide or BCB (bis-benzocyclobutenes) are used as low dielectric material for electronic elements.
- polyimide primarily because of its excellent thermal stability, oxidative stability, high glass transition temperature and mechanical properties. However, they have to deal with problems such as the corrosion of the element and increased dielectric constant due to the high moisture absorption of polyimide, the anisotropic electronic property, the pretreatment step to control the reaction of polyimide with copper wire, and the adhesiveness to metal.
- BCB has comparatively low moisture absorption and dielectric constant, but its adhesiveness to metal is inadequate.
- BCB should undergo a curing process at high temperature since the physical properties are greatly influenced by the curing time and temperature.
- ROMP ring opening metathesis polymerization
- HROMP ring opening metathesis polymerization followed by hydrogenation
- co-polymerization with ethylene and homogeneous polymerization, which are illustrated in the following chemical equation 1.
- thermoplastic resins or thermosetting resins are employed to a substrate of a circuit through reaction injection molding (U.S. Patent No. 5,011 ,730 by Tenny, et al.). Nevertheless, as described above, the resins still exhibit low thermal stability, oxidative stability, and low glass transition temperature.
- cyclic polymers are not adhesive to metal although they are supposed to be used for information or electronic elements. Specifically, the polymers are required to be adhesive to a variety of surfaces, including silicon, silicon oxide, silicon nitride, alumina, copper, aluminum, gold, silver, platinum, titanium, nickel, tantalum, chromium, and other polymers.
- the following process was carried out: treating a substrate of a semiconductor by an organic silicon coupling agent with two functional groups, e.g., amino- propyltriethoxysilane or triethoxyvinylsilane; reacting the substrate with a polymer or a polymer precursor.
- the silyl group was hydrolyzed to make a covalent bond with a hydroxy functional group on the surface of the substrate.
- the cyclic polymer can be used for insulating material, wherein inorganic compounds like silicon oxide or silicon nitride has been mainly employed.
- inorganic compounds like silicon oxide or silicon nitride has been mainly employed.
- T g glass transition temperature
- Polymers that satisfy all the above-described requirements can be employed as low dielectric material for semiconductor or TFT-LCD.
- the amino group attached to a substrate reacts with a functional group of a polymer or a polymer precursor and becomes a bridging group, connecting the substrate and the polymer (U.S. Patent No. 4,831 ,172).
- this method involves a multiple-step process and requires a coupling agent.
- a method of introducing a substituent to a polymer consisting of hydrocarbon is very useful in that it can effectively control the chemical and physical properties of the polymer.
- the method was found to be very difficult to perform because unpaired electrons in the substituent react with an active catalytic site and becomes a catalyst poison. If a cyclic monomer contains a substituent, the molecular weight of the resulting polymer becomes low (U.S. Patent No. 3, 330, 815).
- a method to put a monomer containing a substituent in the latter stage of polymerization process was proposed (U.S. Patent No. 5, 179, 171). Unfortunately, this method was not successful to improve the thermal stability of the polymer, and the polymer's physical and chemical properties, or the adhesiveness to metal were hardly enhanced.
- Another method was to react a substituent with a base polymer under a radical initiator. Yet, in this method one cannot control the grafting site, and only a small amount of radicals are grafted. Most of the radicals are used for cutting polymers to make polymers with small molecular weights, or they are polymerized among themselves without being grafted to the base polymer.
- an object of the present invention to provide an addition copolymer of cyclic olefins and a method for preparing the same, particularly the cyclic olefin copolymer having low dielectric constant, low moisture absorption, high glass transition temperature, excellent thermal stability, oxidative stability, chemical resistance, toughness, and adhesiveness to metal.
- Another object of the present invention is to provide an addition copolymer of cyclic olefins with excellent optical property and a method for preparing the same.
- Still another object of the present invention is to provide an addition copolymer of cyclic olefins and a method for preparing the same, particularly the cyclic olefin copolymer being used for a low dielectric coating agent or a film employed in electronic materials including integrated circuits or multi-chip modules.
- Still another object of the present invention is to provide an addition copolymer of cyclic olefins and a method for preparing the same, particularly the cyclic olefin copolymer for attaching to a substrate made of electronic materials without using a coupling agent.
- Still another object of the present invention is to provide an addition copolymer of cyclic olefins and a method for preparing the same, particularly the cyclic olefin copolymer with excellent adhesiveness to a substrate made of a metal, such as copper, silver or gold.
- a metal such as copper, silver or gold.
- the present invention provides an addition polymer of cyclic monomers containing a substituent with sulfur, or an addition copolymer of cyclic monomers containing a substituent with sulfur and another cyclic monomer.
- a norbornene type compound or a norbornene derivative thereof indicates a monomer that contains at least one norbornene unit as illustrated in Chemical Formula 1 a. ⁇ Chemical Formula 1 a>
- the simplest form of monomer in accordance with the present invention is bicyclo [2.2.1]-hept-2-ene.
- a norbornene type polymer containing sulfur of the invention is obtained by co-polymerization of the compounds illustrated in Chemical Formula 1 , 2 and 3, respectively, in which at least one monomer of each compound contains sulfur, under a transition metal catalyst.
- cyclic monomers containing sulfur are selected from a group comprising the compounds represented by Chemical Formula 1 , 2 and 3, respectively.
