KR101128416B1 - Method of deactivating from polymer solutions - Google Patents

Abstract

The present invention relates to a deactivator composition for effectively deactivating a metal catalyst compound used for polymer polymerization after completion of a reaction and a method for deactivating a metal catalyst compound using the deactivator composition.

 The use of the deactivator composition according to the present invention enables more effective deactivation of the metal catalyst compound compared to conventional deactivator compositions. Therefore, it is possible to effectively inhibit the abnormal reaction between the unreacted monomer remaining in the polymer polymerization solution and the metal catalyst compound after the completion of the polymer polymerization reaction to obtain a polymer having improved uniformity and safety of mechanical properties, and also to decompose and discolor the polymer produced. Can be minimized.

Solution polymerization method, antistatic agent, hydrotalcite

Description

METHODE OF DEACTIVATING FROM POLYMER SOLUTIONS}

The present invention relates to a deactivator composition for effectively deactivating the metal catalyst compound remaining in the polymer polymerization solution after completion of the polymer polymerization, and a method of deactivating the metal catalyst compound using the deactivator.

In general, during the polymerization of the polymer, a transition metal catalyst is added as a reaction catalyst to promote the polymerization reaction, and the transition metal catalyst remains in the polymer polymerization solution after the polymerization reaction.

The transition metal catalyst remaining in the polymer polymerization solution may bring about color change and physical property degradation of the polymer. In addition, when the polymer film is produced, it causes cracking of the film and acts as a major cause of lowering transparency. In addition, there is a problem in that discoloration of the polymer occurs or decomposition occurs due to the transition metal catalyst remaining during molding of the polymer product in a high temperature process, thereby greatly deteriorating physical properties.

As described above, the transition metal catalyst remaining in the polymer polymerization solution after the completion of the polymerization reaction causes an abnormal reaction with the residual monomer or decreases the physical properties of the polymer. A process was needed to remove and recover the metal catalyst.

However, the production process is simplified because the separate recovery and removal process is omitted for the transition metal catalyst compound which is highly activated and the catalyst deactivator remains due to the development of a catalyst deactivator, but the color change due to the transition metal catalyst remaining in the polymer polymerization solution And physical property degradation is not completely solved.

For these reasons, a process for effectively deactivating the transition metal catalyst compound remaining after polymer polymerization is required.

The prior art includes processes for the preparation of olefin polymers, such as the preparation of ethylene or propylene homopolymers or copolymers of ethylene or propylene with higher alpha-olefins using high temperature or solution polymerization processes.

Control of the degree of polymerization and molecular weight of the polymer obtained in the above solution polymerization method can be achieved by adjusting various conditions such as reaction temperature, and the termination of the polymerization reaction is usually terminated by the addition of "inactivator".

U.S. Patent No. 602946 describes common additives such as antioxidants (Anti-Oxidant), steam, alcohols, and ethers as well as hydrotalcite-like compounds. compounds, fatty acid salts, acid acceptors such as metal oxides, and the like are described.

In view of the problems of the prior art as described above, the present invention, after the polymer polymerization using a suitable deactivator, the metal catalyst compound remaining in the polymer polymerization solution more easily removes the polymer that can be generated by the metal catalyst compound It is an object to provide a deactivator composition that is more effective in inhibiting degradation and discoloration and a method of deactivating a metal catalyst compound using the deactivator composition.

In order to achieve the above object, an aspect of the present invention provides an inactivator composition comprising an antistatic agent and hydrotalcite.

A second aspect of the present invention for achieving the above object is a) reacting a polymer polymerization solution comprising a monomer, a metal catalyst compound and a solvent; And b) inactivating the deactivator composition comprising an antistatic agent and hydrotalcite in the polymer polymerization solution to deactivate the metal catalyst compound.

The use of the deactivator composition according to the present invention enables more effective deactivation of the metal catalyst compound compared to conventional deactivator compositions. Therefore, it is possible to effectively suppress the abnormal reaction between the unreacted monomer remaining in the polymer polymerization solution and the metal catalyst compound after the completion of the polymer polymerization reaction, thereby obtaining a polymer having improved uniformity and safety of mechanical properties, and decomposing the prepared polymer and Discoloration can be minimized.

Hereinafter, the present invention will be described in more detail.

The present invention provides an inactivator composition comprising an antistatic agent and hydrotalcite.

