KR100196344B1 - Dinuclear metallocene compound and catalyst thereof for polyolefin - Google Patents

Abstract

The present invention relates to a bimetallic metallocene compound having a heteroatom bridge, useful as a catalyst for producing a polyolefin-based polymer, and is mainly classified into three kinds, that is, a neutral metallocene compound, a cationic metallocene compound, and these Compounds are classified as supported catalysts. The catalyst according to the present invention is a novel bimetallic metallocene compound, and has a specific structure and polymerization properties, thereby producing polyethylene having a unique structure and properties.

Description

[Name of invention]

Bimetalmetallocene Compounds Useful as Catalysts for the Preparation of Polyolefin Polymers

Detailed description of the invention

The present invention relates to a bimetal metallocene compound having a heteroatom bridge, a method for preparing the same, and a method for preparing a polyolefin-based polymer using the same as a polymerization catalyst.

Although many types of metallocene compounds for producing polymers have been known so far, the compounds of the present invention are catalysts of a completely new structure in that they have new types of heteroatomic bridges and bimetals. In other words, the present invention provides an π-electron cyclopentadienyl (Cp), substituted Cp (Cp ^* ), and inoyl, which form a ⁵ -bond, in which a transition metal element of a metallocene is directly bonded. ), A bridge containing heteroatoms is connected between two similar compounds, such as fluorenyl and their substituents, and in particular a metal having one transition metal element bonded to each of the above two ligands. As a rosene complex, especially when this metal is titanium, it is a heteroatom bridged dinuclear titanocene (HBDT), and when this metal is zirconium, it is a heteroatom bridged dinuclear zirconocene (HBDZ). to be. In particular, HBDT compounds and HBDZ compounds are very effective catalysts for the production of polyethylene (hereinafter referred to as PE), and are bonded to heteroatoms and compounds having neutral HBDT and HBDZ compounds, cationic HBDT and HBDZ compounds, HBDT and HBDZ compounds And supporting compounds in the form obtained by synthesis of the ligands and then synthesized.

The HBDT compound of the present invention has the following structure.

or

The HBDZ compound of the present invention has the following structure. There is a movement to change the ink and marking ink) into an ultraviolet curing composition.

[Problems to Solve Invention]

Screen printing has been widely used to form resist patterns on printed wiring boards. However, this screen printing method is not suitable for recent trends such as surface mounting of high density printed wiring boards and components due to frequent problems such as bleeding, exudation or sagging during the printing stage.

To solve these problems, photoresist and liquid photo solder resists in the form of dry films have been developed. Photoresist in the form of a dry film has a drawback that it is easy to form bubbles in the heat compression step, is uncertain in heat resistance and adhesion and is expensive. On the other hand, as a liquid photo solder resist, a solder resist ink composition comprising a partial reaction product obtained mainly from a noblock epoxy resin and acrylic acid is described in, for example, Japanese Patent Laid-Open No. 208337/1985 and et al. 59447/1986. However, in order to develop these ink compositions, the use of organic solvents such as 1,1,1-trichloroethane, trichloroethylene, toluene or cyclohexanone is essential and their use causes problems in terms of working environment and economics. . To solve the problems associated with the use of organic solvents, solder resist ink compositions have been developed that can be developed using dilute aqueous alkali solutions. USP 5009982, for example, describes a resist ink composition comprising a reaction product obtained from a novolak epoxy resin and acrylic acid and a product based on a polybasic acid anhydride. However, in the resist ink composition, furnaces Y1, Y2, Y3 and Y4 are independently cyclopentadienyl, cyclopentadienyl derivatives or indenyl, fluorenyl, or derivatives thereof capable of being bonded to M ⁵ and- A 1, A 2, A 3 are independently of each other a group 1 to 4 element, the spacer Sp may be sandwiched between A 1 and Y 1 or A 3 and Y 2 and the spacer Sp is preferably carbon, oxygen, nitrogen, phosphorus, E 1 and E 2 is a heteroatom preferably nitrogen, oxygen, phosphorus, sulfur and independently of each other forms a site between the Y 1, Y 2, Y 3 and Y 4 ligands, R 1 to R 6 independently of one another are hydrogen, alkyl, aryl, silyl, alkoxy, Aryloxy, siloxy, halogen, a group formed from a combination thereof, or -Sp-Sup where Sp is as described above and Sup is a support, X is hydrogen, alkyl, aryl, silyl, alkoxy, aryloxy, siloxane Is a group formed by halogen, or a combination thereof, n is a metal Depending on the valency may have a value of from zero to four.

