KR102179648B1 - Manufacturing method of polyketone using solid acids - Google Patents

Abstract

The method for producing a polyketone according to the present invention comprises a Group 10 transition metal compound; A ligand having an element of Group 15; And copolymerizing carbon monoxide, an ethylenically unsaturated compound, and one or more olefinically unsaturated hydrocarbon compounds in the presence of a catalyst including a solid acid, wherein the solid acid is a support; solid oxide particles; An anchor group including a phenyl group at the terminal and an alkoxy or amine group; And an acid group.

Description

Manufacturing method of polyketone using solid acid {MANUFACTURING METHOD OF POLYKETONE USING SOLID ACIDS}

The present invention relates to a method for producing a polyketone using a solid acid.

Polyketone (PK) is a material with lower raw material and polymerization process costs compared to general engineering plastic materials such as polyamide, polyester and polycarbonate, and has excellent heat resistance, chemical resistance, impact resistance, and fuel permeability.

Polyketones with these characteristics are included in general-purpose high-performance plastics, have strengths comparable to those of conventional engineering plastics, and have good affinity with rubber. Due to the characteristics of such polyketones, polyketones may be used for tire cords or rubber materials in which conventional paraffin-based aramid fibers are exclusively used.

On the other hand, as a polymerization method of polyketone, a liquid slurry polymerization method is generally used. At this time, alcohol, acetic acid, etc. can be used as the liquid solvent, and each solvent is involved in the initiator of the transition metal catalyst and the chain transfer mechanism to proceed the polymerization reaction, and carbon monoxide and ethylenically unsaturated compounds It ensures easy reactivity between the catalyst and the monomer through the dissolution of the phosphorus monomer.

However, when the polymerization proceeds, the catalyst and the solvent exist in a homogeneous form, and thus may exist anywhere in the polymerization reactor during stirring. Some of the polyketone polymers formed at this time form fouling on the wall of the reactor, the top of the reactor, the stirrer, and the transfer line, causing problems in polymerization properties and processes. In order to solve this problem, when the heterogeneous catalyst developed so far is applied to polyketone polymerization, there is a problem that the activity falls to 1/10 level compared to the application of the existing homogeneous catalyst.

Accordingly, there is a demand for a heterogeneous catalyst capable of reducing fouling without affecting the polymerization activity of the polyketone and a method for producing a polyketone using the same.

It is an object of the present invention to provide a method for producing a polyke using a heterogeneous solid acid.

A method for producing a polyketone according to an embodiment of the present invention includes a group 10 transition metal compound; A ligand having an element of Group 15; And copolymerizing carbon monoxide, an ethylenically unsaturated compound, and one or more olefinically unsaturated hydrocarbon compounds in the presence of a catalyst including a solid acid, wherein the solid acid comprises a spherical solid oxide particle as a support; Acid group; And an anchor group of a compound including a phenyl group at a terminal connecting the solid oxide particle and the acid group to be tripled.

In this case, the content of the solid acid may be 0.03 to 0.30% by weight based on the total weight of the polyketone.

In addition, the solid oxide particles may be at least one selected from the group consisting of SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , CeO ₂ and Y ₂ O ₃ .

The compound containing a phenyl group at the terminal includes an alkoxy or amine group, and the group consisting of triethoxyphenylsilane, trimethoxyphenylsilane, phenyl vinyl ether, diphenylamine, and phenyl-(1-phenylethylidene)amine It may be one or more selected from.

The acids are sulfuric acid, pyrogenic sulfuric acid, sulfur trioxide, trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TfOH), trifluoroacetic acid, paratoluenesulfonic acid (p-TsOH), acetic acid, benzoic acid and chlorosulphonic acid. It may be one or more selected from the group consisting of.

In addition, the catalytic activity of the polyketone may be 15 to 22 kg/g-Pd·hr.