The deactivator composition comprising the antistatic agent and hydrotalcite is a polymer polymerization solution in a state of being dissolved in a small amount of nonpolar solvent as an inactivator used to deactivate the metal catalyst compound (catalyst and cocatalyst component) remaining in the polymer polymerization solution. It can be mixed with. The antistatic agent generally has a hydrophobic group and a hydrophilic group. The hydrophobic group of the antistatic agent mixed in the polymer polymerization solution is excellent in fluidity in the polymer polymerization solution and thus easily accessible to the active catalyst, and the hydrophilic group of the antistatic agent may quickly react with the active catalyst to deactivate the active catalyst. In addition, the hydrotalcite may increase the deactivation reaction effect by adsorbing an acid generated in the deactivation reaction into a plate-like structure. In addition, the antistatic agent has a property of a surfactant, so that the hydrotalcite in the polymer polymerization solution can be easily dispersed in the suspension solution, thereby achieving more effective deactivation of the residual catalyst.

The antistatic agent may be used at least one selected from the compounds represented by the following formula (1) to (3).

In Chemical Formula 1,

R ₁ is an alkyl group having 14 to 17 carbon atoms,

n is an integer of 3-14.

In Chemical Formula 2

R ₂ is an alkyl group having 12 to 17 carbon atoms,

x and y are integers from 1 to 5.

In Chemical Formula 3,

R ₃ is an alkyl group having 17 to 18 carbon atoms,

K, l and m are integers of 3-20.

The antistatic agent is preferably added at 20 ppm to 500 ppm based on the polymer polymerization product. When the antistatic agent is less than 20 ppm, the deactivation efficiency of the metal catalyst compound remaining in the polymer solution may be lowered. When the antistatic agent is higher than 500 ppm, the antistatic agent may be impregnated in the polymer solution, thereby deteriorating the polymer properties and the antistatic agent itself. Can be.

The hydrotalcite is an acid acceptor, and specific examples thereof include DHT-4A (Japan), DHT-4A-2 (Japan), ZHT-4A (Japan), and L-55RII (USA). Reheis Co.) may be used one or more selected from the group consisting of, but is not limited thereto.

The hydrotalcite is preferably added at 50 ppm to 1,000 ppm based on the polymer polymerization product. When the content of the hydrotalcite is less than 50 ppm, the deactivation efficiency of the metal catalyst compound remaining in the polymer solution may be lowered. When the content of the hydrotalcite exceeds 1,000 ppm, the transparency of the prepared polymer may be decreased, and the cloudiness may be increased. The physical properties of may be lowered.

The deactivator composition comprising the antistatic agent and hydrotalcite may further comprise a solvent. The solvent is preferably a nonpolar solvent, and specific examples thereof may include one or more selected from the group consisting of toluene, chloroform, normal hexane, and hydrocarbons having 4 to 10 carbon atoms, but are not limited thereto.

In addition, the present invention comprises the steps of: a) polymerizing a polymer polymerization solution comprising a monomer, a metal catalyst compound and a solvent; b) providing a deactivation method of the metal catalyst comprising mixing the deactivator composition comprising an antistatic agent and hydrotalcite with the polymer polymerization solution to deactivate the metal catalyst compound.

In step a), the monomer may include at least one selected from ethylene and an alphaolefin comonomer copolymerizable with the ethylene.

The alpha olefin comonomer copolymerizable with ethylene includes a diene olefin monomer or a triene olefin monomer having two or more double bonds, and is preferably an alpha olefin having 3 to 20 carbon atoms.

Specific examples of the alpha olefin comonomer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1- Dodecene, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1 , 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethyl styrene, and the like. These monomers may be used in combination of two or more thereof. The alphaolefin comonomers are propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 Preference is given to at least one member selected from the group consisting of tetradecene, 1-hexadecene and 1-aitocene. In addition, the alpha olefin comonomer is more preferably one or more selected from the group consisting of propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene, most preferably 1-octene desirable.

Examples of the solvent include aliphatic hydrocarbons such as benzene, toluene, xylene, cumene, butane, isobutane, pentane, n-hexane, octane, decane, dodecane, hexadecane, octadecane, cyclodecane, and cyclodo Substituent hydrocarbons, such as decane and cyclooctane, petroleum fractions, such as gasoline, kerosene, and diesel, etc. can be used, It is especially preferable to use n-hexane.

In step a), the metal catalyst compound comprises a metal catalyst and a promoter component.

The metal of the metal catalyst may be at least one selected from the group consisting of metals belonging to Groups 4B, 5B, 6B, 7B, 8, 1B and 2B, preferably belonging to Groups 4B and 6B. Metal.

The type of the cocatalyst is not particularly limited, and may be selected without particular limitation as long as it is known in the art. Specific examples of the promoter include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum and triiso Propyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl Aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron triphenylphosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, tripropyl Ammonium tetra (p-tolyl) boron, triethylammonium Tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentaflo Rophenylboron and the like, and more preferred compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, or triphenylcarbonium tetrapentafluorophenylboron.