- m is an integer from 0 to 4; at least one of Ri , R 2 , R 3 and R 4 is a radical containing sulfur; and the remaining R groups are respectively H, straight or branched C1-C20 alkyl, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, vinyl, hydrocarbon substituted or unsubstituted C5-C 12 cycloalkyl, hydrocarbon substituted or unsubstituted C 6 -C 40 aryl, hydrocarbon substituted or unsubstituted C 7 -C ⁇ 5 aralkyl, C3-C20 alkynyl, or halogen.
- R ⁇ R , R3 and R are not a radical containing sulfur, hydrogen or halogen the R 1 and R 2 , or R 3 and R 4 can be connected to each other to form a C C ⁇ o alkylidene group.
- R-j or R 2 can be connected to either
- R 3 or R 4 to form a C -d 2 saturated or unsaturated cyclic group or a C 6 -C ⁇ 7 aromatic cyclic compound.
- Preferable radicals containing sulfur can be selected from a group comprising:
- R' and R"' are respectively straight or branched C- ⁇ -C 20 alkyl, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, vinyl, hydrocarbon substituted or unsubstituted C 5 -C 12 cycloalkyl, hydrocarbon substituted or unsubstituted C 6 -C 40 aryl, hydrocarbon substituted or unsubstituted C 7 -C 1 5 aralkyl, C 3 -C 20 alkynyl;
- R" is respectively straight or branched C- ⁇ -C 20 alkyl, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, vinyl, hydrocarbon substituted or unsubstituted C 5 -C- ⁇ 2 cycloalkyl, hydrocarbon substituted or unsubstituted C 6
- R 5 , Re, 7 and R 8 are respectively hydrogen, straight or branched CrC 20 alkyl, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, vinyl, hydrocarbon substituted or unsubstituted C 5 -C 12 cycloalkyl, hydrocarbon substituted or unsubstituted C 6 -C 40 aryl, hydrocarbon substituted or unsubstituted C 7 -C ⁇ 5 aralkyl, C 3 -C 20 alkynyl, or halogen.
- R 5 and R 6 , or R 7 and R 8 can be connected to each other to form a C C ⁇ o alkylidene group. Moreover, R 5 or R 6 can be connected to either R 3 or R 4 to form a C 4 -C- ⁇ 2 saturated or unsaturated cyclic group or a C 6 -C ⁇ 7 aromatic cyclic compound.
- m is an integer from 0 to 4; one of R 9 and R- 10 is S and the other is 0 COCCH3
- copolymers which are prepared by co-polymerization of more than one kind of cyclic olefins illustrated in Chemical 4, and one of monomers illustrated in Chemical Formula 1 , 2, and 3, respectively.
- cyclic monomers containing either sulfur or other hydrocarbon are synthesized by Diels-Alder reaction of cyclopentadiene (CPD) or substituted cyclopentadiene and substituted dienophile.
- CPD cyclopentadiene
- thiophene or substituted thiophene can be reacted with dienophile according to the Diels- Alder reaction.
- R-i-i, R 12 , R- ⁇ 3 and R- ⁇ are respectively hydrogen, straight or branched CrC 20 alkyl, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, vinyl, hydrocarbon substituted or unsubstituted C 5 -C ⁇ 2 cycloalkyl, hydrocarbon substituted or unsubstituted C 6 -C 4 o aryl, hydrocarbon substituted or unsubstituted C7-C15 aralkyl, C -C 20 alkynyl, or halogen.
- R 11 and R- ⁇ 2 , or R 13 and R 14 can be connected to each other to form a
- R-n or R ⁇ 2 can be connected to either R ⁇ 3 or R to form a C 4 -C ⁇ 2 saturated or unsaturated cyclic group or a C 6 -C ⁇ 7 aromatic cyclic compounds.
- the present invention provides randomly synthesized copolymers employing a monomer represented by Chemical Formula 1 , 2, and 3, respectively, and the compound of Chemical Formula 4.
- solubility of the copolymers described above is influenced by a catalyst used.
- a nickel-based catalyst is preferred because the cyclic copolymer made by the catalyst easily dissolves in hydrocarbon solvents like cyclohexane or toluene.
- palladium-based catalysts when palladium-based catalysts are employed, the solubility of the copolymers made by the catalyst becomes pretty low.
- the difference in solubility is mainly due to a variety of microstructures of the copolymers.
- the polymer of the present invention has a cyclic repeating unit containing sulfur, and the amount thereof is 0.1 to 100 mol%. Preferably, it is 1 to 50 mol%, and more preferably, 5 to 20 mol%.
- a polymer system for preparing copolymers according to the present invention involves at least one norbornene type monomer containing sulfur.
- a group VIII transition metal compound catalyzes over the polymerization of those monomers.
- the polymer system aforementioned comprises a monomer, a catalyst, or a co-catalyst, if necessary and a solvent which then polymerize monomers to yield desired polymers.
- the proper temperature range for the polymerization reaction is from -100 °C to 200 °C. Preferably, it is -60 °C to 90 °C, and more preferably, - 10 °C to 80 °C. In addition, it is recommended to use a solvent having its boiling point higher than the polymerization temperature.
- the preferred molecular weight (Mn) of the polymer of the invention is 10,000 to 1 ,000,000.
- Still another embodiment of the present invention provides addition copolymers of cyclic olefins containing sulfur and a method preparing the same. According to this invention, because sulfur is directly attached to a metal, no by-product is formed when the polymer is attached to a metal.
- multi-cyclic compounds containing a silyl group when they adhere to a metal, produced water or alcohol, e.g., ethanol.
- these by-products are not easily removed in a post-process, and thereby the dielectric constant was raised or metals were eroded.