According to an embodiment of the present invention, by preparing a polyketone using a structurally stable heterogeneous solid acid, the solid acid exists in a heterogeneous state during polymerization, so polymerization can occur only in a solid acid, not in a solution phase, There is an advantage of controlling the molecular weight and particle size of the polyketone because the pH can be adjusted according to the amount of solid acid added.

In addition, as described above, since the solid acid exists in a heterogeneous state and the polymerization site is limited, fouling that may occur during polyketone polymerization can be reduced.

1 shows a result of confirming the chemical bond structure of a polyketone prepared according to an embodiment of the present invention using XPS (X-ray Photoelectron Spectroscopy).

In the present invention, various modifications may be made and various forms may be applied, and specific embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance the possibility of the presence or addition. Further, when a part such as a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where the other part is "directly above", but also the case where there is another part in the middle. Conversely, when a part such as a layer, film, region, plate, etc. is said to be "under" another part, this includes not only the case where the other part is "directly below", but also the case where there is another part in the middle. In addition, in the present application, the term "above" may include a case where it is disposed not only above but also below.

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

A method for preparing a polyketone according to an embodiment includes a Group 10 transition metal compound; A ligand having an element of Group 15; And copolymerizing carbon monoxide, an ethylenically unsaturated compound, and one or more olefinically unsaturated hydrocarbon compounds in the presence of a catalyst including a solid acid.

First, the polyketone is a linear alternating structure, and substantially contains carbon monoxide per molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers have up to 20 carbon atoms, preferably up to 10 carbon atoms. In addition, ethylenically unsaturated hydrocarbons include ethene and α-olefins, such as propene, 1-butene, iso-butene, 1-hexene, and 1-octene. ), or an aryl aliphatic containing an aryl substituent on another aliphatic molecule, and particularly an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons among ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene, and m-isopropyl styrene. The polyketone polymer preferably used in the present invention is a copolymer of carbon monoxide and ethene, or a second ethylenically unsaturated hydrocarbon having at least 3 carbon atoms with carbon monoxide and ethene, especially α-olefins such as propene. It is a terpolymer of the family.

When the polyketone terpolymer is used as the main polymer component of the composition according to the present invention, with respect to each unit containing the second hydrocarbon moiety in the terpolymer, there are at least two units containing an ethylene moiety. It is preferable that there are 10 to 100 units containing the second hydrocarbon moiety.

The polymer ring of the preferred polyketone polymer in the present invention can be represented by the following structural formula 1.

[Structural Formula 1]

-[CO-(-CH2-CH2-)-]x-[CO-(G)]y-

In the above Structural Formula 1, G is an ethylenically unsaturated hydrocarbon, particularly a moiety obtained from an ethylenically unsaturated hydrocarbon having at least 3 carbon atoms, and x:y is preferably at least 1:0.01.

In another embodiment, the polyketone polymer is a copolymer composed of repeating units represented by general formulas (1) and (2), and y/x is preferably 0.03 to 0.3. When the value of the y/x value is less than 0.03, there is a limit to inferior meltability and workability, and when it exceeds 0.3, mechanical properties are inferior. Further, y/x is more preferably 0.03 to 0.1.

-[-CH2CH2-CO]x- (1)

-[-CH2-CH(CH3)-CO]y- (2)

In addition, the melting point of the polymer can be controlled by adjusting the ratio of ethylene and propylene in the polyketone polymer. For example, when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46:4:50, the melting point is about 220℃, but when the molar ratio is adjusted to 47.3:2.7:50, the melting point is adjusted to 235℃.

Polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000 as measured by gel permeation chromatography, are particularly preferred. The physical properties of the polymer are determined according to the molecular weight, depending on the polymer being a copolymer or terpolymer, and in the case of a terpolymer, depending on the properties of the second hydrocarbon moiety present. The melting point of the polymer used in the present invention is 175°C to 300°C, and may be generally 210°C to 270°C, but in the present invention, it is preferable to use a polyketone having a melting point of 210 to 235°C. In addition, the intrinsic viscosity (IV) of the polymer measured at 60°C using a standard customs viscosity measuring device and HFIP (Hexafluoroisopropylalcohol) is 0.5 dl/g to 10 dl/g, and preferably 0.8 dl/g to 4 dl/g. , More preferably, it is 1.1 dl/g-2.5 dl/g. At this time, if the number of intrinsic viscosity is less than 1.1 dl/g, mechanical properties deteriorate, and if it exceeds 2.5 dl/g, processability deteriorates.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. If it is less than 1.5, the polymerization yield is lowered, and if it is more than 2.5, there is a problem that the moldability is lowered. In order to control the molecular weight distribution, it can be adjusted in proportion to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst increases or the polymerization temperature is 100°C or higher, the molecular weight distribution increases.

Hereinafter, the polymerization process of the polyketone polymer will be described in detail.

Carbon monoxide, ethylenically unsaturated compounds and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, especially repeating units derived from carbon monoxide and ethylenically unsaturated compounds, and repeating units derived from propylene-based unsaturated compounds are substantially Polyketones of alternatingly connected structures have excellent mechanical and thermal properties, excellent processability, and high wear resistance, chemical resistance, and gas barrier properties, making them useful materials for various purposes. The high molecular weight substance of this ternary or higher copolymerized polyketone has higher processability and thermal properties, and is considered to be useful as an engineering plastic material having excellent economical efficiency. In particular, it can be used for parts such as gears of automobiles due to its high wear resistance, linings for chemical transport pipes, etc. due to its high chemical resistance, and lightweight gasoline tanks due to its high gas barrier properties. In addition, when an ultra-high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fiber, it is possible to draw a high magnification, and as a fiber with high strength and high modulus of elasticity oriented in the drawing direction, it is a reinforcing material for belts, rubber hoses, tire cords, concrete reinforcing materials. It becomes a very suitable material for building materials or industrial materials.

The method for preparing polyketone is in the presence of (a) a group 10 transition metal compound, (b) a ligand having an element of group 15, and (c) a solid acid-containing catalyst, in a liquid medium containing carbon monoxide, ethylenic and propylene. In the method for producing polyketone by ternary copolymerization of a sexually unsaturated compound, the carbon monoxide, ethylene, and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer, and the mixed solvent is methanol A mixture of 100 parts by weight and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, ketals are formed, the thermal stability may decrease during the process, and if it exceeds 10 parts by weight, the mechanical properties of the product may decrease.

Here, the catalyst is composed of (a) a Group 9, Group 10, or Group 11 transition metal compound of the Periodic Table (IUPAC Nomenclature Revised Edition, 1989), and (b) a ligand having an element of Group 15.

Examples of the Group 10 transition metal compound (a) include complexes of nickel or palladium, carbonate, phosphate, carbamate, sulfonate, and the like, and specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, and trifluoro. Examples include palladium acetate, palladium acetylacetate, palladium chloride, bis(N,N-diethylcarbamate)bis(diethylamine)palladium, palladium sulfate, and the like.

Among them, the transition metal compound (a), which is inexpensive and economically preferable, is a nickel compound, and the transition metal compound (a), which is preferable in terms of the yield and molecular weight of the polyketone, is a palladium compound, and acetic acid in terms of improving catalytic activity and intrinsic viscosity. It is most preferred to use palladium.

Examples of the ligand (b) having an atom of Group 15 include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picoline , Nitrogen ligands such as 2,2'-bikinoline, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino) Butane, 1,3-bis[di(2-methyl)phosphino]propane, 1,3-bis[di(2-isopropyl)phosphino]propane, 1,3-bis[di(2-methoxyphenyl) )Phosphino]propane, 1,3-bis[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]propane, 1,2-bis(diphenylphosphino)cyclohexane, 1,2-bis (Diphenylphosphino)benzene, 1,2-bis[(diphenylphosphino)methyl]benzene, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, 1,2- Bis[[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]methyl]benzene, 1,1'-bis(diphenylphosphino)ferrocene, 2-hydroxy-1,3-bis[di (2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, ((2,2-dimethyl-1,3-di Phosphorus ligands such as oxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine), (cyclohexane-1,1-diylbis(methylene))bis(bis( 2-methoxyphenyl)phosphine, and the like.

