KR101561381B1 - Method for manufacturing polybutene-1 homopolymer or copolymer - Google Patents

Abstract

The present invention relates to a process for producing a polybutene-1 homopolymer, wherein in the process for producing a polybutene-1 homopolymer by polymerization of a monomer containing butene-1 in the presence of a catalyst, propane is used as a reaction solvent Wherein the polybutene-1 homopolymer is a polybutene-1 homopolymer. According to the present invention, by using propane as a reaction solvent, it is possible to use slurry polymerization in addition to solution polymerization, and the post-reaction process can be a flash process, a pelletizing process or a crumb process for treating a polymer in a solution state , And the post-reaction process with slurry polymerization may include a process for slurry treatment.

Description

METHOD FOR MANUFACTURING POLYBUTENE-1 HOMOPOLYMER OR COPOLYMER < RTI ID = 0.0 >

The present invention relates to a process for producing a polybutene-1 homopolymer, and more particularly, to a process for producing a polybutene-1 homopolymer capable of using slurry polymerization in addition to solution polymerization by using propane as a reaction solvent.

Generally, polybutene-1 is a semi-crystalline polymer having 1-butene as a monomer, and is a high molecular weight polyolefin having general properties similar to polyethylene and polypropylene.

Stereoregularity Polybutene-1 has high bending resistance and high compatibility with other polymers and has unique properties such as rheological properties and crystal behavior. It has similar density to polypropylene and low density polyethylene and has melting point similar to high density polyethylene . Also, it has excellent stability such as long-term durability at high temperature. In addition, the stereoregular polybutene-1 has an advantage that it can be easily applied to a conventional polyolefin using a processing machine such as extrusion, injection, or blow molding.

The usable temperature range of the stereoregular polybutene-1 is about -20 to 105 ° C. and is used variously for cold / hot water piping, flexible packaging paper opening, polypropylene film, fiber softener, or hot melt adhesive performance enhancer .

As a method for producing the above-mentioned polybutene-1, a method of producing a hydrocarbon having 4 or more carbon atoms by a solvent and a method of producing 1-butene itself by using a solvent have been reported. However, A method of producing 1-butene itself as a solvent has been used.

Generally, stereoregular polybutene-1 is obtained by polymerizing 1-butene in the presence of an organoaluminum compound such as diethylaluminum chloride and a main catalyst containing titanium trichloride as a main component. In this method, the stereospecificity is not sufficiently high to remove the non-stereoregular polybutene-1. And a process for removing catalyst residues that adversely affects the physical properties of the polymer due to low activity.

The stereoregular polybutene-1 can also be obtained by polymerizing 1-butene in the presence of a catalyst system consisting of titanium supported on magnesium chloride and an internal electron donor. However, this method also has a problem in that a titanium component at a level of ppm (weight) still remains in the polymer because it can not obtain the catalytic activity at the level of conventional high activity polyethylene or polypropylene.

As a specific example of a conventional method for producing stereoregular polybutene-1, Patent Document 1 discloses a process for producing polybutene-1 using a lower hydrocarbon such as normal butane, isobutane, n-pentane, isopentane and cyclopentane as a solvent, A method of preparing polybutene-1 having high stereoregularity in particle form by polymerizing the catalyst, an organoaluminum compound, an external electron donor (Lewis base) and 1-butene at a temperature of 20 ° C to 45 ° C , Thereby solving the problem of separating the solvent from the polybutene-1 thus produced.

This polybutene-1 production method has an advantage that it is not necessary to remove the non-stereoregular polybutene-1 due to the extremely high stereoregularity of 98 or more, and it is easy to separate from the solvent. However, since the catalytic activity is low at 2,360 g / g-cata · 4h, that is, at 590 g / g-cata · h, a catalyst residue removal process for lowering the physical properties of the polymer is required. It is difficult to apply it.

Meanwhile, as a specific example of a conventional method for producing polybutene-1, there is a method in which 1-butene itself is used as a solvent and a monomer, and tributyl aluminum (TIBA) and diisopropyl Dimethoxy silane (DIPMS) and 1-butene in the presence of a magnesium chloride-supported primary catalyst were prepared through a two-step polymerization.

These were able to obtain satisfactory physical properties by producing polybutene-1 having a high stereoregularity, a catalyst residue of 50 ppm or less based on titanium, and a molecular weight distribution of 6 or more through the above-mentioned production method, 1 homopolymer standard of 14,000 g / g-cata · 4h, that is, 3,500 g / g-cata · h. However, the production method of polybutene-1 by the above-mentioned method is a solution polymerization or a bulk polymerization. After the reaction, the flash process and the pelletizing process for treating the polymer in the solution state, There is a problem that the process is limited.