- the addition copolymers of cyclic olefins containing sulfur according to the present invention do not incur the aforementioned problems. That is, no byproduct is formed when the copolymers adhere directly to a metal, and naturally, neither the dielectric constant increase, nor the other metals erode.
- the addition copolymers of cyclic olefins according to the present invention exhibit low dielectric constant and moisture absorption, excellent thermal stability, oxidative stability, chemical resistance, toughness, adhesiveness to metals and optical properties. Furthermore, the cyclic olefin copolymers of the present invention can adhere to a substrate for an electronic material without the aid of a coupling agent, and other metals including copper, silver or gold, thus they are very useful for low dielectric constant coating agents or film for electronic materials, such as, integrated circuits or multi-chip modules.
- the flask was charged with a catalyst solution of 17.3mg of nickel ethylhexanoate in 1 ml of CH 2 CI 2 , a co-catalyst solution of 0.23g of tris(pentafluorophenyl)borane, and 20ml of toluene.
- a catalyst solution of 17.3mg of nickel ethylhexanoate in 1 ml of CH 2 CI 2 a co-catalyst solution of 0.23g of tris(pentafluorophenyl)borane, and 20ml of toluene.
- 0.5 mL (1 M in hexane solution) of triethylalumium (TEA) was put into the resulting solution, and the mixture was stirred for 3 hours at room temperature.
- a solution of 4g of 8-hydroxyquinoline in 20ml of CH 2 CI 2 was again stirred for another 15 hours at room temperature.
- R 2 , R 3 , and R are respectively hydrogen, and m is 0) were added in a 250ml schlenk flask. Then, the flask was charged with a catalyst solution of 15.4mg of nickel ethylhexanoate in 1 ml of CH 2 CI 2 , a co-catalyst solution of 0.2055g of tris(pentafluorophenyl)borane, and 20ml of toluene. 0.45 mL (1 in hexane solution) of triethylalumium (TEA) was put into the resulting solution, and the mixture was stirred for 1 hour at room temperature.
- TEA triethylalumium
- CH 2 SCOCH 3 , R 2 , R3, and R 4 are respectively hydrogen, and m is 0) were added into a 250ml of schlenk flask. Then, the flask was charged with a catalyst solution of 5.0mg of allypalladium chloride dimer in 1 ml of CH 2 CI 2 , a co-catalyst solution of 0.0192g of tncyclohexylphosphine, 18.8mg of lithium tetrakis(pentafluorophenyl)borate, and 10ml of toluene. Then, the mixture was stirred for 3 hours at room temperature.
- the flask was charged with a catalyst solution of 10.5mg of nickel ethylhexanoate in 1ml of CH 2 CI 2 , a co-catalyst solution of 0.1396g of tris(pentafluorophenyl)borane, and 20ml of toluene. 0.303ml (1 M in hexane solution) of triethylalumium (TEA) was put into the resulting solution, and the mixture was stirred for 1 hour at room temperature.
- TEA triethylalumium
- Example 7 Test for Norbornene-ButylNorbornene-SacNorbornene Copolymers on Adhesiveness to a Metal
- copolymers of norbornene compounds containing sulfur in other words, copolymers of cyclic olefins, are useful for low dielectric materials for electronic devices.
- the copolymers have low dielectric constant, excellent thermal stability and strength.
- adhesiveness to metals can be greatly improved since no by-products are generated as the copolymers adhere to metal.
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Abstract
The present invention relates to addition copolymers of cyclic olefins, and in particular, cyclic olefin copolymers of norbornene type compounds containing sulfur to provide excellent adhesiveness to metal, and methods for using the same. Therefore, the present invention provides addition copolymers of cyclic olefins of norbornene type compounds and norbornene type compounds containing sulfur, and methods for preparing the same. The copolymers of norbornene type compounds containing sulfur of the invention are addition copolymers of cyclic olefins, which are very useful for dielectric materials because of their low dielectric constant, excellent thermal stability, strength, and good adhesiveness to metals without generating any by-products while adhering to metal.
Description
ADDITION COPOLYMERS OF CYCLIC OLEFINS CONTAINING SULFUR
BACKGROUND OF THE INVENTION (a) Field of the Invention
The present invention relates to addition copolymers of cyclic olefins. In particular, the present invention relates to cyclic olefin copolymers of norbornene type compounds containing sulfur to provide excellent adhesiveness to metal, and methods for using the same.
(b) Description of the Related Art
Silicon oxides and silicon nitrides have been widely used as inorganic compounds in the electronic material industry. However, due to the increasing need for smaller and more effective devices, the demand for high performance material has increased. Typically considered features for polymers include low dielectric constant, and moisture absorption, excellent adhesiveness to metal, mechanical strength, thermal stability, transparency and high glass transition temperature (Tg>200°C). These polymers can be applied to semiconductors, TFT-LCD insulating films, multi-chip modules, integrated circuit (IC), packaging for an electronic element, low dielectric coating agent or film for optical use, e.g., flat panel display. Polymers such as polyimide or BCB (bis-benzocyclobutenes) are used as low dielectric material for electronic elements.
Many choose polyimide primarily because of its excellent thermal stability, oxidative stability, high glass transition temperature and mechanical properties. However, they have to deal with problems such as the corrosion of the element and increased dielectric constant due to the high moisture absorption of polyimide, the anisotropic electronic property, the pretreatment step to control the reaction of polyimide with copper wire, and the adhesiveness to metal.
On the other hand, BCB has comparatively low moisture absorption and dielectric constant, but its adhesiveness to metal is inadequate. In order
to obtain the desired physical properties, BCB should undergo a curing process at high temperature since the physical properties are greatly influenced by the curing time and temperature.
