KR101455897B1 - Process for Removing Catalyst Residue Containing Metals from Cyclic Olefinic Polymer - Google Patents

Abstract

The present invention relates to a method for removing residues of a metal-containing catalyst from a solution of a cyclic olefin-based polymer obtained by polymerization and hydrogenation of a cyclic olefin-based monomer, comprising the step of reacting a cyclic olefin polymer A method for effectively removing a metal catalyst of a cyclic olefinic polymer, comprising reacting a solution with a functional ion exchange resin.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a process for removing residues of a catalyst containing a metal from a cyclic olefin-

The present invention relates to a process for removing residues of a catalyst containing a metal from a cyclic olefinic polymer, specifically a residue of a catalyst containing tungsten metal, a residue of a catalyst containing aluminum metal and a residue of a catalyst containing ruthenium metal .

The cyclic olefin polymer is a polymer obtained from a cyclic monomer such as norbornene and has excellent transparency, heat resistance, chemical resistance, and very low birefringence and water absorption rate compared to conventional olefin polymers. Thus, CD, DVD, POF Such as an optical material such as a fiber, a retardation film, a capacitor film, an information electronic material such as a low dielectric material, a low-absorbency syringe, a blister packaging, and the like.

Examples of the polymerization method of the cyclic olefin include ring opening metathesis polymerization (ROMP), copolymerization with ethylene, addition polymerization, and the like. In this polymerization reaction, a transition metal such as a metallocene compound, Ni, Pd- A catalyst is used. Depending on the central metal, ligand, and catalyst composition of such catalysts, the nature of the polymerization reaction and the properties of the resulting polymer may vary.

Catalysts used in ROMP include chlorides such as TiCl ₄ and WCl ₆ or organometallic compounds in the form of carbonyl react with cocatalysts in the form of Lewis acids such as R ₃ Al and Et ₂ AlCl to form metal carbene or metal Catalytically active species in the form of metallocyclobutane which react with the double bonds of the olefins and ring through the ring intermediates of the metallacyclobutane into the final products with double bonds (Ivin, KJ; O Donnel, JH; Rooney, JJ; Steward, CD Makromol. Chem., 1979, Vol. In the hydrogenation reaction, a ruthenium catalyst or the like is used.

An example of a conventional method for polymerizing a cyclic olefin-based polymer is a method of polymerizing a monomer through a ROMP reaction and a hydrogenation reaction through a monomer synthesis step (including monomer synthesis step 1 and 2-1 and 2-2 in Reaction Scheme 1) do.

<Reaction Scheme 1>

Where R is the next &Lt; / RTI &gt;

 The hydrocarbon group having 1 to 10 carbon atoms is any one selected from the group consisting of a methyl group, an ethyl group, a propyl group, and a combination thereof, a cyclohexyl group, a cyclohexyl group, and a combination thereof. An aryl group, a propenyl group, and a combination thereof. The term &quot; alkenyl group &quot;

The substituted or unsubstituted hydrocarbon group may be bonded directly to the ring structure, or may be bonded to the ring structure through a linking group.

The linking group may be a bivalent hydrocarbon group having 1 to 10 carbon atoms, a linking group containing oxygen, nitrogen, sulfur or silicon such as a carbonyl group, an oxycarbonyl group, a sphone group, an ether bond, a thioether bond, A siloxane bond, and the like, or a linking group including a plurality of these groups.

The polar group includes a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alcoholic carbonyl group, a cyano group, an amide group, an imide group, an amino group, an acyl group, a sulfonyl group and a carboxyl group. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the carbonyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group, an ethoxycarbonyl group and the like. Is a primary amino group.

Examples of the divalent linking group in the aromatic group having a single bond or a divalent linking group include an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, an arylene group, An arylene group, an oxyarylene group, an oxycarbonyl group, an iminocarbonyl group, a carbonyl group, an acetylene group, a ureylene group, a hetero atom such as sulfur or oxygen, and an amino group. It is also possible to combine two or more of these connecting units.

The aromatic group should include an aromatic group through such a linkage, which includes a monohydroxy leaving group of an aromatic compound.