EP 0 187 034 U.S. Patent No. 6,306,996

In the present invention, by using propane as a reaction solvent, it is possible to use slurry polymerization in addition to solution polymerization, and the post-reaction process can be performed by a flash process, a pelletizing process, or a crumb process And a process after the reaction by slurry polymerization can include a process for slurry treatment, as well as a process for producing a polybutene-1 homopolymer.

In order to achieve the above object, the present invention provides a process for producing a polybutene-1 homopolymer by polymerization of a monomer containing butene-1 in the presence of a catalyst, wherein propane is used as a reaction solvent A method for producing a polybutene-1 homopolymer.

In the present invention, the catalyst may comprise a main catalyst, a cocatalyst, and a cocatalyst.

The main catalyst may be selected from a titanium-based catalyst, a Ziegler-Natta catalyst or a metallocene catalyst, and in particular, the Ziegler-Natta catalyst is a magnesium-supported catalyst in which a transition metal compound and an internal electron donor are supported on a carrier containing magnesium A polymerization catalyst may be used.

The cocatalyst may include organometallic compounds containing Group I metals of the Periodic Table 1 (IA), 2 (IIA), 12 (IIB), 13 (IIIA) or 14 (IVA).

The cocatalyst (or external electron donor) may include at least one member selected from the group consisting of silane compounds, inorganic acids, hydrogen sulfide, ethers, diethers, esters, amines, organic acids and organic acid esters.

Wherein the polymerization reaction is carried out at a temperature ranging from 0 占 폚 to 110 占 폚; Can be carried out in a pressure range from 1 bar to 1000 bar.

The present invention also provides a polybutene-1 homopolymer produced by the above method.

The process for producing the polybutene-1 homopolymer of the present invention can employ slurry polymerization in addition to solution polymerization by using propane as a reaction solvent. The post-reaction process is a flash process for treating a polymer in a solution state, The post-reaction process with slurry polymerization as well as the pelletizing process or the crumb process may include a process for slurry treatment.

Hereinafter, the present invention will be described in detail with reference to examples. The present invention relates to a process for producing a polybutene-1 homopolymer, which comprises introducing solution polymerization and slurry polymerization by using propane as a solvent, which has not been conventionally used in the polymerization process, It is based on the technical idea of enabling the transfer process.

INDUSTRIAL APPLICABILITY The process for producing a polybutene-1 homopolymer of the present invention is a process for producing a polybutene-1 homopolymer by the polymerization reaction of a monomer containing butene-1 in the presence of a catalyst, wherein propane is used as a reaction solvent .

The catalyst may be any known catalyst used in the production of polybutene-1, without limitation, but it is also possible to use, for example, an external electron donor as a cocatalyst and / or cocatalyst that mediates the polymerization reaction with the main catalyst .

The main catalyst is not particularly limited, but one or more selected from a titanium-based catalyst, a Ziegler-Natta catalyst or a metallocene catalyst may be used.

The titanium-based catalyst may be, for example, a titanium trichloride catalyst, a Solvay-type titanium trichloride catalyst, a titanium tetrachloride catalyst, or a silica-supported titanium catalyst.

The Ziegler-Natta catalyst may include, but is not limited to, a magnesium-supported polymerization catalyst having a transition metal compound and an internal electron donor carried on a carrier containing magnesium. The magnesium-supported polymerization catalyst comprises: preparing a homogeneous solution by adding phthalate (PA) to a pretreatment reaction product obtained by reacting a halogen-containing magnesium compound with an active hydrogen-containing organic compound; Adding titanium chloride to the uniform solution to recover a spherical granular carrier; Adding a transition metal compound to the recovered carrier and an internal electron donor having a silicon (Si) atom in a dialkyl propane 1,3-diether structure of formula (1).

The chemical structure of the thus-prepared magnesium-supported polymerization catalyst is not yet known, and includes 1 to 4 parts by weight of titanium, 15 to 30 parts by weight of magnesium, 60 to 80 parts by weight of halogen and 0 to 1 part by weight of silicon (Si) can do.

The internal electron donor of the magnesium-supported polymerization catalyst includes a compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 5 to 20 carbon atoms, R ₆ is an aliphatic hydrocarbon having 1 to 30 carbon atoms or an aromatic hydrocarbon having 5 to 30 carbon atoms, R ₃ , R ₄ and R ₅ are each independently hydrogen or an aliphatic hydrocarbon having 1 to 30 carbon atoms or an aromatic hydrocarbon having 5 to 30 carbon atoms.