Addition copolymers of cyclic olefins have been already introduced in literature. The cyclic olefin copolymers are rich in hydrocarbon content, which make the dielectric constant and moisture absorption very low. A method for polymerizing cyclic monomers comprises ROMP (ring opening metathesis polymerization), HROMP (ring opening metathesis polymerization followed by hydrogenation), co-polymerization with ethylene, and homogeneous polymerization, which are illustrated in the following chemical equation 1.
<Chemical Equation 1 >
The polymer, synthesized by ROMP, has very poor thermal stability and oxidative stability due to the unsaturated main chain, so it is usually used for thermoplastic resins or thermosetting resins. These thermosetting resins are employed to a substrate of a circuit through reaction injection molding (U.S. Patent No. 5,011 ,730 by Tenny, et al.). Nevertheless, as described above, the resins still exhibit low thermal stability, oxidative stability, and low glass transition temperature.
A number of attempts have been made in order to improve the physical properties of resins obtained from the ROMP polymer, and one of them was to hydrogenate the polymer for stabilizing a main chain of the polymer. However, the product, despite increased oxidative stability, showed
decreased thermal stability. Normally, hydrogenation raises the glass transition temperature of the ROMP polymer by approximately 50 °C. Besides, an extra synthesis step raises production costs, and poor mechanical properties of the resulting polymer has made industries hesitate in commercializing the polymer.
In the case of additional polymerization, in which a cyclic monomer was co-polymerized with ethylene with the aid of vanadium catalyst, Apel was produced. Yet, the catalytic activity was very low and a great amount of oligomers was yielded. Research has been published by employing metallocene catalysts of a zirconium group for polymerization in order to obtain a polymer with high molecular weight yet with narrow molecular weight distribution (Plastic News, Feb. 27, 1995, p.24). However, as the density of cyclic monomers gets higher, the catalytic activity decreases, and the glass transition temperature of the copolymer thereof gets lower (Tg <200°C). No matter how the thermal stability is increased, the mechanical strength of the polymer is very weak. Moreover, the polymer has poor chemical resistance, particularly, to hydrocarbon solvents or halogenated hydrocarbon solvents.
Another example of the polymerization of cyclic monomers is norbornene polymerization discovered by Gaylord in 1977 (Gaylord, N.G.; Deshpande, A.B. ; Mandal, B.M. ; Martan, M. J. Macromol. Sci-Chem. 1977, All(5), 1053-1070). At first, the polymerization was catalyzed over [Pd(C6H5CN)Cl2]2, and the yield was 33%. Later, [Pd(CH3CN)4][BF4]2 was used as a catalyst to yield norbornene polymers (Sen, A. ; Lai, T.-W. J. Am. Chem. Soc. 1981 , 103, 4627-4629).
In addition, Kaminsky (University of Hamburg, Germany) introduced a homogeneous polymerization of norbornene employing metallocene catalysts of group IV B transition metal. Unfortunately, the resulting polymers from this method were easily crystallized and were not dissolved in general organic solvents. In addition, the polymers were thermally decomposed at high temperature without exhibiting a. glass transition temperature. For these reasons, no further research efforts have been made in this field (Kaminsky,
W. ; Bark, A., ; Drake, I. Stud. Surf. Catal. 1990, 56,425).
Similar to the polyimide or BCB described above, cyclic polymers are not adhesive to metal although they are supposed to be used for information or electronic elements. Specifically, the polymers are required to be adhesive to a variety of surfaces, including silicon, silicon oxide, silicon nitride, alumina, copper, aluminum, gold, silver, platinum, titanium, nickel, tantalum, chromium, and other polymers.
To enhance the adhesiveness of polyimide and BCB to metal, the following process was carried out: treating a substrate of a semiconductor by an organic silicon coupling agent with two functional groups, e.g., amino- propyltriethoxysilane or triethoxyvinylsilane; reacting the substrate with a polymer or a polymer precursor. In this reaction, the silyl group was hydrolyzed to make a covalent bond with a hydroxy functional group on the surface of the substrate.
Meanwhile, the cyclic polymer can be used for insulating material, wherein inorganic compounds like silicon oxide or silicon nitride has been mainly employed. In order to use polymers for electronic materials, a number of requirements should be met, such as, low dielectric constant, low moisture absorption, excellent adhesiveness to metal, mechanical strength, thermal stability, transparency, and high glass transition temperature (Tg>250°C).
Polymers that satisfy all the above-described requirements can be employed as low dielectric material for semiconductor or TFT-LCD. Here, the amino group attached to a substrate reacts with a functional group of a polymer or a polymer precursor and becomes a bridging group, connecting the substrate and the polymer (U.S. Patent No. 4,831 ,172). However, this method involves a multiple-step process and requires a coupling agent.
In fact, a method of introducing a substituent to a polymer consisting of hydrocarbon is very useful in that it can effectively control the chemical and physical properties of the polymer. However, the method was found to be very difficult to perform because unpaired electrons in the substituent react with an active catalytic site and becomes a catalyst poison. If a cyclic
monomer contains a substituent, the molecular weight of the resulting polymer becomes low (U.S. Patent No. 3, 330, 815). In order to overcome the above-described problem, a method to put a monomer containing a substituent in the latter stage of polymerization process was proposed (U.S. Patent No. 5, 179, 171). Unfortunately, this method was not successful to improve the thermal stability of the polymer, and the polymer's physical and chemical properties, or the adhesiveness to metal were hardly enhanced.