In the above formulas (II) and (IV), Z is a non-coordinating anion, which is not or very weakly coordinated with the metal cation moiety containing Y so that other Lewis bases contain Y of the cation. An anion that does not interfere with the action of the metal moiety, preferably [BQ ₁ Q ₂ Q ₃ ] ^- , where B is boron having a trivalent atom, and Q _{1 to} Q ₄ are each independently hydrogen anion ( Selected from the group consisting of Hydride, Dialkylamido, Alkoxide, Aryl oxide, Hydrocarbyl, Substituted Hydrocarbyl, Organometalloid, etc. It is a radical and one of Q <_1> -Q <_4> may be halide.

The HBDT compound is prepared in three steps as follows:

Wherein A1, A2, A3, E1, E2, R1, R2, R3, R4, R5, R6 and Sp are as defined above, Y is Y1 or Y2, H is a halogen element, Y is Y1 as defined above Or an anion of Y 2 and T is an alkali metal cation.

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R is alkyl, alkoxy and T is an alkali metal or thallium.

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The HBDZ compound is prepared as follows using compound (2) and YMX _n .

In order to use the compound of the present invention as a polymerization catalyst, it is usually supported on a support. For example, the compound of formula (I), (II), (III) or (IV) of the present invention is directly supported on a dehydrated carrier. Examples of the carrier include silica, alumina, magnesium chloride (MgCl ₂ ), zeolite, zeolite, aluminum phosphate (AlPO ₄ ), or zirconia (Zirconia). It is prepared by immersion in the solvent of the compound of (II), (III) or (IV). The cationic HBDT compound (formula (II)) and HBDZ compound (formula (IV)) supported catalyst is a compound in which the compounds of formulas (II) and (IV) are supported on a dehydrated carrier. ) In addition to the method of directly supporting the carrier by activating with a promoter, the neutral HBDT compound (formula (I)) and HBDZ compound (formula (IV)) are supported on a carrier and then activated by a non-aluminum promoter. can do. Here, non-aluminum promoters [R ₁ R ₆ R ₇ ] [BQ ₁ Q ₂ Q ₃ Q ₄ ] or [HNR ₈ R ₉ R ₁₀ ] [BQ ₁ Q ₂ Q ₃ Q ₄ ], and R ₅ to R ₁₀ Is a group consisting of hydrogen, alkyl, aryl, alkoxy, silyl, siloxy and the like, and B and Q _{1 to} Q ₄ are as defined above.

Another method of making the polymerization catalyst of the present invention is to directly form the bimetalmetallocene compound of the present invention together with the carrier by modifying the carrier as in the following reaction.

Here, A, E, M, Y1, Y2, Y3, Y4, (X) n and the like are as described above, Sp is a spacer connecting the ligand Y with the surface of the carrier, carbon, oxygen, nitrogen , Phosphorus and the like. And these Sp can be connected to each other by chemical bonds including carbon, oxygen, nitrogen, phosphorous. The neutral supported catalyst obtained above may be used by treating with a non-aluminum promoter.