The internal electron donor has environmental friendliness unlike the phthalate internal electron donor, which is an environmental hormone-inducing substance frequently used in conventional catalysts, and can also be used as an external electron donor.

Further, the metallocene compound may be at least one selected from the group consisting of pentamethylcyclopentadienyl zirconium trichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, indenyl zirconium trichloride, bis (indenyl) zirconium dichloride, dimethylsilylene- (Dimethylsilylene) -bis (indenyl) zirconium dichloride, (dimethylsilylene) -bis (2-methyl-4-phenylindenyl) zirconium dichloride, (Ethylene) (ethylene) -bis (indenyl) zirconium dichloride, ethylene-bis (indenyl) zirconium dichloride, (Ethylene) -bis (4,7-dimethylindenyl) zirconium dichloride, (tert-butylimide) (tetramethyl-? 5-cyclopentadienyl) zirconium dichloride, 2-ethanediyl < / RTI > zirconium (Tetramethyl-? 5-cyclopentadienyl) silane zirconium dichloride, (methylamide) (tetramethyl-? 5-cyclopentadienyl) -1,2-ethanediyl Zirconium dichloride, and the like, but not limited thereto.

The main catalyst component may be prepared by prepolymerization with an a-olefin such as ethylene or propylene.

In the present invention, the catalyst may also comprise an organometallic compound containing as a cocatalyst a Group I metal of the Periodic Table 1 (IA), 2 (IIA), 12 (IIB), 13 (IIIA) or 14 (IVA)

The organometallic compound includes, but is not limited to, an alkyl aluminum sesquichloride, an alkyl aluminoxane, or a compound of the following formula (2).

(2)

(R _{7) n} MX _{3 -n}

Wherein M is a Group 12 or Group 13 metal, R ₇ is a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, X is a halogen atom, and n is an integer of 1 to 3.

The organometallic compound is selected from the group consisting of diethylaluminum chloride (DEAC), ethylaluminum dichloride (EADC), dinormalbutylaluminum chloride (DNBAC), diisobutylaluminum chloride (DIBAC), ethylaluminum sesquichloride (EASC) (TEA), triisobutyl aluminum (TIBA), trinormal hexyl aluminum (TNHA), trinornal octyl aluminum (TNOA), trinormaldecyl aluminum (TNDA), triethyl zinc, triethyl borane, triisobutyl borane and And methylaluminoxane (MAO), but the present invention is not limited thereto.

The catalyst of the present invention may further comprise at least one cocatalyst selected from the group consisting of silane compounds, inorganic acids, hydrogen sulfide, ethers, diethers, esters, amines, organic acids and organic acid esters.

The cocatalyst (external electron donor) is added in order to maximize the stereospecificity, and it is preferable to use an alkoxysilane compound, preferably an alkoxysilane compound containing an alkyl group or an aryl group. Specific examples include diphenyldimethoxysilane, phenyltrimethoxysilane, isobutylmethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, or diisopropyldimethoxysilane, or a mixture of two or more thereof Can be used.

As the diethere, an internal electron donor, which is a compound represented by the formula (1) having a specific structure having a silicon (Si) atom in the above-mentioned dialkylpropane 1,3-diether structure, may be used as an external electron donor.

delete

In the following, all types of reactors, such as a continuous batch reactor, a tubular reactor, or other reactors, other than the batch reactors, the description of the case of using the batch reactors, and the like are not particularly limited by the batch reactors, will be.

In the first step for preparing the polybutene-1 homopolymer, the solvent is introduced into the reactor. In this case, it is preferable that the organic metal compound and the external electron donor, which are cocatalysts, are added and pre-treated. At this time, the reactor is purged by repeating the introduction of a vacuum and an inert gas into the reactor, and then 1-butene is added to the reactor, and the organometallic compound and the external electron donor are added and mixed thoroughly. The cocatalyst organic metal compound is contacted with a main catalyst component such as a Ziegler-Natta catalyst in the second step to polymerize 1-butene.

Catalyst poisons such as water, oxygen, carbon monoxide, carbon dioxide, acetylene and the like must be removed beforehand in the reactor, and the catalyst poison such as water, oxygen, carbon monoxide, In parallel with the inert gas replacement method, the catalyst poison is removed.

In the second step, the main catalyst component and the inert gas are added, and the mixture is heated to the polymerization temperature while stirring to polymerize. At this time, a molecular weight regulator can be added together. 1-Butene used as a reactive monomer may be added in the same manner as the initial solvent of the reaction, or may be continuously supplied after the catalyst is introduced.