Another method was to react a substituent with a base polymer under a radical initiator. Yet, in this method one cannot control the grafting site, and only a small amount of radicals are grafted. Most of the radicals are used for cutting polymers to make polymers with small molecular weights, or they are polymerized among themselves without being grafted to the base polymer.
In case of using polycyclic compounds containing a silyl group for an insulating film, water or ethanol was produced as a by-product when they are attached to metal. The by-products are not easily removed during the process but raise dielectric constant and erode metals.
SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide an addition copolymer of cyclic olefins and a method for preparing the same, particularly the cyclic olefin copolymer having low dielectric constant, low moisture absorption, high glass transition temperature, excellent thermal stability, oxidative stability, chemical resistance, toughness, and adhesiveness to metal.
Another object of the present invention is to provide an addition copolymer of cyclic olefins with excellent optical property and a method for preparing the same.
Still another object of the present invention is to provide an addition copolymer of cyclic olefins and a method for preparing the same, particularly the cyclic olefin copolymer being used for a low dielectric coating agent or a film employed in electronic materials including integrated circuits or multi-chip
modules.
Still another object of the present invention is to provide an addition copolymer of cyclic olefins and a method for preparing the same, particularly the cyclic olefin copolymer for attaching to a substrate made of electronic materials without using a coupling agent.
Still another object of the present invention is to provide an addition copolymer of cyclic olefins and a method for preparing the same, particularly the cyclic olefin copolymer with excellent adhesiveness to a substrate made of a metal, such as copper, silver or gold. In order to achieve the aforementioned objects, there are provided norbornene type compounds containing sulfur, addition copolymers of cyclic olefins of norbornene type compounds, and methods for preparing the same.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the present invention will now be described with reference to the accompanying Chemical Formulas. The matters defined in the description are nothing but the ones provided to assist a comprehensive understanding of the invention. Also, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.
The present invention provides an addition polymer of cyclic monomers containing a substituent with sulfur, or an addition copolymer of cyclic monomers containing a substituent with sulfur and another cyclic monomer. A norbornene type compound or a norbornene derivative thereof indicates a monomer that contains at least one norbornene unit as illustrated in Chemical Formula 1 a.
<Chemical Formula 1 a>
Therefore, the simplest form of monomer in accordance with the present invention is bicyclo [2.2.1]-hept-2-ene. A norbornene type polymer containing sulfur of the invention is obtained by co-polymerization of the compounds illustrated in Chemical Formula 1 , 2 and 3, respectively, in which at least one monomer of each compound contains sulfur, under a transition metal catalyst.
Furthermore, the cyclic monomers containing sulfur are selected from a group comprising the compounds represented by Chemical Formula 1 , 2 and 3, respectively.
<Chemica! Formula 1 >
When the R^ R , R3 and R are not a radical containing sulfur, hydrogen or halogen the R1 and R2, or R3 and R4 can be connected to each other to form a C Cιo alkylidene group. R-j or R2 can be connected to either
R3 or R4 to form a C -d2 saturated or unsaturated cyclic group or a C6-Cι7 aromatic cyclic compound.
Preferable radicals containing sulfur can be selected from a group comprising:
0 O
II π
S -R" R'-S -R" II II
SR", R'SR", SSR", R'SSR", S(=0)R", 0 , 0 ,
R'S(=0)R", R'C(=S)R", R'C(=S)SR" R'S03H, R'N=C=S,
R" O R"
( H tC ^NH -fCH ^r SR"
R"- ^ SR"
or
R5 and R6, or R7 and R8 can be connected to each other to form a C Cιo alkylidene group. Moreover, R5 or R6 can be connected to either R3 or R4 to form a C4-C-ι2 saturated or unsaturated cyclic group or a C6-Cι7 aromatic cyclic compound.
<Chemical Formula 3>
Another embodiment of the present invention provides copolymers, which are prepared by co-polymerization of more than one kind of cyclic olefins illustrated in Chemical 4, and one of monomers illustrated in Chemical Formula 1 , 2, and 3, respectively.
Specifically, cyclic monomers containing either sulfur or other hydrocarbon are synthesized by Diels-Alder reaction of cyclopentadiene (CPD) or substituted cyclopentadiene and substituted dienophile. Similarly, instead of cyclopentadiene or substituted cyclopentadiene, thiophene or substituted thiophene can be reacted with dienophile according to the Diels- Alder reaction.
<Chemical Formula 4>
Cι-C10 alkylidene group. Moreover, R-n or Rι2can be connected to either Rι3 or R to form a C4-Cι2 saturated or unsaturated cyclic group or a C6-Cι7 aromatic cyclic compounds.
Therefore, the present invention provides randomly synthesized copolymers employing a monomer represented by Chemical Formula 1 , 2, and 3, respectively, and the compound of Chemical Formula 4.
In general, solubility of the copolymers described above is influenced by a catalyst used. Most of time, a nickel-based catalyst is preferred because the cyclic copolymer made by the catalyst easily dissolves in hydrocarbon solvents like cyclohexane or toluene. However, when palladium-based catalysts are employed, the solubility of the copolymers made by the catalyst becomes pretty low. The difference in solubility is mainly due to a variety of microstructures of the copolymers.
The polymer of the present invention has a cyclic repeating unit containing sulfur, and the amount thereof is 0.1 to 100 mol%. Preferably, it is 1 to 50 mol%, and more preferably, 5 to 20 mol%.