In addition to the various catalysts of the present invention, an organometallic compound may be used as a promoter. The organometallic compound is preferably an alkylaluminoxane or an organoaluminum compound, and the alkylaluminoxane is more preferably methylaluminoxane (MAO) or modified aluminooxane (Modified Methylaluminoxane: MMAO). And the organoaluminum compound is more preferably AlR _n X _3n . Wherein R is C1 to C10 alkyl or aryl, X is halogen, n is 1,2 or 3;

Styrene can be polymerized using a catalyst prepared by modifying the catalyst or support supporting the HBDT compound or the HBDZ compound of the present invention and bonding the HBDT compound to the surface thereof. The amount of the polymerization and, based on the styrene is 10 ^-7 to 10 ^-3 mol / L, and preferably 10 ^-6 to 10, more preferably ^-4 mol / L, the polymerization temperature of the catalyst is 0~80 ℃ preferably from 20 to 60 ℃.

EXAMPLE

Hereinafter, although an Example demonstrates this invention, this invention is not limited to an Example.

[Structure and Composition of Catalyst]

The structure of the catalyst was investigated by hydrogen and carbon nuclear magnetic resonance analyzers (H-NMR and C-NMR), and the catalyst components and composition were analyzed by inductive plasma spectroscopy (ICP).

[Polymerization and Copolymerization of Ethylene]

The polymerization and copolymerization of ethylene was carried out in an external temperature controller, a magnetic stirrer, and an organic reactor with a valve capable of supplying monomer and nitrogen. In the nitrogen-substituted glass reactor, the required amount of purified toluene and MAO as a cocatalyst were added, stirred sufficiently, and then the required amount of catalyst was injected to initiate polymerization. After some time, a little methanol was added to terminate the polymerization. The resulting mixture was poured into a large amount of methanol added with hydrochloric acid to obtain a polymer, washed with water and ethanol and then dried in vacuo.

[Catalytic activity]

The weight of PE obtained in the polymerization was measured and the catalytic activity was expressed in kg PE / mol M-h.

[Melting point and crystallization temperature]

Melting point and crystallization temperature of the polymer was measured by differential thermal analyzer (DSC), and the specimen was heated to 200 ° C. and left for 5 minutes and then cooled and warmed up to 20 ° C./min.

Example 1: Synthesis of hexamethyltrisiloxane bis (ŋ ⁵ -cyclopentadienyltitanium trichloride)

[Synthesis of 1,5-dicyclopentadienyl hexamethyltrisiloxane]

10 mmol of 1,5-dichlorohexamethyltrisiloxane was dissolved in 50 mL of THF, and then 200 mmol of sodium cyclopentadiene (2.0 M THF solution) was slowly added at -78 ° C, and the mixture was allowed to react at room temperature for about 5 hours. After the reaction, the solvent was removed, hexane was added, and then filtered to remove LiCl generated during the reaction. Removal of the solvent from the filtered solution yields the desired product as a yellow liquid in 90% yield.

[Synthesis of hexamethyltrisiloxane bis (ŋ ⁵ -cyclopentadienyltitanium trichloride)]

10 mmol of the synthesized 1,5-dicyclopentadienylhexamethyltrisiloxane was dissolved in 50 mL of THF, and then 200 mmol of TiOEt was added at -78 ° C, and stirred at room temperature for 3 to 5 hours to form thallium dianion. . This solution is mixed with a TiCl ₄ (20 mmol) toluene solution prepared in advance at -78 ° C, and the mixed solution is reacted at room temperature for 10 to 15 hours, and then the solvent is removed. Here, 30 ml of CH ₂ Cl ₂ was added, filtered to remove TICl, and then 50 ml of hexane was added to the filtered solution to recrystallize the product. The recrystallized solid product is recrystallized again in CH ₂ Cl ₂ or toluene solution to give the desired product in 50% yield.

Example 2 Polymerization Behavior of Ethylene and Thermal Properties and Molecular Weight of PE Polymer

[Features of this patent catalyst]

In order to investigate the properties of the catalysts (HBDT and HBDZ) prepared in this patent, the catalytic activity of polymers of ethylene, several metallocene polymerization catalysts that can be used in general, HBDT or HBDZ, and the resulting polyethylene (PE) Melting temperature and crystallization temperature were investigated, and the results are shown in Table 1 below.