Ziegler-Natta, etc., into a reactor, adding a molecular weight regulator, pressurizing with an inert gas, and heating the mixture to the polymerization temperature while stirring to polymerize.

At this time, the polymerization reaction temperature is preferably 0 ° C to 110 ° C, more preferably 0 ° C to 90 ° C. In order to induce slurry polymerization, it is more preferable to keep the reaction temperature as low as possible at about 0 캜 to 45 캜.

The pressure to be used is about 1 to 1000 bar, preferably 1 to 60 bar. The polymerization time is, for example, generally about 10 minutes to 20 hours, preferably about 30 minutes to 4 hours, in the case of a batch reaction, and generally about 10 minutes even in a continuous (CSTR) To 20 hours, preferably about 30 minutes to 4 hours.

High polymerization activity can be obtained at such reaction temperature, pressure and time.

Hydrogen is used as a molecular weight regulator to control the polymer molecular weight. On the other hand, the molecular weight of the polymer can be controlled by controlling the reaction temperature.

This second step leads to slurry polymerization in addition to solution polymerization, especially by using propane as a solvent in the reaction system. In this case, appropriate solvent and appropriate reaction temperature can be selected to induce slurry polymerization.

On the other hand, if necessary, alpha -olefins having 2, 3, and 5 to 10 carbon atoms such as ethylene or propylene may be added as comonomers in an amount of 0 to 20 parts by weight based on 100 parts by weight of 1-butene. Accordingly, the polybutene-1 homopolymer or copolymer of the present invention is obtained by copolymerizing 100 parts by weight of 1-butene with 0 to 20 parts by weight of at least one? -Olefin selected from the group consisting of?,?, And? Section.

In the next step, the produced polybutene-1 is stirred in a polymerization reactor or a separate vessel, and stabilizer and additives are added to the mixture.

As the stabilizer and the additive, a phenol-based antioxidant, phosphorus or sulfur-based antioxidant, a heat stabilizer, a nucleating agent and the like which are used in the polyolefin-based resin may be used. Other stabilizers and additives may be further added.

In commercial applications, heat is applied to polybutene-1 for transport after decompression. In the third step, an antioxidant or the like may be added to reduce the degradation due to heat applied to the polybutene-1.

When the polymerization reactor is a batch, it can be directly introduced into the reactor without a separate reactor. In the case of continuous continuous mixing type (CSTR), stabilizer and additive (k) in a container equipped with a separate stirring device or another mixing device, And the mixture can be uniformly mixed.

In the next step, the unreacted monomer is removed after decompression to form a solid. In the fourth step, the polybutene-1 in solid form can be obtained by decompression.

The present invention also provides a polybutene-1 homopolymer produced according to the aforementioned production method. The obtained polybutene-1 homopolymer shows the shape of a solid slurry or powder.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example  One

(a) Preparation of catalyst

50 ml of decane and 3.0 g of magnesium chloride were added to a 1 L four-necked round bottom flask equipped with a magnetic stirrer, a condenser and a temperature sensor under a nitrogen stream, and the mixture was stirred for several minutes. Then, 1 ml of 2-ethylhexanol was added thereto, The temperature was raised to 130 캜 and reacted for 1 hour.

After the reaction for 1 hour, 1.0 g of phthalate was added and the mixture was reacted by stirring for 1 hour under a nitrogen atmosphere at 130 캜. The reaction product of the homogeneous solution thus obtained was cooled to room temperature and titanium tetrachloride was added dropwise at a low temperature over 1 hour and stirred to obtain a slurry containing the solid product.

The solid product was isolated by filtration and washed four times with heptane. After adding 50 ml of toluene to the solid product thus obtained, titanium chloride was added thereto while stirring, and the temperature was raised to 100 ° C. Then, 2-isopropyl-2-isopropyl-2- trimethylsilyllmethyl-1,3-dimethoxy propane) was added dropwise to the mixture, and the mixture was heated to 110 DEG C and reacted for 2 hours.

After the completion of the reaction, the solid product was separated by filtration, washed with heptane four times, heptane was added again, and titanium chloride was added thereto, followed by reaction at 98 ° C for 2 hours. As a result, the solid catalyst component produced here was separated by filtration, and heptane was added to thoroughly carry out the washing operation until the free titanium compound was no longer detected to obtain a solid catalyst component suspended in heptane.

Analysis of the obtained catalyst components using ICP revealed that 2 to 3 wt% of titanium and 16 to 19 wt% of magnesium were present.