Among them, the preferred ligand (b) having an element of Group 15 is a phosphorus ligand having an atom of Group 15, and particularly preferred in terms of the yield of polyketone is 1,3-bis[di(2- Methoxyphenyl)phosphino]propane, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, and in terms of the molecular weight of the polyketone, 2-hydroxy-1,3-bis[ It is di(2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, and it does not require an organic solvent and is safe. Water-soluble 1,3-bis[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]propane, 1,2-bis[[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino] ]Methyl]benzene, which is easy to synthesize, can be obtained in large quantities, and is preferably 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino)butane in terms of economy. The preferred ligand (b) having an atom of Group 15 is 1,3-bis[di(2-methoxyphenyl)phosphino]propane or 1,3-bis(diphenylphosphino)propane, most preferably 1,3-bis[di(2-methoxyphenyl)phosphino]propane, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2 -Methoxyphenyl)phosphine) or (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine.

[Formula 1]

((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) of Formula 1 is a polyketone introduced so far. Expression equivalent to 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane, which is known to exhibit the highest activity among polymerization catalysts It is a material with a simpler structure and a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst in the art and further reducing its manufacturing cost and cost. The preparation method of the ligand for polyketone polymerization catalyst is as follows. Using bis(2-methoxyphenyl)phosphine, 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) ((2,2-dimethyl -1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) is obtained. A method for preparing a ligand for a polyketone polymerization catalyst is provided. . The method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventional 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-) through an easy process in a safe environment where lithium is not used, Methoxyphenyl)phosphine) can be commercially synthesized in large quantities.

On the other hand, it is also preferable to use (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine as the ligand used in the polymerization catalyst. It is as the following scheme.

[Reaction Scheme]

The (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine ligand can be synthesized through the following four steps: First, diethylmalonate and 1, 5-dibromopentane is boiled under sodium ethoxide and ethanol, then reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexanedimethanol, and reacted under tosyl chloride and pyridine to obtain release By reacting this ligand with 2-methoxyphenylphosphine, sodium hydride and dimethyl sulfoxide, the ligand can be obtained, and each step undergoes purification steps such as column chromatography and recrystallization. The purity can be confirmed through nuclear magnetic resonance analysis.

In a preferred embodiment, the method for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises adding bis(2-methoxyphenyl)phosphine and dimethylsulfoxide (DMSO) to a reaction vessel under nitrogen atmosphere and adding sodium hydride at room temperature. Followed by stirring; Adding 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and dimethyl sulfoxide to the obtained mixture, followed by stirring to react; Adding methanol and stirring after completion of the reaction; Adding toluene and water, washing the oil layer with water after layer separation, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And recrystallization of the residue under methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine). It can be done through

Since the appropriate value of the group 10 transition metal compound (a) varies depending on the type of ethylenic and propylene unsaturated compounds selected or other polymerization conditions, the range cannot be uniformly limited, but usually It is 0.01 to 100 millimoles, preferably 0.01 to 10 millimoles, per 1 liter of the capacity of the reaction band. The capacity of the reaction zone refers to the capacity of the liquid phase of the reactor. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 moles, preferably 1 to 3 moles, per 1 mole of the transition metal compound (a).

On the other hand, the solid acid used as the catalyst of the present invention is a support solid oxide particles; Anchor group; And an acid group.

At this time, the solid oxide particles may be at least one selected from the group consisting of SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , CeO ₂ and Y ₂ O ₃ , and preferably silica.