Specific examples of the monovalent hydrogen deficiency include benzene, pentane, naphthalene, azulene, heptarene, biphenylene, indacene, acenaphthalene, phenanthrene, anthracene, fluoransenes, , Naphthacene, prazene, picene, perylene, phenaphene, pentacene, tetraphenylene, hexaphene, penascene, rubicene, coronene, trinaphthylene, heptapene, And one or more of the group consisting of thiophene, thianthrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxathiine, pyrrole, imidazole, pyrazole, The present invention relates to a method for producing a compound represented by the general formula (1) or a salt thereof, wherein the compound is selected from the group consisting of isothiazole, isooxazole, pyridine, pyridine, pyrimidine, pyridine, indolidine, isoindole, indole, indazole, purine, quinolidine, isoquinone, quinoline, Xylylene, cyinoline, pteridine, carbazole, betacarbonyl, phenanthyridine, acry It is preferable to have any one of heterocyclic compounds and substituents thereof selected from the group consisting of pyridine, pyrimidine, phenanthroline, phenadine, phenarazine, phenothiazine, prazine, phenoxy and combinations thereof .

In the case of the norbornene series, the amount of the residual transition metal, which is a catalyst used in the metathesis polymerization, is relatively high, which is a disadvantage of high light absorption. In order to overcome this disadvantage, a catalyst removal process is required. Until now, it has been known that if the catalyst is not removed after the polymerization reaction, the resin becomes colored and acts as a fatal hindrance to commercialization due to the toxicity of the catalyst residue.

An object of the present invention is to provide a catalyst removal method of a cyclic olefin-based polymer which can be recycled using a low-cost ion exchange resin and can provide a high-purity polymer through a simple filtration process.

The present invention relates to a process for the polymerization of a cyclic olefin-based monomer comprising a residue of a catalyst containing tungsten metal, a residue of a catalyst containing an aluminum metal and a residue of a catalyst containing a ruthenium metal, and a solution of the olefin-based polymer, (i) large porous (macropore), (ii) 1 primary amine, secondary amine and OH ^- that the treatment with the functionalized ion exchange resin modified with at least one selected functional group from the group Including,

And a method for removing residues of a catalyst containing a metal from a cyclic olefin-based polymer obtained through polymerization and hydrogenation of an arbitrary cyclic olefin-based monomer.

The present invention can effectively remove the catalyst metal which is essentially added in the polymerization and hydrogenation of the cyclic olefin-based monomer, thereby providing a high-purity cyclic olefin-based polymer at a high yield.

1 is a photograph of a cyclic olefin-based polymer film obtained from Comparative Example 1,
Figs. 2 to 3 are photographs of the cyclic olefin-based polymer films obtained from Examples 1 and 2, from which the catalyst residues have been removed, respectively.

The process of the present invention originates from any cyclic olefinic polymer solution comprising a residue of a catalyst containing a metal obtained via polymerization of a cyclic olefinic monomer, specifically a ROMP polymerization and a hydrogenation process. Here, the catalyst used for preparing the cyclic olefin-based polymer is a catalyst containing tungsten metal, a catalyst containing aluminum metal and a catalyst containing ruthenium metal.

The total amount of residues of the catalyst containing tungsten metal, the residues of the catalyst containing aluminum metal and the residues of the catalyst containing ruthenium metal, optionally present in the solution of the ROMP polymerized and hydrogenated cyclic olefinic polymer, Of about 100 to about 3,000 ppm.

Optionally the ROMP polymerized and hydrogenated cyclic olefin based polymer solution which can be treated by the process according to the invention optionally contains ROMP polymerized and hydrogenated cyclic olefin based polymer in an amount of 5 to 10% by weight, preferably 5% by weight or less have. If the solid content in the polymer solution is too high, the effect of removing the catalyst is deteriorated. Therefore, it is preferable to adjust the solid content in the polymer solution within the above range.

Polymerization of the optionally cyclic olefinic monomer and the process for obtaining the hydrogenated cyclic olefinic polymer solution are not critical as long as they comprise the three residues of the catalyst containing the metal mentioned above, .

Optionally, polymerization of the cyclic olefinic monomer and the hydrogenated cyclic olefinic polymer are made in a polymer solution by dissolving in a solvent selected from a polar solvent such as toluene, methylene chloride and N-methyl-2-pyrrolidone.

It is preferable that the contacting of the cyclic olefin polymer solution with the ion exchange resin is carried out at a temperature of 10 to 60 DEG C for 1 to 24 hours to obtain the content of the functionalized ion exchange resin of the present invention And it is preferable in terms of considering the ion exchange capacity.

Considering the removal efficiency of the catalyst, the removal efficiency is further improved by increasing the amount of the ion exchange resin with respect to the content of the polymer in the polymer solution. However, even if the amount exceeds 2 times, the removal efficiency is not remarkably improved. The amount is preferably within 2 times the weight of the polymer.

The ion exchange resin used to remove the catalyst of the present invention is (i) a porous and large, (ii) 1 primary amine, secondary amine, OH ^- is modified with at least one functional group selected from the group.