(b) Polybutene -1 Polymerization

After repeating the vacuum and nitrogen substitution processes for a 1 liter stainless steel autoclave, 0.068 g of the solid catalyst component prepared above, 0.44 mmol of diisobutylmethoxysilane, 0.15 g of triethylaluminum chloride (TEA) , 1.12 mmol of hydrogen and 196 g of propane. Additional pressure of 36 bar was applied with nitrogen, then the reactor temperature was raised to 40 < 0 > C. Subsequently, 85 g of 1-butene (1-butene) was continuously added over 3 hours, and polymerization was further continued for 3 hours. The reactor stirring speed was 500 rpm.

Thereafter, the reactor was depressurized to remove unreacted 1-butene monomer, and the obtained polymer was dried at 40 캜 under vacuum for 24 hours.

The polybutene-1 polymer obtained by drying shows the shape of solid slurry and powder.

Comparative Example  One

A polybutene-1 polymer was prepared under the same conditions as in Example 1, except that 1-butene was added instead of propane in the reactor.

The polymer does not have a slurry form or a powder form after drying and can be confirmed to be coated in a film form.

Claims (18)

1. A process for producing a polybutene-1 homopolymer by the polymerization reaction of a monomer containing butene-1 in the presence of a Ziegler-like catalyst, characterized by comprising the step of polymerizing a polybutene-1 homopolymer , ≪ / RTI &
Wherein the catalyst is a magnesium-supported polymerization catalyst in which a transition metal compound and an internal electron donor are supported on a carrier containing magnesium. delete delete delete The magnesium-supported polymerization catalyst according to claim 1, wherein the magnesium-supported polymerization catalyst is a polybutene-1 homopolymer comprising 1 to 4 parts by weight of titanium, 15 to 30 parts by weight of magnesium, 60 to 80 parts by weight of halogen and 0 to 1 part by weight of silicon ≪ / RTI > The method for producing a polybutene-1 homopolymer according to claim 1, wherein the internal electron donor is a compound represented by the following formula
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 5 to 20 carbon atoms, R ₆ is an aliphatic hydrocarbon having 1 to 30 carbon atoms or an aromatic hydrocarbon having 5 to 30 carbon atoms, R ₃ , R ₄ and R ₅ are each independently hydrogen or an aliphatic hydrocarbon having 1 to 30 carbon atoms or an aromatic hydrocarbon having 5 to 30 carbon atoms. delete The catalyst of claim 1, wherein the catalyst is a polybutene-based catalyst comprising an organometallic compound as a cocatalyst and containing Group I metals of the Periodic Table 1 (IA), 2 (IIA), 12 (IIB), 13 (IIIA) 1 < / RTI > The process for producing a polybutene-1 homopolymer according to claim 8, wherein the organometallic compound is an alkyl aluminum sesquichloride, an alkylaluminoxane,
(2)
(R _{7) n} MX _{3 -n}
Wherein M is a Group 12 or Group 13 metal, R ₇ is a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, X is a halogen atom, and n is an integer of 1 to 3. The method of claim 9, wherein the organometallic compound is selected from the group consisting of diethylaluminum chloride (DEAC), ethylaluminum dichloride (EADC), dinormalbutylaluminum chloride (DNBAC), diisobutylaluminum chloride (DIBAC), ethylaluminum sesquichloride (TEA), triethylaluminum (TEA), triisobutylaluminum (TIBA), trinormal hexylaluminum (TNHA), trinornalooctylaluminum (TNOA), trinormaldecylaluminum Triisobutylborane, triisobutylborane, triisobutylborane, and methylaluminoxane (MAO). The catalyst according to claim 1, wherein the catalyst is selected from the group consisting of polybutene-1-ene catalysts containing at least one cocatalyst selected from the group consisting of silane compounds, inorganic acids, hydrogen sulfide, ethers, diethers, esters, amines, organic acids, ≪ / RTI > The method for producing a polybutene-1 homopolymer according to claim 11, wherein the promoter is an alkoxysilane compound. delete The process for producing a polybutene-1 homopolymer according to claim 1, wherein the polymerization reaction temperature is from 0 ° C to 110 ° C. The process for producing a polybutene-1 homopolymer according to claim 1, wherein the polymerization reaction temperature is 0 ° C to 90 ° C. The process for producing a polybutene-1 homopolymer according to claim 1, wherein the temperature of the polymerization reaction is 0 ° C to 45 ° C. The process for producing a polybutene-1 homopolymer according to claim 1, wherein the pressure of the polymerization reaction is from 1 bar to 1000 bar. The process for producing a polybutene-1 homopolymer according to claim 1, wherein the polymerization time is from 10 minutes to 20 hours.