In addition, the solid oxide particles are preferably inorganic in the form of spherical solid oxide particles having a particle diameter of 5 nm to 500 nm, and more preferably an oxide form having no impurities on the surface by having a size of 10 to 500 nm. If the particle diameter of the solid oxide particles is less than 5 nm, self-aggregation of the solid oxide particles occurs, and when it exceeds 500 nm, the total surface area of the solid oxide particles becomes small, preventing it from functioning as a solid acid. do.

On the other hand, the compound containing a phenyl group at the terminal is an anchor group, and it is preferable to contain a phenyl group in order to bond the solid oxide particles as a support and the acid functional group on the surface of the solid acid in a chemically stable structure. . Further, the anchor group group is preferably a compound having a phenyl group at the terminal and an alkoxy or amine group that reacts with the solid support layer particles. Specific examples of the compound containing a phenyl group at the terminal and containing an alkoxy or amine group include triethoxyphenylsilane, trimethoxyphenylsilane, phenyl vinyl ether, diphenylamine, and It may be one or more selected from the group consisting of phenyl-(1-phenylethylidene)amine, but is not limited thereto.

In order to prepare a compound containing a phenyl group at the terminal in a sol state, it is preferable that the compound containing a phenyl group at the terminal is an alkoxy silane compound, and the step of preparing a sol state using triethoxyphenylsilane (TEPS) is specifically described. Explained as.

The alkoxy silane-based sol can be synthesized by mixing a silane such as TEPS in an alcohol solvent, and adding a certain amount of water and an acidic solution to perform a hydration reaction. For example, after mixing an alkoxy silane such as TEPS in an alcohol solvent such as methanol to a concentration of 0.1 to 5M, water is added so that the molar ratio of TEPS:H ₂ O is about 1:0.1 to 10, and the concentration of acid is A silane-based sol can be synthesized by adding an acidic solution such as hydrochloric acid or nitric acid to a concentration of 5Х10 ^-4 ∼0.5M to cause a hydration reaction.

On the other hand, in the step of stirring and reacting the solid oxide particles modified with a phenyl group and an acid (acid), the weight ratio of the solid oxide particles modified with the phenyl group and the acid may be 1:0.0001 to 1.0, preferably 1:0.01 to 0.5 If the concentration of the acid is too low, the hydrolysis reaction rate is too low to be unrealistic, and the catalytic activity is low because the concentration of the acid in the obtained solid acid is also low, and if the concentration of the acid is too high, the hydrolysis and condensation reactions are too high. In consideration of the low chemical and thermal stability of the violently obtained solid acid, it may be more preferably 1:0.05 to 0.5.

In addition, non-limiting examples of acids include sulfuric acid, pyrogenic sulfuric acid, sulfur trioxide, trifluoroacetic acid (TFA), trifluoromethanesulfonic acid (TfOH), trifluoroacetic acid, paratoluenesulfonic acid (p-TsOH), acetic acid. , It may be one or more selected from the group consisting of benzoic acid and chlorosulfonic acid, and is preferably an acid containing a sulfone group such as sulfuric acid, TfOH, p-TsOH, and the like. It is preferable that the concentration of such an acid is 30 to 70%, and if the concentration is less than 30%, the strength of the acid decreases, making it difficult to show acidity, and if it exceeds 70%, the problem occurs in that the particles are browned and the color changes. do.

A method of preparing a solid acid according to an embodiment comprises the steps of reacting a solid oxide particle with a compound containing a phenyl group at the terminal to prepare a solid oxide particle modified with a phenyl group; And it may include the step of reacting the solid oxide particles modified with the phenyl group and an acid (acid).

More specifically, prior to the step of preparing the solid oxide particles modified with a phenyl group, treating the solid oxide particles with an initiator; And preparing a compound containing a phenyl group at the terminal in a sol state, but is not limited thereto.

On the other hand, the stirring can be heated at 0 to 200°C for 5 minutes to 24 hours, preferably at 25 to 100°C for 1 to 12 hours, and ultrasonic irradiation or microwave irradiation can be used to increase the reaction rate. have.