In the foregoing and in the following description, it is understood that the term "macroporous" has a meaning conventionally used in ion exchange terms. The macroporous ion exchange resin consists of two continuous phase, continuous porous phase and continuous gel polymer phase, and they have permanent voids which can be measured by nitrogen BET. The macroporous ion exchange resin typically has a surface area in the range of 7 to 1,500 m 2 / g and an average pore diameter in the range of 50 to 1,000,000 Å. Typical macroporous resins often have an average pore volume of greater than 0.7 mg / g. Such resins typically comprise crosslinked copolymers, especially styrene-divinylbenzene copolymers.

It is necessary that the ion exchange resin be macroporous, but this condition (i) is insufficient for itself and condition (ii) must be satisfied at the same time. Thus, a suitable ion exchange resin is preferably functionalized by at least one functional group selected from primary amines, secondary amines and OH &lt; ^- &gt;.

For example, the ion exchange resin according to one embodiment of the present invention is functionalized with a trimethylammonium group.

&Lt; Formula 1 >

The reason why such an ion exchange resin effectively removes the various metal-containing catalyst residues of the present invention can not be clearly established, but it can be understood that it is presumably related to the spectroscopic series. In the ligand field theory, it is possible to rank ligands that act most weakly with metal ions, from the ligand that causes the smallest crystal-cleavage to cause the largest cleavage of the crystal, Although the ligand does not act uniformly, it can be very usefully used. The order from the weakest long ligand to the strongest long ligand is called the spectrochemical series.

I- <Br- <Cl- <F-, OH- <H2O <NCS- <NH3 <en <CO, CN-

------ weak intestinal ligand ------ / - medium intestinal ligand - / --- strong intestinal ligand ---- /

The ion exchange resin of the present invention is functionalized, and these functional groups act on the catalyst metal ions such as W, Al, Ru, and adsorb them to effectively remove the catalyst metal.

After reacting the cyclic olefin-based polymer containing the metal-containing catalyst residues with the ion-exchange resin, the ion-exchange resin containing the metal ion can be separated by simple filtration, and the separated anion- Solution, and the metal ion can be extracted and converted into a recoverable salt for reuse.

Hereinafter, one example will be described in order to show that the removal method of the present invention is efficient in proceeding the catalyst removal process after continuously performing the ROMP polymerization and the hydrogenation process using the cyclic olefin-based monomer, But the present invention is not limited thereto.

The method of ROMP polymerization and hydrogenation of the cyclic olefin-based monomer according to one embodiment of the present invention can be summarized by the following reaction formula 2. The cyclic olefin-based polymer obtained by polymerization and hydrogenation of the cyclic olefin-based monomer (hereinafter referred to as COP ) Was adjusted to the solid content concentration with toluene solution and the residue of the catalyst containing W, Al, and Ru metals was removed using an ion exchange resin.

<Reaction Scheme 2>

Specifically, the catalyst containing tungsten metal is WCl ₆ , the catalyst containing aluminum metal is (C ₂ H ₅ ) ₂ AlCl, and the catalyst containing ruthenium metal is RuHCl (CO) (PPH ₃ ) ₃ .

Specifically, the COP toluene solution was transferred to a stirrable 200 L bath.

COP polymer ion exchange resin in Bath containing ^- a (AMP16, the functional group _{^{-N + (CH 3) 3 OH}} , macropore, bulk density 670g / L, and the true specific gravity is 1.08 the functionalization of the ion-exchange resin, product Samyang Corporation) And the mixture was weighed and placed in a bath. The mixture was stirred at room temperature for about 18 to 60 hours. Next, the ion exchange resin was removed through a filter. The COP polymer with the ion exchange resin removed was precipitated in methanol. The precipitated COP was separated from the solvent by using a filter, followed by vacuum drying (at 60 ° C for at least 12 hours) to completely remove the solvent to obtain a high purity COP polymer.

The amount of each catalyst remaining in the solution of the cyclic olefin polymer obtained from the above-mentioned reaction formula 2 before the treatment with the ion exchange resin and the amount of each catalyst after the catalyst was removed by the above method was analyzed by ICP-MS (PerkinElmer, model ELAN DRC II) The results are shown in Table 1 below.

A hot-pressed film was prepared by using the cyclic olefin-based polymer before removal of the catalyst and the cyclic olefin-based polymer after removal of the catalyst (carried out under the conditions of 10 wt% ion exchange resin, polymer content 5 wt%, stirring time 18 hr) The photographed photographs are shown in Figs. 1 to 3, respectively. Fig. 1 is a film according to Comparative Example 1, Fig. 2 is a film according to Example 1, and Fig. 3 is a film according to Example 2. Fig. The transmittance and haze of the prepared film were evaluated by the following measurement methods, and the results are shown in Table 1 below.