The polymerization activity of ethylene using HBDT compounds was slightly smaller than that of CpTiCl ₃ or Cp ₂ TiCl ₂ , but the melting and crystallization temperatures of polymerized PE are similar to those of polymers obtained from other catalysts. . Depending on the catalyst, such as varying the component ratio or the polymerization temperature, and can adjust the molecular weight of PE 10 ^{4-10 6,} particularly over the 100,000 to 1,000,000, wherein the molecular weight distribution (polydispersity index) is shown relatively wide as 3.0 to 8.0.

The catalytic activity and thermal properties were changed according to the amount of cocatalyst used. That is, as the number of cocatalysts increased to some extent, the catalytic activity increased and the melting and crystallization temperatures of PE slightly increased. However, as the polymerization temperature increases, the catalytic activity decreases, and the melting temperature and crystallization temperature of PE are low.

In the case of polymerization of ethylene using HBDZ compound, the polymerization activity was almost the same as that of Cp ₂ ZrCl ₂ or Ind ₂ ZrCl ₂ , and the melting temperature and crystallization temperature of PE were similar. The molecular weight of PE was relatively high and appeared to be 100,000 or more, especially the molecular weight distribution was found to be higher than 4.0.

Polymerization conditions: [A1] / [Ti] = 1,000; [A1] / [Zr] = 10,000; 40 ° C .;

Catalytic activity: kg polymer M mol-h-atm.

As can be seen from the table above, the polymerization behavior of the HBDT compound as a catalyst showed lower catalytic activity than that of the catalyst which can be used normally. However, the molecular weight of the HBDT compound was much higher than that of CpTiCl ₃ having a structure similar to It is shown. Compared with the general Cp ₂ ZrCl ₂ and Ind ₂ ZrCl ₂ , the activity was obtained with HBDZ, and the molecular weight of PE was significantly increased.

[Thermal Properties of Polymers under Polymerization Conditions]

The previously prepared catalyst HBDZ can be used together with the MAO cocatalyst to polymerize ethylene, and the effects of the amount of MAO and catalyst and polymerization temperature on the catalytic activity and the enthusiasm of the polymer are shown in Table 2.

Catalytic Activity: kg PE / mol Zr-atm-h

As can be seen above, as the amount of the cocatalyst MAO increases, the melting temperature and crystallization temperature do not change significantly, but the catalytic activity tends to increase. However, the degree of increase in catalytic activity was different depending on the polymerization temperature, so the increase in catalytic activity was more pronounced at 40 ° C. The molecular weight decreased as the amount of MAO or polymerization temperature increased.

Claims (3)

Bimetalmetallocene compound represented by the following structural formula: Wherein M is a metal and a transition metal element of Groups 3-10, Y1 and Y2 are independently of each other cyclopentadienyl, a cyclopentadienyl derivative capable of bonding with M ⁵ and indenyl or fluorenyl, A1, A2, and A3 are each independently a group 1 to 4 element, and A1 and Y1 or A3 and Y2 may be interleaved with a spacer Sp, and E1 and E2 are heteroatoms independently of each other and are located between Y1 and Y2 ligands. And R 1 to R 6 are each independently a group formed of hydrogen, alkyl, aryl, silyl, alkoxy, aryloxy, siloxy, halogen or a combination thereof -Sp-Sup where Sp is as described above and Sup is And X is a group formed of hydrogen, alkyl, aryl, silyl, alkoxy, aryloxy, siloxy, halogen, or a combination thereof, and n is 0-4 depending on the type and valence of the metal. Can be. The compound of claim 1, wherein M is a lanthanum-based element; Sp is carbon, oxygen, nitrogen or phosphorus as spacer; E1 and E2 are bimetallic metallocene compounds that are nitrogen, oxygen, phosphorus or sulfur. The bimetallic metallocene compound according to claim 2, wherein M is titanium or zirconium.