In addition, the solid acid obtained in the step of reacting by stirring the solid oxide particles modified with a phenyl group and an acid may further include washing and drying.

In the case of the conventional solid acid, a high temperature of 200°C or higher is required in the firing step during the manufacturing process, and there is a problem that most of the produced catalysts exhibit unstable properties in a polar solvent, but the solid according to an embodiment of the present invention The manufacturing method of the acid does not require a high temperature during the manufacturing process, and thus the prepared solid acid exhibits stable properties even in a polar solvent.

In addition, the solid acid prepared as described above can be applied to a heterogeneous catalyst. Specifically, the solid acid of the present invention is a spherical solid oxide particle (support), a compound containing a phenyl group at the end and an alkoxy or amine group (anchor group, anchor group) in order to maintain stable performance even in an organic solvent or a polar solvent, It is characterized by consisting of three groups of acid groups (functional groups), and an example of such a solid acid is shown in Formula 2 below.

[Formula 2]

As shown in Chemical Formula 2, spherical solid particles as a support may serve to maintain a solid form without dissolving the prepared solid acid in a polar solvent or any organic solvent.

In addition, alkoxysilane containing a phenyl group as an anchor group has a structure that plays an intermediate role to stably support a sulfone acid functional group on the spherical support particles, even in polar solvents. Chemically, it has a characteristic of stably supporting a sulfone functional group.

In addition, such a solid acid having a structure containing a sulfone group in a chemically stable manner shows stable performance in an organic solvent or a polar solvent environment, and can be used as a solid acid in a heterogeneous catalyst.

As a result, such a solid acid is not dissolved in methanol, which is a solvent, and thus exists in a heterogeneous state during polymerization, so that polymerization of polyketone can occur only in a solid acid, not in a solution. In addition, there is an advantage that the molecular weight and particle size can be adjusted because the pH can be adjusted according to the input amount of the solid acid. In addition, as the solid acid exists in a heterogeneous state and the polymerization site is limited, fouling that may occur during polyketone polymerization can be reduced.

On the other hand, the input amount (content) of the solid acid is preferably 0.03 to 0.30% by weight, and more preferably 0.03 to 0.20% by weight, based on the total weight of the polyketone. If the input amount of the solid acid is less than 0.03% by weight, the pH is too high and the catalytic activity is low, or abnormalities in the physical properties of the polyketone may occur, and if it exceeds 0.30% by weight, the pH is too low to cause browning of the polyketone powder. Will occur.

Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Α-olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and α-methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins, such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic acid esters, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Among these, preferred ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, and most preferably ethylene.

The three-way copolymerization of carbon monoxide with the ethylenically unsaturated compound and the propylene unsaturated compound is caused by a catalyst comprising the group 10 transition metal compound (a), a ligand having an element of group 15 (b), and a solid acid. The catalyst is produced by contacting the two components. Any method can be adopted as a method of contacting. That is, in a suitable solvent, the two components may be premixed and used, or the two components may be separately supplied to the polymerization system and brought into contact within the polymerization system.

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, and a gas phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution are used. The polymerization may be a batch type or a continuous type. As the reactor used for polymerization, a known reactor can be used as it is or processed. The polymerization temperature is not particularly limited, and is generally 40 to 180°C, preferably 50 to 120°C. There is also no restriction on the pressure during polymerization, but it is generally normal pressure to 20 MPa, preferably 4 to 15 MPa.

Linearly alternating polyketones are formed by the polymerization method as described above, and the catalytic activity of the polyketone may be 15 to 22 kg/g-Pd·hr.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only illustrative of the present invention, and the present invention is not limited by the following examples.