In step b), when the deactivator composition comprising an antistatic agent and hydrotalcite in the polymer polymerization solution is added to the polymer polymerization solution, the concentration ratio of the deactivator composition and the polymer polymerization solution is 1:10 to 1: 100 volume. It is preferably in the range of%, more preferably in the range of 1:20 to 1: 50% by volume. When the concentration ratio of the polymer polymerization solution and the deactivator composition including the antistatic agent and the hydrotalcite is in the above range, the activity of the metal catalyst compound can be sufficiently reduced, and it is also excellent in terms of economics.

In addition, the deactivator including the antistatic agent and the hydrotalcite may be introduced during the transfer from the reactor to the flash drum after the polymerization reaction or during the transfer to the twin screw extruder, and is preferably added during the flash drum transfer.

After the step of deactivating the metal catalyst compound by mixing the deactivator composition including an antistatic agent and hydrotalcite with the polymer polymerization solution of step b), a small amount of deactivated metal catalyst compound may be present in the polymer polymerization solution. Since the content of the deactivated metal catalyst compound is less than 5 ppm, no special removal process is required.

The deactivation method of the metal catalyst compound may further include extracting a by-product generated in the polymer polymerization step after the deactivation step of the metal catalyst compound.

The by-products generated in the polymer polymerization step may be removed by using a vacuum pump after injecting a carrier material capable of transferring the by-products into a barrel or a feeder of the extruder.

As the transfer material, by-products generated during the deactivation process of the metal catalyst compound, in particular, a polar or nonpolar material having affinity with polar and nonpolar organic compounds may be used. Specifically, nitrogen gas, carbon dioxide, water, steam or a mixture thereof may be used, but is not limited thereto.

Hereinafter, a method for deactivating a metal catalyst of the present invention will be described in detail with reference to the accompanying drawings.

The polymer polymerization solution containing the monomer, the metal catalyst compound and the solvent is continuously injected into the reactor 4 containing triethylaluminum for removing polar impurities such as moisture in the reactor, and then 100 to 20 to 150 ° C. The polymer resin is prepared by stirring for 1 minute to 1 hour at a speed of 1,000 rpm.

The prepared polymer resin is added to the deactivator composition comprising an antistatic agent and hydrotalcite according to the present invention through a metering pump during transfer to the flash drum (6).

The injected deactivator composition can achieve deactivation of the metal catalyst compound in the polymer polymerization solution.

In the flash drum 6, the polymer polymerization solution is first removed at least 50 wt% of the solvent and the unreacted monomer under a constant temperature and a constant pressure, and is supplied to the twin screw extruder 8 through a transfer pump 7 while maintaining a liquid state. do. The by-products generated by the solvent, the unreacted monomer and the polymer polymerization reaction supplied to the twin screw extruder 8 are nitrogen gas, carbon dioxide, water, steam, or mixtures thereof introduced into the twin screw extruder 8 through a conveying material injection nozzle 11. Can be removed secondarily.

Thereafter, the twin screw extruder 8 is heated to a temperature of 100 to 240 ° C., and the solvent and the unreacted monomer are removed to less than 20 ppm in the process of extruding, and the polymer resin is pelletized by the granulator 10. Can be.

Hereinafter, the present invention will be described in detail by the following examples and comparative examples. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following examples.

Examples 1-7

A deactivator composition was prepared by dispersing DHT-4A and DHT-4A2 (Japan Kyowa Co., Ltd.) in the contents shown in Table 1 with an antistatic agent in 1000 cc of normal hexane as a CRODA atmer 163 and a hydrotalcite compound. .

Comparative Examples 1 to 5

Inactivator composition was prepared by dispersing DHT-4A (Japan Kyowa Co., Ltd.) in a content of the following in Table 1 with an anti-static agent in the normal hexane 1000 cc CRODA atmer 163 and a hydrotalcite compound.

Experimental Example

(Production of polyethylene)

In a 1.50 L stainless autoclave reactor with a stirrer, 3.36 kg / h n-hexane, 1.10 kg / hr ethylene, 1- (N-methyl-1,2,3,4-tetrahydroquinoline-8 as a transition metal catalyst -Yl) -2,3,4,5-tetramethylcyclopentadienyl titanium (IV) trichloride 0.5 μmol / min, 2 μmol / min triphenylcarbonium tetrapentafluorophenylborone as cocatalyst and reactor 10 μmol / min of triethylaluminum for removing polar impurities such as water was continuously injected, followed by continuous reaction at 150 ° C. to prepare 800 g of polystyrene per hour. The deactivator composition prepared in Examples 1 to 5 and Comparative Examples 1 to 5 was continuously introduced into the flash drum using a metering pump. The solution polyethylene in the flash drum was transferred to a twin screw extruder using a pump. Thereafter, nitrogen gas was added to remove the polar solvent and the non-polar organic substance generated from the polymerization solvent, the unreacted monomer, and the deactivation process, and then a pellet-type polyethylene was prepared using a twin screw extruder having a granulator fixed at 100 to 240 ° C.