A polymer system for preparing copolymers according to the present invention involves at least one norbornene type monomer containing sulfur. A group VIII transition metal compound catalyzes over the polymerization of those monomers. Thus, similar to other conventional polymerization methods, the polymer system aforementioned comprises a monomer, a catalyst, or a co-catalyst, if necessary and a solvent which then polymerize monomers to yield desired polymers.
The proper temperature range for the polymerization reaction is from -100 °C to 200 °C. Preferably, it is -60 °C to 90 °C, and more preferably, - 10 °C to 80 °C. In addition, it is recommended to use a solvent having its boiling point higher than the polymerization temperature. The preferred molecular weight (Mn) of the polymer of the invention is 10,000 to 1 ,000,000.
Still another embodiment of the present invention provides addition copolymers of cyclic olefins containing sulfur and a method preparing the same. According to this invention, because sulfur is directly attached to a metal, no by-product is formed when the polymer is attached to a metal.
Typically, multi-cyclic compounds containing a silyl group, when they adhere to a metal, produced water or alcohol, e.g., ethanol. Unfortunately, these by-products are not easily removed in a post-process, and thereby the dielectric constant was raised or metals were eroded. On the contrary, the addition copolymers of cyclic olefins containing sulfur according to the present invention do not incur the aforementioned problems. That is, no byproduct is formed when the copolymers adhere directly to a metal, and naturally, neither the dielectric constant increase, nor the other metals erode. In short, the addition copolymers of cyclic olefins according to the present invention exhibit low dielectric constant and moisture absorption, excellent thermal stability, oxidative stability, chemical resistance, toughness, adhesiveness to metals and optical properties. Furthermore, the cyclic olefin
copolymers of the present invention can adhere to a substrate for an electronic material without the aid of a coupling agent, and other metals including copper, silver or gold, thus they are very useful for low dielectric constant coating agents or film for electronic materials, such as, integrated circuits or multi-chip modules.
The present invention will be described in more detail by referring to the examples below, which are not intended to be limiting.
EXAMPLE Example 1 . Synthesis of Norbomene-ButylNorbornene-SacNorbomene Copolymers
80ml of toluene, 10g (106.38 mmol) of norbornene, 1.86g (12.494 mmol) of butylnorbomene, 1 .14g (6.26 mmol) of Sacnorbomene of Chemical Formula 1 (where Ri is CH2SCOCH3, R2, R3, and R4 are respectively hydrogen, and m is 0) were added into a 250ml of schlenk flask. Then, the flask was charged with a catalyst solution of 17.3mg of nickel ethylhexanoate in 1 ml of CH2CI2, a co-catalyst solution of 0.23g of tris(pentafluorophenyl)borane, and 20ml of toluene. 0.5 mL (1 M in hexane solution) of triethylalumium (TEA) was put into the resulting solution, and the mixture was stirred for 3 hours at room temperature. After 3 hours of polymerization reaction, to the above reactant was added a solution of 4g of 8-hydroxyquinoline in 20ml of CH2CI2, and the mixture was again stirred for another 15 hours at room temperature. White copolymers were precipitated by adding the resulting solution into an excessive amount of ethanol. The precipitates were collected using a glass funnel. Then, the precipitates were dissolved in cyclohexane for a re-precipitation, and were collected again over a glass funnel. After several repetitions of this procedure, final precipitates were vacuum dried at 65°C for 24 hours to yield 5.7g of Norbomene-Butylnorbomene-SacNorbornene copolymers (yield: 43.58 wt % based on monomers).
Example 2. Synthesis of Norbornene-SacNorbornene Copolymers
100ml of toluene, 20g (212 mmol) of norbornene, and 2.038g (1 1.2
mmol) of Sacnorbomene of Chemical Formula 1 (where Ri is CH2SCOCH3,
R2, R3, and R are respectively hydrogen, and m is 0) were added in a 250ml schlenk flask. Then, the flask was charged with a catalyst solution of 15.4mg of nickel ethylhexanoate in 1 ml of CH2CI2, a co-catalyst solution of 0.2055g of tris(pentafluorophenyl)borane, and 20ml of toluene. 0.45 mL (1 in hexane solution) of triethylalumium (TEA) was put into the resulting solution, and the mixture was stirred for 1 hour at room temperature.
Following the 1-hour reaction, to the above reactant was added a solution of 4g of 8-hydroxyquinoline in 20ml of CH2CI2, and the mixture was again stirred for another 15 hours at room temperature. By adding the resulting solution into an excessive amount of ethanol, white copolymers were precipitated.
The precipitates were collected using a glass funnel. Then, the precipitates were dissolved in cyclohexane for a re-precipitation, and were collected again over a glass funnel. After several repetitions of this procedure, final precipitates were vacuum dried at 65°C for 24 hours to yield
5.7g of Norbomene-Butylnorbornene-SacNorbornene copolymers (yield:
43.58 wt % based on monomers).
Example 3. Synthesis of Butylnorbornene-Sacnorbornene Copolymers 100ml of toluene, 10g (67.1 mmol) of butylnorbornene, and 1.14g
(6.26 mmol) of Sacnorbomene of Chemical Formula 1 (where R-j is
CH2SCOCH3, R2, R3, and R4 are respectively hydrogen, and m is 0) were added into a 250ml of schlenk flask. Then, the flask was charged with a catalyst solution of 5.0mg of allypalladium chloride dimer in 1 ml of CH2CI2, a co-catalyst solution of 0.0192g of tncyclohexylphosphine, 18.8mg of lithium tetrakis(pentafluorophenyl)borate, and 10ml of toluene. Then, the mixture was stirred for 3 hours at room temperature.