[Production Example 1]

1g silica powder (0.5㎛) was added to 0.01M potassium persulfate (K ₂ S ₂ O ₈ ) solution, and then stirred at 80°C for 2 hours to provide a hydroxyl group on the silica surface. ) Was created. Thereafter, the initiator-treated silica particles were filtered with a filter having a pore size of 0.22 μm, and the initiator solution remaining with a methanol solution was washed and dried in an oven at 80° C. to obtain 1 g of surface-treated silica powder. Thereafter, anhydrous ethyl alcohol (Ethyl alcohol) as a solvent and water for hydrolysis were used to prepare Sol, and as a catalyst, 1N hydrochloric acid and Triethoxyphenylsilane (TEPS) containing a phenyl group as a functional group were used. 100ml of sol was prepared in the ratio of EtOH/TEPS=4, H ₂ O/TEPS=2, and HCl/TEPS=0.01.

Into 100 ml of the sol solution prepared above, 1 g of silica particles treated with the initiator were put into a reactor, and after mixing, a silylation reaction was performed at 40° C. for 2 hours. Modified-silica particles are filtered with a filter with a pore size of 0.22㎛, washed with the sol solution remaining with a methanol solution, dried in an oven at 80℃, and modified with a phenyl group (modified-silica powder). ) 1g was obtained.

Thereafter, 1 g of silica particles modified with the phenyl group were added to 100 ml of a 30% sulfuric acid solution, and a sulfonation reaction was performed at 60° C. for 12 hours or longer. Thereafter, after filtering with a filter having a pore size of 0.22 μm, the remaining sulfuric acid solution was washed with a methanol solution and then dried in an oven at 80° C. to obtain 1 g of sulfonated-silica powder.

[Comparative Preparation Example 1]

During the sulfonation reaction, a sulfonated silica powder was obtained through the same procedure as in Preparation Example 1, except that a 15% sulfuric acid solution was used instead of a 30% sulfuric acid solution.

[Comparative Preparation Example 2]

A sulfonated silica powder was obtained through the same procedure as in Preparation Example 1, except that silica powder having a particle diameter of 0.5 μm was used instead of silica powder having a particle diameter of 1.0 μm.

[Example 1]

0.0332 g of (2,2-dimethyl-1,3-dioxane-5,5-diyl) bis(methylene))bis(bis(2-methoxyphenyl)phosphine) was dissolved in 20 mL of acetone and palladium acetate 0.0112 g Was dissolved by adding. At the start of polymerization, 0.342 g of the solid acid prepared in Preparation Example 1 was added, followed by stirring to prepare a catalyst solution. After adding 1,960 mL of methanol and 32 mL of water to the stainless reactor, the solution was purged with 3.5 bar nitrogen three times to remove air. After filling 150 g of propylene into a 4 L reactor, the temperature of the reactor was increased to 82.5 degrees Celsius. While stirring the stirrer, it was charged up to 56 bar at a ratio of carbon monoxide:ethylene=1:1. Polymerization was initiated while introducing the catalyst solution prepared above with a high-pressure pump, and the pressure of the polymerization reactor was supplemented with carbon monoxide:ethylene=1:1 at 82.5°C for 2 hours to maintain 56 bar. Thereafter, polymerization was completed by holding for 25 minutes without supplying monomers. After polymerization, the methanol slurry was filtered and washed several times with methanol to obtain a polyketone powder.

The chemical bond structure of the polyketone polymer was confirmed using X-ray Photoelectron Spectroscopy (XPS), and the results are shown in FIG. 1. As a result of XPS spectrum analysis, a Si peak was confirmed at a BE value of 100.6, which can be seen as polymerization by a silica-supported solid acid.

[Examples 2 to 3 and Comparative Examples 1 to 2]

Each polyketone was prepared through the same procedure as in Example 1, except that the content of the solid acid was adjusted as described in Table 1 below.

[Comparative Examples 3 to 5]

Polyketone was prepared through the same process as in Example 1, except that the solid acid shown in Table 1 was added instead of the solid acid prepared in Preparation Example 1, and the content was adjusted as shown in Table 1 below.