(1) Transmittance: Measured according to JIS K 7361.

(2) Haze: Measured according to JIS K 7136.

Before catalyst removal
(Comparative Example 1) After catalyst removal Lab (100ml)
(Example 1) Pilot (200L)
(Example 2) W content 2304 ppm 62 ppm 302ppm Al content 1430 ppm 149 ppm 560ppm Ru content 154 ppm 14 ppm 76 ppm Permeability 88% 90% 90% Haze 3.8 5.6 4.9

Table 2 shows the results obtained by removing the catalyst while changing the amount of the ion exchange resin, the content of the polymer, and the treatment time in the cyclic olefin polymer solution as shown in Table 2 below.

In solvent
Ion exchange water treatment
(wt%) In solvent
Polymer content
(wt%) Stirring time
(hour) The residual catalyst amount (ICP-MS analysis) W (ppm) Al (ppm) Ru (ppm) One 10 5 18 158 285 39 2 20 10 22 1193 2819 85 3 20 10 60 1662 3845 101

The results of Table 3, which are provided by reference, are for confirming the removal efficiency of the catalyst according to the variation of the amount of ion exchange resin with respect to the high molecular weight. Here, the measurement of the amount of aluminum catalyst was not carried out. The amount of tungsten catalyst before the removal of the catalyst was 1,020 ppm, and the amount of Ru catalyst was 209 ppm.

Ion exchange water treatment
/ High molecular weight
(wt%) In solvent
Polymer content
(wt%) Stirring time
(hour) The residual catalyst amount (ICP-MS analysis) W (ppm) Ru (ppm) One 20/100 5 18hr 404 55 2 50/100 5 18hr 56 19 3 100/100 5 18hr 19 40 4 200/100 5 18hr <10 <5

From the results of the above Examples, a low-priced ion exchange resin having macropores and amine groups as functional groups on a toluene solution of COP polymer synthesized using W, Al, and Ru catalysts, It is possible to produce COP of high purity which is suitable for an optical film.

Inexpensive ion exchange resins, which are inexpensive and insoluble, are expected to be more economical than conventional columns or extraction processes because they can be recycled and provide high purity polymers through a simple filtration process.

In order to confirm the superiority of the catalyst removal efficiency of the ion exchange resin of the present invention, the catalyst removal treatment was carried out by changing the ion exchange resin and the porous ion exchange resin having only functional groups as shown in the following Table 4, Respectively. At this time, the amount of each ion exchange resin was 1 times as high as the polymer resin content. Again, no measurement of the amount of aluminum catalyst was performed. The amount of tungsten catalyst before the removal of the catalyst was 1,020 ppm, and the amount of Ru catalyst was 209 ppm.

product name manufacturer The residual catalyst amount (ICP-MS analysis) W (ppm) Ru (ppm) Functionalized ion exchange resin example Si-DMT Samyangsa 929 124 CR11 Samyangsa 875 160 SAR12 Samyangsa 1030 153 Examples of Porous Ion Exchange Resins SP825 Samyangsa 744 62 SP207 Samyangsa 798 67

Claims (6)

A cyclic olefin-based polymer obtained through polymerization and hydrogenation of any cyclic olefin-based monomer including residues of a catalyst containing tungsten metal, residues of a catalyst containing aluminum metal, and residues of a catalyst containing ruthenium metal With a functionalized ion exchange resin modified with one or more functional groups selected from (i) macropores and (ii) primary amines, secondary amines and OH ^- groups.
A method for removing a residue of a catalyst containing a metal from a cyclic olefin-based polymer obtained through polymerization and hydrogenation of any cyclic olefin-based monomer. The process according to claim 1, wherein the solution of the cyclic olefinic polymer comprises a total of 100 to 3,000 ppm of a residue of a catalyst containing tungsten metal, a residue of a catalyst containing aluminum metal and a catalyst containing ruthenium metal How to do it. The method of claim 1 wherein the solution of the cyclic olefinic polymer comprises a solvent selected from toluene, methylene chloride and N-methyl-2-pyrrolidone. The method of claim 1, wherein the solution of the cyclic olefinic polymer has a solids content of less than 5 weight percent. The process according to claim 1, wherein the treatment with the functionalized ion exchange resin is carried out by contacting at a temperature of 10 to 60 DEG C for 1 to 24 hours. The method of claim 1, wherein the treated anion exchange resin particles are treated with a functionalized ion exchange resin and then the separated anion exchange resin particles containing metal ions are treated with a hydrated inorganic hydroxide solution to convert the metal ions into a recoverable salt &Lt; / RTI &gt;

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