(Yellow Index measurement)

Polyethylene in the form of pellets prepared using the deactivator compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were measured by Observer 2 degrees with C light source by ASTM D1925 method using HunterLab's ColorFlex colorimeter. The results are shown in Table 1 below.

Hydrotalcite Compounds (ppm) Antistatic Agent (ppm)
(CRODA company Atmer 163) Yellow index DHT-4A DHT-4A2 Example 1 250 - 100 3.5 Example 2 - 250 100 3.4 Example 3 50 - 20 4.8 Example 4 1000 500 4.2 Example 5 250 50 4.0 Example 6 250 200 4.3 Example 7 250 250 4.5 Comparative Example 1 - - - 13.4 Comparative Example 2 250 - 8.4 Comparative Example 3 - - 100 5.7 Comparative Example 4 40 - - 11.1 Comparative Example 5 250 - 500 5.9

According to the results of the Examples and Comparative Examples, it was evaluated that the yellow index of the pellet-type polymer prepared when the antistatic agent and the hydrotalcite were used as the catalyst deactivator at the same time, which is a conventional inactivator composition of the present invention It has been shown that it has a significant effect on deactivating the metal catalyst compound compared to the technique of using an antistatic agent or hydrotalcite alone.

1: metal catalyst 2: promoter

3: monomer 4: reactor

5: Deactivator Composition 6: Flash Drum

7: transfer pump 8: twin screw extruder

9: vacuum pump 10: granulator

11: Feeding material injection nozzle

Claims (13)

a) reacting a polymer polymerization solution comprising a monomer, a metal catalyst compound and a solvent; b) deactivating the metal catalyst compound by mixing the reaction product of the polymer polymerization solution with an inactivating agent composition comprising at least one antistatic agent and hydrotalcite in the compound of Formulas 1 to 3, Wherein the antistatic agent is included in an amount of 20 to 500 ppm based on the reaction product of the polymer polymerization solution. [Formula 1]

In Chemical Formula 1, R ₁ is an alkyl group having 14 to 17 carbon atoms, n is an integer of 3-14. [Formula 2]

In Chemical Formula 2 R ₂ is an alkyl group having 12 to 17 carbon atoms, x and y are integers from 1 to 5.  (3)

In Chemical Formula 3, R ₃ is an alkyl group having 17 to 18 carbon atoms, K, l and m are integers of 3-20. delete delete The method of claim 1, wherein the hydrotalcite is a group consisting of DHT-4A (Japan), DHT-4A-2 (Japan), ZHT-4A (Japan) and L-55RII (USA Reheis) Method for inactivating a metal catalyst compound, characterized in that at least one selected from. The method of claim 1, wherein the hydrotalcite is included at 50 to 1000 ppm based on the polymer polymerization product. The method according to claim 1, wherein the concentration ratio of the polymer polymerization solution and the deactivator composition when mixing is in the range of 1: 10 to 1: 100% by volume. 20 to 500 ppm of at least one antistatic agent among the compounds of the following Chemical Formulas 1 to 3 based on the reaction solution including the metal catalyst compound; And Hydrotalcite Deactivator composition of a metal catalyst compound comprising: [Formula 1]

In Chemical Formula 1, R ₁ is an alkyl group having 14 to 17 carbon atoms, n is an integer of 3-14.  [Formula 2]

In Chemical Formula 2 R ₂ is an alkyl group having 12 to 17 carbon atoms, x and y are integers from 1 to 5.  (3)

In Chemical Formula 3, R ₃ is an alkyl group having 17 to 18 carbon atoms, K, l and m are integers of 3-20. delete delete The method of claim 7, wherein the hydrotalcite is a group consisting of DHT-4A (Japan), DHT-4A-2 (Japan), ZHT-4A (Japan) and L-55RII (USA Reheis) Deactivator composition, characterized in that at least one selected from. The deactivator composition according to claim 7, wherein the hydrotalcite is included in an amount of 50 to 1000 ppm based on the reaction solution including the metal catalyst compound. 8. The deactivator composition of claim 7, wherein the deactivator composition further comprises a nonpolar solvent. The deactivator composition according to claim 12, wherein the nonpolar solvent is at least one selected from the group consisting of toluene, chloroform, normal hexane and a hydrocarbon solvent having 4 to 10 carbon atoms.

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