Following the 1 -hour reaction, to the above reactant was added a solution of 4g of 8-hydroxyquinoline in 20ml of CH2CI2, and the mixture was again stirred for another 15 hours at room temperature. By adding the resulting solution into an excessive amount of ethanol, white copolymers were precipitated.
Example 4. Synthesis of Norbomene-Butylnorbomene-SacNorbomene Copolymers
100ml of toluene, 10g (106.2 mmol) of norbornene, and 5.66g (38mmol) of butylnorbomene, and 1.064g (7.59 mmol) of Sacnorbomene of Chemical Formula 1 (where Ri is CH2SCOCH3, R2, R3, and R are respectively hydrogen, and m is 0) were added to a 250ml schlenk flask. Then, the flask was charged with a catalyst solution of 10.5mg of nickel ethylhexanoate in 1ml of CH2CI2, a co-catalyst solution of 0.1396g of tris(pentafluorophenyl)borane, and 20ml of toluene. 0.303ml (1 M in hexane solution) of triethylalumium (TEA) was put into the resulting solution, and the mixture was stirred for 1 hour at room temperature.
Following the 1-hour reaction, to the above reactant was added a solution of 4g of 8-hydroxyquinoline in 20ml of CH2CI2, and the mixture was again stirred for another 15 hours at room temperature. By adding the resulting solution into an excessive amount of ethanol, white copolymers were precipitated.
The precipitates were collected using a glass funnel. Then, the precipitates were dissolved in cyclohexane for a re-precipitation, and were collected again over a glass funnel. After several repetitions of this procedure, final precipitates were vacuum dried at 65°C for 24 hours to yield 1.62g of Norbornene-Butylnorbomene-SacNorbomene copolymers (yield: 43.58 wt % based on monomers). Example 5. Synthesis of Butylnorbornene-SacNorbornene Copolymers
100ml of toluene, 10g (67.1 mmol) of butylnorbomene, and 0.1922g (1.37 mmol) of Sacnorbomene of Chemical Formula 1 (where Ri is CH2SCOCH3, R2, R3, and R4 are respectively hydrogen, and m is 0) were added into a 250ml of schlenk flask. Then, the flask was charged with a catalyst solution of 4.728mg of nickel ethylhexanoate in 1ml of CH2CI2, a co- catalyst solution of 0.2055g of tris(pentafluorophenyl)borane, and 20ml of toluene. 0.137ml (1 M in hexane solution) of triethylalumium (TEA) was put into the resulting solution, and the mixture was stirred for 1 hour at room temperature.
Following the 1-hour reaction, to the above reactant was added a solution of 4g of 8-hydroxyquinoline in 20ml of CH2CI2, and the mixture was again stirred for another 15 hours at room temperature. By adding the resulting solution into an excessive amount of ethanol, white copolymers were precipitated.
Example 6. Synthesis of Norbomene-Butylnorbomene-COSacNorbornene Copolymers
100ml of toluene, 10g (106.2 mmol) of norbornene, and 1.167g (7.5 mmol) of COSacnorbomene of Chemical Formula 1 (where Ri is CH2SCOCH3, R2, R3, and R4 are respectively hydrogen, and m is 0) were added into a 250ml of schlenk flask. Then, the flask was charged with a catalyst solution of 10.5mg of nickel ethylhexanoate in 1ml of CH2CI2, a co- catalyst solution of 0.1396g of tris(pentafluorophenyl)borane, and 20ml of toluene. 0.303ml (1 M in hexane solution) of triethylalumium (TEA) was put into the resulting solution, and the mixture was stirred for 1 hour at room temperature.
Following the 1-hour reaction, to the above reactant was added a solution of 4g of 8-hydroxyquinoline in 20ml of CH2CI2, and the mixture was again stirred for another 15 hours at room temperature. By adding the resulting solution into an excessive amount of ethanol, white copolymers were precipitated.
Example 7. Test for Norbornene-ButylNorbornene-SacNorbornene Copolymers on Adhesiveness to a Metal
A test on adhesiveness to metals was undertaken for Norbomene- ButylNorbornene-SacNorbornene copolymer, which was prepared from the Examples as described above. First, the copolymer was dissolved in mesithylene to the amount of 5wt%, and the solution coated on a glass plate patterned with chromium, aluminum and tungsten to a thickness of 0.317μm. Then the thin film was cut by a 5 mm-square check, and a 180° -tape test was carried out. In the results, out of 9 checks in total, none of checks were detached from the glass by the tape.
Accordingly, copolymers of norbornene compounds containing sulfur,
in other words, copolymers of cyclic olefins, are useful for low dielectric materials for electronic devices. The copolymers have low dielectric constant, excellent thermal stability and strength. In particular, adhesiveness to metals can be greatly improved since no by-products are generated as the copolymers adhere to metal.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims
1. An addition copolymer of cyclic olefins of norbornene type compounds containing sulfur.
2. The copolymer according to claim 1 , in which the norbornene type compound containing sulfur is selected from a group comprising Chemical Formula 1 , 2 and 3;
<Chemical Formula 1>
3. The copolymer according to claim 2, wherein radicals of Chemical Formula 1 are selected from a group comprising:
O O
II II
S -R" R'-S -R" II II
SR", R'SR", SSR", R'SSR", S(=0)R", O , O
R'S(=0)R", R'C(=S)R", R'C(=S)SR", R'S03H, R'N=C=S,
4. The copolymer according to claim 1 , wherein the norbornene type compound is illustrated in Chemical Formula 4:
<Chemical Formula 4>
5. A method for preparing addition copolymers of cyclic olefins and norbornene type compounds containing sulfur with a catalytic system of VIII family metal wherein
(a) norbornene type compounds are selected from a group comprising compounds illustrated in Chemical Formula 1 , Chemical Formula 2, and Chemical Formula 3, respectively;
(b) more than one cyclic olefins are selected from the group illustrated in Chemical Formula 4
<Chemical Formula 1>
R 5
Re wherein m is an integer from 0 to 4; R5, R6,' R7 and R8 are respectively hydrogen, linear or branched C1-C20 alkyl, alkoxy, alkoxysilyl, alkylperoxy, alkylcarbonyloxy, aryloxy, aryloxysilyl, alkenyl, vinyl, hydrocarbon substituted or unsubstituted C5-Cι2 cycloalkyl, hydrocarbon substituted or unsubstituted C6-C40 aryl, hydrocarbon substituted or unsubstituted C7-Cι5 aralkyl, C3-C2o alkynyl, or halogen, where R5 and R6, or R7 and R8 can be connected to each other to form a C C-io alkylidene group, or R5 or R6 can be connected to either R7 or R8 to form a C -C12 saturated or unsaturated cyclic group or a C6-C17 aromatic cyclic compound;
<Chemical Formula 3>
0
C0CCH3 other is ; and
<Chemical Formula 4>
6. The method according to claim 5, wherein radicals of Chemical Formula 1 are selected from a group comprising:
O O
II n
S — R" R'— S — R" II II
SR", R'SR", SSR", R'SSR", S(=0)R", O , O
R'S(=0)R", R'C(=S)R", R'C(=S)SR", R'S03H, R'N=C=S,
Applications Claiming Priority (2)
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| KR2000/85990 | 2000-12-29 | ||
| KR1020000085990A KR20020056602A (en) | 2000-12-29 | 2000-12-29 | Addition copolymers of cycloolefins containing sulfur groups and method for preparing the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007084764A (en) * | 2005-09-26 | 2007-04-05 | Jsr Corp | Coating material and manufacturing method thereof |
| CN102731721A (en) * | 2012-05-08 | 2012-10-17 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN104693423A (en) * | 2015-02-02 | 2015-06-10 | 华东师范大学 | Cross-linkable high dielectric norbornene copolymer and norbornene cross-linked polymer and preparation methods thereof |
| WO2015176588A1 (en) * | 2014-05-21 | 2015-11-26 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method therefor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100708976B1 (en) * | 2005-04-18 | 2007-04-18 | 주식회사 엘지화학 | Norbornene copolymer in which sulfonic acid group is introduced and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11184090A (en) * | 1997-10-13 | 1999-07-09 | Fuji Photo Film Co Ltd | Positive type photoresist composition for exposure with far ultraviolet ray |
| DE19900977A1 (en) * | 1998-06-30 | 2000-01-05 | Ind Tech Res Inst | Unsaturated and hydrogenated polymers useful in thin-film coating composition, photoresist or blend |
| WO2000046267A1 (en) * | 1999-02-05 | 2000-08-10 | The B.F. Goodrich Company | Method of preparing norbornene sulfonamide polymers |
| WO2000046268A1 (en) * | 1999-02-05 | 2000-08-10 | The B.F. Goodrich Company | Norbornene sulfonamide polymers |
| WO2000053657A1 (en) * | 1999-03-12 | 2000-09-14 | The B.F. Goodrich Company | Processes for making polymers containing pendant cyclic anhydride groups |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5929181A (en) * | 1997-06-09 | 1999-07-27 | The B.F.Goodrich Co. | Method for preparation of copolymers of ethylene/norbornene-type monomers with nickel catalysts |
-
2000
- 2000-12-29 KR KR1020000085990A patent/KR20020056602A/en not_active Ceased
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2001
- 2001-12-28 WO PCT/KR2001/002291 patent/WO2002053622A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11184090A (en) * | 1997-10-13 | 1999-07-09 | Fuji Photo Film Co Ltd | Positive type photoresist composition for exposure with far ultraviolet ray |
| DE19900977A1 (en) * | 1998-06-30 | 2000-01-05 | Ind Tech Res Inst | Unsaturated and hydrogenated polymers useful in thin-film coating composition, photoresist or blend |
| WO2000046267A1 (en) * | 1999-02-05 | 2000-08-10 | The B.F. Goodrich Company | Method of preparing norbornene sulfonamide polymers |
| WO2000046268A1 (en) * | 1999-02-05 | 2000-08-10 | The B.F. Goodrich Company | Norbornene sulfonamide polymers |
| WO2000053657A1 (en) * | 1999-03-12 | 2000-09-14 | The B.F. Goodrich Company | Processes for making polymers containing pendant cyclic anhydride groups |
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| DATABASE WPI Week 199939, Derwent World Patents Index; AN 1999-461290 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007084764A (en) * | 2005-09-26 | 2007-04-05 | Jsr Corp | Coating material and manufacturing method thereof |
| CN102731721A (en) * | 2012-05-08 | 2012-10-17 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN102731721B (en) * | 2012-05-08 | 2014-07-02 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| WO2015176588A1 (en) * | 2014-05-21 | 2015-11-26 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method therefor |
| CN104693423A (en) * | 2015-02-02 | 2015-06-10 | 华东师范大学 | Cross-linkable high dielectric norbornene copolymer and norbornene cross-linked polymer and preparation methods thereof |
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