Catalytic acid Solid acid input amount (g) Catalyst activity (kg/g-Pd·hr) IV(dl/g) Particle size (Dv50, ㎛) Presence or absence of fouling Powder color Example 1 Manufacturing Example 1 0.342 20.201 1.010 31 radish White Example 2 Manufacturing Example 1 0.228 20.080 0.927 32 radish White Example 3 Manufacturing Example 1 0.114 15.583 0.751 33 radish White Comparative Example 1 Manufacturing Example 1 0.456 20.330 1.018 30 radish Brown Comparative Example 2 Manufacturing Example 1 0.057 10.115 0.523 31 radish White Comparative Example 3 Comparative Production Example 1 0.114 10.751 0.550 22 radish White Comparative Example 4 Comparative Production Example 2 0.114 6.091 0.428 19 radish White Comparative Example 5 TFA 0.057 17.420 1.181 38 U White

Looking at Table 1, it can be seen that the catalytic activity is low when the solid acid input amount is less than 0.114 g (Comparative Example 2), and when the solid acid input amount exceeds 0.342 g (Comparative Example 1), the catalytic activity when solid acid is added. It can be confirmed that this sharp decrease occurs, and the browning phenomenon of the polyketone powder occurs. In addition, in the case of using trifluoroacetic acid (TFA) in the related art (Comparative Example 5), it was found that the catalyst and the solvent, methanol, were homogeneous, and fouling occurred in many places.

On the other hand, when the concentration of sulfuric acid is less than 30% during the production of the solid acid (Comparative Example 3), the strength of the acid is reduced, and it can be confirmed that the catalytic activity is significantly lower than that of the Example, despite the same amount of input as Example 3 and the solid acid. have. In addition, in the case of using silica having a particle diameter of more than 500 nm when preparing the solid acid (Comparative Example 4), the total surface area of the solid oxide particles became small, so that it could not play a role as a solid acid. In spite of the same, it can be seen that the catalytic activity is remarkably low compared to the examples.

On the other hand, when the polyketone is polymerized using a solid acid as in the example, it exhibits an activity of 15 to 22 kg/g-Pd·hr, which is similar or more than when polymerization is performed using the conventional TFA (Comparative Example 5). You can see that it is a level. In addition, when using a solid acid, the intrinsic viscosity of the polyketone is 0.7 to 1.1 dl/g, increased compared to the conventional TFA (Comparative Example 5), and the particle size (Dv50) can be adjusted to a level of 31 to 33 μm. Through this, it can be seen that the molecular weight and particle size of the polyketone can be controlled by controlling the amount of the solid acid. In addition, only about 0.06% by weight of the solid acid was added compared to the polymerized polyketone powder, which makes it possible to reduce fouling and control the molecular weight and particle size without affecting the physical properties of the polyketone, and the catalyst and solvent (methanol) are heterogeneous. Because it is heterogeneous, the polymerization site is limited, which is effective in reducing fouling.

Although the above has been described with reference to the preferred embodiments of the present invention, those skilled in the art or those of ordinary skill in the art will not depart from the spirit and scope of the present invention described in the claims to be described later. It will be understood that various modifications and changes can be made to the present invention within the scope of the invention.

Therefore, the technical scope of the present invention should not be limited to the content described in the detailed description of the specification, but should be determined by the claims.

Claims (5)

Group 10 transition metal compounds; A ligand having an element of Group 15; And preparing a polyketone by copolymerizing carbon monoxide, an ethylenically unsaturated compound, and one or more olefinically unsaturated hydrocarbon compounds in the presence of a catalyst comprising a solid acid,
The solid acid is a spherical solid oxide particles as a support; Acid group; And an anchor group of triethoxyphenylsilane, which is a compound containing a phenyl group at a terminal connecting the solid oxide particle and the acid group,
The solid oxide particle is SiO ₂ , the particle diameter of the solid oxide particle is 10 to 500 nm, the acid group is a sulfone group,
The content of the solid acid is 0.03 to 0.30% by weight based on the total weight of the polyketone,
The polyketone has a catalytic activity of 15 to 22 kg/g-Pd·hr and a particle size (Dv50) of 31 to 33 μm.

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